TWI363070B - - Google Patents

Description

1363070 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a crosslinked polymer particle and a method of producing the same. [Prior Art] Crosslinked polymer particles having a high degree of crosslinking and excellent heat resistance and chemical resistance can be applied and put to practical use in resin films starting from various electrical and electronic materials such as various spacers and conductive fine particles. It is used in various fields such as modifiers for lubrication properties, carriers for chromatography, and components for biomedicine. In general, these crosslinked polymer particles can be produced by a method such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the suspension polymerization, the cross-linkable monomer is polymerized as an oil droplet in an aqueous medium by mechanical force to produce a crosslinked polymer particle. In the case of emulsion polymerization, the upper limit of the ratio of the general crosslinkable monomer is about 0.2% by mass. Further, the obtained crosslinked polymer particles had a particle diameter in the range of 0.1 to Ι. Ομπι, and it was not possible to obtain crosslinked polymer particles having a particle diameter exceeding Ιμη. Patent Document 1 discloses a method in which emulsion polymerization can be stably carried out by using a special seed even if a cross-linking monomer of 20.0% by mass or more is used. However, the range of the particle diameter obtained by the method is the same as that of the general emulsion polymerization. 1~1 .Ομιη. Thus, it is difficult to obtain crosslinked polymer particles having a particle diameter exceeding Ιμπ by emulsion polymerization. Patent Document 2 discloses that an organic compound having a small solubility in water is absorbed as a swelling aid in the first stage of the seed polymer, and after it is in the range of -5 to 1363070, the monomer which is soluble in water to some extent is absorbed in the seed polymerization. The second step of the monomer swelling particles is formed, and the swelling polymerization method of the polymerization monomer is carried out in the particle shape. In this method, a large amount of crosslinkable monomer can be used, and as a result, crosslinked polymer particles having a uniform particle diameter distribution of a size of Ιμπι or more can be produced. However, since the swelling aid used in the method has a significantly low solubility in water, it has a drawback that it takes a long time to absorb the first step of the seed polymer. However, residual oil droplets which are not absorbed in the seed polymer sometimes form coarse particles after polymerization. Patent Document 3 discloses crosslinking by a dispersion polymerization method using 20% by mass or more of a crosslinkable vinyl monomer. The method of manufacturing particles. In this method, monodisperse particles of several micrometers can be produced to some extent. However, when the particle diameter exceeds 2.5 μm, the aggregation and aggregation of the particles increase, and it is extremely difficult to obtain monodisperse particles. Further, when a hydrophilic or water-soluble polymerizable monomer is copolymerized, it is easy to cause aggregation and fusion, so that it becomes difficult to obtain a single layer of monodisperse particles. Patent Document 4 discloses a method of producing a crosslinked polymer particle by copolymerizing an unsaturated monomer having a hydrophilic functional group or an active hydrogen group with a crosslinkable monomer in a precipitation polymerization method similar to the dispersion polymerization method. . This method can obtain a monodisperse particle of several μη efficiently. Patent Document 5 discloses that an uncrosslinked mother particle having a functional group is reacted with an epoxy compound, an oxazoline compound or an amine compound to cause a parent particle to be mixed. The method of the union. In this method, the uncrosslinked particles can be crosslinked. However, since the reacted compound has high reactivity, the crosslinking reaction is carried out mainly on the surface of the particles, and the core-shell structure tends to be formed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 4] JP-A-2006-282772 (Patent Document 5) Patent No. 42 1 5 5 2 1 φ [Non-Patent Document] [Non-Patent Document 1] Journal of Polymer Science. Part A: Polymer Chemistry, ( (USA), 31, 3, 25 7 (1 993) [Disclosure] In order to solve the problem of the invention, for example, in the case of the mother particles, when the functional group derived from the hydrophilic monomer is contained on the surface and inside of the particles, The compression deformation recovery rate # and the compression characteristics of the compression failure strength are difficult to achieve a sufficient level of polymer particle system. For example, when the polymer particles are covered with a metal layer to form conductive particles, it is extremely important that the polymer particles have good compression characteristics when used for an anisotropic conductive adhesive. Further, when a metal plating layer is formed by plating treatment on the surface of the polymer particles simultaneously with the compression characteristics, it is expected to form a plating layer having high uniformity and good adhesion. However, since the functional group derived from the hydrophilic monomer is not on the surface of the particles, since the plating formation property cannot be obtained, it is necessary to carry out the pre-plating treatment step. In this case, it is difficult to obtain an excellent polymer 1363070 particle which has excellent compression characteristics and is excellent in plating formability. The main object of the present invention is to provide a polymer particle having a good compression property while forming a plating layer on the surface in a good state. Means for Solving the Problems The present invention relates to a first amine-based compound having two or more amine groups by having a mother particle formed of a crosslinked polymer having a functional group, and one of the aforementioned functional groups The step of reacting the functional group with the amine group to further crosslink the crosslinked polymer (a), and after the step (a), by using a second amine compound different from the first amine compound having an amine group The reaction of the above-mentioned functional group remaining in the crosslinked polymer, which has the production method of the step (b) of the mother particles and the crosslinked polymer particles of the amine group derived from the second amino group compound Crosslinking polymer particles. By using the crosslinking of the first amine-based compound, it is possible to impart good compression characteristics to the crosslinked polymer particles. Further, by the introduction of the amine group of the second amine group compound, the crosslinked polymer particles which can form the shovel layer on the surface in a good state can be obtained. More specifically, for example, a Pd ionomer is used as a plating catalyst, and when the crosslinked polymer particles are subjected to plating, the Pd ionomer can be closely adhered to the crosslinked polymer particles, and the plating layer is applied. Not only can it be formed under good uniformity, but also the adhesion strength between the plating layer and the crosslinked polymer particles can be improved. It is preferred that the second amine group compound and the functional group in the mother particle are reacted at 60 t or less. By using a highly reactive amino group compound, there is no substantial influence on the compression characteristics of the particles, and an amine group can be easily introduced. -8 to 1363070 It is preferred that the above second amino group compound has two or more amine groups. The second amino compound having an aziridine group is preferred. The aziridine group of the second amino group compound reacts with a functional group (for example, a carboxyl group) in the mother particle at a relatively low temperature (for example, 60 ° C or lower), so that the amine particle can be efficiently and surely introduced into the surface of the mother particle. base. The average particle diameter of the crosslinked polymer particles is preferably from 0.1 to ΙΟμηη. The Cv 粒子 of the particle diameter