JP2016124934A - Resin, resin particles, and method for producing resin particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin particles which are obtained by using a resin having high dispersibility into a fluid in a liquid state or a supercritical state, and a fluid in a liquid state or a supercritical state, have a sufficiently narrow particle size distribution, and have excellent low-temperature meltability.SOLUTION: A resin (a) has a monomer (m1) as an essential constituent monomer, has a ratio of 0.1-35 wt.% of the monomer (m1) based on the weight of the resin (a), and satisfies the following conditions 1 and 2: [condition 1] the resin (a) has a glass transition temperature (TGa) and/or a melting point (TMa), at least one thereof is 30-150°C, and a weight average molecular weight of the resin (a) is 200,000 or less; and [condition 2] a number average molecular weight of the monomer (m1) is 100-30,000, and a solubility parameter (SP value) of the monomer (m1) is 7.0-9.5.SELECTED DRAWING: None

Description

  The present invention relates to a resin, resin particles, and a method for producing resin particles. Specifically, the present invention relates to a resin using a liquid or supercritical fluid, resin particles, and a method for producing resin particles.

Conventionally, as a method of forming particles having excellent low-temperature meltability in a non-aqueous medium, a resin solution is mechanically dispersed in a liquid or supercritical fluid in the presence of a fine particle dispersant to form fine particles, and then decompressed. Thus, a method of obtaining resin particles (for example, Patent Document 1) is known.
According to the method of dispersing a resin solution in a liquid or supercritical fluid in the presence of the above fine particle dispersant, when inorganic fine particles such as hydrophobic silica are used as the dispersant, the low-temperature meltability is insufficient. Yes, when resin fine particles are used, particles with a narrow particle size distribution (Dv / Dn is 1.20) can be obtained to some extent, but particles with a narrower particle size distribution cannot be obtained. It was difficult to obtain resin particles having both low-temperature meltability.
As a method for solving the above problem, for example, Patent Document 2 is known. However, even in this method, it is difficult to obtain particles having a narrow particle size distribution because the resin used for the fine particles is partly soluble in a mixture of carbon dioxide and a solvent, and the soluble matter serves as a binder for the particles. It was.

JP 2010-132851 A International Publication No. 2011/152008

  An object of the present invention is a resin that is highly dispersible in a liquid or supercritical fluid, and has a sufficiently narrow particle size distribution obtained by using a fluid in a liquid or supercritical state and is excellent in low-temperature meltability. It is to obtain the resin particles.

The present invention has been made in view of the above circumstances in the prior art. That is, the present invention is a resin (a) having the monomer (m1) as an essential constituent monomer, and the proportion of the monomer (m1) is 0.1 to 0.1 based on the weight of the resin (a). Resin (a) characterized by being 35% by weight and satisfying the following conditions 1 and 2.
[Condition 1] The resin (a) has a glass transition temperature (TGa) and / or a melting point (TMa), at least one of which is 30 ° C. or higher and 150 ° C. or lower, and the weight average molecular weight of the resin (a) is 200,000 or lower.
[Condition 2] The number average molecular weight of the monomer (m1) is 100 or more and 30000 or less, and the solubility parameter [SP value] of the monomer (m1) is 7.0 to 9.5.

The resin of the present invention and the resin particles using the resin of the present invention have high affinity for various media, and particularly high affinity for hydrophobic media. Therefore, even when another medium is added to the medium in which the resin is dispersed and the resin particles using the resin are dispersed, the dispersion stability can be maintained. Similarly, dispersion stability can be maintained even if one medium is removed by volatilization from two or more kinds of mixed media.
The resin particles obtained by the resin of the present invention, the resin particles, and the resin particle production method have a sufficiently narrow particle size distribution, excellent low-temperature meltability, and good resistance to heat and heat resistance of the resin particles.

Experimental equipment used to create resin particles.

The present invention is described in detail below. Resin (a) contains the monomer (m1) whose solubility parameter [SP value: (cal / cm ³ ) ^1/2 ] is 7 to 9.5 as an essential constituent monomer.
The SP value of (m1) is usually 7.0 to 9.5, preferably 7.1 to 9.2, more preferably 7.2 to 8.9, still more preferably 7.3 to 8.5, Preferably it is 7.4-8.2. When the SP value is less than 7.0 or exceeds 9.5, the dispersion stability of the fine particles (A) containing the resin (a) is deteriorated during the production of the resin particles (C). 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 = (ΔE / 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.

  The resin (a) of the present invention is a resin polymerized using the monomer (m1) as an essential constituent unit, and the proportion of the monomer (m1) is 0.1 to 35% by weight, preferably It is 0.5 to 34% by weight, more preferably 1.0 to 33% by weight, still more preferably 3.0 to 32% by weight, and particularly preferably 5.0 to 30% by weight. When the ratio of the monomer (m1) is 0.1% by weight or less, the interfacial tension with the hydrophobic medium is high, and it becomes difficult to disperse the resin in the hydrophobic medium. On the other hand, when the proportion of the monomer (m1) exceeds 35% by weight, the viscosity and elasticity of the resin are lowered, and the storage stability and heat resistance are lowered.

In the present invention, the resin (a) may be either a crystalline resin (a1) or an amorphous resin (a2). In the case of an amorphous resin, when the glass transition temperature is (TGa), and in the case of a crystalline resin, the melting point is (TMa), at least one of (TGa) and (TMa) is 30 ° C. or higher and 150 ° C. Although it is in the following range, it is preferably in the range of 35 ° C. or more and 140 ° C. or less, more preferably in the range of 40 ° C. or more and 130 ° C. or less, further preferably in the range of 45 ° C. or more and 120 ° C. or less, and particularly preferably in the range of 50 ° C. or more and 110 ° C. The range is as follows.
When the temperature is lower than 30 ° C., the storage stability and heat resistance of the product using the resin (a) are lowered. On the other hand, when the temperature is higher than 150 ° C., problems such as difficulty in molding the resin (a) and defective fixing occur when heat fixing as a coating agent.
The glass transition temperature (TGa) and the melting point (TMa) can be measured by differential scanning calorimetry (hereinafter referred to as DSC).

<Melting point (TMa)>
Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was cooled to 0 ° C., then the temperature was increased at a rate of temperature increase of 10 ° C./min, and the endothermic change was measured. A graph of “endothermic amount” and “temperature” is drawn, and the temperature corresponding to the maximum peak of the endothermic amount is defined as the melting point (TMa).

<Glass transition point (TGa)>
The glass transition point is a physical property unique to amorphous resins. In measurement of the maximum peak temperature of heat of fusion, the baseline extension line below the maximum peak temperature in the graph of “endothermic heat generation” and “temperature” The temperature corresponding to the intersection with the tangent indicating the maximum slope from the rising portion of the maximum peak to the peak of the maximum peak is defined as the glass transition point (TGa).

  In the present invention, the weight average molecular weight of the resin (a) is 200,000 or less, preferably 1500 or more and 180000 or less, more preferably 2000 or more and 160000 or less, further preferably 2500 or more and 150,000 or less, and particularly preferably 3000 or more and 140000 or less. . When the molecular weight of the resin (a) is in the above range, the dispersibility of the resin (a) in the hydrophobic medium is good, and TMa and / or TGa are 30 ° C. or higher and 150 ° C. or lower.

In the present invention, the number average molecular weight (hereinafter referred to as Mn) of the monomer (m1) is 100 or more and 30000 or less. From the viewpoint of the interfacial tension with the hydrophobic medium, it is preferably 150 or more and 25000 or less, more preferably 200 or more and 20000 or less, and further preferably 250 or more and 15000 or less. When the number average molecular weight of the monomer (m1) is less than 100, the interfacial tension with the hydrophobic medium becomes high, and it becomes difficult to disperse the resin (a) in the hydrophobic medium. On the other hand, when the number average molecular weight of the monomer (m1) is larger than 30000, a large amount of unreacted monomer (m1) remains after the synthesis or a polymer with little introduction of the monomer (m1) is generated, and the resin The storage stability and heat resistance of the product using (a) are lowered, and the dispersibility in a hydrophobic medium is lowered.
In the present invention, the weight average molecular weight (hereinafter referred to as Mw) and Mn of the monomer and the resin are 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: 50 ° C
Sample solution: 2.5 g / L THF (tetrahydrofuran) solution 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)

  The monomer (m1) may be any monomer as long as it is a monomer corresponding to the above SP value. From the viewpoint of dispersion stability in carbon dioxide, a monomer containing a silicone ( one or more selected from the group consisting of m11), a perfluoroalkyl-containing monomer (m12), an alkyl group-containing monomer (m13) having 8 to 30 carbon atoms, and an alkylene oxide adduct-containing monomer (m14). It is preferable that it is a monomer. When the hydrophobic medium is carbon dioxide in a liquid or supercritical state, a silicone-containing monomer (m11) and a perfluoroalkyl-containing monomer (m12) are particularly preferable.

  Examples of the resin (a) in the present invention include, but are not limited to, vinyl resins, polyester resins, polyurethane resins, polyurea resins, polyepoxy resins and composite resins of these resins.

  When the resin (a) is a vinyl resin, examples of the monomer (m1) include vinyl monomers.

Examples of the silicone-containing monomer (m11) include a silicone-containing vinyl monomer (m111), which is a compound having a silicone chain and a vinyl polymerizable unsaturated group. Examples of the silicone chain include polydimethylsiloxane, Examples include those in which a part of polydimethylsiloxane is substituted with an alkyl group having 2 to 20 carbon atoms (ethyl group, propyl group, butyl group, octyl group, decyl group, etc.) and / or a phenyl group. Examples of the vinyl polymerizable unsaturated group include a (meth) acryl group.
Specific examples of (m11) include (meth) acryl-modified silicone and the like, and examples thereof include those represented by the following formula: R ₃ SiO (R ₂ SiO) aSiR ₂ Q
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. The number Q is an organic modifying group containing a (meth) acryl group. Examples of Q _{are, -C 3 H 6 OCOC (CH} 3) = CH 2, -C 3 H 6 OCOCH = CH 2 and the like. ]
In the above, (meth) acryl means acryl and / or methacryl, and the same description method is used hereinafter.

