JP4718392B2 - Resin particles and resin dispersion - Google Patents

Description

  The present invention relates to a resin dispersion and resin particles. More specifically, the present invention relates to resin particles and aqueous dispersions thereof useful for various applications such as powder coating materials, electrophotographic toners, and electrostatic recording toners.

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

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

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is the following nine inventions. In the following, the invention described as [2] or “second invention” is a reference invention.
[1] A core / shell composed of one or more film-like shell layers (P) made of the first resin (a) and one core layer (Q) made of the second resin (b) Type resin particles (C2), wherein the weight ratio of (P) and (Q) is (0.1: 99.9) to (70:30), and the volatile content of (C2) is 2 wt% And (a) is a softening start temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature of 0 to 120 ° C. and the outflow temperature. And a resin particle containing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit.
[2] An aqueous dispersion (W) of resin particles (A) made of the first resin (a), the second resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) Alternatively, the solvent solution (O) is mixed, (O) is dispersed in (W), and when (b0) or the solvent solution is used, (b0) is further reacted and (W) The aqueous dispersion (X1) of the resin particles (C1) obtained by forming the resin particles (B) consisting of (b) and having the resin particles (A) attached to the surfaces of the resin particles (B) ) Where the difference in sp value (Δsp) between (a) and (b) is K, and the natural logarithmic value [ln (Mw)] of the weight average molecular weight of (a) is H, H) is included in the inside including the side of the quadrilateral ABCD composed of the following four points A, B, C, and D, and (a) is a component unit. Aqueous resin dispersion, which is a resin acid (salt) group-containing a (meth) acrylamide containing from 1 to 30 wt%.
A (0.3, ln3000), B (1.5, ln1000),
C (1.3, ln200000), D (0.1, ln200000)
[3] An aqueous dispersion (W) of resin particles (A) made of the first resin (a), the second resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) Alternatively, the solvent solution (O) is mixed, (O) is dispersed in (W), and when (b0) or the solvent solution is used, (b0) is further reacted and (W) The aqueous dispersion (X1) of the resin particles (C1) obtained by forming the resin particles (B) consisting of (b) and having the resin particles (A) attached to the surfaces of the resin particles (B) ), Wherein (a) is a softening onset temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature and the outflow temperature of 0 to 120 ° C. And a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit is 1 to An aqueous resin dispersion characterized by being a resin containing 30% by weight.
[4] Aqueous dispersion (W) of resin particles (A) comprising the first resin (a), the second resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) Alternatively, the solvent solution (O) is mixed, (O) is dispersed in (W), and when (b0) or the solvent solution is used, (b0) is further reacted, and (A) Resin particles (C1) in which the resin particles (A) are adhered to the surfaces of the resin particles (B) obtained by forming the resin particles (B) made of (b) in the aqueous dispersion (W). ) Aqueous dispersion (X1), wherein (a) contains a structural unit of the following organic acid metal salt (m), and / or (A) contains the following organic acid metal salt (m), (A) is a resin containing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit. An aqueous resin dispersion characterized by being.
Organic acid metal salt (m): One or more salts selected from carboxylates, sulfonates, and phosphates of metals selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr.
[5] Resin particles obtained by removing the aqueous medium from the aqueous resin dispersion (X1) of any one of [2], [3], and [4].

[6] In the aqueous resin dispersion (X1) of any one of the above [2], [3], and [4], (A) attached to (B) is dissolved in a solvent, and / or Alternatively, it is composed of resin particles (C21) obtained by melting and forming a shell layer (P) in which (A) is formed on the surface of the core layer (Q) composed of (B). Aqueous resin dispersion (X2).
[7] Resin particles obtained by removing the aqueous medium from the aqueous resin dispersion (X2) of [6].
[8] An aqueous dispersion (W) of resin particles (A) made of the first resin (a), the second resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) Alternatively, the solvent solution (O) is mixed, (O) is dispersed in (W), and when (b0) or the solvent solution is used, (b0) is further reacted, and (A) By forming the resin particles (B) comprising (b) in the aqueous dispersion (W), the aqueous resin particles (C1) obtained by attaching the resin particles (A) to the surfaces of the resin particles (B). Dispersion (X1) is obtained, and in (X1), (A) attached to (B) is dissolved in a solvent and / or melted to constitute (B). Resin particles (C) obtained by forming a shell layer (P) in which (A) is formed on the surface of the core layer (Q) 21) an aqueous resin dispersion, wherein (a) is a resin containing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit. (X2).
[9] Resin particles obtained by removing the aqueous medium from the aqueous resin dispersion (X2) of [8].

[10] An aqueous dispersion (W) of resin particles (A) comprising the first resin (a), the second resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) Alternatively, the solvent solution (O) is mixed, (O) is dispersed in (W), and when (b0) or a solvent solution thereof is used, (b0) is further reacted, and (A) Aqueous dispersion of the resin particles (C1) in which the resin particles (A) are adhered to the surfaces of the resin particles (B) by forming the resin particles (B) of (b) in the aqueous dispersion (W). A body (X1) is obtained, and in (X1), (A) attached to (B) is dissolved in a solvent and / or melted to obtain a core layer composed of (B) ( Aqueous resin particles (C21) having a shell layer (P) in which (A) is coated on the surface of Q) A method for producing resin particles in which a fat dispersion (X2) is obtained and an aqueous medium is further removed from (X2), wherein (a) is 1 to 30 sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit. A production method characterized by being a resin containing wt%.

The resin dispersion of the present invention and the resin particles obtained therefrom have the following effects.
1. Excellent thermal and charging properties and uniform particle size.
2. Excellent heat storage stability and powder flowability.
3. Excellent particle surface smoothness (especially when having a shell layer formed into a film).
4). Since the resin particles can be obtained by dispersion in water, they can be produced at low cost.
5. The mechanical properties of the heat-melted coating film are also good.

A core composed of one or more film-like shell layers (P) made of the first resin (a) of the first invention and one core layer (Q) made of the second resin (b) In the shell-type resin particles (C2), the weight ratio of the shell layer (P) and the core layer (Q) is selected from the viewpoints of particle size uniformity, storage stability, fixability, etc. of the resin particles (C2) ( 0.1: 99.9) to (70:30) is preferable, more preferably (1:99) to (50:50), and particularly preferably (1.5: 98.5) to (30:70). It is. When the weight of the shell portion is too small, the blocking resistance may be lowered. On the other hand, if the shell portion is too heavy, fixing properties, particularly low-temperature fixing properties, may be deteriorated.
(P) may be formed of two or more layers (for example, 2 to 5 layers), but one layer is preferable.
Further, the volatile content of (C2) is usually 2% or less, more preferably 1% or less. If the volatile content exceeds 2%, the heat-resistant storage stability may decrease. In the present invention, the volatile matter means a decrease in weight after heating the sample at 150 ° C. for 45 minutes. In the above and the following, “%” means “% by weight” unless otherwise specified.

  In the first, eighth and tenth inventions, the resin (a) contains 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit to form a shell layer (P). Any resin can be used as long as it can be used. In the second invention, (a) contains 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit, and an sp value difference K from the resin (b) to be used; Any resin can be used as long as the value H [ln (Mw)] obtained by taking the natural logarithm of the weight average molecular weight (Mw) of a) meets the above conditions and can form an aqueous dispersion (W). Can be used. In the third invention, (a) contains 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit, and the above softening start temperature, glass transition temperature, outflow temperature, and glass Any resin that has a difference between the transition temperature and the outflow temperature and can form the aqueous dispersion (W) can be used. In the fourth invention, (a) is any resin that contains 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit and can form an aqueous dispersion. Can also be used. In the present invention, sulfonic acid (salt) means sulfonic acid and / or sulfonate, and (meth) acrylamide means acrylamide and / or methacrylamide. The same description method is used for other compounds.

The sulfonic acid (salt) group-containing (meth) acrylamide, which is a constituent unit of the resin (a), preferably has 7 to 15 carbon atoms, and 2- (meth) acrylamide-2-alkyl (4 to 12 carbon atoms). A sulfonic acid (salt) is more preferable.
Specific examples include 2- (meth) acrylamide-2-methylpropanesulfonic acid (salt), 2- (meth) acrylamide-n-butanesulfonic acid (salt), 2- (meth) acrylamide-n-hexanesulfonic acid. (Salt), 2- (meth) acrylamide-n-octanesulfonic acid (salt), 2- (meth) acrylamide-n-dodecanesulfonic acid (salt), 2- (meth) acrylamide-n-tetradecanesulfonic acid (salt) ), 2- (meth) acrylamide-2-phenylpropanesulfonic acid (salt), 2- (meth) acrylamide-2,2,4-trimethylpentanesulfonic acid (salt), 2- (meth) acrylamide-2-methyl Phenylethanepropanesulfonic acid (salt), 2- (meth) acrylamide-2- (4-chlorophenyl) propanesulfonic acid ( ), 2- (meth) acrylamide-2-carboxylmethylpropanesulfonic acid (salt), 2- (meth) acrylamide-2- (2-pyridine) propanesulfonic acid (salt), 2- (meth) acrylamide-3- Examples include methylbutanesulfonic acid (salt) and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid (salt). Of these, 2- (meth) acrylamido-2-methylpropanesulfonic acid (salt) is preferred.