of the crosslinked polymer particles is preferably 10% or less. Crosslinking polymerization # The lower the Cv値 of the particle diameter of the particles, the more the conductive particles obtained by crosslinking the polymer particles are used for the anisotropic conductive adhesive, and the subsequent reliability can be further improved. The crosslinked polymer forming the above-mentioned mother particles is preferably one having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a glycidyl group. These functional groups react efficiently with the amine groups of the first amino compound to form a crosslinked structure in the parent particles. The above-mentioned mother particles are preferably those obtained by suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization or seed polymerization. The crosslinked polymer forming the above-mentioned mother particles is preferably a copolymer obtained by copolymerizing a monomer mixture containing a monomer having 2 or more unsaturated double bonds of 10% by mass or more. Thereby, the compression characteristics of the crosslinked polymer particles can be efficiently improved. The monomer having two or more unsaturated double bonds preferably contains at least one selected from the group consisting of divinylbenzene and di(meth)acrylate, and the mother particles after the step (a) are at 180 ° C. 40% or more of the compression deformation recovery rate and the compression fracture strength of 1 〇mN or more are preferred 1363070. The present invention relates to an electroconductive particle which can be provided by the crosslinked polymer particles related to the above invention. The method of manufacturing the step (C) of plating is obtained. The conductive particles according to the present invention are used, for example, as conductive particles for an anisotropic conductive adhesive. In the step (c), it is preferred to apply plating to the crosslinked polymer particles used as the plating catalyst for the Pd ionomer. On the other hand, the present invention relates to a method of producing crosslinked polymer particles. The manufacturing method of the present invention comprises the steps (a) and (b), wherein the step (a) is a mother particle formed by a crosslinked polymer having a functional group, and the first one having two or more amine groups The step of contacting the amine-based compound to further crosslink the cross-linked polymer by reacting a part of the functional group with the amine group; and the step (b) is followed by the step of (a) The reaction of the second amino group compound different in the first amino group compound with the aforementioned functional group remaining in the crosslinked polymer to obtain an amine group derived from the second amine group compound bonded to the mother particle The step of crosslinking the polymer particles. The above-mentioned method of the present invention can obtain crosslinked polymer particles which can form a plating layer in a good state on the surface while having good compression characteristics. In the step (a), the ratio of the amine group contained in the first amino group compound is preferably 0.1 to 5 equivalents based on 1 equivalent of the aforementioned functional group in the mother particle. In the step (b), the ratio of the reactive group contained in the second amino group-containing compound to the aforementioned functional group is preferably 0.1 to 5 equivalents based on 1 equivalent of the aforementioned functional group in the mother particle. Treating mother particles by using these ratios of amine-based compounds

When S -10- 1363070, crosslinked polymer particles having excellent compression characteristics and plating formability can be obtained. EFFECT OF THE INVENTION The present invention provides a polymer particle which has a good compression property and which forms a plating layer in a good state on the surface. φ Embodiment of the Invention Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The crosslinked polymer particles of the present embodiment are obtained by a production method comprising the following steps, steps (a) and (b), wherein the first step is prepared by forming a crosslinked polymer having a functional group. The step of the mother particle: the step (a) is: contacting the mother particle with the first amine compound having two or more amine groups, and crosslinking by one of the functional groups of the functional group and the amine group Step (a) of further crosslinking of the polymer: step (b) is after the step (a) by remaining a second amine compound different from the first amine compound having an amine group and remaining in the crosslinked polymer The reaction of the aforementioned functional group to obtain a crosslinked polymer particle having a mother particle and an amine group derived from the second amino group compound bonded to the mother particle. FIG. 1 shows an embodiment of the crosslinked polymer particle. Pattern diagram. The crosslinked polymer particles 1 shown in Fig. 1 are a mother particle 1 having a mother particle 10 and a particulate crosslinked polymer, and a crosslinked portion X derived from a first amine compound which crosslinks the crosslinked polymer. Modified -11-1363070 part R having an amine group derived from a second amino group compound. The crosslinked portion X is distributed on the entire surface and the inside of the mother particle 10. The modifying portion R is mainly distributed on the surface of the mother particle 10. The crosslinked polymer constituting the mother particle 10 is, for example, a styrene resin, an acrylic resin, a methacrylic resin, a polyethylene resin, a polypropylene resin, a polyoxyn resin, a polyester resin, or a polyurea. An alkyl resin, a polyamine resin, an epoxy resin, a polyvinyl butyral resin, a rosin resin, a fluorene resin, a phenol resin, a melamine resin, a guanamine resin, or an oxazoline system A resin, a carbodiimide-based resin or a hardened resin obtained by crosslinking these. These may be used alone or in combination of two or more. In these polymers, a functional group (carboxyl group, epoxy group, epoxy group, etc.) which reacts with the first amine compound and the second amine compound may be introduced. . The preferred mother particles 10 are particles of a crosslinked polymer formed by copolymerization of a monomer mixture of a plurality of monomers having an unsaturated double bond. The monomer mixture 'e.g., a monomer having a polyfunctional group having two or more unsaturated double bonds, and a monomer having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, and a glycidyl group. The content of the polyfunctional monomer having two or more unsaturated double bonds in the monomer mixture is preferably 10% by mass or more based on the entire monomer mixture. Thereby, it is particularly easy to form crosslinked polymer particles having a high recovery rate of compression deformation. When the crosslinked polymer particles have a high recovery rate of compression deformation, when the crosslinked polymer particles are used as the polymer particles constituting the conductive particles of the heteroconductive conductive adhesive, the connection resistance caused by the passage of time can be suppressed. Increased to achieve higher continuity of reliability. From this point of view, the monomer

