JP4732981B2 - Core / shell type resin particles - Google Patents

Description

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

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a core-shell type resin particle composed of one or more film-like shell layers (P) made of resin (a) and one core layer (Q) made of resin (b). (D), wherein the weight ratio of (P) and (Q) is (0.1: 99.9) to (70:30), and (b) is a polyester resin (b1) and / or (b1). ) As a structural unit, and (b1) is titanium halide (e1), titanium diketone enolate (e2), titanium carboxylate (e3), titanyl carboxylate (e4), And a carboxylic acid titanyl salt (e5), a titanium-containing compound (e6) represented by the following general formula (I) or (II), and a titanium-containing compound (e7) represented by the following general formula (III) At least one selected from A resin particle which is a polycondensation polyester resin obtained is formed in the presence of down-containing catalyst (e).
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR < ₁ >) q (II)
_{Ti (-Z) r (-OR 2} ) s (III)
[In the formulas (I) and (II), X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. In the case of a polyalkanolamine, other OH groups May be condensed in the molecule with an OH group directly bonded to the same Ti atom to form a ring structure, or may be repeatedly condensed between molecules with an OH group directly bonded to another Ti atom to form a repeating structure. It may be. The degree of polymerization in the case of forming a repeating structure is 2-5. R ₁ is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
[In the formula (III), R ₂ is H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. Z is a residue obtained by removing one carboxyl group H from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, other carboxyl groups are polycondensed in the molecule with an OR group in the same molecule. A structure may be formed, or a structure containing 2 to 5 Ti atoms may be formed by polycondensation between an OR group of another molecule and the molecule. r = 1 to 3 and s = 1 to 3, and the sum of r and s is 4. ]

The resin particles of the present invention have the following effects.
1. Excellent charging and thermal characteristics and uniform particle size.
2. Excellent heat storage stability and powder flowability.
3. Excellent particle surface smoothness.
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.

The core-shell type resin particle (D) of the present invention comprises one or more film-like shell layers (P) made of the resin (a) and a polyester resin (b1) and / or (b1) as structural units. It is comprised with 1 core layer (Q) which consists of resin (b) which consists of resin (b2) to contain. (P) may be formed of two or more layers (for example, 2 to 5 layers), but one layer is preferable.
In the present invention, the weight ratio of the shell layer (P) and the core layer (Q) is usually (0.1: 99. 9) to (70:30), preferably (1:99) to (50:50), more preferably (1.5: 98.5) to (30:70). 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.

  The volatile content of the resin particles (D) is preferably 2% or less, more preferably 1% or less. When the volatile content is 2% or less, the heat-resistant storage stability is good. 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 below, “%” means “% by weight” unless otherwise specified.

The core / shell type resin particles (D) of the present invention may be resin particles produced by any method and process, but as an example of the production method of the core / shell type resin particles, the following production is possible. Examples include methods (1) to (3).
(1): An example of a method for forming a core particle and simultaneously forming a core-shell structure.
Resin (b) consisting of an aqueous dispersion (W) of resin particles (A) consisting of resin (a) and resin (b2) containing polyester resin (b1) and / or (b1) as constituent units, or a solvent thereof A method of mixing the solution (O), dispersing (O) in (W), and forming resin particles (B) comprising (b) in (W). In this case, the resin particles (A) adhere to the surface of (B) simultaneously with the granulation of the resin particles (B) to form an aqueous dispersion (X1) of the resin particles (C), from which the aqueous medium is removed. Built. At this time, when the aqueous dispersion (X2) of the resin particles (D) in which the surface (A) of the resin particles (C) is coated is not formed, the film is treated to form a coating (A). A shell layer (P) is formed. This step may be performed at any stage after (X1) is obtained.

(2): The resin particles (B) made of the resin (b) made of (b1) and / or (b2) prepared in advance are coated with the coating agent (W ′) made of the resin (a), and if necessary A method for producing core-shell type resin particles (D) by coating the shell layer. 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.

(3): A method of preparing core particles and changing the vicinity of the surface of the core particles to another shell resin by physically and / or chemically operating the core particles. Resin particles (B) comprising the resin (b) comprising the resin (b1) and / or (b2) are prepared in advance, and the surface of (B) is subjected to heat treatment and / or chemical treatment (such as acid and amine neutralization). Thus, there is a method of changing the single particle (B) to the core-shell type resin particle (D).
Among these, the production method (1) is preferable.

In the present invention, a resin other than a polyurethane resin is used as the resin (a). The resin (a) can be any resin as long as it can form the shell layer (P), and may be a thermoplastic resin or a thermosetting resin.
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, polycarbonate resins, and the like. As the resin (a), two or more of the above resins may be used in combination. Among these, a polyester resin, an epoxy resin, a vinyl resin, and a combination thereof are preferable from the viewpoint that a shell layer is easily formed.

An aqueous dispersion (W) of fine spherical resin particles (A) for obtaining resin particles (D) having excellent heat-resistant storage stability and charging characteristics, and having a uniform particle size, and when produced by the production method (1) ), The resin (a) preferably contains a sulfonate anion group (—SO ₃ ⁻ ). The total content of sulfonic acid 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.
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. And when manufacturing using said manufacturing method (1) or (2), resin (a) is easy to disperse | distribute in an aqueous medium, and the aqueous dispersion (W) of a fine spherical resin particle (A) is easy. Can get to. Moreover, the blocking resistance and charging characteristics of the resulting resin particles (D) are improved.

Furthermore, in order to obtain an aqueous dispersion (W) of fine spherical resin particles (A) from the viewpoint of charging characteristics and when produced by the production method (1), the resin (a) contains a carboxyl group. It is preferable to do. 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 10% 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 more preferably 9.5%, particularly preferably 9%, most preferably 8%.
When the base neutralization rate and the carboxyl group content are at least the lower limit of the above range, the charging characteristics of the resulting resin particles (D) are improved.
Examples of the base that forms the neutralized salt include ammonia, monoamine having 1 to 30 carbon atoms, polyamine (12), quaternary ammonium, alkali metal (sodium, potassium, etc.), and alkaline earth metal (calcium salt). , 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). , Lauryldimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, monoamines and polyamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are 3 having 3 to 20 carbon atoms. Grade monoamine.
Moreover, the preferable carbon number of the monomer containing the carboxyl group or its salt which forms a vinyl-type resin and a polyester resin is 3-30, More preferably, it is 3-15, Most preferably, it is 3-8.

From the viewpoint of charging characteristics, the organic acid metal salt (m) (a metal carboxylate selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr, sulfonic acid as a constituent unit of the resin (a) is used. It is preferable that the organic acid metal salt (m) is contained in the shell layer (P). When (m) is contained, resin particles (D) particularly excellent in charging characteristics can be obtained. As the organic acid constituting (m), a carboxylic acid is preferable. Among metals, Zn and Fe are preferable, and Zn is more preferable.
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 examples include higher fatty acids having 12 to 35 carbon atoms such as acids, and metal salts of carboxyl group-containing vinyl monomers constituting vinyl resins described later. As specific examples of the sulfonic acid metal salt, those exemplified as the metal salt of the alkylbenzene sulfonic acid having 7 to 30 carbon atoms and the sulfone group-containing vinyl monomer constituting the vinyl resin described later are preferable. 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 (D). 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 for containing (m) in the resin particles (D), a resin 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 to the method using (a), when manufacturing using the manufacturing method (1) or (2), an aqueous resin dispersion in which (m) is contained in the resin particles (A) may be used. Moreover, the method of using the resin particle (A) which used these methods together may be used. Among these, the method of containing (m) in (A) is preferable from the viewpoint of easy adjustment.
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 (D) 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%.

  Hereinafter, vinyl resin, polyester resin, and epoxy resin, which are preferable resins as the resin (a), will be described in detail.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer 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, other α-olefins, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene 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.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropanesulfonic acid, 2- ( T) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-C18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, Propylene, butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and Sulfate ester or sulfonic acid group-containing monomers represented by 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-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

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

(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 butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, 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, heptadecyl (meth) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two The alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxy] Ethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) mono Acrylate, methyl alcohol ethylene oxide (hereinafter referred to as EO 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] (9-2) vinyl (thio) ether, for example Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-butyl (9-3) Vinyl ketones such as vinyl, such as vinyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, 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 the case of using a vinyl-based resin containing a structural unit of the organic acid metal salt (m) as (a), this resin is, for example, Al as at least a part of the monomer among the monomers (2) to (4). , Ti, Cr, Mn, Fe, Zn, Ba, and Zr can be obtained by using one or more metal salts. 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 the copolymer of vinyl monomers, any of the monomers (1) to (10) described above is a binary or higher number, and preferably the carboxyl group content in the shell layer (P) is 0.00. Examples include polymers copolymerized at an arbitrary ratio so as to be 1 to 10%. For example, 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- Examples thereof include divinylbenzene copolymers, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymers, and salts of these copolymers.

  When the resin particles (A) are produced by the production method (1) or (2) and the resin (a) forms the resin particles (A) in the aqueous dispersion (X1), at least under the conditions for forming (X1). It must be not completely dissolved in water. Therefore, when the vinyl resin is a copolymer, the ratio between the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10% or more. It is preferable that it is 30% or more. When the ratio of the hydrophobic monomer is 10% or less, the vinyl resin becomes water-soluble, and the particle size uniformity of the resin particles (C) and the resin particles (D) obtained therefrom is impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (g) and a polyol (h) having 3 to 8 or more valences, and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (i) and 3 to 6 or more valences. Examples thereof include the above polycarboxylic acids (j) and acid anhydrides or lower alkyl esters thereof.
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.