Examples of the base that forms the sulfonate include ammonia, monoamine having 1 to 30 carbon atoms, polyamine (16), quaternary ammonium described later, alkali metals (sodium, potassium, etc.), and alkaline earth metals (calcium salts). , Magnesium salts, etc.).
Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), and tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine). , Lauryl dimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, monoamines and polyamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are 3 having 3 to 20 carbon atoms. Grade monoamine.

In the fourth invention, from the viewpoint of charging characteristics, the unit of the organic acid metal salt (m) is contained as a constituent unit of the resin (a) and / or the organic acid metal is contained in the resin particle (A). It is essential to contain the salt (m). When (m) is contained, resin particles particularly excellent in charging characteristics are obtained, which is preferable. As the organic acid constituting (m), a carboxylic acid is preferable. Among metals, Zn and Fe are preferable, and Zn is more preferable.
Among these, it is preferable that (A) is contained in (A) because adjustment is easy.

The resin (a) is a resin other than a polyurethane resin containing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit, and even a thermoplastic resin is a thermosetting resin. Also good.
Examples of (a) include vinyl resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin (a), two or more of the above resins may be used in combination. Among these, a vinyl resin is preferable from the viewpoint that it is easy to introduce a sulfonic acid (salt) group-containing (meth) acrylamide by using it as a part of a monomer to be addition copolymerized. In the case of other than vinyl resins, esterification is performed after synthesizing a vinyl copolymer of a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group, or an amino group and a sulfonic acid (salt) group-containing (meth) acrylamide. The reaction such as amidation is performed.

In the present invention, an aqueous dispersion (X1) of resin particles (C1) having a uniform particle size is obtained in order to obtain an aqueous dispersion (W) of fine spherical resin particles (A), excellent in heat-resistant storage stability and charging characteristics. ), The resin (a) contains a sulfonic acid anion group (—SO ₃ ⁻ ). The sulfonic acid anion group (—SO ₃ ⁻ ) is derived from a monomer having a sulfonic acid (salt) group-containing (meth) acrylamide as an essential component and other sulfonic acid anion groups used as necessary.
The total content of sulfonate anion groups (—SO ₃ ⁻ ) is preferably 0.001 to 10% based on the weight of (a). The lower limit is more preferably 0.002%, and the upper limit is more preferably 5%, particularly preferably 2%, and most preferably 1%. Further, a sulfonic acid anion group to form the resin (-SO ₃ ^-) preferred carbon number of the monomer containing 3 to 50, more preferably 3 to 30, particularly preferably from 4 to 15.
When the sulfonate anion group (—SO ₃ ⁻ ) group content is not less than the lower limit of the above range and the carbon number of the monomer containing the sulfonate anion group (—SO ₃ ⁻ ) forming the resin is not more than the upper limit of the above range. The resin (a) is easily dispersed in an aqueous medium, and an aqueous dispersion (W) of fine spherical resin particles (A) can be easily obtained. The obtained resin particles (C1) or (C2) [(C2) contains (C21). Hereinafter, “(C1) or (C2)” may be referred to as (C). The anti-blocking property and charging property of

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

Examples of the base that forms the neutralized salt include the same bases as the base that forms the sulfonate.
Among these, preferred are alkali metals, quaternary ammoniums, monoamines and polyamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are 3 having 3 to 20 carbon atoms. Grade monoamine.
In the case of vinyl resins and polyester resins, the monomer containing a carboxyl group or a salt thereof forming them preferably has 3 to 30, more preferably 3 to 15, particularly preferably 3 to 8. is there.

Hereinafter, the vinyl resin which is a preferable resin as (a) will be described in detail.
The vinyl resin is a polymer obtained by copolymerizing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide and another vinyl monomer in the monomer. Examples of the other vinyl monomers include the following (1 ) To (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, 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 and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes, such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

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

(3) Sulfonic group-containing vinyl monomers other than sulfonic acid (salt) group-containing (meth) acrylamide, vinyl sulfate monoester compounds 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 having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid 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-hydroxypropanesulfonic acid, alkyl (having 3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2-30) Oxyalkylene (eth , Propylene, butylene: may be single, random, or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, And sulfuric acid ester or sulfonic acid group-containing monomers represented by the following general formulas (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)

CH2COOR '
｜
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 monomers and salts thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 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 preferred, and sodium salts and salts of tertiary monoamines having 3 to 20 carbon atoms are more preferred.

(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 (6-2) amide Containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic acid Amides, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, Cyanostyrene, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide Diethylaminoethyl (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 monomers: nitrostyrene, etc.

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

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

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms. Dialkyl maleate (dialkyl maleate) (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes Vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight), such as diaryloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc. 300) Mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate Rate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO hereinafter) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [polyhydric alcohols Poly (meth) acrylate: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] (9-2) Vinyl (thio) ether, 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-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, Acetoxystyrene, phenoxystyrene, etc. (9-3) vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfones, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

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

  In this 4th invention, when using the vinyl-type resin containing the structural unit of organic acid metal salt (m) as (a), this resin, for example as said monomer (2)-( Among 4), it is obtained by using one or more metal salts selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr. The amount of these organic acid metal salt monomers (m) used in all monomers used for polymerization is preferably 5 to 60%. The lower limit is more preferably 10%, and the upper limit is more preferably 50%.

As a vinyl-based resin, 1 to 30% by weight of the sulfonic acid (salt) group-containing (meth) acrylamide and any of the monomers (1) to (10) described above are binary or more, Preferably, a polymer copolymerized at an arbitrary ratio so that the content of carboxyl groups in the resin particles (A) is 0.1 to 30%.
As a monomer copolymerized with a sulfonic acid (salt) group-containing (meth) acrylamide, (meth) acrylic acid (salt) [a metal salt as a salt in particular], having 5 to 12 carbon atoms (5 to 11 and 12). Monomers containing at least one selected from (meth) acrylic acid esters [particularly alkyl esters] and styrene are preferred (a vinyl resin having these monomers as constituent units is obtained).
Even when a resin other than a vinyl resin is used as the resin (a), a resin having a vinyl polymer portion having these monomers as constituent units is preferable.
Specific examples of the copolymer include 2- (meth) acrylamide-2-methylpropanesulfonic acid (salt)-(meth) acrylic acid ester- (meth) acrylic acid copolymer, 2- (meth) acrylamide-2- Methylpropanesulfonic acid (salt)-(meth) acrylic acid copolymer, 2- (meth) acrylamide-2-methylpropanesulfonic acid (salt)-(meth) acrylic acid ester copolymer, 2- (meth) acrylamide -2-Methylpropanesulfonic acid (salt)-(meth) acrylic acid ester- (meth) acrylic acid-styrene copolymer, salts of these copolymers, and the like.

  The content of the sulfonic acid (salt) group-containing (meth) acrylamide unit contained in the vinyl monomer copolymer is usually 1 to 30% based on the weight of the vinyl monomer copolymer. Preferably it is 2-25%, More preferably, it is 5-20%. When it is less than 1%, the charging characteristics of (C) are deteriorated, and when it exceeds 30%, the powder fluidity of (C) is deteriorated.

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

  As the resin (a), a resin that satisfies the requirements of the first (also the third invention) and the second invention is preferable. When the charging characteristics are important, the resin (a) may also satisfy the requirements of the fourth invention. preferable.

In the fourth invention, other than the method using the resin (a) in which a structural unit of a metal organic acid salt (m) selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr is introduced. In addition, the aqueous resin dispersion of the fourth invention may be obtained by a method of incorporating (m) into the resin particles (A). Moreover, the method of using the resin particle (A) which used these methods together may be used.
Among organic acid metal salts (m), specific examples of carboxylic acid metal salts include (alkyl substituted) benzoic acid, (alkyl substituted) salicylic acid, aromatic acids having 7 to 35 carbon atoms such as naphthenic acid, and stearin. Preferred are higher fatty acids having 12 to 35 carbon atoms such as acids, and those exemplified as metal salts of carboxyl group-containing vinyl monomers constituting the vinyl resin. Specific examples of the sulfonic acid metal salt include those exemplified as the alkylbenzene sulfonic acid having 7 to 30 carbon atoms and the metal salt of the sulfone group-containing vinyl monomer constituting the vinyl resin. What was illustrated as a metal salt of the phosphoric acid group containing vinyl monomer which comprises vinyl resin as a metal phosphate is preferable. Among these, oil-soluble metal salts are more preferable in order to exhibit the charging effect of the resin particles (C). From the viewpoint of composition, carboxylic acid metal salts are more preferable, and Zn salts and Fe salts of carboxylic acids are particularly preferable.
As a method of containing the organic acid metal salt (m) in (A), if the resin (a) is not reactive with the precursor of the resin (a), it may be added before the preparation of (a). It is preferable to mix with (a) after preparation.
Although there is no restriction | limiting in particular in the usage rate of the structural unit of these organic acid metal salt (m), and organic acid metal salt (m), These total amount with respect to the resin particle (C1) obtained is 0.01 to 10%. It is preferable that The lower limit is more preferably 0.05%, and the upper limit is more preferably 1%.

The core-shell type resin particles (C2) of the first invention may be resin particles produced by any method and process. As a method for producing the core-shell type resin particles, the following method is used. Production methods (I) to (III) and the like can be mentioned.
(I): An example of a method of making a core-shell structure at the same time as creating core particles.
The aqueous dispersion (W) of the resin particles (A) made of the resin (a) and the resin (b) [including the precursor (b0)] or the solvent solution (O) thereof are mixed, and in (W) (O) is dispersed in the resin particles, and the resin particles (B) comprising (b) are formed 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 an aqueous dispersion (X1) of core-shell type resin particles (C1). Built by removing. At this time, when the surface of (C1) is not formed into a film, a film forming treatment may be performed, and this step may be performed at any stage after obtaining (X1).