S -12-1363070 The content of the polyfunctional monomer having two or more unsaturated double bonds in the mixture is preferably from 10 to 80% by mass, more preferably from 10 to 60% by mass, preferably further. It is 1G to 50% by mass. The mother particles 10 are preferably obtained by a method of dissolving a monomer mixture and performing solution polymerization in a medium which is substantially insoluble in the formed crosslinked polymer. As a bulk polymerization, a crosslinked polymer can be formed without a solvent. Examples of the solution polymerization include (1) emulsification in an aqueous solution or φ suspension polymerization, (2) a nonaqueous organic solvent or a mixed solvent of water and a nonaqueous organic solvent, and dispersion polymerization in the presence of a dispersant. (3) A method of combining the above (1) or (2) with a seed polymerization method. A copolymer having a hydrophilic functional group or the like can be easily produced, and a copolymer having a hydrophilic functional group or the like can be easily produced without using a seed particle which is easy to control in a step after washing or the like, and a particle having a hydrophilic functional group can be easily obtained. Precipitation polymerization is preferred because particles with excellent deformation recovery rate at high compression displacement are preferred. The monomer having two or more unsaturated double bonds is not particularly limited, and for example, a polyfunctional ethylenic monomer which is suitably selected from general use, and a polyfunctional (meth) acrylate acid can be used. Specific examples of the polyfunctional monomer include divinylbenzene; divinylbiphenyl; divinylnaphthalene; (poly)ethylene glycol di(meth)acrylate; (poly)propylene glycol di( (poly)alkanediol di(meth)acrylate such as (meth)acrylate and (poly)tetramethyl glycol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate , 丨, 8-octyl diol di(meth) acrylate, 〗 〖, 9-decanediol di(meth) acrylate, -13- 1363070 l, l-nonanediol di(meth) acrylate , M2_dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl-1,5-pentane Alcohol di(meth)acrylate, butyl ethyl propylene glycol di(meth) acrylate, 3-methyl-1,7-octanediol di(meth) acrylate and 2-methyl-1,8 - alkanediol di(meth)acrylate such as octanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, four Methylol methane tri(methyl) propylene Acid ester, tetramethylolpropane tetra(meth) acrylate, pentaerythritol tri(meth) acrylate 'ethoxylated cyclohexane dimethanol di(meth) acrylate, ethoxylated bisphenol A II (Meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, propoxylated ethoxylated bisphenol A di(meth) acrylate, l, l, i- hydroxymethyl Ethane di(meth)acrylate, 1,1,1-paraxylhydroxyethane tri(meth)acrylate, 1,1,1-paraxylmethylpropane triacrylate, diallyl benzene Dicarboxylate and its isomers, and triallyl isocyanurate and its derivatives. As a commercially available polyfunctional monomer, NK esters (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, and A-GLY i manufactured by Shin-Nakamura Chemical Co., Ltd.) can be cited. !], A-9300, AD-TMP, AD-TMP-4CL, ATM-4E, A-DPH). These monomers may be used singly or in combination of two or more kinds. Among these, it is preferred that the polyfunctional monomer contains at least one selected from the group consisting of divinylbenzene and polyfunctional (meth) acrylate. By using these monomers, the compression set recovery rate of the obtained crosslinked polymer particles can be more easily improved. From the same point of view, the polyfunctional monomer contains bis(meth) propylene -14-

S 1363070 acid ester is preferred, and alkanediol di(meth)acrylate is more preferred. The carbon number of the alkanediol is preferably from 6 to 18, more preferably from 8 to 12. Examples of the radical polymerizable monomer having a carboxyl group include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, and monobutyl maleate. Various unsaturated mono or dicarboxylic acids or unsaturated dibasic acids. These can be used alone or in combination of two or more types. # A radically polymerizable monomer having an epoxy group, for example, may be selected from the group consisting of epoxypropyl (meth)acrylate, (β-methyl)epoxypropyl (meth)acrylate, and 3,4-ring. Oxycyclohexyl (meth) acrylate, allyl epoxidized propyl ether, 3,4-epoxy vinylcyclohexane, bis(β-methyl)epoxypropyl methionate and Bis(β-methyl)epoxypropyl fumarate. Further, an epoxy group-containing compound can be used to introduce an epoxy group into the crosslinked polymer. The compound having an epoxy group may, for example, be ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, hexamethyl glycol diepoxypropyl ether or cyclohexanediol diepoxypropyl group. Epoxy propyl ether of an aliphatic polyhydric alcohol such as polyethylene glycol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, and pentaerythritol tetraepoxypropyl ether Epoxy propyl ether of polyalkylene glycol of polyether glycol, dipropylene glycol diepoxypropyl ether and polytetramethylene glycol diepoxypropyl ether, polyepoxypropyl compound of polyester resin, polydecylamine A resin-based polyepoxypropyl compound, a bismuth-based epoxy resin, a phenolic epoxy resin for phenol paint, and an epoxy urethane resin. These can be used alone or in combination of two or more types. The monomer mixture may also contain a monofunctional -15-1363070 monomer having one unsaturated double bond. The ratio of the monofunctional monomer is preferably from 0 to 7 % by mass based on the entire monomer mixture. The ratio of the monofunctional monomer is preferably from 5 to 7 % by mass, more preferably from 10 to 70% by mass, still more preferably from 15 to 7 % by mass. As the monofunctional monomer, for example, (i) styrene, fluorene methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, fluorene-ethyl styrene may be mentioned. , m-ethylstyrene, ρ-ethylstyrene, 2,4-dimethylstyrene, ρ-η-butylstyrene, p_t_butylstyrene, ρ_η_hexylstyrene, ρ-η-xin Styrene, ρ·η-mercaptostyrene, ρ-η-mercaptostyrene, ρ-η-dodecylstyrene, ρ_methoxystyrene, ? Styrene or its derivatives such as phenylstyrene, ρ-chlorostyrene and 3,4-dichlorostyrene, (ii) methyl acrylate, ethyl acrylate, propyl acrylate, η-butyl acrylate, acrylic acid Isobutyl ester, hexyl acrylate, 2-ethylhexyl acrylate, η-octyl acrylate 'dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α _Chloromethyl acrylate, methyl methacrylate 'ethyl methacrylate, propyl methacrylate, η-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, methacrylic acid 2- Ethylhexyl ester, η-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate and stearyl methacrylate, (meth) acrylate, (iii) vinyl acetate, C Vinyl esters such as vinyl acetate, benzoic acid vinyl and vinyl butyrate, N-vinyl such as (iv) N-vinylpyrrole, N-vinylcarbazole, N-vinyl anthracene and N-vinylpyrrolidone Compound, (v) fluorinated vinyl, vinyl fluoride, tetrafluoroethylene, six Propylene, acrylate, trifluoroethyl acrylate and tetrafluoropropyl group containing the fluorinated alkyl (meth) acrylate, (vi) and butadiene

S -16-1363070 A conjugated diene such as isoprene. These may be used alone or in combination of two or more. Among them, styrene or its derivatives '(meth) acrylate and vinyl ester are also preferred. By using these, the mother particles having the above physical properties can be efficiently obtained. As the polymerization initiator used in the radical polymerization for producing the mother particles, a known radical polymerization initiator can be used. Specific examples of the radical polymerization initiator include peroxides such as benzamidine peroxide, cumene hydroperoxide, t-butyl hydroperoxide, sodium persulfate, and ammonium persulfate, and even An azo compound such as nitrogen diisobutyronitrile, azodimethylbutyronitrile or azobisisovaleronitrile. These may be used alone or in combination of two or more. Specific examples of the polymerization solvent used in the production of the mother particles by solution polymerization include water, methanol, ethanol, 1-propanol '2-propanol, 1-butanol, 2-butanol, and isobutylene. Alcohol, tert-butyl alcohol '1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-amyl alcohol, 1-hexanol®, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-B Alcohols such as keto-1-hexanol, benzyl alcohol and cyclohexanol; methyl cyproterone, ethyl cyproterone, isopropyl celecoxib, butyl ceramide, and diethylene glycol monobutyl ether Ether ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl acetonate, (hospital) cyanidin, B Esters such as carbitol alcohol acetate and butyl carbitol acetate; pentane, 2-methylbutane, η-hexane, cyclohexyl, 2-methylpentane' 2,2- Dimethylbutane, 2,3-dimethylbutane, Gengyuan, η-Xinyuan, isooctane, 2,2,3-trimethylpentane, decane, decane-17-1363070, Cyclopentane, methyl Aliphatic or aromatic hydrocarbons such as pentane, methylcyclohexane, ethylcyclohexane, p-menthane, dicyclohexyl, benzene, toluene, xylene and ethylbenzene: carbon tetrachloride, trichloro Ethyl halides such as ethyl, chlorobenzene and tetrabromoethane; acids such as ethyl ether 'dimethyl ether, trioxane and tetrahydrofuran: acetals such as methylal and diethyl acetal; formic acid and acetic acid And fatty acids such as propionic acid; nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide, dimethyl submilling, acetonitrile and N-methyl-2-pyrrolidone, etc. Nitrogen contains organic compounds and the like. These may be used alone or in combination of two or more. Among them, acetonitrile is preferred from the viewpoint of preventing particle agglutination. When the mother particles are produced, a dispersant, a stabilizer, an emulsifier, a surfactant, or the like can be suitably selected. Examples of the dispersant and stabilizer include polyhydroxystyrene, polystyrenesulfonic acid, vinylphenol-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, and styrene-ethylene. Polystyrene derivatives such as phenol-(meth) acrylate copolymer; poly(meth)acrylic acid, poly(methyl) acrylamide, polyacrylonitrile, polyethyl (meth) acrylate, and polybutylene Poly(meth)acrylic acid derivatives such as methacrylic acid esters; polyvinyl alkane such as polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether and polyisobutyl vinyl ether a vinyl ether derivative; a cellulose derivative such as cellulose, methyl cellulose 'cellulose acetate, nitrocellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose; Polyvinyl acetate derivatives such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, and polyvinyl acetate; polyvinyl pyridine,

