TW201144341A - Cross-linked polymer particle and method for producing same - Google Patents

Abstract

Disclosed is a cross-linked polymer particle that can be obtained by a production method provided with a step (a) in which a mother particle formed from a cross-linked polymer having functional groups is brought into contact with an amino compound having two or more amino groups, and the cross-linked polymer is further cross-linked by a reaction of the functional groups and amino groups. This amino compound includes low molecular weight amino compounds with molecular weights less than 500.

Description

201144341 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to crosslinked polymer particles and a method for producing the same. [Prior Art] The crosslinked polymer particles having a high degree of cross-linking and excellent heat resistance and chemical resistance have been applied to the sliding properties of resin films including various spacers, conductive fine particles, and the like. Various fields such as modifiers, chromatography supports, and biomedical devices have been put into practical use. Generally, the crosslinked polymer particles are produced by a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In suspension polymerization, a cross-linkable monomer can be polymerized in a suspended state in an aqueous medium as an oil droplet by mechanical force to produce a crosslinked polymer particle. In the emulsion polymerization, the upper limit of the ratio of the crosslinkable monomer is usually about 2.0% by mass. Further, the obtained crosslinked polymer particles have a particle diameter ranging from 0.1 to 1.0 μm, which means that a particle size exceeding Ιμηη cannot be obtained. Patent Document 1 discloses a method in which emulsion polymerization can be stably carried out by using a special seed even if a crosslinkable monomer is used in an amount of 20.0% by mass or more. However, the particle size range obtained by this method is 0.1 to Ι.Ομηι as in the usual emulsion polymerization method. Therefore, it is difficult to obtain crosslinked polymer particles having a particle diameter exceeding Ιμηι by emulsion polymerization. Patent Document 2 discloses a swelling polymerization method in which a particle shape directly polymerizes a monomer, which is subjected to a first stage of absorption of a seed polymer by using an organic compound having a small water solubility as a swelling aid, and then - 5- 201144341 The second stage of forming monomeric swelling particles by absorbing a certain amount of soluble monomers in the water into the seed polymer. According to this method, as a result of using a large amount of crosslinkable monomer, it is possible to produce a crosslinked polymer particle having a uniform particle size of 1 μm or more. However, the swelling aid used in the method has a significantly lower solubility in water, so that it takes a long time to absorb the swelling aid in the first stage of the seed polymer. Further, the oil droplets remaining after being absorbed by the seed polymer may be formed into coarse particles after polymerization. In Patent Document 3, a method of producing crosslinked particles by a dispersion polymerization method using 20% by mass or more of a crosslinkable vinyl monomer is disclosed. According to this method, it is possible to produce monodisperse particles of several micrometers or so. However, if the particle diameter exceeds 2.5 μτη, the aggregation and aggregation of the particles increase, and it is very difficult to obtain single-dispersed particles. Further, when the hydrophilic or water-soluble polymerizable monomer is copolymerized, aggregation and aggregation are likely to occur, so that it is more difficult to obtain monodisperse particles. In Patent Document 4, when a precipitation polymerization method similar to the dispersion polymerization method is reported, cross-linking polymerization is produced by copolymerizing an unsaturated monomer having a hydrophilic functional group or an active hydrogen group with a crosslinkable monomer. The method of particle. According to this method, monodisperse particles of several μm can be obtained efficiently. Patent Document 5 discloses a method of crosslinking mother particles by reacting an uncrosslinked mother particle having a functional group with an epoxy compound, an oxazoline compound or an amine compound. According to this method, although the uncrosslinked particles can be crosslinked, since the reacted compound has high reactivity, the crosslinking reaction is mainly carried out on the surface of the particles, and there is a tendency to form a core structure [Prior Art Document] [ Patent literature]

Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -282772 Patent Document 5: Japanese Patent No. 42 1 5 5 2 1 [Non-Patent Document] Non-Patent Document 1: Journal of Polymer Science·Part A: Polymer Chemistry, (USA) , 3 1, 3 257 ( 1 993 ) [Problem to be Solved by the Invention] According to the conventional method, for example, when the mother particles contain a functional group derived from a hydrophilic monomer on the surface and inside of the particles, it is difficult to obtain a compression deformation recovery rate and a compression fracture strength. A sufficient degree of polymer particles can be achieved in terms of compression characteristics. For example, when polymer particles are covered with a metal layer to form conductive particles, and they are used for an anisotropic conductive adhesive, it is extremely important that the polymer particles have good compression characteristics. Further, at the same time as the compression characteristics, when a metal plating layer is formed by plating treatment on the surface of the polymer particles, it is required to form a tantalum layer having high uniformity and good adhesion. However, when the functional group derived from the hydrophilic monomer is not on the surface of the particle, it is difficult to obtain a polymer particle which is excellent in plating formability while having excellent compression characteristics. Therefore, the main object of the present invention is to provide a polymer particle which has good compression characteristics while forming a plating layer in a good state on its surface. 201144341 [Means for Solving the Problem] The present invention relates to a crosslinked polymer particle which can be contacted with an amine compound having a crosslinked polymer having a functional group and an amine compound having two or more amine groups The method for producing the step (a) in which the aforementioned functional group is reacted with the aforementioned amine group to crosslink the crosslinked polymer. The above amine-based compound contains a low molecular weight amine compound having a molecular weight of less than 5 Å. The above crosslinked polymer particles of the present invention have good compression characteristics and can form a plating layer in a good state on the surface thereof. By using a low molecular weight amine compound having a molecular weight of less than 500, it can be efficiently crosslinked to the inside of the mother particle, and the compression property can be improved. As an example of the particles synthesized by precipitation polymerization, the mother particles obtained by copolymerizing a hydrophilic monomer generally have a low compressive property because the amount of the crosslinkable monomer is small. By using a compound having two or more amine groups to crosslink the mother particles having a functional group derived from a carboxyl group of a hydrophilic monomer, and thereby obtaining a crosslinked polymer particle having a compression property and a good plating formability. The ammonium compound preferably further comprises a high molecular weight amine compound having a molecular weight of from 500 to 10,000. By using a high molecular weight amine compound having a molecular weight of 500 to 10,000, a large amount of an amine group can be introduced on the surface of the mother particle, and the plating formability can be further improved. The average particle diameter of the crosslinked polymer is preferably from 0.1 to 10 μm. The Cv 粒径 of the particle diameter of the crosslinked polymer particles is preferably at most 10%. If the particle diameter Cv of the crosslinked polymer particles is low, the conductive particles obtained by crosslinking the polymer particles may be more