  Specific examples of the silicone-containing vinyl monomer (m11) include X22-2475 (made by Shin-Etsu Silicone), X22-174DX (made by Shin-Etsu Silicone), X22-2426 (made by Shin-Etsu Silicone), FM0711 (Chisso) Manufactured by Co., Ltd.), FM0721 (manufactured by Chisso Corporation), FM0725 (manufactured by Chisso Corporation), TM-0701 (manufactured by Chisso Corporation), TM-0701T (manufactured by Chisso Corporation), S710 (manufactured by Chisso Corporation), and the like. However, examples of the acrylic-modified silicone include X22-1615 (manufactured by Shin-Etsu Silicone) and X22-1618 (manufactured by Shin-Etsu Silicone).

Examples of the fluorine-containing monomer (m12) include a fluorine-containing vinyl monomer (m121) and the like. Specifically, perfluoroolefins such as tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene; Fluorovinyl ethers such as perfluoro (alkyl vinyl ether), perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3-dioxole), perfluoro (2-methylene-4-methyl-1, 3-dioxolane), and perfluorobutenyl vinyl ether; hydrogen atom-containing fluoroolefins such as vinylidene fluoride, trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3,3,3-trifluoro -2-Triff Oromethylpropene, 3,3,3-trifluoropropene, and perfluoro (butyl) ethylene; polyfluoroalkyl (meth) acrylates such as 1,1-dihydroperfluorooctyl (meth) acrylate, (perfluoromethyl) Methyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, and 2- (perfluorobutyl) ethyl (meth) acrylate; fluorostyrene, such as α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene, α, β, β-trifluorostyrene, α-trifluoromethylstyrene, 2,4,6-tri (tri Fluoromethyl) styrene, 2,3,4,5 6-pentafluorostyrene, 2,3,4,5,6-pentafluoro-α-methylstyrene, and 2,3,4,5,6-pentafluoro-β-methylstyrene; and the like.
Among these, polyfluoroalkyl (meth) acrylate is preferable, the polyfluoroalkyl group is an even number having 2 to 12 carbon atoms, and the alkyl moiety has 0 to 3 carbon atoms. ) (Meth) acrylate is more preferred. Specific examples include (perfluoromethyl) methyl (meth) acrylate, (2-perfluoroethyl) ethyl (meth) acrylate, (2-perfluorobutyl) ethyl (meth) acrylate, and (2-perfluorohexyl) ethyl. Examples include (meth) acrylate, (2-perfluorooctyl) ethyl (meth) acrylate, (2-perfluorodecyl) ethyl (meth) acrylate, and (2-perfluorododecyl) ethyl (meth) acrylate.

Examples of the alkyl group-containing monomer (m13) having 8 to 30 carbon atoms (the carbon number of the entire alkyl group) include an alkyl group-containing vinyl monomer (m131) and the like, and a branched alkyl group having 8 to 30 carbon atoms. (Meth) acrylate etc. which have this. Specific examples of (m13) include 2-ethylhexyl (meth) acrylate, 2-ethyldodecyl (meth) acrylate, 2-ethylhexadecyl (meth) acrylate, 2-ethylheptadecyl (meth) acrylate, and 2-ethyloctadecyl. (Meth) acrylate, 2-ethyleicosyl (meth) acrylate, and 2-decyltetradecyl (meth) acrylate are mentioned. Among these, alkyl (meth) acrylates having 12 to 28 carbon atoms in the alkyl group are preferable, and 2-decyltetradecyl (meth) acrylate is more preferable.
In the above, (meth) acrylate means acrylate and / or methacrylate, and the same description method is used hereinafter.

Examples of the alkylene oxide adduct-containing monomer (m14) include an alkylene oxide adduct-containing vinyl monomer (m141). A polyoxyethylene chain and a part of the polyoxyethylene chain have 2 to 20 carbon atoms. Examples thereof include those substituted with an alkyl group (ethyl group, propyl group, butyl group, octyl group, decyl group, etc.) and / or a phenyl group.
RO (CH ₂ RO) aOCRQ
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. The number Q is an organic modifying group containing a (meth) acryl group. Examples of Q _{are, -C 3 H 6 OCOC (CH} 3) = CH 2, -C 3 H 6 OCOCH = CH 2 and the like. ]
Specific examples include methoxypolyethylene glycol (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate.

  On the other hand, examples of the monomer (m2) exhibiting crystallinity include the following monomers excluding the monomer (m1), but a resin (a) containing (m1) and (m2) as constituent monomers (a ).

  The composition of the crystalline monomer (m2) is not particularly limited, but a monomer containing a vinyl group (m201), a monomer containing a hydroxyl group (m202), a monomer containing an amino group (m203) And a monomer (m204) containing an epoxy. Preferable specific examples of the monomer (m201) containing a vinyl group include alkyl (meth) acrylates having an alkyl group having 12 to 50 carbon atoms, aliphatic vinyl hydrocarbons, and the like.

From the viewpoint of storage stability of the resin particles (C), the carbon number of the alkyl group of the alkyl (meth) acrylate having an alkyl group with 12 to 50 carbon atoms is 12 or more, preferably 14 or more, more preferably 18 or more. Further, from the viewpoint of fixability, it is 50 or less, preferably 40 or less, more preferably 30 or less. The alkyl group is preferably a linear one. As dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, and the like, preferred are octadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate.
Examples of the aliphatic vinyl hydrocarbon include ethylene and propylene.
Of these, alkyl (meth) acrylates having an alkyl group with 12 to 50 carbon atoms are preferred.

  The content of the structural unit of the crystalline monomer (m2) in the crystalline resin is preferably from 30 to 99.9% by weight, more preferably from 33 to 90% by weight, and particularly preferably from the viewpoint of fixability. -80% by weight, most preferably 40-70% by weight.

The crystalline resin may contain a vinyl monomer other than the above (m1) and (m2) as a structural unit. Examples of other vinyl monomers include the following (1) to (11).
(1) Vinyl hydrocarbon:
(1-1) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as (di) cyclopentadiene; terpenes such as pinene.
(1-2) 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 monomer and salt thereof: unsaturated monocarboxylic acid having 3 to 30 carbon atoms, unsaturated dicarboxylic acid and anhydride and monoalkyl (1 to 24 carbon atoms) ester thereof such as (meta ) 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 Carboxyl group-containing vinyl monomers such as esters and cinnamic acid.
(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α- Methyl styrene sulfonic acid and the like; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, and sulfuric acid ester or sulfonic acid group-containing vinyl monomer; and salts thereof.
(4) Phosphoric acid group-containing vinyl monomer and salt thereof: (meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoester, for example, 2- (meth) acryloyloxyethyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (Meth) acryloyloxyalkyl (C1-24) phosphonic acids, for example 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: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, Crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.
(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 monomer: 3 such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like (6-5) Nitro group-containing vinyl, such as quaternized products of quaternary amine group-containing vinyl monomers (quaternized with quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate) Monomer: Nitrostyrene or the like.
(7) Epoxy group-containing vinyl monomer: glycidyl (meth) acrylate, p-vinylphenylphenyl oxide and the like.
(8) Vinyl monomer containing halogen element: Chlorine-containing vinyl monomer, such as vinyl chloride, vinylidene chloride, allyl chloride, chlorostyrene, dichlorostyrene, chloromethylstyrene, chloroprene; bromine-containing vinyl monomer For example, vinyl bromide, bromostyrene; fluorine-containing vinyl monomers such as perfluoroolefin [tetrafluoroethylene, hexafluoropropylene, etc.], perfluorovinyl ether [perfluoro (alkyl vinyl ether), perfluoro (1,3-dioxole) ), Perfluoro (2-methylene-4-methyl-1,3-dioxolane), perfluorobutenyl vinyl ether, etc.], hydrogen atom-containing fluoroolefin [vinylidene fluoride, trifluoroethylene, 1,2-difluoroe Len, vinyl fluoride, trifluoropropylene, perfluoro (butyl) ethylene, etc.], polyfluoroalkyl (meth) acrylate [1,1-dihydroperfluorooctyl (meth) acrylate, (perfluoromethyl) methyl (meth) Acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, etc.], fluorostyrene [α-fluoro Styrene, β-fluorostyrene, α, β-difluorostyrene, α-trifluoromethylstyrene, 2,4,6-tri (trifluoromethyl) styrene, and the like.
(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 11 carbon atoms or branched alkyl group having 3 to 7 carbon atoms [methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc.], dialkyl fumarate (the two alkyl groups are linear or branched having 2 to 8 carbon atoms) Or an alicyclic group), a dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) aryl. Roxyalkanes [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 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) Acrylates [of polyhydric alcohols Poly (meth) acrylate: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] ,
(9-2) Vinyl (thio) ether, such as vinyl methyl ether,
(9-3) Vinyl ketones such as vinyl methyl ketone.
(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
(11) Macromonomer having a resin chain with Mn of 300 to 100,000 (preferably 500 to 50,000) such as polyester chain and polyurethane chain:
As a composition of the part of a polyester chain and a polyurethane chain, the thing similar to the polyester resin and polyurethane resin mentioned later is mentioned.

  The resin (a) 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.

  In order to impart an acidic functional group or a basic functional group to the surface of the fine particles (A), a resin having an acidic functional group or a basic functional group may be used as the resin (a), or the fine particles (A). In order to impart these functional groups, surface treatment may be performed.

  As the resin (a) having an acidic functional group, a monomer having an acidic functional group (for example, the carboxyl group-containing vinyl monomer (2), the sulfone group-containing vinyl monomer (3), etc.) is copolymerized. Vinyl resin and the like.

  Examples of the resin (a) having a basic functional group include a vinyl resin copolymerized with a monomer having a basic functional group [for example, the amino group-containing vinyl monomer (6-1)]. .