  As the diol (g), an alkylene glycol 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.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Alkylene oxide (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (Addition mole number 1-120); AO (EO, PO, BO, etc.) addition product (addition mole number 2-30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); polylactone diol (polyε- Caprolactone diol, etc.); and polybutadiene diol.

As the diol (g), in addition to the diol having no functional group other than the above hydroxyl group, a diol (g1) having another functional group may be used. Examples of (g1) 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 [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid and 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include 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 tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine, lauryldimethylamine, etc.) and / or alkali metals (sodium salt, etc.).
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 (h) 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 adduct (addition mole number 2-30) of trisphenols (trisphenol PA, etc.); AO adduct (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxy Ethyl (meth) acrylate and other Copolymer of alkenyl monomers, etc.]; and the like.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (i) 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 acid (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 trivalent to hexavalent or higher polycarboxylic acid (j) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid (i) or 3-6 or more polycarboxylic acid (j), the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

When a polyester resin containing a structural unit of an organic acid metal salt (m) is used as (a), this resin is, for example, a polyester having a residue of COOH (acid value is preferably 1 to 100, more preferably 5 ˜50) and at least one part of the COOH group is obtained as a salt of at least one metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr.
As a method for forming a metal salt, for example, it can be obtained by reacting a polyester having a COOH group with a hydroxide of the corresponding metal.

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (14), polyepoxide (14) and active hydrogen-containing compound (T) {water, polyol [the diol (g) and trivalent or higher polyol (h)], dicarboxylic acid (I) a polyaddition product of a trivalent or higher polycarboxylic acid (j), polyamine (12), polythiol (13) or the like}, or a polyepoxide (14) and a dicarboxylic acid (i) or a trivalent or higher polycarboxylic acid. Examples thereof include cured products of acid (j) with acid anhydrides.

  The polyepoxide (14) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (14). The epoxy equivalent of the polyepoxide (14) (molecular weight per epoxy group) is usually 65 to 1000, 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 (14) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

Examples of polyamine (12) 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 polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines 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 (13) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  In the production method (1) for the resin particles of the present invention, the aqueous dispersion (W) of the resin particles (A) made of the resin (a) and the resin (b1) and / or the resin (b2) (b2) ) Or its solvent solution (O), and (O) is dispersed in (W) to form resin particles (B) made of (b), and the surface of the resin particles (B) By adsorbing the resin particles (A) to the resin particles (C), the resin particles (C) are prevented from being united with each other, and (C) is not easily split under high shear conditions. Thereby, the particle diameter of (C) is converged to a constant value, and the effect of improving the uniformity of the particle diameter of (C) and the resin particles (D) obtained therefrom is exhibited. Therefore, the resin particles (A) have such a strength that they are not destroyed by shearing at the temperature at the time of dispersion, are hardly dissolved in water, and are not easily dissolved in (b) or the solvent solution (O) thereof. It is mentioned as a preferable characteristic.

  When the resin particles (D) of the present invention are obtained by the production method (1), the sp value of the resin particles (A) with respect to the resin particles (B) (the method of calculating the sp value in the present invention is Polymer Engineering and Science, February. 1974, Vol. 14, No. 2 P. 147 to 154), and by controlling the molecular weight of the resin (a), the particle surfaces of the resin particles (C) and the resin particles (D) obtained therefrom are made smooth. can do.

The sp value difference (Δsp) between the resin (a) and the resin (b) used for the resin particles of the present invention 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. Preferably it is done. [Especially, when the resin particles of the present invention are obtained by the production method (1)] (a) and (b) may be selected from known resins, but when adjusting the Mw of (a), The method described later can be mentioned.
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 the quadrangle A ″ B ″ C ″ D ″ composed of the 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 and are difficult to be melted by heat, and the smoothness of the resin particles (D) becomes insufficient. 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. In addition, when the point (K, H) is on the right side 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.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (a) are measured under the following conditions by using gel permeation chromatography (GPC) per tetrahydrofuran (THF) soluble content. .
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: TOSOH standard polystyrene (TSK standard POLYSTYRENE) 12 points (Mw 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
In addition, the molecular weight which shows the maximum peak height on the obtained chromatogram is called peak top molecular weight.

  In the case of the production method (1), from the viewpoint of reducing dissolution of the resin particles (A) in water or a solvent used for dispersion, the molecular weight, sp value, crystallinity, and molecular weight between crosslinking points of the resin (a). Etc. are preferably adjusted as appropriate.

  The number average molecular weight of the resin (a) (measured by GPC, hereinafter sometimes abbreviated as Mn) is usually from 10 to 5 million, preferably from 2 to 5 million, more preferably from 500 to 500,000, 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 (D), 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.

The glass transition temperature (Tg) of the resin (a) is usually 20 ° C. to 250 ° C., preferably from the viewpoint of the particle size uniformity of the resin particles (D), powder fluidity, heat resistance during storage, and stress resistance. Is 30 ° C to 230 ° C, more preferably 40 ° C to 200 ° C, particularly preferably 50 ° C to 100 ° C. If the Tg is lower than the temperature at which the aqueous resin dispersion (X1) is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of particle size is reduced.
Further, the Tg of the shell layer (P) comprising (a) and (m) if necessary is preferably 20 to 200 ° C., more preferably 30 to 100 ° C., particularly preferably 40 to 80 ° 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).
Above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

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 usually 40 ° C. to 270 ° C., preferably 50 ° C. to 250 ° C., more preferably from the viewpoint of heat resistance during storage, stress resistance, and fixing properties to the paper surface. Is from 60 ° C to 220 ° C, particularly preferably from 70 ° C to 160 ° C, and the outflow temperature (T1 / 2) is usually from 60 ° C to 300 ° C, preferably from 65 ° C to 280 ° C, more preferably from 70 ° C to 250 ° C. Particularly preferably, the temperature is 80 ° C to 180 ° C. 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 a flow tester measurement or the like.

  The temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2) of the resin (a) is usually 0 ° C. to 120 ° C., preferably 0 ° C. to 100 ° C., more preferably 0 ° C. to 90 ° C., particularly preferably. Is 0 ° C to 80 ° C. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

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

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

  In the Shore D hardness which is a standard of hardness, the hardness of the shell layer (P) is usually 30 or more, particularly preferably in the range of 45 to 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 case of producing by the production method (1), in the aqueous dispersion (W) of the resin particles (A), a solvent miscible with water (acetone, methyl ethyl ketone, etc.) is contained in the solvent (u) described later in addition to water. May be. At this time, 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 (C). Even if it is a seed | species and what kind of content may be sufficient, what is not left in the resin particle (D) after drying using 40% or less of the total amount with water is preferable.

When manufacturing by the said manufacturing method (1) or (2), the method to make resin (a) the aqueous dispersion of resin particle (A) is not specifically limited, The following [1]-[8] are mentioned. It is done.
[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. [5] A resin solution 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. After obtaining resin particles by spraying in the form of a mist, the resin particles are dispersed in water in the presence of a suitable dispersant [6] polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, Condensation polymerization, etc. The polymer reaction mode may be added to a resin solution prepared by dissolving a resin prepared in a solvent, or a resin solution preliminarily heated and dissolved in a solvent is allowed to precipitate, and then resin particles are precipitated. , Removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant [7] polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation) A resin solution prepared by dissolving a resin prepared in any polymerization reaction mode such as 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. Method [8] A 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 Method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier

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

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

As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
Examples of the quaternary ammonium salt type surfactant include tertiary amines having 3 to 40 carbon atoms and quaternizing agents (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 the amine salt type surfactant, a primary to tertiary amine is selected from 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 (2 to 6 carbon atoms) and the like can be mentioned.

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, etc.) inorganic or organic acid salts and triethanolamine monostearate, stearamide ethyl diethyl Such as tertiary mineral or organic acid salts of amines such as chill ethanolamine.

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

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

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

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

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

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

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

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

Examples of AO include EO, PO, and BO.
Of these, EO and random or block adducts of EO and PO are preferred.
The number of moles of AO added is preferably 10 to 50 moles, and 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 monolaurate, sorbitan dilaurate, sorbitan dioleate, and sucrose monostearate. Can be mentioned.

  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 dispersion, or may be added to the emulsified dispersion [in the oil phase containing the resin (b)].
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 necessary during emulsification dispersion, or may be added to the emulsified dispersion [in the oil phase containing the resin (b)].
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.

  In the present invention, the particle diameter of the resin particles (A) used in the production method (1) is usually smaller than the particle diameter of the resin particles (B) to be formed. The value of [volume average particle diameter of resin particles (A)] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the particle size distribution of (D) obtained tends to be wide.

The volume average particle diameter of the resin particles (A) can be appropriately adjusted within the above range of particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (D) having a desired particle diameter.
The volume average particle diameter of (A) is generally preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain a resin particle (D) having a volume average particle diameter of 1 μm, it is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles ( In the case of obtaining D), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm of particles (D) are preferably 0.05 to 30 μm, particularly preferably. 0.1 to 20 μm.
The volume average particle size is determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, 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 obtain, 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.