S -18- 1363070 polyvinylpyrrolidone, polyethyleneimine and poly-2-methyl-2-nitrogen polymer derivatives; polychlorovinyl and polyvinylidene vinyl derivatives; poly A polyoxyalkylene such as methyl oxa oxide is a hydrophobic or hydrophilic dispersant and a stabilizer. These can be used in combination of two or more kinds. Examples of the emulsifier (surfactant) include an alkylbenzenesulfonic acid φ naphthalenesulfonate such as a lauryl alkyl sulfate or a sodium dodecylbenzenesulfonate, a fatty acid salt, an alkyl phosphate, and an alkyl group. Sulfosin anion emulsifier; cationic emulsifier such as alkylamine salt, fourth ammonium salt, alkylamine oxide; polyethylene oxide alkyl ether ethane alkyl ether, polyethylene oxide A nonionic emulsifier such as allyl ether, polyepoxy 'phenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester or poly fatty acid ester. These can be used alone or in more than two types. In the step (a), for example, the mother particles are brought into contact with the first solution of the solvent containing the first amine # and the solvent of the first amine compound, and a part of the functional groups in the particles are back-stepped with the amine group. The crosslinked polymer is crosslinked. The first solution is impregnated with only the masterbatch or impregnated into the inner region. The first amino group compound is one or two or more organic compounds having two or more amine groups (preferably). As the first amine-based compound, a linear or branched amine and an alicyclic diamine are preferred. As the specific diamine of the aliphatic diamine, a salt such as ethyl diamine, propyl diamine, 1,4-butane diamine, or oxazoline, etc. a betaine such as an alkyl phenate and a polyethylene oxide alkyl oxirane, or a hydrazine compound, which may be a parent, a second sub-group of an amine-based aliphatic group. 6-hexanedi-19 _ 1363070 1,8_octane-monoamine, 1,9-壬院-amine, 2-methyl-1,8-octylamine diamine, 1,1 fluorene-decanediamine 1,12-dodecanediamine, %methyl-oxime,5.pentanediamine' 2,2,4-trimethyl-1,6-hexanediamine, 2 4 4_trimethyl _ 丨, 6 hexane diamine and 5-methyl-1,9-nonanediamine. Examples of the alicyclic diamine include cyclohexane monoamine, methylcyclohexanediamine, and isophorone diamine. P_phenylenediamine, m-phenylenediamine, xylenediamine, 4,4,diaminodiphenylmethane and 4,4'-diaminodiphenylphosphonium, 44,_ can be used. An aromatic diamine such as diaminodiphenyl ether. These diamines may be used alone or in combination of two or more. As the younger than the above diamine, a triamine or a tetraamine may be used. The average molecular weight of the first amino group compound is preferably from 50 to 3,000, more preferably from 50 to 1,000. When the average molecular weight of the first amino group compound exceeds 3 Å, there is a tendency that it is difficult to crosslink to the inside of the particles. The first amino group compound is soluble in an organic solvent. Typical examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl propionate, and cyproterone acetate. And other vinegar; pentamidine, 2-methylbutyl, η-hexa, cyclohexyl, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, Heptane, η-octane, isooctane, 2,2,3-trimethylpentane, decane, decane, cyclopentane, methylcyclopentane, methylcyclohexane, ethylcyclohexane Aliphatic or aromatic hydrocarbons such as alkane, decyl-menthane, benzene, toluene, xylene and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chlorobenzene and tetramethane; Ethers such as alkyl ether, dimethyl ether 'trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; nitropropene, nitrobenzene, pyridine, dimethylformamide, dimethyl Base-20- 1363070 Sulfur and nitrogen such as arsenic and acetonitrile contain organic compounds. These may be used alone or in combination of two or more. When the first amino group-based compound is a water-soluble or hydrophilic organic compound, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or 2-butanol may be used in addition to the above organic solvent. Isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-amyl alcohol, 1-hexyl Alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethylbutanol '1·heptanol, 2-heptanol' 3-heptanol, 2-octanol, Alcohols such as 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol; methyl acesulfame, ethyl acesulfame, isopropyl celecoxime, butyl quercetin and diethylene glycol An ether alcohol such as butyl ether. These may be used alone or in combination of two or more. The solvent constituting the first solution is preferably a solvent which substantially dissolves the mother particles and dissolves the first amine compound. When the first amino group compound is in a liquid form, the reaction of the functional group in the mother particle with the first amine group compound can be carried out without a solvent. 0 Examples of the solvent constituting the first solution include γ-butyrolactone, glycerin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butane. Alcohols such as alcohols and η-butanol, hydrocarbons such as toluene, xylene, η-octane and η-dodecane, fatty acids such as linoleic acid, polyethylene glycol, dimethyloxane, water, Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-decanol, 2-methyl-1-butanol, isoamyl alcohol, tert-pentyl alcohol, l-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl Alcohols such as butanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol; methyl race-21 - 1363070 Ether alcohols such as saponin, ethyl acesulfame, isopropyl acesulfame, butyl cyanidin and diethylene glycol monobutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexane Ketones such as ketones; esters such as ethyl acetate, butyl acetate, ethyl propionate and cyproterone; pentane, 2-methylbutane, η-hexane, cyclohexane, 2-methyl Kepentane ' 2,2-two Butane '2,3-dimethylbutane' heptane, η-octane, isooctane, 2,2,3-trimethylpentane, decane, decane, cyclopentane, methyl Aliphatic or aromatic hydrocarbons such as cyclopentane, methylcyclohexane, ethylcyclohexane, decyl-menthane, dicyclohexyl, benzene, toluene, xylene and ethylbenzene: carbon tetrachloride, three Halogenated hydrocarbons such as ethyl, chlorobenzene and tetrabromoethane; ethers such as ethyl ether, dimethyl ether, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; formic acid And fatty acids such as acetic acid and propionic acid; sulfur, nitrogen and other organic compounds such as nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide and dimethyl sulfoxide. a water-soluble and hydrophilic medium such as a lower alcohol such as water, methanol or ethanol, an ether alcohol such as methyl sialic acid or ethyl cyanidin, a mixture of water and a lower alcohol, such as a mixture of water and an ether alcohol, toluene, dimethyl Mercaptoamine (DMF), tetrahydrofuran (THF), methyl ethyl ketone (oxime), methyl isobutyl ketone (oxime), acetone, oxime-methyl-2-pyrrolidone (oxime), dichloromethane, and four Chlorine extended ethyl is preferred. A lower alcohol such as water, methanol or ethanol, a mixture of water and a lower alcohol such as methanol or ethanol, a mixture of water and a lower alcohol such as methanol or ethanol, and a water-soluble and hydrophilic medium such as a mixture of