JP2011127102A - Resin particle and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle which is excellent in fixation at a low temperature (fusion at a low temperature) and has a sufficiently narrow size distribution, and to provide a manufacturing method using a nonaqueous solvent such as a liquid or supercritical fluid or an aqueous solvent to obtain the resin particle which has a sufficiently narrow size distribution. <P>SOLUTION: The resin particle comprises a fine-grain (A) which is adhered to a surface of a resin particle (B) comprising a resin (b) or which is formed with a film comprising a resin (a) on the surface of the resin particle (B), wherein the fine-grain (A) comprises the resin (a) which has a vinyl monomer (d1) as an essential constituent unit, and the vinyl monomer (d1) has a polyester chain and a number-average molecular weight of 500-100,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin particle and a method for producing the resin particle using a non-aqueous medium such as a liquid or a supercritical fluid, or an aqueous medium.

Conventionally, as a method of forming particles in a non-aqueous medium, a method of spraying a resin solution into a supercritical fluid (see, for example, Patent Documents 1 and 2), supercritical in the presence of a fine particle dispersant such as an organic pigment or silicon oxide. A method in which a resin melted by heating and melting in a fluid is mechanically dispersed to form fine particles and then reduced in pressure to obtain resin particles (see, for example, Patent Document 3), a supercritical fluid in the presence of a fine particle dispersant and an activator There is known a method (for example, Patent Documents 4 and 5) in which a resin solution is mechanically dispersed therein to form fine particles and then decompressed to obtain resin particles.
WO97 / 31691 pamphlet WO95 / 01221 pamphlet JP-A-2005-107405 JP 2006-321830 A JP 2007-277511 A

  According to the method of spraying the resin solution into the supercritical fluid, particles having excellent powder characteristics, electrical characteristics, etc., since no hydrophilic component is required and no surface active substance remains in the resin particles or on the surface. However, it is difficult to obtain a sharp particle size distribution. According to the above-mentioned method of dispersing a resin melted by heating in a supercritical fluid, it is said that particles having excellent powder characteristics, electrical characteristics, etc. and having a narrow particle size distribution can be obtained. It is difficult to say that the particle size distribution of the particles is sufficiently narrow. Further, in the technique of the above document, since the resin particle surface is coated with an organic pigment, silicon oxide or the like, there is a problem that the low-temperature fixability is inferior when used as resin particles for electrophotographic toner. According to the method of dispersing the resin solution in the supercritical fluid in the presence of the fine particle dispersant and the activator, it is difficult to obtain particles with a narrow particle size distribution because the resin particles are aggregated.

  An object of the present invention is to provide resin particles having excellent low-temperature fixability (low-temperature meltability) and having a sufficiently narrow particle size distribution, and a non-aqueous medium such as a liquid or supercritical fluid, or an aqueous medium, and a particle size distribution. It is to find a production method for obtaining sufficiently narrow resin particles.

The present invention has been made in view of the above circumstances in the prior art. That is, the present invention is the following four inventions.
(I) Resin particles in which fine particles (A) containing a resin (a) having a polyester chain and having a vinyl monomer (d1) having a number average molecular weight of 500 to 100,000 as an essential constituent unit contain a resin (b) Resin particles characterized in that they are fixed on the surface of (B) or a film containing resin (a) is formed on the surface of resin particles (B).
(II) A dispersion in which fine particles (A) containing a resin (a) are dispersed in carbon dioxide (X) in a liquid or supercritical state, and a solvent (S) solution (L) of the resin (b). By mixing and dispersing (L) in the (X) dispersion of (A), the fine particles (A) are fixed to the surface of the resin particles (B) containing the resin (b) and the solvent (S). The resin particles (C) are formed, and then the liquid particles or the supercritical carbon dioxide (X) and the solvent (S) are removed to obtain the resin particles (C). Method.
(III) A non-aqueous dispersion in which fine particles (A) containing a resin (a) are dispersed in a non-aqueous organic solvent (N) and a solvent (S) solution (L) of the resin (b) are mixed. Resin particles in which fine particles (A) are fixed to the surface of resin particles (B) containing resin (b) and solvent (S) by dispersing (L) in the non-aqueous dispersion of (A) The method for producing resin particles according to (I), comprising the step of forming the resin particles (C) by forming (C) and then removing the non-aqueous organic solvent (N) and the solvent (S).
(IV) An aqueous dispersion in which fine particles (A) containing the resin (a) are dispersed in an aqueous medium and a solvent (S) solution (L) of the resin (b) are mixed, and the aqueous solution of (A) By dispersing (L) in the dispersion, resin particles (C) in which the fine particles (A) are fixed to the surfaces of the resin particles (B) containing the resin (b) and the solvent (S) are formed, Subsequently, the manufacturing method of the resin particle of (I) including the process of obtaining resin particle (C) by removing an aqueous medium and a solvent (S).

  The resin particles of the present invention and the resin particles obtained by the production method of the present invention have a sufficiently narrow particle size distribution, and the resin particles have a low-temperature melting property and good heat and moisture heat and heat resistance.

It is a flowchart of the experimental apparatus used for preparation of the resin particle in this invention.

The present invention is described in detail below.
In the present invention, the resin (a) contained in the fine particles (A) has a polyester chain, and the vinyl monomer (d1) having a number average molecular weight (hereinafter referred to as Mn) of 500 to 100,000 is an essential component. Any type of resin can be used as long as it is a unit and can be fixed to the surface of the resin particle (B) containing the resin (b) or a film can be formed on the surface of the resin particle (B). And may be a thermoplastic resin or a thermosetting resin.

  The resin (a) has a polyester chain, and the vinyl monomer (d1) whose Mn is 500 to 100,000 is an essential constituent unit, whereby the fine particles (A) of the resin particles (B) containing the resin (b) It becomes easy to adhere to the surface, and it is easy to obtain particles having a narrow particle size distribution by stabilizing the resin particles (C). When Mn of the vinyl monomer (d1) is smaller than 500, the melting point or glass transition temperature of the resin (a) is lowered, and the storage stability of the resin particles (C) is deteriorated. If Mn of the vinyl monomer (d1) is larger than 100,000, the dispersibility of the fine particles (A) is deteriorated, and the particle size distribution of the resin particles (C) is deteriorated. Mn of the vinyl monomer (d1) is preferably 600 to 70000, more preferably 700 to 50000.

In the present invention, the Mn of the resin is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (an example): 2 TSKgel GMHXL + TSKgel Multipore HXL-M [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
In the above and below, “%” means “% by weight” unless otherwise specified.

Examples of the polyester chain portion in the vinyl monomer (d1) include polycondensates of diol (11) and dicarboxylic acid (13), and lactone ring-opening polymer (p).
Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diol (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.] (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.); castor oil-based polyol; and polybutadiene diol.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and AO adducts of bisphenols, more preferred are linear alkylene glycols having 2 to 12 carbon atoms, and particularly preferred is 1,4-butane. Diol, 1,6-hexanediol, and 1,10-decanediol.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.).
Of these, preferred are alkane dicarboxylic acids having 4 to 36 carbon atoms, alkene dicarboxylic acids having 4 to 20 carbon atoms, and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and more preferably 4 to 36 carbon atoms. Straight chain alkane dicarboxylic acids, particularly preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid.
In addition, as dicarboxylic acid (13), you may use the acid anhydride of the above-mentioned thing, or a C1-C4 lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
The method for obtaining a polyester chain by reacting the diol (11) and the dicarboxylic acid (13) may be a normal method for producing a polyester resin.

As the lactone ring-opening polymer (p), the polyol containing the diol (11) is used as an initiator, and if necessary, in the presence of a catalyst, a monolactone having 3 to 12 carbon atoms (one ester group in the ring). And those having a hydroxyl group at the terminal. In addition, (p) may be modified at its terminal so as to become, for example, a carboxyl group.
Examples of the polyol include diols (11) such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. The polyol (12) may be used in combination.
Examples of the monolactone monomer include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Of these, ε-caprolactone is preferable from the viewpoint of crystallinity.
As the catalyst, for example, commonly used catalysts such as acids such as inorganic acids and organic acids, metal chlorides, oxides and hydroxides, fatty acid metal salts, and organometallic compounds can be used.
Of these, organic tin compounds (dibutyltin oxide, methylphenyltin oxide, etc.), organic titanium compounds (tetra-n-propyl titanate, tetraisopropyl titanate, etc.), and organic halogenated tin compounds (monobutyltin trichloride, etc.) are preferred.
The addition amount of the catalyst is preferably 0.1 to 5000 ppm with respect to the entire reaction system. The lactone ring-opening polymer (p) can be obtained by polymerization at a reaction temperature of 100 to 230 ° C., preferably in an inert atmosphere.
The ring-opening polymerization reaction may be performed without a solvent, or a reaction solvent may be used. As the reaction solvent, one or more known organic solvents such as toluene, benzene, ethylbenzene, hexane and pentane can be used.

As a method for producing a vinyl monomer (d1) having a polyester chain,
(1) A method for introducing an unsaturated group capable of radical polymerization into a polyester chain by esterifying the polyester with a hydroxyl group-containing vinyl monomer (5) or a carboxyl group-containing vinyl monomer (2),
(2) The polyester and hydroxyl group-containing vinyl monomer (5) are subjected to a urethanation reaction with polyisocyanate (15) to produce a monomer having a urethane bond by introducing a radical polymerizable unsaturated group into the polyester chain. Method,
(3) A method for introducing an unsaturated group capable of radical polymerization into a polyester chain by ring-opening polymerization of the monolactone having 3 to 12 carbon atoms using the hydroxyl group-containing vinyl monomer (5) as an initiator,
Etc.
Any of these methods may be used, but a preferable method is the method (1) or (2), which can be selected from many raw materials, and more preferably a monomer having a mild reaction condition and a urethane bond. (2) is obtained. When the vinyl monomer (d1) has a urethane bond, the crystallinity becomes high and the storage stability of the resin particles (C) becomes good.
As (d1), a commercially available product having a corresponding composition can be used.

Examples of the hydroxyl group-containing vinyl monomer (5) include hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and (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. Is mentioned.
Of these, hydroxyethyl (meth) acrylate is preferred.
In addition, the said-(meth) acryl means --acryl and / or --methacryl, and uses the same description method hereafter.

  Examples of the carboxyl group-containing vinyl monomer (2) include unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (alkyl having 1 to 24 carbon atoms, methyl, ethyl, etc.) esters. For example, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, Citraconic acid monoalkyl ester, cinnamic acid and the like.

As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4′- and / or Or 4,4'-diphenylmethane diisocyanate (MDI) etc. are mentioned.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). .
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.

  Resin (a) is used in addition to vinyl monomer (d1), perfluoroalkyl (alkyl) (meth) acrylate (d2) and / or non-resin from the viewpoint of charging characteristics of resin particles (C) under high temperature and high humidity. It is preferable to have a saturated dicarboxylic acid (anhydride) (d3) as a structural unit.

The perfluoroalkyl (alkyl) (meth) acrylate (d2) is preferably a perfluoroalkyl group having an even number of 2 to 12 carbon atoms and a (alkyl) moiety having 0 to 3 carbon atoms. Specific examples include (2-perfluoroethyl) ethyl (meth) acrylate, (2-perfluorobutyl) ethyl (meth) acrylate, (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl). ) Ethyl (meth) acrylate, (2-perfluorodecyl) ethyl (meth) acrylate, and (2-perfluorododecyl) ethyl (meth) acrylate. In addition, 2,2,2-trifluoroethyl (meth) acrylate, in which the carbon number of the perfluoroalkyl group is 1 and the carbon number of the (alkyl) portion is 1, is also preferable. (D2) may be a single monomer or a combination of plural monomers.
Of these, more preferred are (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl) ethyl (meth) acrylate, and (2-perfluorodecyl) ethyl (meta) from the viewpoint of chargeability. ) Acrylate, (2-perfluorododecyl) ethyl (meth) acrylate.
Unsaturated dicarboxylic acid (anhydride) (d3) means unsaturated dicarboxylic acid and / or its anhydride, preferably unsaturated dicarboxylic acid having 3 to 30 carbon atoms and its anhydride. Examples include acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and the like. (D3) may use 2 or more types together. Of these, maleic anhydride is more preferable from the viewpoint of chargeability.

  The content of (d1) in the resin (a) is preferably 20 to 100%, more preferably 25 to 90%, and particularly preferably 30 to 80%. When the content of (d1) is 20% or more, the resin particles (C) have excellent storage stability and low-temperature meltability due to crystal melting and sharp melting, and charging characteristics under high temperature and high humidity are good. Become.

The content (total) of (d2) and / or (d3) in the resin (a) is preferably 0 to 50%, more preferably 0.001 to 40%, more preferably 0.01 to 35%, Especially preferably, it is 0.1 to 30%. When the content of (d2) and / or (d3) is 50% or less, the degree of crystallinity increases and the storage stability of the resin particles (C) becomes good.
The total content of monomers other than (d1), (d2), and (d3) in (a) is preferably 50% or less, more preferably 30% or less. When the content of monomers other than (d1), (d2), and (d3) is 50% or less, the degree of crystallinity increases and the storage stability becomes better.