S -8- 201144341 Improving connection reliability when used for an anisotropic conductive adhesive 》 The crosslinked polymer forming the above-mentioned mother particles preferably has at least one selected from the group consisting of a carboxyl group, an epoxy group and an epoxy propyl group. A functional group. The functional groups react efficiently with the amine groups of the amine compound to form a crosslinked structure in the parent particles. The above mother particles are preferably polymers obtainable 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 1% by mass or more of a monomer having two or more unsaturated double bonds. Thereby, the compression characteristics of the crosslinked polymer particles can be particularly improved. The monomer having two or more unsaturated double bonds is preferably at least one selected from the group consisting of divinylbenzene and di(meth)acrylate. The mother particles after the step (a) preferably have a compression set recovery ratio of 40% or more and a compressive fracture strength of 10 m or more at 180 °C. Further, the present invention relates to an electroconductive particle obtainable by the production method comprising the step (c) of plating the crosslinked polymer particles of the present invention. The conductive particles of the present invention can be used as, for example, conductive particles for an anisotropic conductive adhesive. In the step (c), the Pd ion complex is preferably used as a plating catalyst to apply the plating to the crosslinked polymer particles. In another aspect, the invention relates to a method of making crosslinked polymer particles. The production method of the present invention comprises contacting a mother particle formed of a crosslinked polymer having a functional group with an amine compound having two or more amine groups, and reacting the functional group with an amine group, thereby causing a crosslinked polymer Then proceed to step (a) of cross-linking -9 - 201144341. The amine compound contains a low molecular weight amine compound having a molecular weight of less than 500. According to the method of the present invention, crosslinked polymer particles having good compression characteristics while forming a plating layer in a good state on the surface thereof can be obtained. In the step (a), the proportion of the amine group of the amine compound is relative to the mother particle. The intermediate functional group 1 equivalent is preferably from 0.1 to 5 equivalents. By treating the mother particles with the amine-based compounds in the same ratio, crosslinked polymer particles having particularly excellent compression characteristics and plating formability can be obtained. Further, the present invention relates to an anisotropic conductive adhesive comprising an adhesive resin and the above-mentioned conductive particles dispersed in the adhesive resin. [Effect of the Invention] According to the present invention, a polymer particle having a good compression property and capable of forming a plating layer on a surface thereof in a good state is provided. [Embodiment] Hereinafter, a preferred embodiment 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 using a step of preparing a mother particle formed of a crosslinked polymer having a functional group, and contacting the mother particle with an amine compound having two or more amine groups. The above-mentioned functional group is reacted with an amine group to thereby obtain a production method of the step (a) in which the crosslinked polymer is further crosslinked. Fig. 1 is a schematic view showing an embodiment of crosslinked polymer particles.

-10- 201144341 The parent polymer particle 1 in Fig. 1 includes the mother particle 10, the parent particle 10 which is a particulate parent polymer, and the parent cell derived from the amine compound which crosslinks the crosslinked polymer. a moiety X and a modifying moiety R having an amine group derived from an amine compound. The crosslinked portion X is distributed over the entire surface of the mother particle 10 and the entire interior. The modifier is mainly applied to 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 fluorene resin, a polyester resin, or a polyamine group. Formate resin, polyamine resin, epoxy resin, polyvinyl butyral resin, rosin resin, oxime resin, phenol resin, melamine resin, oxime resin, oxazoline resin A carbodiimide-based resin and a cured resin obtained by subjecting these to a crosslinking reaction. These may be used alone or in combination of two or more. Among the polymers, a functional group (carboxyl group, epoxy group, and epoxypropyl group) 0, which is introduced with a reaction with an amine compound, is preferably composed of a plurality of monomers having an unsaturated double bond. The particles of the crosslinked polymer formed by copolymerization of the monomer mixture. The monomer mixture contains, for example, a polyfunctional monomer having two or more unsaturated double bonds and a monomer having at least one hydrophilic functional group selected from the group consisting of a carboxyl group, an epoxy group, and a glycidyl group. The polyfunctional monomer having two or more unsaturated double bonds in the monomer mixture is preferably contained in an amount of 10% by mass or more based on the entire monomer mixture. Thereby, it is particularly easy to form crosslinked polymer particles having a high compression deformation recovery rate. When the compression-deformation recovery rate of the cross-linked polymer particles is high, the polymer cross-linking particles are used as polymer particles constituting the electroconductive particles of the anisotropic conductive adhesive, and when used in -11 - 201144341, they are connected with time. The increase in resistance can be suppressed, achieving higher connection reliability. From this point of view, the polyfunctional monomer having two or more unsaturated double bonds in the monomer mixture preferably contains from 1 to 80% by mass, more preferably from 1 to 60% by mass, even more preferably from 10 to 10% by mass. ~50% by mass. The mother particles 10 are preferably obtained by a solution polymerization method in a solvent which dissolves the monomer mixture and substantially does not dissolve the formed crosslinked polymer. A crosslinked polymer may also be formed in the absence of a solvent such as a bulk polymerization. As for solution polymerization, there are, for example, (1) emulsification or suspension polymerization in an aqueous solution, (2) in a non-aqueous organic solvent or water and a non-aqueous system. In the solvent mixture, the dispersion polymerization is carried out in the presence of a dispersant, and (3) the method of the above (1) or (2) and the seed polymerization method are combined. The treatment in the step after the particle size is easy to control, the washing, and the like becomes easy, and the use of the seed particles can not only obtain the micron-sized particles of interest but also can easily produce a copolymer having a hydrophilic functional group, which can be easily obtained. Precipitation polymerization is preferably used for the reason of particles having excellent deformation recovery rate at the time of compression displacement. The monomer having two or more unsaturated double bonds is not particularly limited, and is suitably selected, for example, from a polyfunctional vinyl monomer and a polyfunctional (meth) acrylate which are usually used. Specific examples of the polyfunctional monomer include divinylbenzene; divinylbiphenyl; divinylnaphthalene, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(methyl). (poly)alkylene glycol di(meth)acrylate such as acrylate, (poly)butylene glycol di(meth)acrylate; 1,6·hexanediol di(meth)acrylate, 1,8 -octanediol di(methyl