The polyester resin (b1) used in the present invention and the resin (b2) containing (b1) as a structural unit may be a polycondensation polyester resin in which (b1) is formed in the presence of a titanium-containing catalyst (e). For example, any known resin composition can be used, and for the specific example of (b1), the same composition as in (a) can be used. (B1) and (b2) can be appropriately selected depending on the application and purpose. The content of the polyester resin (b1) in (b) or (b1) as a structural unit is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more.
Examples of the polyester resin (b1) include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. As the polyol, the diol (g) and a polyol having 3 to 8 or more valences (h) are used. As the polycarboxylic acid or its acid anhydride or its lower alkyl ester, the dicarboxylic acid (i), 3 to 6 valences are used. Or more polycarboxylic acids (j) and acid anhydrides or lower alkyl esters thereof.
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.

  The polyester resin (b1) preferably contains the alkylene glycol having 2 to 36 carbon atoms (particularly 1,2-propylene glycol) as a structural unit from the viewpoint of thermal properties, and the amount used is diol (g). And 50% or more with respect to the total of the polyol (h), more preferably 60% or more, and particularly preferably 70% or more.

  The resin (b2) is not particularly limited as long as it contains the polyester resin (b1) as a structural unit, and examples thereof include a polyurethane resin containing (b1) as a structural unit.

As the polyurethane resin, polyisocyanate (11) and active hydrogen-containing compound (T) {water, polyol [diol (g) [including diol (g1) having a functional group other than hydroxyl group], and 3 to 8 valences or Further polyol (h)], polycarboxylic acid [dicarboxylic acid (i), and polycarboxylic acid (j) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, A ring-opening polymer of a lactone having 6 to 12 carbon atoms, a polyaddition product of a polyamine (12), a polythiol (13), and a combination thereof, and (11) and an active hydrogen-containing compound (T). A terminal isocyanate group prepolymer and an equivalent of primary and / or secondary monoamines relative to the isocyanate groups of the prepolymer. (15) and reacting the obtained, an amino group-containing polyurethane resins, polyurethane resins obtained by using as at least part of the active hydrogen-containing compound (T) (b1). The content of (b1) in (T) is preferably 40% or more, more preferably 70% or more, particularly preferably 90% or more, and most preferably 100%.
In addition, 0.1 to 10% of content of the carboxyl group in a polyurethane resin is preferable.

  As polyisocyanate (11), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (except for carbon in NCO group) Formula polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 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 a small amount (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 (12) and polythiol (13) include those described above.
Examples of the primary and / or secondary monoamine (15) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).
Examples of the diol (g), 3 to 8 or more polyol (h), dicarboxylic acid (i) and 3 to 6 or more polycarboxylic acid (j) include those described above.

In the present invention, from the viewpoint of charging characteristics of the resin particles (D), titanium halide (e1), titanium diketone enolate (e2), titanium carboxylate (e3), titanyl carboxylate (e4), titanyl carboxylate At least one selected from the group consisting of (e5), a titanium-containing compound (e6) represented by the following general formula (I) or (II), and a titanium-containing compound (e7) represented by the following general formula (III) A polycondensation polyester resin (b1) formed in the presence of a seed titanium-containing catalyst (e) is used. When only a polymerization catalyst other than (e), for example, zinc acetate, tetrabutoxy titanate, or dibutyltin oxide is used, the effect as in the present invention cannot be obtained.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR < ₁ >) q (II)
_{Ti (-Z) r (-OR 2} ) s (III)
[In the formulas (I) and (II), X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. In the case of a polyalkanolamine, other OH groups May be condensed in the molecule with an OH group directly bonded to the same Ti atom to form a ring structure, or may be repeatedly condensed between molecules with an OH group directly bonded to another Ti atom to form a repeating structure. It may be. The degree of polymerization in the case of forming a repeating structure is 2-5. R ₁ is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
[In the formula (III), R ₂ is H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. Z is a residue obtained by removing one carboxyl group H from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, other carboxyl groups are polycondensed in the molecule with an OR group in the same molecule. A structure may be formed, or a structure containing 2 to 5 Ti atoms may be formed by polycondensation between an OR group of another molecule and the molecule. r = 1 to 3 and s = 1 to 3, and the sum of r and s is 4. ]

  The amount of (e) used is not particularly limited, but the lower limit is preferably 0.01%, more preferably 0.02%, based on the total weight of the polyol and polycarboxylic acid used to obtain the polyester resin. 0.03% is particularly preferred and 0.05% is most preferred. The upper limit is preferably 5%, more preferably 2%, particularly preferably 1.5%, and most preferably 0.8%. When it is 0.01% or more, the effect as a polycondensation catalyst is sufficiently obtained, and when it is 5% or less, high catalytic action is obtained according to the amount of catalyst. In addition, when the amount is within the above catalyst amount, the necessary properties of the toner when the obtained polyester resin is used as a toner binder, particularly, the image quality of the photoreceptor under low temperature and low humidity conditions are improved.

  Of (e), titanium halide (e1) is not particularly limited, and examples thereof include dichlorotitanium, trichlorotitanium, tetrachlorotitanium, trifluorotitanium, tetrafluorotitanium, and tetrabromotitanium.

  The titanium diketone enolate (e2) is not particularly limited, and examples thereof include titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, and titanyl acetylacetonate. Of these (e2), titanium acetylacetonate is preferred.

Although it does not specifically limit as carboxylate titanium (e3), For example, C1-C32 aliphatic carboxylate titanium (e3-1), C7-C38 aromatic carboxylate titanium (e3-2), etc. are mentioned. Can be mentioned. In the case of titanium polycarboxylate having a valence of 2 or more, the number of carboxyl groups coordinated to titanium may be one or more, and a free carboxyl group may exist without being coordinated to titanium.
Although it does not specifically limit as (e3-1), For example, aliphatic monocarboxylic acid titanium (e3-1a), aliphatic dicarboxylic acid titanium (e3-1b), aliphatic tricarboxylic acid titanium (e3-1c), and 4- Examples thereof include octavalent or higher aliphatic polycarboxylic acid titanium (e3-1d).
Although it does not specifically limit as (e3-1a), For example, titanium formate, titanium acetate, titanium propionate, titanium octoate, etc. are mentioned. (E3-1b) is not particularly limited, and examples thereof include titanium oxalate, titanium succinate, titanium maleate, titanium adipate, and titanium sebacate. Although it does not specifically limit as (e3-1c), For example, hexane tricarboxylic acid titanium, isooctane tricarboxylic acid titanium, etc. are mentioned. Although it does not specifically limit as (e3-1d), For example, octane tetracarboxylic acid titanium, decane tetracarboxylic acid titanium, etc. are mentioned.
Although it does not specifically limit as (e3-2), For example, aromatic monocarboxylic acid titanium (e3-2a), aromatic dicarboxylic acid titanium (e3-2b), aromatic tricarboxylic acid titanium (e3-2c), and 4- Examples include octavalent or higher aromatic titanium polycarboxylate (e3-2d).
Although it does not specifically limit as (e3-2a), For example, a titanium benzoate etc. are mentioned. (E3-2b) is not particularly limited. For example, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalenedicarboxylate, titanium 4,4-biphenyldicarboxylate, 2,5-toluenedicarboxylic acid Examples thereof include titanium oxide and titanium anthracene dicarboxylate. Although it does not specifically limit as (e3-2c), For example, trimellitic acid titanium, 2,4,6- naphthalene tricarboxylic acid titanium, etc. are mentioned. Although it does not specifically limit as (e3-2d), For example, pyromellitic acid titanium, 2,3,4,6- naphthalene tetracarboxylic acid titanium, etc. are mentioned.
Among these (e3), (e3-2) is preferable, and (e3-2b) is more preferable.

Although it does not specifically limit as carboxylate titanyl (e4), For example, C1-C32 aliphatic carboxylate titanyl (e4-1), C7-38 aromatic carboxylate titanyl (e4-2), etc. Can be mentioned. In the case of divalent or higher polycarboxylic acid titanyl, the number of carboxyl groups coordinated to titanium may be one or more, and a free carboxyl group may exist without being coordinated to titanium.
Although it does not specifically limit as (e4-1), For example, aliphatic monocarboxylic acid titanyl (e4-1a), aliphatic dicarboxylic acid titanyl (e4-1b), aliphatic tricarboxylic acid titanyl (e4-1c), and 4- And octavalent or higher aliphatic polycarboxylic acid titanyl (e4-1d).
Although it does not specifically limit as (e4-1a), For example, titanyl formate, titanyl acetate, titanyl propionate, titanyl octoate, etc. are mentioned. Although it does not specifically limit as (e4-1b), For example, titanyl oxalate, titanyl succinate, titanyl maleate, titanyl adipate, titanyl sebacate, etc. are mentioned. Although it does not specifically limit as (e4-1c), For example, hexane tricarboxylic acid titanyl, isooctane tricarboxylic acid titanyl, etc. are mentioned. Although it does not specifically limit as (e4-1d), For example, octane tetracarboxylic acid titanyl, decane tetracarboxylic acid titanyl, etc. are mentioned.
Although it does not specifically limit as (e4-2), For example, aromatic monocarboxylic acid titanyl (e4-2a), aromatic dicarboxylic acid titanyl (e4-2b), aromatic tricarboxylic acid titanyl (e4-2c), and 4- Examples include octavalent or higher titanyl aromatic polycarboxylic acid (e4-2d).
(E4-2a) is not particularly limited, and examples thereof include titanyl benzoate. Although not particularly limited as (e4-2b), for example, titanyl phthalate, titanyl terephthalate, titanyl isophthalate, titanyl 1,3-naphthalenedicarboxylate, titanyl 4,4-biphenyldicarboxylate, 2,5-toluenedicarboxylic acid Examples thereof include titanyl acid and titanyl anthracene dicarboxylate. Although it does not specifically limit as (e4-2c), For example, a trimellitic acid titanyl, 2,4,6- naphthalene tricarboxylic acid titanyl etc. are mentioned. Although it does not specifically limit as (e4-2d), For example, pyromellitic acid titanyl, 2,3,4,6-naphthalene tetracarboxylic acid titanyl etc. are mentioned.