Examples of the resin (a) include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Is mentioned. As the resin (a), two or more of the above resins may be used in combination. Among these, from the viewpoint of easily obtaining a liquid or supercritical carbon dioxide (X) dispersion, non-aqueous organic solvent (N) dispersion, or aqueous dispersion of resin particles, a vinyl resin and a polyurethane resin are preferable. , Epoxy resins, polyester resins, and combinations thereof, more preferably vinyl resins from the viewpoint of easy introduction of a desired functional group as a part of the vinyl monomer (d1) or a monomer to be addition copolymerized.
In the case of other than vinyl resin, after synthesizing a vinyl polymer having a polyester chain and having a structural unit of vinyl monomer (d1) having Mn of 500 to 100,000, a reaction such as esterification or amidation is performed, or A resin other than these vinyl resins having a vinyl group and a vinyl monomer containing (d1) are copolymerized.

Hereinafter, the vinyl resin which is a preferable resin as (a) will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer, having a polyester chain and having a Mn of 500 to 100,000, a perfluoroalkyl (alkyl) (meth) acrylate (d2), and Examples of vinyl monomers other than the unsaturated dicarboxylic acid (anhydride) (d3) include the following (1) to (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, α-olefins other than those described above; 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 (di) cyclopentadiene; terpenes such as pinene.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, such as α-methylstyrene, 2,4-dimethylstyrene and the like; and vinylnaphthalene.

(2) Carboxyl group-containing vinyl monomers other than (d3) and metal salts thereof:
C3-C30 unsaturated monocarboxylic acid, C3-C30 unsaturated dicarboxylic acid monoalkyl (C1-C24) ester, for example, (meth) acrylic acid, maleic acid monoalkyl ester, fumaric acid mono Carboxyl group-containing vinyl monomers such as alkyl esters, crotonic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid monoalkyl esters and cinnamic acid.

(3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides , For example, sulfopropyl (meth) acrylate, and vinyl monomers containing sulfate ester or sulfonic acid group; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
The above.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, etc.
(6-2) Amide group-containing vinyl monomer: (meth) acrylamide, N-methyl (meth) acrylamide, etc.
(6-3) Nitrile group-containing vinyl monomer: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc.
(6-4) Quaternary ammonium cation group-containing vinyl monomers: tertiary amines such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized products of group-containing vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate), etc.
(6-5) Nitro group-containing vinyl monomer: nitrostyrene and the like.

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

(8) Halogen element-containing vinyl monomers other than (d2):
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters other than (d1) and (d2), vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or Alicyclic groups), dialkyl maleates (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes Monomers [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (Mn300) Mono (meth) acrylate, Polypropylene glycol (Mn500) monoacrylate Methyl alcohol ethylene oxide 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, such as vinyl methyl ether,
(9-3) Vinyl ketones such as vinyl methyl ketone.

(10) Other vinyl monomers:
(10-1) Isocyanate group-containing monomer;
(10-2) a monomer having a dimethylsiloxane group, such as isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate;
(Meth) acrylic modified silicone with structure shown in the following formula
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) aSi (CH ₃ ) ₂ R
However, a is an average value of 15-45, and R is an organic modification group containing a (meth) acryl group. As examples of _{R, -C 3 H 6 OCOC (CH} 3) = CH 2 and the like.

  As a copolymer of vinyl monomers, one or more monomers selected from the above vinyl monomers (d1) and (d2), (d3), and (1) to (10) may be binary or higher. Examples include polymers copolymerized at an arbitrary ratio by number, for example, vinyl monomer (d1) -maleic anhydride copolymer, vinyl monomer (d1)-(2-perfluoroethyl) ethyl (meth) acrylate copolymer Polymer, vinyl monomer (d1)-(meth) acrylic acid ester copolymer, vinyl monomer (d1)-(meth) acrylic acid copolymer, vinyl monomer (d1) -acrylonitrile copolymer, vinyl monomer (d1)- Styrene copolymer, vinyl monomer (d1) -divinylbenzene copolymer, vinyl monomer (d1) -styrene sulfonic acid copolymer Vinyl monomer (d1) -styrene- (meth) acrylic acid copolymer, vinyl monomer (d1) -styrene- (meth) acrylic acid ester copolymer, vinyl monomer (d1)-(2-perfluoroethyl) ethyl ( And (meth) acrylate-maleic anhydride copolymer, vinyl monomer (d1) -styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, and the like.

  Examples of the method for producing the vinyl resin include known vinyl monomer polymerization methods such as solution polymerization, bulk polymerization, and suspension polymerization.

The resin (a) may be a crystalline resin (a1) or an amorphous resin, but is preferably a crystalline resin (a1).
In the present invention, “crystallinity” means that the ratio (softening point / Ta) between the softening point and the maximum peak temperature (Ta) of melting heat is 0.8 to 1.55, and differential scanning calorimetry (DSC). In FIG. 4, it indicates that the endothermic amount does not change stepwise but has a clear endothermic peak. “Non-crystalline” means that the ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / Ta) is greater than 1.55.
Even if the resin is a block body of a crystalline resin and an amorphous resin, the differential scanning calorimetry (DSC) has a clear endothermic peak, and the softening point and the maximum peak temperature of melting heat (Ta) When the ratio is 0.8 to 1.55, this is also a crystalline resin.

The softening point and the maximum peak temperature (Ta) of heat of fusion are values measured as follows. <Softening point>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

<Maximum peak temperature of melting heat (Ta)>
Measurement is performed using a differential scanning calorimeter (DSC) {for example, DSC210 manufactured by Seiko Denshi Kogyo Co., Ltd.}.
A sample to be used for the measurement of (Ta) is melted at 130 ° C. as a pretreatment, and then cooled at a rate of 1.0 ° C./min from 130 ° C. to 70 ° C., and then 0.5% from 70 ° C. to 10 ° C. The temperature is lowered at a rate of ° C / min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min, and the endothermic change is measured, and the graph of “endothermic amount” and “temperature” is drawn. Let the endothermic peak temperature at 100 ° C. be Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, the sample was cooled to 0 ° C. by DSC at a rate of temperature decrease of 10 ° C./min, and then the temperature was increased at a rate of temperature increase of 20 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of the calorific value is the maximum peak temperature (Ta) of the heat of fusion.

  The melting point of the crystalline resin (a1) is preferably 40 to 110 ° C, more preferably 45 to 100 ° C, particularly preferably 50 to 90 ° C. When the melting point of the crystalline resin (a1) is 40 ° C. or higher, the resin particles (C) of the present invention are difficult to block even during long-term storage. If it is 110 degrees C or less, the low temperature meltability of (C) is favorable. The melting point can be measured from an endothermic peak in differential scanning calorimetry (hereinafter referred to as DSC).

  Mn of the resin (a) is preferably 1000 or more, more preferably 1500 or more, particularly preferably 2000 or more, from the viewpoint of carrier contamination when the resin particles (C) are used as base particles for an electrophotographic toner. It is. Further, from the viewpoint of the melt viscosity of (C), it is preferably 1000000 or less, more preferably 500000 or less, particularly preferably 300000 or less, and most preferably 150,000 or less.

The fine particles (A) containing the resin (a) may contain a resin (a ′) in addition to the resin (a) having the vinyl monomer (d1) as an essential structural unit. The composition of the resin (a ′) is the same as that of (a) except that (d1) is not a structural unit, and two or more kinds may be used in combination. Further, (a ′) is also preferably a crystalline resin, more preferably aliphatic or aromatic polyester resin, aliphatic polyurethane and / or polyurea resin, and polyolefin.
The total content of (a ′) is preferably 0 to 50% with respect to the total weight of (a) and (a ′). Moreover, the fine particle which coat | covered resin (a ') with resin (a) may be sufficient. Moreover, it is preferable that melting | fusing point of the mixture of (a) and (a ') is 40-150 degreeC.

  Regarding the resin (a ′) in the fine particles (A), an aliphatic or aromatic polyester resin, aliphatic polyurethane and / or polyurea resin, and polyolefin, which are preferable resins, will be described.

Aliphatic or aromatic polyester resins include lactone ring-opening polymers and polycondensed polyester resins.
The composition of the lactone ring-opening polymer and the production method thereof are the same as those of the lactone ring-opening polymer (p).
The molecular weight of the lactone ring-opening polymer is preferably that having a weight average molecular weight (hereinafter referred to as Mw) determined by gel permeation chromatography (GPC) of 1000 to 80000. The glass transition temperature (Tg) is preferably -100 to 40 ° C, more preferably -80 to 0 ° C. The melting point is preferably 50 to 100 ° C.
(P) may be a commercially available product such as H1P, H5, H7 of the Placel series manufactured by Daicel Chemical Industries, Ltd. (both m = about 60 ° C. and Tg = about −60 ° C.) Crystalline polycaprolactone), 240 (m = 58-61 ° C., Mw 10000), 230 (m = 55-58 ° C., Mw 6300), 220 (m = 45-55 ° C., Mw 4000), 210 (m = 46-48 ° C. , Mw1900).

As the aliphatic or aromatic polycondensation polyester resin, the above diol (11) and dicarboxylic acid (13) can be used, and in particular, linear aliphatic diol having 2 to 50 carbon atoms and carbon number. A linear aliphatic dicarboxylic acid having an alkylene chain of 2 to 50 as an essential constituent unit, and the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is 10 to 52, A crystalline polyester resin having a structural unit of an aromatic dicarboxylic acid having 6 to 30 carbon atoms is preferable if necessary.
From the viewpoint of the storage stability of the resin particles (C), the aliphatic or aromatic polycondensation polyester resin has a total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid of 10 or more. More preferably, it is 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, and particularly preferably 40 or less.

From the viewpoint of crystallinity of the resin (a ′), the number of carbon atoms in the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more. Preferably it is 4 or more. Further, from the viewpoint of fixability of the resin particles (C), it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diol are 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol.
The number of carbon atoms of the alkylene chain of the linear aliphatic dicarboxylic acid having an alkylene chain of 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, particularly from the viewpoint of the crystallinity of the resin (a ′). Preferably it is 4 or more. Further, from the viewpoint of fixability of the resin particles (C), it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic dicarboxylic acid are adipic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid.
In addition, from the viewpoint of storage stability of the resin particles (C) containing the aromatic polyester resin, the aromatic dicarboxylic acid preferably has 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms, and particularly preferably 8 to 20 carbon atoms. It is. Preferable examples of the aromatic dicarboxylic acid having 6 to 30 carbon atoms are phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

  In the case of an aromatic polyester resin, from the viewpoint of resin strength, the dicarboxylic acid is preferably a combination of a linear aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the aromatics based on the total of the linear aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. The ratio of the group dicarboxylic acid is preferably 90% or less, more preferably 1 to 85%, and particularly preferably 3 to 80%.

Examples of the aliphatic polyurethane resin, the aliphatic polyurea resin, and the aliphatic polyurethane / polyurea resin include the diol (11), diamine (a divalent one of the polyamine (16) described later), and diisocyanate (the polyisocyanate described above). (15) is a divalent one, and in particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and / or a linear aliphatic having an alkylene chain having 2 to 50 carbon atoms. A diamine and a linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms are essential structural units, and the total carbon number of the alkylene chain of the diol and / or diamine and the alkylene chain of the diisocyanate A crystalline polyurethane and / or polyurea resin having a number of 10 to 52 is preferred.
A linear aliphatic diisocyanate having a polyester diol obtained by reacting a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms with the dicarboxylic acid (13) and an alkylene chain having 2 to 50 carbon atoms. Polyurethane resin obtained from
Aliphatic polyurethane and / or polyurea resin, from the viewpoint of storage stability of the resin particles (C), carbon number of alkylene chain of diol and / or diamine (when using a mixture of diol and diamine, the weight ratio The total number of carbon atoms of the average alkylene chain) and the alkylene chain of the diisocyanate is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of the fixability of (C), 52 or less is preferable, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

The preferred carbon number of the alkylene chain and preferred specific examples of the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms are the same as those in the aliphatic or aromatic polycondensation polyester resin.
The number of carbon atoms in the alkylene chain of the linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, particularly from the viewpoint of the crystallinity of the resin (a ′). Preferably it is 4 or more. Further, from the viewpoint of fixability of the resin particles (C), it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diamine are tetramethylene diamine and hexamethylene diamine.
In addition, the number of carbon atoms in the alkylene chain of the linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, from the viewpoint of the crystallinity of the resin (a ′). Especially preferably, it is 4 or more. Further, from the viewpoint of fixability of the resin particles (C), it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diisocyanate are tetramethylene diisocyanate and hexamethylene diisocyanate.

  Examples of the polyolefin include polyethylene and polypropylene.

  The aliphatic or aromatic polyester resin can be produced by reacting a low molecular polyol and / or a polyalkylene ether diol having an Mn of 1000 or less with a polycarboxylic acid, a method by ring-opening polymerization of a lactone, a low molecular diol and a lower alcohol. Known production methods such as a method of reacting with a carbonic acid diester (such as methanol) can be mentioned.

  Examples of the production method of the aliphatic polyurethane and / or polyurea resin include known production methods such as a method of reacting a low molecular weight polyol (including the polyester polyol obtained by the above method) and / or a low molecular weight diamine with a diisocyanate. .

  Examples of the method for producing polyolefin include known polymerization methods such as addition polymerization.