(II): The resin particles (B) made of the resin (b) prepared in advance are coated with the coating agent (W ′) made of the resin (a), and if necessary, the shell layer is formed into a core shell. A method for producing mold resin particles (C2). 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 limited. For example, a dispersion of resin particles (B) or (B) prepared in advance in an aqueous dispersion (W) of resin particles (A) made of resin (a) is dispersed. Examples thereof include a method and a method in which the solution (a) is applied to (B) as a coating agent.

(III) A method in which a core particle is prepared and the vicinity of the surface of the core particle is physically and / or chemically manipulated to be changed to another shell resin. Resin particles (B) made of resin (b) are prepared in advance, and the surface of (B) is subjected to heat treatment and / or chemical treatment (such as acid and amine neutralization) to form single particles (B) as cores. There is a method of changing to shell type resin particles (C2).
Among these, the production method (I) is preferable.

  In the second, third, fourth, eighth and tenth inventions and the production method (I) in the first invention, the resin particles (A) comprising the resin (a) and, if necessary, the organic acid metal salt (m), The aqueous dispersion (W) is mixed with the resin (b) or its solvent solution, or the precursor (b0) of the resin (b) or its solvent solution (O), and (O) is dispersed in (W). When the resin particles (B) made of (b) are formed, the resin particles (C1) are united by adsorbing the resin particles (A) on the surfaces of the resin particles (B). It also prevents (C1) from splitting under high shear conditions. Thereby, the particle diameter of (C1) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, the resin particles (A) have a strength that is not broken by shearing at the temperature at which they are dispersed, are not easily dissolved or swelled in water, (b) or a solvent solution thereof (b0 ) Or it is difficult to dissolve in the solvent solution.

  In the second invention, the sp value of the resin particle (A) with respect to the resin particle (B) (the method for calculating the sp value is according to Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). In addition, the particle surface of the resin particle (C1) can be smoothed by controlling the molecular weight of the resin particle (A).

In the second invention, the difference in sp value (Δsp) between the resin (a) and the resin (b) is K, and the natural logarithm of the weight average molecular weight (Mw) of the resin (a) is ln (Mw) as H. (A) and (b) are selected so that the point (K, H) is included in the inside including the side of the rectangle ABCD composed of the following four points A, B, C, D shown in FIG. Is done.
A (0.3, ln3000), B (1.5, ln1000),
C (1.3, ln200000), D (0.1, ln200000)
The point (K, H) is preferably included in the inside including the side of the quadrangle A′B′C′D ′ composed of the following four points A ′, B ′, C ′, and D ′. More preferably, it is included in the inside including the side of a quadrangle A ″ B ″ C ″ D ″ composed of points A ″, B ″, C ″, D ″.
A ′ (0.3, ln3200), B ′ (1.45, ln1500),
C ′ (1.3, ln100,000), D ′ (0.15, ln100,000)

A ″ (0.3, ln3400), B ″ (1.4, ln2000),
C ″ (1.3, ln50000), D ″ (0.2, ln50000)

  When the point (K, H) is below the straight line AB, the resin particles (A) are easily dissolved in a solvent or the like at the time of granulation, and granulation may not be successful. Further, when the point (K, H) is above the straight line CD, the resin particles (A) do not swell at all in the solvent or the like, and the resin particles (C1) have insufficient smoothness due to difficulty in heat melting. It may lead to a decrease in powder fluidity. Further, when the point (K, H) is to the left of the straight line AD, since the sp value difference between the resin (a) and the resin (b) is small, the resin particles (A) are dissolved in the resin (b) solution. Granulation may not be successful. Further, when the point (K, H) is to the right of the straight line BC, the difference in sp value between the resin (a) and the resin (b) is large, and the resin particles (A) do not swell at all in the solvent and the smoothness of the particles If the point (K, H) is positioned to the right, that is, if the sp value difference between the resin (A) and the resin (B) is further widened, the resin (A) The adsorptive power of the resin (B) may decrease, and granulation may become difficult.

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) with water or a solvent used for dispersion, the molecular weight, sp value, crystallinity, molecular weight between crosslinking points, etc. of the resin (a) are determined. It is preferable to adjust appropriately.

  The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the resin (a) is usually from 10 to 5 million, preferably from 2 to 5 million, more preferably from 500 to 500,000, and the sp value is , Usually 7-18, preferably 8-14. The melting point (measured by DSC) of the resin (a) is usually 50 ° C. or higher, preferably 80 to 200 ° C. When it is desired to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (C), a crosslinked structure may be introduced into the resin (a). Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. When the crosslinked structure is introduced into the resin (a), the molecular weight between crosslinking points is usually 50 or more, preferably 500 or more, and more preferably 1000 or more.

In the present invention, the peak top molecular weight, number average molecular weight (Mn), and weight average molecular weight (Mw) of resins other than polyurethane, such as polyester resins, are gel permeation chromatography (GPC) for tetrahydrofuran (THF) solubles. Is measured under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Detection device: Refractive index detector Reference material: 12 points (Mw 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) Standard polystyrene (TSK standard POLYSTYRENE)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight.
Moreover, Mn and Mw of the polyurethane resin that can be used as the resin (b) described later are measured under the following conditions using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α
TSKgel α-M
Measurement temperature: 40 ° C
Sample solution: 0.125% dimethylformamide solution Injection volume: 100 μl
Flow rate: 1 ml / min Detection device: Refractive index detector Reference material: 12 points (Mw 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) Standard polystyrene (TSK standard POLYSTYRENE)

The glass transition temperature (Tg) of the resin (a) is usually 20 ° C. to 250 ° C., preferably from the viewpoints of the particle size uniformity of the resin particles (C), powder flowability, heat resistance during storage, and stress resistance. Is 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C, particularly preferably 71 ° C to 100 ° C. If the Tg is lower than the temperature at which the 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.
The Tg of the resin particles (A) comprising (a) and optionally (m) is preferably 20 to 200 ° C., more preferably 40 to 100 ° C., particularly preferably 70 to 90 ° C. for the same reason. is there.
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).

For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 10.0 mm

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

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

  The temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2) of the resin (a) is preferably 0 ° C to 120 ° C, more preferably 0 ° C to 110 ° C, and particularly preferably 0 ° C to 105 ° C. Most preferably, it is 0 ° C to 90 ° C. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

  Moreover, the preferable temperature difference of the glass transition temperature (Tg) and softening start temperature (Ts) of resin (a) is 0 degreeC-100 degreeC, More preferably, it is 0 degreeC-70 degreeC, More preferably, it is 0 degreeC-50 degreeC. Especially preferably, it is 0 degreeC-35 degreeC. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

  When adjusting the glass transition temperature (Tg), softening start temperature (Ts), and outflow temperature (T1 / 2) of the resin (a), the molecular weight of (a) and / or the monomer composition constituting (a) It can be easily adjusted by changing As a method of adjusting the molecular weight (Mn and Mw) of (a) (the higher the molecular weight, the higher the temperature), a known method may be used. For example, polymerization is performed by a sequential reaction such as a polyester resin. In the case of polymerization by a chain reaction such as a vinyl resin, adjustment of the polymerization initiator amount and chain transfer agent amount, reaction temperature, and reaction concentration can be adjusted. Can be mentioned. In order to adjust the temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2), a combination of the molecular weight of (a) and the monomer composition constituting (a) may be appropriately selected. .

  The resin (a) used in the first and third inventions has a softening start temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a glass transition of 0 to 120 ° C. It is a resin that has all the differences between temperature and effluent temperature.

  In Shore D hardness, which is a hardness standard, the hardness of the resin particles (A) is usually 30 or more, particularly preferably in the range of 45-100. Moreover, it is preferable that the hardness when immersed in water or in a solvent for a certain time is also in the above range.

  In the aqueous dispersion (W) of the resin particles (A), a solvent miscible with water (acetone, methyl ethyl ketone, etc.) may be contained in the solvent (u) described later in addition to water. In this case, any solvent may be used as long as it does not cause aggregation of the resin particles (A), does not dissolve the resin particles (A), and does not interfere with granulation of the resin particles (C1). Even if it is a seed | species and what kind of content may be sufficient, what is not left in the resin particle (C) after drying using 40% or less of the total amount with water is preferable.

The method for converting the resin (a) to the aqueous dispersion (W) of the resin particles (A) is not particularly limited, and the following [1] to [8] can be mentioned.
[1] In the case of a vinyl resin, an aqueous dispersion of resin particles (A) is directly formed by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. Process [2] In the case of polyaddition or condensation resin such as polyester resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant if necessary. And a method of producing an aqueous dispersion of resin particles (A) by heating or adding a curing agent thereafter [3] In the case of polyaddition or condensation resin such as polyester resin, a precursor ( Monomers, oligomers, etc.) or solvent solutions thereof (preferably in liquid form, and may be liquefied by heating), and then water added to phase inversion emulsification, A method for producing an aqueous dispersion of resin particles (A) by adding a curing agent or the like [4] In advance, any polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) The resin prepared by the above method may be pulverized using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then classified to obtain resin particles, and then in the presence of a suitable dispersant. Method of dispersing in water [5] Resin solution in which a 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.) is dissolved in a solvent A method of dispersing resin particles in water in the presence of an appropriate dispersant after the resin particles are obtained by spraying in a mist state [6] Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation) in advance , Condensation polymerization, etc. A resin solution prepared by dissolving a resin prepared in a solvent may be added, or a resin solution may be precipitated by cooling a resin solution previously heated and dissolved in a solvent, Next, after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of a suitable dispersant [7] polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, A resin solution prepared by dissolving a resin prepared by any polymerization reaction mode such as condensation polymerization in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and the solvent is removed by heating or decompression. Removal method [8] A resin prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. Method of phase inversion emulsification by adding water after dissolving a suitable emulsifier in the solution

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (s), water-soluble polymer (t) and the like can be used. Moreover, a solvent (u), a plasticizer (v), etc. can be used together as an auxiliary agent for emulsification or dispersion.