-12- 201144341 )Acrylate, 1,9-nonanediol di(meth)acrylate, ι,1〇-nonanediol di(meth)acrylate, 1,12-dodecanediol di Methyl)propionate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate , butyl ethyl propylene glycol di(meth) acrylate, 3-methyl-1,7-octanediol di(meth) acrylate, 2-methyl- l, 8-octanediol di(methyl) Alkanediol-based di(meth)acrylate such as acrylate; neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolethane methane (a) Acrylate, tetramethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxycyclohexanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(A) Acrylate, tricyclodecane dimethanol di(meth) acrylate, ethoxylated bisphenol A di(meth) acrylate, 1,1,1- cis (hydroxymethyl) ethane di ( Methacrylate Ester, 1,1,1-paraxyl(hydroxymethyl)ethane tri(meth)acrylate, cis (hydroxymethyl)propane triacrylate, diallyl phthalate and isomers thereof, isocyanide Triallyl urate and its derivatives. As for commercially available polyfunctional monomers, examples include Nakamura Chemical Industry Co., Ltd. to NK ESTER (A-TMPT-6P0, A-TMPT-3 E0, A-TMM-3LMN 'A-GLY Series, 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, the polyfunctional monomer preferably 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 resulting crosslinked polymer particles is more easily improved -13-201144341. Based on the same viewpoint, the monomer having a polyfunctional group preferably contains a bis(methenoic acid ester, more preferably an alkylene glycol di(meth) acrylate. The number of the alkyl groups is preferably from 6 to 18 carbon atoms, more preferably carbon. Numbers 8 to 12. Examples of the radical polymerizable monomer having a carboxyl group are, for example, an acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, monobutyl methacrylate, and monobutyl maleate. An unsaturated mono- or dicarboxylic acid or a dibasic acid. These may be used alone or in combination of two or more. The radically polymerizable single system having an epoxy group is derived from (meth) propyl acrylate, (methyl) Acrylic (/3-methyl)glycidyl acrylate) 3,4-epoxycyclohexyl acrylate, allyl epoxypropyl 3,4-epoxy vinylcyclohexane, maleic acid The (no-methyl) ring and the rich acid di(/3-methyl) glycidyl ester were selected. Other compounds having an epoxy group may also be used to crosslink and introduce an epoxy group. Examples of compounds having an epoxy group are, for example, ethylene glycol.

Ethylene diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triether and pentaerythritol tetraglycidyl ether of aliphatic polyols, propylene glycol diglycidyl ether, polypropylene glycol Glycidyl ether of polyalkylene glycol of glycidyl ether and tetrabutylglycidyl ether, polymer of polyester resin, polyepoxypropyl compound of polyamine resin, bisphenol oxime resin, phenol A novolak-based epoxy resin, and an epoxy-based amine-based resin. These may be used alone or in combination of two or more. The monomer mixture may also comprise a single monomer having one unsaturated double bond. The proportion of the monofunctional monomer is preferably a monomer mixture based on a carbon of a propanol such as acrylic acid, unsaturated acrylic acid, (methyl ether, oxypropyl acrylate, diethylene oxide diglycidyl ether) , such as the diol di-epoxy group of the epoxy ester functional group

S -14- 201144341 0~70% by mass. The proportion of the monofunctional monomer is more preferably from 5 to 7 % by mass, still more preferably from 10 to 70% by mass, still more preferably from 15 to 70% by mass. /〇. As the monofunctional monomer, for example, (i) styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, o-ethyl styrene, M-ethylstyrene, p-ethylstyrene, 24_dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octyl Styrene, p-n-decylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, Styrene or its derivative of 3,4-dichlorostyrene, etc. (ii) methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, acrylic acid 2 -ethylhexyl ester, n-octyl acrylate, lauryl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate 'methyl α-chloro acrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, A 2-ethylhexyl acrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc., (iii) vinyl acetate Vinyl esters of esters, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. (iv) vinylpyrrole, N-vinylcarbazole, N-vinylfluorene, N-vinylpyrrolidone, etc. a vinyl compound, (v) a fluoroalkyl group-containing (meth) acrylate such as fluorinated ethylene, vinylidene fluoride, tetrafluoroethylene, distilled fluoropropene, trifluoroethyl acrylate or tetrafluoropropyl acrylate. (vi) a conjugated diene such as butadiene or isoprene. These can be used alone or in combination of two or more. Among these, styrene or a derivative thereof, (meth) acrylate and vinyl ester are preferred. By using these, the mother particles having the above physical properties can be efficiently obtained. A known radical polymerization initiator can be used as the polymerization initiator used in the radical polymerization for producing the mother particles. Specific examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, cumyl hydroperoxide, t-butyl hydroperoxide, sodium persulfate, ammonium persulfate, and azoisobutyronitrile. An azo compound such as azobismethylbutyronitrile or azobisisovaleronitrile. These may be used alone or in combination of two or more. Specific examples of the polymerization solvent used for the agent for producing the mother particles by solution polymerization include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, and the like. Tributanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, third pentanol, 1-hexanol, 2-methyl-1- Pentanol, 4-methyl-2-pentanol, 2-ethylbutanol, b-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzene Alcohols such as methanol and cyclohexanol: methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, ether glycol of diethylene glycol monobutyl ether, etc.; propanol, A Ketones such as ethyl ethyl ketone, methyl isobutanol and cyclohexanone: ethyl acetate, butyl acetate, ethyl propionate, (alkyl) cellosolve acetate, ethyl carbitol acetate Ester such as butyl carbitol acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3 - dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, decane, cyclopentane, methylcyclopentane, methylcyclohexane Alkane, B Cyclohexane, p-capane,

S -16- 201144341 Dicyclohexyl, benzene, toluene hydrocarbons; carbon tetrachloride, hydrocarbons; diethyl ether, dimethyl ether methylal, diethyl acetyl fatty acid; nitropropene, dimethylformamidine Amine, dimethyl or the like containing sulfur or nitrogen, or combining two or more kinds, preferably when acetonitrile is used as a mother particle, an emulsifier and a surfactant are used as a dispersant and an aene sulfonic acid or a vinyl phenol. Poly(meth) propylene oxime ester, poly(meth) propylene, polymethyl vinyl ether, polyvinyl chloride, polyethylene, cellulose acetate, nitric acid, etc., such as a (meth) acrylate copolymer copolymer Aliphatic or aromatic trichloroethylene, chlorobenzene, etc., hydroxypropylcellulose, vinyl alcohol, polyvinyl butylpolyvinyl acetate derivatives, polyethylenimine, poly-2, xylene, ethylbenzene, etc. , halogen such as tetrabromoethane, ethers such as trioxane or tetrahydrofuran; acetals such as aldehydes; aliphatic nitrobenzene 'dimethylamine such as formic acid, acetic acid, and propionic acid, monoethanolamine, pyridine, and kea Anthracene, acetonitrile, N-methyl-2-pyrrolidone compound, and the like. These can be used alone. In these, from the viewpoint of preventing particle agglomeration, a dispersing agent, a stabilizer, and a 0-setting agent can be appropriately selected, and examples thereof include polyhydroxystyrene, polystyrene-(meth)acrylate copolymer, and styrene-poly. , styrene-vinylphenol-(meth)polystyrene derivative; poly(meth)acrylic acid derivative of poly(meth)acrylic acid amine, polyacrylonitrile, poly(meth)acrylic acid butyl acetate, etc. Ethyl vinyl ether, polybutyl vinyl ether, polyisobutylene ether derivatives; cellulose derived from cellulose, methyl cellulose cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose carboxymethyl cellulose, etc. : Polyaldehyde, polyethylene formaldehyde, polyvinyl acetate, etc.; nitrogen-containing polymer derived from polyvinylpyridine, polyvinylpyrrolidone-methyl-2-oxazoline, etc.-17- 201144341; polyvinyl chloride And a polyhalogenated hexene derivative such as polyvinylidene chloride; a polyhydric or hydrophilic dispersant such as a polyoxyalkylene derivative such as polydimethyl siloxane or a stabilizer; These may be used alone or in combination of two or more. As the emulsifier (surfactant), for example, an alkylsulfate salt of sodium laurate or the like, an alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate, an alkylnaphthalenesulfonate, a fatty acid salt or an alkane Anionic emulsifier such as a phosphate or an alkyl sulfosuccinate; a cationic emulsifier such as an alkylamine salt, a quaternary ammonium salt, an alkylbetaine or an amine oxide; a polyoxyethylene alkyl ether; Nonionic emulsification of oxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, etc. These may be used alone or in combination of two or more. In the step (a), for example, the mother particles are brought into contact with a solution containing an amine group compound and a solvent capable of dissolving the amine group compound, and the functional group in the mother particles is reacted with the amine group to thereby crosslink the crosslinked polymer. The solution of the amine compound is only impregnated into the surface portion of the mother particle or impregnated into the inner region. As the above amine-based compound, one or two or more compounds having two or more amine groups are used. From the viewpoint of improvement in plating formability, a compound having a plurality of primary or secondary amines such as polyethylenimine and pentaethylhexylamine is preferred. From the standpoint of improving the compression characteristics, the amine compound preferably contains a low molecular weight amine compound having a molecular weight of less than 500. Further, the plating composition is not improved, and the amine compound preferably contains a high molecular weight amine compound having a molecular weight of 500 to 1 0000. It is best to use low molecular weight amine compounds and high molecular weight amines.