  The production method of the fine particles (A) may be any production method. Specific examples include a dry production method [resin (a) constituting the fine particles (A) and (a ′) as necessary, such as a jet mill, etc. Method of dry pulverization by a known dry pulverizer], method of manufacturing by wet [resin (a) and, if necessary, powder of (a ′) is dispersed in an organic solvent, and by a known wet disperser such as a bead mill or a roll mill Method of wet pulverization, method of spray drying resin (a) and, if necessary, solvent solution of (a ′) by spray drier, etc., resin (a) and solvent solution of (a ′) if necessary by adding poor solvent or cooling Method of supersaturation and precipitation, method of dispersing resin (a) and, if necessary, solvent solution of (a ′) in water or organic solvent, resin (a) and, if necessary, precursor of (a ′) in water Legal, soap-free Emulsion polymerization method, seed polymerization method, a method of polymerizing by suspension polymerization, resin (a) and if necessary (a ') a method of the precursor in an organic solvent is polymerized by dispersion polymerization or the like] and the like. Further, after the fine particles (A ′) of the resin (a ′) are synthesized by the above method, the crystalline resin (a) is formed on the surface of the (A ′) by a known coating method, seed polymerization method, mechanochemical method, or the like. May be. Among these, from the viewpoint of easy production of the fine particles (A), a wet production method is preferable, and a precipitation method, an emulsion polymerization method, and a dispersion polymerization are more preferable.

  The fine particles (A) may be used as they are, and for example, silane is used in order to impart the adsorptivity to the resin particles (B) or to modify the powder characteristics and electrical characteristics of the resin particles (C) of the present invention. The surface may be modified by surface treatment with a coupling agent such as a system, titanate or aluminate, surface treatment with various surfactants, coating treatment with a polymer, or the like. It is preferable that either one of the fine particles (A) and the resin particles (B) has an acidic functional group on at least its surface, and the other has at least a basic functional group on its surface.

  The fine particles (A) and the resin particles (B) may have an acidic functional group or a basic functional group therein. Examples of the acidic functional group include a carboxylic acid group and a sulfonic acid group. Examples of basic functional groups include primary amino groups, secondary amino groups, and tertiary amino groups.

  Resin having acidic functional group or basic functional group as resin (a) or resin (b) in order that fine particles (A) and resin particles (B) provide at least an acidic functional group or basic functional group on the surface thereof May be used, or surface treatment may be performed to impart these functional groups to the fine particles (A) and the resin particles (B).

  Examples of the resin (a) having an acidic functional group include a vinyl resin obtained by copolymerization of a monomer having an acidic functional group (for example, the aforementioned carboxyl group-containing vinyl monomer, sulfone group-containing vinyl monomer).

  Examples of the resin (a) having a basic functional group include a vinyl resin obtained by copolymerizing a monomer having a basic functional group (for example, the aforementioned amino group-containing vinyl monomer).

The resin particles (B) are composed of the resin (b). In the present invention, the resin (b) is not particularly limited, and the thermoplastic resin (b1), the resin (b2) obtained by finely crosslinking the thermoplastic resin, or the thermoplastic resin as a sea component and the cured resin as an island component. And a polymer blend (b3) and the like may be used in combination.
The thermoplastic resin (b1) may be any of a crystalline resin, an amorphous resin, and a composite resin (block resin) in which a crystalline resin and an amorphous resin are bonded. For example, a vinyl resin, a polyurethane resin, or an epoxy resin. , Polyester resins, and composite resins (block resins) thereof. Among these, a vinyl resin, a polyurethane resin, a polyester resin, a composite resin thereof, and a combination thereof are preferable from the viewpoint that a dispersion of fine spherical resin particles is easily obtained.
Specific examples of the case where the thermoplastic resin (b1) is a crystalline resin (including a crystalline resin portion of a composite resin in which a crystalline resin and an amorphous resin are bonded) include the resin (a ′) and The same thing is mentioned.

  When the thermoplastic resin (b1) is an amorphous resin, the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. As the vinyl monomer, the same ones as described above can be used, but the vinyl monomer (d1) having a polyester chain and Mn of 500 to 100,000, perfluoroalkyl (alkyl) (meth) acrylate (d2), and Unsaturated dicarboxylic acid (anhydride) (d3) may not be used.

Examples of polyester resins include polycondensates of polyols and polycarboxylic acids (including acid anhydrides and lower alkyl esters thereof). Examples of the polyol include a diol (11) and a trivalent or higher polyol (12), and examples of the polycarboxylic acid include a dicarboxylic acid (13) and a trivalent or higher polycarboxylic acid (14).
The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜1 / 1, particularly preferably 1.3 / 1 to 1.02 / 1.

Examples of the diol (11) include those described above.
Examples of the trivalent or higher polyol (12) include 3 to 8 or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trisphenols (such as trisphenol PA) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins, acrylic polyols [copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers] Etc.].

Examples of the dicarboxylic acid (13) include those described above.
Examples of the trivalent or higher (3 to 6 or higher) polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

  As the dicarboxylic acid (13) or the trivalent or higher polycarboxylic acid (14), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  As the polyurethane resin, the polyisocyanate (15) and the active hydrogen group-containing compound (D) {water, polyol [the diol (11) and the trivalent or higher polyol (12)], the dicarboxylic acid (13), and the above And polyaddition products with trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17) and the like}.

The following are mentioned as an example of a polyamine (16).
Aliphatic polyamines (C2 to C18):
[1] Aliphatic polyamine {C2-C6 alkylenediamine (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, etc.}}
[2] These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitutes [dialkyl (C1 to C3) aminopropylamine, etc.]
[3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]
[4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.),
-Alicyclic polyamines (C4-C15):
1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Aromatic polyamines (C6-C20):
[1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine and the like; nucleus-substituted alkyl group [C1-C4 alkyl such as methyl, ethyl, n- and i-propyl, butyl, etc.] Aromatic polyamines such as 2,4- and 2,6-tolylenediamine etc.), and mixtures of various proportions of these isomers [2] nuclear substituted electron withdrawing groups (Cl, Br, I, Aromatic polyamines having halogens such as F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc. [methylene bis-o-chloroaniline, etc.]
[3] Aromatic polyamines having secondary amino groups [partial or all of —NH ₂ of the aromatic polyamines of the above [1] to [2] are —NH—R ′ (R ′ is a lower group such as methyl or ethyl) Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamine (C4 to C15):
Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
・ Polyamide polyamine:
Low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as the above alkylene diamines, polyalkylene polyamines, etc.)
・ Polyether polyamine:
Hydrates of cyanoethylated polyether polyols (such as polyalkylene glycols).

  Examples of polythiol (17) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol and the like.

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (18), polyepoxide (18) and active hydrogen group-containing compound (D) {water, polyol [diol (11) and trivalent or higher valent polyol (12)], dicarboxylic acid Acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17), etc.} polyaddition product, or polyepoxide (18) and dicarboxylic acid (13) or higher polyvalent polyvalent acid. Examples include cured products of carboxylic acid (14) with acid anhydrides.

  The polyepoxide (18) is not particularly limited as long as it has two or more epoxy groups in the molecule. 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 (18). The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the crosslinked structure becomes dense and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, those having an epoxy equivalent of 65 or more are synthesized. Easy.

  Examples of the polyepoxide (18) 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 the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether and bisphenol A diglycidyl ether. 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. Further, as the aromatic polyepoxy compound, triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, and the above two reactants are reacted with polyol. The resulting glycidyl group-containing polyurethane (pre) polymer and a diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine. Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide. The alicyclic polyepoxy compound also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether. 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. The aliphatic polyepoxy compound also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

  The resin (b2) obtained by microcrosslinking a thermoplastic resin refers to a resin in which a crosslinked structure is introduced and the Tg of the resin (b) is 20 to 200 ° C. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. As a specific example, for example, when a polyester is selected as the resin (b2), a crosslinked structure is introduced by using a polyol or polycarboxylic acid at the time of polymerization, or a compound having a functional group number of 3 or more in both. be able to. When a vinyl resin is selected as the resin (b2), a crosslinked structure can be introduced by adding a monomer having two or more double bonds during polymerization.

  The polymer blend (b3) having a thermoplastic resin as a sea component and a cured resin as an island component has a Tg of 20 to 200 ° C. and a softening start temperature of 40 to 220 ° C., specifically vinyl resin and polyester Resins, polyurethane resins, epoxy resins and mixtures thereof.

  The Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000, and the solubility parameter (SP value, details will be described later) is preferably 7 to 18, more preferably. 8-14. Moreover, when it is desired to modify the thermal characteristics of the resin particles (C) of the present invention, the resin (b2) or the resin (b3) may be used.

  When the resin (b) is an amorphous resin, the glass transition temperature (Tg) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. At 20 ° C. or higher, the storage stability of the resin particles (C) is good. In addition, Tg in this invention is a value calculated | required from DSC measurement.

  The softening start temperature when the resin (b) is an amorphous resin is preferably 40 ° C to 220 ° C, more preferably 50 ° C to 200 ° C. Above 40 ° C, long-term storage is good. Below 220 ° C., the fixing temperature does not increase and there is no problem. In addition, the softening start temperature in this invention is a value calculated | required from a flow tester measurement.

  The volume average particle size of the resin particles (B) is preferably 1 to 10 μm, more preferably 2 to 8 μm.

  The resin particle (C) of the present invention is a resin in which the fine particles (A) are fixed on the surface of the resin particles (B) or the surface of the resin particles (B) is coated with the fine particles (A) ( It is the particle | grains in which the membrane | film | coat containing a) was formed. The fine particles (A) fixed on the surface of the resin particles (B) do not include the case where (A) simply adheres to the surface of (B) and easily desorbs.

  The particle size of the fine particles (A) is smaller than the particle size of the resin particles (B). The value of particle size ratio [volume average particle size of fine particles (A) / [volume average particle size of resin particles (C) of the present invention]] is preferably 0.001 to 0.3, more preferably 0.002 to 0.002. It is 0.2, more preferably 0.003 to 0.1, and particularly preferably 0.01 to 0.08. Within the above range, (A) is efficiently adsorbed on the surface of (B), so the particle size distribution of the obtained resin particles (C) of the present invention becomes narrow.

  The volume average particle diameter of the fine particles (A) is preferably 0.01 to 0.5 μm, and particularly preferably 0.015 to 0.4 μm. The volume average particle size is determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba Seisakusho), a laser type particle size distribution measuring device (for example, LA-920: manufactured by Horiba Seisakusho), Multisizer III (Beckman).・ Measured by Coulter, Inc.

  The volume average particle diameter of the resin particles (C) of the present invention is preferably 1 to 10 μm, more preferably 2 to 8 μm, and further preferably 3 to 6 μm. When it is 1 μm or more, handling properties as a powder are improved. When it is 10 μm or less, the resolution of an image when it is used as an electrophotographic toner is improved.

  The ratio of the volume average particle diameter [DV] of the resin particles (C) of the present invention to the number average particle diameter [DN] of the resin particles (C) of the present invention is preferably 1.0 to 1. 5, More preferably, it is 1.0-1.4, Most preferably, it is 1.0-1.3. When it is 1.5 or less, powder characteristics (fluidity, charging uniformity, etc.) and image resolution are remarkably improved.

From the viewpoint of particle size uniformity, powder flowability, storage stability, and the like, the resin particles (C) of the present invention comprise 5% or more of the surface of the resin particles (B) as fine particles (A) or (A It is preferably covered with a film containing the resin (a) derived from), more preferably 30% or more. 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 (%) = 100 × [surface area of (B) of the portion covered with the film derived from (A) or (A)] / [covered with the film derived from (A) or (A) (B) surface area of the portion + area of the portion where the surface of (B) is exposed]

In the resin particles (C) of the present invention, the weight ratio of the resin (a) constituting the fine particles (A) and the resin (b) constituting the resin particles (B) is preferably (0.1: 99.9). It is-(30:70), More preferably, it is (0.2: 99.8)-(20:80). It is preferable that the weight ratio of the resin (a) and the resin (b) is within this range because both low-temperature meltability and long-term storage stability are compatible.
When the resin (a) is a crystalline resin (a1), the weight ratio of the crystalline resin (a1) in the resin particles (C) of the present invention is the endothermic peak inherent to (a1) by a known method such as DSC. It can be measured by a method of calculating from the endothermic amount.

Examples of the method for producing the resin particles (C) of the present invention include the following (1) to (3).
The resin particles may be described as liquid or supercritical carbon dioxide (X) [hereinafter referred to as carbon dioxide (X). ], It is preferable that it is the following manufacturing methods (1).
Manufacturing Method (1) [Second Invention]
A dispersion in which fine particles (A) containing the resin (a) are dispersed in carbon dioxide (X) and a solvent (S) solution (L) of the resin (b) are mixed, and the (X) of (A) ) By dispersing (L) in the dispersion, resin particles (C) in which the fine particles (A) are fixed to the surface of the resin particles (B) containing the resin (b) and the solvent (S) are formed. Then, the production method for obtaining resin particles by removing carbon dioxide (X) and solvent (S).

Moreover, when manufacturing a resin particle in a non-aqueous organic solvent (N), it is preferable that it is the following manufacturing methods (2).
Manufacturing Method (2) [Third Invention]
A non-aqueous dispersion in which fine particles (A) containing a resin (a) are dispersed in a non-aqueous organic solvent (N) and a solvent (S) solution (L) of the resin (b) are mixed, and (A Resin particles (C) in which fine particles (A) are fixed to the surface of resin particles (B) containing resin (b) and solvent (S) by dispersing (L) in a non-aqueous dispersion of And then removing the nonaqueous organic solvent (N) and the solvent (S) to obtain resin particles.