water and an ether alcohol are more preferable. These may be used alone or in combination of two or more. In the step (a), the temperature at which the first amino group compound is reacted may be, depending on the kind of the solvent, preferably from 10 ° C to 250 ° C, more preferably from 100 to 250 ° C, and particularly from -22 to 1363070. °C~25 0°C. The reaction time is a time required for the completion of the crosslinking reaction, and the amount of the amine compound to be used and the amount of addition are greatly affected by the type of the functional group in the mother particle, the viscosity and concentration of the solution, etc., but are carried out, for example, at 180 °C. ~24 hours, preferably 6 to 10 hours. Even if the reaction time is prolonged, crosslinked polymer particles can be obtained, but practical long-term demand is not a good countermeasure. Further, if the reaction time is extremely short, cross-linking may not proceed sufficiently. φ In step (b), for example, the parent particle crosslinked by the first amine compound is contacted with a second solution containing a second amine compound and a solvent for dissolving the second amine compound, by crosslinking The reaction of the functional group remaining in the polymer with the second amine compound gives a crosslinked polymer particle having a mother particle and an amine group bonded to the 'master particle. The second amino group-based compound is an organic compound having a reactive group which reacts with a functional group such as a carboxyl group remaining in the crosslinked polymer. The reactive group of the second amino group compound and the functional group in the crosslinked polymer are preferably reacted at 60 ° C or lower, #更优选为〇60 ° C, particularly preferably 2〇~60 ° C, Combined with a crosslinked polymer. As a result, an amine group derived from the second amino group compound is introduced into the mother particle. The second amino group-based compound is preferably an aziridine compound having two or more aziridine groups (preferably N-substituted aziridine groups) as a reactive group for reacting with a functional group in the crosslinked polymer. The second amino group _, for example, is selected from the group consisting of trimethylolpropane-tri-β-azapropanyl propionate, tetramethylolmethane-tri-β-azapropylcyclopropionate, hydrazine, hydrazine -hexamethyl-1,6-bis-1-azapropanylcarboxy decylamine '4,4'-bis(ethylidene carbonylamino)diphenylmethane, and -23- 1363070 2,2 - at least one nitrogen propylene ring compound in the group of bis(hydroxymethyl)butanol gin[3-(1-azapropylcyclo)propionate]. Among them, from the viewpoint of reactivity, 2,2-bis(hydroxymethyl)butanol gin[3-(1-azapropylcyclo)propionate] is preferred. The solvent constituting the second solution is preferably a solvent which does not substantially dissolve the mother particles and dissolves the second amino group compound. This specific example is the same as the solvent of the first solution. In the step (b), the temperature at which the second amino group compound is reacted is preferably 0 to 60 ° C, more preferably 20 to 60 ° C. The reaction time is, for example, 1 to 24 hours, preferably about 3 to 12 hours. Even if the reaction time is elongated, crosslinked polymer particles can be obtained, but practical long-term demand is not a good countermeasure. Further, when the reaction time is extremely short, the reaction may not proceed sufficiently. The amount of the first amino group compound in the step (a) is preferably 0.1 to 5 in terms of the equivalent of the functional group 'amine group of the mother particle. More preferably 0.5 to 3. The amount of the second amino group compound in the step (b) is preferably 0.1 to 5, more preferably 0.5 to 3, based on the functional group of the mother particle. When the equivalent ratio is excessively small or excessively large, the effect of improving the compression characteristics or improving the plating formability tends to be small. The average particle diameter of the crosslinked polymer particles is preferably from 0.1 to 50 μm, more preferably from 2 to 30 μm, still more preferably from 0.3 to 20 μm, most preferably from 0.5 to 5 μm, and the average particle diameter of the polymer particles is 〇.1~1〇μπι is better. When the average particle diameter is too small, the crosslinked polymer particles may be easily aggregated. The Cv 粒子 of the particle diameter (diameter) of the crosslinked polymer is preferably 15% or less. (When v値 exceeds 15%, the performance of -24-1363070 tends to decrease in various applications of crosslinked polymer particles. For example, when crosslinked polymer particles are used for conductive particles constituting an anisotropic conductive adhesive The reliability tends to be lowered, or the quantitative property of the crosslinked polymer particles used in the biopsy element tends to decrease. From the same viewpoint, the Cv値 of the particle diameter is preferably 10% or less. Preferably, it is 5% or less, and more preferably 4% or less. The average particle diameter of the crosslinked polymer particles and the Cv 粒径 of the particle diameter can be determined by the following method: φ η disperse the particles in water using an ultrasonic dispersing device The dispersion liquid containing 1% by mass of particles was prepared. 2) The dispersion was measured by a particle size distribution meter (SysmexFlow, manufactured by Sysmex) and observed by a microscope of about 20,000, and the coefficient of variation Cv of the average particle diameter and the particle diameter was calculated. The recovery rate of the compression set measured by the mother particles after the step (a) at 180 ° C is generally 30% or more, preferably 40% or more, more preferably 50% or more, and particularly preferably 50 to 65%. When the compression deformation recovery rate is low, the elastic force is not sufficient, and there is a tendency that contact failure is likely to occur in applications such as an anisotropic conductive adhesive requiring high elasticity. The compression deformation recovery rate was obtained by compressing the particles from the center at a speed of 0.33 mN/sec to 5 mN, and conversely reducing the load at a speed of 〇33 mN / sec, and measuring the relationship between the load enthalpy and the compression displacement. The ratio of the displacement from the point of the reverse load to the displacement of the final charge (L 1 ), the displacement from the point of self-reversal to the displacement of the initial load ( (L2 ) (L1/L2 ), expressed in % is called compression. Deformation recovery rate. The compressive breakdown strength measured at 180 ° C of the mother particles after the step (a) is preferably -10 mN or more, preferably by a step of applying plating on the crosslinked polymer particles according to the present embodiment. In the method (c), conductive particles can be produced. In the step (c), it is preferred to use a Pd ion dislocation as a plating catalyst, and to apply the crosslinked polymer particles to the plating. As described above, the crosslinked polymer particles of the present embodiment have a high compression deformation recovery ratio and are highly likely to have excellent elastic properties. Therefore, when the crosslinked polymer particles are used to form conductive particles, the substrate used for indirect termination of the electrode may be damaged, or the possibility of penetration may be low, and even if the compression deformation is high, high-precision spacing can be maintained. Sexuality or stability is highly likely to succeed. Further, since the crosslinked polymer particles of the present embodiment have the above-described characteristics, they are not only in the field of electrical materials, but also in paints, coating agents, light diffusing agents, cosmetics, medical or biopsy elements, agricultural chemicals, building materials, and the like. It is also useful in a wide range of fields. [Embodiment] [Examples] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the invention is not limited to the following embodiments. 