  Moreover, in order to improve the adsorptivity of the fine particles (A) and the resin particles (B), the resin (a) has the same composition as the resin (b) contained in the resin particles (B) as a part of its structural unit. It is preferable to have a structural unit of the macromonomer (11) having a resin chain with Mn of 500 to 100,000.

From the above, monomers other than the monomer (m1) having an SP value of 7 to 9 and the crystalline vinyl monomer (m2) constituting the resin (a) are carboxyl group-containing vinyl monomers. Preferred are the monomer (2), the sulfone group-containing vinyl monomer (3), the amino group-containing vinyl monomer (6-1), and the macromonomer (11) having a resin chain with Mn of 500 to 100,000. More preferably, (2) and (11).
The total content of vinyl monomers other than (m1) and (m2) in the structural unit of the crystalline resin is preferably 50% by weight or less, more preferably 1 to 47% by weight, particularly preferably 5 to 45%. % By weight, most preferably 10-40% by weight.

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

Examples of the silicone-containing hydroxyl monomer (m112) include a compound having a silicone chain and a hydroxyl group. Examples of the silicone chain include polydimethylsiloxane and polydimethylsiloxane, a part of which is an alkyl group having 2 to 20 carbon atoms ( Ethyl group, propyl group, butyl group, octyl group, decyl group, etc.) and / or those substituted with a phenyl group.
Specific examples of (m112) include carbinol-modified silicones, such as those represented by the following formula: R ₃ SiO (R ₂ SiO) aSiR ₂ OH 1)
_{R 3 SiO (R 2 SiO)} aSiR 2 C (ROH) 2 R 2)
HOR ₂ SiO (R ₂ SiO) aSiR ₂ OH 3)
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. Is a number. ]

Specific examples of the silicone-containing hydroxyl monomer (m112) include 1) X22-170BX (manufactured by Shin-Etsu Silicone), X22-170DX (manufactured by Shin-Etsu Silicone), and (manufactured by Chisso Corporation).
2) X22-176DX (manufactured by Shin-Etsu Silicone), X22-176GX-A (manufactured by Shin-Etsu Silicone), FM-DA11 (manufactured by Chisso Corporation), FM-DA21 (manufactured by Chisso Corporation), FM-DA26 (Chisso Corporation) Company-made).
3) KF-6000 (made by Shin-Etsu Silicone), KF-6001 (made by Shin-Etsu Silicone), KF-6002 (made by Shin-Etsu Silicone), KF-6003 (made by Shin-Etsu Silicone), KF-2200 (made by Shin-Etsu Silicone), FM -4411 (made by Chisso Corporation), FM-4421 (made by Chisso Corporation), FM-4425 (made by Chisso Corporation), and the like.

  As the fluorine-containing hydroxyl monomer (m122), a compound having a perfluoroalkyl chain having 2 or more carbon atoms and a hydroxyl group, specifically, 1H, 1H-trifluoroethanol, 1H, 1H-pentafluoropropanol, 6- (Perfluoroethyl) hexanol, 1H, 1H-heptafluorobutanol, 3- (perfluorobutyl) propanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,3,3- Tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 1H, 1H-2,5-di (trifluoromethyl) -3,6- Dioxane decafluorononal, 6- (perfluoro-1- Tilethyl) hexanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 2H-hexafluoro-2-propanol, 1H, 1H, 3H Hexafluorobutanol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6 , 7,7-dodecafluoro-1,8-octanediol, 2,2-bis (trifluoromethyl) propanol, and the like.

Examples of the hydroxyl group monomer (m132) having an alkyl group having 8 to 30 carbon atoms (carbon number of the entire alkyl group) in the side chain include compounds having an alkyl group having 8 to 30 carbon atoms. Among these, an alkyl chain having 12 to 28 carbon atoms in the alkyl group is preferable. Specific examples of (m132) include the following formula.
HOH ₂ CCHRCH ₂ OH
[However, R is one or more groups selected from an alkyl group having 8 to 30 carbon atoms and a phenyl group (each R may be the same or different). ]

  Specific examples of (m132) include 1,2-decanediol, 1,2-dodecanediol, 1,2-undecanediol, 1,2-stearyldiol, 1,2-behenyldiol, 1,3-dodecanediol. 1,4-dodecanediol and the like.

As the alkylene oxide adduct-containing hydroxyl monomer (m142), a polyoxyethylene chain, a part of the polyoxyethylene chain is an alkyl group having 2 to 20 carbon atoms (ethyl group, propyl group, butyl group, octyl group, decyl group) Group) and / or a group substituted with a phenyl group, for example, the following formula.
RO (CH ₂ RO) aOH
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. Is a number. ]

The silicone-containing amino group monomer (m113) is a compound having a silicone chain and an amino group. As the silicone chain, polydimethylsiloxane, a part of polydimethylsiloxane is an alkyl group having 2 to 20 carbon atoms ( Ethyl group, propyl group, butyl group, octyl group, decyl group, etc.) and / or those substituted with a phenyl group.
Specific examples of (m113) include amino-modified silicones, and examples thereof include the following formulas.
H ₂ NR ₂ SiO (R ₂ SiO) aSiR ₂ NH ₂
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. Is a number.

  Specific examples of the silicone-containing amino group monomer (m113) include PAM-E (made by Shin-Etsu Silicone), KF-8010 (made by Shin-Etsu Silicone), X-22-161A (made by Shin-Etsu Silicone), X-22-161B. (Shin-Etsu Silicone), KF-8012 (Shin-Etsu Silicone), KF-8008 (Shin-Etsu Silicone), X-22-1660B-3 (Shin-Etsu Silicone), X-22-9409 (Shin-Etsu Silicone), FM- 3311 (made by Chisso Corporation), FM-3321 (made by Chisso Corporation), FM-3325 (made by Chisso Corporation) and the like.

  The fluorine-containing hydroxyl monomer (m123) is a compound having a perfluoroalkyl chain having 2 or more carbon atoms and an amino group, specifically, 1H, 1H-heptafluorobutylamine, 1H, 1H-tridecafluoroheptyl. Examples include tilamine.

Examples of the amino group monomer (m133) having an alkyl group having 8 to 30 carbon atoms in the side chain (the carbon number of the entire alkyl group) include compounds having an alkyl group having 8 to 30 carbon atoms. Among these, an alkyl chain having 12 to 28 carbon atoms in the alkyl group is preferable. Specific examples of (m133) include the following formula.
H ₂ NH ₂ CCHRCH ₂ NH ₂
[However, R is one or more groups selected from an alkyl group having 8 to 30 carbon atoms and a phenyl group (each R may be the same or different).

  Specific examples of (m133) include 1,2-decanediamine, 1,2-dodecanediamine, 1,2-undecanediamine, 1,2-stearyldiamine, 1,2-behenyldiamine, 1,3-dodecanediamine. 1,4-dodecanediamine and the like.

  As the alkylene oxide adduct-containing amino group monomer (m143), a polyoxyethylene chain, a part of the polyoxyethylene chain is an alkyl group having 2 to 20 carbon atoms (ethyl group, propyl group, butyl group, octyl group, Decyl group, etc.) and / or those substituted with a phenyl group.

The silicone-containing epoxy group monomer (m114) is a compound having a silicone chain and an epoxy group. As the silicone chain, polydimethylsiloxane, a part of polydimethylsiloxane is an alkyl group having 2 to 20 carbon atoms ( Ethyl group, propyl group, butyl group, octyl group, decyl group, etc.) and / or those substituted with a phenyl group. In the above, the epoxy includes aliphatic epoxy and / or alicyclic epoxy.
Specific examples of (m114) include epoxy-modified silicone and the like.
R ₃ SiO (R ₂ SiO) aSiR ₂ RCHOCH ₂ 1)
H ₂ COHCR ₃ SiO (R ₂ SiO) aSiR ₂ RCHOCH ₂ 2)
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. Is a number.

  Specific examples of the silicone-containing epoxy group monomer (m114) include X-22-173BX (manufactured by Shin-Etsu Silicone) and X-22-173DX (manufactured by Shin-Etsu Silicone) as 1). 2) X-22-163 (made by Shin-Etsu Silicone), KF-105 (made by Shin-Etsu Silicone), X-22-163A (made by Shin-Etsu Silicone), X-22-163B (made by Shin-Etsu Silicone), X-22 -163C (manufactured by Shin-Etsu Silicone), X-22-169AS (manufactured by Shin-Etsu Silicone), X-22-169B (manufactured by Shin-Etsu Silicone), and the like.

  The fluorine-containing epoxy group monomer (m124) is a compound having a perfluoroalkyl group having 2 or more carbon atoms and an epoxy group. Specifically, CHEMINOX FAEP-4 (manufactured by Unimatec), CHEMINOX FAEP-6 (manufactured by Unimatec) ), MF-120 (Mitsubishi Materials Electronics), E-5244 (Daikin Industries), E-5444 (Daikin Industries), E-5644 (Daikin Industries), E-7432 (Daikin Industries), E -7632 (made by Daikin Industries).

As an epoxy group monomer (m134) which has an alkyl group, the compound which has a C8-C30 alkyl group is mentioned. Among these, an alkyl chain having 12 to 28 carbon atoms in the alkyl group is preferable. Specifically, (m134) is exemplified by the following formula.
H ₂ C (CHR) aCHOCH ₂
[However, R is one or more groups selected from alkyl groups having 1 to 30 carbon atoms and phenyl groups (each R may be the same or different) a is an average value of 3 to 1000. It is. ]

  Specific examples of (m134) include 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyoctadecane. 1,2-epoxyhexadecane, 1,2-epoxyeicosane, stearyl glycidyl ether and the like.

