WO2011114993A1 - Particule de polymère réticulé et méthode de production de ladite particule - Google Patents

Particule de polymère réticulé et méthode de production de ladite particule Download PDF

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WO2011114993A1
WO2011114993A1 PCT/JP2011/055678 JP2011055678W WO2011114993A1 WO 2011114993 A1 WO2011114993 A1 WO 2011114993A1 JP 2011055678 W JP2011055678 W JP 2011055678W WO 2011114993 A1 WO2011114993 A1 WO 2011114993A1
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particles
crosslinked polymer
particle
amino
amino compound
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優 渡邊
高井　健次
憂子 永原
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日立化成工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to crosslinked polymer particles and a method for producing the same.
  • Crosslinked polymer particles with a high degree of crosslinking and excellent heat resistance and chemical resistance include various spacers, electrical and electronic materials such as conductive fine particles, resin film sliding property modifiers, chromatography carriers, It is applied and put into practical use in various fields such as biomedical devices.
  • these crosslinked polymer particles are produced by a method such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
  • cross-linked polymer particles can be produced by polymerizing the cross-linkable monomer as oil droplets in an aqueous medium by mechanical force.
  • the upper limit of the ratio of the crosslinkable monomer is about 2.0% by mass.
  • the range of the particle diameter of the obtained crosslinked polymer particles is 0.1 to 1.0 ⁇ m, and it is said that particles having a particle diameter exceeding 1 ⁇ m cannot be obtained.
  • Patent Document 1 discloses a method in which emulsion polymerization can be stably performed by using a special seed, even when 20.0% by mass or more of a crosslinkable monomer is used.
  • the range of the particle diameter obtained by this method is 0.1 to 1.0 ⁇ m, which is the same as that of ordinary emulsion polymerization. Thus, it is difficult to obtain crosslinked polymer particles having a particle diameter exceeding 1 ⁇ m by emulsion polymerization.
  • Patent Document 2 discloses a first step in which an organic compound having low solubility in water is absorbed into a seed polymer as a swelling aid, and then a monomer soluble in water to some extent is absorbed into the seed polymer to form monomer swelling particles.
  • a swelling polymerization method is disclosed in which a monomer is polymerized while maintaining the particle shape. According to this method, it becomes possible to use many crosslinkable monomers, and as a result, crosslinked polymer particles having a size of 1 ⁇ m or more and a uniform particle size distribution can be produced.
  • Patent Document 3 discloses a method for producing crosslinked particles by a dispersion polymerization method using 20% by mass or more of a crosslinkable vinyl monomer. According to this method, it is possible to produce monodisperse particles of about several microns to some extent. However, when the particle diameter exceeds 2.5 ⁇ m, the aggregation and fusion of the particles increases, and it is very difficult to obtain monodisperse particles. Moreover, when a hydrophilic or water-soluble polymerizable monomer is copolymerized, it is more difficult to obtain monodisperse particles because aggregation and fusion are likely to occur.
  • a crosslinked polymer particle is produced by copolymerizing an unsaturated monomer having a hydrophilic functional group or an active hydrogen group with a crosslinkable monomer when performing a precipitation polymerization method similar to the dispersion polymerization method.
  • a method has been reported. According to this method, monodisperse particles of several ⁇ m can be obtained efficiently.
  • Patent Document 5 reports a method of crosslinking mother particles by reacting uncrosslinked mother particles having a functional group with an epoxy compound, an oxazoline compound, or an amino compound. According to this method, although it is possible to crosslink uncrosslinked particles, since the reactivity of the compound to be reacted is high, the crosslinking reaction tends to proceed mainly on the particle surface and a core-shell structure tends to be formed.
  • the mother particle contains a functional group derived from a hydrophilic monomer on the surface and inside of the particle
  • a sufficient level is achieved in terms of compression characteristics such as compression deformation recovery rate and compression fracture strength.
  • compression characteristics such as compression deformation recovery rate and compression fracture strength.
  • polymer particles are covered with a metal layer to form conductive particles that are used in an anisotropic conductive adhesive, it is extremely important that the polymer particles have good compression properties.
  • simultaneously with compression characteristics when forming a metal plating layer on the surface of polymer particles by plating, it is required to form a plating layer having high uniformity and good adhesion.
  • a main object of the present invention is to provide polymer particles that have good compression characteristics and can form a plating layer on the surface in a good state.
  • the present invention includes a step of bringing a mother particle formed from a crosslinked polymer having a functional group into contact with an amino compound having two or more amino groups, and further crosslinking the crosslinked polymer by a reaction between the functional group and the amino group.
  • the present invention relates to a crosslinked polymer particle that can be obtained by a production method comprising
  • the amino compound includes a low molecular weight amino compound having a molecular weight of less than 500.
  • the cross-linked polymer particles according to the present invention have a good compression property and can form a plating layer on the surface in a good state.
  • a low molecular weight amino compound having a molecular weight of less than 500 the inside of the mother particle can be efficiently cross-linked, and the compression characteristics can be improved.