  Although it does not specifically limit as carboxylic acid titanyl salt (e5), For example, (e4-1b), (e4-1c), (e4-1d), (e4-2b), (e4-2c), or (e4- 2d) alkali metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, barium, etc.) salts [(e5-1b), (e5-1c), (e5 -1d), (e5-2b), (e5-2c), and (e5-2d)]. Among these (e5), titanyl maleate and titanyl oxalate are preferable.

In the catalyst (e6) represented by the general formula (I) or (II), X is a residue obtained by removing the H atom of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, The number of nitrogen atoms, that is, the total number of primary, secondary, and tertiary amino groups is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).
In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. A ring structure may be formed by polycondensation with a directly bonded OH group in the molecule, or a repeating structure may be formed by polycondensation between molecules with an OH group directly bonded to another Ti atom. The degree of polymerization in the case of forming a repeating structure is 2-5. When the degree of polymerization is 6 or more, the catalytic activity is lowered, so that the oligomer component is increased, which causes deterioration of the blocking property of the resin particles.
Preferred as X are residues of monoalkanolamine (especially ethanolamine), dialkanolamine (especially diethanolamine) and trialkanolamine (especially triethanolamine), particularly preferred are those of triethanolamine Residue.
R ₁ is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, and Examples include β-ethoxyethyl group. Of these R _{1 s} , H and an alkyl group having 1 to 4 carbon atoms not containing an ether bond are preferable, and H, an ethyl group, and an isopropyl group are more preferable.

In formula (I), m is an integer of 1-4, Preferably it is an integer of 2-4. n is an integer of 0 to 3, preferably an integer of 0 to 2. The sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably the same.

Specific examples of the titanium-containing catalyst (e6) represented by the general formula (I) include titanium tetrakis (monoethanolamate), titanium monohydroxytris (triethanolamate), and titanium dihydroxybis (triethanol). Aminate), titanium trihydroxytriethanolamate, titanium dihydroxybis (diethanolamate), titanium dihydroxybis (monoethanolamate), titanium dihydroxybis (monopropanolamate), titanium dihydroxybis (N-methyldiethanolamate) , Titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium and N, N, N ′, N′-tetrahydroxyethylethylenediamine Reaction products, and polycondensates between within or molecules of these molecules.
Examples of the intramolecular or intermolecular polycondensate include compounds represented by the following general formula (I-1), (I-2), or (I-3).

[Wherein, Q ₁ and Q ₆ are H, or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Q _{2 to} Q ₅ and Q _{7 to} Q ₉ are alkylene groups having 1 to 6 carbon atoms. X is a residue obtained by removing one OH group H from a mono- or polyalkanolamine having 2 to 12 carbon atoms. ]

  Specific examples of those represented by the general formula (II) include titanyl bis (triethanolaminate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanylhydroxytriethanolamate, Examples include titanyl ethoxytriethanolamate, titanyl isopropoxytriethanolamate, and intramolecular or intermolecular polycondensates thereof. Such as a polycondensate. Examples of the intramolecular or intermolecular polycondensate include compounds represented by the following general formula (II-1) or (II-2).

[Wherein, Q ₁ and Q ₆ are H, or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Q < ₂ > -Q < ₅ > is a C1-C6 alkylene group. ]

  Among these (e6), preferred are titanium dihydroxybis (triethanolamate), titanium dihydroxybis (diethanolamate), titanium monohydroxytris (triethanolamate), titanium tetrakis (ethanolamate), and titanylhydroxy. Intramolecular polycondensate [below (e61)] or intermolecular polycondensate [below (e63)], titanium monohydroxy of triethanolaminate, titanyl bis (triethanolaminate), titanium dihydroxybis (triethanolaminate) Intramolecular polycondensate of tris (triethanolaminate) (below (e62)), and combinations thereof, more preferably titanium dihydroxybis (triethanolaminate), titanium Um monohydroxy tris (triethanolaminate), in their molecular polycondensates [(e61) and (e62)], in particular (e61).

  These titanium-containing catalysts (e6) can be stably obtained by reacting, for example, commercially available titanium dialkoxybis (alcohol aminate; manufactured by Dupont, etc.) at 70 to 90 ° C. in the presence of water. it can. The polycondensate can be obtained by further distilling off the condensed water at 100 ° C. under reduced pressure.

In the catalyst (e7) represented by the general formula (III), R ₂ is H, or C 1-24 which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. It is a hydrocarbon group. Carbon number of a hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-4.
Specific examples of the hydrocarbon group having 1 to 24 carbon atoms include an aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing an ether bond and / or a hydroxyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, β-ethoxyethyl group, β-hydroxyethyl group, etc.), aromatic hydrocarbon group, and an aromatic group containing an ether bond and / or a hydroxyl group. Group hydrocarbon group [phenyl group; hydroxyphenyl group; EO, PO, and BO having 2 to 4 carbon atoms such as bisphenol A, bisphenol F, and bisphenol S] Residues excluding OH, etc.].
Among these R ₂ , a hydrocarbon group having 1 to 6 carbon atoms is preferable, and an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-hexyl group are particularly preferable. Are an n-propyl group, an isopropyl group, and an n-butyl group.

Z is a residue obtained by removing H of one carboxyl group from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, another carboxyl group is the same as that bonded to a Ti atom to form a residue. OR ₂ group in the molecule {hydroxyl group bonded directly to Ti atom (when R ₂ is H), alkoxy group (when R ₂ is hydrocarbon group), or hydrocarbon containing R ₂ having 1 to 2 hydroxyl groups The hydroxyl group in the case of a group may be polycondensed in the molecule to form a ring structure, and may be polycondensed between an OR ₂ group (similar to the above) of another molecule of the titanium-containing catalyst (a) between the molecules. A repeating structure containing a plurality of Ti atoms may be formed.
The aromatic carboxylic acid preferably has 7 to 50 carbon atoms, and includes benzoic acids (benzoic acid, parahydroxybenzoic acid, paramethylbenzoic acid, etc.), aromatic monocarboxylic acids such as naphthalene monocarboxylic acid; phthalic acids ( Terephthalic acid, isophthalic acid, orthophthalic acid, etc.), naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid, and the like.
In the case of an aromatic polycarboxylic acid, a repeating structure containing a plurality of Ti atoms may be formed by the plurality of carboxyl groups as described above. In this case, the number of Ti atoms in one molecule is 2 to 5 It is. When the number of Ti atoms in one molecule is 6 or more, the catalytic activity is lowered, which is not preferable.
Preferred as Z are residues of phthalic acids (terephthalic acid, isophthalic acid, orthophthalic acid, etc.), and residues of benzoic acids (benzoic acid, parahydroxybenzoic acid, paramethylbenzoic acid, etc.), and particularly preferred are Residues of terephthalic acid, isophthalic acid, and orthophthalic acid.

  In the formula (III), r = 1 to 3 and s = 1 to 3, and the sum of r and s, that is, the valence number of Ti atom is 4. Preferably, r = 1 to 2 and s = 2 to 3. When r exceeds 3, the catalytic activity decreases, and when s exceeds 3, the hydrolysis resistance decreases, both of which are unfavorable for polyester production. When r is 1 or 2, the catalyst activity is particularly high and preferable. When the valence number of Ti atom is other than 4, it is not preferable even if the structure is similar to the formula (III), the catalytic activity is inferior or the side reaction occurs.

  Specific examples of the compound represented by the general formula (III) include titanium triisopropoxybenzene carboxylate, titanium tributoxybenzene carboxylate, titanium triisopropoxyterephthalate, titanium tributoxyterephthalate, titanium triisopropoxyisophthalate, titanium. Triisopropoxyphthalate, titanium diisopropoxydibenzenecarboxylate, titanium dibutoxydibenzenecarboxylate, titanium diisopropoxy diterephthalate, titanium dibutoxy diterephthalate, titanium diisopropoxy diisophthalate, titanium diisopropoxy diphthalate, Titanium dihydroxydibenzenecarboxylate, titanium dihydroxyditerephthalate, titanium dihydroxydiisophthalate, titanium dihi Loki Siji phthalate, and the like These intramolecular or intermolecular polycondensates.

  The titanium-containing catalyst (e7) used in the present invention preferably has a solubility in water at 30 ° C. of [5 g / 100 ml] or less, and [2 g / 100 ml] or less, from the viewpoint of catalytic activity during polyester polymerization. Is more preferable, and [1 g / 100 ml] or less is particularly preferable. When the solubility is [5 g / 100 ml] or less, the catalyst is hardly subjected to hydrolysis during the polymerization reaction, which is preferable from the viewpoint of sustainability of the catalyst activity.

