JP2009096994A - Nonaqueous resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous resin dispersion excellent in heat resistant preservation stability and containing resin particles having a homogeneous particle diameter and shape. <P>SOLUTION: This nonaqueous resin dispersion is produced by dispersing core/shell-type resin particles (C) in a nonaqueous organic solvent (L) having a dielectric constant at 20°C of 1 to 4. The core/shell-type resin particles (C) comprise a shell layer (P) of one or more coating-like layers containing a first resin (a), and a core layer (Q) of one layer containing a second resin (b) and having a weight ratio of (P):(Q) of 1:99 to 70:30. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a non-aqueous resin dispersion. More specifically, the present invention relates to a non-aqueous resin dispersion useful for various applications such as an electrophotographic liquid developer, an electrostatic recording liquid developer, an oil-based ink for an inkjet printer, and an ink for electronic paper.

As a non-aqueous resin dispersion having a uniform particle size and shape, and excellent thermal characteristics, chemical stability, etc., the resin was previously melted and further heated above the softening point of the resin. A non-aqueous resin dispersion obtained by dispersing in a nonpolar medium by mechanical stirring and then cooling has been proposed (see Patent Document 1).
JP 09-179354 A

However, in this method, since the viscosity of the resin is not sufficiently lowered and the particles are not refined, the particle size distribution of the obtained resin particles may not be sharp. In addition, as a non-aqueous resin dispersion for use in liquid developers for paints, electrophotography, electrostatic recording, electrostatic printing, etc., the colorant contained in the main resin is exposed on the surface of the resin particles and is sufficiently It could not be said that the resin performance (heat-resistant storage stability, etc.) could be exhibited.
The present invention has been made in view of the above circumstances in the prior art. That is, an object of the present invention is to provide a non-aqueous resin dispersion that is excellent in heat-resistant storage stability and has a uniform particle size and shape.

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.
(I) 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). A non-aqueous organic solvent in which the core-shell type resin particles (C) having a weight ratio of P) and (Q) of (1:99) to (70:30) have a relative dielectric constant of 1 to 4 at 20 ° C. A non-aqueous resin dispersion dispersed in (L).
(II) Non-aqueous resin dispersion (W) in which resin particles (A) containing the first resin (a) are dispersed in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. ) And a solvent solution (O1) in which the second resin (b) is dissolved in an organic solvent (M) having a solubility parameter of 9.5 to 20, or a precursor of the resin (b) in (M) The solvent solution (O2) in which the body (b0) is dissolved is mixed, and (O1) or (O2) is dispersed in (W). When (O2) is used, (b0) is further reacted. The non-aqueous resin particles (D) having 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 (W). A resin dispersion (X1) is obtained, (M) is further distilled off from (X1), (A) is formed into a film, and a core composed of (B) A non-aqueous resin dispersion (X2) of core-shell type resin particles (C) in which a shell layer (P) in which (A) is formed on the surface of the layer (Q) is formed is obtained. A method for producing a non-aqueous resin dispersion.

The non-aqueous resin dispersion of the present invention has the following effects.
1. The particle size and shape of the resin particles contained are uniform.
2. Excellent heat storage stability and fluidity.

  One-layer core containing one or more film-like shell layers (P) containing the first resin (a) and the second resin (b) in the non-aqueous resin dispersion of the first invention In the core-shell type resin particles (C) composed of the layer (Q), the weight ratio of (P) and (Q) [(P) :( Q)] is the particle size uniformity of (C) From the viewpoint of the storage stability of the non-aqueous resin dispersion, it is (1:99) to (70:30), preferably (5:95) to (50:50), more preferably (10:90 to 35:65). When the weight of the shell portion is too small, the blocking resistance may be lowered. Moreover, when the weight of a shell part is too much, a particle size uniformity may fall. (P) may be formed of two or more layers (for example, 2 to 5 layers), but one layer is preferable.

As the non-aqueous organic solvent (L) in which the resin particles (C) are dispersed, it is necessary to use a solvent having a relative dielectric constant of 1 to 4 at 20 ° C. from the viewpoint of dispersion stability of (C).
For example, 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: exon) Company name), shell sol 70, shell sol 71 (shell sol: trade name of shell oil), Amsco OMS, Amsco 460 (amsco: product name of spirits), silicone oil, liquid paraffin, etc. It can be used by mixing.
Among these, from the viewpoint of odor, a solvent having a boiling point of 100 ° C. or higher is preferable, hydrocarbon solvents having 10 or more carbon atoms (such as dodecane, isododecane, and liquid paraffin) and silicone oil are more preferable, and liquid paraffin is particularly preferable. It is.
In the present invention, the dielectric constant is measured using a bridge method (JIS C2101-1999). An empty capacitance C ₀ (pF) before filling the sample and an equivalent parallel capacitance C _x (pF) at the time of filling the sample are measured, and a dielectric constant ε is calculated by the following formula (1). The relative permittivity is given by the product of this ε and the relative permittivity of air 1.000585.
ε = C _x / C ₀ (1)
The solvent contained in the non-aqueous resin dispersion of the first invention is preferably substantially only the non-aqueous organic solvent (L), but preferably 1% in the non-aqueous resin dispersion. Hereinafter, it may further contain other organic solvent in a range of 0.5% or less.
In the above and below, “%” means “% by weight” unless otherwise specified.

The resin (a) has a solubility in the non-aqueous organic solvent (L) of preferably 1% or less, and more preferably 0.5% or less. If the solubility of (a) is 1% 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 in which (a) is dissolved in (L) until saturation is reached, and the insoluble matter is precipitated by centrifugation. A value obtained by removing 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 as Y / y × 100 [%].

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.
The difference between the solubility parameters of (L) and (k) (hereinafter referred to as sp value. The calculation method is based on Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). If it is below (especially 1 or below), (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, and from the viewpoint of ease of synthesis, a straight hydrocarbon chain having 12 to 27 carbon atoms and a branched hydrocarbon having 12 to 27 carbon atoms. A chain and a polydimethylsiloxane chain are 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 exhibits crystallinity.
The content of the molecular chain (k) in the resin (a) is preferably 10 to 90%, more preferably 15 to 80%, and particularly preferably 20 to 60%.

The resin (a) may be thermoplastic or thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, Examples thereof include melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. As the resin (a), two or more of the above resins may be used in combination.
Among these, 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 the molecular chain (k) is a side chain. More preferably, the vinyl resin (m) having a molecular chain (k) and, if necessary, a (co) polymer of the vinyl monomer (m) with another vinyl monomer, Another resin (composite resin) having a combined 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, an amino group and a vinyl monomer (m) having a molecular chain (k), Reactions such as esterification, amidation, and urethanization are performed.
In the present invention, the (co) polymer means a homopolymer or copolymer of monomers.

  Hereinafter, the vinyl resin which is a preferable resin as (a) will be described in detail. The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer. As described above, a vinyl monomer having a molecular chain (k) having a sp value difference of 2 or less from the non-aqueous organic solvent (L) ( More preferred are (co) polymers of m) and optionally other vinyl monomers.

  Although it does not specifically limit as a vinyl monomer (m) which has a molecular chain (k) in a side chain, The following monomers (m1)-(m4) etc. are mentioned, You may use 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:
Unsaturated monocarboxylic acid, mono-linear alkyl (alkyl C12-27) ester of unsaturated dicarboxylic acid, etc. are mentioned. Examples of the unsaturated monocarboxylic acid and unsaturated dicarboxylic acid include (meth) Examples thereof include carboxyl group-containing vinyl monomers having 3 to 24 carbon atoms such as acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and the like. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter.
Specific examples include stearyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (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:
Examples thereof include mono-branched alkyl (alkyl carbon number 12 to 27) ester of unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, and the above-mentioned unsaturated monocarboxylic acid and unsaturated dicarboxylic acid are the same as those in (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 (manufactured by Shin-Etsu Silicone).

(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 represents an integer of 0 to 3, q represents any of 2, 4, 6, 8, 10, and 12, and Z represents a hydrogen atom or a fluorine atom. Is shown.)
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, [(2-perfluorododecyl) ethyl] (Meth) acrylic acid ester is mentioned.
Among these (m), (m1), (m2), and (m3) are preferred, and (m1) and (m2) are more preferred.

  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 (12), and two or more kinds may be used in combination.