  • mother particles obtained by copolymerizing a hydrophilic monomer generally tend to have low compression characteristics due to a small amount of the crosslinkable monomer.
  • Cross-linked polymer with good compression characteristics and good plating formability by post-crosslinking mother particles having functional groups such as carboxyl groups derived from hydrophilic monomers with compounds having two or more amino groups Particles can be obtained.
  • the amino compound preferably further contains a high molecular weight amino compound having a molecular weight of 500 to 10,000.
  • a high molecular weight amino compound having a molecular weight of 500 to 10,000 in combination, a large number of amino groups can be introduced on the surface of the mother particles, and the formability of the plating can be further improved.
  • the average particle size of the crosslinked polymer particles is preferably 0.1 to 10 ⁇ m.
  • the Cv value of the particle diameter of the crosslinked polymer particles is preferably 10% or less. When the Cv value of the particle diameter of the crosslinked polymer particles is low, the connection reliability when the conductive particles obtained from the crosslinked polymer particles are used for the anisotropic conductive adhesive is further improved.
  • the cross-linked polymer that forms the mother particle preferably has at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, and a glycidyl group. These functional groups efficiently react with the amino group of the amino compound, and a crosslinked structure is formed in the mother particle.
  • the mother particles are preferably particles that can be obtained by suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization or seed polymerization.
  • the crosslinked polymer forming the mother particle is preferably a copolymer formed by copolymerizing a monomer mixture containing 10% by mass or more of a monomer having two or more unsaturated double bonds. .
  • the monomer having two or more unsaturated double bonds preferably contains at least one selected from divinylbenzene and di (meth) acrylate.
  • the mother particles after the step (a) preferably have a compression deformation recovery rate of 40% or more and a compression fracture strength of 10 mN or more at 180 ° C.
  • the present invention also relates to conductive particles that can be obtained by a production method including the step (c) of plating the crosslinked polymer particles according to the present invention.
  • the conductive particles according to the present invention are useful, for example, as conductive particles for anisotropic conductive adhesives.
  • step (c) the crosslinked polymer particles are preferably plated using a Pd ion complex as a plating catalyst.
  • the present invention relates to a method for producing crosslinked polymer particles.
  • a mother particle formed from a cross-linked polymer having a functional group is brought into contact with an amino compound having two or more amino groups, and the cross-linked polymer is formed by a reaction between the functional group and the amino group.
  • a cross-linking step (a) is provided.
  • the amino compound includes a low molecular weight amino compound having a molecular weight of less than 500.
  • the ratio of the amino group of the amino compound is preferably 0.1 to 5 equivalents relative to 1 equivalent of the functional group in the mother particle.
  • the present invention also relates to an anisotropic conductive adhesive comprising a binder resin and the conductive particles dispersed in the binder resin.
  • polymer particles that have good compression characteristics and can form a plating layer in a good state on the surface thereof.
  • the crosslinked polymer particle according to the present embodiment comprises a step of preparing a mother particle formed from a crosslinked polymer having a functional group, and bringing the mother particle into contact with an amino compound having two or more amino groups. And a step (a) of further crosslinking the crosslinked polymer by a reaction between the amino group and the amino group.
  • FIG. 1 is a schematic view showing an embodiment of a crosslinked polymer particle.
  • a crosslinked polymer particle 1 shown in FIG. 1 includes a mother particle 10, a mother particle 10 that is a particulate crosslinked polymer, a crosslinked portion X derived from an amino compound that crosslinks the crosslinked polymer, and an amino group derived from the amino compound.
  • the modification part R has.
  • the cross-linked portion X is distributed over the entire surface and inside of the base particle 10.
  • the modified portion R is mainly disposed on the surface of the base particle 10.
  • the cross-linked 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 silicone resin, a polyester resin, a polyurethane resin, a polyamide resin, or an epoxy resin.
  • the mother particle 10 is preferably a crosslinked polymer particle formed by copolymerization of a monomer mixture composed of a plurality of types of monomers having an unsaturated double bond.
  • the monomer mixture is, for example, at least one hydrophilic functional group selected from the group consisting of a multifunctional monomer having two or more unsaturated double bonds, a carboxyl group, an epoxy group, and a glycidyl group.
  • the monomer mixture preferably contains 10% by mass or more of a polyfunctional monomer having two or more unsaturated double bonds with respect to the whole monomer mixture.
  • a polyfunctional monomer having two or more unsaturated double bonds are particularly easily formed.
  • the monomer mixture is preferably a polyfunctional monomer having two or more unsaturated double bonds, more preferably 10 to 80% by mass, still more preferably 10 to 60% by mass, and much more.
  • the content is preferably 10 to 50% by mass.
  • the mother particles 10 are preferably obtained by a solution polymerization method in a medium in which the monomer mixture is dissolved and the resulting crosslinked polymer is not substantially dissolved. It is also possible to form a crosslinked polymer in the absence of a solvent as in bulk polymerization.
  • Solution polymerization includes (1) emulsion or suspension polymerization performed in an aqueous solution, (2) dispersion polymerization performed in the presence of a dispersant in a non-aqueous organic solvent or a mixed solvent of water and a non-aqueous organic solvent, ( 3) A method of combining the above (1) or (2) with a seed polymerization method may be mentioned.