1. Synthesis of Mother Particles Synthesis Example 1 Each of the following compounds was placed in a three-neck beaker of 100 mL, and heated in a water bath of 8 ° C, and was mixed for about 6 hours with a stirrer to form -26-1363070. A mother particle formed from a crosslinked polymer. • DVB-960 (Nippon Steel Chemical, containing Divinylbenzene (DVB) 96% by mass of 'Ethyl Ethylbenzene (EVB) 3% by mass): 4.9g • Methyl acrylate (Wako Pure Chemical): 2.1g • Azobisisobutyronitrile (AIBN, Wako Pure Chemical Industries): 〇.6g • Acetonitrile (Wako Pure Chemicals): 70g Next, the mother particles are separated by filtration using an adsorption filter device, repeating # 3 to 5 times by The isopropyl alcohol (IP A ' and Wako Pure Chemical Industries, Ltd.) was washed and filtered, and after vacuum drying, powdery mother particles were obtained. The particle diameter of the obtained mother particles was measured by SEM observation to obtain spherical monodisperse particles having an average particle diameter of 4.Ιμηη. The particle diameter of Cv 値 was 2.3%. Synthesis Example 2 Each of the following compounds was placed in a 100 mL three-neck beaker at a time while being heated in a water bath at 80 ° C, and stirred for about 6 hours using a stirrer to form a mother particle formed of a crosslinked polymer. • DVB-960: 2.8g • Methacrylic acid: 4.2g • AIB N : 0.6 g • Acetonitrile: 70 g Next, the mother particles are separated by filtration using an adsorption filter device, and repeated 3 to 5 times with isopropyl alcohol. After washing and filtering (IPA, Wako Pure Chemical Industries, Ltd.), the powdery mother particles were obtained after vacuum drying. The particle diameter of the obtained mother particles was measured by S EM observation, and spherical monodisperse particles having an average particle diameter of -27 to 1363070 3.1 μm were obtained. The particle diameter Cv 値 was 3.0%. Synthesis Example 3 Each of the following compounds was placed in a three-neck beaker of 100 μL, and heated in a water bath at 80 ° C, and stirred for about 6 hours using a stirrer to form mother particles formed of a crosslinked polymer. • DVB-960: 0.9g • 1,1〇-nonanediol diacrylate (human-〇〇〇, Xinzhongcun Chemical Industry): 2.7g • Methacrylic acid: 2g • 11--(--sour acid: 1.4g • AIBN: 0.07g • Acetonitrile: 70g Next, the mother particles are separated by filtration using an adsorption filter device, and repeated 3 to 5 times by washing and filtering with isopropyl alcohol (IPA, Wako Pure Chemical Industries). The powdery mother particles were obtained by vacuum drying, and the particle diameter of the obtained mother particles was measured by SEM observation, and then spherical monodisperse particles having an average particle diameter of 2.8 μm were obtained. The cv 粒子 of the particle diameter was 2.7%. The compression deformation recovery ratio and compression fracture strength of each of the mother particles obtained in Synthesis Examples 1 to 3. The results of the induction measurement are shown in Table 1. -28- 1363070 [Table 1] Parent particle diameter (μηι) Cv (%) Compression Recovery rate (%) Compressive fracture strength_ Synthesis Example 1 4.1 2.3 32 8 Synthesis Example 2 3.1 3.0 25 4 Synthesis Example 3 2.8 2.7 25 6 2. Preparation of crosslinked polymer particles and conductive particles and evaluation Example 1 (Step a) one time the mixture of the ratio shown below is placed in a lOOmL pitch beaker, The mixture was stirred for 1 hour at room temperature to obtain a dispersion liquid. The dispersion was heated in an oil bath at 180 ° C for about 6 hours under a nitrogen stream. • Master particles of Synthesis Example 1: 5 parts by weight • Six Methyldiamine (Wako Pure Chemical Industries, Ltd.): 1 part by weight (0.5 equivalents for the carboxyl group in the mother particle) • γ-butyrolactone (Wako Pure Chemical Industries, Ltd.): 94 parts by weight

Next, the particles were separated by filtration using an adsorption filtration apparatus, washed and filtered by IP crucible, and then vacuum-dried to obtain powdery mother particles (particles la) crosslinked by hexamethylenediamine. The obtained mother particles have a compression deformation recovery ratio of 61% at 180 ° C and a compressive fracture strength of 16 mN (step b) in a 100 ml L eggplant beaker at a time in a mixture of the ratios shown below, in the chamber. Stir for 12 hours at room temperature. -29- 1363070 • Particles la: 5 parts by weight • 2,2-bis(hydroxymethyl)butanol ginseng [3-(1-Azapropylcyclo)propionate] (P Z-33, Nippon Catalyst) : 3 parts by weight (the ratio of the aziridine group to the carboxyl group in the mother particle is 3 equivalents) • IPA: 92 parts by weight Next, the particles are separated by filtration using an adsorption filter device, and repeatedly washed and filtered by IPA. The mixture was vacuum dried to obtain a powdery crosslinked polymer particle (particle lab) into which an amine group was introduced. (Step c) Ni plating for the particle lab was applied to produce crosslinked polymer particles and conductive particles composed of the Ni plating layer covering the same. (Giving a catalyst) The stock solution of Activator Neoganth 834 (an aqueous solution of an ionic-amino-based error-solving agent, trade name) manufactured by Atotech Japan Co., Ltd. was diluted with water to 40 mL/L, and adjusted to pH 10_5 to prepare a 1-base type of base contact. Media. The particle lab was immersed in the alkali catalyst solution at 35 ° C for 10 minutes to adsorb the palladium complex on the surface of the particle lab. The particle lab was recovered by adsorption filtration and washed with water. The particle lab is then suspended in water again. Here, dimethylamine borane was added to 〇.1 g/L to reduce the palladium complex on the surface of the particle lab, and a suspension of particles 1 a b supported on the surface of palladium was obtained. -30- 1363070 (without electrosurgical shovel) The above suspension is heated to 80 ° C, where electroless Ni-P plating solution (trade name: NIPS-100, manufactured by Keli Chemical Industry Co., Ltd.) It is slowly dripped by the quantitative pump and applied to the particle lab for plating. The plating time is 60 minutes. Thereby, a plating layer is formed on the surface of the particle lab. Thereafter, the order of adsorption filtration, water washing, adsorption filtration, and drying was carried out to obtain conductive particles having a plating layer by electroless Ni-P plating. With respect to the conductive particles obtained by φ, the plating layer was formed under good uniformity, and no irregularities were observed on the surface of the plating layer. (Missing treatment and particle evaluation) 'The obtained conductive particles were subjected to pulverization under the conditions of a crushing pressure of 11 MPa by jet honing. The electroconductive particles after the disintegration treatment were observed by an electron microscope to perform photographing. Adjust to the magnification of 100 pixels in each photo, and take 10 shots per change to the shooting location. • For these 10 photos (the total number of particles = 10,000), the number of particles not covered by the mineral layer and the number of plating sheets were investigated. If a large amount of agglomeration occurs before the mashing treatment, the plating layer is not completely covered, and particles in which most of the resin portions are exposed are generated. Further, when the adhesion between the resin particles and the plating layer is not good, the plating is peeled off during the pulverization treatment, and a large amount of the plating sheet is generated after the pulverization treatment. Therefore, for the conductive particles after the pulverization treatment, the number of particles not completely covered by the plating layer is small (the number of particles completely covered by the plating layer is large), and if the plating sheet is small, the mineralizing treatment liquid is The particle dispersibility was good, and it was judged that the adhesion between the resin particles and the plating layer was also excellent. For the observation after the disintegration -31 - 1363070, the mineral sheet is almost non-existent. Example 2 (Step a) A mixture of the ratio shown below was charged in a 100 ml L eggplant beaker at a time, and the mixture was stirred at room temperature for 1 hour to obtain a dispersion. The dispersion was heated in an oil bath at 180 ° C for about 6 hours under a nitrogen stream. • Master particle of Synthesis Example 2: 5 parts by weight • Hexamethylenediamine (Wako Pure Chemical Industries, Ltd.): 1.5 parts by