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

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and anhydrides thereof and monoalkyl (alkyl group having 1 to 11 carbon atoms) esters such as (meth) acrylic acid, (anhydrous) maleic acid, fumarate Carboxyl group-containing vinyl monomers such as acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, maleic acid monomethyl ester, fumaric acid monoethyl ester, 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 such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; And alkyl derivatives thereof having 2 to 24 carbon atoms, such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3 -(Meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropane Sulfonic acid, 2- (meta Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, Butylene: single, random, or block) sulfate of mono (meth) acrylate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and the following general formula Sulfate ester or sulfonic acid group-containing monomers represented by (1-1) to (1-3); and salts thereof.

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

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

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

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

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

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

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

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, ( (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N- Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group Vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethyl Aminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc. (6-6) Urethane group-containing vinyl monomer: hydroxyethyl (meth) acrylate and monofunctional isocyanate compound (carbon number 2 such as phenyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, etc. To 24 monoisocyanate, etc.), equimolar 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, tolylene diisocyanate Equimolar reactants such as polyisocyanate (15) described later, etc.]

(7) Epoxy group-containing vinyl monomer:
Glucidyl (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 esters such as 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-ethoxyacrylate, (meth) acrylic acid alkyl ester having 1 to 11 carbon atoms (straight or branched) [methyl (meth) acrylate, (meth ) Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate) (2 Is an alkyl group having 2 to 8 carbon atoms, a straight chain, branched chain or alicyclic group), dialkyl maleate (dialkyl maleate) (two alkyl groups having 2 to 8 carbon atoms) Straight chain, branched chain or cycloaliphatic groups), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxy Vinyl monomers having a polyalkylene glycol chain such as butane, tetrametaallyloxyethane, etc. [polyethylene glycol (number average molecular weight 300) mono (meth) acrylate, polypropylene glycol (number average molecular weight 500) monoacrylate, methyl alcohol ethylene oxide ( Ethylene oxide is abbreviated as “EO” below. ) Acrylate, 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.] etc. (9-2) Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl Ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-di Dro 1,2-pyran, 2-butoxy-2′-vinyloxy diethyl ether, vinyl 2-ethyl mercapto ethyl ether, acetoxy styrene, phenoxy styrene, etc. (9-3) Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl Phenyl ketone;
Vinyl sulfones, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

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

Among other vinyl monomers other than these vinyl monomers (m), vinyl esters such as (meth) acrylic acid alkyl esters having a C 1-11 alkyl group and vinyl monomers having a polyalkylene glycol chain, carboxyl groups A vinyl-containing monomer, a sulfone group-containing vinyl monomer, an amino group-containing vinyl monomer, and a urethane group-containing vinyl monomer are preferred.
More preferable among the (meth) acrylic acid alkyl esters having an alkyl group having 1 to 11 carbon atoms are methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Among the vinyl monomers having a polyalkylene glycol chain, it is a (meth) acrylic acid polyethylene glycol ester (Nippon Yushi Bremer PE-350, etc.). Among the carboxyl group-containing vinyl monomers, (meth) acrylic acid , Crotonic acid, itaconic acid, and maleic acid. Among the sulfone group-containing vinyl monomers, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid (such as Sanyo Chemical Industries Eleminol JS-2), and poly (n = 2-30) Oxyalkylene (ethylene, propylene, buty (Single, random, or block) mono (meth) acrylate sulfate ester (such as Eleminol RS-30 manufactured by Sanyo Chemical Industries), among amino group-containing vinyl monomers, aminoethyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and among urethane group-containing vinyl monomers, are equimolar reaction products 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 (linear and / or branched) ester- (Meth) acrylic acid, vinyl acetate- (meth) acrylic acid- (meth) acrylic acid ester, alkyl (meth) acrylate (linear and / or branched) ester- (meth) acrylic acid polyethylene glycol ester, ( Alkyl acrylate (linear 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 Esters, alkyl (meth) acrylates (linear and / or branched) esters- (meth) acrylic acid-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol esters, alkyl (meth) acrylates (direct (Chain 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-hydroxyethyl (meth) acrylate and equimolar reaction product of phenyl isocyanate, alkyl (meth) acrylate (linear and / or branched) ester- (meth) acrylic acid- (meth) Examples thereof include an equimolar reaction product of acrylic acid polyethylene glycol ester-hydroxyethyl (meth) acrylate and phenyl isocyanate, and a salt of a copolymer of these monomers.
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 branched) ester- (meth) acrylic acid-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, (meth) acrylic acid alkyl (linear and / or branched) ester- ( (Meth) acrylic acid polyethylene glycol ester, (meth) acrylic acid alkyl (linear and / or branched) ester-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, (meth) acrylic acid alkyl (direct) Chain and / or Bifurcation) 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) It is an equimolar reaction product of acrylic acid- (meth) acrylic acid polyethylene glycol ester-hydroxyethyl (meth) acrylate and phenyl isocyanate.
In addition, the same thing can be illustrated about the composition of the vinyl (co) polymer frame | skeleton in other resin which has a vinyl (co) polymer frame | skeleton, and a preferable thing is also the same.

Molecular chain having a 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 the vinyl resin having a vinyl polymer skeleton (k The content of the vinyl monomer (m) having) is preferably 10% or more, more preferably 10 to 90%, particularly preferably 15 to 80%, and most preferably 20 to 60%.
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). ) Can be 1% or less, and the resin particles (C) are difficult to unite.

  A (co) polymer in which the resin (a) is a vinyl monomer (m) having a molecular chain (k) having a sp value difference of 2 or less from that of the non-aqueous organic solvent (L) and, if necessary, other vinyl monomers A vinyl monomer (m1) having a skeleton and 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 are used as (m). In this case, the weight ratio of (m1) to (m2) is preferably (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. 20-20: 80, most preferably 70: 30-30: 70.

The resin (a) has a (co) polymer skeleton of a vinyl monomer (m) and, if necessary, another vinyl monomer, 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, the following surface composition ratio of (C) is 0.75 to 0.98 from the viewpoint of dispersion stability of the resin particles (C). Preferably, it is 0.80 to 0.95, more 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 core / shell type resin particles (C) constituting the non-aqueous resin dispersion of the first invention may be resin particles produced by any method and process, but the core / shell type resin particles are produced. Examples of the method include the following production methods (I) to (III).
(I): An example of a method of making a core-shell structure at the same time as creating core particles.
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.

(II): 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 a resin particle produced by an emulsion polymerization aggregation method, a resin particle produced by a pulverization method, or any production method. . The coating method is not particularly limited, and for example, the resin particles (B) or (B) non-aqueous prepared in advance in the non-aqueous resin dispersion (W) of the resin particles (A) containing the resin (a). Examples thereof include a method of dispersing the resin dispersion and a method of sprinkling the solution (a) as a coating agent in (B).

(III) A method in which core particles are prepared and the vicinity of the surface of the core particles is physically and / or chemically manipulated to be changed to another shell resin. Resin (b) -containing resin particles (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 a core. -There is a method of changing to shell type resin particles (C).
Among these, the production method (I) is preferable.

Since the non-aqueous resin dispersion of the resin particles (C) of the first invention is obtained by the production method of the second invention described below, the resin particles having a uniform particle diameter are further obtained. preferable.
In the production method of the second invention, the non-aqueous resin dispersion (W) of the resin particles (A), the solvent solution (O1) of the organic solvent (M) of the resin (b), or the precursor of the resin (b) The organic solvent (M) in the body (b0) is mixed with a solvent solution (O2), (O1) or (O2) is dispersed in (W), and resin particles (B) containing (b) are obtained. When formed, 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. It is hard to be done. 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 improving 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).

  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 crosslinking points, etc. of the resin (a) are appropriately adjusted. It is preferable to do this.

  The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the resin (a) is preferably from 1 to 5 million, more preferably from 2 to 5 million, particularly preferably from 500 to 500,000. . The sp value is preferably 7 to 18, and more preferably 8 to 14. The melting point of the resin (a) (measured by DSC, hereinafter the melting point is measured by DSC) is preferably 0 ° C. or higher, more preferably 30 to 200 ° C.