Moreover, when manufacturing a resin particle in an aqueous medium, it is preferable that it is the following manufacturing methods (3).
Manufacturing Method (3) [Fourth Invention]
The aqueous dispersion in which the fine particles (A) containing the resin (a) are dispersed in an aqueous medium and the solvent (S) solution (L) of the resin (b) are mixed, and the aqueous dispersion of (A) The resin particles (C) in which the fine particles (A) are fixed to the surfaces of the resin particles (B) containing the resin (b) and the solvent (S) are formed by dispersing (L) in And a method for producing resin particles by removing the solvent (S).

The production method (1) [second invention] will be described in detail.
As the fine particles (A) used in the production method of the second invention, the fine particles (A) described above can be used. The same applies to the manufacturing methods (2) and (3).

The fine particles (A) used in the production method of the second invention have a swelling degree (hereinafter referred to as swelling degree) of carbon dioxide (X) of 16% at a glass transition temperature (Tg) or a temperature lower than the melting point. The following fine particles are preferable, more preferably 10% or less, and particularly preferably 5% or less. When the fine particles (A) having a swelling degree of 16% or less are used, the particle size distribution of the resin particles becomes narrow.
A method for measuring the degree of swelling can be measured using a magnetic suspension balance. The details of the method for measuring the degree of swelling are described in J. Org. Supercritical Fluids. 19, 187-198 (2001).
When the degree of swelling of the fine particles (A) by carbon dioxide (X) is 16% or less, the reason why the resin particles having a sufficiently narrow particle size distribution can be obtained is that the fine particles (A) can suppress aggregation of the resin particles. is there.

The crystallinity of the crystalline resin (a1) used in the production method of the second invention is preferably 20 to 95% from the viewpoint of suppression of swelling by carbon dioxide (X) and adsorptivity to the resin particles (B). More preferably, it is 30 to 90%. The degree of crystallinity is obtained by calculating the heat of fusion (ΔHm (J / g)) from the area of the endothermic peak using DSC, and calculating the degree of crystallinity (%) by the following formula based on the measured ΔHm.
Crystallinity = (ΔHm / a) × 100
In the above formula, a is the heat of fusion when extrapolated so that the degree of crystallinity is 100%.

  In the second invention, any method may be used to disperse the fine particles (A) in carbon dioxide (X). For example, (A) and (X) are charged in a container, and stirring, ultrasonic irradiation, etc. Examples thereof include a method of directly dispersing (A) in (X) and a method of introducing a dispersion liquid in which fine particles (A) are dispersed in a solvent (S) into (X).

  The weight ratio of the fine particles (A) to the weight of carbon dioxide (X) is preferably 50% or less, more preferably 30% or less, and particularly preferably 0.1 to 20%. If it is this range, a resin particle (C) can be manufactured efficiently.

  Examples of the solvent (S) used for the dispersion of the fine particles (A) include the same solvents (S) as those used for the solution (L) of the resin (b) described later. In view of the dispersibility of the fine particles (A), an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.) and an ester solvent (ethyl acetate, butyl acetate, etc.) are preferable.

  The weight ratio between the fine particles (A) and the solvent (S) is not particularly limited, but the fine particles (A) are preferably 50% or less, more preferably 30% or less, particularly preferably with respect to the solvent (S). Is 1-20%. Within this range, the fine particles (A) can be efficiently introduced into (X).

  The method for dispersing the fine particles (A) in the solvent (S) is not particularly limited, but the fine particles (A) are charged into the solvent (S) and directly dispersed by stirring, ultrasonic irradiation, or the like. And crystallization by dissolving in a solvent (S).

  In this manner, a dispersion (X0) in which the fine particles (A) are dispersed in carbon dioxide (X) is obtained. As the fine particles (A), those having a swelling degree in the above-described range and not stably dissolved in (X) but stably dispersed in (X) are preferable.

  Insoluble content of resin (b) with respect to solvent (S) in an equal weight mixture of resin (b) and solvent (S) used in solution (L) of (b) in the standard state (23 ° C., 0.1 MPa) Is preferably 20% or less, more preferably 15% or less, based on the weight of the resin (b). If the insoluble matter weight is 20% or less, the particle size distribution of the obtained resin particles (C) becomes narrow.

Moreover, 9-16 are preferable and, as for the solubility parameter (SP value) of the said solvent (S), More preferably, it is 10-15. The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume, as shown below.
SP = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

Examples of the solvent (S) for dissolving the resin (b) in the production method (1) include ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether). , Cyclic ethers, etc.), ester solvents (acetic acid esters, pyruvate esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohol solvents (methanol, ethanol, isopropanol, fluorine-containing alcohols, etc.) , Aromatic hydrocarbon solvents (toluene, xylene, etc.), and aliphatic hydrocarbon solvents (octane, decane, etc.). A mixed solvent of two or more of these solvents, or a mixed solvent of these organic solvents and water can also be used.
Preferably, from the viewpoint of easy particle formation, a mixed solvent (particularly, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, and a mixed solvent of acetone and water) is used. is there.

  The solution (L) of the resin (b) is produced by dissolving the resin (b) in the solvent (S). The concentration of the resin (b) with respect to the weight of the solution (L) is preferably 10 to 90%, more preferably 20 to 80%.

  Since the solution (L) of the resin (b) is dispersed in (X), it preferably has an appropriate viscosity. From the viewpoint of particle size distribution, it is preferably 100 Pa · s or less, more preferably 10 Pa at 25 ° C. -S or less. The solubility of the resin (b) in (X) is preferably 3% or less, more preferably 1% or less.

  In the dispersion step of dispersing the resin (b) solution (L) in the production method (1) in carbon dioxide (X), the following dispersion stabilizer (E) can be used. The dispersion stabilizer (E) is a compound having at least one of a dimethylsiloxane group and a functional group containing fluorine. Furthermore, it is preferable to have a chemical structure having affinity for the resin (b) together with a dimethylsiloxane group and a fluorine-containing group having affinity for carbon dioxide.

For example, when the resin (b) is a vinyl resin, the dispersion stabilizer (E) is preferably a vinyl resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
As the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group, methacryl-modified silicone is preferable and has a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) aSi (CH ₃ ) ₂ R
However, a is an average value of 15-45, and R is an organic modification group containing a methacryl group. An example of R includes —C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ .

  Specific examples of the fluorine-containing monomer (M1-2) include perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE); perfluoro (alkyl vinyl ether) ) (PFAVE), perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3-dioxole) (PFDD), perfluoro- (2-methylene-4-methyl-1,3- Peroxo vinyl ethers such as dioxolane) (MMD), perfluorobutenyl vinyl ether (PFBVE); vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3, 3, 3-trifluoro-2-to Hydrogen-containing fluoroolefins such as fluoromethylpropene, 3,3,3-trifluoropropene, perfluoro (butyl) ethylene (PFBE); 1,1-dihydroperfluorooctyl acrylate (DPFOA), 1,1-dihydroper Fluorooctyl methacrylate (DPFOMA), 2- (perfluorooctyl) ethyl acrylate (PFOEA), 2- (perfluorooctyl) ethyl methacrylate (PFOEMA), 2- (perfluorohexyl) ethyl methacrylate (PFHEMA), 2- (Per Polyfluoroalkyl (meth) acrylates such as fluorobutyl) ethyl methacrylate (PFBEMA); α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene α, β, β-trifluorostyrene, α-trifluoromethylstyrene, 2,4,6-trifluoro (trifluoromethyl) styrene, 2,3,4,5,6-pentafluorostyrene, 2,3,4 , 5,6-pentafluoro-α-methylstyrene, 2,3,4,5,6-pentafluoro-β-methylstyrene and the like.

When the resin (b) is a urethane resin, the dispersion stabilizer (E) is preferably a urethane resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
(M1-1) is preferably a polysiloxane having a functional group containing active hydrogen, such as amino-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, or mercapto-modified silicone. (M1-2) includes 2,2-bis (4-hydroxyphenyl) hexafluoropropane, fluorine-containing group polyols such as 3,3,4,4-tetrafluoro-1,6-hexanediol, fluorine-containing groups ( Fluorine compound having a functional group containing active hydrogen such as poly) amine, fluorine-containing group (poly) thiol, bis (isocyanatomethyl) perfluoropropane, bis (isocyanatomethyl) perfluorobutane, bis (isocyanatomethyl) Fluorine-containing (poly) isocyanates such as perfluoropentane and bis (isocyanatomethyl) perfluorohexane are preferred.

  When the resin (b) has an acid value, the dispersion stabilizer (E) preferably has an amino group from the viewpoint of dispersibility. The acid value of the resin (b) is preferably 1 to 50, more preferably 3 to 40, and most preferably 5 to 30. The amino group may be primary, secondary, or tertiary, and is introduced at any position on the side chain, one end, both ends, or both ends of the side chain of a compound containing a fluorine-containing group or a dimethylsiloxane group. May be used.

  As the dispersion stabilizer (E), for example, a monomer (or reactive oligomer) having a dimethylsiloxane group (M1-1) and / or a monomer (M1-2) containing fluorine, and the resin (b) described above are used. A copolymer with a constituting monomer (for example, a copolymer of methacryl-modified silicone and methyl methacrylate, a copolymer of heptafluorobutyl methacrylate and methyl methacrylate, or the like) is preferable. The form of copolymerization may be random, block or graft, but block or graft is preferred.

  When the resin (b) has an acid value, the fine particles (A) preferably have an amino group on the particle surface from the viewpoint of dispersion stability. The amino group may be primary, secondary, or tertiary, and the form in which the amino group is incorporated is not particularly limited. For example, a compound having an amino group is contained in the fine particles (A) by a method such as dispersion or impregnation. A method of using a compound having an amino group as a component constituting the fine particles (A), a method of reacting an amino group-containing coupling agent on the surface of the fine particles (A), an amino group-containing compound on the surfaces of the fine particles (A) And the like.

The addition amount of the dispersion stabilizer (E) is preferably from 0.01 to 50%, more preferably from 0.02 to 40%, particularly preferably from 0.02% to the weight of the resin (b) from the viewpoint of dispersion stability. 03 to 30%. The preferable Mw range of the dispersion stabilizer (E) is 100 to 100,000, more preferably 200 to 50,000, and particularly preferably 500 to 30,000. Within this range, the dispersion stabilizing effect of (E) is improved.
In addition, also in a manufacturing method (2), a dispersion stabilizer (E) can be used at a dispersion | distribution process.

  In the present invention, other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers) in the resin particles (B) containing the resin (b) and the solvent (S) , Antioxidants, anti-blocking agents, heat stabilizers, flame retardants, etc.). As a method of incorporating other additives into the resin particles (B), the resin (b) or the solvent (S) solution (L) of (b) and the additive are mixed in advance, It is preferable to add and disperse the mixture.

  In the second invention, any method may be used for dispersing the solution (L) of the resin (b) in the dispersion (X0) in which the fine particles (A) are dispersed in carbon dioxide (X). Good. Specific examples include a method of dispersing the solution (L) of the resin (b) in the dispersion (X0) with a stirrer or a disperser, and the solution (L) of the resin (b) in (X) (A ) Is dispersed in a dispersion (X0) in which particles are dispersed through a spray nozzle to form droplets, the resin in the droplets is supersaturated, and resin particles are precipitated (ASES: Aerosol Solvent Extraction System). The solution (L) and dispersion (X0) are simultaneously ejected from a separate tube together with a high pressure gas, an entrainer, etc. from a coaxial multiple tube (double tube, triple tube, etc.) A method of obtaining particles by applying external stress to the droplets to promote fragmentation (known as SEDS: Solution Enhanced Dispersion by Supercritical Fluids) And a method of irradiating ultrasonic waves.

In this manner, the solvent (S) solution (L) of the resin (b) is dispersed in the dispersion (X0) in which (A) is dispersed in carbon dioxide (X), and the fine particles (A) are dispersed on the surface. Resin particles (C) in which fine particles (A) are fixed to the surface of resin particles (B) containing resin (b) and solvent (S) by growing the dispersed resin (b) particles while adsorbing them. Form. A dispersion in which (C) is dispersed in (X) is referred to as dispersion (X1).
The dispersion (X1) is preferably a single phase. That is, it is not preferable that the solvent (S) phase is separated in addition to the phase containing carbon dioxide (X) in which (C) is dispersed. Therefore, it is preferable to set the amount of the solution (L) of (b) with respect to the dispersion (X0) so that the solvent phase is not separated. For example, 90% or less is preferable with respect to (X0), more preferably 5 to 80%, and particularly preferably 10 to 70%.
The amount of (S) contained in the resin particles (B) containing the resin (b) and the solvent (S) after the formation of the dispersion (X1) is preferably 10 to 90%, more preferably 20 ~ 70%.
The weight ratio of the resin (b) to carbon dioxide (X) is preferably (b) :( X) is 1: (0.1-100), more preferably 1: (0.5-50). Especially preferably, it is 1: (1-20).

  In the present invention, liquid carbon dioxide refers to the triple point of carbon dioxide (temperature = −57 ° C., pressure = 0.5 MPa) and the criticality of carbon dioxide on the phase diagram represented by the temperature axis and pressure axis of carbon dioxide. It represents carbon dioxide, which is the temperature / pressure condition of the part surrounded by the gas-liquid boundary line passing through the point (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line, and is supercritical The carbon dioxide in the state represents carbon dioxide which is a temperature / pressure condition higher than the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

  In the production method (1) of the second invention, the operation performed in carbon dioxide (X) is preferably performed at the temperature described below. That is, in order to prevent carbon dioxide from undergoing a phase transition in the pipe during decompression to block the flow path, the temperature is preferably 30 ° C. or higher, and fine particles (A), resin particles (B), resin particles (C ) Is preferably 200 ° C. or lower. Furthermore, 30-150 degreeC is preferable, More preferably, it is 34-130 degreeC, Especially preferably, it is 35-100 degreeC, Most preferably, it is 40-80 degreeC. The same applies to the temperature of the dispersion (X0) and the dispersion (X1). In the production method of the second invention, the operation carried out in carbon dioxide (X) can be carried out at a temperature above or below the Tg or melting point of the fine particles (A), but at a temperature below the Tg or melting point. It is preferable.