weight (0.5 equivalents for the carboxyl group in the mother particle) • γ-butyrolactone (and 93.5 parts by weight of the medicinal product continued, and the particles were separated by filtration using an adsorption filter device. After repeated washing and filtration by IP ,, the powdered mother particles which were crosslinked by hexamethylenediamine were obtained by vacuum drying. (Particle 2a). The obtained mother particles have a compression deformation recovery ratio of 51% at 180 ° C and a compression fracture strength of 1 1 mN. (Step b) A mixture of the ratio shown below was charged in a 100 mL eggplant-shaped beaker, and stirred at room temperature for 12 hours. Particle 2 a : 5 parts by weight • PZ-33 : 4.5 parts by weight (the ratio of the aziridine group to the carboxyl group in the mother particle is 3 equivalents) • IPA: 92 parts by weight - 32 - 1363070 Next 'Using adsorption filtration equipment The particles were separated by filtration, washed and filtered by IP A, and dried under vacuum to obtain powdery crosslinked polymer particles (particles 2ab) into which an amine group was introduced. (Step c) By the same operation as in Example 1, 'Ni plating was applied to the particles 2ab' to produce crosslinked polymer particles and # conductive particles composed of the Ni plating layer covering the same. With respect to the obtained conductive particles, the plating layer was formed under good uniformity. No irregularities were observed on the surface of the plating layer. Also, for the observation after the disintegration, almost no plating sheet exists. Example 3 (Step a) A mixture of the ratios shown below was charged in a 100 mL front beaker at a time. The mixture was stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The # dispersion was heated in an oil bath at 180 ° C for about 6 hours under a stream of nitrogen. • Master particle of Synthesis Example 3: 5 parts by weight • Hexamethylenediamine (Wako Pure Chemical Industries): 1 part by weight (0.5 equivalents for the carboxyl group of the parent particle) • γ-butyrolactone (and Pure medicine) 94 parts by weight

Next, the particles were separated by filtration using an adsorption filtration apparatus, and the powdery mother particles (particles 3 a ) which were crosslinked by hexamethylenediamine were obtained by washing and filtering by IΡ 重复, followed by vacuum drying. The obtained mother particles have a compression set recovery ratio of 45% at 180 ° C and a compressive fracture strength of 12 mN -33 to 1363070 (step b) in a 100 mL eggplant-shaped beaker once with a mixture of the ratios shown below at room temperature. Stir for 12 hours. Particle 3 a : 5 parts by weight • PZ-33: 3 parts by weight (the ratio of the aziridine group to the carboxyl group in the mother particle is 3 equivalents) • IP A ·· 92 parts by weight Next, the particles are filtered using an adsorption filter device After separation and repeated washing and filtration by IPA, the mixture was vacuum dried to obtain powdery crosslinked polymer particles (particles 3ab) into which an amine group was introduced. (Step c) Ni plating was applied to the particles 3ab in the same manner as in Example 1 to produce crosslinked polymer particles and conductive particles composed of the Ni plating layer covering the particles. With respect to the obtained conductive particles, the plating layer was formed with good uniformity, and no irregularities were observed on the surface of the plating layer. Also, for the observation after the disintegration, almost no plating sheet exists. Comparative Example 1 The mother particles synthesized in Synthesis Example 2 were used as they were, and the compression characteristics 'and the formation state of the plating layer were evaluated. -34- 1363070 Comparative Example 2 The mother particle treatment of Synthesis Example 1 and the production and evaluation of the conductive particles were carried out in the same manner as in Example 1 except that hexylamine was used instead of hexamethylenediamine in the step a. . Comparative Example 3 In the step b, the mother particle treatment of Synthesis Example 1 and the production and measurement of the conductive particles were carried out in the same manner as in Example 1 except that PZ-33 was used as the hexamethylenediamine. Comparative Example 4 The mother particle treatment of Synthesis Example 1 and the production of the conductive particles and evaluation thereof were carried out in the same manner as in Example 1 except that the step b was carried out without the step b.

Comparative Example 5 The treatment of the mother particles of Synthesis Example 1 and the production of the conductive particles and evaluation thereof were carried out in the same manner as in Example 1 except that Step a was not carried out. -35- 1363070 [Table 2] Compression Deformation Recovery Rate (%) Compressive Destructive Strength_ Uniformity of Plating Layer Plating Sheet after Uneven Concavation of Plating Layer Example 1 61 16 Good Μ j\\\ Example 2 51 11 Good Μ y y*\\ Example 3 45 12 Good Μ Ji\\ Comparative Example 1 28 4 Good There are Comparative Examples 2 32 8 Good Group Sister Comparative Example 3 32 8 Bad There are Comparative Examples 4 61 16 Bad There is a comparative example 5 32 8 good ffnr m 4rrt Μ The evaluation results are shown in Table 2. The crosslinked polymer particles obtained in the respective examples had good compression characteristics. Further, on the surface of the crosslinked polymer particles of the respective examples, a plating layer was formed under good uniformity. There was almost no plating sheet obtained by dissolving the conductive particles, and it was confirmed that the resin particles and the plating layer were in close contact with each other. On the other hand, each of the particles of the comparative example was insufficient in both compression characteristics and plating properties. As is apparent from the above experimental results, the present invention provides a crosslinked polymer particle which has a good compression property and which forms a plating layer in a good state on the surface. Industrial Applicability It is known that the crosslinked polymer particles of the present invention satisfy the useful properties as particles of a conductive material which is used for an anisotropic conductive film or a conductive paste. Further, since the crosslinked polymer particles obtained by the production method of the present invention have excellent heat resistance, chemical resistance, reactivity, and solution dispersibility, they are applicable to liquid crystal spacers, conductive fine particles, and conductive materials using the same. Static electricity

S-36-l363〇7 〇 load imaging agent, surface modification agent for silver salt film, film for tape, thermal stabilizer for paper, thermal and electronic industry, toner, etc., adhesive, adhesive, light diffusion Agents, coatings, paper coatings, chemical recording materials such as information recording papers, chemical substances, fragrances, low shrinkage agents, paper, dental materials, resin modifiers, etc., in the general industrial field, added to liquid or powder Cosmetics such as lubricants or body pigments, cosmetics, antigens, and antigen-antibody reaction particles, such as biomedical fields, pharmaceuticals and pesticides, construction, and automotive. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows an embodiment of crosslinked polymer particles. [Main component symbol description] 1 : Mother particle 10 : Crosslinked polymer particle -37-

Claims (1)