  • a copolymer having a hydrophilic functional group as well as a desired micron-size particle can be obtained without using a seed particle.
  • Precipitation polymerization is preferably employed because, for example, it is possible to easily produce particles with excellent deformation recovery rate at high compression displacement.
  • the monomer having two or more unsaturated double bonds is not particularly limited, and is appropriately selected from, for example, commonly used polyfunctional vinyl monomers and polyfunctional (meth) acrylic acid esters.
  • polyfunctional monomer examples include divinylbenzene; divinylbiphenyl; divinylnaphthalene; (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and (poly) tetramethylene glycol di (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate; 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl- 1,5-pentanediol di (meth
  • NK esters (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, A-GLY series, manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300, AD-TMP, AD-TMP-4CL, ATM-4E, A-DPH) and the like. These monomers may be used alone or in combination of two or more.
  • the polyfunctional monomer contains at least one selected from divinylbenzene and polyfunctional (meth) acrylic acid ester.
  • the polyfunctional monomer preferably contains di (meth) acrylic acid ester, and more preferably alkanediol di (meth) acrylate.
  • the alkanediol preferably has 6 to 18 carbon atoms, more preferably 8 to 12 carbon atoms.
  • radical polymerizable monomer having a carboxyl group examples include various unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate and monobutyl maleate.
  • unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate and monobutyl maleate.
  • An acid or an unsaturated dibasic acid is mentioned. These may be used alone or in combination of two or more.
  • radical polymerizable monomer having an epoxy group examples include glycidyl (meth) acrylate, ( ⁇ -methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4- It is selected from epoxy vinylcyclohexane, di ( ⁇ -methyl) glycidyl malate and di ( ⁇ -methyl) glycidyl fumarate.
  • An epoxy group may be introduced into the crosslinked polymer using a compound having another epoxy group.
  • the compound having an epoxy group include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether.
  • Glycidyl ethers of aliphatic polyhydric alcohols such as, glycidyl ethers of polyalkylene glycols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and polytetramethylene glycol diglycidyl ether, polyglycidylated polyester resins Resin-based polyglycidyl compounds, bisphenol A series of epoxy resins, phenol novolak-based epoxy resins, as well as epoxy urethane resin. These may be used alone or in combination of two or more.
  • the monomer mixture may contain a monofunctional monomer having one unsaturated double bond.
  • the proportion of this monofunctional monomer is preferably 0 to 70% by mass of the total monomer mixture.
  • the proportion of the monofunctional monomer is more preferably 5 to 70% by mass, still more preferably 10 to 70% by mass, and still more preferably 15 to 70% by mass.
  • Examples of the monofunctional monomer include (i) styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, ⁇ -methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene.
  • radical polymerization initiator used in radical polymerization for producing mother particles
  • a known radical polymerization initiator can be used.
  • the radical polymerization initiator include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, peroxides such as sodium persulfate and ammonium persulfate, azobisisobutyronitrile, azobismethylbutyro Examples thereof include azo compounds such as nitrile and azobisisovaleronitrile. These may be used alone or in combination of two or more.
  • polymerization solvents used for producing mother particles by solution polymerization include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1 -Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2- Alcohols such as pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, ethyl cellosolve, isopropyl cello Sol , Ether alcohols such as butyl cellosolve
  • a dispersant When producing the mother particles, a dispersant, a stabilizer, an emulsifier, a surfactant and the like may be appropriately selected and used.
  • Dispersants and stabilizers include polyhydroxystyrene, polystyrene sulfonic acid, vinylphenol- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid ester copolymer, styrene-vinylphenol- (meth) acrylic Polystyrene derivatives such as acid ester copolymers; poly (meth) acrylic acid derivatives such as poly (meth) acrylic acid, poly (meth) acrylamide, polyacrylonitrile, pothiethyl (meth) acrylate, polybutyl (meth) acrylate; polymethyl vinyl ether , Polyvinyl alkyl ether derivatives such as polyethyl vinyl ether, polybutyl vinyl ether, polyisobutyl vinyl ether; cellulose, methyl cellulose, cellulose acetate, cellulose nitrate, hydroxymethyl cellulose, Cellulose derivatives such as droxyethyl cellulose, hydroxy
  • emulsifiers include alkyl sulfate salts such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, alkylnaphthalene sulfonates, fatty acid salts, alkyl phosphates, and alkylsulfosuccinates.
  • Anionic emulsifiers such as alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides; polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkylphenyls
  • Nonionic emulsifiers such as ether, sorbitan fatty acid ester, glycerin fatty acid ester, and polyoxyethylene fatty acid ester are listed. These may be used alone or in combination of two or more.
  • step (a) for example, the mother particle is brought into contact with a solution containing an amino compound and a solvent in which the amino compound is dissolved, and the crosslinked polymer is further crosslinked by a reaction between a functional group and the amino group in the mother particle.