In the present invention, the Mn and weight average molecular weight (hereinafter abbreviated as Mw) of resins other than polyurethane resins such as vinyl resins are as follows for the tetrahydrofuran (THF) soluble content using gel permeation chromatography (GPC). Measured under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α
TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

The glass transition temperature (Tg) of the resin (a) is preferably 10 ° C. to 250 ° C. from the viewpoints of particle size uniformity, powder flowability, heat resistance during storage, and stress resistance of the resin particles (C). More preferably, it is 20 degreeC-230 degreeC, More preferably, it is 30 degreeC-200 degreeC, Most preferably, it is 40 degreeC-100 degreeC. If the Tg is lower than the temperature at which the non-aqueous resin dispersion (X1) is prepared, 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 the shell layer (P) containing (a) is preferably 10 to 200 ° C, more preferably 20 to 100 ° C, and particularly preferably 30 to 85 ° C for the same reason.
In addition, Tg in this invention is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).

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

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] Is mentioned.
[1] In the case of vinyl resin, a non-aqueous resin dispersion of resin particles (A) is directly formed 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 polyaddition or condensation type resins such as polyester resins and polyurethane resins, a non-aqueous organic solvent (L) in the presence of a suitable 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 and a polyurethane resin, in a precursor (monomer, 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] Resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same shall apply hereinafter) The resin particles are obtained by pulverization using a fine pulverizer and then classification, 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.
In the methods [1] to [6], as the dispersant used in combination, a known surfactant (s), oil-soluble polymer (t), and the like can be used. Moreover, an organic solvent (u), a plasticizer (v), etc. can be used together as a dispersion aid.

  Examples of the surfactant (s) include an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), and a nonionic surfactant (s-4). Is mentioned. The surfactant (s) may be a combination of two or more surfactants. Specific examples of (s) include those described below and JP-A-2002-284881.

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

As the carboxylic acid or a salt thereof, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms or a salt thereof can be used. For example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, olein Examples thereof include mixtures of acids, linoleic acid and ricinoleic acid, and higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like.
Examples of the salt include salts such as sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, and alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).

Examples of sulfate salts include higher alcohol sulfate salts (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters (EO or PO 1 to 10 moles of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated fats and oils having a carbon number of 12 to 50 or neutralized by neutralization), sulfated fatty acid esters (unsaturated fatty acids (carbon number) 6-40) lower alcohols (one obtained by sulfating and neutralizing esters of 1 to 8 carbon atoms) and sulfated olefins (one obtained by sulfating and neutralizing olefins having 12 to 18 carbon atoms) can be used.
Examples of the salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

  Examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, alcohol synthesized using a Ziegler catalyst (for example, trade name: ALFOL). 1214: manufactured by CONDEA) and alcohol synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: Tridecanol) : Manufactured by Kyowa Hakko, trade names: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.) and the like.

Examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt and octyl alcohol EO 3 mol adduct sulfate ester salt.
Examples of sulfated oils include sulfate salts such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow and sheep fat.
Examples of sulfated fatty acid esters include sulfate salts such as butyl oleate and butyl ricinoleate.
Examples of the sulfated olefin include trade name: TEPOL (manufactured by Shell).

  Examples of the carboxymethylated salt include carboxymethylated salts of aliphatic alcohols having 8 to 16 carbon atoms and EO or carboxymethylated salts of 1 to 10 mol adducts of aliphatic alcohols having 8 to 16 carbon atoms. Can be used.

  Examples of the salt of a carboxymethylated product of an aliphatic alcohol include octyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol carboxymethylated sodium salt, and the like. It is done.

  Examples of carboxymethylated salts of EO 1 to 10 mol adducts of aliphatic alcohols include, for example, octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated sodium salt, and tridecanol EO5 mol addition. Carboxymethylated sodium salt and the like.

As the sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester salt, α-olefin sulfonate, igepon T-type and other sulfonates of aromatic ring-containing compounds can be used.
Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate.

Examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate and the like.
Examples of the sulfosuccinic acid diester salt include sulfosuccinic acid di-2-ethylhexyl ester sodium salt.
Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether and styrenated phenol sulfonate.

As the phosphate ester salt, a higher alcohol phosphate ester salt, a higher alcohol EO adduct phosphate ester salt and the like can be used.
Examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt.
Examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
The quaternary ammonium salt type surfactant includes a tertiary amine having 3 to 40 carbon atoms and a quaternizing agent (for example, alkylating agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, and EO). For example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, poly Examples thereof include oxyethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate.

As amine salt type surfactants, primary to tertiary amines are inorganic acids (eg hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid). , Gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid, etc.).
Examples of the primary amine salt-type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Alternatively, organic acid salts and higher fatty acid (carbon number 8 to 40, stearic acid, oleic acid, etc.) salts of lower amines (having 2 to 6 carbon atoms) can be used.

Examples of the secondary amine salt type surfactant include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms.
Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (for example, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adduct of aliphatic amine (2 to 40 carbon atoms), alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0) -7-undecene), nitrogen-containing heterocyclic aromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methylimidazole) And 4,4'-dipyridyl) and inorganic acid salts or organic acid salts and triethanolamine monostearate, stearamide ethyl diethyl Such as tertiary mineral or organic acid salts of amines such as chill ethanolamine.

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

  As the carboxylate type amphoteric surfactant, an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant, an imidazoline type amphoteric surfactant and the like are used. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include a compound represented by the general formula (2).

_{[R-NH- (CH 2)} n-COO] mM (2)
[Wherein R is a monovalent hydrocarbon group; n is 1 or 2; m is 1 or 2; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium cation, an amine cation, an alkanolamine cation, etc. It is. ]

  Examples of the double-sided active agent represented by the general formula (2) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (eg, sodium stearylaminopropionate, sodium laurylaminopropionate); alkyl ( Examples thereof include C4-C24) aminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

  The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule, for example, alkyl (having 6 to 40 carbon atoms) dimethyl betaine. (Stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), C6-C40 amide betaines (coconut oil fatty acid amidopropyl betaine, etc.), alkyls (C6-C40) dihydroxyalkyls (C6-C40) Examples include betaine (such as lauryl dihydroxyethyl betaine).

  The imidazoline type amphoteric surfactant is an amphoteric surfactant having a cation part having an imidazoline ring and a carboxylic acid type anion part. For example, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoli Examples include nitrobetaine.

  Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaines such as pentadecyl sulfotaurine Examples include amphoteric surfactants, sulfonate amphoteric surfactants, and phosphate ester type amphoteric surfactants.

As the nonionic surfactant (s-4), an alkylene oxide (hereinafter referred to as AO) addition type nonionic surfactant, a polyvalent alcohol type nonionic surfactant, and the like can be used.
AO addition type nonionic surfactants can be used to directly apply AO (2 to 20 carbon atoms) to higher alcohols having 8 to 40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms or alkylamines having 8 to 40 carbon atoms. AO is added to the esterified product obtained by adding a higher fatty acid or the like to a polyalkylene glycol obtained by adding AO to glycol or by reacting a higher fatty acid with a polyhydric alcohol. Or by adding AO to a higher fatty acid amide.

Examples of AO include EO, PO, and BO.
Of these, EO and random or block adducts of EO and PO are preferred.
The number of moles of AO added is preferably 10 to 50 moles, and preferably 50 to 100 moles of EO is EO.

  As the AO addition type nonionic surfactant, for example, oxyalkylene alkyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number 8 to 40) (for example, octyl alcohol EO 20 mol adduct, lauryl alcohol EO 20 mol) Adducts, stearyl alcohol EO 10 mol adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (alkylene having 2 to 24 carbon atoms, higher fatty acid having 8 carbon atoms) -40) (for example, stearyl acid EO 10 mol adduct, lauric acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (alkylene having 2 to 24 carbon atoms, polyhydric alcohol having 3 to 3 carbon atoms) 40, carbon number of higher fatty acids -40) (for example, lauric acid diester of polyethylene glycol (polymerization degree 20), oleic acid diester of polyethylene glycol (polymerization degree 20), etc.); polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon) 8 to 40) (for example, nonylphenol EO 4 mol adduct, nonylphenol EO 8 mol PO 20 mol block adduct, octylphenol EO 10 mol adduct, bisphenol A · EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxyalkylene Alkylamino ethers (alkylene having 2 to 24 carbon atoms, alkyl having 8 to 40 carbon atoms) and (for example, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct, etc.); polyoxy Lucylene alkanolamide (C2-C24 of alkylene, C8-C24 of amide (acyl moiety)) (for example, EO 10 mol adduct of hydroxyethyl lauric acid amide, EO 20 mol adduct of hydroxypropyl oleic acid amide, etc.) Is mentioned.