  These titanium-containing catalysts (e7) can be obtained, for example, by reacting a commercially available titanium tetraalkoxide and an aromatic carboxylic acid in ethyl acetate at 70 to 90 ° C.

  Among these (e), preferably titanium diketone enolate (e2), titanium carboxylate (e3), titanyl carboxylate (e5), titanium-containing compound represented by general formula (I) or (II) (E6) and a titanium-containing compound (e7) represented by the general formula (III), more preferably a titanium carboxylate (e3) and a titanium-containing compound (e7).

As the resin (b) of the present invention, any known resin other than (b1) and / or (b2) can be used as long as the effects of the present invention are not impaired. Specific examples thereof include resins having the same composition as the above (a) and resins having the same composition as the above polyurethane resin and other than (b1) and (b2). (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, and a combination thereof, more preferably a polyurethane resin and a polyester resin, and particularly preferably 1,2- Polyurethane resins and polyester resins containing propylene glycol as a structural unit.
The content of other resins (particularly vinyl resins) in (b) is preferably 30% or less, more preferably 20% or less, particularly preferably 10% or less, most preferably from the viewpoint of resin physical properties. 0%.

The sp value of the resin (b) is preferably such that the difference in sp value from the resin (a) is within the above range, but is preferably 7 to 18, more preferably 8 to 14, and particularly preferably 9 to 14. .
Further, the Mn, melting point, and Tg of the resin (b) may be appropriately adjusted within a preferable range depending on the application.
For example, when the resin particles (D) are used as a slush molding resin or a powder coating, the Mn of (b) is usually 2,000 to 500,000, preferably 4,000 to 200,000. The melting point (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, Mn in (b) is usually 20,000 to 10,000,000, preferably 40,000 to 2,000,000. The melting point 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 for 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 of (b) is usually 20 ° C to 300 ° C, preferably 80 ° C to 250 ° C. Tb of (b) is usually 20 ° C to 200 ° C, preferably 40 ° C to 150 ° C.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight when a polyurethane resin is used as (b) are measured under the following conditions. In the case of a resin other than a polyurethane resin, the measurement conditions for the resin (a) may be the same.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α
TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Injection volume: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: TOSOH standard polystyrene (TSK standard POLYSTYRENE) 12 points (Mw 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
Standard reagent: Stylon (Asahi Kasei)

In the present 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 the shell resin (a) may be peeled off from the core resin (b) even if it is formed once. 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 resin particles (B) in the production method (1)] are used, the adsorptive power As a result, the core-shell mold can be easily formed, and the shell resin (a) is not peeled off from the core resin (b).
[3]: When producing the aqueous resin dispersion (X1) or the coating agent (W ′) that is an aqueous liquid, the resin (a) has an acidic functional group such as a carboxyl group, a phosphate group, or a sulfonate group. In the case of a resin (generally, 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 resin dispersion (X1) 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. In the case of a resin having a basic functional group such as an ammonium base (generally, the molecular weight per basic functional group is preferably 1,000 or less), the adsorptive power increases as the pH of the aqueous medium increases. . 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 becomes stronger. 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 (D) are formed in an aqueous medium in the production method, the resin particles (D) 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 freeze drying)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

The shape of the resin particle (D) of the present invention can be controlled by the following method according to the production method.
(1) In the case of production method (1) 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. The weight average molecular weight (measured by GPC) of the resin particles (A) is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, still more preferably 2,000 to 200,000, and particularly preferably 3,000 to 100,000. .

(1) In the case of the production method (2) and the production method (3) In either production method, the shape of the resin particles (B) prepared in advance is greatly affected, and the resin particles (D) It becomes almost the same shape. However, when (B) is distorted, if more coating agent (W ′) is used in the production method (2), it becomes spherical. Further, in the manufacturing method (3), when heat treatment higher than the Tg of (B) is performed, (D) becomes spherical.

From the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (D), 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

  When the resin particles (D) are obtained by the production method (1), an aqueous dispersion (W) of the resin particles (A) made of the resin (a) and a resin made of the resins (b1) and / or (b2) (B) or its solvent solution (O) is mixed, (O) is dispersed in (W), and the resin particles (A) adhere to the surface of the resin particles (B) made of the resin (b). An aqueous dispersion (X2) of resin particles (D) having a structure having a coating formed from (A) on the surface of (B) is formed from the aqueous dispersion (X1) of resin particles (C) having the structure Thereafter, the aqueous medium is removed from the aqueous resin dispersion (X2). The above-mentioned method is mentioned as a method of removing an aqueous medium.

When the resin particles (D) of the present invention are produced by the production method (1), when the resin (b) composed of the resin (b1) and / or (b2) or the solvent solution (O) thereof is dispersed, A dispersing device can be used.
The dispersing apparatus is not particularly limited as long as it is generally marketed as an emulsifier or a dispersing machine. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (specialized chemical industry) Batch emulsifiers such as Ebara Milder (Ebara Seisakusho Co., Ltd.), TK Fillmix, TK Pipeline Homo Mixer (Special Mechanics Kogyo Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.), Thrasher, Continuous emulsifiers such as Trigonal wet milling machine (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer ( Nanomizer), APV Gaurin (Gaurin) and other high-pressure emulsifiers, Membrane emulsifier (Chilling Industries) and other membrane emulsification , 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 manufacturing by the said manufacturing method (1), when mixing and disperse | distributing resin (b) which consists of resin (b1) and / or (b2) with the aqueous dispersion (W) of the resin particle (A), resin (b) 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 is usually 10 to 50,000 mPa · s (measured with a B-type viscometer), preferably 100 to 10,000 mPa · s from the viewpoint of particle size uniformity.
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) is not particularly limited as long as it is a solvent that can dissolve the resin (b1) and / or (b2) at room temperature or under heating. Specifically, the solvent (u) The same thing is illustrated. The preferred one varies depending on the types of the resins (b1) and (b2), but it is preferred that the difference in sp value from (b1) and / or (b2) is 3 or less. Further, from the viewpoint of the particle size uniformity of the resin particles (D), a solvent that dissolves the resin (b) but hardly dissolves the resin particles (A) made of the resin (a) is preferable.

  Moreover, in the said manufacturing method (1), the usage-amount of the aqueous dispersion (W) with respect to 100 parts of resin (b) which consists of resin (b1) and / or (b2), Preferably it is 50-2,000 weight part, More preferably, it is 100-1,000 weight part. 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, when the resin particles (D) are obtained by the production method (1), the resins (a) and (b) in which the above points (K, H) are included in a specific range, or the softening start By using a resin (a) having physical properties such as temperature (Ts), glass transition temperature (Tg), and flow-out temperature (T1 / 2), for example, a solvent solution of (b) (especially the following preferred solvent) is used. When used, the solvent is preferably used in the aqueous resin dispersion (X1) in an amount of 10 to 50% (especially 20 to 40%) and removed at 40 ° C. or less, preferably 1% or less (especially 0.5% or less). The aqueous resin dispersion (X2) of the resin particles (D) in which the resin particles (A) are dissolved in a solvent to form a film and the film of (A) is formed on the surface of (B) is obtained simply by solvent. Often obtained. However, even when the film of (A) is not formed, or even when the film from at least a part of (A) is formed, the smoothness of the film on the surface of the resin particles (D) 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. An aqueous resin dispersion (X2) of resin particles (D) having the following formula is obtained, and (D) obtained therefrom is preferable from the viewpoint of excellent storage stability.
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.

The solvent used when the resin particles (A) are dissolved to form a film may be added to (X1) when forming the film, but as a raw material for obtaining (X1), a resin (b ), And using the solvent without removing it immediately after the formation of the resin particles (B), it is easier to dissolve (A) because the solvent is contained in (B). Yes, 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, and more preferably ethyl acetate from the viewpoint of film formation.
The solvent concentration in the aqueous resin dispersion (X1) when (A) is dissolved in the solvent is preferably 3 to 60%, more preferably 10 to 45%, and particularly preferably 15 to 30%. Moreover, melt | dissolution is performed by stirring aqueous resin dispersion (X1) for 1 to 10 hours, for example, and the temperature at the time of melt | dissolution is 15-45 degreeC, and 15-30 degreeC is more preferable.

When (A) is melted to form a film on the surface of (B), the solid content [content of components other than water and solvent] in the aqueous resin dispersion (X1) is preferably 1 to 50%, Preferably, it is adjusted to 5 to 30%. Further, 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. The method of heating at 1 degreeC for 1 to 300 minutes is mentioned preferably.
In addition, as a film-forming treatment method, the aqueous dispersion (X1) of resin particles (C) having a solvent content of 2% or less is heat-treated, and (A) is melted on the core (Q) so that the surface becomes A preferable heat treatment temperature for obtaining the smooth resin particles (D) is not less than the Tg of (A) and a temperature range of not more than 80 ° C. is preferable. The surface smoothness of the resin particles (D) obtained when the heat treatment temperature is lower than the Tg of (A) hardly changes. Moreover, when heat-processing at the temperature exceeding 80 degreeC, a shell (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).

When the resin particles (D) of the present invention are produced by the production method (1), the resin particles (C) as an intermediate are substantially larger than the relatively small resin particles (A) and the relatively large resin. It is composed of particles (B), and (A) is present attached to the surface of (B). The resin particles (D) are obtained by dissolving and / or melting (A) after adhering to (B), and forming a coating from (A) 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 reduce the difference in the sp value in the range as small as possible within the above range (for example, 2 or less).