  • the solution of the amino compound is impregnated only in the surface layer portion or the inner region of the mother particle.
  • amino compound one or more compounds having two or more amino groups are used. From the viewpoint of improving the formability of plating, compounds having a large amount of primary or secondary amines such as polyethyleneimine and pentaethylenehexamine are preferable.
  • the amino compound preferably contains a low molecular weight amino compound having a molecular weight of less than 500 from the viewpoint of improving compression characteristics.
  • the amino compound preferably contains a high molecular weight amino compound having a molecular weight of 500 to 10,000 in order to improve the formability of plating. It is particularly preferable to use a low molecular weight amino compound and a high molecular weight amino compound in combination.
  • the molecular weight of the low molecular weight amino compound is preferably 50 or more and less than 500, more preferably 50 to 400, still more preferably 50 to 300.
  • the molecular weight of the high molecular weight amino compound is preferably 500 to 10,000, more preferably 500 to 5,000.
  • the amino compound is preferably an aliphatic diamine having a linear or alkyl side chain.
  • Specific examples of the aliphatic diamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octane.
  • the amino compound may contain an alicyclic diamine and / or an aromatic diamine.
  • Alicyclic diamines include cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine.
  • Aromatic diamines include p-phenylene diamine, m-phenylene diamine, xylene diamine, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl ether.
  • those having a molecular weight of less than 500 can be used as low molecular weight amino compounds.
  • the amino compound may contain polyamines such as triamine and tetraamine in addition to the diamine.
  • polyamines such as triamine and tetraamine in addition to the diamine.
  • High molecular weight polyethyleneimine is suitable as a high molecular weight amino compound.
  • amino compounds are used alone or in combination of two or more.
  • the reaction between the mother particle and two or more kinds of amino compounds can be carried out all at once, or each amino compound can be added stepwise to advance the reaction.
  • the amino compound may be dissolved in an organic solvent.
  • organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, 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, nonane, cyclopentane, methylcyclopentane, methyl Aliphatic or aromatic hydrocarbons such as cyclohexane, ethylcyclohexane, p-menthane, benzene, toluene,
  • amino compound is a water-soluble or hydrophilic organic compound, in addition to the above organic solvent, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl- Alcohols such as 2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, ethyl cellosolve, Isopropyl cello Bed, butyl cellosolve, ether
  • the reaction solvent for reacting the functional group in the mother particle with the amino group is preferably a solvent in which the mother particle is not substantially dissolved and the amino compound is dissolved.
  • the reaction between the functional group in the mother particle and the amino compound may be performed in the absence of a solvent.
  • reaction solvent examples include alcohols such as ⁇ -butyrolactone, glycerin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and n-butanol.
  • alcohols such as ⁇ -butyrolactone, glycerin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and n-butanol.
  • Hydrocarbons such as toluene, xylene, n-octane, n-dodecane, fatty acids such as linoleic acid, polyethylene glycol, dimethyl silicone, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 -Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl -1-pentanol Alcohols such as 4-methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol;
  • water preferably, water, a lower alcohol such as methanol or ethanol, an ether alcohol such as methyl cellosolve or ethyl cellosolve, a mixture of water and lower alcohol, a water-soluble and hydrophilic medium such as a mixture of water and ether alcohol, toluene, dimethyl
  • a lower alcohol such as methanol or ethanol
  • an ether alcohol such as methyl cellosolve or ethyl cellosolve
  • a mixture of water and lower alcohol a water-soluble and hydrophilic medium
  • a mixture of water and ether alcohol toluene
  • dimethyl examples include formamide (DMF), tetrahydrofuran (THF), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, N-methyl-2-pyrrolidone (NMP), dichloromethane, tetrachloroethylene, and more preferably water, methanol.
  • a lower alcohol such as 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, or a mixture of water and ether alcohol.
  • a water-soluble and hydrophilic media may be used alone or in combination of two or more.
  • the temperature at which the amino compound is reacted in step (a) depends on the type of solvent, but is preferably 10 ° C. to 250 ° C., more preferably 100 to 250 ° C., and even more preferably 180 ° C. to 250 ° C.
  • the reaction time may be the time required for the crosslinking reaction to be almost completed, and greatly depends on the amino compound used and the amount added, the type of functional group in the mother particle, the viscosity and concentration of the solution, etc. It is about 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 it is not a good practice to take a long time in practice. Moreover, when reaction time is extremely short, bridge
  • the amount of the amino compound in the step (a) is preferably 0.1 to 5, more preferably 0.5 to 3, in terms of an equivalent ratio of amino groups to functional groups of the mother particles. If this equivalent ratio is too small or excessively large, the effect of improving the compression characteristics and improving the formability of plating tends to be reduced.
  • the average particle diameter of the crosslinked polymer particles is preferably 0.1 to 50 ⁇ m, more preferably 0.2 to 30 ⁇ m, still more preferably 0.3 to 20 ⁇ m, and most preferably 0.5 to 5 ⁇ m. If the average particle size is small, the crosslinked polymer particles may easily aggregate.
  • the Cv value (coefficient of variation) of the particle diameter (diameter) of the crosslinked polymer is preferably 15% or less.