As the alkylene oxide adduct-containing epoxy group monomer (m144), a polyoxyethylene chain, a part of the polyoxyethylene chain is an alkyl group having 2 to 20 carbon atoms (ethyl group, propyl group, butyl group, octyl group, Decyl group, etc.) and / or those substituted with a phenyl group.
RO (CH ₂ RO) aOH
[However, R is one or more groups selected from an alkyl group having 1 to 20 carbon atoms and a phenyl group (each R may be the same or different), and a is an average value of 3 to 1000. Is a number. ]

A monomer other than (m1) and (m2) may be used as a constituent component of the resin.
For example, as a constituent monomer of a polyester resin, a polyol and a polycarboxylic acid (including an acid anhydride and a lower alkyl ester thereof) and the like can be mentioned. As the polyol, a diol (12) and a trivalent or higher polyol ( 13), and examples of the polycarboxylic acid include dicarboxylic acid (14) and trivalent or higher polycarboxylic acid (15).
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 / 1.2, particularly preferably 1.3 / 1 to 1/1.

  Diol (12) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; Examples include polylactone diol (such as poly ε-caprolactone diol) and polybutadiene diol. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Examples of the trivalent or higher polyol (13) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol PA, etc.) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins, acrylic polyols [copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Polymer, etc.].

  Dicarboxylic acids (14) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); Branched dialkyl dicarboxylic acids [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid etc.); Group dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher (3 to 6 or higher) polycarboxylic acid (15) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

  As the dicarboxylic acid (14) or the trivalent or higher polycarboxylic acid (15), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Similar to the polyester resin, monomers other than (m1) and (m2) may be used as a constituent component of the polyurethane resin.
For example, as a constituent monomer of the polyurethane resin, polyisocyanate (16) and active hydrogen group-containing compound (D) {water, polyol [the diol (12) and trivalent or higher valent polyol (13)], dicarboxylic acid ( 14) polyaddition products with polycarboxylic acid (15), polyamine (17), polythiol (18), etc. having a valence of 3 or more, and the like.

As polyisocyanate (16), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanate, araliphatic 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, methylcyclohexylene diisocyanate (hydrogenated TDI), and the like. .
Specific examples of the aromatic aliphatic 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.

The following are mentioned as an example of a polyamine (17).
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-C4) or hydroxyalkyl (C2-C4) substituted products [dialkyl (C1-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 to C15) (such as xylylenediamine, tetrachloro-p-xylylenediamine),
-Alicyclic polyamines (C4 to 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 and the like
[3] Aromatic polyamine having a secondary amino group [a part or all of —NH ₂ of the aromatic polyamine of the above (4) to (6) is —NH—R ′ (R ′ is a lower group such as methyl, ethyl, etc.] Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Polyamide polyamine: low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylene diamine, polyalkylene polyamine, etc.)
-Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

  Examples of polythiol (18) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

Similarly to the polyester resin, monomers other than (m1) and (m2) may be used as a constituent component of the polyurea resin.
For example, as a constituent monomer of the polyurea resin, a polyaddition product of the polyamine (17) and the polyisocyanate (16) may be mentioned.

Similarly to the polyester resin, monomers other than (m1) and (m2) may be used as a constituent component of the epoxy resin.
For example, as a constituent monomer of the epoxy resin, polyepoxide (19), active hydrogen group-containing compound (D) {water, polyol [the diol (12) and trivalent or higher valent polyol (13)], dicarboxylic acid (14 ) Or higher polyvalent polycarboxylic acids (15), polyamines (17), polythiols (18), etc.}, polyepoxides (19) and dicarboxylic acids (14) or trivalent or higher polycarboxylic acids ( 15) a cured product with an acid anhydride.

  The polyepoxide (19) is not particularly limited as long as it has two or more epoxy groups in the molecule. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the 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 (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compound include glycidyl ethers and glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, and glycidylated products 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. Furthermore, as the aromatic polyepoxy compound in the present invention, triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, polyol reacts with the two reactants. The glycidyl group-containing polyurethane (pre) polymer obtained by the above-mentioned process 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 trisglycidyl melamine. 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. In the present invention, the aliphatic polyepoxy compound also includes (co) polymers of diglycidyl ether and glycidyl (meth) acrylate. Among these, an aliphatic polyepoxy compound and an aromatic polyepoxy compound are preferable. Two or more polyepoxides may be used in combination.

  The resin (a) may be described as carbon dioxide (X) in a liquid or supercritical state (hereinafter referred to as carbon dioxide (X)) at a temperature lower than the glass transition temperature (TGa) or lower than the melting point (TMa). ] The swelling degree of the resin (a) (hereinafter referred to as swelling degree) is preferably 16% or less, more preferably 10% or less, and further preferably 5% or less. When the degree of swelling exceeds 16%, the resin (a) swells and softens when the resin particles using liquid or supercritical carbon dioxide (X) described later are produced, and the aggregation of the resin particles cannot be suppressed. The particle size distribution of the resin particles deteriorates.

  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).

  The resin (a) preferably has a dissolution amount in a hexane / acetone mixed medium of 30% by weight or less from the viewpoint of dispersion stability in a hydrophobic medium and from the viewpoint of the particle size distribution of the resin particles (C) described later. More preferably, it is 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

  The amount of dissolution in the present invention is the maximum mass (g) that can be dissolved in 100 g of a hexane / acetone mixed medium. The measurement temperature is 30 ° C. The method for measuring the amount of the resin (a) dissolved in the hexane / acetone mixed medium is as follows. The resin (a) is mixed at a concentration of 10% by weight with a mixed solvent of hexane / acetone (mixing weight ratio = 76/24, SP value = 8) After being dissolved at 50 ° C. or higher in the mixture, the mixture is allowed to stand at 30 ° C. for 2 hours, and then solid-liquid separation is performed using centrifugation, and the supernatant and the dry weight of the precipitate can be measured.

In the case where the monomer (m1) is a silicone-containing monomer (m11), when the resin (a) is used as a coating agent, the silicone part in the resin (a) is easily oriented on the surface layer, which is characteristic of silicone. The resin (a) preferably satisfies (Si-1) / (Si-0) ≧ 1.05 from the viewpoint of obtaining a dispersion function in an aqueous or hydrophilic silicone medium. More preferably (Si-1) / (Si-0) ≧ 1.1, still more preferably (Si-1) / (Si-0) ≧ 1.15, and particularly preferably (Si-1) / (Si −0) ≧ 1.2.
(Si-1): Amount of surface silicon of the resin (a1) after the resin (a) and liquid or supercritical carbon dioxide (X) are mixed and processed (Si-0): normal pressure of the resin (a) Surface silicon content of resin (a0) after heat softening treatment in nitrogen

When the monomer (m1) is a perfluoroalkyl-containing monomer (m12), when the resin (a) is used as a coating agent, the perfluoro part in the resin (a) is easily oriented on the surface layer, and the Aqueous and antifouling properties can be obtained. In addition, when the resin particles are coated, the resin (a) preferably satisfies (F-1) / (F-0) ≧ 1.05 from the viewpoint of improving the negative chargeability. More preferably (F-1) / (F-0) ≧ 1.1, still more preferably (F-1) / (F-0) ≧ 1.15, preferably (F-1) / (F −0) ≧ 1.2.
(F-1): Amount of surface silicon of the resin (a1) after the resin (a) and liquid or supercritical carbon dioxide (X) are mixed and treated (F-0): normal pressure of the resin (a) Surface silicon content of resin (a0) after heat softening treatment in nitrogen

  The method of mixing the resin (a) and liquid or supercritical carbon dioxide (X) into (a1) is as follows. The resin (a) is charged into a high-pressure apparatus, and the pressure is increased from 40 ° C./normal pressure to 40 ° C./6 MPa. After mixing in liquid or supercritical carbon dioxide (X) for 1 hour, the pressure is reduced to carbon dioxide (X). Is removed to obtain the resin (a1).

On the other hand, the method of heat-softening the resin (a) in atmospheric pressure nitrogen to make it (a0) is as follows. Resin (a0) can be obtained by leaving the resin (a) at 40 ° C. for 1 hour under normal pressure and nitrogen atmosphere.

The amount of surface silicon and the amount of surface fluorine were measured using XPS (device used: AXIS Ultra, manufactured by Kratos).
As described above, the surface silicon ratio and / or the surface fluorine ratio of the resin (a) before and after being mixed with the liquid or supercritical carbon dioxide (X) are (Si-1) / (Si-0) ≧ It is preferable that 1.05 and (F-1) / (F-0) ≧ 1.05.
When the ratio is 1.05 or more, when the resin (a) is dispersed in the hydrophobic medium, the hydrophobic groups in the resin (a) are easily reoriented on the surface layer, and the dispersion becomes good. On the other hand, when the ratio is less than 1.05, reorientation of the hydrophobic group to the surface layer does not occur, and therefore, poor dispersion occurs due to insufficient amount of the hydrophobic group on the surface layer of the resin (a).

  In order to stably disperse the resin (a) in the hydrophobic medium, (Si-1) / (Si-0) ≧ 1.05 or (F-1) / (F-0) ≧ 1.05 The number average molecular weight of the monomer (m1) is preferably 100 or more and 30000 or less. If it is less than 100, the affinity for the hydrophobic medium is insufficient, and dispersion is unstable. On the other hand, when it is larger than 30000, the orientation speed becomes slow due to steric hindrance and the dispersion becomes unstable.

  When the resin (a) is a crystalline resin, the melting point is preferably 50 to 110 ° C, more preferably 53 to 100 ° C, particularly preferably 55 to 90 ° C, and most preferably 60 to 80 ° C. When the melting point is 50 ° C. or higher, the resin particles (C) of the present invention are difficult to block even during long-term storage.

The degree of crystallinity of the crystalline resin is preferably 20 to 95%, more preferably 30 to 80%, from the viewpoint of suppression of swelling by carbon dioxide (X) and adsorptivity to the resin particles (B). . The degree of crystallinity is obtained by calculating the heat of fusion (ΔHm (J / g)) from the endothermic peak area 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 measured as follows.
The amount of heat of fusion of the resin, which is a sample having the same composition as the resin to be measured, is measured by DSC, and the method is in accordance with JISK0131 (1996) (X-ray diffraction analysis general rule 13 crystallinity measurement (2) absolute method). Measure crystallinity. 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.