  In the production method of the second invention, the operation performed in carbon dioxide (X) is preferably performed at the pressure described below. That is, in order to satisfactorily disperse the resin particles (C) in (X), the pressure is preferably 7 MPa or more, and preferably 40 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 7.5-35 MPa, More preferably, it is 8-30 MPa, Most preferably, it is 8.5-25 MPa, Most preferably, it is 9-20 MPa. The same applies to the pressure in the container forming the dispersion (X0) and the dispersion (X1).

  In the production method of the second invention, the temperature and pressure of the operation performed in carbon dioxide (X) are such that the resin (b) does not dissolve in (X) and (b) can be aggregated and united. It is preferable to set within. Usually, the target dispersion tends to not dissolve in (X) at lower temperatures and lower pressures, and (b) tends to aggregate and coalesce at higher temperatures and pressures. The same applies to the dispersion (X0) and the dispersion (X1).

In the carbon dioxide (X) in the second invention, other substances (e) are appropriately contained in order to adjust physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. Examples thereof include inert gases such as nitrogen, helium, argon, and air.
The weight fraction of carbon dioxide (X) in the total of carbon dioxide (X) and the other substance (e) is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

  When the fine particles (A) contain the crystalline resin (a1), after forming the resin particles (C), if necessary, as a further step, the crystalline resin (a1) preferably has a melting point minus 50. The fine particles (A) adhering to the surface of the resin particles (B) are melted by heating to a temperature equal to or higher than 0 ° C., more preferably a melting point minus 10 ° C. or higher, and more preferably higher than the melting point. A step of fixing the surface of (B) or forming a film derived from the fine particles (A) to form the resin particles (C ′) can also be performed. From the viewpoint of suppressing the aggregation of (C ′), the heating time is preferably 0.01 to 1 hour, more preferably 0.05 to 0.7 hour.

In the resin particles (C) of the present invention obtained by the production method of the second invention, the fine particles (A) are once fixed on the surface of the resin particles (B), but the composition of the resin (a) and the resin (b) Depending on the type of solvent (S), fine particles (A) are formed into a film during the manufacturing process, and a film containing resin (a) in which (A) is formed on the surface of (B) is formed. May be. The same applies to the manufacturing methods of the third and fourth inventions described later.
The finally obtained resin particles (C) of the present invention are those in which fine particles (A) are fixed on the surface of the resin particles (B), those in which a film derived from (A) is formed, Any part of the film may be used.
In addition, the surface state and shape of the resin particle (C) of the present invention can be observed by, for example, a photograph obtained by enlarging the surface of the resin particle 10,000 times or 30,000 times using a scanning electron microscope (SEM).

  From the dispersion (X1) in which the resin particles (C) are dispersed, the carbon dioxide (X) and the solvent (S) are usually removed under reduced pressure to obtain the resin particles (C) of the present invention. At that time, the pressure may be reduced stepwise by providing independent pressure-controlled containers in multiple stages, or may be reduced to normal temperature and normal pressure at a stretch. The method of collecting the obtained resin particles is not particularly limited, and examples thereof include a method of filtering with a filter and a method of centrifuging with a cyclone or the like. The resin particles may be collected after depressurization, or once collected under high pressure before depressurization, and then depressurized. As a method of taking out resin particles from high pressure when collecting under high pressure and then depressurizing, the collection container may be depressurized by batch operation, and continuous extraction operation is performed using a rotary valve. May be.

  After the formation of the resin particles (C) (including the case of the resin particles (C ′)), it is preferable to perform a step of removing or reducing the solvent (S) before the above-described removal step by reduced pressure. That is, when (C) contains the solvent (S) in the dispersion (X1) dispersed in (X), if the container is decompressed as it is, the solvent dissolved in (X1) condenses and resin particles In some cases, the resin particles (C) may be re-dissolved, or the resin particles (C) may be joined together when the resin particles (C) are collected. As a method for removing or reducing the solvent, for example, a dispersion (X1) containing resin particles (C) obtained by dispersing the solvent (S) solution (L) of the resin (b) in (X). ) And carbon dioxide (X) are further mixed to extract the solvent (S) from the resin particles (C) into the phase of carbon dioxide (X). Next, the solvent (S) -containing (X) is removed from the solvent (S). It is preferable to replace with (X) not containing S) and then reduce the pressure.

  In the mixing method of the dispersion (X1) in which the resin particles (C) are dispersed in carbon dioxide (X) and (X), (X) having a pressure higher than (X1) may be applied, and (X1) May be added to (X) at a lower pressure than (X1), but the latter is more preferable from the viewpoint of ease of continuous operation. The amount of (X) mixed with (X1) is preferably 1 to 50 times the volume of (X1), more preferably 1 to 40 times, and most preferably from the viewpoint of preventing coalescence of the resin particles (C). 1 to 30 times. By removing or reducing the solvent contained in the resin particles (C) as described above, and then removing (X), it is possible to prevent the resin particles (C) from being combined.

  As a method of replacing carbon dioxide (X) containing solvent (S) with (X) not containing solvent (S), the resin particles (C) are once supplemented with a filter or cyclone, and then the solvent is maintained while maintaining the pressure. A method of circulating carbon dioxide (X) until (S) is completely removed can be mentioned. The amount of (X) to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, most preferably 1 to 1 times the volume of (X1) from the viewpoint of solvent removal from the dispersion (X1). 30 times.

The production method (2) [third invention] will be described in detail.
The non-aqueous organic solvent (N) used in the third invention is preferably an organic solvent having a solubility of the resin (b) of 1% or less in the solvent (S). If the solubility of the resin (b) is 1% or less, it is preferable that the resin particles (C) are difficult to unite with each other. The solubility of the resin (b) in the non-aqueous organic solvent (N) is determined from the non-aqueous dispersion containing the insoluble component (b) in which (b) is dissolved in (N) until saturation is reached. The weight of the supernatant obtained by sedimentation of the dissolved component by centrifugation, and the weight of the residue after drying at the boiling point of the non-aqueous organic solvent (N) with a vacuum dryer is taken as the value.
Specifically, it is calculated by the following procedure.
The non-aqueous dispersion (25 ° C.) is centrifuged at 3000 rpm for 10 minutes, and about 2 g (wg) of the supernatant is collected in an aluminum container. Further, the supernatant is dried with a vacuum dryer under a reduced pressure of 20 mmHg for 1 hour under the temperature condition of the boiling point of the non-aqueous organic solvent (N), and the weight of the residue is weighed. If the weight of the residue at this time is Wg, the solubility of the resin (b) in the non-aqueous organic solvent (N) can be calculated by W / w × 100 [%].
Specifically, the non-aqueous organic solvent (N) is preferably a hydrocarbon solvent (hexane, octane, decane, dodecane, isododecane, liquid paraffin, etc.) and silicone oil.

  In the third invention, any method may be used to disperse the fine particles (A) in the non-aqueous organic solvent (N). For example, (A) and (N) are charged in a container, stirred, sprayed, ultrasonic Examples thereof include a method in which (A) is directly dispersed in (N) by irradiation and a method in which the solvent dispersion in (A) is introduced into (N). The fine particles (A) are preferably those that do not dissolve in (N) and are stably dispersed in (N).

The solubility parameter (SP value) of the solvent (S) for dissolving the resin (b) used in the third invention is preferably in the range of 9.5 to 20, and more preferably 10 to 19. When the SP value of the organic solvent (S1) is within this range, when the solvent (S) solution (L) of the resin (b) is dispersed in the non-aqueous organic solvent (N), (S) is (N) It is preferable that the particle size distribution of the resin particles (C) is not widened without being extracted.
When a mixed solvent is used as the solvent (S), the SP value is assumed to satisfy the additivity rule, and the average value calculated from the SP value of each solvent is preferably within the above range.

  As the solvent (S) used in the third invention, a solvent suitable for the combination with the resin (b) within the above range can be appropriately selected, and aromatic hydrocarbons such as toluene, xylene, ethylbenzene, tetralin and the like. Solvent: Aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene Halogen solvents such as: ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. ester or ester ether solvents; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol Ether solvents such as monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t- Alcohol solvents such as butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and these Two or more types of mixed solvents are mentioned.

  For example, when a polyester resin, a polyurethane resin, or an epoxy resin is selected as the resin (b), preferable solvents (S) include acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent of two or more of these. be able to.

  Any method may be used for preparing the solution (L) by dissolving the resin (b) in the solvent (S). For example, the resin (b) is added to the solvent (S). And a stirring method and a heating method.

The content of the resin (b) in the solution (L) is preferably 10 to 90%, more preferably 20 to 80%.
Since the solvent (S) solution (L) of the resin (b) is dispersed in (N), it is preferable to have an appropriate viscosity. From the viewpoint of particle size distribution, preferably at 25 ° C., preferably 100 Pa · s or less, More preferably, it is 10 Pa · s or less.

  Manufacturing method of the third invention [the same applies to the manufacturing method of the fourth invention described later. In the solvent (S) solution (L) of the resin (b), other additives (coloring agent, mold release agent, charge control agent, antioxidant, anti-blocking agent, heat stabilizer, fluidizing agent) Etc.) and other additives can be contained in the resulting resin particles (C).

  In the production method of the third invention, the non-aqueous dispersion in which the fine particles (A) are dispersed in the non-aqueous organic solvent (N) and the solvent (S) solution (L) of the resin (b) are mixed. By dispersing (L) in the non-aqueous dispersion of (A) and forming resin particles (B) containing (b) and (S) in the non-aqueous dispersion of (A) A non-aqueous dispersion of resin particles (C) having a structure in which the fine particles (A) are fixed to the surfaces of the resin particles (B) is obtained.

  The use amount of the non-aqueous dispersion of fine particles (A) with respect to 100 parts by weight of the resin (b) is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (b) is good, and if it is 2,000 parts by weight or less, it is economical.

When dispersing the solvent (S) solution (L) of the resin (b) in the non-aqueous dispersion of the fine particles (A), a dispersing device can be used.
The dispersion apparatus used in the production method of the third invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. Is mentioned.

As a method of removing the solvent (S) and the non-aqueous organic solvent (N) from the non-aqueous dispersion of the resin particles (C) and (C) to obtain the resin particles (C),
[1] A method of drying the solvent (S) and the non-aqueous organic solvent (N) 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] A method in which the solvent (S) and the non-aqueous organic solvent (N) are frozen and dried (so-called lyophilization),
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify using an air classifier etc. as needed, and can also be made into a predetermined particle size distribution.
During the manufacturing process such as the solvent removal process, the fine particles (A) are formed into a film, and a film containing the resin (a) in which the (A) is formed into a film is formed on the surface of the resin particles (C). There is a case.

  According to the production methods (1) and (2) of the second and third inventions, it is possible to produce the resin particles (C) of the invention substantially free of a surfactant having a hydrophilic group. . Here, the surfactant having a hydrophilic group is an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), a nonionic surfactant ( s-4). Examples of the anionic surfactant (s-1) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates and phosphate esters. Examples of the cationic surfactant (s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of the amphoteric surfactant (s-3) include a carboxylate amphoteric surfactant, a sulfate ester amphoteric surfactant, a sulfonate amphoteric surfactant, and a phosphate ester amphoteric surfactant. Can be mentioned. Examples of the nonionic surfactant (s-4) include an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant.

  Specific examples of these surfactants include those described in International Publication WO 03/106541. Usually, resin particles produced using a surfactant having a hydrophilic group in an aqueous solvent substantially contain a surfactant having a hydrophilic group.

As a method for analyzing that the resin particles do not substantially contain a surfactant having a hydrophilic group, a known surface wettability evaluation (Color Material Association, No. 73 [3], 2000, P132 to 138). ). The surface wettability evaluation method is as follows.
That is, 0.1 g of resin particles are put into a 100 ml beaker, 20 ml of ion-exchanged water is added thereto, the mixture is stirred with a magnetic stirrer, and the resin particles are floated on the liquid surface. The weight of acetone (Wa) and the weight of water (Ww) are eliminated with three significant figures, and the solubility parameter (δm) on the surface of the resin particles is calculated from the equation (1).
δm = (9.75 × Wa + 23.43 × Ww) / (Wa + Ww) (1)

  If the solubility parameter (δm) on the surface of the resin particle is 9.8 to 21, preferably 9.8 to 20, it is judged that the resin particle does not substantially contain a surfactant having a hydrophilic group. . When δm is 9.8 to 21, the moisture resistance storage resistance of the resin particles is good. This measurement method cannot measure less than 9.8.

The production method (3) [fourth invention] will be described in detail.
In the fourth invention, the aqueous medium constituting the aqueous dispersion in which the fine particles (A) are dispersed contains, in addition to water, an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) in the solvent (S). May be. In this case, the organic solvent contained does not cause aggregation of the fine particles (A) and the resin particles (B), does not dissolve (A) and (B), and prevents granulation of the resin particles (C). As long as there is no problem, any kind and any content may be used, but the resin particles after drying (C) using 40% or less of the total amount of water and organic solvent Those which do not remain in are preferred.