  • the Cv value exceeds 15% the performance of the crosslinked polymer particles in various uses tends to be lowered.
  • the connection reliability when the crosslinked polymer particles are used for conductive particles constituting an anisotropic conductive adhesive is reduced, and the quantitativeness when the crosslinked polymer particles are used for a biopsy element is reduced.
  • the Cv value of the particle diameter is preferably 10% or less, more preferably 5% or less, and still more preferably 4% or less.
  • the average particle diameter and the Cv value of the particle diameter of the crosslinked polymer particles are determined by the following measurement method. 1) Disperse particles in water using an ultrasonic dispersion facility to prepare a dispersion containing 1% by mass of particles. 2) About 20,000 dispersions are observed with a particle size distribution meter (Sysmex Flow, manufactured by Sysmex) under a microscope, and the average particle size and the coefficient of variation Cv of the particle size are calculated.
  • the compression deformation recovery rate measured at 180 ° C. of the mother particles after the step (a) is usually 30% or more, preferably 40% or more, more preferably 50% or more, and further preferably 50 to 65%. It is. If this compression deformation recovery rate is low, the elastic force is insufficient, and there is a tendency that poor contact is likely to occur in applications such as anisotropic conductive adhesives that require high elasticity.
  • the compression deformation recovery rate is the relationship between the load value and the compression displacement in the process of compressing particles from the center to 5 mN at a speed of 0.33 mN / sec and then reducing the load at a speed of 0.33 mN / sec. It is obtained by measuring.
  • Compressive deformation recovery is the ratio (L1 / L2) of the displacement (L1) from the point where the load is reversed to the final unloading value and the displacement (L2) from the point where the load is reversed to the initial load value (%). Rate.
  • the compressive fracture strength measured at 180 ° C. of the mother particles after the step (a) is preferably 10 mN or more.
  • the crosslinked polymer fine particles according to the present embodiment have a high compression deformation recovery rate as described above, there is a high possibility of excellent elasticity. For this reason, when the crosslinked polymer fine particles are used as a conductive material, there is a low possibility of damaging or penetrating a substrate used for connection between electrodes. Even if the conductive material is highly compressed and deformed, there is a high possibility of exhibiting high-precision gap retention and stable connection reliability. Since the crosslinked polymer particles according to the present embodiment have the characteristics as described above, not only in the field of electric materials, but also paints, coating agents, light diffusing agents, cosmetics, medicines or biopsy elements, agricultural chemicals, building materials, etc. Useful in a wide range of fields.
  • FIG. 2 is a cross-sectional view showing an embodiment of the anisotropic conductive adhesive.
  • a film-like anisotropic conductive adhesive 20 shown in FIG. 2 is composed of a binder resin 3 and conductive particles 5 dispersed in the binder resin 3.
  • the electroconductive particle 5 has the crosslinked polymer particle which concerns on this embodiment, and the metal layer (metal plating layer) which covers this crosslinked polymer particle.
  • the binder resin 3 is not particularly limited, but is preferably an insulating adhesive composition.
  • This insulating adhesive composition includes, for example, at least one component selected from a thermoplastic resin, a thermosetting resin, and an elastomer.
  • thermoplastic resins include vinyl resins such as vinyl acetate resins, vinyl chloride resins, acrylic resins and styrene resins; polyolefins; ethylene-vinyl acetate copolymers; polyamide resins; styrene-butadiene-styrene block copolymers.
  • thermosetting resin is selected from, for example, an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
  • the thermosetting resin is usually contained in the binder resin 3 together with the curing agent.
  • the thermosetting resin may be any one of a room temperature curing type, a thermosetting type, a light curing type, and a moisture curing type.
  • the elastomer is selected from, for example, styrene-butadiene copolymer rubber, chloroprene rubber, and acrylonitrile-styrene block copolymer rubber. These resins may be used alone or in combination of two or more.
  • the insulating adhesive composition as the binder resin 3 may be, for example, an extender, a softener (plasticizer), an adhesive improver, an antioxidant (anti-aging agent), a heat stabilizer, if necessary.
  • Various additives such as a light stabilizer, an ultraviolet absorber, a colorant, a flame retardant, and an organic solvent may be included.
  • the anisotropic conductive adhesive according to this embodiment can be obtained, for example, by a method in which conductive particles are added to a binder resin, mixed uniformly, and the conductive particles are dispersed.
  • An anisotropic conductive adhesive containing a binder resin and conductive particles is applied to the release treatment surface of a release material such as release paper and release film in a state where it is dissolved by heating as it is or dissolved or dispersed in a solvent.
  • a film-like anisotropic conductive adhesive can be obtained by the method of drying or cooling as needed.
  • the dispersion state of the conductive particles in the anisotropic conductive adhesive is not particularly limited.
  • the conductive particles may be uniformly dispersed in the binder resin, or may be distributed unevenly in the vicinity of the surface layer of the film.
  • the form of the anisotropic conductive adhesive is not limited to a film, and may be, for example, a paste or ink.