  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.).

The sulfate ester salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters salts (EO or PO 1 to 10 moles of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated fats or 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 having 1 to 8 carbon atoms) sulfated and neutralized) and sulfated olefins (one having 12 to 18 carbon atoms sulfated and neutralized) 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 sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates, sulfonates of Igepon T-type and other 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.
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, higher alcohol phosphate ester salt, 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 and the like).
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 (eg 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 AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant can be used.
The AO addition type nonionic surfactant is a compound having 8 to 40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms, alkylamine having 8 to 40 carbon atoms, or the like. AO is added to an 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, preferred are EO and random or block adducts of EO and PO.
The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% of the AO is preferably 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.

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

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

The plasticizer (v) may be added to the aqueous medium as needed during the emulsification dispersion, or may be added to the emulsified dispersion [in the oil phase containing the resin (b) or (b0)].
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 obtained particle size distribution of (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 ( In the case of obtaining C), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm of particles (C) are preferably 0.05 to 30 μm, particularly preferably. 0.1 to 20 μm.
In addition, the volume average particle size is determined by laser type particle size distribution measuring device LA-920 (manufactured by Horiba), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, or the like. Can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by 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 resin (b) of the present invention, any resin can be used as long as it is a known resin, and specific examples thereof include those similar to (a) and polyurethane resins. (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 Polyester resin and polyurethane resin containing 1,2-propylene glycol as a structural unit.
Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin which are preferable resins as (b) will be described in detail.

Examples of the vinyl resin include those exemplified as the vinyl resin used for the resin (a). However, the amount of the sulfonic acid (salt) group-containing (meth) acrylamide used as a raw material monomer is arbitrary and may not be used.
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, ( (Meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, Examples thereof include styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymers, and salts of these copolymers.

Examples of 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 3 to 8 or more valences (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and 3 to 6 or more valences. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably from 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

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

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol 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-dimethyloloctanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; 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 monomer]; 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 acids having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acids 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 tri- or hexavalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid (13) or 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.

In addition, in this 4th invention, when using the polyester resin containing the structural unit of organic acid metal salt (m) as (a), this resin is polyester (acid value is preferable, for example) which has the residue of COOH, for example 1 to 100, more preferably 5 to 50), and at least one part of the COOH group is a salt of at least one metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr. Is obtained.
As a method for forming a metal salt, for example, it is obtained by reacting a polyester having a COOH group with a hydroxide of the corresponding metal.

  Polyurethane resins include polyisocyanate (15) and active hydrogen-containing compounds {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 [dicarboxylic acid (13), and polycarboxylic acid (14) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon number 6-12 lactone ring-opening polymers, polyamines (16), polythiols (17), and combinations thereof, and the like, and terminal isocyanate group prepolymers obtained by reacting (15) with active hydrogen-containing compounds. An equal amount of primary and / or secondary monoa with respect to the isocyanate groups of the polymer and the prepolymer Down (18) and reacting the obtained, and amino group-containing polyurethane resins.

  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 polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and minor amounts (eg 5-20%] )) With a trifunctional or higher functional polyamine]]: phosgenates: 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 (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the 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-hex 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 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aroma such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Polyamines (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, diethylto Range amine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′- Tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-di Minodiphenylmethane, 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'-diaminodiphenylsulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substitution electrons Aromatic polyamines having an attractive group (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2- Chlor-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-di Lol-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'-methylene (4-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [1] A part or all of —NH _{2 in} the aromatic polyamine of [3] is replaced by —NH—R ′ (where 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 polyamines (more than 2 moles per mole of acid) Polyether polyamines such as low molecular weight polyamide polyamines obtained by condensation with (the above alkylene diamines, polyalkylene polyamines, etc.) Hydrides of cyanoethylation products of Le polyols (polyalkylene glycol and the like).

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

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

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

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

  Examples of the polyepoxide (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 glycidyl ether of phenol 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 Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

The 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 such that the difference in sp value from the resin (a) is within the range of the second invention, but is usually 7-18, preferably 8-14, more preferably 9-14. is there.
For example, when the resin particles (C) and the resin particles (B) are used as a slush molding resin and a powder coating, the Mn in (b) is usually 2,000 to 500,000, preferably 4,000 to 200,000. is there. The melting point of (b) (measured by DSC, hereinafter the melting point is a measured value by DSC), usually 0 ° C. to 200 ° C., preferably 35 ° C. to 150 ° C. Tb of (b) is usually −60 ° C. to 100 ° C., preferably −30 ° C. to 60 ° C.
When used as a standard particle for electronic component manufacturing spacers such as liquid crystal displays and electronic measuring machines, the Mn in (b) is usually 20,000 to 10,000,000, preferably 40,000 to 2,000,000. The melting point (measured by DSC, hereinafter the melting point is a measured value by DSC) of (b) is usually 40 ° C to 300 ° C, preferably 70 ° C to 250 ° C. Tb of (b) is usually −0 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C.
When used as a toner used in electrophotography, electrostatic recording, electrostatic printing, etc., the Mn of (b) is usually 1,000 to 5,000,000, preferably 2,000 to 500,000. The melting point (measured by DSC, hereinafter the melting point is a measured value by DSC) of (b) is usually 20 ° C. to 300 ° C., preferably 80 ° C. to 250 ° C. The Tg of (b) is usually 20 ° C to 200 ° C, preferably 40 ° C to 200 ° C. The sp value of (b) is usually 8 to 16, preferably 9 to 14.

In the first invention, the adsorption force of the resin (a) constituting the core layer (Q) to the resin (b) constituting the shell layer (P) can be controlled by the following method.
[1]: When the resin (a) and the resin (b) are made to have positive and negative charges, an adsorption force is generated. In this case, as the charges of the resin (a) and the resin (b) are increased, the adsorption is increased. The force becomes strong and the shell resin (a) is not peeled off from the core resin (b).
[2]: When the resin (a) and the resin (b) have the same polarity (both positive or both negative), the adsorption force of the shell resin (a) to the core resin (b) is weakened. It is difficult to form a core / shell type, and even if formed once, the shell resin (a) may be peeled off from the core resin (b). In this case, generally, the use of the surfactant (s) and / or the water-soluble polymer (t) [especially those having a reverse charge to the resin particles (A) and resin particles (B)] nurtures the adsorptive power, It becomes easy to form a shell mold and the shell resin (a) does not peel from the core resin (b).
[3]: A resin in which the resin (a) has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group when the aqueous dispersion (W) and the coating agent (W ′) that is an aqueous liquid are produced. (In general, the molecular weight per acidic functional group is preferably 1,000 or less), the lower the pH of the aqueous medium, the stronger the adsorptive power. Conversely, the higher the pH, the weaker the adsorption power.
[4]: When producing the aqueous dispersion (W) or the coating agent (W ′) which is an aqueous liquid, the resin (a) is a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium. In the case of a resin having a basic functional group such as a base (generally, the molecular weight per basic functional group is preferably 1,000 or less), the adsorptive power becomes stronger as the pH of the aqueous medium becomes higher. Conversely, the lower the pH, the weaker the adsorption power.
[5]: When the difference between the sp values of the resin (a) and the resin (b) (Δsp value) is reduced, the adsorption force increases. However, if the Δsp value is too small, the resin (a) and the resin (b) may be dissolved, and the core / shell type particles may be lost.

When the resin particles (C2) are formed in an aqueous medium in the production methods (I) to (III), the resin particles (C2) can be obtained by removing the aqueous medium from the aqueous resin dispersion. As a method of removing the aqueous medium,
[1]: A method of drying an aqueous resin dispersion under reduced pressure or normal pressure [2]: A method of solid-liquid separation with a centrifuge, a spacula filter, a filter press, etc., and drying the resulting powder [3]: Method of freezing aqueous resin dispersion and drying (so-called lyophilization)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify using an air classifier etc. as needed, and can also be made into a predetermined particle size distribution.

The shape of the resin particles (C2) of the first invention can be controlled by the following method according to the production method.
(1) In the case of production method (I) The particle shape and particle surface properties can be controlled by controlling the difference in sp value between the resin particles (A) and the resin particles (B) and the molecular weight of the resin particles (A). it can. When the difference in sp value is small, irregularly-shaped and smooth surface particles are easily obtained, and when the difference in sp value is large, spherical particles having a rough surface are easily obtained. Moreover, when the molecular weight of (A) is large, particles having a rough surface are easily obtained, and when the molecular weight is small, particles having a smooth surface are easily obtained. 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 particles (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, the weight average molecular weights of preferable resin particle (A) are 100-1 million, More preferably, it is 1000-500,000, More preferably, it is 2000-200,000, Most preferably, it is 3000-100,000.