  As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct and the like can be used. The polyhydric alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

  Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan dilaurate, sorbitan dioleate, and sucrose monostearate.

  Examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO 10 mol adduct, ethylene glycol monostearate EO 20 mol adduct, trimethylolpropane monostearate EO 20 mol PO 10 mol random adduct, sorbitan monolaurate. EO 10 mol adduct, sorbitan distearate EO 20 mol adduct, sorbitan dilaurate EO 12 mol PO 24 mol random adduct and the like.

  Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

  Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO 10 mol adduct and stearyl glycoside EO 20 mol PO 20 mol random adduct. Can be mentioned.

The oil-soluble polymer (t) is, for example, a compound having at least one group of an alkyl group having 4 or more carbon atoms, a dimethylsiloxane group, and a functional group containing fluorine. Further, it preferably has a chemical structure having an affinity for the resin (b) together with an alkyl group, a dimethylsiloxane group and a fluorine-containing group having an affinity for the non-aqueous organic solvent (L).
More specifically, among the above 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 containing fluorine (M1-3) And a copolymer of the vinyl monomer constituting the resin (b) described above is preferable. The form of copolymerization may be random, block or graft, but block or graft is preferred.

  The organic solvent (u) used for obtaining 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.

The plasticizer (v) may be added to the non-aqueous organic solvent (L) as needed during the dispersion, or [the solvent of the organic solvent (M) containing the resin (b) or (b0)]. In solution (O1) or (O2)].
As a plasticizer (v), it is not limited at all, The following are illustrated.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) used in the present invention is usually smaller than the particle size of the formed resin particles (B). From the viewpoint of particle size uniformity, the particle size ratio [volume of the resin particles (A) The value of [average particle diameter] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is 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 size of (A) is generally preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain resin particles (C) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles ( When C) is obtained, it is preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm when it is desired to obtain particles (C), preferably 0.05 to 30 μm, particularly preferably. 0.1 to 20 μm.
The volume average particle size is determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using the laser Doppler method as an optical system, and the like. Can be measured. If there is a difference in the measured particle size between the measuring devices, the measured value of ELS-800 is adopted.
In addition, since the said particle size ratio is easy to be obtained, 0.1-300 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. More preferably, it is 0.5-250 micrometers, Most preferably, it is 1-200 micrometers.

As the second resin (b) used in the present invention, any resin can be used as long as it is a known resin, and specific examples thereof can be the same as those of the resin (a). (B) can select a preferable thing suitably according to a use and the objective.
In general, the resin (b) is preferably a 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 Polyester resins and polyurethane resins containing 2-propylene glycol as structural units.
Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin which are preferable resins as (b) will be described in detail.

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 in (b) include styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meta ) Acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, styrene -Styrenesulfonic acid- (meth) acrylic acid ester copolymers and salts of these copolymers.

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

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

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

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

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

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

Polyurethane resin includes polyisocyanate (15) and active hydrogen-containing compound {water, polyol [including 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 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon A ring-opening polymer of a lactone of formulas 6 to 12, a polyamine (16), a polythiol (17), a polyaddition product of these, etc.}, and a terminal isocyanate group obtained by reacting (15) with an active hydrogen-containing compound An equal amount of primary and / or secondary modules relative to the prepolymer and the isocyanate groups of the prepolymer. Obtained by reacting an amine (18), and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10%.

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

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

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

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

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

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and an 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 trivalent to hexavalent or higher polycarboxylic acid (14), the polyamine (16), the polythiol (17), etc.}, or the polyepoxide (19) and the dicarboxylic acid (13) or a cured product of an acid anhydride of a polycarboxylic acid (14) having a valence of 3 to 6 or more, and the like.

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

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

The Mn, melting point, Tg, and sp value of the resin (b) may be appropriately adjusted within a preferable range depending on the application.
The sp value of the resin (b) is preferably 7 to 18, more preferably 8 to 14, and particularly preferably 9 to 14.
For example, when used as a liquid developer used for electrophotography, electrostatic recording, electrostatic printing, etc., the Mn of (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. is there. The melting point of (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. The sp value of (b) is preferably 8-16, more preferably 9-14.

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

The adsorptive power of the resin particles (A) for obtaining the resin particles (D) and (C) with respect 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. In this case, the resin particles ( The larger the charge of each of A) and resin particles (B), the stronger the adsorption force and the higher the coverage of the resin particles (A) to the resin particles (B).
[2] When the non-aqueous resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative), The rate tends 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 is reduced. Go up.
[3] When the Δsp value of the resin (a) and the resin (b) is decreased, 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 used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifier such as Special Machine Industries Co., Ltd., Ebara Milder (Ebara Manufacturing Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (Special Machine Industries Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), fine flow mill (Pacific Kiko Co., Ltd.), microfluidizer (Mizuho Kogyo Co., Ltd.) ), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin) Membrane emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of homogenizing the particle diameter.

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 (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 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. 20, preferably 10-19. As (M), when a mixed solvent is used, the sp value is assumed to satisfy the additivity rule, and the 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 sp value can be appropriately selected. Toluene, xylene, ethylbenzene Aromatic hydrocarbon solvents such as tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, methyl bromide, methyl iodide, methylene dichloride Halogen solvents such as carbon tetrachloride, trichloroethylene, perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl ether, tetrahydrofuran (hereinafter, Described as THF), dioxane. Ether solvents such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n -Alcohol solvents such as propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N- Examples include heterocyclic compound solvents such as methyl pyrrolidone, and mixed solvents of two or more of these.
From the viewpoint of odor, the boiling point of (M) is preferably 100 ° C. or lower, and more preferably 90 ° C. or lower so that it can be easily distilled off from the non-aqueous resin dispersion (X1).

For example, 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. Can be mentioned.
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. For example, the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin). And polyester resin), (b0) is a combination of a prepolymer (α) having a reactive group and a curing agent (β), and (b0) when the resin (b) is a vinyl resin. Includes the above-mentioned vinyl monomers (which may be used alone or in combination) and their solvent solutions.

  When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to make 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 (similar to the surfactant (s) is exemplified) and an oil-soluble initiator. And 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, etc.

(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), 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile) etc.

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

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method of forming the resin (b) by reacting the precursor (b0), a solvent solution containing the reactive group-containing prepolymer (α), the curing agent (β) and the organic solvent (M) is used. Resin particles (A) containing resin (b) by dispersing the resin particles (A) in a 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. Examples thereof include a method of adding and 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 more 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 And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; Phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof That.
Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

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

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of two or more structural components And the like.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ] Is preferably 2/1 to 1.01 / 1, more preferably 1.5 / 1 to 1.01 / 1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.
In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1.01 / 1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2. 5/1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and 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, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that resin particles (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) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d ).
(Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof.

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

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

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

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

  Examples of the compound (β2) that can react 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 preferable, and (β2a) is more preferable.

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

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

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

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

  The resin (b) obtained by reacting the precursor (b0) composed of the reactive group-containing prepolymer (α) and the curing agent (β) in a non-aqueous medium is the resin particles (B) and the resin particles (C). It becomes a component. The Mw of the resin (b) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3,000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000. ~ 1 million.

  Further, 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, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) in a non-aqueous medium and a resin not reacted (dead polymer). .

  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. If it is 50 parts by weight or more, the dispersed state of (b) is good, and if it is 2,000 parts by weight or less, it is economical.

In the 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 attached to the surfaces of the resin particles (B). Under the conditions that the non-aqueous organic solvent (L) remains in the dispersion, it is preferably distilled off to 1% or less (particularly 0.5% or less) in the obtained non-aqueous resin dispersion (X2). However, a part of (L) (low boiling point component) may be distilled off together with (M).
Examples of the method of distilling off include 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.

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 the following preferred solvent is used, The solvent (M) is preferably used in the non-aqueous resin dispersion (X1) in an amount of 10 to 50% (especially 20 to 40%) until 40 ° C. or less, preferably 1% or less (especially 0.5% or less). By removing the solvent from (M), the resin particles (A) are dissolved in the solvent to form a film, and the film-like shell containing the resin (a) on the surface of the core layer (Q) composed of (B) In many cases, a non-aqueous resin dispersion (X2) of the resin particles (C) on which the layer (P) is formed is obtained.
From the viewpoint of film formation, preferred among (M) are tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate, and more preferred are acetone and ethyl acetate.