Although it does not specifically limit as a method of producing the aqueous dispersion of microparticles | fine-particles (A), The following [1]-[8] are mentioned.
[1] In the case of vinyl resin, an aqueous dispersion of fine particles (A) is directly produced by a polymerization reaction such as suspension polymerization, emulsion polymerization, seed polymerization or dispersion polymerization using a monomer as a starting material. Method.
[2] In the case of a polyaddition or condensation resin such as a polyester resin, a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant if necessary, and then A method of producing an aqueous dispersion of fine particles (A) by curing the precursor by heating to a temperature or adding a curing agent.
[3] In the case of a polyaddition or condensation resin such as a polyester resin, a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof (preferably a liquid, which may be liquefied by heating) is necessary. A method of producing an aqueous dispersion of fine particles (A) by dissolving an appropriate emulsifier, adding water to effect phase inversion emulsification, and adding a curing agent to cure the precursor.
[4] A resin previously prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same applies to the polymerization reaction in the following section). A method in which resin particles are obtained by pulverization using a fine pulverizer such as a mechanical rotary type or a jet type and then classified, and then dispersed in an aqueous medium in the presence of an appropriate dispersant.
[5] After obtaining resin particles by spraying a resin solution in which a resin prepared by a polymerization reaction is dissolved in an organic solvent in the form of a mist, the resin particles are dispersed in an aqueous medium in the presence of an appropriate dispersant. Method.
[6] The resin particles are precipitated by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent, or by cooling a resin solution previously heated and dissolved in an organic solvent. A method of removing resin and obtaining resin particles, and then dispersing the resin particles in an aqueous medium in the presence of an appropriate dispersant.
[7] A method in which a resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the organic solvent is removed by heating or decompression.
[8] A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, and then water is added to perform phase inversion emulsification.

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant, water-soluble polymer, or the like can be used. Moreover, a solvent (C), a plasticizer, etc. can be used together as an auxiliary agent for emulsification or dispersion. Specific examples thereof include those described in JP-A-2002-284881. Moreover, as an organic solvent, the thing similar to a solvent (S) is mentioned.

  In the production method of the fourth invention, the solvent (S) used in the solvent (S) solution (L) of the resin (b) is preferably one having a high affinity with (b). From the viewpoint of film formation, tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate are preferable, and ethyl acetate is more preferable.

  In the production method of the fourth invention, the aqueous dispersion in which the fine particles (A) are dispersed in an aqueous medium and the solvent (S) solution (L) of the resin (b) are mixed, and the aqueous solution of (A) is mixed. By dispersing (L) in the dispersion, the resin particles (B) containing the resin (b) and the solvent (S) are formed in the aqueous dispersion of (A). An aqueous dispersion of resin particles (C) having a structure in which (A) is fixed to the surface can be obtained.

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

  When the solvent (S) solution (L) of the resin (b) is dispersed in the aqueous dispersion (A), a dispersing device can be used. Examples of the dispersing device include those described above.

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

The resin particle (C) of the present invention changes the particle size of the fine particles (A) and the resin particles (B) and the coverage of the surface of the resin particles (B) with the coating derived from the fine particles (A) or (A). Thus, desired irregularities can be imparted to the particle surface. Furthermore, by controlling the temperature and pressure during decompression, a porous body having bubbles inside can be obtained, and the specific surface area can be increased. When it is desired to improve the powder fluidity, the resin particles preferably have a BET specific surface area of 0.5 to 5.0 m ² / g. The BET specific surface area is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement 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 the resin particles (C) of the present invention 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 resin particles (C) of the present invention obtained by the production method of the present invention have a sharp particle size distribution and, in the case of the second and third inventions, usually do not contain a water-soluble surfactant or ionic substance. Is hydrophobic. Accordingly, the resin particle (C) of the present invention is a matrix particle for electrophotographic toner, an additive for coating, an additive for adhesive, an additive for cosmetics, an additive for paper coating, a resin for slush molding, a powder coating, an electronic Spacer for parts production, catalyst carrier, base particle for electrostatic recording toner, base particle for electrostatic printing toner, standard particle for electronic measuring instrument, particle for electronic paper, carrier for medical diagnosis, chromatographic filler, electrorheological fluid It is useful as a particle for use.
In the resin particles (C) of the present invention, when the fine particles (A) contain a crystalline resin (a1) having a melting point of 40 to 110 ° C., the effect of being excellent in low-temperature meltability and heat-resistant storage stability. Therefore, it is particularly useful as a base particle for an electrophotographic toner.

  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.

The following swelling degree, crystallinity, number average molecular weight (Mn), melting point, glass transition temperature, and volume average particle diameter were measured by the following methods.
<Measurement method of swelling degree>
A sample (5 mg) was collected, and the weight at which carbon dioxide in a supercritical state at 40 ° C. and 10 MPa permeated into the sample was measured using a magnetic suspension balance (MSB-SCC / SCW Nippon Bell Co., Ltd.). The degree of swelling (%) was determined.
<Measurement method of crystallinity>
A sample (5 mg) was collected and placed in an aluminum pan, and the temperature was increased from room temperature to a temperature increase rate of 20 ° C./min using DSC (differential scanning calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.). The amount of heat of fusion (ΔHm (J / g)) determined from the area of the endothermic peak was determined while changing. Based on the measured ΔHm, the degree of crystallinity (%) was calculated by the following formula.
Crystallinity = (Heat of fusion / a) × 100
In the above formula, a is measured as follows.
Measurement method according to JISK0131 (1996) (X-ray diffraction analysis general rule 13 crystallinity measurement (2) absolute method) by measuring the heat of fusion of a resin having the same composition as the resin to be measured by DSC Measure the crystallinity at When the heat of fusion is plotted on the vertical axis and the crystallinity is plotted on the horizontal axis, the standard data is plotted, and a straight line is drawn from the two points of that point and the origin, and extrapolated so that the crystallinity is 100% The value obtained by calculating the amount of heat of fusion is a.

<Measuring method of number average molecular weight (Mn)>
Each sample was dissolved in tetrahydrofuran at a concentration of 2.5 g / L and measured by GPC using polystyrene as a standard substance.
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: 2 TSKgel GMHXL) + TSKgel Multipore HXL-M (made by Tosoh Corporation)
<Measuring method of melting point>
A sample (5 mg) is collected and placed in an aluminum pan, and the DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII NanoTechnology Co., Ltd.) is used to absorb heat by crystal melting at a heating rate of 10 ° C./min. The peak temperature (° C.) was determined.
<Measuring method of glass transition temperature (Tg)>
5 mg of each sample was weighed, and the glass transition temperature was measured at a heating rate of 10 ° C. per minute by DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.).
<Measurement method of volume average particle diameter>
After 5 mg of the sample was dispersed in 10 g of ion-exchanged water, measurement was performed with Multisizer III (manufactured by Coulter).

Production Example 1 <Preparation of Resin (b-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 831 parts of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 703 parts of terephthalic acid, 47 parts of adipic acid, and tetrabutoxy as a condensation catalyst 0.5 part of titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the water produced. 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 87 ° C. After cooling to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a polyester resin (b-1). Mn of the polyester resin (b-1) was 1900, and the glass transition temperature was 45 ° C.

Production Example 2 <Preparation of Resin (b-2)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts of propylene glycol, 683 parts of terephthalic acid, 67 parts of adipic acid, 38 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate as a condensation catalyst The reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 172 parts. When the softening point reached 160 ° C., it was taken out, cooled to room temperature, pulverized and granulated to obtain a polyester resin (b-2). Mn of the polyester resin (b-2) was 5700, and the glass transition temperature was 63 ° C.

Production Example 3 <Preparation of Resin (b-3)>
24 parts of xylene was charged into an autoclave equipped with a stir bar and a thermometer, and mixed monomer 2 of butyl acrylate / methyl methacrylate / styrene / 2-ethylhexyl acrylate (25% / 33% / 40% / 2%) 1,000 parts and 1 part of a polymerization catalyst azobismethoxydimethylvaleronitrile were dropped at 170 ° C. over 3 hours. Volatilization was performed at normal pressure while raising the temperature to 180 ° C., and when the temperature reached 180 ° C., the pressure was switched to reduced pressure, and devolatilization was performed over 2 hours to obtain a vinyl resin (b-3). The Mn of this resin was 10500, and the glass transition temperature was 62 ° C.

Production Example 4 <Preparation of Resin (b-4)>
A reaction vessel equipped with a stir bar and a thermometer was charged with 44 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 32 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, this reaction solution was put into a solution in which 140 parts of HS2H-500S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, manufactured by Toyokuni Seiyaku Co., Ltd.) was dissolved in 140 parts of MEK, and 4 at 80 ° C. Reacted for hours. Volatilization was performed at normal pressure while raising the temperature to 120 ° C., and when the temperature reached 120 ° C., the pressure was switched to reduced pressure and devolatilization was performed over 2 hours to obtain a polyester / polyurethane composite resin (b-4). This resin had a Mn of 14,000 and a melting point of 62 ° C.

Production Example 5 <Preparation of Resin Solution (L-1)>
In a container equipped with a stirrer, 228 parts of resin (b-1) obtained in Production Example 1 was added to solvent (S-1), which is a mixed solvent consisting of 490 parts of acetone, 175 parts of methanol, and 35 parts of ion-exchanged water. Then, 57 parts of the resin (b-2) obtained in Production Example 2 and 15 parts of carbon black were charged and stirred until the resin (b-1) and the resin (b-2) were completely dissolved. L-1) was obtained. Solvent (S-1) is a resin (b) insoluble matter weight 0.1% or less with respect to the weight of resin (b) in the equal weight mixture of resin (b) and solvent (S-1). ) Was 11.8.

Production Example 6 <Preparation of Resin Solution (L-2)>
In a container equipped with a stirrer, 285 parts of a solvent (S-2), which is a mixed solvent composed of 490 parts of acetone and 210 parts of methanol, 285 parts of the resin (b-3) obtained in Production Example 3, and 15 parts of carbon black Was stirred until the resin (b-3) was completely dissolved to obtain a resin solution (L-2). The solvent (S-2) is a resin (b) insoluble matter weight of 0.1% or less with respect to the weight of the resin (b) in an equal weight mixture of the resin (b) and the solvent (S-2). ) Was 11.3.

Production Example 7 <Preparation of Resin Solution (L-3)>
In a container equipped with a stirrer, a solvent (S-3) which is a mixed solvent composed of 630 parts of acetone and 70 parts of ion-exchanged water, 285 parts of the resin (b-4) obtained in Production Example 4, and carbon black 15 parts were charged and stirred until the resin (b-4) was completely dissolved to obtain a resin solution (L-3). Solvent (S-1) is 0.1% or less by weight of resin (b) insoluble in solvent (S-3) with respect to the weight of resin (b) in an equal weight mixture of resin (b) and solvent (S-3) The SP value of the solvent (S-3) was 10.5.

Production Example 8 <Preparation of Vinyl Monomer Intermediate (d0-1)>
428 parts of 2-hydroxyethyl methacrylate was dropped into 572 parts of TDI and reacted at 55 ° C. for 4 hours to obtain a vinyl monomer intermediate (d0-1).

Production Example 9 <Preparation of Vinyl Monomer Intermediate (d0-2)>
428 parts of 2-hydroxyethyl methacrylate was dropped into 552 parts of HDI and reacted at 80 ° C. for 8 hours to obtain a vinyl monomer intermediate (d0-2).

Production Example 10 <Preparation of Vinyl Monomer Intermediate (d0-3)>
428 parts of 2-hydroxyethyl methacrylate was dropped into 730 parts of IPDI and reacted at 90 ° C. for 8 hours to obtain a vinyl monomer intermediate (d0-3).

Production Example 11 <Preparation of vinyl monomer (d1-1) solution>
480 parts of HS2H-500S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, produced by Toyokuni Oil Co., Ltd.) is dissolved in 500 parts of THF at 70 ° C., and 20 parts of vinyl monomer intermediate (d0-1) is added dropwise. The mixture was reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (d1-1) solution. Mn of (d1-1) was 5000.

Production Example 12 <Preparation of vinyl monomer (d1-2) solution>
490 parts of HS2H-1000S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, manufactured by Toyokuni Oil Co., Ltd.) was dissolved in 500 parts of THF at 70 ° C., and 10 parts of vinyl monomer intermediate (d0-1) was added dropwise. The mixture was reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (d1-2) solution. Mn of (d1-2) was 10,000.

Production Example 13 <Preparation of vinyl monomer (d1-3) solution>
450 parts of NIPPOLAN 4073 (1,6-hexanediol / adipic acid-based crystalline polyester resin, manufactured by Nippon Polyurethane) was dissolved in 500 parts of THF at 70 ° C., and 50 parts of vinyl monomer intermediate (d0-1) was dropped. The mixture was reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (d1-3) solution. Mn of (d1-3) was 2000.

Production Example 14 <Preparation of vinyl monomer (d1-4) solution>
500 parts of PLACCEL FM5 (vinyl monomer having a polycaprolactone chain, manufactured by Daicel) was dissolved in 500 parts of THF at 70 ° C. to obtain a vinyl monomer (d1-4) solution. Mn of (d1-4) was 700.