(2) In the case of production method (II) and production method (III) Both production methods greatly affect the shape of the resin particles (B) prepared in advance, and the resin particles (C2) are almost the same as the resin particles (B). It becomes the same shape. However, when (B) is distorted, if more coating agent (W ′) is used in the production method (II), it becomes spherical. In addition, in the production method (III), when a heat treatment higher than the Tg of (B) is performed, (C2) becomes spherical.

From the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C2), 70% or more of the surface of the core layer (Q), preferably 80% or more, more preferably 90% or more, Particularly preferably, 95% or more is covered with the shell layer (P). The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [area of the portion covered by (P) / area of the portion covered by (P) + area of the exposed portion of (Q)] × 100

In the second, third, fourth, eighth, and tenth inventions and the production method (I) for obtaining the resin particles of the first invention, the adsorptive power of the resin particles (A) to the resin particles (B) Can be controlled by the following method.
[1]: When the aqueous dispersion (W) is produced, if the resin particles (A) and the resin particles (B) have positive and negative charges, an adsorption force is generated. In this case, the resin particles (A ), The greater the charge of each of the resin particles (B), the stronger the adsorptive power and the greater the coverage of the resin particles (A) on the resin particles (B).
[2]: When the aqueous dispersion (W) is produced, if the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative), the coverage ratio Tend to go down. In this case, in general, when the surfactant (s) and / or the water-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased.
[3]: When the aqueous dispersion (W) is produced, the resin (a) is a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is When the pH of the aqueous medium is lower, the coverage is higher. Conversely, the higher the pH, the smaller the coverage.
[4]: When the aqueous dispersion (W) is produced, the resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium base ( In general, the molecular weight per basic functional group is preferably 1,000 or less), and the higher the pH of the aqueous medium, the greater the coverage. Conversely, the coverage decreases as the pH is lowered.
[5]: When the Δsp value of the resin particles (A) and the resin particles (B) is decreased, the coverage is increased.

In the second, third, fourth, eighth and tenth inventions and the production method (I) for obtaining the resin particles of the first invention, the aqueous resin dispersion (X1) is a resin comprising the resin (a). The aqueous dispersion (W) of the particles (A) and the resin (b) or a solvent solution (O) thereof are mixed, and (O) is dispersed in (W). In (W), an aqueous dispersion of resin particles (C1) having a structure in which (A) is attached to the surface of (B) can be obtained by forming resin particles (B) made of (b). it can.
Alternatively, the aqueous dispersion (W) of the resin particles (A) made of the resin (a) and the precursor (b0) of the resin (b) or the solvent solution (O) thereof are mixed, and (W) O) is dispersed, and (b0) is further reacted to form resin particles (B) consisting of (b) in the aqueous dispersion (W) of (A). It can be obtained as an aqueous dispersion of resin particles (C1) having a structure in which (A) is attached to the surface.

In the case of dispersing the resin (b) or its solvent solution, or the precursor (b0) of the resin (b) or its solvent solution, 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 Gaulin) 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 uniform particle size.

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

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

  When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to obtain a resin (b) includes, for example, an oil-soluble initiator, monomers, and, if necessary, a solvent (u). An oil phase comprising a method of dispersing and suspending an oil phase in water in the presence of a water-soluble polymer (t) and performing a radical polymerization reaction by heating (so-called suspension polymerization method), monomers and, if necessary, a solvent (u) Is emulsified in an aqueous dispersion (W) of resin particles (A) containing an emulsifier (same as the surfactant (s)) and a water-soluble initiator, and a radical polymerization reaction is performed by heating. And a method (so-called emulsion polymerization method).

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

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

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

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

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method of forming the resin (b) by reacting the precursor (b0), an oil phase containing a reactive group-containing prepolymer (α) and a curing agent (β) and, if necessary, a solvent (u) is used. The resin particles (A) are dispersed in an aqueous dispersion, and the reactive group-containing prepolymer (α) and the curing agent (β) are reacted by heating to form resin particles (B) made of the resin (b). Method: Reactive group-containing prepolymer (α) or a solvent solution thereof is dispersed in an aqueous dispersion of resin particles (A), and a water-soluble curing agent (β) is added thereto and reacted to obtain resin (b). A method of forming resin particles (B) comprising: a reactive group-containing prepolymer (α) or a solvent solution thereof as a resin when the reactive group-containing prepolymer (α) is cured by reacting with water. By dispersing the particles (A) in the aqueous dispersion (W), water and Examples thereof include a method of reacting to form the resin particles (B) comprising (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). There is a combination.
[2]: The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) capable of reacting with an active hydrogen-containing group. combination.
Among these, [1] is more preferable from the viewpoint of the reaction rate in water.
In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; Phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof That.
Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

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

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1]: A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2]: The functional group of the constituent component is left at the terminal by using one of two or more constituent components in excess, and further contains a functional group and a reactive group capable of reacting with the remaining functional group. Examples include a method of reacting a compound.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol [diol (11) etc.] and polycarboxylic acid [dicarboxylic acid (13) etc.] is hydroxyl group [OH] and carboxyl group [COOH]. The equivalent ratio [OH] / [COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1. In the case of other skeletons 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 an 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 usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1. 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high.
The Mn of the reactive group-containing prepolymer (α) is usually 500 to 30,000, preferably 1,000 to 20,000, and more preferably 2,000 to 10,000.
The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is usually not more than 2,000 poise, preferably not more than 1,000 poise at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of solvent.

Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d ).
(Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, 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) include those similar to the diol (11) and 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 (ketimine compound etc.);
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 preferable, and (α2b) is particularly preferable.
Examples of the organic group blocked with the compound from which the amino group can be removed include those similar to the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), and polyacid halide (β2e). Can be mentioned. Of these, (β2a) and (β2b) are 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) include the dicarboxylic acid (13), and examples of the polycarboxylic acid include those similar to the polycarboxylic acid (14), and preferable ones are also the same.

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

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

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

  Also, 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 an 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 an aqueous medium and an unreacted resin.

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

In the present invention, the physical properties such as the resins (a) and (b) in which the point (K, H) of the second invention is included in a specific range, or (Ts) and (Tg) of the third invention. By using the resin (a) having, for example, when the solvent solution of (b) or (b0) (especially the following preferred solvent) is used, the solvent is preferably added to the aqueous resin dispersion (X1) in an amount of 10 to 10. Using 50% (especially 20 to 40%), removing the solvent at 40 ° C. or less, preferably 1% or less (especially 0.5% or less), the resin particles (A) are dissolved in the solvent to form a film. In many cases, an aqueous resin dispersion (X2) of resin particles (C21) in which the coating (A) is formed on the surface of (B) is obtained. However, even when the coating film of (A) is not formed or when the coating film is formed from at least a part of (A), the smoothness of the coating film on the surface of the resin particles (C) is further improved. Therefore, when the following operation is performed, a coating having a smooth surface (shell layer (P)) formed from (A) on at least a part of the surface of the core layer (Q) composed of (B), preferably the entire surface. It is preferable from the point that the aqueous resin dispersion (X2) of the resin particles (C21) having the above is obtained and the storage stability of (C21) obtained therefrom is excellent.
Examples of the method include a method of dissolving (A) attached to (B) in a solvent, and a method of heating the aqueous resin dispersion (X1) to melt (A) to form a film, These methods may be used in combination.

A solvent used when the resin particles (A) are dissolved in a solvent to form a film may be added to (X1) when forming the film, but as a raw material for obtaining (X1), a resin (b ) Or a solvent solution of the precursor (b0), and using the solvent without removing it immediately after the formation of the resin particles (B), the solvent is contained in (B) (A ) Is easily dissolved, and it is preferable that the resin does not aggregate.
As a solvent, a thing with high affinity with (b) is preferable, and the thing similar to the said solvent (u) is mentioned as a specific example. Preferred among (u) are tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate from the viewpoint of film formation, and more preferably ethyl acetate.
The solvent concentration in the aqueous resin dispersion when (A) is dissolved in the solvent is preferably 3 to 60%, more preferably 10 to 45%, and particularly preferably 15 to 30%. The dissolution is performed by stirring the aqueous resin dispersion, for example, for 1 to 10 hours, and the temperature during dissolution is preferably 15 to 45 ° C, and more preferably 15 to 30 ° C.

When (A) is melted to form a film on the surface of (B), the solid content [content of components other than water and solvent] in the aqueous resin dispersion (X1) is preferably 1 to 50%, Preferably, it is adjusted to 5 to 30%. The solvent content 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 solvent content 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.
It is to be noted that, as a film-forming treatment method, the aqueous dispersion (X1) of resin particles (C1) having a solvent content of 2% or less is heat-treated, and (A) is melted on the core (Q) to obtain a more surface. However, a preferable heat treatment temperature for obtaining smooth resin particles (C21) is not less than Tg of (P) and a temperature range of not more than 80 ° C. is preferable. The surface smoothness of the resin particles (C21) obtained when the heat treatment temperature is less than the Tg of (P) hardly changes. Moreover, when heat-processing at the temperature exceeding 80 degreeC, a shell (P) may peel from a core.
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).