Even when the film of (A) is not formed, or even when the film from at least a part of (A) is formed, in order to further improve the smoothness of the film on the surface of the resin particles (C), When the following operation is performed, a coating-like shell layer (P) having a smooth surface formed from (A) is formed on at least a part of the surface of the core layer (Q) composed of (B), preferably the entire surface. A non-aqueous resin dispersion (X2) of the resin particles (C) that are contained is obtained, and this is preferable from the viewpoint that the dispersion stability of (C) in (X2) is excellent.
Examples of the method include a method in which (A) attached to (B) is dissolved in a solvent, and a method in which (A) is melted to form a film by heating the non-aqueous resin dispersion (X1). 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.
Among the organic solvents (M), preferred from the viewpoint of film formation are tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate, and more preferably ethyl acetate.
The concentration of the solvent (M) in the non-aqueous resin dispersion (X1) when (A) is dissolved in the solvent is preferably 3 to 50%, more preferably 10 to 40%, and particularly preferably 15 to 30. %. Moreover, melt | dissolution is performed by stirring nonaqueous resin dispersion liquid (X1) for 1 to 10 hours, for example, and the temperature at the time of melt | dissolution is 15-45 degreeC, and 15-30 degreeC is more preferable.

When (A) is melted to form a film on the surface of (B), the solid content [content of components other than solvent] in the non-aqueous resin dispersion (X1) is preferably 1 to 50%, more preferably Is adjusted to 5-30%. Further, the content of the organic solvent (M) at this time is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.5% or less. When the solid content in (X1) is high or the content of (M) exceeds 2%, aggregates may be generated when the temperature of (X1) is raised to 60 ° C. or higher. The heating conditions at the time of melting are not particularly limited as long as (A) is melted. For example, the stirring is preferably 40 to 100 ° C, more preferably 60 to 90 ° C, and particularly preferably 60 to 80 ° C. A method of heating at a temperature of preferably 1 to 300 minutes can be mentioned.
In addition, it is set as the method of a film-forming process, the non-aqueous resin dispersion liquid (X1) of the resin particle (D) whose content of an organic solvent (M) is 2% or less is heat-processed, and (A) comprises (B) The preferred heat treatment temperature for obtaining resin particles (C) having a smoother surface by melting on the core layer (Q) is not less than Tg of the resin (a) and not more than 80 ° C. A range is preferred. 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).
Among these (A) film-forming methods, preferred methods are a method of melting (A) and a combination of a method of dissolving (A) and a method of melting (A).

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

  In the case of the production method (II) and the production method (III), the shape is greatly influenced by the shape of the resin particles (B) prepared in advance, and the resin particles (C) have almost the same shape as the resin particles (B). become. However, when (B) is distorted, if more coating agent (W ′) is used in the production method (II), it becomes spherical. Further, in the production method (III), when a heat treatment at a temperature higher than the Tg of (B) is performed, (C) becomes spherical.

  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 comprised with the film-form shell layer (P) containing -70% resin (a), and the core layer (Q) containing 30-99% resin (b). Preferably, it is composed of 5 to 50% (P) and 50 to 95% (Q), more preferably 10 to 35% (P) and 65 to 90% (Q).

Further, from the viewpoints of particle size uniformity of the resin particles (C), fluidity of the non-aqueous resin dispersion (X2), storage stability, etc., the surface of the resin particles (B) in the resin particles (C) 5 % Or more, preferably 30% or more, more preferably 50% or more, and particularly preferably 80% 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 with the shell layer (P) / area of the portion covered with the shell layer (P) + area of the portion where the core layer (Q) is exposed] × 100

From the viewpoint of particle size uniformity, the coefficient of variation of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 1 to 26%.
The variation coefficient of the volume distribution is measured by a particle size distribution measuring device such as a laser type particle size distribution measuring device LA-920 (manufactured by Horiba Seisakusho).
In addition, the value of [volume average particle diameter / number average particle diameter] of the resin particles (C) is preferably 1.0 to 1.4 in terms of particle diameter uniformity, and is 1.0 to 1.2. More preferably.
The volume average particle size of (C) varies depending on the application, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, most preferably 100 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

  The resin particles (C) constituting the non-aqueous resin dispersion of the present invention include resin particles (A) and resin particles (B), and a film-like shell layer (P) containing the resin (a). By changing the coverage of the surface of the resin particles (B) due to, desired irregularities can be imparted to the particle surfaces. From the viewpoint of fluidity, the surface average centerline roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoints of fluidity and melt leveling. In that case, the resin particles (B) are preferably spherical. (C) preferably has an average circularity of 0.96 to 1.0. The average circularity is 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). In a predetermined container, 100 to 150 ml of water from which impure solids have been previously removed is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) to a dispersion concentration of 3,000 to 10,000 / μL. To measure the shape and distribution of the resin particles.

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) during the production of the non-aqueous resin dispersion (X1). ) By changing the surface coverage, the depth of the resin particles (B) in (X1) / the depth at which the resin particles (A) are embedded on the non-aqueous medium interface, the particle surface is changed. It can be made smooth, or desired irregularities can be imparted to the particle surface.
The coverage of the surface of the resin particle (B) with the resin particle (A) and the depth at which the resin particle (A) is embedded on the resin particle (B) side can be controlled by the following method.
[1] When the non-aqueous resin dispersion (X1) of the resin particles (D) is produced, if the resin particles (A) and the resin particles (B) have positive and negative charges, the coverage and depth are reduced. growing. In this case, the coverage and the depth increase as the electric charges of the resin particles (A) and the resin particles (B) are increased.
[2] When producing the non-aqueous resin dispersion (X1) of the resin particles (D), the resin particles (A) and the resin particles (B) are charged with the same polarity (both positive or both negative). If it has, it will tend to decrease the coverage and decrease the depth. In this case, in general, when the surfactant (s) and / or the oil-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased. Further, when the oil-soluble polymer (t) is used, the depth decreases as the molecular weight of the oil-soluble polymer (t) increases.
[3] The coverage and depth increase as the difference in sp value between resin (a) and resin (b) decreases.

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, antiblocking agents, heat stabilizers, flame retardants, etc.) may be mixed. 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.

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

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

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

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

The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. Moreover, Tg of (d) becomes like this. Preferably it is 40-90 degreeC from a viewpoint of the heat-resistant storage stability of non-aqueous resin dispersion liquid (X2), More preferably, it is 50-80 degreeC.
Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the mechanical strength of the resin particles (C) is good.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in a solvent (for example, toluene or xylene) and heating to 100 to 200 ° C. It is obtained by dropping together with butyl peroxide, tertiary butyl peroxide benzoate, etc.) and then distilling off the solvent.
The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total weight of the raw material (d).

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

As a method of mixing the wax (c) and the modified wax (d), [1] a method of melt-kneading at a temperature equal to or higher than the respective melting points, [2] (c) and (d) in the organic solvent (u) (3) (c) and (d) are dissolved in an organic solvent (u) by dissolving or suspending them in a solution and then precipitating them in a liquid by cooling crystallization, solvent crystallization, etc. And the like, after being dissolved or suspended therein, mechanically wet pulverized by a disperser, and the like. Among these, the method [2] is preferable.
As a method of dispersing the wax (c) and the modified wax (d) in (b), (c), (d), and (b) are made into a solvent solution or a dispersion, respectively, The method of mixing etc. is mentioned.

In the non-aqueous resin dispersion of the present invention, the particle size and shape of the resin particles in the dispersion are uniform. Therefore, the non-aqueous resin dispersion of the present invention is useful as a liquid developer for paints, electrophotography, electrostatic recording, electrostatic printing, etc., oil-based inks for inkjet printers, and inks for electronic paper. As other applications, it is also useful for cosmetics, electronic component manufacturing spacers, and electrorheological fluids. When these uses are used, known dyes, pigments and magnetic powders can be used as colorants. Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Examples include rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, prilliant green, phthalocyanine green, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, magnetite, iron black and the like.
The amount of the colorant used is preferably 0.5 to 15% based on the weight of the resin (b) when using a dye or pigment, and preferably 20 to 150 when using magnetic powder. %.
In order to control the chargeability, as the charge control agent, for example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt ( Fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments and a sulfo group, a carboxyl group, such as polymer compounds having a functional group such as quaternary ammonium salts. The amount of the charge control agent used is preferably 0 to 5% 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 thereto. In the following description, “parts” indicates parts by weight.