S -18- 201144341 Base compound. The molecular weight of the low molecular weight amine compound is preferably less than 500 Å, more preferably 50 to 400, and still more preferably 5 Å to 30,000. The molecular weight of the high-base compound is preferably from 500 to 1 0000, more preferably 5 〇〇. The amine compound is preferably a lipid having a linear or alkyl side chain. Specific examples of the aliphatic diamine include ethylenediamine, Propylenediamine, diamine, 1,6-hexanediamine, 1,8-octanediamine, hydrazine, 9-decanediyl-1,8-octanediamine, hydrazine, oxime decane Diamine, iota, 12-dodecylmethyl-I, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexane, limb trimethyl-1,6-hexane Diamine and 5-methyl-1,9-decanediamine. Amine compounds may also contain alicyclic diamines and/or aromatics to alicyclic diamines such as cyclohexanediamine, methylcyclohexane Alkyl sulphonyl diamine. Examples of aromatic diamines are p-phenylenediamine, amine 'xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-phenyl fluorene and 4 , 4'-diaminodiphenyl ether. Among the above amine compounds, the molecular weight may be less than 500. The amine compound may be used as an amine compound. The amine compound may contain a tertiary amine in addition to the above diamine. High molecular weight polyethylenimine is a suitable high-molecular compound. One or a combination of two or more kinds of particles and two or more kinds of amine-based compounds can be carried out in a stepwise manner by adding each of the amine-based compounds. The amine-based compound can also be dissolved in an organic solvent. Acetone 'methyl ethyl ketone, methyl isobutyl 50 or more, molecular weight amine - 5000 ° aliphatic diamine 1,4-butane amine, 2-methyldiamine, 3 -?, 2,4,4- Diamines and di- and m-phenylenediamines are used for the amination of low molecular weight amines and tetraamines. Mothers are also organic solvent ketones, cyclohexyl-19- 201144341 Ketones and other ketones: acetic acid Esters such as ethyl ester, butyl acetate, ethyl propionate, and cellosolve acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2- Dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, decane, cyclopentane, A Aliphatic or aromatic hydrocarbons such as cyclopentane, methylcyclohexane, ethylcyclohexane, p-captan, benzene, toluene, xylene, ethylbenzene; carbon tetrachloride, trichloroethylene Chlorobenzene, tetrabromide a halogenated hydrocarbon such as an alkane; an ether such as diethyl ether, dimethyl ether, trioxane or tetrahydrofuran: an acetal such as methylal or diethyl acetal; nitropropene, nitrobenzene or pyridine , dimethyl carbamide, dimethyl hydrazine, acetonitrile, and the like, and organic compounds such as sulfur and nitrogen. These may be used alone or in combination of two or more kinds. If the amine compound is water-soluble or hydrophilic As the organic compound, in addition to the above organic solvent, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, butanol, 1- Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, third pentanol, 1-hexanol, 2-methyl-1-pentanol, 4·A Base-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol' benzyl alcohol, cyclohexanol And other alcohols; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, ether glycol such as diethylene glycol monobutyl ether. These can be used alone or in combination of two or more types. The reaction solvent for carrying out the reaction of the functional group in the mother particle with the amine group is preferably a solvent which can dissolve the amine compound without substantially dissolving the mother particles. When the amine compound is in a liquid form, the reaction of the functional group in the mother particle with the amine compound can also be carried out without a solvent.