  Resin particles (C1) are an aqueous dispersion (W) of resin particles (A) made of resin (a), a solvent solution of resins (b) and (b), a precursor (b0) of (b), or (B0) is mixed with the solvent solution (O), and (O) is dispersed in (W). In the case of (b0), (b0) is reacted to form resin (b), and resin (b The aqueous dispersion (X1) of the resin particles (C1) having a structure in which the resin particles (A) are attached to the surface of the resin particles (B) made of) and / or the surface of (B) from (A) After forming the aqueous dispersion (X2) of the resin particles (C21) having a structure having the formed coating, the aqueous resin dispersion (X1) or (X2) [hereinafter referred to as “(X1) or (X2)” This may be described as (X). It is obtained by removing the aqueous medium from Examples of the method for removing the aqueous medium include the same methods as the method for removing the aqueous medium from the aqueous dispersion (C2) in the method for producing resin particles of the first invention.

The resin particles (C1) are substantially composed of relatively small resin particles (A) and relatively large resin particles (B), and (A) is attached to the surface of (B). To do. The resin particles (C21) are those in which (A) is dissolved and / or melted after adhering to (B), and the coating from (A) is formed on the surface of (B).
When it is desired to further increase the adhesion of both particles, when dispersed in an aqueous medium, (A) and (B) have positive and negative charges, or (A) and (B) are identical. In the case of having a charge, a surfactant (s) or a water-soluble polymer (t) having a charge opposite to (A) and (B) is used, or resin (a) and resin (b) It is effective to make the difference in the sp value of ()) as small as possible within the above range (for example, 2 or less).

  The resin particles (C) are composed of 0.01 to 60% (A) and 40 to 99.99% (B) from the viewpoints of particle size uniformity and storage stability of the resin particles (C). More preferably 0.1 to 50% (A) and 50 to 99.9% (B), particularly preferably 1 to 45% (A) and 55 to 99% (B). .

From the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C1), 5% or more of the surface of the resin particles (B), preferably 30% or more, more preferably 50% or more, Particularly preferably, 80% or more is covered with the resin particles (A). The surface coverage of (C1) 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 resin particles (A) / area of the portion covered with the resin particles (A) + area of the portion where the resin particles (B) are exposed] × 100
The surface coverage in the case of (C21) is the same as (C2) of the first invention.

From the viewpoint of particle size uniformity, the variation coefficient of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1 to 15%.
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, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

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

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, it is preferable that the particles (A) and the particles (B) are also spherical. (C) preferably has an average circularity of 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment 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 toner.

In the second, third, fourth, eighth and tenth inventions and the production method (I) for obtaining the resin particles of the first invention, the resin particles (C) are resin particles (B) of the resin particles (A). ), Particle diameter ratio, and resin particle (B) surface coverage with resin particles (A) in aqueous resin dispersion (X1), resin particles (B) in aqueous resin dispersion (X1) / aqueous medium By changing the depth at which the resin particles (A) are embedded on the resin particle (B) side on the interface, the particle surface can be smoothed or desired irregularities can be imparted to the particle surface.
The coverage of the surface of the resin particles (B) with the resin particles (A) and the depth at which the resin particles (A) are embedded on the resin particles (B) side can be controlled by the following method.
[1]: When the aqueous resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) are made to have positive and negative charges, the coverage and depth are increased. 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 the 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 coating The rate decreases and the depth tends to decrease. In this case, generally, when the activator (s) and / or the water-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased. Moreover, when using water-soluble polymer (t), depth becomes small, so that the molecular weight of water-soluble polymer (t) is large.
[3]: When the aqueous resin dispersion (X1) is produced, the resin (a) has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally a molecular weight per acidic functional group). Is preferably 1,000 or less), the lower the pH of the aqueous medium, the greater the coverage and depth. Conversely, the higher the pH, the smaller the coverage and depth.
[4]: Resin having a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium base when the aqueous resin dispersion (X1) is produced. (In general, the molecular weight per basic functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the greater the coverage and depth. Conversely, the lower the pH, the smaller the coverage and depth.
[5]: The coverage and the depth increase as the SP value difference between the resin (a) and the resin (b) decreases.

In the resin particles (A) and / or (B) constituting the resin particles (C), additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, oxidation agents) Inhibitor, blocking inhibitor, heat stabilizer, flame retardant, etc.) may be mixed. As a method of adding an additive in (A) or (B), the aqueous resin dispersion (X1) may be mixed in an aqueous medium, but the resin (a) or the resin (b It is more preferable that the mixture is added and dispersed in an aqueous medium after mixing an additive).
In the present invention, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium, and may be added after the particles are formed. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method, or the additive can be impregnated with the solvent (u) and / or the plasticizer (v). .
When the charge control agent consisting of the organic acid salt (m) is contained in the resin particles (A) as an additive, the charging characteristics are preferably improved.
Examples of (m) include those described above, and the amount used is also the same.

In addition, in the present invention in general, particularly in the third invention, the resin particle (B) contains, as the additive, a resin (b), a wax (c), and a modified wax (d) grafted with a vinyl polymer chain. Then, heat-resistant storage stability improves more and it is preferable.
The content of (c) in (B) is preferably 20% or less, more preferably 1 to 15%. The content of (d) is preferably 10% or less, more preferably 0.5 to 8%. The total content of (c) and (d) is preferably 25% or less, more preferably 1 to 20%.

The wax (c) is dispersed in the resin (b) after being previously melt-kneaded with the modified wax (d) and / or heat-dissolved and mixed in the presence of the solvent (u).
Examples of the wax (c) include polyolefin wax, paraffin wax, carbonyl group-containing wax, and mixtures thereof. Among these, paraffin wax (c1) is particularly preferable. Examples of (c1) include petroleum waxes whose main component is a linear saturated hydrocarbon having a melting point of 50 to 90 ° C. and a carbon number of 20 to 36.
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, Mn of the wax is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is dispersed in the resin (b) after being melt-kneaded with a modified wax (d) grafted with a vinyl polymer chain and / or heat-dissolved and mixed in the presence of the 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 the same monomers as the monomers (1) to (10) constituting the vinyl resin. Among these, (1) is particularly preferred. , (2), and (6). The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. The Tg of (d) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, from the viewpoint of heat resistant storage stability of the resin particles (C).
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), heating to 100 to 200 ° C., and then converting the vinyl monomer to a peroxide initiator (benzoyl peroxide, diter It is obtained by dripping together with a butyl peroxide, tertiary butyl peroxide benzoate, etc.) and polymerizing, 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 higher than the melting point of each, [2] dissolving (c) and (d) in the solvent (u) Alternatively, after suspending, precipitation in liquid by cooling crystallization, solvent crystallization, etc., or precipitation in gas by spray drying, etc. [3] (c) and (d) in solvent (u) Examples of the method include dissolving or suspending, and then mechanically wet-grinding with a disperser. Among these, the method [2] is preferable.
As a method of dispersing the wax (c) and the modified wax (d) in (b), (c), (d), and (b) are made into a solvent solution or a dispersion, respectively, The method of mixing etc. is mentioned.

  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 aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 130 parts of isopropanol was charged. Under stirring, 120 parts of butyl acrylate, 80 parts of styrene, 55 parts of methacrylic acid, 30 parts of 2-acrylamido-2-methylpropanesulfonic acid, A mixed solution of 62 parts of benzoyl oxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W1]. The volume average particle diameters of [fine particle dispersion W1] measured by LA-920 and ELS-800 were both 0.09 μm. A portion of [fine particle dispersion W1] was dried to isolate the resin component. The resin component had a Tg of 72 ° C. by DSC measurement, a softening start temperature of 98 ° C., and an outflow temperature of 175 ° C.

Production Example 2 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, water 753 parts, alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2, Sanyo Chemical Industries) 8 parts, butyl acrylate 77 parts, styrene 58 parts, methacrylic acid 38 Part, 2-acrylamido-2-methylpropanesulfonic acid 20 parts, ammonium persulfate 1 part, surfactant (polyoxysorbitan monooleate) 9 parts and stirred at 400 rpm for 15 minutes, white milk A turbid liquid was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous vinyl resin dispersion (fine particle dispersion W2). The volume average particle diameters of [fine particle dispersion W2] measured by LA-920 and ELS-800 were both 0.05 μm. A portion of [fine particle dispersion W2] was dried to isolate the resin component. The resin component had a Tg of 60 ° C. by DSC measurement, a softening start temperature of 110 ° C., and an outflow temperature of 198 ° C.

Production Example 3 (Production of aqueous dispersion of resin particles (A))
A reaction vessel equipped with a stir bar and thermometer was charged with 132 parts of isopropanol. Under stirring, 82 parts of butyl acrylate, 82 parts of styrene, 79 parts of methacrylic acid, 30 parts of 2-acrylamido-2-methylpropanesulfonic acid, A mixed solution of 60 parts of benzoyl oxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W3]. The volume average particle diameters of [fine particle dispersion W3] measured by LA-920 and ELS-800 were both 0.10 μm. A portion of [fine particle dispersion W3] was dried to isolate the resin component. Tg by DSC measurement of the resin was 75 ° C., the softening start temperature was 100 ° C., and the outflow temperature was 160 ° C.

Production Example 4 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 150 parts of isopropanol was charged. Under stirring, 122 parts of butyl acrylate, 91 parts of styrene, 61 parts of methacrylic acid, 30 parts of 2-acrylamido-2-methylpropanesulfonic acid, excess A mixed solution of 1.0 part of benzoyl oxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W4]. The volume average particle diameters of [fine particle dispersion W4] measured by LA-920 and ELS-800 were both 0.10 μm. A part of [fine particle dispersion W4] was dried to isolate the resin component. The resin component had a Tg of 95 ° C. by DSC measurement, a softening start temperature of 120 ° C., and an outflow temperature of 225 ° C.