Production Example 1 (Production of non-aqueous resin dispersion 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 a mixture of 80 parts of azobismethoxydimethylvaleronitrile and 0.5 parts of azobismethoxydimethylvaleronitrile were stirred and mixed at 20 ° C. to prepare a monomer solution, which was then charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, 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 under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A resin dispersion [fine particle dispersion W1] was obtained. The volume average particle diameter of [fine particle dispersion W1] measured by LA-920 was 0.040 μm (molecular chain (k), that is, sp value of silicone chain 8.5). The solubility of the resin in liquid paraffin (the concentration of the resin contained in the supernatant obtained by centrifuging the [fine particle dispersion W1]) was 0.5%.

Production Example 2 (Production of non-aqueous resin dispersion 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, 110 parts of methyl methacrylate, 2-decyltetradecyl methacrylate 80 Part, 10 parts of hydroxyethyl methacrylate and 0.5 part of azobismethoxydimethylvaleronitrile were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, and then cooled to room temperature. To 50 parts of this polymerization solution, 1 part of urethane-modified polyester b4 (described later) and 0.1 part of dibutyltin oxide are added and reacted at 50 ° C. for 5 hours to obtain methacrylic acid / 2-decyltetradecyl methacrylate / hydroxyethyl methacrylate. A block copolymer solution of copolymer and polyester was obtained. 50 parts of this block copolymer solution was further added dropwise to 80 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W2] was obtained. The volume average particle diameter of [fine particle dispersion W2] measured by LA-920 was 0.060 μm (molecular chain (k), that is, sp value of 2-decyltetradecyl group: 8.3). The solubility of the resin in the liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W2]) was 0.2%.

Production Example 3 (Production of non-aqueous resin dispersion 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, 110 parts of methyl methacrylate, 2- (perfluorooctyl methacrylate) ) 80 parts of ethyl (CHEMINOX FAMAC-8, manufactured by Unimatec), 10 parts of hydroxyethyl methacrylate and 0.5 part of azobismethoxydimethylvaleronitrile were charged and stirred and mixed at 20 ° C. to obtain a monomer solution. Adjusted and charged into 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 a separate container, aged at 40 ° C. for 3 hours, and then cooled to room temperature. To 50 parts of this polymerization solution, 1 part of urethane-modified polyester b4 described later and 0.1 part of dibutyltin oxide are added and reacted at 50 ° C. for 5 hours to give methyl methacrylate / methacrylic acid 2- (perfluorooctyl) ethyl / A block copolymer solution of hydroxyethyl methacrylate copolymer and polyester was obtained. 50 parts of this block copolymer solution was further added dropwise to 80 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W3] was obtained. The volume average particle diameter of [fine particle dispersion W3] measured by LA-920 was 0.050 μm (molecular chain (k), that is, sp value of 2- (perfluorooctyl) ethyl group: 9.2). The solubility of the resin in the liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W3]) was 0.2%.

Production Example 4 (Production of non-aqueous resin dispersion 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 a mixture of 80 parts of azobismethoxydimethylvaleronitrile and 0.5 parts of azobismethoxydimethylvaleronitrile were stirred and mixed at 20 ° C. to prepare a monomer solution, which was then charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, and then cooled to room temperature. 50 parts of this polymerization solution was further dropped into 80 parts of silicone oil (relative dielectric constant: 2.7, sp value: 8.5) under stirring, and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A resin dispersion [fine particle dispersion W4] was obtained. The volume average particle diameter of [fine particle dispersion W4] measured by LA-920 was 0.040 μm (molecular chain (k), that is, sp value of silicone chain 8.5). The solubility of the resin in the silicone oil (the concentration of the resin contained in the supernatant obtained by centrifuging the [fine particle dispersion W4]) was 0.2%.

Production Example 5 (Production of non-aqueous resin dispersion 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, 30 parts of methyl methacrylate, 128 parts of behenyl methacrylate, methacrylic acid A mixture of 32 parts of 2-decyltetradecyl, 10 parts of an equimolar reaction product of hydroxyethyl methacrylate and phenyl isocyanate, and 0.5 parts of azobismethoxydimethylvaleronitrile was stirred and mixed at 20 ° C. The solution was prepared and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, methyl methacrylate / A behenyl methacrylate / 2-decyl tetradecyl methacrylate / hydroxyethyl methacrylate and phenyl isocyanate equimolar reactant copolymer was obtained. 50 parts of this copolymer solution was further added dropwise to 50 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W5] was obtained. The volume average particle diameter of [fine particle dispersion W5] measured by LA-920 was 0.040 μm (molecular chain (k), that is, sp value of behenyl group and 2-decyltetradecyl group 8.3). 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 W5]) was 0.8%.

Production Example 6 (Production of non-aqueous resin dispersion 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, 40 parts of methyl methacrylate, 40 parts of behenyl methacrylate, methacrylic acid 40 parts of 2-decyltetradecyl, 40 parts of equimolar reaction product of hydroxyethyl methacrylate and phenyl isocyanate, 40 parts of polyethylene glycol methacrylate (Blenmer AE-400 manufactured by NOF Corporation), 0.5 part of azobismethoxydimethylvaleronitrile The monomer solution was prepared by stirring and mixing at 20 ° C. to prepare a monomer solution. 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 a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, methyl methacrylate / A behenyl methacrylate / 2-decyltetradecyl methacrylate / hydroxyethyl methacrylate and phenyl isocyanate equimolar reaction product / polyethylene glycol ester methacrylate copolymer was obtained. 50 parts of this copolymer solution was further added dropwise to 50 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W6] was obtained. The volume average particle diameter of [fine particle dispersion W6] measured by LA-920 was 0.050 μm (molecular chain (k), that is, sp value of behenyl group and 2-decyltetradecyl group 8.3). The solubility of the resin in liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W6]) was 0.4%.

Production Example 7 (Production of non-aqueous resin dispersion 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, 40 parts of methyl methacrylate, 24 parts of behenyl methacrylate, methacrylic acid A mixed solution of 96 parts of 2-decyltetradecyl, 40 parts of polyethylene glycol methacrylate (Blemmer AE-400 manufactured by NOF Corporation) and 0.5 part of azobismethoxydimethylvaleronitrile was charged and stirred and mixed at 20 ° C. The polymer solution was prepared and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, methyl methacrylate / A behenyl methacrylate / 2-decyltetradecyl methacrylate / polyethylene glycol ester methacrylate copolymer was obtained. 50 parts of this copolymer solution was further added dropwise to 50 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W7] was obtained. The volume average particle diameter of [fine particle dispersion W7] measured with LA-920 was 0.040 μm (molecular chain (k), that is, sp value of behenyl group and 2-decyltetradecyl group 8.3). The solubility of the resin in the liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W7]) was 0.4%.

Production Example 8 (Production of non-aqueous resin dispersion 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, 40 parts of methyl methacrylate, 80 parts of behenyl methacrylate, methacrylic acid A mixed solution of 80 parts of 2-decyltetradecyl and 0.5 parts of azobismethoxydimethylvaleronitrile was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, methyl methacrylate / A behenyl methacrylate / 2-decyl tetradecyl methacrylate copolymer was obtained. 50 parts of this copolymer solution was further added dropwise to 50 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W8] was obtained. The volume average particle diameter of [fine particle dispersion W8] measured with LA-920 was 0.040 μm (molecular chain (k), that is, sp value of behenyl group and 2-decyltetradecyl group 8.3). The solubility of the resin in the liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W8]) was 0.4%.