From the viewpoint of particle size uniformity, the coefficient of variation in volume distribution of the resin particles (D) 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 (D) is preferably 1.0 to 1.4 in terms of particle size uniformity, and is 1.0 to 1.2. More preferably.
The volume average particle diameter of (D) varies depending on the application, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

When the resin particles (D) of the present invention are produced by the production method (1), the particle diameters of the resin particles (A) and the resin particles (B), and the resin particles in the aqueous resin dispersion (X1) ( Covering rate of resin particle (B) surface by A) [or covering rate of core layer (Q) surface by shell layer (P)], on resin particle (B) / aqueous medium interface in aqueous resin dispersion (X1) By changing the depth at which the resin particles (A) are embedded on the resin particle (B) side, the particle surface can be smoothed or desired irregularities can be imparted to the particle surface.
When it is desired to improve the powder fluidity, the BET specific surface area of (D) is preferably 0.5 to 5.0 m ² / g. 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 (D) 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 (D) is preferably spherical from the viewpoint of powder fluidity, melt leveling properties and the like. In that case, it is preferable that the particles (A) and the particles (B) are also spherical. (D) preferably has an average circularity of 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) to a dispersion concentration of 3,000 to 10,000 / μL. To measure the shape and distribution of the resin particles.

When the resin particles (D) of the present invention are produced by the production method (1), the resin particles (B) by the resin particles (A) in the resin particles (C) that are intermediates in the aqueous resin dispersion (X1). The surface coverage and the depth at which the resin particles (A) are embedded on the resin particle (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 tends to decrease and the depth decreases. In this case, in general, the use of 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)] increases the coverage. 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]: Coverage and depth increase as the difference in sp value between resin (a) and resin (b) decreases.

Additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers) in the shell layer (P) and / or the core layer (Q) constituting the resin particles (D) , Antioxidants, antiblocking agents, heat stabilizers, flame retardants, etc.) may be mixed. As a method for adding an additive in (P) or (Q), in the case of the production method (1), the aqueous resin dispersion (X1) may be mixed in an aqueous medium. More preferably, the resin (a) or the resin (b) and the additive are mixed in advance, and then the mixture is added and dispersed in the aqueous medium.
Further, 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 comprising the organic acid salt (m) is contained in the shell layer (P) 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 the present invention, when the core layer (Q) contains, as the additive, the resin (b), the wax (c), and the modified wax (d) grafted with a vinyl polymer chain, the heat-resistant storage stability Is more preferable.
The content of (c) in (Q) is preferably 20% or less, more preferably 1 to 15%. The content of (d) is preferably 10% or less, more preferably 0.5 to 8%. The total content of (c) and (d) is preferably 25% or less, more preferably 1 to 20%.

The wax (c) is preliminarily dispersed in the resin (b1) or (b2) after being melt-kneaded with the modified wax (d) in the absence of a solvent and / or heated, 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 a mixture thereof. Among these, paraffin wax (c1) is particularly preferable. Examples of (c1) include petroleum waxes having a melting point of 50 to 90 ° C. and a main component of a linear saturated hydrocarbon having 20 to 36 carbon atoms.
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 core layer (Q), and the control of the dispersion state is facilitated.

  The modified wax (d) is obtained by grafting a vinyl polymer chain onto the wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same. Examples of the vinyl monomer constituting the vinyl polymer chain of (d) include the same monomers as the monomers (1) to (10) constituting the vinyl resin. Among these, (1) 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 (D).
Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the mechanical strength of the resin particles (D) is good.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in a solvent (for example, toluene or xylene) and heating to 100 to 200 ° C., and then converting the vinyl monomer to a peroxide initiator (benzoyl peroxide, diter It can be obtained by dropping 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.
Examples of the oil-soluble peroxide polymerization initiator include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, and t-butyl peroxide. Oxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobuty T-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t- Butyl peroxyacetate, t-butyl peroxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumylper Oxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5- Hydroperoxide and cumene peroxide.

  Examples of the water-soluble peroxide polymerization initiator include hydrogen peroxide, peracetic acid, ammonium persulfate, potassium persulfate, and sodium persulfate.

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 include a method of 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. A mixed solution of 3 parts by Kasei Kogyo) and 62 parts of benzoyl peroxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 335 parts of ionic water under 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 0.1 μm. A portion of [fine particle dispersion W1] was dried to isolate the resin component. Tg by DSC measurement of the resin content was 80 ° C., the softening start temperature was 105 ° C., and the outflow temperature was 160 ° C.

Production Example 2 (Production of aqueous dispersion of resin particles A)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 377 parts of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 350 parts of dimethyl terephthalate, 40 parts of adipic acid, 3- ( 2,3-dihydroxypropoxy) -1-propanesulfonic acid (32 parts) and tetrabutoxy titanate (0.3 parts) as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the methanol produced. It was. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction was performed under reduced pressure of 5 to 20 mmHg, and the reaction product was taken out. The resin taken out was cooled to room temperature and then pulverized to form particles. Next, 30 parts of acetone was added to 30 parts of this resin to dissolve, and 2.5 parts of triethylamine was further added. By adding 270 parts of water to this well-stirred solution, an aqueous polyester resin dispersion [fine particle dispersion W2] was obtained. The volume average particle diameter of [fine particle dispersion W2] measured by ELS-800 was 0.05 μm. A part of [fine particle dispersion W2] was dried to isolate the resin component, and the glass transition temperature was 60 ° C., the softening start temperature was 90 ° C., and the outflow temperature was 155 ° C. by flow tester measurement. It was.

Production Example 3 (Production of aqueous dispersion of resin particles A)
In a reaction vessel equipped with a stirrer and a thermometer, 753 parts of water, 8 parts of sodium salt of alkylallylsulfosuccinic acid (Eleminol JS-2, manufactured by Sanyo Chemical Industries), 58 parts of styrene, 58 parts of methacrylic acid, 77 butyl acrylate Parts, 1 part of ammonium persulfate, and 9 parts of a surfactant (polyoxysorbitan monooleate) were added and stirred at 300 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and then an aqueous dispersion of a vinyl resin (styrene-methacrylic acid-butyl acrylate-alkylallylsulfosuccinic acid sodium salt copolymer) [fine particles Dispersion liquid W3] was obtained. The volume average particle diameters of [fine particle dispersion W3] measured by LA-920 and ELS-800 were both 0.05 μm. A portion of [fine particle dispersion W3] was dried to isolate the resin component. Tg by DSC measurement of the resin was 60 ° C., the softening start temperature was 110 ° C., and the outflow temperature was 198 ° C.

Production Example 4 [Synthesis of Titanium-Containing Catalyst (e)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube capable of bubbling in liquid, 1617 parts of titanium diisopropoxybis (triethanolaminate) and 126 parts of ion-exchanged water are bubbled in liquid with nitrogen. Then, the temperature was gradually raised to 90 ° C., and reaction (hydrolysis) was performed at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolaminate). Furthermore, the intramolecular polycondensate (e-1) [the above formula (e61)] was obtained by reacting at 100 ° C. under reduced pressure for 2 hours (dehydration condensation).

Production Example 5 [Synthesis of titanium-containing catalyst (e)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube capable of bubbling in the liquid, 126 parts of ethyl acetate and 200 parts of terephthalic acid are placed and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. Then, 1617 parts of titanium tetraisopropoxide was added dropwise to react at 60 ° C. for 4 hours to obtain a slurry-like reaction mixture. The reaction mixture is filtered off with filter paper and dried at 40 ° C./20 kPa · s to obtain a mixture of titanium triisopropoxy terephthalate and unreacted terephthalic acid (e-2) (titanium triisopropoxy terephthalate concentration 65%). It was. The solubility of (e-2) in water was [0.6 g / 100 ml], and the solubility of titanium triisopropoxyterephthalate obtained by further purification in water was [0.9 g / 100 ml].

Production Example 6 [Synthesis of Titanium-Containing Catalyst (e)]
520 parts of ethyl acetate and 340 parts of isophthalic acid are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe capable of bubbling in liquid, and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. While adding 284 parts of titanium tetraisopropoxide dropwise, the reaction was carried out at 60 ° C. for 5 hours to obtain a slurry-like reaction mixture. The reaction mixture was filtered off with a filter paper and dried at 40 ° C./20 kPa · s to obtain a mixture of titanium diisopropoxy diisophthalate and unreacted isophthalic acid (e-3) (titanium diisopropoxy diisophthalate concentration 95). %). The solubility of (e-3) in water was [0.3 g / 100 ml], and the solubility of titanium diisopropoxydiisophthalate obtained by further purification in water was also [0.3 g / 100 ml].

Production Example 7 [Synthesis of titanium-containing catalyst (e)]
520 parts of ethyl acetate and 244 parts of benzoic acid are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe capable of bubbling in liquid, and gradually heated to 60 ° C. under bubbling in liquid with nitrogen. Then, 284 parts of titanium tetraisopropoxide was added dropwise and reacted at 60 ° C. for 5 hours, and then 50 parts of ion-exchanged water was added and reacted for 30 minutes to obtain a reaction mixture as a slurry. The reaction mixture was filtered off with filter paper and dried at 40 ° C./20 kPa · s to obtain titanium dihydroxydibenzenecarboxylate (e-4). The solubility of (e-4) in water was [0.1 g / 100 ml].