Production Example 15 <Preparation of vinyl monomer (d1-5) solution>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 473 parts of 1,6-hexanediol, 246 parts of terephthalic acid, 175 parts of isophthalic acid, 213 parts of 2,6-naphthalenedicarboxylic acid, and a condensation catalyst 2 parts of tetrabutoxy titanate were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the water produced. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while distilling off generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and then returned to normal pressure to 180 ° C. After cooling, 17 parts of maleic anhydride was added and reacted for 90 minutes, and then taken out. The recovered water was 126 parts. The taken-out resin was cooled to room temperature and then pulverized to obtain particles. The Mn of this resin was 2000 and the melting point was 100 ° C. 500 parts of this resin was dissolved in 500 parts of THF at 70 ° C. to obtain a vinyl monomer (d1-5) solution.

Production Example 16 <Preparation of vinyl monomer (d1-6) solution>
750 parts of bisphenol A / PO2 molar adduct, 317 parts of isophthalic acid, and 2 parts of tetrabutoxy titanate as a condensation catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, at 180 ° C. under a nitrogen stream. And reacted for 8 hours while distilling off the water produced. Next, while the temperature was gradually raised to 230 ° C., the reaction was carried out for 4 hours while distilling off the water produced under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg, followed by cooling to 180 ° C. and taking out. The recovered water was 69 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a polyester resin. The glass transition temperature of the polyester resin was 55 ° C. 475 parts of this polyester resin was dissolved in 500 parts of THF at 70 ° C., 25 parts of vinyl monomer intermediate (d0-1) was added dropwise and reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (d1-6) solution. Mn of (d1-6) was 4000.

Production Example 17 <Preparation of vinyl monomer (d1-7) solution>
480 parts of HS2H-500S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, manufactured by Toyokuni Oil Co., Ltd.) is dissolved in 500 parts of THF at 70 ° C., and 20 parts of vinyl monomer intermediate (d0-2) is added dropwise. For 8 hours at 90 ° C. to obtain a vinyl monomer (d1-7) solution. Mn of (d1-7) was 5000.

Production Example 18 <Preparation of vinyl monomer (d1-8) solution>
476 parts of HS2H-500S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, manufactured by Toyokuni Oil Co., Ltd.) is dissolved in 500 parts of THF at 70 ° C., and 24 parts of vinyl monomer intermediate (d0-3) is added dropwise. The mixture was reacted at 90 ° C. for 8 hours to obtain a vinyl monomer (d1-8) solution. Mn of (d1-8) was 5000.

Comparative Production Example 1 <Preparation of vinyl monomer (d1′-1) solution>
500 parts of PLACCEL FM2D (vinyl monomer having a polycaprolactone chain, manufactured by Daicel) was dissolved in 500 parts of THF at 70 ° C. to obtain a vinyl monomer (d1′-1) solution. Mn of (d1′-1) was 360.

Production Example 19 <Preparation of Resin (a-1)>
Reaction vessel equipped with stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube [the same applies to the reaction vessel used in the following resin (a) production example. Into a glass beaker, 196 parts of THF and 1.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged in a glass beaker at 20 ° C. The monomer solution was prepared by stirring and mixing at, and charged into the dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state. The resin (a-1) was obtained by removing under reduced pressure. This resin had a crystallinity of 90%, a melting point of 70 ° C., and Mn of 32500.

Production Example 20 <Preparation of Resin (a-2)>
A reaction vessel was charged with 560 parts of a vinyl monomer (d1-1) solution, and 316 parts of THF, 120 parts of maleic acid, and 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were placed in another glass beaker. Charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state. The resin (a-2) was obtained by removing under reduced pressure. The crystallinity of this resin was 70%, the melting point was 65 ° C., and Mn was 7500.

Production Example 21 <Preparation of Resin (a-3)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-1) solution was charged, and in another glass beaker, 316 parts of THF, 60 parts of maleic acid, 60 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-3). This resin had a crystallinity of 70%, a melting point of 65 ° C., and Mn of 7500.

Production Example 22 <Preparation of Resin (a-4)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-2) solution was charged, and in another glass beaker, 316 parts of THF, 60 parts of maleic acid, 60 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-4). The crystallinity of this resin was 80%, the melting point was 69 ° C., and Mn was 15000.

Production Example 23 <Preparation of Resin (a-5)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-3) solution was charged, and in another glass beaker, 316 parts of THF, 60 parts of maleic acid, 60 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. The resin (a-5) was obtained by removing under reduced pressure. This resin had a crystallinity of 50%, a melting point of 54 ° C., and Mn of 3000.

Production Example 24 <Preparation of Resin (a-6)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-4) solution was charged, and in another glass beaker, 316 parts of THF, 60 parts of maleic anhydride, 60 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. The resin (a-6) was obtained by removing under reduced pressure. The crystallinity of this resin was 20%, the melting point was 15 ° C., and Mn was 1000.

Production Example 25 <Preparation of Resin (a-7)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-5) solution was charged, and in another glass beaker, 319 parts of THF, 60 parts of fumaric acid, 60 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), One part of 2,2′-azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-7). The crystallinity of this resin was 70%, the melting point was 100 ° C., and Mn was 5000.

Production Example 26 <Preparation of Resin (a-8)>
In a reaction vessel, 560 parts of a vinyl monomer (d1-1) solution was charged, and in another glass beaker, 316 parts of THF, 120 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 2,2′- 4 parts of azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise over 2 hours at 70 ° C. in a sealed state. Removal under reduced pressure gave Resin (a-8). The crystallinity of this resin was 70%, the melting point was 65 ° C., and Mn was 7500.

Production Example 27 <Preparation of Resin (a-9)>
Into a reaction vessel, 560 parts of a vinyl monomer (d1-1) solution was charged, and in another glass beaker, 316 parts of THF and behenyl acrylate (an acrylate of an alcohol having a straight-chain alkyl group having 22 carbon atoms: Blemmer VA [NOF) (Made by Co., Ltd.)] 120 parts and 4 parts of benzoyl peroxide were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-9). The crystallinity of this resin was 90%, the melting point was 68 ° C., and Mn was 7500.

Production Example 28 <Preparation of Resin (a-10)>
In a reaction vessel, 160 parts of a vinyl monomer (d1-6) solution was charged, and in another glass beaker, 516 parts of THF, 120 parts of styrene, 80 parts of methacrylic acid, 120 parts of butyl acrylate, 2,2′-azobis (2, 4-dimethylvaleronitrile) was charged, and the mixture was stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-10). The crystallinity of this resin was 0%, the glass transition temperature was 55 ° C., and Mn was 7500.

Production Example 29 <Preparation of Resin (a-11)>
Into a reaction vessel, 560 parts of a vinyl monomer (d1-7) solution was charged, and in another glass beaker, 317 parts of THF, 60 parts of maleic acid, 60 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-11). The crystallinity of this resin was 72%, the melting point was 67 ° C., and Mn was 12,500.

Production Example 30 <Preparation of Resin (a-12)>
Into a reaction vessel, 560 parts of a vinyl monomer (d1-8) solution was charged, and in another glass beaker, 320 parts of THF, 60 parts of maleic acid, 60 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 2,2′-azobis (2,4-dimethylvaleronitrile) 0.5 part was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-12). The crystallinity of this resin was 68%, the melting point was 64 ° C., and Mn was 56200.

Production Example 31 <Preparation of Resin (a-13)>
In a reaction vessel, 240 parts of a vinyl monomer (d1-1) solution was charged, and in another glass beaker, 477 parts of THF, 60 parts of maleic acid, 60 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , 160 parts of behenyl acrylate (acrylate of an alcohol having a linear alkyl group with 22 carbon atoms: Bremer VA [manufactured by NOF Corporation)], 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) Was stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave Resin (a-13). This resin had a crystallinity of 64%, a melting point of 60 ° C., and Mn of 16,400.

Production Example 32 <Preparation of Resin (a-14)>
In a reaction vessel, 400 parts of the vinyl monomer (d1-1) solution was charged, and in another glass beaker, 397 parts of THF, 5 parts of maleic acid, 15 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) Then, 180 parts of styrene and 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours from the end of the addition, THF was added at 80 ° C. for 3 hours. The resin (a-14) was obtained by removing under reduced pressure. This resin had a crystallinity of 52%, a melting point of 55 ° C., and Mn of 19,400.

Comparative Production Example 2 <Preparation of Resin (a′-1)>
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene and behenyl acrylate (an acrylate of an alcohol having a linear alkyl group with 22 carbon atoms: Bremer VA [manufactured by NOF Corporation]) 150 parts and 8 parts of AIBN (azobisisobutyronitrile) were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state. The resin (a′-1) was obtained by removing under reduced pressure. The crystallinity of this resin was 90%, the melting point was 65 ° C., and Mn was 10,000.

Comparative Production Example 3 <Preparation of Resin (a′-2)>
A reaction vessel was charged with 560 parts of a vinyl monomer (d1′-1) solution, and 316 parts of THF, 120 parts of maleic acid, 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were placed in another glass beaker. Was stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. over 2 hours in a sealed state. The resin (a′-2) was obtained by removing under reduced pressure. The crystallinity of this resin was 30%, the melting point was 0 ° C., and Mn was 1000.

Production Example 33 <Preparation of Fine Particle (A-1) Dispersion>
After mixing 700 parts of normal hexane and 300 parts of the resin (a-1) obtained in Production Example 19, zirconia beads having a particle diameter of 0.3 mm were used in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). The mixture was pulverized to obtain a milky white fine particle (A-1) dispersion. The volume average particle diameter of the fine particles (A-1) in this dispersion was 0.4 μm, and the degree of swelling was 1%.

Production Example 34 <Preparation of Fine Particle (A-2) Dispersion to Fine Particle (A-13) Dispersion>
In Production Example 33, instead of Resin (a-1), Resins (a-2) to (a-9) and (a-11) to (a-14) obtained in Production Examples 20 to 32 were respectively used. A milky white fine particle (A-2) dispersion to fine particle (A-13) dispersion was obtained in the same manner as in Production Example 33, except that it was used. Tables 1 and 2 show the volume average particle diameter and the degree of swelling of the fine particles (A-2) to (A-13) in this dispersion.

Production Example 35 <Preparation of aqueous dispersion of fine particles (A-14)>
After mixing 700 parts of ion-exchanged water and 300 parts of the resin (a-10) obtained in Production Example 28, zirconia beads having a particle size of 0.3 mm were obtained with a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). The mixture was pulverized to obtain a milky white fine particle (A-14) aqueous dispersion. The volume average particle diameter of the fine particles (A-14) in this dispersion was 0.1 μm, and the degree of swelling was 5%.

Production Example 36 <Preparation of Fine Particle (A-15) Aqueous Dispersion, Fine Particle (A-16) Aqueous Dispersion>
In Production Example 35, instead of Resin (a-10), Resin (a-3) and (a-4) obtained in Production Examples 21 and 22 were used in the same manner as Production Example 35, respectively. Milky white fine particle (A-15) aqueous dispersion and fine particle (A-16) aqueous dispersion were obtained. Table 2 shows the volume average particle diameter and the degree of swelling of the fine particles (A-15) and (A-16) in this dispersion.

Comparative Production Example 4 <Preparation of Fine Particle (A′-1) Dispersion, Fine Particle (A′-2) Dispersion>
In Production Example 33, the same procedure as in Production Example 33 except that instead of the resin (a-1), the resins (a′-1) and (a′-2) obtained in Comparative Production Examples 2 and 3 were used, respectively. As a result, milky white comparative fine particle (A′-1) dispersion and fine particle (A′-2) dispersion were obtained. Table 2 shows the volume average particle diameter and the degree of swelling of the fine particles (A′-1) and (A′-2) in the dispersion.

Example 1
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. The resin solution (L-1) was charged in the resin solution tank T1, and the fine particle (A-1) dispersion was charged in the fine particle dispersion tank T2. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 9 MPa and 40 ° C., and the fine particle (A-1) dispersion was introduced from the tank T2 and the pump P2. Next, the resin solution (L-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1 while stirring the inside of the dispersion tank T3 at 2000 rpm. After the introduction, the pressure inside T3 was 14 MPa.

The weight ratio of the composition charged into the dispersion tank T3 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts The weight of carbon dioxide introduced was determined from the temperature of carbon dioxide (40 ° C) and the pressure (15 MPa). The density was calculated from the equation of state described in the following document (1), and was calculated by multiplying this by the volume of the dispersion tank T3.
Literature (1): Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

  After introducing the resin solution (L-1), the mixture was stirred for 1 minute to obtain a dispersion (X1). After opening the valve V1 and introducing carbon dioxide into T4 from P3, the dispersion (X1) was introduced into T4, and the opening degree of V2 was adjusted so that the pressure was kept constant during this time. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin solution introduced into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the fine particles (A-1) were fixed to the surface of the resin particles (B-1) formed from the resin solution (L-1), and resin particles (C-1) were generated. Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5 by holding the pressure at 14 MPa by the pressure adjusting valve V2 while introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4. At the same time, the resin particles (C-1) were captured by the filter F1. The operation of introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4 is to introduce carbon dioxide when 5 times the weight of carbon dioxide introduced into the dispersion tank T3 is introduced into the particle recovery tank T4. Stopped. At the time of this stop, the operation of replacing carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (C-1) in the filter F1 was completed. Furthermore, the pressure regulating valve V2 is opened little by little, the inside of the particle recovery tank is reduced to atmospheric pressure, and the resin particle (B) -derived film formed on the surface of the resin particle (B) supplemented by the filter F1. (C-1) was obtained.