S -20- 201144341 As for the above reaction solvent, r-butyrolactone, glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, n-butanol , hydrocarbons such as toluene, xylene, n-octane, n-dodecane, fatty acids of the sub-class, polyethylene glycol, dimethyl anthracene, water, methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, third, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol tripentol, 1 -hexanol, 2-methyl-1.heptanol, 4-methyl-2-heptanol, 2-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2 - alcohols such as ethyl-1-, benzyl alcohol, cyclohexanol; methyl cellosolve, ethyl cellosolve propyl cellosolve, butyl cellosolve, ether glycol ketone such as diethylene glycol monobutyl ether , ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl ester, butyl acetate, ethyl propionate, and cellosolve acetate; penta 2-methylbutane , n-hexane, cyclohexane, 2-methylpentane, 2,2-dibutane ' 2,3-dimethylbutane, pentane, n-octane, isooctane, 2,2 methyl pentane Alkane, decane, decane An aliphatic or aromatic hydrocarbon such as cyclopentane, methylcyclopentane, methylalkane, ethylcyclohexane, p-captan, dicyclohexyl, benzene, toluene, benzene, ethylbenzene; tetrachloro a halogenated hydrocarbon such as carbon, triene, chlorobenzene or tetrabromoethane; an ether such as diethyl ether, dimethyl ether, heterocyclohexane or tetrahydrofuran; methylal, diethyl acetal acetal; formic acid And fatty acids such as acetic acid and propionic acid; organic compounds containing sulfur and nitrogen such as nitropropene, benzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide, and dimethylhydrazine. It is preferably a lower alcohol such as water or methyl alcohol, a mixture of an ether alcohol and a lower alcohol such as methyl cellosolve or ethyl cellosolve, a water-soluble mixture of water and an ether alcohol, and a 1,2-alcohol, etc. Oleic acid, butanol, diethylhexanol, iso-propionic acid ethane, methyl, 3-tricyclohexachlorodichloroethane, or the like, or water-based solvent - 201144341 solvent, Toluene, dimethylformamide (DMF), tetrahydrofuran (THF), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, N-methyl-2-pyrrolidone (NMP), Methylene chloride, tetrachloroethylene, etc., more preferably 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, water and ether alcohol. A water soluble and hydrophilic medium for the mixture. These may be used alone or in combination of two or more types. The temperature at which the amine compound is reacted in the step (a) is determined by the kind of the solvent, but is preferably from 10 ° C to 250 ° C, more preferably from 100 to 250 ° C, still more preferably from 180 ° C. 250 ° C. The reaction time may be a time required for the crosslinking reaction to be substantially complete, and may be, for example, substantially different depending on the amine compound to be used, the amount of the compound to be used, the type of the functional group in the mother particle, the viscosity and concentration of the solution, and the like. It is 5 to 24 hours at 180 ° C, preferably about 6 to 10 hours. Even if the reaction time is lengthened, crosslinked polymer particles can be obtained, but practically, it takes a long time to be a suitable countermeasure. Further, if the reaction time is extremely short, crosslinking may not be sufficiently performed. The amount of the amino group compound in the step (a) is preferably from 0.1 to 5, more preferably from 0.5 to 3, based on the amine equivalent ratio of the functional group of the mother particle. When the equivalent ratio is too small or too large, the effect of improving the compression characteristics or the improvement of the plating formability becomes small. The average particle diameter of the crosslinked polymer particles is preferably from 0.1 to 50 μm, more preferably from 0.2 to 30 μm. It is preferably 0.3 to 2 0 μηι, preferably 0.5 to 5 μιη. If the average particle diameter is small, there is a possibility that the crosslinked polymer particles are easily aggregated. The Cv 値 (coefficient of variation) of the crosslinked polymer particle diameter (diameter) is preferably -22-201144341 1 5 % or less. c v値 exceeds 15 ° /. At the time, there is a tendency that the properties of the crosslinked polymer particles are lowered in various ways. For example, when the crosslinked polymer particles are used for the conductive particles of the conductive conductive adhesive, the connection reliability is lowered, and when the polymer particles are used for the bio-inspection element, there is a quantitative decrease. From the same viewpoint, the Cv 粒径 of the particle diameter is preferably 10% or less, more preferably hereinafter less preferably 4% or less. The Cv値 system of the average particle diameter and particle diameter of the crosslinked polymer particles was determined by the following measurement method. 1) The particles were dispersed in water using an ultrasonic dispersing device, and a dispersion containing 1% by mass of the particles was prepared. 2) Using a particle size distribution meter (SYSMEXFLOW, SYSMEX, approximately 20,000 particles of the dispersion were observed under a microscope, and the average particle diameter and the coefficient of variation C v of the particles were calculated. The mother particles after the step (a) were measured at 180 ° C. The compression deformation recovery rate is usually 30% or more, preferably 40% or more, more preferably 50% or more, and more preferably 50 to 65%. If the compression deformation recovery rate is low, the elastic force is insufficient to require high elasticity. There is a tendency to cause poor contact in applications such as conductive adhesives. The compression deformation recovery rate is reduced by 0.33 mN / sec by compressing the particles from the center at a speed of 0.33 mN/sec to 5 mN. In the process, the relationship between the load enthalpy and the compression displacement is obtained. The ratio of the displacement from the load to the final load (L1) and the displacement from the reversal point to the initial weight (L2) (L1/L2) is % indicates 値 as the compressive deformation recovery rate " The compressive damage measured by the mother particles after the step (a) at 180 °C is 5%.) The heavy back-retraction -23- 201144341 is preferably 10mN or more. The cross-linked polycondensation of this embodiment As described above, the fine particles of the composite have a high recovery rate of compression deformation, so that the possibility of excellent elasticity is high. Therefore, when the crosslinked polymer fine particles are used as the conductive material, there is a low possibility that the substrate for connection between the electrodes is scratched and penetrated. The conductive material is highly compressed and deformed, and the possibility of high-accuracy interval retention or stable connection reliability is also high. Since the crosslinked polymer particles of the present embodiment have the above characteristics, they are useful not only in the field of electrical materials, but also in coatings, coating agents, light diffusing agents, cosmetics, medical or biological inspection elements, agricultural chemicals, building materials, and the like. Also useful for the field. Fig. 2 is a cross-sectional view showing an embodiment of an anisotropic conductive adhesive. The film-shaped anisotropic conductive adhesive 20 shown in Fig. 2 is composed of an adhesive resin 3 and conductive particles 5 dispersed in the adhesive resin 3. The conductive particles 5 have the crosslinked polymer particles of the present invention and a metal layer (metal plating layer) coated with the crosslinked polymer particles. The adhesive resin 3 is not particularly limited, but is preferably an insulating adhesive composition. The insulating adhesive composition (adhesive resin 3) contains, for example, at least one component selected from the group consisting of a thermoplastic resin, a thermosetting resin, and an elastomer. The thermoplastic resin is selected from, for example, a vinyl resin such as a vinyl acetate resin, a vinyl chloride resin, an acrylic resin, or a styrene resin; a polyolefin; an ethylene-vinyl acetate copolymer; a polyamide resin; a butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer and a thermoplastic block copolymer of such hydrogenated adducts. The thermosetting resin is selected from, for example, an epoxy resin, a urethane resin -24 to 201144341, a polyimide resin, and an unsaturated polyester resin. The thermosetting resin is usually contained in the adhesive resin 3 together with its hardener. The thermosetting resin may be any of a room temperature curing type, a heat curing type, a photo hardening type, and a moisture curing type. The elastomeric system is selected, for example, from styrene-butadiene copolymer rubber, chloroprene rubber, and acrylonitrile-styrene block copolymer rubber. These resins may be used singly or in combination of two or more. As an insulating adhesive composition of the adhesive resin 3, if necessary, it may contain, for example, an extender, a softener (plasticizer), an adhesion improver, an antioxidant (anti-aging agent), a heat stabilizer, and light. Various additives such as stabilizers, ultraviolet absorbers, colorants, flame retardants, and organic solvents. The anisotropic conductive adhesive of the present embodiment can be obtained, for example, by adding conductive particles to an adhesive resin, uniformly mixing the conductive particles, and dispersing the conductive particles. It is applied to a release-treated surface of a release material such as a release paper or a release film by directly dissolving or dissolving or dispersing the isotropic conductive adhesive containing the adhesive resin and the conductive particles in a solvent. The film-form anisotropic conductive adhesive can be obtained by drying or cooling, and the conductive state of the conductive particles in the anisotropic conductive adhesive is not particularly limited. The conductive particles may be uniformly dispersed in the adhesive resin, or may be partially disposed near the surface layer of the film. The form of the anisotropic conductive adhesive is not limited to the film, and may be, for example, a paste or an ink. EXAMPLES The following examples are set forth to more specifically illustrate the present invention. However, the present invention is not limited to the embodiments. 1. Synthesis of Mother Particles Synthesis Example 1 Each of the following compounds was fed in a 100 mL three-necked flask, and heated in a water bath of 8 (TC) while stirring in a stirrer for about 6 hours to form a mother of self-crosslinking polymer. Particles • DVB-960 (Nippon Steel Chemical, containing 96% by mass of divinylbenzene (DVB), ethyl styrene (EVB) 3% by mass): 4_9g • Methacrylic acid (Wako Pure Chemical): 2.1g • Azobisisobutyronitrile (AIBN, Wako Pure Chemical Industries): 〇.6g • Acetonitrile (Wako Pure Chemical Industries): 7〇g Next, use a suction filtration device to filter the mother particles 'Using isopropanol (IPA, Wako Pure Chemicals) After washing and filtering for about 3 to 5 times, 'vacuum drying to obtain powdery mother particles. The particle size of the obtained mother particles is s EM observed and measured, and is spherical monodisperse of the average particle size of 4 · 1 μηι Particles: C ν 値 of the particle size was 2.3%. Synthesis Example 2 Each of the following compounds was fed into a 100 mL three-necked flask at a time, and was heated at 80° (in a water bath) while stirring in a mixer for about 6 hours. Mother particles formed from self-crosslinking polymers • DVB-960 : 2.8 g • methacryl : 4.2g