Production Example 8 (Production of resin b)
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (18.8 mol) of propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid (2.5 mol) ), And 3 parts of titanium terephthalate as a condensation catalyst were allowed to react for 8 hours at 180 ° C. in a nitrogen stream while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a 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 9 (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 titanium terephthalate as a condensation catalyst were allowed to react for 8 hours at 180 ° C. in a nitrogen stream while distilling off the produced methanol. 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 10 (Production of resin b)
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (18.8 mol) of propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid (2.5 mol) And 3 parts of potassium titanyl oxalate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a 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 b3]. Mn of [Polyester b3] was 7800.

Production Example 11 (Production of Resin b)
[Synthesis of nonlinear polyester]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 557 parts (17.5 moles) of propylene glycol, 569 parts (7.0 moles) of dimethyl terephthalate, 184 parts (3.0 moles) of adipic acid And 3 parts of potassium titanyl oxalate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours 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 b4]. Mn of [Polyester b4] was 8300.

Production Example 12 (Production of Resin b)
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (18.8 mol) of propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid (2.5 mol) ), And 3 parts of titanium acetylacetonate as a condensation catalyst were allowed to react for 8 hours at 180 ° C. in a nitrogen stream while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a 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 b5]. Mn of [Polyester b5] was 8000.

Production Example 13 (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 titanium acetylacetonate as a condensation catalyst were allowed to react for 8 hours at 180 ° C. in a nitrogen stream while distilling off the produced methanol. 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 into particles to obtain [Polyester b6]. Mn of [Polyester b6] was 8500.

Production Example 14 [Synthesis of linear polyester resin]
A linear polyester resin [Polyester b7] was obtained by reacting in the same manner as [Polyester b1] in Production Example 8 except that the condensation catalyst was replaced with titanium dihydroxybis (triethanolaminate), cooling to room temperature, and pulverizing.
[Polyester b7] contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 11, Tg of 60 ° C., Mn of 6860, and Mp of 20100. The ratio of components having a molecular weight of 1500 or less was 0.9%.

Production Example 15 [Synthesis of Non-Linear Polyester Resin]
A non-linear polyester resin [Polyester b8] was obtained by reacting in the same manner as [Polyester b2] in Production Example 9 except that the condensation catalyst was replaced with titanium dihydroxybis (triethanolaminate), cooling to room temperature, and pulverizing.
[Polyester b8] did not contain THF-insoluble matter, Tg was 60 ° C., Mn was 8720, and Mp was 43970. The ratio of components having a molecular weight of 1500 or less was 0.6%.

Production Example 16 [Synthesis of Linear Polyester Resin] The reaction was conducted in the same manner as [Polyester b1] in Production Example 8 except that it was replaced with titanyl bis (triethanolaminate). ] Was obtained.
[Polyester b9] contained no THF-insoluble matter, and had an acid value of 6, a hydroxyl value of 13, Tg of 57 ° C., Mn of 6600, and Mp of 18200. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 17 [Synthesis of Non-Linear Polyester Resin]
A non-linear polyester resin [Polyester b10] was obtained by reacting in the same manner as [Polyester b2] in Production Example 9 except that the condensation catalyst was replaced with titanyl bis (triethanolaminate), cooling to room temperature, and pulverizing.
[Polyester b10] contained no THF-insoluble matter, Tg was 65 ° C., Mn was 6300, and Mp was 412190. The ratio of components having a molecular weight of 1500 or less was 0.2%.

Production Example 18 [Synthesis of linear polyester resin]
A linear polyester resin [Polyester b11] was obtained by reacting in the same manner as [Polyester b1] in Production Example 8 except that the condensation catalyst was changed to (e1), cooling to room temperature, and pulverizing.
[Polyester b11] contained no THF-insoluble matter, and had an acid value of 6, a hydroxyl value of 17, Tg of 63 ° C., Mn of 6330, and Mp of 21,200. The ratio of components having a molecular weight of 1500 or less was 0.9%.

Production Example 19 [Synthesis of Non-Linear Polyester Resin]
A non-linear polyester resin [polyester b12] was obtained by reacting in the same manner as [polyester b2] in Production Example 9 except that the polycondensation catalyst was replaced with (e1), cooling to room temperature, and pulverizing.
[Polyester b12] contained no THF-insoluble matter, and Mn was 41190. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 20 [Synthesis of linear polyester resin]
A linear polyester resin [Polyester b13] was obtained by reacting in the same manner as [Polyester b1] in Production Example 8 except that the condensation catalyst was changed to (e2), cooling to room temperature, and pulverizing.
[Polyester b13] contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 14, Tg of 60 ° C., Mn of 6550, and Mp of 19400. The ratio of components having a molecular weight of 1500 or less was 0.9%.

Production Example 21 [Synthesis of Non-Linear Polyester Resin]
A non-linear polyester resin [polyester b14] was obtained by reacting in the same manner as [polyester b2] in Production Example 9 except that the polycondensation catalyst was replaced with (e2).
[Polyester b14] contained no THF-insoluble matter, and had an acid value of 15, a hydroxyl value of 15, Tg of 70 ° C., Mn of 4320, and Mp of 11950. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 22 [Synthesis of linear polyester resin]
A linear polyester resin [Polyester b15] was obtained by reacting in the same manner as [Polyester b1] in Production Example 8 except that the condensation catalyst was changed to (e3), cooling to room temperature, and pulverizing.
[Polyester b15] contained no THF-insoluble matter, and had an acid value of 5, a hydroxyl value of 13, Tg of 61 ° C., Mn of 7260, and Mp of 21,500. The ratio of components having a molecular weight of 1500 or less was 0.4%.

Production Example 23 [Synthesis of Non-Linear Polyester Resin]
Except that the polycondensation catalyst was changed to (e3), the reaction was carried out in the same manner as in [Polyester b2] in Production Example 9, cooled to room temperature and pulverized to obtain a non-linear polyester resin [Polyester b16].
[Polyester b16] contained no THF-insoluble matter, and had an acid value of 14, a hydroxyl value of 15, Tg of 70 ° C., Mn of 4520, and Mp of 11950. The ratio of components having a molecular weight of 1500 or less was 0.2%.

Production Example 24 [Synthesis of Linear Polyester Resin] The reaction was conducted in the same manner as in [Polyester b1] in Production Example 8 except that the condensation catalyst was replaced with (e4). ] Was obtained.
[Polyester b17] contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 11, Tg of 61 ° C., Mn of 6840, and Mp of 20600. The ratio of components having a molecular weight of 1500 or less was 0.9%.

Production Example 25 [Synthesis of Non-Linear Polyester Resin]
A non-linear polyester resin [polyester b18] was obtained by reacting in the same manner as [polyester b2] in Production Example 9 except that the polycondensation catalyst was replaced with (e4), cooling to room temperature, and pulverizing.
[Polyester b18] contained no THF-insoluble matter, had a hydroxyl value of 15, Tg of 70 ° C., Mn of 3320, and Mp of 15150. The ratio of components having a molecular weight of 1500 or less was 0.8%.

Production Example 26 (Production of Resin b)
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (18.8 mol) of propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid (2.5 mol) ), And 3 parts of dibutyltin oxide as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a 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 b19]. Mn of [Polyester b19] was 6890.

Production Example 27 (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 dibutyltin oxide as a condensation catalyst were allowed to react at 180 ° C. for 8 hours 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 into particles to obtain [Polyester b20]. The Mn of [Polyester b20] was 3810.

Production Example 28 (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 b1] 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 size of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.3 μm.

Production Example 29 (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 substitution, 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 30 (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 31 (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 32 (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 33 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b3] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 3].

Production Example 34 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b4] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 4].

Production Example 35 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b5] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 5].

Production Example 36 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b6] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 6].

Production Example 37 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b7] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 7].

Production Example 38 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b8] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 8].

Production Example 39 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b9] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 9].

Production Example 40 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b10] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 10].

Production Example 41 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b11] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 11].

Production Example 42 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b12] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 12].

Production Example 43 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b13] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 13].

Production Example 44 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b14] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 14].

Production Example 45 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b15] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 15].

Production Example 46 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b16] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 16].

Production Example 47 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b17] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 17].

Production Example 48 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b18] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 18].

Production Example 49 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b19] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 19].

Production Example 50 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b20] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin solution 20].

Example 1
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. 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. The mixture was then transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised to distill off ethyl acetate until the concentration reached 0.5% or less at 35 ° C., and (P) appeared on the surface of (Q). An aqueous resin dispersion (XF1) of the formed resin particles 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
Example 1 except that 48 parts of [resin solution 3] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 4] are used instead of 12 parts of [resin solution 2]. In the same manner as above, an aqueous resin dispersion (XF2) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F2) were obtained.

Example 3
Example 1 except that 48 parts of [Resin Solution 5] are used instead of 48 parts of [Resin Solution 1] of Example 1, and 12 parts of [Resin Solution 6] are used instead of 12 parts of [Resin Solution 2]. In the same manner as above, an aqueous resin dispersion (XF3) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F3) were obtained.

Example 4
Example 1 except that 48 parts of [resin solution 7] are used instead of 48 parts of [resin solution 1] in Example 1, and 12 parts of [resin solution 8] are used instead of 12 parts of [resin solution 2]. In the same manner as above, an aqueous resin dispersion (XF4) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F4) were obtained.

Example 5
Example 1 except that 48 parts of [resin solution 9] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 10] are used instead of 12 parts of [resin solution 2]. In the same manner as above, an aqueous resin dispersion (XF5) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F5) were obtained.