Example 2
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-2) dispersion was used in the same manner as in Example 1 except that the fine particles (A ) -Derived resin particles (C-2) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 2 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-2) dispersion 45 parts Carbon dioxide 550 parts

Example 3
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-3) dispersion was used in the same manner as in Example 1, except that the fine particles (A ) -Derived resin particles (C-3) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 3 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-3) dispersion 45 parts Carbon dioxide 550 parts

Example 4
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-4) dispersion was used in the same manner as in Example 1 except that the fine particles (A ) Was fixed to obtain resin particles (C-4). The weight ratio of the composition charged into the dispersion tank T3 in Example 4 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-4) dispersion 45 parts Carbon dioxide 550 parts

Example 5
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-5) dispersion was used in the same manner as in Example 1 except that the fine particle (A-5) dispersion was used on the surface of the resin particle (B). ) -Derived resin particles (C-5) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 5 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-5) dispersion 45 parts Carbon dioxide 550 parts

Example 6
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-6) dispersion was used in the same manner as in Example 1 except that the fine particle (A-6) dispersion was used on the surface of the resin particle (B). ) -Derived resin particles (C-6) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 6 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-6) dispersion 45 parts Carbon dioxide 550 parts

Example 7
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-7) dispersion was used in the same manner as in Example 1 except that the fine particle (A-7) dispersion was used on the surface of the resin particle (B). ) Was fixed to obtain resin particles (C-7). The weight ratio of the composition charged into the dispersion tank T3 in Example 7 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-7) dispersion 45 parts Carbon dioxide 550 parts

Example 8
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-8) dispersion was used in the same manner as in Example 1, except that the fine particles (A ) Was fixed to obtain resin particles (C-8). The weight ratio of the composition charged into the dispersion tank T3 in Example 8 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-8) dispersion 45 parts Carbon dioxide 550 parts

Example 9
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-9) dispersion was used in the same manner as in Example 1, except that the fine particles (A ) Was fixed to obtain resin particles (C-9). The weight ratio of the composition charged into the dispersion tank T3 in Example 9 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-9) dispersion 45 parts Carbon dioxide 550 parts

Example 10
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-10) dispersion was used in the same manner as in Example 1 except that the fine particle (A-10) dispersion was used on the surface of the resin particle (B). ) Was fixed to obtain resin particles (C-10). The weight ratio of the composition charged into the dispersion tank T3 in Example 10 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-10) dispersion 45 parts Carbon dioxide 550 parts

Example 11
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-11) dispersion was used in the same manner as in Example 1 except that the fine particle (A-11) dispersion was used. ) Was fixed to obtain resin particles (C-11). The weight ratio of the composition charged into the dispersion tank T3 in Example 11 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-11) dispersion 45 parts Carbon dioxide 550 parts

Example 12
In Example 1, instead of the fine particle (A-1) dispersion, the fine particle (A-12) dispersion was used in the same manner as in Example 1 except that the fine particle (A-12) dispersion was used on the surface of the resin particle (B). ) Was fixed to obtain resin particles (C-12). The weight ratio of the composition charged into the dispersion tank T3 in Example 12 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-12) dispersion 45 parts Carbon dioxide 550 parts

Example 13
In Example 1, in place of the fine particle (A-1) dispersion, the fine particle (A-13) dispersion was used in the same manner as in Example 1, except that the fine particles (A ) Was fixed to obtain resin particles (C-13). The weight ratio of the composition charged into the dispersion tank T3 in Example 13 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-13) dispersion 45 parts Carbon dioxide 550 parts

Example 14
In Example 1, fine particles (A) are formed on the surface of the resin particles (B) in the same manner as in Example 1 except that the resin solution (L-2) is used instead of the resin solution (L-1). Adhered resin particles (C-14) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 14 is as follows.
Resin solution (L-2) 270 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts

Example 15
In Example 1, fine particles (A) were formed on the surface of the resin particles (B) in the same manner as in Example 1 except that the resin solution (L-3) was used instead of the resin solution (L-1). Adhered resin particles (C-15) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 15 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts

Example 16
In Example 1, except that the ratio of the resin solution (L-1) and the fine particle (A-1) dispersion was changed, the surface of the resin particle (B) was derived from the fine particles (A) in the same manner as in Example 1. Resin particles (C-16) having the coating film obtained were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 16 is as follows.
Resin solution (L-1) 305 parts Fine particle (A-1) dispersion 10 parts Carbon dioxide 550 parts

Example 17
Into a beaker, normal decane and fine particle (A-3) dispersion are charged, mixed with a homomixer (manufactured by Primix) at a rotation speed of 16000 rpm for 10 seconds, and then the raw material dispersion (L-1) is charged all at once with stirring. And dispersed for 1 minute to obtain a dispersion. Further, the dispersion was removed with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and the film derived from the fine particles (A) on the surface of the resin particles (B) Resin particles (C-17) were obtained. The weight ratio of the charged composition in Example 17 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-3) dispersion 45 parts Normal decane 120 parts

Example 18
In Example 17, in place of the fine particle (A-3) dispersion, the fine particle (A-4) dispersion was used in the same manner as in Example 17 except that the fine particle (A-4) dispersion was used. ) -Derived resin particles (C-18) were obtained. The weight ratio of the charged composition in Example 18 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-4) dispersion 45 parts Normal decane 120 parts

Example 19
In a beaker, 45 parts of an aqueous dispersion of fine particles (A-14), 80 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 300 parts of ion-exchanged water are mixed and stirred, and 270 parts of the resin solution (L-1) is mixed. Then, using a TK homomixer (manufactured by Tokushu Kika), mixing was performed at a rotation speed of 12,000 rpm for 10 minutes. After mixing, the mixture is poured into a reaction vessel equipped with a stirrer and a thermometer, and the solvent is removed at 50 ° C. for 2 hours, followed by filtration and drying to form fine particles (A) on the surface of the resin particles (B). The resin particle (C-19) to which was fixed was obtained. The weight ratio of the composition charged into the beaker in Example 19 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-14) aqueous dispersion 45 parts 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate 80 parts Ion-exchanged water 300 parts

Example 20
In Example 19, in the same manner as in Example 19 except that the fine particle (A-15) aqueous dispersion was used instead of the fine particle (A-14) aqueous dispersion, fine particles were formed on the surface of the resin particle (B). Resin particles (C-20) having a coating derived from (A) were obtained. The weight ratio of the composition charged into the beaker in Example 20 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-15) aqueous dispersion 45 parts 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate 80 parts Ion-exchanged water 300 parts

Example 21
In Example 19, fine particles (A-16) were dispersed on the surface of the resin particles (B) in the same manner as in Example 19 except that the fine particles (A-16) aqueous dispersion was used instead of the fine particles (A-14) aqueous dispersion. Resin particles (C-21) having a coating derived from (A) were obtained. The weight ratio of the composition charged into the beaker in Example 21 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-16) aqueous dispersion 45 parts 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate 80 parts Ion-exchanged water 300 parts

Comparative Example 1
Comparative resin particles (C′-1) were obtained in the same manner as in Example 1 except that the fine particle (A-1) dispersion was not charged. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 1 is as follows.
Resin solution (L-1) 270 parts Carbon dioxide 550 parts

Comparative Example 2
In Example 1, in place of the fine particle (A-1) dispersion, fine particle (A′-1) dispersion was used in the same manner as in Example 1 except that fine particles ( Comparative resin particles (C′-2) to which A ′) was fixed were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 2 is as follows.
Resin solution (L-1) 270 parts Fine particle (A'-1) dispersion 45 parts Carbon dioxide 550 parts

Comparative Example 3
In Example 1, instead of the fine particle (A-1) dispersion, fine particles (A′-2) were used on the surface of the resin particles (B) in the same manner as in Example 1 except that the fine particles (A′-2) dispersion was used. Comparative resin particles (C′-3) on which a film derived from A ′) was formed were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 3 is as follows.
Resin solution (L-1) 270 parts Fine particle (A'-2) dispersion 45 parts Carbon dioxide 550 parts

Evaluation Results For the resin particles obtained in Examples 1 to 21 and Comparative Examples 1 to 3, the volume average particle size, particle size distribution, heat resistant storage resistance, moisture heat resistant storage resistance, low temperature meltability (by the evaluation methods described below ( The melting temperature was evaluated, and the results are shown in Tables 3 and 4.
<Evaluation of volume average particle size and particle size distribution>
Resin particles are dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle size and volume average particle size / number average particle size of the resin particles (denoted as C in the table) are measured using a Coulter counter [Multi Sizer III (manufactured by Beckman Coulter, Inc.)]. The smaller the volume average particle size / number average particle size, the sharper the particle size distribution.

<Evaluation of heat-resistant storage stability>
The heat resistant storage stability of the resin particles was evaluated by the following method. That is, the resin particles were allowed to stand for 24 hours in a dryer adjusted to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
A: Blocking does not occur.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs and does not disperse even when force is easily applied with a finger or the like.
<Evaluation of moisture and heat resistant storage stability>
The moisture resistance and heat resistant storage stability of the resin particles was evaluated by the following method. That is, the resin particles were allowed to stand for 24 hours in a thermo-hygrostat adjusted to 50 ° C. and 80% humidity, and evaluated according to the following criteria according to the degree of blocking.
A: Blocking does not occur.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs and does not disperse even when force is easily applied with a finger or the like.

<Evaluation of low-temperature meltability (melting temperature)>
The melting temperature was evaluated by the following method.
Using a commercially available corona charging spray gun on a standard zinc phosphate-treated steel plate made by Nippon Test Panel, resin particles are electrostatically coated so that the film pressure is 20 to 40 μm, and the baking temperature is changed for evaluation. The minimum temperature at which the surface smoothness by visual confirmation after baking for 5 minutes was good was measured.

  The physical property values of the constituent raw materials of the resin particles of the present invention and comparative resin particles, and the evaluation results of the resin particles are shown in Tables 1 to 4.

  The resin particles obtained in the examples had a small volume average particle size / number average particle size and a sharp particle size distribution, whereas the resin particles obtained in Comparative Example 1 aggregated and had a particle size distribution. Was significantly worse. Moreover, although the resin particle obtained in the Example is excellent in heat-resistant storage stability and moisture-resistant heat-resistant storage property, these are inferior in the resin particle obtained in Comparative Example 3. Further, the resin particles obtained in the examples (particularly Examples 1 to 18, 20 to 21) are excellent in low-temperature meltability (low melting temperature), but the resin particles in Comparative Example 2 are inferior in low-temperature meltability. It was.

  The resin particles of the present invention are the base particles for electrophotographic toner, paint additives, cosmetic additives, paper coating additives, slush molding resins, powder paints, spacers for manufacturing electronic components, and electronic measuring instruments. It is useful as standard particles, electronic paper particles, medical diagnostic carriers, electrorheological particles, and other resin particles for molding.

T1: Resin solution tank T2: Fine particle dispersion tank T3: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C.)
F1: Ceramic filter (mesh: 0.5 μm)
T5: Solvent trap B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1: Valve V2: Pressure adjustment valve

Claims (8)

  Resin particles (B) in which the fine particles (A) containing a resin (a) having a polyester chain and having a vinyl monomer (d1) having a number average molecular weight of 500 to 100,000 as an essential constituent unit contain a resin (b) Resin particles (C), wherein the resin particles (C) are fixed to the surface of the resin particles, or a film containing the resin (a) is formed on the surface of the resin particles (B).   Resin particle | grains of Claim 1 whose resin (a) is crystalline resin and whose melting | fusing point is 40-110 degreeC.   The resin particles according to claim 1 or 2, wherein the vinyl monomer (d1) has a urethane bond.   The resin (a) further comprises perfluoroalkyl (alkyl) (meth) acrylate (d2) and / or unsaturated dicarboxylic acid (anhydride) (d3) as a constituent unit. The resin particle of description.   The content of (d1) in the structural unit of the resin (a) is 20 to 100% by weight, and the perfluoroalkyl (alkyl) (meth) acrylate (d2) and / or the unsaturated dicarboxylic acid (anhydride) (d3 The resin particles according to any one of claims 1 to 4, wherein the total content of   A dispersion in which fine particles (A) containing a resin (a) are dispersed in carbon dioxide (X) in a liquid or supercritical state and a solvent (S) solution (L) of the resin (b) are mixed, Resin particles in which fine particles (A) are fixed to the surface of resin particles (B) containing resin (b) and solvent (S) by dispersing (L) in the (X) dispersion of (A). The method according to any one of claims 1 to 5, further comprising the step of obtaining resin particles (C) by forming (C) and then removing carbon dioxide (X) and solvent (S) in a liquid or supercritical state. The manufacturing method of the resin particle of description.   The non-aqueous dispersion in which the fine particles (A) containing the resin (a) are dispersed in the non-aqueous organic solvent (N) and the solvent (S) solution (L) of the resin (b) are mixed, and (A Resin particles (C) in which fine particles (A) are fixed to the surface of resin particles (B) containing resin (b) and solvent (S) by dispersing (L) in a non-aqueous dispersion of The method for producing resin particles according to claim 1, further comprising a step of obtaining resin particles (C) by removing the non-aqueous organic solvent (N) and the solvent (S). .   An aqueous dispersion in which fine particles (A) containing the resin (a) are dispersed in an aqueous medium and a solvent (S) solution (L) of the resin (b) are mixed, and the aqueous dispersion of (A) The resin particles (C) in which the fine particles (A) are fixed to the surfaces of the resin particles (B) containing the resin (b) and the solvent (S) are formed by dispersing (L) in The manufacturing method of the resin particle of any one of Claims 1-5 including the process of obtaining the resin particle (C) by removing a solvent and a solvent (S).