S -26- 201144341 • AIBN : 0.6g • Acetonitrile: 70g Next, the mother particles are filtered using a suction filtration device, washed with isopropyl alcohol (IPA, Wako Pure Chemical Industries, Ltd.) and filtered for 3 to 5 times. Vacuum drying gave powdery mother particles. The particle diameter of the obtained mother particles was observed by SEM and measured to be spherical monodisperse particles having an average particle diameter. The particle size was 3.0% by enthalpy. » Synthesis Example 3 The following compounds were fed in a 100 mL three-necked flask, and heated in a water bath of 80 ° C while stirring in a mixer for about 6 hours to form a self-crosslinking polymerization. The parent particle formed by the object. • DVB-960: 0.9g • 1,10-decanediol diacrylate (A-DOD, Xinzhongcun Chemical Industry): 2.7g • Methacrylic acid: 2g • 11-undecenoic acid: 1.4g • AIBN · · 0.07g • Acetonitrile: 7〇g Next, the mother particles are filtered using a suction filtration device, washed with isopropyl alcohol (IPA, Wako Pure Chemical Industries, Ltd.) and filtered for 3 to 5 times, and then vacuum dried to obtain a powder. Parent particle. The particle diameter of the obtained mother particles was observed by SEM and measured to obtain spherical monodisperse particles having an average particle diameter of 2.8 μηη. The particle size of Cv 値 was 2.7%. -27-201144341 The compression deformation recovery ratio and the compression fracture strength of each of the mother particles obtained in Synthesis Examples 1 to 3 were measured. The results of the measurements are summarized in Table 1. [Table 1] Particle size (μηι) Cv (°/〇) Compression recovery ratio (%) Compressive fracture strength (IV) 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) A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and 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 nitrogen stream. • Master particle of Synthesis Example 1: 5 parts by weight • Hexanediamine (molecular weight: 16.2): 1 part by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • Polyethylenimine (molecular weight 300) : 0.8 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • r-butyrolactone: 93.2 parts by weight Next, the particles are filtered using a suction filtration device, washed with IPA and filtered repeatedly. After about 3 to 5 times, it was vacuum-dried to obtain powdery mother particles (particles 1 a ) which were crosslinked by hexane diamine and polyethylenimine. The obtained mother particles have a compression set recovery ratio of 56% at 180 ° C, and the compression failure strength is

S -28- 201144341 1 6mN 〇 (Step C) The particles 1 a were subjected to Ni plating by the following operation to prepare conductive particles composed of the crosslinked polymer particles and the Ni plating layer coated thereon. (catalyst supply) A stock solution of the active agent Neoganth 83 4 (trade name, aqueous solution of palladium ion-amine-based complexing agent) manufactured by ATOTECH Co., Ltd. was diluted with water to 40 mL/L to adjust to pH 10.5 to prepare a single-liquid base. Catalyst fluid. In the base vehicle, the particles la were immersed at 35 ° C for 10 minutes to adsorb a palladium complex on the surface of the particles la, and the particles 1 a were recovered by suction filtration and washed with water. Subsequently, the particles la are suspended in water. Among them, a palladium complex of the surface of the particle la was reduced by feeding dimethylamine borane to 0.1 g/L to obtain a suspension of the palladium-loaded particles la on the surface. (electroless plating) The above suspension was heated to 80 ° C, and an electroless Ni-P plating solution (manufactured by Hitachi Chemical Co., Ltd., trade name: NIPS-100) was slowly added dropwise by a metering pump. The particles la are plated. The plating time is 60 minutes. Thereby, a plating layer is formed on the surface of the particle la. Subsequently, suction filtration, water washing, suction filtration, and drying were sequentially performed to obtain conductive particles having a plating layer caused by electroless Ni-P plating. The obtained conductive particles were formed into a plating layer with good uniformity, and no irregularities were observed on the surface of the plating layer. -29 - 201144341 (Disintegration treatment and particle evaluation) The obtained conductive particles were subjected to a pulverization treatment at a crushing pressure of 0·1 MPa by a jet honing machine. The conductive particles after the disintegration treatment were observed by an electron microscope and photographed. Adjust the magnification so that each photo is taken with 1 000 particles, and 10 shots are taken for each change of the shooting place. For the 10 photos (the total number of particles = 10,000), the number of particles not completely coated with the plating layer and the number of plated sheets were investigated. If there is a large amount of agglutination treatment, it is impossible to completely coat the plating layer, and there are many particles in a state in which the resin is partially exposed. Further, when the adhesion between the resin particles and the plating layer is not good. The plating was peeled off by the pulverization treatment, and a large amount of plating sheets occurred after the pulverization treatment. Therefore, in the conductive particles after the pulverization treatment, if the number of particles which are not completely coated by plating is small (the number of the coating-coated lipid particles is large), and the plating sheet is preferable, it is judged to be plated. The particles in the treatment liquid have good dispersibility and excellent adhesion between the resin particles and the plating layer. In the observation after the disintegration, the presence of the plating sheet was hardly confirmed. Example 2 A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated under a nitrogen stream at 18 (TC oil bath for about 6 hours. • Master particle of Synthesis Example 1: 5 parts by weight • Hexanediamine (molecular weight 116.2): 1 part by weight (amine group relative to mother The ratio of carboxyl groups in the particles is 1 equivalent)