Example 6
Example 1 except that 48 parts of [resin solution 11] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 12] are used instead of 12 parts of [resin solution 2]. In the same manner, an aqueous resin dispersion (XF6) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F6) were obtained.

Example 7
Example 1 except that 48 parts of [resin solution 13] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 14] are used instead of 12 parts of [resin solution 2]. In the same manner as above, an aqueous resin dispersion (XF7) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F7) were obtained.

Example 8
Example 1 except that 48 parts of [resin solution 15] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 16] are used instead of 12 parts of [resin solution 2]. In the same manner, an aqueous resin dispersion (XF8) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F8) were obtained.

Example 9
Example 1 except that 48 parts of [resin solution 17] are used instead of 48 parts of [resin solution 1] of Example 1, and 12 parts of [resin solution 18] are used instead of 12 parts of [resin solution 2]. In the same manner as above, an aqueous resin dispersion (XF9) of resin particles (P) formed on the surface of (Q) and resin particles (F9) were obtained.

Example 10
In the same manner as in Example 1 except that 10.5 parts of [Fine Particle Dispersion Liquid W1] in Example 1 are used instead of 10.5 parts of [Fine Particle Dispersion Liquid W1], (P) An aqueous resin dispersion (XF10) of resin particles formed with resin particles (F10) was obtained.

Comparative Example 1
Example 1 except that 48 parts of [Resin Solution 19] are used instead of 48 parts of [Resin Solution 1] of Example 1, and 12 parts of [Resin Solution 20] are used instead of 12 parts of [Resin Solution 2]. In the same manner as above, an aqueous resin dispersion (XF11) of resin particles in which (P) was formed on the surface of (Q) and resin particles (F11) were obtained.

Comparative Example 2
Resin particles (Q) are coated on the surface of (Q) in the same manner as in Example 1 except that 2.9 parts of [fine particle dispersion W3] is used instead of 10.5 parts of [fine particle dispersion W1] of Example 1. An aqueous resin dispersion (XF12) of resin particles to which A) was attached and resin particles (F12) were obtained.

Comparative Example 3
With 48 parts of [resin solution 7] instead of [resin solution 1] 48 parts of Example 1, using 12 parts of [resin solution 8] in place of 12 parts of [resin solution 2], [fine particle dispersion W1] Resin particles in which resin particles (A) are attached to the surface of (Q) in the same manner as in Example 1 except that 2.9 parts of [fine particle dispersion W3] are used instead of 10.5 parts. Aqueous resin dispersion (XF13) and resin particles (F13) were obtained.

Comparative Example 4
Instead of 48 parts of [Resin Solution 1] of Example 1 , 48 parts of [Resin Solution 15] and 12 parts of [Resin Solution 16] instead of 12 parts of [Resin Solution 2] [Fine Particle Dispersion W1] Resin particles in which resin particles (A) are attached to the surface of (Q) in the same manner as in Example 1 except that 2.9 parts of [fine particle dispersion W3] are used instead of 10.5 parts. Aqueous resin dispersion (XF14) and resin particles (F14) were obtained.

Comparative Example 5
(P) is formed on the surface of (Q) in the same manner as in Example 1 except that 360 parts of [fine particle dispersion W1] is used instead of 10.5 parts of [fine particle dispersion W1] of Example 1. An aqueous resin dispersion (XF15) of resin particles and resin particles (F15) were obtained.

Example of measuring physical properties The resin particles (F1) to (F15) obtained in Examples 1 to 10 and Comparative Examples 1 to 5 were dispersed in water, and the particle size distribution was measured with a Coulter counter. Further, the average circularity, charging characteristics, heat-resistant storage stability, and low-temperature fixability of the resin particles (F1) to (F15) were measured. The results are shown in Tables 1 and 2. In addition, (circle) means the inside of square ABCD and x means the exterior.

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

[Charging characteristics]
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. It was set in a turbula shaker mixer (manufactured by Willy a Baschofen) and stirred for 2 minutes at a rotation speed of 90 rpm. 0.2 g of the mixed powder after stirring is loaded into a blow-off powder charge measuring device (TB-203, manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel mesh is set, and the blow pressure is 10 KPa and the suction pressure is 5 KPa. Then, the charge amount of the residual iron powder was measured, and the charge amount of the resin particles per unit weight was calculated. For toners, the higher the negative charge amount, the better the charging characteristics.

[Heat-resistant storage stability 1]
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.
[Heat-resistant storage stability 2]
A 100 ml capacity plastic cup containing 2 g of resin particles was placed in a dryer controlled to 50 ° C. for 72 hours, and evaluated according to the following criteria based on the degree of blocking.
A: When the plastic cup after the test is tilted at 45 degrees, the resin particles flow.
○: Resin particles do not flow even if the plastic cup after the test is tilted 45 degrees, but 4
Resin particles when gently stimulated by tapping the bottom of the cup while tilted at 5 degrees
Flows.
△: The above conditions of ◎ and ○ are not satisfied, but it is easy to apply force by gently picking it with your fingers.
scatter.
X: Blocking occurs and does not return to the state of the resin particles before the test 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 (D) was evaluated by a photograph magnified 10,000 times and 30,000 times.
A: There is no unevenness on the surface, and it is very smooth.
○: Some irregular parts are observed on the surface, but there is almost no unevenness on the whole and it is smooth.
Δ: There are irregularities on the entire surface, but the particulate matter derived from the resin (a) cannot be confirmed.
X: The particle | grains which are extremely uneven | corrugated on the whole surface, or consist of resin (a) can be confirmed.

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

Claims (8)

Core-shell type resin particles (D) composed of one or more film-like shell layers (P) made of resin (a) and one core layer (Q) made of resin (b). The weight ratio of (P) and (Q) is (0.1: 99.9) to (70:30), and (b) is the polyester resin (b1) and / or (b1) as a structural unit. A resin comprising the resin (b2) contained therein, wherein (b1) is a titanium halide (e1), a titanium diketone enolate (e2), a titanium carboxylate (e3), a titanyl carboxylate (e4), and a titanyl carboxylate At least one selected from the group consisting of (e5), a titanium-containing compound (e6) represented by the following general formula (I) or (II), and a titanium-containing compound (e7) represented by the following general formula (III) Seed titanium-containing catalyst (e) Resin particles, which is a polycondensation polyester resin obtained is formed in the presence.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR < ₁ >) q (II)
_{Ti (-Z) r (-OR 2} ) s (III)
[In the formulas (I) and (II), X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. In the case of a polyalkanolamine, other OH groups May be condensed in the molecule with an OH group directly bonded to the same Ti atom to form a ring structure, or may be repeatedly condensed between molecules with an OH group directly bonded to another Ti atom to form a repeating structure. It may be. The degree of polymerization in the case of forming a repeating structure is 2-5. R ₁ is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
[In the formula (III), R ₂ is H or a hydrocarbon group having 1 to 24 carbon atoms which may contain 1 to 3 ether bonds and / or 1 to 2 hydroxyl groups. Z is a residue obtained by removing one carboxyl group H from an aromatic mono- or polycarboxylic acid. In the case of polycarboxylic acid, other carboxyl groups are polycondensed in the molecule with an OR group in the same molecule. A structure may be formed, or a structure containing 2 to 5 Ti atoms may be formed by polycondensation between an OR group of another molecule and the molecule. r = 1 to 3 and s = 1 to 3, and the sum of r and s is 4. ] The resin particles (D) have a volatile content of 2% by weight or less, and the resin (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 The resin particle according to claim 1, which has a difference between a glass transition temperature of 0 to 120 ° C and an outflow temperature. The resin particles according to claim 1 or 2, wherein the resin (a) is at least one resin selected from a polyester resin, an epoxy resin, and a vinyl resin. Resin (a) is a sulfonic acid anion group (-SO ₃ ^-): (a) resin particles according to any one of claims 1 to 3, containing 0.001 to 10% by weight, based on the weight of the. The resin particle according to any one of claims 1 to 4, wherein the polyester resin (b1) contains an alkylene glycol having 2 to 36 carbon atoms as a structural unit. The resin particles (D) are mixed with the aqueous dispersion (W) of the resin particles (A) made of the resin (a) and the resin (b) or a solvent solution (O) thereof. ) Is dispersed, and resin particles (B) made of (b) are formed in (W), whereby (A) is adhered to the surface of (B), and an aqueous dispersion of resin particles (C) (X1) is obtained, and in (X1), a resin layer (D) having a shell layer (P) formed by coating (A) on the surface of the core layer (Q) composed of (B) The resin particles according to any one of claims 1 to 5, which are obtained by forming an aqueous dispersion (X2) of (D) by removing the aqueous medium from (X2). When the difference in sp value (Δsp) between the resin (a) and the resin (b) is K, and the natural logarithm [ln (Mw)] of the weight average molecular weight of (a) is H, the point (K, H) is The resin particle according to any one of claims 1 to 6, which is contained inside including a side of a quadrilateral ABCD composed of the following four points A, B, C, and D.
A (0.3, ln3000), B (1.5, ln1000),
C (1.3, ln200000), D (0.1, ln200000) 7. Use for slush molding resin, powder coating, electronic component manufacturing spacer, standard particle for electronic measuring device, electrophotographic toner, electrostatic recording toner, electrostatic printing toner or hot melt adhesive. Or a resin particle according to any one of the above.

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