  • Synthesis synthesis example 1 of mother particles The following compounds were charged all at once into a 100 mL three-necked flask and stirred for about 6 hours using a stirrer while heating in a water bath at 80 ° C. to form mother particles formed from a crosslinked polymer.
  • DVB-960 Nippon Steel Chemical, 96% by weight of divinylbenzene (DVB), 3% by weight of ethylvinylbenzene (EVB)): 4.9 g ⁇ Methacrylic acid (Wako Pure Chemical Industries): 2.1g ⁇ Azobisisobutyronitrile (AIBN, Wako Pure Chemical Industries): 0.6g ⁇ Acetonitrile (Wako Pure Chemical Industries): 70g
  • the mother particles are filtered off using a suction filtration facility, and washing and filtration with isopropyl alcohol (IPA, Wako Pure Chemical Industries) are repeated about 3 to 5 times, followed by vacuum drying to obtain powdery mother particles. It was.
  • IPA isopropyl alcohol
  • the particle diameter of the obtained mother particle was measured by SEM observation, it was a spherical monodisperse particle having an average particle diameter of 4.1 ⁇ m.
  • the Cv value of the particle diameter was 2.3%.
  • Synthesis example 2 The following compounds were charged all at once into a 100 mL three-necked flask and stirred for about 6 hours using a stirrer while heating in a water bath at 80 ° C. to form mother particles formed from a crosslinked polymer.
  • DVB-960 2.8g ⁇ Methacrylic acid: 4.2 g ⁇ AIBN: 0.6g -Acetonitrile: 70 g
  • the mother particles are filtered off using a suction filtration facility, and washing and filtration with isopropyl alcohol (IPA, Wako Pure Chemical Industries) are repeated about 3 to 5 times, followed by vacuum drying to obtain powdery mother particles. It was.
  • IPA isopropyl alcohol
  • the particle diameter of the obtained mother particle was measured by SEM observation, it was a spherical monodisperse particle having an average particle diameter of 3.1 ⁇ m.
  • the Cv value of the particle diameter was 3.0%.
  • Synthesis example 3 The following compounds were charged all at once into a 100 mL three-necked flask and stirred for about 6 hours using a stirrer while heating in a water bath at 80 ° C. to form mother particles formed from a crosslinked polymer.
  • DVB-960 0.9g ⁇ 1,10-decanediol diacrylate (A-DOD, Shin-Nakamura Chemical): 2.7 g ⁇ Methacrylic acid: 2g ⁇ 11-Undecenoic acid: 1.4g ⁇ AIBN: 0.07g -Acetonitrile: 70 g
  • the mother particles are filtered off using a suction filtration facility, and washing and filtration with isopropyl alcohol (IPA, Wako Pure Chemical Industries) are repeated about 3 to 5 times, followed by vacuum drying to obtain powdery mother particles. It was.
  • IPA isopropyl alcohol
  • the particle diameter of the obtained mother particle was measured by SEM observation, it was a spherical monodisperse particle having an average particle diameter of 2.8 ⁇ m.
  • the Cv value of the particle diameter was 2.7%.
  • the particles are filtered using a suction filtration facility, and washing and filtration with IPA are repeated about 3 to 5 times, followed by vacuum drying, and powdery mother particles crosslinked with hexamethylenediamine and polyethyleneimine ( Particles 1a) were obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 56%, and the compression fracture strength was 16 mN.
  • Activator Neo Gantt 834 (trade name, palladium ion-amino complexing agent aqueous solution) manufactured by Atotech Japan Co., Ltd. is diluted to 40 mL / L with water, adjusted to pH 10.5, and a one-component alkaline catalyst A liquid was prepared.
  • the particles 1a were immersed in this alkaline catalyst solution at 35 ° C. for 10 minutes to adsorb the palladium complex on the surfaces of the particles 1a.
  • the particles 1a were collected by suction filtration and washed with water. Thereafter, the particles 1a were again suspended in water. Thereto was added dimethylamine borane at 0.1 g / L to reduce the palladium complex on the surface of the particles 1a, and a suspension of particles 1a with palladium supported on the surface was obtained.
  • Electroless plating The suspension was heated to 80 ° C., and an electroless Ni—P plating solution (manufactured by Hitachi Chemical Co., Ltd., trade name: NIPS-100) was gradually added dropwise through a metering pump to particles 1a. Plating treatment was performed. The plating time was 60 minutes. Thereby, the plating layer was formed on the surface of the particle 1a. Thereafter, suction filtration, water washing, suction filtration, and drying were sequentially performed to obtain conductive particles having a plating layer by electroless Ni—P plating. In the obtained conductive particles, the plating layer was formed with good uniformity, and no irregularities were observed on the surface of the plating layer.
  • an electroless Ni—P plating solution manufactured by Hitachi Chemical Co., Ltd., trade name: NIPS-100
  • the obtained conductive particles were pulverized by a jet mill under a pulverization pressure of 0.1 MPa.
  • the plating is peeled off by the crushing treatment, and a large amount of plated pieces are generated after the crushing treatment.