Production Example 5 (Production of aqueous dispersion of resin particles (A))
An aqueous vinyl resin dispersion [fine particle dispersion W5] was obtained in the same manner as in Production Example 2 except that 38 parts of methacrylic acid in Production Example 2 were replaced with 19 parts of methacrylic acid and 19 parts of methacrylic acid Zn salt. . The volume average particle diameters of the fine particle dispersion measured by LA-920 and ELS-800 were both 0.08 μm. A part of [Fine Particle Dispersion W5] was dried to isolate the resin component. The Tg of the resin component measured by DSC was 72 ° C., the softening start temperature was 115 ° C., and the outflow temperature was 205 ° C.

Production Example 6 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stir bar and a thermometer, 130 parts of isopropanol was charged. Under stirring, 120 parts of butyl acrylate, 80 parts of styrene, 85 parts of methacrylic acid, 1 part of 2-acrylamido-2-methylpropanesulfonic acid, A mixed solution of 62 parts of benzoyl oxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W6]. The volume average particle diameters of [fine particle dispersion W6] measured by LA-920 and ELS-800 were both 0.09 μm. A part of [fine particle dispersion W6] was dried to isolate the resin component. The resin component had a Tg of 72 ° C. by DSC measurement, a softening start temperature of 98 ° C., and an outflow temperature of 175 ° C.

Production Example 7 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stir bar and a thermometer, 130 parts of isopropanol was charged, and under stirring, 110 parts of butyl acrylate, 70 parts of styrene, 10 parts of methacrylic acid, 85 parts of 2-acrylamido-2-methylpropanesulfonic acid, A mixed solution of 62 parts of benzoyl oxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W7]. The volume average particle diameters of [fine particle dispersion W7] measured by LA-920 and ELS-800 were both 0.09 μm. A portion of [fine particle dispersion W7] was dried to isolate the resin component. Tg by DSC measurement of the resin content was 78 ° C., the softening start temperature was 110 ° C., and the outflow temperature was 210 ° C.

Production Example 8 (Production of aqueous dispersion of resin particles (A))
A reaction vessel equipped with a stir bar and thermometer was charged with 132 parts of isopropanol, and under stirring, 82 parts of 2-ethylhexyl acrylate, 82 parts of styrene, 79 parts of acrylic acid, 30 parts of 2-acrylamido-2-methylpropanesulfonic acid A mixed solution of 60 parts of benzoyl peroxide (containing 25% water) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W8]. The volume average particle diameters of [fine particle dispersion W8] measured by LA-920 and ELS-800 were both 0.10 μm. Part of [fine particle dispersion W8] was dried to isolate the resin component. The resin component had a Tg of 62 ° C. by DSC measurement, a softening start temperature of 93 ° C., and an outflow temperature of 145 ° C.

Production Example 9 (Production of resin (b))
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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 moles) of dimethyl ester, 180 parts (2.5 moles) of adipic acid and 3 parts of tetrabutoxy titanate as a condensation catalyst were added while distilling off the methanol produced at 180 ° C. in a nitrogen stream. 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 10 (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 were allowed to react 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 propylene glycol and water produced under a nitrogen stream, and further, the reaction was 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, then 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 11
In a reaction vessel equipped with a stir bar and a thermometer, 2000 parts of polycaprolactone diol having a hydroxyl number of 56 (Placcel L220AL, manufactured by Daicel Chemical Industries, Ltd.) is charged, heated to 110 ° C., and dehydrated under a reduced pressure of 3 mmHg for 1 hour. Went. Subsequently, 457 parts of IPDI were added and reacted at 110 ° C. for 10 hours to obtain [Urethane Prepolymer 1] having an isocyanate group at the terminal. [Nurethane Prepolymer 1] had an NCO content of 3.6%.

Production Example 12
A reaction vessel equipped with a stir bar and a thermometer was charged with 50 parts of ethylenediamine and 300 parts of MIBK, and reacted at 50 ° C. for 5 hours to obtain [curing agent 1] which is a ketimine compound.

Production Example 13 (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. [Vinyl resin b3] had a weight average molecular weight of 14,000 by GPC and a glass transition point of 60 ° C.

Production Example 14 (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. Further, after reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, cooling to 110 ° C., adding 17 parts of isophorone diisocyanate in toluene, reacting at 110 ° C. for 5 hours, then removing the solvent, weight average molecular weight 72, [Urethane-modified polyester b4] having an NCO content of 0.7% and an NCO content of 0.7% was obtained.

Production Example 15 (Production of resin (b))
As in Production Example 14, 570 parts of bisphenol A / EO 2 molar 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 16 (Production of colorant dispersion)
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.), 20 parts of [Polyester b2] and 56 parts of ethyl acetate were stirred and dispersed uniformly. Phthalocyanine was finely dispersed to obtain [Colorant Dispersion Liquid 1]. The volume average particle diameter of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.3 μm.

Production Example 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.) and 76 parts of ethyl acetate were stirred and uniformly dispersed. [Colorant dispersion 2] was obtained. The volume average particle diameter of [Colorant Dispersion Liquid 2] measured by LA-920 was 0.3 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 ethyl acetate are added, heated to 78 ° C. and sufficiently dissolved. After cooling to 30 ° C. over time, the wax was crystallized into fine particles and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 1].

Production Example 20 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b1] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 1].

Production Example 21 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b2] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 2].

Production Example 22 (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 ethyl acetate were stirred and dispersed uniformly to obtain [resin solution 3].

Production Example 23 (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 ethyl acetate to obtain [resin solution 4]. A part 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
In a beaker, 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] are placed at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 15.4 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Then, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and the core layer (B) ( An aqueous resin dispersion (XF1) of resin particles in which the shell layer (P) in which (A) was formed on the surface of Q) was formed was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain resin particles (F1) with a volatile content of 0.5% or less.

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 1], and 10 parts of [colorant dispersion 1] The mixture was stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed to obtain [resin solution 1B].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (“ELEMINOL MON-7” manufactured by Sanyo Chemical Industries) ) 10 parts was added and dissolved uniformly. Then, at 25 ° C., 75 parts of [resin solution 1B] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (XF2) of resin particles in which the shell layer (P) in which (A) was formed on the surface of Q) was formed was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain resin particles (F2) with a volatile content of 0.5% or less.

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, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (“ELEMINOL MON-7” manufactured by Sanyo Chemical Industries) ) 10 parts was added and dissolved uniformly. Next, 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. Next, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (XF3) of resin particles in which the shell layer (P) in which (A) was formed on the surface of Q) was formed was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain resin particles (F3) with a volatile content of 0.5% or less.

Example 4
In a beaker, 60 parts of [resin solution 1], 27 parts of [wax dispersion 1], 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 1C].
In a beaker, 97 parts of ion-exchanged water, 11 parts of [fine particle dispersion W3], 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) 10 The portion was added and dissolved uniformly. Then, at 25 ° C., 75 parts of [resin solution 1C] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration became 0.5% or less, and the core layer composed of (B) ( An aqueous resin dispersion (XF4) of resin particles in which the shell layer (P) in which (A) was formed on the surface of Q) was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain resin particles (F4) with a volatile content of 0.5% or less.

Example 5
The aqueous resin dispersion (XF4) obtained in Example 4 was heated to 70 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the surface of (Q) composed of (B) ( An aqueous resin dispersion (XF5) of resin particles formed with a shell layer (P) in which A) was further coated was obtained. Subsequently, filtration and drying were similarly performed to obtain resin particles (F5).

Example 6
In a beaker, 276 parts of [resin solution 4], 10 parts of trimethylolpropane tribehenate (melting point: 58 ° C., melt viscosity: 24 cps) as a release agent, and 25 parts of [colorant dispersion liquid 2] are placed at 25 ° C. Then, the mixture was stirred at 12,000 rpm with a TK homomixer and uniformly dissolved and dispersed to obtain [resin solution 4A].
In a beaker, 443 parts of ion-exchanged water, 15 parts of [fine particle dispersion W5], 2 parts of sodium carboxymethyl cellulose, and 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) 40 The portion was added and dissolved uniformly. Next, at 25 ° C., while stirring the TK homomixer at 12,000 rpm, 300 parts of [resin solution 4A] was added and stirred for 10 minutes. Next, this mixed solution was transferred to a Kolben equipped with a stirrer and a thermometer, heated to distill off ethyl acetate, further heated to 70 ° C. and reacted for 5 hours, and the core layer constituted by (B) An aqueous resin dispersion (XF6) of resin particles having (A) attached to the surface of (Q) was obtained. Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain a resin particle (F6) with a volatile content of 0.5% or less.

Example 7
The aqueous resin dispersion (XF6) obtained in Example 6 was heated to 70 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the surface of the core layer (Q) composed of (B) An aqueous resin dispersion (XF7) of resin particles in which a shell layer (P) in which (A) was formed into a film was formed was obtained. Subsequently, filtration and drying were similarly performed to obtain resin particles (F7).

Example 8
The core layer constituted by (B) in the same manner as in Example 4 except that 10.5 parts of [Fine particle dispersion W8] is used instead of 10.5 parts of [Fine particle dispersion W3] in Example 4. An aqueous resin dispersion (XF8) of resin particles in which a shell layer (P) in which (A) was formed on the surface of (Q) was formed, and resin particles (F8) were obtained.