Production Example 9 (Production of non-aqueous resin dispersion 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, 20 parts of methyl methacrylate, 20 parts of methacrylic acid, stearyl methacrylate. 48 parts, 32 parts of 2-decyltetradecyl methacrylate, 40 parts of dimethylaminoethyl methacrylate, 40 parts of polyethylene glycol ester methacrylate (Blenmer AE-400 manufactured by NOF Corporation), 0.5 parts of azobismethoxydimethylvaleronitrile Was stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 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 a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, methyl methacrylate / A methacrylic acid / behenyl methacrylate / methacrylic acid 2-decyltetradecyl / dimethylaminoethyl methacrylate / methacrylic acid polyethylene glycol ester copolymer was obtained. 50 parts of this copolymer solution was further added dropwise to 50 parts of liquid paraffin under stirring (relative dielectric constant 2.0, sp value 8.6), and THF was distilled off at 40 ° C. under a reduced pressure of 300 mmHg. A non-aqueous resin dispersion [fine particle dispersion W9] was obtained. The volume average particle diameter of the [fine particle dispersion W9] measured by LA-920 was 0.040 μm (molecular chain (k), that is, sp value of stearyl group 8.2, sp value of 2-decyltetradecyl group 8.3). The solubility of the resin in the liquid paraffin (the concentration of the resin contained in the supernatant liquid obtained by centrifuging the [fine particle dispersion W9]) was 0.4%.

Production Example 10 (Production of resin (b))
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (1,8.8 mol) of 1,2-propylene glycol (hereinafter 1,2-propylene glycol is referred to as propylene glycol), terephthalic acid 716 parts (7.5 mol) of dimethyl ester, 180 parts (2.5 mol) of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were added while distilling off the produced methanol under a nitrogen stream at 180 ° C. The reaction was allowed for 8 hours. Next, while gradually raising the temperature up to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water generated under a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point becomes 150 ° C. It was taken out at the time. The recovered propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles to obtain [Polyester b1]. Mn of [Polyester b1] was 8000.
The number of moles in () means a relative molar ratio (the same applies hereinafter).

Production Example 11 (Production of resin (b))
[Synthesis of nonlinear polyester]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 557 parts (17.5 moles) of propylene glycol, 569 parts (7.0 moles) of dimethyl terephthalate, 184 parts (3.0 moles) of adipic acid ), And 3 parts of tetrabutoxy titanate as a condensation catalyst, and reacted for 8 hours at 180 ° C. while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 175 parts (5.5 mol). Next, the mixture was cooled to 180 ° C., 121 parts (1.5 mol) of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. and normal pressure, and when the softening point reached 180 ° C. After taking out and cooling to room temperature, it was pulverized and granulated to obtain [Polyester b2]. Mn of [Polyester b2] was 8500.

Production Example 12
In a reaction vessel equipped with a stir bar and thermometer, 2000 parts of polycaprolactone diol having a hydroxyl number of 56 (Placcel L220AL, manufactured by Daicel Chemical Industries, Ltd.) is charged, heated to 110 ° C. and dehydrated under a reduced pressure of 3 mmHg for 1 hour. Went. Subsequently, 457 parts of IPDI were added and reacted at 110 ° C. for 10 hours to obtain [Urethane Prepolymer 1] having an isocyanate group at the terminal. The NCO content of [Urethane Prepolymer 1] was 3.6%.

Production Example 13
In a reaction vessel equipped with a stir bar and a thermometer, 50 parts of ethylenediamine and 300 parts of MIBK were charged and reacted at 50 ° C. for 5 hours to obtain [curing agent 1] which is a ketimine compound.

Production Example 14 (Production of resin (b))
452 parts of xylene was placed in an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and after substitution with nitrogen, a mixed monomer of 845 parts of styrene and 155 parts of n-butyl acrylate at 170 ° C., and di- A mixture of 6.4 parts of t-butyl peroxide and 125 parts of xylene was added dropwise over 3 hours. After dropping, the mixture was aged at 170 ° C. for 1 hour to complete the polymerization. Thereafter, the solvent [vinyl resin b3] was obtained by removing the solvent under reduced pressure. Mw by GPC of [vinyl resin b3] was 14,000, and Tg was 60 ° C.

Production Example 15 (Production of resin (b))
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 343 parts of bisphenol A · EO 2 molar adduct, 166 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed and reacted at 230 ° C. for 8 hours at normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, then cooled to 110 ° C., 17 parts of isophorone diisocyanate was added in toluene, the reaction was carried out at 110 ° C. for 5 hours, then the solvent was removed, and Mw 72,000, NCO [Urethane-modified polyester b4] having a content of 0.7% was obtained.

Production Example 16 (Production of resin (b))
As in Production Example 15, 570 parts of bisphenol A · EO 2 mol adduct and 217 parts of terephthalic acid were polycondensed at 230 ° C. for 6 hours under normal pressure, and Mn 2,400, hydroxyl value 51, acid value 5 were not modified. [Polyester b5] was obtained.

Production Example 17 (Production of Colorant Dispersion)
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.), 20 parts of [Polyester b2] and 56 parts of acetone were stirred and dispersed uniformly. Was finely dispersed to obtain [Colorant Dispersion Liquid 1]. The volume average particle diameter of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.2 μm.

Production Example 18 (Production of modified wax)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. Sun Wax LEL-400: softening point 128 ° C.) were added, and after nitrogen replacement, 170 parts were obtained. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax 1]. The sp value of the graft chain of [modified wax 1] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1872, Mw was 5194, and Tg was 56.9 ° C.

Production Example 19 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of paraffin wax (melting point: 73 ° C.), 1 part of [modified wax 1] and 33 parts of acetone are added, heated to 78 ° C. and sufficiently dissolved for 1 hour. The wax was cooled to 30 ° C. to crystallize the wax into fine particles, and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 1].

Production Example 20 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of carnauba wax (melting point 80 ° C.) and 33 parts of acetone are introduced, heated to 78 ° C. to dissolve sufficiently, and cooled to 30 ° C. in 1 hour. The wax was crystallized into fine particles and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 2].

Production Example 21 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b1] and 10 parts of acetone were stirred and uniformly dispersed to obtain [Resin Solution 1].

Production Example 22 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b2] and 10 parts of acetone were stirred and uniformly dispersed to obtain [Resin Solution 2].

Production Example 23 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Vinyl resin b3] and 10 parts of acetone were stirred and uniformly dispersed to obtain [Resin solution 3].

Production Example 24 (Production of resin solution)
200 parts of [urethane-modified polyester b4] and 800 parts of [polyester b5] were dissolved and mixed in 1,800 parts of acetone to obtain [resin solution 4]. A portion of [resin solution 4] was dried under reduced pressure to isolate the resin component. The resin component had a Tg of 55 ° C. as measured by DSC.

Example 1
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 50 parts of liquid paraffin and 25 parts of [fine particle dispersion W1] were placed and dispersed uniformly. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer. The temperature was raised and acetone was distilled off at 35 ° C. under a reduced pressure of 300 mmHg until the concentration reached 0.5% or less. A non-aqueous resin dispersion (X-1) of resin particles in which resin particles derived from the dispersion W1] were formed into a film was obtained. The concentration of acetone was quantified by gas chromatography (FID method, GC2010 manufactured by Shimadzu Corporation) (the same applies hereinafter).

Example 2
In a beaker, 48 parts of [resin solution 1], 6 parts of [urethane prepolymer 1], 0.2 part of [curing agent 1], 27 parts of [wax dispersion 2], and 10 parts of [colorant dispersion 1] The mixture was stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed to obtain [resin solution 1B].
In a beaker, 50 parts of liquid paraffin and 25 parts of [fine particle dispersion W1] were placed and dispersed uniformly. Then, at 25 ° C., 75 parts of [resin solution 1B] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. under a reduced pressure of 300 mmHg until the concentration reached 0.5% or less. A non-aqueous resin dispersion (X-2) of resin particles in which resin particles derived from the dispersion W1] were formed into a film was obtained.

Example 3
In a beaker, put 60 parts of [resin solution 3], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1], and stir at 8,000 rpm with a TK homomixer at 25 ° C. Was dissolved and dispersed in [resin solution 3A].
In a beaker, 50 parts of liquid paraffin and 25 parts of [fine particle dispersion W1] were placed and dispersed uniformly. Then, at 25 ° C., 75 parts of [resin solution 3A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. under a reduced pressure of 300 mmHg until the concentration reached 0.5% or less. A non-aqueous resin dispersion (X-3) of resin particles in which resin particles derived from the dispersion W1] were formed into a film was obtained.