  • the number of particles not completely covered with the plating layer is small (the number of particles completely covered with the plating layer is large), and the number of plated pieces is small, It can be determined that the dispersibility of the particles in the plating solution is good and that the adhesion between the resin particles and the plating layer is excellent. In the observation after crushing, the presence of the plated piece was hardly confirmed.
  • Example 2 A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 6 hours under a nitrogen stream.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Hexamethylenediamine (molecular weight 116.2): 1 part by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 93.1 parts by weight
  • the particles are filtered off using a suction filtration facility, and after washing with IPA and filtration about 3 to 5 times, vacuum drying is performed and powdery mother particles (particles) crosslinked with hexamethylenediamine and polyethyleneimine (particles) 2a) was obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 54%, and the compression fracture strength was 15 mN.
  • Example 3 A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 6 hours under a nitrogen stream.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Hexamethylenediamine (molecular weight 116.2): 1 part by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 93.1 parts by weight
  • the particles are filtered off using a suction filtration facility, and after washing with IPA and filtration about 3 to 5 times, vacuum drying is performed and powdery mother particles (particles) crosslinked with hexamethylenediamine and polyethyleneimine (particles) 3a) was obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 53%, and the compression fracture strength was 16 mN.
  • Example 4 A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 6 hours under a nitrogen stream.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Hexamethylenediamine (molecular weight 116.2): 1 part by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 93.1 parts by weight
  • the particles are filtered off using a suction filtration facility, and after washing with IPA and filtration about 3 to 5 times, vacuum drying is performed and powdery mother particles (particles) crosslinked with hexamethylenediamine and polyethyleneimine (particles) 4a) was obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 55%, and the compression fracture strength was 16 mN.
  • Example 5 A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 6 hours under a nitrogen stream.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Hexamethylenediamine (molecular weight 116.2): 1 part by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 93.1 parts by weight
  • the particles are filtered off using a suction filtration facility, and after washing with IPA and filtration about 3 to 5 times, vacuum drying is performed and powdery mother particles (particles) crosslinked with hexamethylenediamine and polyethyleneimine (particles) 5a) was obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 57%, and the compression fracture strength was 16 mN.
  • Example 6 (Process a) A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 6 hours under a nitrogen stream.
  • the particles are filtered off using a suction filtration facility, washed with IPA and filtered about 3 to 5 times, and then dried in a vacuum to form powdery mother particles crosslinked with ethylenediamine and polyethyleneimine (particles 6a) Got.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 51%, and the compression fracture strength was 11 mN.
  • Example 7 (Process a) A 100 mL eggplant flask was charged with the following proportion of the mixture at one time and stirred at room temperature for 1 hour using a stirrer to obtain a dispersion. The dispersion was heated in a 180 ° C. oil bath for about 12 hours under a nitrogen stream.
  • -Mother particles of Synthesis Example 3 5 parts by weight-Pentaethylenehexamine (molecular weight 232.4): 0.27 parts by weight (the ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent) Polyethyleneimine (molecular weight 300): 1 part by weight (ratio of amino group to carboxyl group in the mother particle is 1 equivalent) ⁇ ⁇ -Butyrolactone (Wako Pure Chemical) 93.7 parts by weight
  • the particles are filtered using a suction filtration facility, and washing and filtration with IPA are repeated about 3 to 5 times, followed by vacuum drying, and powdery mother particles crosslinked with pentamethylenehexamine and polyethyleneimine ( Particles 7a) were obtained.
  • the compression deformation recovery rate at 180 ° C. of the obtained mother particles was 45%, and the compression fracture strength was 12 mN.
  • Ni particles were applied to the particles 7a to produce conductive particles composed of crosslinked polymer particles and a Ni plating layer covering the particles.
  • the plating layer was formed with good uniformity, and no irregularities were observed on the surface of the plating layer. Moreover, in the observation after crushing, the presence of the plated piece was hardly confirmed.
  • 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 Except having used the mixture of the following ratio as a raw material in the process a, the process of the mother particle of the synthesis example 1 and preparation and evaluation of the electroconductive particle were performed by the same operation as Example 1.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Hexylamine (molecular weight 100): 1.7 parts by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 92.3 parts by weight
  • Comparative Example 3 Except having used the mixture of the following ratio as a raw material in the process a, the process of the mother particle of the synthesis example 1 and preparation and evaluation of the electroconductive particle were performed by the same operation as Example 1.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Polyethyleneimine (molecular weight 600): 0.9 parts by weight (ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 91.4 parts by weight
  • Comparative Example 4 Except having used the mixture of the following ratio as a raw material in the process a, the process of the mother particle of the synthesis example 1 and preparation and evaluation of the electroconductive particle were performed by the same operation as Example 1.