Example 9
The aqueous resin dispersion (XF8) obtained in Example 8 was heated to 70 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the surface of (Q) composed of (B) ( An aqueous resin dispersion (XF9) of resin particles formed with a shell layer (P) in which A) was further coated was obtained. Subsequently, filtration and drying were performed in the same manner to obtain resin particles (F9).

Comparative Example 1
The aqueous resin dispersion (XF1) obtained in Example 1 was heated to 85 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the aqueous resin separated from (Q) by peeling off (P). A dispersion (XF′1) was obtained. Subsequently, filtration and drying were performed in the same manner, and (P) was removed by filtration to obtain resin particles (F′1) consisting only of (Q).

Comparative Example 2
A core layer constituted by (B) in the same manner as in Example 2 except that 2.9 parts of [Fine particle dispersion W2] is used instead of 15.4 parts of [Fine particle dispersion W1] in Example 1. An aqueous resin dispersion (XF′2) of resin particles having the resin particles (A) attached to the surface of (Q) and resin particles (F′2) were obtained.

Comparative Example 3
The aqueous resin dispersion (XF2) obtained in Example 2 was heated to 85 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the aqueous resin separated from (Q) by peeling off (P). A dispersion (XF′3) was obtained. Subsequently, filtration and drying were performed in the same manner, and (P) was removed by filtration to obtain resin particles (F′3) consisting only of (Q).

Comparative Example 4
The aqueous resin dispersion (XF3) obtained in Example 3 was heated to 85 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the aqueous resin separated from (Q) by peeling off (P). A dispersion (XF′4) was obtained. Subsequently, filtration and drying were performed in the same manner, and (P) was removed by filtration to obtain resin particles (F′4) consisting only of (Q).

Comparative Example 5
In the same manner as in Example 7 except that [Fine Particle Dispersion Liquid W3] is used instead of [Fine Particle Dispersion Liquid W3] in Example 4, (A) is formed on the surface of the core layer (Q) composed of (B). An aqueous resin dispersion (XF′5) and resin particles (F′5) of resin particles to which are attached) were obtained.

Comparative Example 6
The aqueous resin dispersion (XF′5) obtained in Comparative Example 5 was heated to 70 ° C. with stirring and stirred for 1 hour, then cooled to 25 ° C., and the core layer (Q) composed of (B) An aqueous resin dispersion (XF′6) of resin particles having a slightly film-formed (A) attached to the surface was obtained. Subsequently, filtration and drying were performed in the same manner to obtain resin particles (F′6).

Comparative Example 7
In the same manner as in Example 6 except that [Fine particle dispersion W2] is used instead of [Fine particle dispersion W5] in Example 6, (A) ) To which an aqueous resin dispersion (XF′7) and resin particles (F′7) were obtained.

Comparative Example 8
In the same manner as in Example 1, except that [Fine particle dispersion W1] is used instead of [Fine particle dispersion W1] in Example 1, (A) is formed on the surface of the core layer (Q) composed of (B). An aqueous resin dispersion (XF′8) and resin particles (F′8) of resin particles in which a shell layer (P) with a coating of) was formed were obtained.

Comparative Example 9
In the same manner as in Example 1, except that [Fine particle dispersion W1] is used instead of [Fine particle dispersion W1] in Example 1, (A) is formed on the surface of the core layer (Q) composed of (B). An aqueous resin dispersion (XF′9) and resin particles (F′9) of resin particles in which a shell layer (P) with a coating of) was formed were obtained.

Example of measuring physical properties The resin particles (F1) to (F9) and (F′1) to (F′9) obtained in Examples 1 to 9 and Comparative Examples 1 to 9 are dispersed in water to determine the particle size distribution in a Coulter counter. Measured with Further, the average circularity, charging characteristics, heat-resistant storage stability, and low-temperature fixability of the resin particles were measured. The results are shown in Tables 1-2. In addition, (circle) means the inside of square ABCD of 2nd invention, and x means the exterior.

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

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

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

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

[Surface smoothness]
Using a scanning electron microscope (SEM), the surface of the resin particle (C) 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 consist of resin (a) can be confirmed.

  Since the resin dispersion and resin particles of the present invention have a uniform particle size and are excellent in charging characteristics, heat-resistant storage stability, etc., spacers for manufacturing electronic parts such as slush molding resins, powder paints, and liquid crystals, electronic measuring instruments This is extremely useful as a standard particle, a toner used for electrophotography, electrostatic recording, electrostatic printing, etc., various hot melt adhesives, and other resin particles used for molding materials.

It is a graph which shows the relationship between the sp value difference (K) of (a) and (b) of this 2nd invention, and the natural logarithm value ln (Mw) (H) of the weight average molecular weight (Mw) of (a). . It is a conceptual diagram which shows the flowchart in the flow tester measurement of a resin particle.

Claims (13)

  Core-shell type resin composed of one or more film-like shell layers (P) made of the first resin (a) and one core layer (Q) made of the second resin (b) Particle (C2), wherein the weight ratio of (P) and (Q) is (0.1: 99.9) to (70:30), and the volatile content of (C2) is 2% by weight or less And (a) has a softening onset temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature and the outflow temperature of 0 to 120 ° C. Resin particles comprising 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit.   The resin (a) is a resin containing at least one selected from (meth) acrylic acid (salt), (meth) acrylic acid ester having 5 to 12 carbon atoms, and styrene as a structural unit. Resin particles.   The resin particles according to claim 1 or 2, wherein (b) is at least one resin selected from a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl resin.   (C2) is an aqueous dispersion (W) of resin particles (A) comprising (a) and a resin (b) or a solvent solution thereof, or a precursor (b0) of a resin (b) or a solvent solution thereof ( O) is mixed, (O) is dispersed in (W), and when (b0) or a solvent solution thereof is used, (b0) is further reacted to form an aqueous dispersion (W) of (A). ) To form an aqueous dispersion (X1) of resin particles (C1) in which (A) is adhered to the surface of (B) by forming resin particles (B) consisting of (b) in In (X1), the resin particles (C21) in which the shell layer (P) in which (A) is formed on the surface of the core layer (Q) composed of (B) are formed, An aqueous dispersion (X2) of (C21) was obtained, and the aqueous medium was removed from (X2). Resin particles according to any one of claims 1 to 3.   The resin for slush molding, powder paint, spacer for manufacturing electronic parts, standard particles for electronic measuring equipment, electrophotographic toner, electrostatic recording toner, electrostatic printing toner or hot melt adhesive. Or a resin particle according to any of the above.   An aqueous dispersion (W) of resin particles (A) made of the first resin (a) and a second resin (b) or a solvent solution thereof, or a precursor (b0) of a resin (b) or a solvent thereof When the solution (O) is mixed, (O) is dispersed in (W), and (b0) or a solvent solution thereof is used, (b0) is further reacted, and (b) The aqueous dispersion (X1) of the resin particles (C1) obtained by forming the resin particles (B) comprising the resin particles (B) and having the resin particles (A) attached to the surfaces of the resin particles (B). (A) has a softening start temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature and the outflow temperature of 0 to 120 ° C. 1 to 30 sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit % Aqueous resin dispersion, which is a resin containing.   The aqueous resin dispersion according to claim 6, wherein (a) contains 0.1 to 30 wt% of a carboxyl group that may be at least partially neutralized with a base.   The aqueous resin dispersion according to claim 6 or 7, wherein (B) comprises a resin (b), a wax (c), and a modified wax (d) grafted with a vinyl polymer chain. 7. (b) is at least one resin selected from polyester resins, polyurethane resins, epoxy resins, and vinyl resins. The aqueous resin dispersion described. Claim 6 Resin particles obtained by removing an aqueous medium from the aqueous resin dispersion described. Claim 6 In the aqueous resin dispersion described, (A) attached to (B) is dissolved in a solvent and / or melted, whereby core layer (Q) composed of (B) is formed. An aqueous resin dispersion (X2) comprising resin particles (C21) obtained by forming a shell layer (P) having (A) coated on the surface. Resin particles comprising the aqueous resin dispersion of claim 11, wherein the (X2) is an aqueous medium removed. An aqueous dispersion (W) of resin particles (A) made of the first resin (a) and a second resin (b) or a solvent solution thereof, or a precursor (b0) of a resin (b) or a solvent thereof The solution (O) is mixed, (O) is dispersed in (W), and when (b0) or a solvent solution thereof is used, (b0) is further reacted to obtain an aqueous dispersion of (A) An aqueous dispersion (X1) of resin particles (C1) in which the resin particles (A) are adhered to the surfaces of the resin particles (B) by forming the resin particles (B) made of (b) in (W). In (X1), by dissolving (A) adhering to (B) in a solvent and / or melting, the core layer (Q) composed of (B) is obtained. Aqueous resin dispersion of resin particles (C21) having a shell layer (P) with (A) coated on the surface X2) to give a, a process for the preparation of the resin particles to remove aqueous medium from the addition (X2), (a) the initial softening temperature of forty to two hundred seventy ° C., a glass transition temperature of 20 to 250 [° C., 60 to 300 ° C. And a difference between the glass transition temperature of 0 to 120 ° C. and the outflow temperature, and a resin containing 1 to 30% by weight of a sulfonic acid (salt) group-containing (meth) acrylamide as a structural unit Manufacturing method.

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