  The number average molecular weight Mn of the resin (a) is preferably 1000 or more, more preferably 1500 or more, particularly preferably 2000 or more, and most preferably 10,000 or more, from the viewpoint of durability of the resin particles (C). 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 SP value of the resin (a) is preferably 6 to 14 and more preferably 8 to 12 from the viewpoint of dispersion stability of the fine particles (A) containing (a) at the time of production of the resin particles (C).

  The production method of the fine particles (A) containing the resin (a) may be any production method, but as a specific example, a method of producing by a dry method [(a) constituting the fine particles (A) is a known method such as a jet mill, etc. A method of dry pulverization using a dry pulverizer], a method of manufacturing in a wet manner (a method in which the powder of (a) is dispersed in an organic solvent and wet pulverized by a known wet disperser such as a bead mill or a roll mill, A method of spray-drying the solvent solution with a spray dryer or the like, a method of precipitating the solvent solution of (a) by supersaturation by adding a poor solvent or cooling, a method of dispersing the solvent solution of (a) in water or an organic solvent, (a The method of polymerizing the precursor of) in water by emulsion polymerization, soap-free emulsion polymerization, seed polymerization, suspension polymerization, etc., and the method of polymerizing the precursor of (a) by dispersion polymerization in an organic solvent] But It is below. 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 resin particle (B) contains the resin (b). In the present invention, as the resin (b), a thermoplastic resin (b1), a resin (b2) obtained by finely crosslinking the thermoplastic resin, or a polymer blend containing a thermoplastic resin as a sea component and a cured resin as an island component ( b3), and two or more of them may be used in combination.
The thermoplastic resin (b1) may be any of a crystalline resin, an amorphous resin, or 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 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.

Examples of the vinyl resin include (co) polymers of vinyl monomers similar to those constituting the vinyl resin used for the resin (a). However, the crystalline vinyl monomer (m2) having an SP value of 7.0 to 9.5 may be omitted.
Examples of the vinyl monomer copolymer include polymers obtained by copolymerizing any of the monomers (1) to (11), (m1), and (m2) at an arbitrary ratio. Styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (Meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

  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 SP value is preferably 7 to 18, more preferably 8 to 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 particles (C) of the present invention are obtained by fixing the fine particles (A) containing the resin (a) to the surface of the resin particles (B), or fine particles (A) on the surface of the resin particles (B). These are resin particles formed by forming a film with a film. 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), and the particle size ratio [volume average particle size of the fine particles (A) / [volume average particle size of the resin particles (C) of the present invention]. The value of is preferably 0.001 to 0.3, more preferably 0.002 to 0.2, still 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 resin particles (C) of the present invention are resin particles (C) in which the fine particles (A) containing (a) are fixed to the surface of the resin particles (B) containing the resin (b) or formed into a film. The particle size of the fine particles (A) is smaller than the particle size of the resin particles (B), and the particle size of the fine particles (A) is 0.01 to 1.0 μm. The particle size of the fine particles (A) is preferably 0.02 to 0.8 μm, more preferably 0.03 to 0.6 μm, still more preferably 0.04 to 0.4 μm, and particularly preferably 0.05 to 0.2 μm. It is.

  The volume average particle size of the fine particles (A) is determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba, Ltd.), a laser particle size distribution measuring device (for example, LA-920: manufactured by Horiba, Ltd.), Multisizer. It can be measured with III (manufactured by Beckman Coulter).

  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.

  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: DV / DN is preferably 1.0 to 1.3, more preferably Is 1.0 to 1.2, particularly preferably 1.0 to 1.18, and most preferably 1.0 to 1.17. When it is 1.3 or less, powder characteristics (fluidity, charging uniformity, etc.) and image resolution are remarkably improved.

From the viewpoints of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C) of the present invention, the surface coverage of the resin particles (B) by the coatings derived from the fine particles (A) or (A) is 5% or more is preferable, and 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 (a: b) of the resin (a) constituting the fine particles (A) and the resin (b) constituting the resin particles (B) is preferably (0.1). : 99.9) to (30:70), and more preferably (0.2: 99.8) to (20:80). It is preferable that the weight ratio of the resin (a) and the resin (b) is within this range since both low-temperature fixability and long-term storage stability are compatible.
For example, when the resin (a) is a crystalline resin, the weight ratio of the resin particles (C) is determined by a known method, for example, the weight ratio of the crystalline resin from the endothermic amount of the endothermic peak inherent to the crystalline resin by DSC. It can be measured by the method of calculating.

The resin particles (C) of the present invention are preferably obtained by the following production method of producing in liquid or supercritical carbon dioxide (X).
Manufacturing method (1)
The resin (b) is contained by dispersing the fine particles (A) and the precursor (b0) of the resin (b) in carbon dioxide (X) in a liquid or supercritical state and further reacting the precursor (b0). Production of resin particles (C) by forming resin particles (C) with fine particles (A) fixed on the surfaces of the resin particles (B) to be removed, and then removing carbon dioxide (X) in a liquid or supercritical state Method.
Manufacturing method (2)
The fine particles (A) and the solution (L) obtained by dissolving the resin (b) in the solvent (S) are dispersed in carbon dioxide (X) in a liquid or supercritical state, and the resin (b) and the solvent (S) are dispersed. The resin particles (C1) in which the fine particles (A) are fixed are formed on the surface of the resin particles (B1) to be contained, and then the carbon dioxide (X) and the solvent (S) in a liquid or supercritical state are removed to thereby remove the resin particles A production method for obtaining (C).
Manufacturing method (3)
The fine particles (A) and a solution (L0) obtained by dissolving the precursor (b0) of the resin (b) in the solvent (S) are dispersed in carbon dioxide (X) in a liquid or supercritical state, and the precursor ( b0) is reacted to form resin particles (C1) in which fine particles (A) are fixed on the surface of resin particles (B1) containing resin (b) and solvent (S), and then in a liquid or supercritical state A method for producing resin particles (C) by removing carbon dioxide (X) and solvent (S).

The production method (2) will be described in detail.
The insoluble content of the resin (b) with respect to the solvent (S) in the equal weight mixture of the solvent (S) and the resin (b) at 23 ° C. and 0.1 MPa is preferably relative to the weight of the resin (b). It is 20 weight% or less, More preferably, it is 15 weight% or less. If the insoluble matter weight is 20% by weight or less, the particle size distribution of the obtained resin particles becomes narrow.
The same applies to the case where the precursor (b0) is used instead of the resin (b) in the production method (3), and the case where a mixture of the resin (b) and the precursor (b0) is used.
Further, after forming the resin particles (C1), the liquid or supercritical carbon dioxide (X) containing the solvent (S) is replaced with carbon dioxide not containing the solvent (S), and (C1) The solvent (S) contained in may be removed, and then the carbon dioxide may be removed under reduced pressure.

  The SP value of the solvent (S) is preferably 9 to 16 and more preferably 10 to 15 from the viewpoint of two-phase separation from carbon dioxide and the viewpoint of dissolving the resin.

  Specific examples of the solvent (S) include, for example, ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvents (acetic acid, etc.). Esters, pyruvic acid esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohols (methanol, ethanol, 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.

From the viewpoint of easy particle formation, dimethylformamide, cyclic ether, pyruvate, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, 2-hydroxyisobutyric acid ester, lactic acid ester, fluorine-containing solvents Alcohol is preferred.
Examples of the cyclic ether include 1,4-dioxane and 1,3-dioxolane.
Examples of pyruvate esters include methyl pyruvate and ethyl pyruvate.
Examples of the ethylene glycol monoalkyl ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Examples of 2-hydroxyisobutyric acid ester include methyl 2-hydroxyisobutyrate.
Examples of the lactic acid ester include methyl lactate and ethyl lactate.
Examples of the fluorine-containing alcohol include 2,2,3,3-tetrafluoropropanol and trifluoroethanol.
As the mixed solvent, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, a mixed solvent of acetone and water, and a mixed solvent of methyl ethyl ketone and water are preferable.
The same applies to the solvent (S) in the production method (3).

The solution (L) of the resin (b) is produced by dissolving the resin (b) in the solvent (S). The concentration of the resin (b) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight with respect to the weight of the solution (L).
The concentration of the precursor (b0) in the solution (L0) in the production method (3) is also the same.

  In the dispersion step of dispersing the resin (b) solution (L) in the production method (2) in carbon dioxide (X), the following dispersant (g) can be used. The dispersant (g) is a compound having at least one of a dimethylsiloxane group and a fluorine-containing functional group. 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 dispersant (g) may be a vinyl resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. preferable.
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. As examples of _{R, -C 3 H 6 OCOC (CH} 3) = CH 2 and the like.

  Moreover, as a monomer (M1-2) containing a fluorine, the fluorine-containing vinyl monomer of the vinyl monomers (8) containing the said halogen element is mentioned.

When the resin (b) is a urethane resin, the dispersant (g) is a urethane resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. preferable.
(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 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.

  Moreover, when resin (b) has an acid value, it is preferable that a dispersing agent (g) has an amino group from a dispersible viewpoint. 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.

  Examples of the dispersant (g) include a monomer (or reactive oligomer) having a dimethylsiloxane group (M1-1) and / or a monomer (M1-2) containing fluorine, and the above-described resin ( A copolymer with the monomer constituting b) is preferable (for example, a copolymer of methacryl-modified silicone and methyl methacrylate, a copolymer of heptafluorobutyl methacrylate and methyl methacrylate, etc.). 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 dispersant (g) is preferably 0.01 to 50% by weight, more preferably 0.02 to 40% by weight, particularly preferably 0, based on the weight of the resin (b) from the viewpoint of dispersion stability. 0.03 to 30% by weight. The range of preferable Mw of a dispersing agent (g) is 100-100,000, More preferably, it is 200-50,000, Most preferably, it is 500-30,000. Within this range, the dispersion stabilizing effect of the dispersant (g) is improved.
In addition, also in manufacturing method (1) and (3), a dispersing agent (g) can be used at a dispersion | distribution process.