1363070 Patent Application No. 100105803 A crosslinked polymer particle characterized by being capable of contacting a mother particle formed of a crosslinked polymer having a functional group with a first amine compound having two or more amine groups, by the aforementioned functional group a step of reacting a part of the group with the aforementioned amine group to further crosslink the aforementioned crosslinked polymer (a), after the aforementioned step (a), by a second difference from the aforementioned first 'amine compound having an amine group a step of reacting an amine compound with the aforementioned functional group remaining in the crosslinked polymer to obtain the mother particle, and a crosslinked polymer particle bonded to the parent particle and having an amine group derived from the second amine compound (b) ) by the manufacturing method. 2. The crosslinked polymer particle of claim 1, wherein the second amine compound is reacted with the aforementioned functional group at 60 ° C or lower. 3. The crosslinked polymer particle of claim 1, wherein the second amine compound has two or more amine groups. 4. The crosslinked polymer particle of claim 2, wherein the second amine compound has two or more amine groups. 5. The crosslinked polymer particle of claim 1, wherein the second amine compound has an aziridinyl group. 6. The crosslinked polymer particle of claim 2, wherein the second amine compound has an aziridinyl group. 7. The crosslinked polymer particle of claim 3, wherein the second amine compound has an aziridinyl group. 1363070 8. The crosslinked polymer particle of claim 4, wherein the second amine compound has an aziridinyl group. 9. The crosslinked polymer particles according to claim 1, wherein the average particle diameter is 〇.1 to 1 〇μηι, and the particle diameter Cv 値 is 10% or less. 10. The crosslinked polymer particles of claim 2, wherein the average particle diameter is 0.1 to ΙΟμιη, and the particle diameter Cv 値 is 10% or less. 11. The crosslinked polymer particles according to item 3 of the patent application, wherein the average particle diameter is 〇·1~1〇μπι, and the Cv値 of the particle diameter is 10% or less. 12. The crosslinked polymer particles according to item 4 of the patent application, wherein the average particle diameter is 〇·1~1 Ομιη, and the Cv値 of the particle diameter is 10% or less. 13. The crosslinked polymer particles according to claim 5, wherein the average particle diameter is 〇 · 1 to 1 〇 μ m, and the particle diameter C v 値 is 1 〇 % or less. 14. The crosslinked polymer particles according to claim 6, wherein the average particle diameter is 0.1 to 1 Ομηι, and the particle diameter Cv 値 is 1% or less. 15. The crosslinked polymer particles according to claim 7, wherein the average particle diameter is 0.1 to ΙΟμιη, and the particle diameter Cv 値 is 10% or less. 16. The crosslinked polymer particles according to claim 8 wherein the average particle diameter is 0.1 to ΙΟμιη, and the particle diameter Cv 値 is 10% or less. 17. The crosslinked polymer particles according to claim 1, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 18. The crosslinked polymer particle of claim 2, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. The crosslinked polymer particle of claim 3, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. -2- 1363070. The crosslinked polymer particle of claim 4, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. The crosslinked polymer particles according to claim 5, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 2. The crosslinked polymer particles of claim 6, wherein the functional group is at least one selected from the group consisting of an epoxy group and a epoxidized group. The crosslinked polymer particles, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 24. The crosslinked polymer particles according to claim 8, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 2. The crosslinked polymer particles according to claim 9, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 26. The crosslinked polymer particles according to claim 10, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. The crosslinked polymer particles according to the first aspect of the invention, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 28. The crosslinked polymer particle of claim 12, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 29. The crosslinked polymer particle of claim 13, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 30. The crosslinked polymer particle of claim 14, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. The crosslinked polymer particle of claim 15, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 1363070 32. The crosslinked polymer particle of claim 16, wherein the functional group is at least one selected from the group consisting of an epoxy group and a glycidyl group. 33. The crosslinked polymer particles of any one of item 32, wherein the aforementioned mother particles are obtained by suspension polymerization 'emulsification polymerization, dispersion polymerization, precipitation polymerization or seed polymerization. The crosslinked polymer particle according to any one of claims 1 to 32, wherein the crosslinked polymer is a copolymer containing 1% by mass of a monomer having 2 or more unsaturated double bonds. a copolymer formed from a monomer mixture. 35. The crosslinked polymer particle of claim 33, wherein the crosslinked polymer is a copolymer formed by copolymerizing a monomer mixture containing 10% by mass of a monomer having 2 or more unsaturated double bonds . 3. The crosslinked polymer particles according to claim 34, wherein the monomer having the two or more unsaturated double bonds contains at least one selected from the group consisting of divinylbenzene and di(meth)acrylate. The crosslinked polymer particle according to any one of claims 1 to 32, wherein the mother particle after the aforementioned step (a) has a compression set recovery ratio of 40% or more at 180 ° C. And the compressive fracture strength of 10mN or more. 3. The crosslinked polymer particle of claim 3, wherein the mother particle after the step (a) has a compression set recovery ratio of 4% or more at 180 ° C, and l〇mN The above compression damage strength. 3. The crosslinked polymer particle of claim 1, wherein the mother particle after the step (a) has a compression set recovery at 1333070 and a compression breakdown of 1 OmN or more at 180 °C. strength. 40. The crosslinked polymer particle of claim 35, wherein the mother particle after the step (a) has a compression set recovery ratio of 40% or more and a compressive fracture strength of 10 mN or more at 180 ° C. . 41. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating to the crosslinked polymer particles according to any one of claims 1 to 32. . 42. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating to the crosslinked polymer particles of claim 33. 43. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating of the crosslinked polymer particles of claim 34 of the patent application. 44. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating to the crosslinked polymer particles of claim 35 of the patent application. 45. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating of the crosslinked polymer particles of claim 37 of the patent application. 46. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating to the crosslinked polymer particles of claim 38 of the patent application. 47. An electroconductive particle characterized by the production method comprising the step (c) -5 - 1363070 for applying a plating of the crosslinked polymer particles of claim 39 of the patent application. 48. An electroconductive particle characterized by the production method comprising the step (c) of applying a plating to the crosslinked polymer particles of claim 40 of the patent application. 49. The electroconductive particle of claim 41, wherein in the step (c), the Pd ion dislocation is used as a plating catalyst, and the crosslinked polymer particles are plated. a method for producing a crosslinked polymer particle, comprising: contacting a mother particle formed of a crosslinked polymer having a functional group with a first amine compound having two or more amine groups, The step of (a), after the step (a), further reacting a part of the functional group with the amine group to further crosslink the crosslinked polymer, and the first amine compound having an amine group The reaction of the diamine compound with the aforementioned functional group remaining in the crosslinked polymer to obtain the above-mentioned mother particles, and a step of binding the polymer particles to the mother particles and having the amine group derived from the second amine compound ( b). 5. The production method according to claim 50, wherein in the step (a), the amine group ratio of the first amine compound is 0.1 to 5 equivalents based on 1 equivalent of the functional group in the mother particle. In the above step (b), the ratio of the reactive group to be reacted with the functional group of the second amine compound is 0.1 to 5 equivalents based on 1 equivalent of the functional group in the mother particle.