Example 4
In a beaker, 60 parts of [resin solution 4], 27 parts of [wax dispersion 2], and 10 parts of [colorant dispersion 1] are stirred at 8,000 rpm with a TK homomixer at 25 ° C. Was dissolved and dispersed in [resin solution 4A].
In a beaker, 50 parts of liquid paraffin and 25 parts of [fine particle dispersion W1] were placed and dispersed uniformly. Then, at 25 ° C., 75 parts of [resin solution 4A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. under a reduced pressure of 300 mmHg until the concentration reached 0.5% or less. A non-aqueous resin dispersion (X-4) of resin particles in which resin particles derived from the dispersion W1] were formed into a film was obtained.

Example 5
Except for changing [fine particle dispersion W1] to [fine particle dispersion W2], in the same manner as in Example 1, non-aqueous resin particles in which resin particles derived from [fine particle dispersion W2] are coated and adhered to the surface A resin dispersion (X-5) was obtained.

Example 6
Except for changing [fine particle dispersion W1] to [fine particle dispersion W3], in the same manner as in Example 1, non-aqueous resin particles in which resin particles derived from [fine particle dispersion W3] are coated and adhered to the surface A resin dispersion (X-6) was obtained.

Example 7
Resin particles derived from [fine particle dispersion W1] are coated on the surface in the same manner as in Example 1 except that [fine particle dispersion W1] is changed to [fine particle dispersion W4] and liquid paraffin is changed to silicone oil. A non-aqueous resin dispersion (X-7) of resin particles that were converted and adhered was obtained.

Example 8
In a beaker, 48 parts of [resin solution 1], 12 parts of [resin solution 2], and 25 parts of [colorant dispersion 1] are stirred at 8,000 rpm with a TK homomixer at 25 ° C. It was dissolved and dispersed to obtain [resin solution 5A].
In a beaker, 50 parts of liquid paraffin and 10 parts of [fine particle dispersion W5] were uniformly dispersed. Then, at 25 ° C., 75 parts of [resin solution 5A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer. The temperature was raised and acetone was distilled off at 35 ° C. under a reduced pressure of 300 mmHg until the concentration reached 0.5% or less. A non-aqueous resin dispersion (X-8) of resin particles coated with resin particles derived from the dispersion W5] was obtained.

Example 9
Resin in which resin particles derived from [fine particle dispersion W6] are coated on the surface and adhered in the same manner as in Example 8, except that 10 parts of [fine particle dispersion W5] are changed to 30 parts of [fine particle dispersion W6]. A non-aqueous resin dispersion (X-9) of particles was obtained.

Example 10
Resin in which resin particles derived from [fine particle dispersion W7] are coated on the surface and adhered in the same manner as in Example 8, except that 10 parts of [fine particle dispersion W5] are changed to 60 parts of [fine particle dispersion W7]. A non-aqueous resin dispersion (X-10) of particles was obtained.

Example 11
Resin in which resin particles derived from [fine particle dispersion W7] are coated on the surface and adhered in the same manner as in Example 8, except that 10 parts of [fine particle dispersion W5] are changed to 30 parts of [fine particle dispersion W8]. A non-aqueous resin dispersion (X-11) of particles was obtained.

Example 12
Resin in which resin particles derived from [fine particle dispersion W9] are coated on the surface and adhered in the same manner as in Example 8, except that 10 parts of [fine particle dispersion W5] are changed to 30 parts of [fine particle dispersion W9]. A non-aqueous resin dispersion (X-12) of particles was obtained.

Comparative Example 1
[Fine particle dispersion W1] A non-aqueous resin dispersion (X′-1) of resin particles having no shell was obtained in the same manner as in Example 1 except that 25 parts were changed to 25 parts liquid paraffin.

Measurement Example of Physical Properties Resin particles (X-1) to (X-12) and (X′-1) obtained in Examples 1 to 12 and Comparative Example 1 are dispersed in liquid paraffin, and the particle size distribution is laser diffraction / scattering. It measured with the type | formula particle size distribution measuring apparatus (The Horiba make, LA-920). Further, the physical properties of the resin particles were measured. The results are shown in Table 1.

Surface composition ratio [(C + Si + F) / (C + Si + F + O)] of resin particles contained in the non-aqueous resin dispersion, solubility of (A) in (L), volume average particle diameter, coefficient of variation of volume distribution, and average circularity Is measured by the method described above.
The particle surface smoothness, fixability, and heat-resistant storage stability are as follows.

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

[Fixability 1]
The non-aqueous resin dispersion is suspended on the paper surface and uniformly applied to a bar coater (# 10, gap 22.9 μm) (other methods may be used as long as they can be uniformly applied). 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 at which cold offset occurred was measured.

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

[Heat resistant storage stability]
The non-aqueous resin dispersion was allowed to stand for 24 hours in a dryer temperature-controlled at 50 ° C., and then the particle size distribution was measured and evaluated according to the following criteria based on the change in the particle size distribution before and after heating.
○: 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 non-aqueous resin dispersion of the present invention is effective as a liquid developer for paints, electrophotography, electrostatic recording, electrostatic printing, etc., oil-based inks for inkjet printers, and inks for electronic paper. Further, as other applications, it is also useful for cosmetics, electronic component manufacturing spacers, and electrorheological fluids.

Claims (13)

  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) Core-shell type resin particles (C) having a weight ratio of (Q) of (1:99) to (70:30) are non-aqueous organic solvents (L) having a relative dielectric constant of 1 to 4 at 20 ° C. Non-aqueous resin dispersion dispersed in   The non-aqueous resin dispersion according to claim 1, wherein the solubility of (a) in (L) is 1% by weight or less.   The non-aqueous resin dispersion according to claim 1 or 2, 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 non-aqueous resin dispersion 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. The non-aqueous resin dispersion according to claim 4, which is at least one selected from a vinyl monomer (m3) and a vinyl monomer (m4) having a fluoroalkyl chain having 4 to 20 carbon atoms.   6. (m) contains (m1) and (m2), and the weight ratio of (m1) to (m2) is (m1) :( m2) = 90: 10 to 10:90. Aqueous resin dispersion. The non-aqueous resin dispersion 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: Based on element strength measured by X-ray photoelectron analysis,
Value of (C + Si + F) / (C + Si + F + O)   The non-aqueous resin dispersion according to any one of claims 1 to 7, wherein (b) is at least one resin selected from vinyl resins, polyester resins, polyurethane resins, and epoxy resins.   The non-aqueous resin dispersion 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 non-aqueous resin dispersion 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 non-aqueous resin dispersion according to any one of claims 1 to 10, which is for paints, electrophotographic liquid developers, electrostatic recording liquid developers, ink jet printer oil-based inks, or electronic paper inks.   A non-aqueous resin dispersion (W) in which resin particles (A) containing the first resin (a) are dispersed in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C .; A solvent solution (O1) in which the second resin (b) is dissolved in an organic solvent (M) having a solubility parameter of 9.5 to 20, or a precursor (b0) of the resin (b) in (M) ) Is dissolved in the solvent solution (O2), (O1) or (O2) is dispersed in (W), and when (O2) is used, (b0) is further reacted, Non-aqueous resin dispersion of resin particles (D) having a structure in which resin particles (A) are attached to the surfaces of resin particles (B) by forming resin particles (B) containing (b) in W) A liquid (X1) is obtained, (M) is further distilled off from (X1), (A) is formed into a film, and Non-aqueous resin dispersion according to any one of claims 1 to 11 to the surface (A) are those which coat of shell layer (P) is obtained by being formed of a layer (Q).   A non-aqueous resin dispersion (W) in which resin particles (A) containing the first resin (a) are dispersed in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C .; A solvent solution (O1) in which the second resin (b) is dissolved in an organic solvent (M) having a solubility parameter of 9.5 to 20, or a precursor (b0) of the resin (b) in (M) ) Is dissolved in the solvent solution (O2), (O1) or (O2) is dispersed in (W), and when (O2) is used, (b0) is further reacted, Non-aqueous resin dispersion of resin particles (D) having a structure in which resin particles (A) are adhered to the surfaces of resin particles (B) by forming resin particles (B) containing (b) in W) (X1) is obtained, (M) is further distilled off from (X1), (A) is formed into a film, and the core layer (Q) composed of (B) A non-aqueous resin dispersion liquid (X2) of core-shell type resin particles (C) having a shell layer (P) formed by coating (A) on the surface is obtained. Manufacturing method.