  In the present 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 (A ) Directly in (X), and a method in which a dispersion in which fine particles (A) are dispersed in a solvent (T) is introduced into (X).

  The weight ratio (% by weight) 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 (C1) can be manufactured efficiently.

  Examples of the solvent (T) include the same solvent (S). 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 (% by weight) of the fine particles (A) and the solvent (T) is not particularly limited, but the fine particles (A) are preferably 50 or less, more preferably 30 or less, with respect to the solvent (T). Especially preferably, it is 20 or less. Within this range, the fine particles (A) can be efficiently introduced into (X).

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

  In this manner, a dispersion (X0) in which (A) is 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.

  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 · s or less. is there. The solubility of the resin (b) in (X) is preferably 3% or less, more preferably 1% or less.

  In the present 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). 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 carbon dioxide (X) ( A) A method in which the dispersion (X0) in which A is dispersed is sprayed through a spray nozzle to form droplets, the resin in the droplets is supersaturated, and resin particles are precipitated (ASES: Aerosol Solvent Extraction). System (known as System), coaxial multiple tube (double tube, triple tube, etc.) from solution (L), solution (L0), resin (b) precursor (b0), dispersion (X0) A method of obtaining particles by ejecting particles from different pipes together with high-pressure gas, entrainer, etc., and applying external stress to the droplets to promote fragmentation (SEDS: Solution Enhanced Dispersion by) (Known as Supercritical Fluids), a method of irradiating ultrasonic waves, and the like. The same applies to the solution (L0) of the precursor (b0) of the resin (b) and the precursor (b0) of the resin (b) in the production methods (3) and (1).

In this way, while dispersing the solution (L) of the resin (b) in the dispersion (X0) in which (A) is dispersed in carbon dioxide (X) and adsorbing the fine particles (A) on the surface, By growing particles of the dispersed resin (b), resin particles (C1) in which the fine particles (A) are fixed to the surface of the resin particles (B1) containing the resin (b) and the solvent (S) are formed. A dispersion in which (C1) is dispersed in (X) is referred to as dispersion (X1).
The dispersion (X1) is preferably a single phase. That is, when the resin (b) solution (L) is used, it is not preferable that the solvent (S) phase is separated in addition to the phase containing carbon dioxide (X) in which (C1) 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, it is preferably 90% by weight or less with respect to (X0), more preferably 5 to 80% by weight, and particularly preferably 10 to 70% by weight.
In addition, when the solution (L) of the resin (b) or the solution (L0) of the precursor (b0) of the production method (3) is used, resin particles containing the resin (b) and the solvent (S) ( The amount of (S) contained in B1) is preferably 10 to 90% by weight, more preferably 20 to 70% by weight.
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). The same applies to the weight ratio of the precursor (b0) and carbon dioxide (X) in the production methods (1) and (3).

  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 (2) of the present 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 solid phase transition in the pipe during decompression and blocking the flow path, the temperature is preferably 0 ° C. or higher, and the fine particles (A), the resin particles (B1), and the resin particles (C1). ) Is preferably 200 ° C. or lower. Furthermore, 5-150 degreeC is preferable, More preferably, it is 10-130 degreeC, Most preferably, it is 15-100 degreeC, Most preferably, it is 20 degreeC-80 degreeC. The same applies to the temperature of the dispersion (X0) and the dispersion (X1). The same applies to the manufacturing methods (1) and (3). In the production methods (1) to (3) of the present invention, the operation performed in carbon dioxide (X) can be performed at a temperature higher or lower than the Tg or melting point of the fine particles (A). It is preferable to carry out at a temperature below.

  In the production method (2) of the present 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 (C1) in (X), it is preferably 1.5 MPa or more, and preferably 40 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 1.7-35 MPa, More preferably, it is 2.0-30 MPa, Especially preferably, it is 2.2-25 MPa, Most preferably, it is 2.3-20 MPa. The same applies to the pressure in the container forming the dispersion (X0) and the dispersion (X1). The same applies to the manufacturing methods (1) and (3).

  In the production method (2) of the present 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 the range. 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). The same applies to the manufacturing methods (1) and (3).

  In the carbon dioxide (X) in the present invention, other substances (e) may be 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 other substances (e) in the present invention is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more. is there.

  From the dispersion (X1) in which the resin particles (C1) are dispersed, carbon dioxide (X) is 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. When collecting the resin particles under high pressure after collecting under high pressure, the collection container may be depressurized by batch operation, or the continuous extraction operation is performed using a rotary valve. May be.

  When the fine particles (A) contain a crystalline resin, after forming the resin particles (C1), if necessary, as a further step, the crystalline resin, preferably the melting point minus 50 ° C. or more, more preferably By heating to a melting point minus 10 ° C. or higher, more preferably higher than the melting point, the fine particles (A) adhering to the surface of the resin particles (B) are melted, and the fine particles (A) are applied to the surfaces of the resin particles (B). A step of forming a resin particle (C2) by forming a film derived from fixing or fine particles (A) can also be performed. From the viewpoint of suppressing aggregation of (C2), the heating time is preferably 0.01 to 1 hour, more preferably 0.05 to 0.7.

In the resin particles (C) of the present invention obtained by the production methods (1) to (3) of the present invention, the fine particles (A) are once fixed on the surface of the resin particles (B) or (B1). Depending on the composition of a) and resin (b) and the type of solvent (S) or (T), fine particles (A) are formed into a film during the production process, and (A) is formed on the surface of (B). May be formed.
The resin particles (C) of the present invention are those in which the fine particles (A) are fixed on the surface of the resin particles (B), those in which a film derived from (A) is formed, and a part of (A) is formed into a film Any of the above 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).

  After forming the resin particles (C1) [including the case of the resin particles (C2)], it is preferable to perform a step of removing or reducing the solvent (S) as a further step as necessary. That is, when the solvent (S) is contained in the dispersion (X1) in which (C1) is dispersed in carbon dioxide (X), when the container is decompressed as it is, the solvent dissolved in (X1) is condensed and the resin When the particles (C1) are redissolved or the resin particles (C1) are collected, there may be a problem that the resin particles (C1) are united with each other. As a method for removing or reducing the solvent, for example, a dispersion containing resin particles (C1) obtained by dispersing a solution (L) of the solvent (S) of the resin (b) in (X) ( X1) is further mixed with carbon dioxide [preferably carbon dioxide (X)] to extract the solvent (S) from the resin particles (C1) into the carbon dioxide phase, and then carbon dioxide containing the solvent (S). Is preferably replaced with carbon dioxide not containing the solvent (S) [preferably carbon dioxide (X)], and then the pressure is reduced.

  In the mixing method of the dispersion (X1) in which the resin particles (C1) are dispersed in carbon dioxide (X) and carbon dioxide, carbon dioxide having a higher pressure than (X1) may be added. ) Although it may be added to carbon dioxide at a lower pressure, the latter is more preferable from the viewpoint of ease of continuous operation. The amount of carbon dioxide mixed with (X1) is preferably 1 to 50 times, more preferably 1 to 40 times, most preferably 1 from the viewpoint of preventing coalescence of the resin particles (C1). ~ 30 times. By removing or reducing the solvent contained in the resin particles (C1) as described above and then removing carbon dioxide, it is possible to prevent the resin particles (C1) from being united.

  As a method of replacing carbon dioxide containing the solvent (S) with carbon dioxide not containing the solvent (S), the resin (C1) is once supplemented with a filter or cyclone, and then the solvent (S) is maintained while maintaining the pressure. A method of circulating carbon dioxide until it is completely removed can be mentioned. The amount of carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, most preferably 1 to 30 times the volume of (X1) from the viewpoint of solvent removal from the dispersion (X1). Is double.

Next, the production method (1) will be described in detail.
In the present invention, the precursor (b0) of the resin (b) is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin, (B0) includes the above-mentioned vinyl monomers (which may be used alone or in combination), and the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin, polyester resin). In the case of (b0), a combination of the prepolymer (α) having a reactive group and the curing agent (β) is exemplified.

  When a vinyl monomer is used as the precursor (b0), (b0) may contain a commonly used initiator. Examples of the initiator include peroxide polymerization initiator (I) and azo polymerization initiator (II). Further, the redox polymerization initiator (III) may be formed by using the peroxide polymerization initiator (I) and the reducing agent in combination. Furthermore, you may use 2 or more types together from (I)-(III).

  When the initiator is used, it is preferable to mix with the monomer in advance before dispersing (b0) in carbon dioxide (X). The polymerization temperature is preferably 40 to 100 ° C, more preferably 60 to 90 ° C.

As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). The following (1), (2), etc. are mentioned as a combination of the reactive group which a reactive group containing prepolymer ((alpha)) and a hardening | curing agent ((beta)).
(1): The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). There is a combination.
(2) The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) capable of reacting with an active hydrogen-containing group. combination.

  In the combination (1), the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof . Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy), and (αz) are preferable, and (αx) and (αz) are particularly preferable. Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like. Examples of the polyester (αx) include a polycondensate of diol (12) and dicarboxylic acid (14), polylactone (a ring-opening polymerization product of ε-caprolactone), and the like. Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin. Examples of polyurethane (αz) include polyaddition product of diol (12) and polyisocyanate (16), polyaddition product of polyester (αx) and polyisocyanate (16), and the like.

  As a method of incorporating a reactive group into polyester (αx), epoxy resin (αy), polyurethane (αz), etc., (1): by using one of two or more components in excess, A method of leaving a functional group at the end, (2): by using one of two or more constituent components in excess, the functional group of the constituent component can be left at the end and further reacted with the remaining functional group Examples include a method of reacting a compound containing a functional group and a reactive group. In the above method (1), a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent component is preferably 2 as the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. / 1-1 / 1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of prepolymers having other skeletons and other end groups, the ratios are the same except that the constituent components are changed. In the said method (2), an isocyanate group containing prepolymer is obtained by making polyisocyanate react with the preprimer obtained by the said method (1), and blocked isocyanate group containing prepolymer is made to react with blocked polyisocyanate. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride. The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The molar ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and other end groups, the ratios are the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The Mw of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 4,000 to 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, at 100 ° C. Setting it to 200 Pa · s or less is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of solvent.

  Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Of these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines (β1a) and (Β1d). (Β1a) is exemplified by those similar to polyamine (17). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and mixtures thereof.

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

  Examples of the polyol (β1b) are the same as the diol (12) and the polyol (13). Diol (12) alone or a mixture of diol (12) and a small amount of polyol (13) is preferred.

  Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

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

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

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

  Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (16), and preferred ones are also the same.

  Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (19), and preferred ones are also the same.

  Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred. Examples of the dicarboxylic acid (β2c-1) include the same as the dicarboxylic acid (14), and examples of the polycarboxylic acid include the polycarboxylic acid (15), and preferable examples thereof are also the same.

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

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

  When the combination of the prepolymer (α) having a reactive group and the curing agent (β) is used as the precursor (b0), in the dispersion (X0) in which the fine particles (A) are dispersed in carbon dioxide (X) The method of reacting (b0) is not particularly limited, but a method of mixing (α) and (β) immediately before dispersing (b0) in (X0) and reacting at the same time as dispersing is preferred. Although reaction time is selected by the reactivity by the structure of the reactive group which prepolymer ((alpha) has), and the combination of a hardening | curing agent ((beta)), Preferably it is 5 minutes-24 hours. The reaction may be completed in (X0) before depressurization, or may be allowed to react to some extent at (X0), depressurized and (C) is taken out, and then aged in a thermostatic bath or the like to be completed. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of reaction of an isocyanate and an active hydrogen compound. The reaction temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

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

In addition, a reactive group-containing prepolymer (α) and a polymer that does not react with the curing agent (β) during reaction of the reactive group-containing prepolymer (α) with the curing agent (β) [so-called dead polymer] are incorporated into the system. It can also be contained. In this case, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) and an unreacted resin.
In the case of the production method (1), the above-mentioned matters and the precursor during dispersion using the precursor (b0) of the resin (b) instead of the solution (L) obtained by dissolving the resin (b) in the solvent (S) Except for reacting (b0), this is the same as Production Method (2).

The production method (3) will be described in detail.
Instead of the solvent (S) solution (L) of the resin (b), the solvent (S) solution (L0) of the precursor (b0) of the resin (b) is used to react the precursor (b0) during dispersion. Except for the above, it is the same as the manufacturing method (2).

  According to the said manufacturing method (1)-(3), the resin particle (C) of this invention which does not contain the surfactant which has a hydrophilic group substantially can be manufactured. 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) and the like.

  Specific examples of these surfactants include those described in International Publication WO2003 / 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 exchange water is added thereto, stirred with a magnetic stirrer, the resin particles are floated on the liquid surface, acetone is dripped little by little, and the resin particles floating on the 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 resin particle surface 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. . If δm is 9.8 to 21, the moisture resistance storage stability of the resin particles is good, and the electrical properties, fluidity, and fixability when used as resin particles for electrophotographic toners under high humidity are good. . This measurement method cannot measure less than 9.8.

The resin particle (C) is obtained by changing 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). Desired unevenness can be imparted to the 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 BET specific surface area of the resin particles is preferably 0.5 to 5.0 m ² / g. The BET specific surface area was measured (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen) using a specific surface area meter such as QUANTASORB (manufactured by Cantachrome Instruments Japan GK). Is. 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) obtained by the production method of the present invention have a sharp particle size distribution and are usually hydrophobic because they do not contain a water-soluble surfactant or ionic substance. Therefore, the resin particles (C) of the present invention are the base particles of an electrophotographic toner, paint additives, adhesive additives, cosmetic additives, paper coating additives, slush molding resins, powder paints, It is also useful as a spacer for manufacturing electronic parts, a carrier for catalysts, standard particles for electronic measuring instruments, particles for electronic paper, medical diagnostic carriers, chromatographic fillers, particles for electrorheological fluids, and the like.

  Moreover, in the resin particle (C) of the present invention, when the fine particles (A) contain a crystalline resin having a melting point of 50 to 110 ° C., it is particularly excellent in low-temperature meltability and excellent in heat-resistant storage stability.

  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, number average molecular weight (Mn), weight average molecular weight (Mw), melting point, and glass transition temperature were measured by the following methods. The SP value was calculated by the method described above.
<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 Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw)>
It was measured by GPC by the method described above.

Production Example 1 <Preparation of Resin (b-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 438 parts of sebacic acid, 682 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed at 190 ° C. The reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and it took out when Mn became 5,400. The resin taken out was cooled to room temperature and then pulverized into particles (b-1). The melting point (TMA) of (b-1) was 66 ° C., Mn was 5,400, and the hydroxyl value was 31.

Production Example 2 <Preparation of Resin (b-2) for Comparative Example>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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 parts 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-2). This resin had Mn of 1900 and Tg of 45 ° C.

Production Example 3 <Preparation of Macromonomer (M-1) Solution>
A container equipped with a stirrer was charged with 400 parts of THF and 229 parts of tolylene diisocyanate, and the air in the reaction container was purged with nitrogen, followed by heating to 40 ° C. Next, 171 parts of hydroxyethyl methacrylate was added dropwise over 1 hour, 0.1 part of triethylamine was added, and the reaction was carried out at 40 ° C. for 1 hour to obtain a vinyl monomer (M0-1) solution having an isocyanate group at the molecular end. Next, 398 parts of THF and 398 parts of resin (b-2) are charged into a container equipped with a stirrer, and the air in the reaction container is purged with nitrogen, and then heated to uniformly form resin (b-2) at 70 ° C. Dissolved in. To this, 56 parts of a vinyl monomer (M0-1) solution was added dropwise over 1 hour, 0.1 part of triethylamine was added and reacted at 70 ° C. for 3 hours to obtain a macromonomer (M-1) solution. The NCO content of the macromonomer (M-1) solution was 0.0%.

Example 1 <Preparation of Resin (a-1)>
In an autoclave equipped with a stirrer and a thermometer, (b-1) 105 parts, diol-modified silicone (SP value 7.6, Mn5,000, JNC: FM-DA21) 79 parts as a monomer, hydrogenated bisphenol A81 parts, 650 parts of toluene, and 84 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 5 hours, and then the solvent was removed to obtain (a-1). This resin had Mn of 14,000, Mw of 32,000, and a melting point (TMA) of 55 ° C.

Example 2 <Preparation of Resin (a-2)>
In an autoclave equipped with a stir bar and a thermometer, 105 parts of (b-1) and 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (SP Value 7.9, Mn414, manufactured by Daikin: A-7412) 79 parts, 59 parts of hydrogenated bisphenol A, 650 parts of toluene, 106 parts of isophorone diisocyanate were reacted at 90 ° C. for 5 hours, and then the solvent was removed. (A-2) was obtained. This resin had Mn of 32,000, Mw of 70,000, and a melting point (TMA) of 56 ° C.

Example 3 <Preparation of Resin (a-3)>
In an autoclave in which a stir bar and a thermometer were set, (b-1) 105 parts, carbinol-modified silicone (SP value 7.6, Mn 2,000, manufactured by Shin-Etsu Chemical Co., Ltd .: KF-6001) 79 parts as a monomer, 45 parts of hydrogenated bisphenol A, 24 parts of 2,2-bis (hydroxymethyl) propionic acid, 650 parts of toluene, and 96 parts of isophorone diisocyanate were reacted at 90 ° C. for 5 hours, and then the solvent was removed (a- 3) was obtained. This resin had Mn of 17,000, Mw of 35,000, and a melting point (TMA) of 54 ° C.

Comparative Example 1 <Preparation of Resin (a′-1)>
In a reaction vessel equipped with a stirrer, 500 parts of THF was charged and the air in the reaction vessel was purged with nitrogen, followed by heating to reflux temperature. Next, 160 parts of behenyl acrylate, 60 parts of methacrylic acid, 200 parts of the macromonomer (M-1) solution obtained in Production Example 3, methacryl-modified silicone (SP value 7.6, Mw 12,000, Shinetsu) as the monomer (Chemical Industry: X22-2426) A mixture of 80 parts and 1.5 parts of azobisisobutyronitrile was appropriately placed in a reaction vessel in 2 hours and then aged at reflux temperature for 6 hours to give a vinyl resin (a′-1 ) Containing fine particles (A′-1) dispersion. The Mn of the vinyl resin (a′-1) obtained by removing the medium was 104,000, Mw was 260,000, and the melting point was 65 ° C.

Production Example 4 <Preparation of Fine Particle (A-1) Dispersion>
In a reaction vessel equipped with a stirrer, 100 parts of (a-1) and 349 parts of THF were charged and dissolved at 50 ° C. to obtain a solution of (a-1), and then hexane was added to the reaction vessel equipped with another stirrer. Into 551 parts, a dispersion of fine particles (A-1) was obtained. The volume average particle diameter of the fine particles (A-1) was 0.07 μm, and the degree of swelling was 4%.

Production Example 5 <Preparation of Fine Particle (A-2) Dispersion>
In a reaction vessel equipped with a stirrer, 100 parts of (a-2) and 349 parts of THF were charged and dissolved at 50 ° C. to obtain a solution of (a-2), and then hexane was added to the reaction vessel equipped with another stirrer. Into 551 parts, a dispersion of fine particles (A-2) was obtained. The volume average particle diameter of the fine particles (A-2) was 0.07 μm, and the degree of swelling was 4%.

Production Example 6 <Preparation of Fine Particle (A-3) Dispersion>
In a reaction vessel equipped with a stirrer, 100 parts of (a-3) and 900 parts of acetone were charged and dissolved at 50 ° C., and then cooled to 0 ° C. to obtain a dispersion of fine particles (A-3). The volume average particle diameter of the fine particles (A-3) was 0.08 μm, and the degree of swelling was 7%.