  • -Mother particles of Synthesis Example 1 5 parts by weight-Polyethyleneimine (molecular weight 1200): 0.9 parts by weight (the ratio of amino groups to carboxyl groups in the mother particles is 1 equivalent)
  • ⁇ ⁇ -butyrolactone 91.4 parts by weight
  • the cross-linked polymer particles according to the present invention have been found to satisfy characteristics useful as particles used in conductive materials including anisotropic conductive films and conductive pastes. Furthermore, since the crosslinked polymer particles obtained by the production method of the present invention are excellent in heat resistance, chemical resistance, reactivity, and solution dispersibility, spacers for liquid crystals, conductive fine particles and conductive materials using the same, Electrostatic developer, silver salt film surface modifier, magnetic tape film modifier, thermal paper running stabilizer, toner and other electrical and electronic industries, ink, adhesive, adhesive, light diffusing agent, paint , Addition to chemical field such as paper coating agent such as paper coating and information recording paper, general industrial field such as fragrance, low shrinkage agent, paper, dental material, resin modifier, liquid or powder cosmetics It can be suitably used in a wide range of fields such as cosmetics such as slip agents and extender pigments, biological and medical fields such as living body and antigen-antibody reaction test particles, pharmaceutical and agrochemical fields, building fields, and automobile fields.
  • cosmetics such as slip agents

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Conductive Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Non-Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemically Coating (AREA)

Abstract

L'invention concerne une particule de polymère réticulé qui peut être obtenue par une méthode de production indiquée avec une étape (a) dans laquelle une particule mère formée d'un polymère réticulé ayant des groupes fonctionnels est mise en contact avec un composé aminé ayant au moins deux groupes amines, et le polymère réticulé est ensuite davantage réticulé par une réaction des groupes fonctionnels et des groupes amines. Ce composé aminé inclut des composés aminés de faible poids moléculaire avec des poids moléculaires inférieurs à 500.
PCT/JP2011/055678 2010-03-15 2011-03-10 Particule de polymère réticulé et méthode de production de ladite particule WO2011114993A1 (fr)

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JP2015054874A (ja) * 2013-09-10 2015-03-23 積水化学工業株式会社 接着剤
JP2016060776A (ja) * 2014-09-16 2016-04-25 綜研化学株式会社 有機無機複合樹脂粒子およびその製造方法
CN114133732A (zh) * 2021-12-06 2022-03-04 中广核俊尔(浙江)新材料有限公司 一种辐照交联用聚酰胺母粒及其制备方法和应用

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JP7454108B2 (ja) * 2022-01-18 2024-03-21 松本油脂製薬株式会社 粒子、及びその用途

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JPH06228225A (ja) * 1993-02-04 1994-08-16 Hitachi Chem Co Ltd 架橋重合体粒子の製造法
JPH07118340A (ja) * 1993-10-26 1995-05-09 Nippon Zeon Co Ltd エチレンアミン類で修飾した親水性ゲル粒子
JPH08319467A (ja) * 1995-05-25 1996-12-03 Soken Chem & Eng Co Ltd 導電性粒子および異方導電性接着剤
JP2001206954A (ja) * 2000-01-26 2001-07-31 Sekisui Chem Co Ltd 架橋微粒子の製造方法及び架橋微粒子
JP2004217762A (ja) * 2003-01-14 2004-08-05 Nisshinbo Ind Inc 硬化型粒子及びその製造方法

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JPS61277105A (ja) * 1985-05-31 1986-12-08 積水フアインケミカル株式会社 導電性微球体
JPS62101605A (ja) * 1985-10-29 1987-05-12 Nagasaki Pref Gov 吸着性樹脂の合成方法
JPH03197512A (ja) * 1989-12-26 1991-08-28 Tosoh Corp 吸水性樹脂の製造方法
JPH03215504A (ja) * 1990-01-22 1991-09-20 Nippon Oil & Fats Co Ltd 架橋重合体微粒子及びそれを含む塗料組成物
JPH04226110A (ja) * 1990-06-14 1992-08-14 Kao Corp 架橋重合体微粒子
JPH0586205A (ja) * 1991-04-26 1993-04-06 Hitachi Chem Co Ltd 架橋重合体粒子の製造法
JPH06200046A (ja) * 1992-01-28 1994-07-19 Sanyo Chem Ind Ltd 改質された高吸水性樹脂の製法および樹脂
JPH06228225A (ja) * 1993-02-04 1994-08-16 Hitachi Chem Co Ltd 架橋重合体粒子の製造法
JPH07118340A (ja) * 1993-10-26 1995-05-09 Nippon Zeon Co Ltd エチレンアミン類で修飾した親水性ゲル粒子
JPH08319467A (ja) * 1995-05-25 1996-12-03 Soken Chem & Eng Co Ltd 導電性粒子および異方導電性接着剤
JP2001206954A (ja) * 2000-01-26 2001-07-31 Sekisui Chem Co Ltd 架橋微粒子の製造方法及び架橋微粒子
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015054874A (ja) * 2013-09-10 2015-03-23 積水化学工業株式会社 接着剤
JP2016060776A (ja) * 2014-09-16 2016-04-25 綜研化学株式会社 有機無機複合樹脂粒子およびその製造方法
CN114133732A (zh) * 2021-12-06 2022-03-04 中广核俊尔(浙江)新材料有限公司 一种辐照交联用聚酰胺母粒及其制备方法和应用

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