S -30- 201144341 • Polyethylenimine (molecular weight 600): 0.9 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • r-butyrolactone: 93.1 parts by weight Next, using suction The filter device filters the particles, washes them with IPA, and filters them for about 3 to 5 times, and then vacuum-driates them to obtain powdery mother particles (particles 2a) obtained by crosslinking hexanediamine and polyethylenimine. The obtained mother particles had a compression set recovery ratio of 54% at 180 ° C and a compressive fracture strength of 15 rnN 〇 (Step C). By performing the same operation as in Example 1, the particles 2a were subjected to Ni plating to prepare a cross-linking. Conductive particles composed of polymer particles and a Ni plating layer coated thereon. In the obtained conductive particles, the plating layer was formed with good uniformity, and no unevenness was observed on the surface of the plating layer. In the observation after the disintegration, the presence of the plating sheet was hardly confirmed. Example 3 A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and 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 nitrogen stream. • Master particle of Synthesis Example 1: 5 parts by weight • Hexanediamine (molecular weight 116.2): 1 part by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • The polyethylenimine (molecular weight: 1200) : 9 parts by weight (amine phase 201144341 for the carboxyl group in the mother particles is 1 equivalent) ♦ r - butyrolactone: 93.1 parts by weight Next, the particles are filtered using a suction filtration device, washed with IP A and After filtering for about 3 to 5 times, it was vacuum-dried to obtain powdery mother particles (particles 3 a ) which were crosslinked by hexane diamine and polyethylenimine. The obtained mother particles had a compression set recovery at 53 ° C of 53% and a compressive fracture strength of 16 mN. (Step C) By subjecting the particles 3a to Ni plating in the same manner as in Example 1, conductive particles composed of crosslinked polymer particles and a Ni plating layer coated thereon were produced. In the obtained conductive particles, the plating layer was formed with good uniformity, and no unevenness was observed on the surface of the plating layer. In the observation after the disintegration, the presence of the plating sheet was hardly confirmed. Example 4 A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and 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 nitrogen stream. • Master particle of Synthesis Example 1: 5 parts by weight • Hexanediamine (molecular weight: 116·2): 1 part by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • Polyethylenimine (molecular weight 1 800 ) : 0.9 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent)

S -32- 201144341 • r -butyrolactone: 93.1 parts by weight Next, the particles were filtered using a suction filtration device, washed with IPA and filtered for about 3 to 5 times, and then dried in vacuo to obtain hexanediamine and Powdered mother particles (particles 4a) formed by cross-linking of ethyleneimine. The obtained mother particles had a compression set recovery ratio of 55% at 180 ° C and a compressive fracture strength of 16 mN 〇 (Step C). By the same operation as in Example 1, the particles 4a were subjected to Ni plating to prepare a crosslinked polymerization. Conductive particles composed of particles and a Ni deposit coated with the particles. In the obtained conductive particles, the plating layer was formed with good uniformity, and no unevenness was observed on the surface of the plating layer. In the observation after the disintegration, the presence of the plating sheet was hardly confirmed. Example 5 A mixture of the following ratios was fed into a three-necked flask of 100 mL at a time, and 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 nitrogen stream. • Master particle of Synthesis Example 1: 5 parts by weight • Hexanediamine (molecular weight: 16.2): 1 part by weight (1 equivalent of the amine group to the carboxyl group in the mother particle) • Polyethylenimine (molecular weight 1 0000 ) : 0.9 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • 7 -butyrolactone: 93.1 parts by weight - 33 - 201144341 Next, the particles are filtered using a suction filtration device, and washed with IPA. After filtering and filtering for about 3-5 times, it was vacuum-dried to obtain powdery mother particles (particles 5a) obtained by crosslinking hexanediamine and polyethylenimine. The obtained mother particles had a compression set recovery rate of 5 7% at 180 ° C and a compressive fracture strength of 16 mN. (Step c) By subjecting the particles 5a to Ni plating in the same manner as in Example 1, conductive particles composed of the crosslinked polymer particles and the Ni plating layer coated therewith were produced. In the obtained conductive particles, the plating layer was formed with good uniformity, and no unevenness was observed on the surface of the plating layer. In the observation after the disintegration, the presence of the ore sheet was hardly confirmed. Example 6 (Step a) A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and stirred at room temperature for 1 hour using a stirrer. Dispersions. 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 • Ethylenediamine (molecular weight 60.2): 1 part by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • The polyethylenimine (molecular weight 1 200 ) : 1.8 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • r - butyrolactone (Wako Pure Chemical Industries, Ltd.): 91.7 parts by weight

S -34- 201144341 Next, the particles were filtered using a suction filtration device, washed with IP A and filtered for 3 to 5 times, and then vacuum dried to obtain cross-linking from ethylenediamine and polyethylenimine. Powdered mother particles (particles 6a). The resulting masterbatch had a compression set recovery of 51% at 180 t and a compressive failure strength of 1 1 mN. (Step c) By the same operation as in Example 1, the particles 6a were subjected to Ni plating to prepare conductive particles composed of the crosslinked polymer particles and the Ni plating layer coated thereon. In the obtained conductive particles, the plating layer was formed with good uniformity, and no unevenness was observed on the surface of the plating layer. In the observation after the disintegration, the presence of the plating sheet was hardly confirmed. Example 7 (Step a) A mixture of the following ratios was fed in a 100 mL three-necked flask at a time, and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated under a nitrogen stream at 18 °C in an oil bath for about 12 hours. • Masterbatch of Synthesis Example 3: 5 parts by weight • Pentaethylhexamine (molecular weight: 232.4): 0.27 parts by weight (amine) The ratio of the base to the carboxyl group in the mother particle is 1 equivalent) • Polyethylenimine (molecular weight 300): 1 part by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent) • 7 - Ester (Wako Pure Chemicals): 93.7 parts by weight -35- 201144341 Next, the particles were filtered using a suction filtration device, washed with IP A and filtered for 3 to 5 times, and then vacuum dried to obtain an ethylidene group. Powdered mother particles (particles 7a) obtained by cross-linking hexamine and polyethylenimine. The resulting mother particles have a compression set recovery of 45% at 18 ° C and a compressive failure strength of 12 mN 〇 (step c) By subjecting the particles 7a to Ni plating in the same manner as in Example 1, conductive particles composed of the crosslinked polymer particles and the Ni plating layer coated thereon were prepared, and the obtained conductive particles were excellent. Uniformity forms a plating layer, no unevenness is observed on the surface of the plating layer, and observation after disintegration The presence of the plating sheet was hardly observed. 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. Comparative Example 2 In the step a, a mixture of the following ratios was used. In the same manner as in Example 1, the treatment of the mother particles of Synthesis Example 1 and the production and evaluation of the conductive particles were carried out in the same manner as in Example 1. The mother particles of Synthesis Example 1: 5 parts by weight • Hexylamine (molecular weight: 100): 1.7 parts by weight (the ratio of the amine group to the carboxyl group in the mother particle is 1 equivalent)