Production Example 7 <Preparation of Resin (b-3)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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 parts 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-3). This resin had Mn of 1900 and Tg of 45 ° C.

Production Example 8 <Preparation of Resin (b-4)>
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 mixture was allowed to react 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-4). This resin had Mn of 5700 and Tg of 63 ° C.

Production Example 9 <Preparation of Resin Solution (L-1)>
In a container equipped with a stirrer, 594 parts of acetone and 6 parts of ion-exchanged water are mixed solvent (S-1), 292 parts of resin (b-3) obtained in Production Example 7, and Production Example 8 108 parts of the resin (b-4) obtained in the above was added and stirred until the resin (b-3) and the resin (b-4) were completely dissolved to obtain a resin solution (L-1).

Production Example 29 <Preparation of Dispersant (g-1) Solution>
(B-1) 284 parts, isophorone diisocyanate 29 parts and toluene 687 parts were charged in an autoclave equipped with a stir bar and a thermometer, reacted at 90 ° C., and a precursor having an isocyanate group at the molecular end (g0-1 ) A solution was obtained. Next, 66 parts of amino-modified silicone (SP value 7.6, Mn 10,000, manufactured by Shin-Etsu Chemical Co., Ltd .: KF-8008) was added to a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube. After adding 792 parts of THF and replacing the air in the reaction vessel with nitrogen, 108 parts of the (g0-1) solution adjusted to 40 ° C. was appropriately placed in the reaction vessel in 2 hours and then aged at 40 ° C. for 2 hours. Then, the solvent was removed to obtain a dispersant (g-1). Next, 500 parts of dispersant (g-1) and 500 parts of acetone were charged in an autoclave equipped with a stir bar and a thermometer and dissolved at 90 ° C. to obtain a solution (G-1) of dispersant (g-1). It was.

Example 4
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99 wt%) was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the pressure was adjusted to 3 MPa and 30 ° C. The resin solution tank L1 was charged with the resin solution (L-1) and the dispersant solution (G-1), and the fine particle dispersion tank T2 was charged with the fine particle (A-1) dispersion. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 3 MPa and 30 ° C., and the fine particle (A-1) dispersion was introduced from the tank T2 and the pump P2. Next, while stirring the inside of the dispersion tank T3 at 1000 rpm, the resin solution (L-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1. After the introduction, the pressure inside T3 was 3 MPa.

In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L-1) 272 parts Fine particle (A-1) dispersion 86 parts Dispersant solution (G-1) 47 parts Carbon dioxide 586 parts The weight of carbon dioxide introduced is the temperature of carbon dioxide (30 ° C) The density of carbon dioxide was calculated from the state equation described in the following document from the pressure (3 MPa) and multiplied by the volume of the dispersion tank T3.
Literature: 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 cooled to 15 ° 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 6 MPa by the pressure regulating 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 in which the film derived from the fine particles (A) is formed on the surface of the resin particles (B) supplemented by the filter F1. Particles (C-1) were obtained.

Examples 5 and 6
Resin particles were obtained in the same manner as in Example 1 except that instead of the fine particle (A-1) dispersion, a fine particle (A-2) dispersion and a fine particle (A-3) dispersion were used. Resin particles (C-2) and resin particles (C-3) in which a coating derived from the fine particles (A) was formed on the surface of (B) were obtained.

Comparative Example 2
In the same manner as in Example 1 except that the fine particle (A′-1) dispersion was used instead of the fine particle (A-1) dispersion in Example 4, the fine particles (A Comparative resin particles (C′-1) on which a film derived from “) was formed were obtained.

  Table 1 shows the raw materials and physical property values of the resin particles of the present invention and comparative resin particles.

Evaluation Results For the resin particles obtained in Examples 4 to 6 and Comparative Example 2, the surface wettability, particle size distribution, heat resistant storage resistance, moisture heat resistant storage resistance, and low temperature meltability (melting temperature) were evaluated by the following evaluation methods. The results are shown in Table 2.
<Evaluation of particle size distribution>
Resin particles are dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1% by weight), and the volume average particle size / number average particle size of the resin particles (denoted as C in the table) is set to a Coulter counter [Multisizer III (Beckman・ Made by 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 15 hours in a dryer adjusted to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied 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 15 hours in a thermostatic oven controlled at 50 ° C. and humidity 80%, and evaluated according to the following criteria depending on the degree of blocking.
○: 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>
Using the resin particles obtained in Examples 1 to 3 and Comparative Example 1, 1.0% by weight of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to each resin particle and mixed well using a mixer. Aerosil R972 Produced resin particles for evaluation of low-temperature meltability uniformly adhered to the surface of the resin particles.
5 mg of each of the obtained samples was weighed and melted at a low temperature (melting temperature) at a heating rate of 10 ° C. per minute by DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology). Evaluated. If the melting temperature is 125 ° C. or lower, it is judged that the low-temperature melting property is very excellent.

  The resin particles obtained in Examples 4 to 6 had a small volume average particle size / number average particle size, a sharp particle size distribution, and excellent low-temperature meltability, whereas the resin particles obtained in Comparative Example 1 Had inferior particle size distribution.

  The resin particles of the present invention include paint additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, electronic measuring instrument standard particles, and electronic paper particles. It is useful as a carrier for medical diagnosis, electrorheological particles, base particles of electrophotographic toner, and other molding resin particles.

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 (12)

A resin (a) having the monomer (m1) as an essential constituent monomer, wherein the proportion of the monomer (m1) is 0.1 to 35% by weight based on the weight of the resin (a); The resin (a) characterized by satisfying the following conditions 1 and 2.
[Condition 1] The resin (a) has a glass transition temperature (TGa) and / or a melting point (TMa), at least one of which is 30 ° C. or higher and 150 ° C. or lower, and the weight average molecular weight of the resin (a) is 200,000 or lower.
[Condition 2] The number average molecular weight of the monomer (m1) is 100 or more and 30000 or less, and the solubility parameter [SP value] of the monomer (m1) is 7.0 to 9.5.   Monomer (m1) is a silicone-containing monomer (m11), a perfluoroalkyl-containing monomer (m12), an alkyl group-containing monomer (m13) having 8 to 30 carbon atoms, and an alkylene oxide adduct-containing single amount The resin (a) according to claim 1, which is one or more monomers selected from the group consisting of the body (m14).   The resin (a) according to claim 1 or 2, wherein the amount of the resin (a) dissolved at 30 ° C in a hexane / acetone mixed medium (mixing weight ratio = 76/24) is 30% by weight or less.   The resin (a) according to any one of claims 1 to 3, which is at least one selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, polyurea resins and polyepoxy resins. The resin (a) according to any one of claims 1 to 4, wherein the monomer (m1) includes a silicone-containing monomer (m11) and satisfies the following condition 3.
[Condition 3] (Si-1) / (Si-0) ≧ 1.05
(Si-1): Amount of surface silicon of the resin (a1) after the resin (a) and liquid or supercritical carbon dioxide (X) are mixed and processed (Si-0): normal pressure of the resin (a) Surface silicon content of resin (a0) after heat softening treatment in nitrogen The resin (a) according to any one of claims 1 to 4, wherein the monomer (m1) includes a perfluoroalkyl-containing monomer (m12), and the resin (a) satisfies the following condition 4.
[Condition 4] (F-1) / (F-0) ≧ 1.05
(F-1): Surface fluorine content of resin (a1) after mixing treatment of resin (a) and carbon dioxide (X) in liquid or supercritical state (F-0): Resin (a) at normal pressure Surface fluorine content of resin (a0) after heat softening treatment in nitrogen   The degree of swelling of the resin (a) with carbon dioxide (X) in a liquid or supercritical state at a temperature lower than the glass transition temperature (TGa) or lower than the melting point (TMa) is 16% or less. (A).   A resin particle (C) in which the fine particles (A) containing the resin (a) according to any one of claims 1 to 7 are fixed to the surface of the resin particles (B) containing the resin (b), Resin particles (C) in which the weight ratio (a: b) between (a) and the resin (b) is (0.1: 99.9) to (30:70).   The resin (b) is contained by dispersing the fine particles (A) and the precursor (b0) of the resin (b) in carbon dioxide (X) in a liquid or supercritical state and further reacting the precursor (b0). Forming resin particles (C) having fine particles (A) fixed on the surfaces of the resin particles (B) to be obtained, and then removing carbon dioxide (X) in a liquid or supercritical state to obtain resin particles (C) The manufacturing method of the resin particle (C) of Claim 8 containing this.   The fine particles (A) and the solution (L) obtained by dissolving the resin (b) in the solvent (S) are dispersed in carbon dioxide (X) in a liquid or supercritical state, and the resin (b) and the solvent (S) are dispersed. The resin particles (C1) in which the fine particles (A) are fixed are formed on the surface of the resin particles (B1) to be contained, and then the carbon dioxide (X) and the solvent (S) in a liquid or supercritical state are removed to thereby remove the resin particles The manufacturing method of the resin particle (C) of Claim 8 including the process of obtaining (C).   The fine particles (A) and a solution (L0) obtained by dissolving the precursor (b0) of the resin (b) in the solvent (S) are dispersed in carbon dioxide (X) in a liquid or supercritical state, and the precursor ( b0) is reacted to form resin particles (C1) in which fine particles (A) are fixed on the surface of resin particles (B1) containing resin (b) and solvent (S), and then in a liquid or supercritical state The manufacturing method of the resin particle (C) in any one of Claim 8 including the process of obtaining the resin particle (C) by removing the carbon dioxide (X) and solvent (S).   After forming the resin particles (C1), the liquid or supercritical carbon dioxide (X) containing the solvent (S) is replaced with carbon dioxide not containing the solvent (S), and contained in (C1) The method for producing resin particles (C) according to claim 10 or 11, wherein the solvent (S) to be removed is removed, and then the pressure is reduced to remove carbon dioxide.

Images