S-36-201144341 • r-butyrolactone: 92.3 parts by weight. Comparative Example 3 The synthesis was carried out in the same manner as in Example 1 except that the mixing of the following ratios was carried out in the step a. Production of conductive particles and evaluation thereof. • Master particle of Synthesis Example 1: 5 parts by weight • Polyethylenimine (molecular weight 600): The ratio of carboxyl groups in the mother particles was 1 equivalent) • Butyrolactone: 91.4 parts by weight Comparative Example 4 Except in step a The production of the synthesized conductive particles and the evaluation thereof were carried out in the same manner as in Example 1 using the following ratios. • Master particle of Synthesis Example 1: 5 parts by weight • Polyethylenimine (molecular weight 1200) The ratio of carboxyl groups in the mother particles is 1 equivalent) • r - butyrolactone: 91.4 parts by weight as a raw material, Treatment of 1 mother particle and 〇·9 parts by weight (treatment of the parent particle of column 1 in addition to the amine-based compound and ·. 9 parts by weight (amine-phase-37-201144341 (Table 2) compression Recovery rate (%) Compressive failure strength (mN) Uniformity of plating layer Plating sheet after unevenness of the plating layer Example 1 56 16 Good {fuc No Example 2 54 15 Good No Example 3 53 16 good without fte Example 4 55 14 good inL • frrr m Example 5 57 18 good ^m*. m no example 6 51 11 good / frTf - M Μ /»,, example 7 45 12 good Arrr Μ comparison Example 1 33 7 Defective Comparative Example 2 32 8 Defective Comparative Example 3 30 8 Good Comparative Example 4 33 9 Good fnr. m Arrr No evaluation results are shown in Table 2. Crosslinked polymers obtained in each example The particles have good compression properties, and the crosslinked polymer particles of the examples The sub-surface can be formed into a plating layer with good uniformity. Further, since the electroconductive particles are almost free of ore-deposited pieces after disintegration, it is confirmed that the resin particles and the plating layer are excellent in adhesion. In contrast, the particles of the particles are compared. The compression characteristics and the plating properties are not sufficient. From the above experimental results, it was confirmed that according to the present invention, crosslinked polymer particles having good compression characteristics and forming a plating layer on a good surface thereof can be provided. It is understood that the crosslinked polymer particles of the present invention satisfy the useful properties of particles used as an electrically conductive material represented by an anisotropic conductive film or a conductive paste. Further, the crosslinked polymerization obtained by the process of the present invention Particle due to

S-38-201144341 Excellent in heat resistance, chemical resistance, reactivity, and solution dispersibility, so it can be preferably used in the following fields: spacers for liquid crystals, conductive fine particles, conductive materials using them, and electrostatic charges. Developers, surface modifiers for silver salt films, film modifiers for magnetic tapes, thermal stability paper travel stabilizers, carbon and other electrical properties, electronics industry, inks, adhesives, adhesives, light diffusers, General industrial fields such as chemical fields such as paints, paper coatings, and data recording papers, such as chemical agents, aromatic agents, low shrinkage agents, paper, dental materials, and resin modifiers, liquid or powder cosmetics. A wide range of fields such as cosmetics, bio-antigens, and antigen-antibody reaction-inspection particles, such as a slip agent or an extender pigment, and the like, such as biology, medical treatment, medicine, agriculture, construction, and automotive. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an embodiment of crosslinked polymer particles. 2 is a schematic view showing an embodiment of an anisotropic conductive adhesive [Description of main components] 1 : Crosslinked polymer particles 3 : Adhesive resin 5 : Conductive particles 10 : Parent particles 20 : Anisotropic conductivity Follow-39-

Claims (1)

201144341 VII. Patent Application Range: 1. A crosslinked polymer particle characterized in that it is contacted with an amine compound having a crosslinked polymer having a functional group and an amine compound having two or more amine groups. And the method for producing the step (a) wherein the functional group is reacted with the amine group to further crosslink the crosslinked polymer, and the amine compound is a low molecular weight amine compound having a molecular weight of less than 5,000. . 2. The crosslinked polymer particles of claim 1, wherein the amine compound 尙 contains a high molecular weight amine compound having a molecular weight of from 50 to 10,000. 3. The crosslinked polymer particles according to claim 1 or 2, wherein the average particle diameter is 0.1 to 10/zm, and the Cv値 of the particle diameter is 10% or less. The crosslinked polymer particles according to any one of claims 1 to 3, wherein the functional group is at least selected from the group consisting of a carboxyl group, an epoxy group, and a glycidyl group (Glycidyl). 1 species. The crosslinked polymer particles according to any one of claims 1 to 4, wherein the mother particles are particles obtainable by suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization or seed polymerization. 6. The crosslinked polymer particles according to any one of the above claims, wherein the crosslinked polymer is a monomer having 2 or more mass% of a double bond having 2 or more unsaturated double bonds. A copolymer formed by copolymerization of a monomer mixture. 7. The crosslinked polymer particle of claim 6, wherein S-40-201144341 wherein the monomer having two or more unsaturated double bonds comprises divinylbenzene and di(meth)acrylate The crosslinked polymer particles according to any one of the preceding claims, wherein the parent particles after the step (a) have a content of 40% or more at 180 t. The compression deformation recovery rate and the compression failure strength above l〇mN. A conductive particle obtained by the production method comprising the step (c) of plating the crosslinked polymer particles according to any one of claims 1 to 8. 10. The conductive particles according to claim 9, wherein in the step (c), the crosslinked polymer is plated by using a Pd ion complex as a plating catalyst. A method for producing a crosslinked polymer particle, comprising: contacting a mother particle formed of a crosslinked polymer having a functional group with an amine compound having two or more amine groups, and allowing the functional group to The amine group is reacted to further crosslink the crosslinked polymer (a), and the amine compound is a low molecular weight amine compound having a molecular weight of less than 500. 12. The method for producing a crosslinked polymer particle according to claim 11, wherein in the step (a), the ratio of the amine group of the amine compound is 1 equivalent to the functional group in the parent particle. It is 0.1 to 5 equivalents. 13. An anisotropic conductive adhesive which is provided with an adhesive resin and is dispersed in the adhesive resin as disclosed in claim 9 or 2011. S -42-