WO2022260159A1 - Particules enrobées, procédé de production de particules enrobées, composition de résine et structure de connexion - Google Patents

Particules enrobées, procédé de production de particules enrobées, composition de résine et structure de connexion Download PDF

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Publication number
WO2022260159A1
WO2022260159A1 PCT/JP2022/023409 JP2022023409W WO2022260159A1 WO 2022260159 A1 WO2022260159 A1 WO 2022260159A1 JP 2022023409 W JP2022023409 W JP 2022023409W WO 2022260159 A1 WO2022260159 A1 WO 2022260159A1
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Prior art keywords
particles
conductive
coated
insulating
particle
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PCT/JP2022/023409
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English (en)
Japanese (ja)
Inventor
理 杉本
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN202280041129.XA priority Critical patent/CN117461095A/zh
Priority to JP2022538342A priority patent/JPWO2022260159A1/ja
Priority to KR1020237029689A priority patent/KR20240019751A/ko
Publication of WO2022260159A1 publication Critical patent/WO2022260159A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

  • the present invention relates to coated particles using conductive particles with insulating particles.
  • the present invention also relates to a method for producing the coated particles, a resin composition using the coated particles, and a bonded structure.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder resin.
  • the anisotropic conductive material is used to obtain various connection structures.
  • Examples of the connection using the anisotropic conductive material include connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), Examples include connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)) and connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)).
  • conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles, are sometimes used.
  • a film portion may be formed on the surface in order to prevent the insulating particles from detaching from the main body of the conductive particles before conductive connection.
  • Patent Documents 1 and 2 disclose conductive particles with insulating particles having a coating portion on the surface.
  • a conductive particle body having a conductive layer on the surface, an insulating resin layer (coating) covering the surface of the conductive particle body, and on the surface of the conductive particle body
  • a conductive particle with insulating particles (coated particle) is disclosed, which comprises a plurality of insulating particles arranged in a .
  • the average thickness of the resin layer is 1/6 or less of the average particle diameter of the conductive particle main body, and the average particle diameter of the insulating particles is 1 of the average thickness of the resin layer. 0.5 to 3.5 times.
  • conductive particles with insulating particles (coated particles ) is disclosed.
  • the conductive particle body with insulating particles has conductive particles having at least a conductive part on the surface, and a plurality of insulating particles arranged on the surface of the conductive particles.
  • the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, and the average height of the protrusions is 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the coating has a first coating portion covering the conductive particles and a second coating portion covering the surface of the insulating particles, and the first The ratio of the thickness of the coating portion to the average particle size of the insulating particles is 2/3 or more and 3 or less.
  • anisotropic conductive material produced by using agglomerated conductive particles with insulating particles or agglomerated coated particles and a binder resin
  • the anisotropic conductive material is coated and then connected. Particles are not evenly distributed between the upper and lower electrodes, and as a result, it may be difficult to sufficiently improve conduction reliability.
  • agglomerated particles tend to cause short circuits between laterally adjacent electrodes that should not be connected, and may reduce the insulation reliability between laterally adjacent electrodes.
  • conductive particles with insulating particles and a covering portion are provided, and the conductive particles with insulating particles are arranged on the surfaces of the conductive particles and the conductive particles. and a plurality of insulating particles, the conductive particles have base particles and a conductive portion disposed on the surface of the base particles, and the coating portion covers the surface of the conductive portion At least a portion and at least a portion of the surface of the insulating particles are coated, the material of the coating portion contains a polymerizable monomer, and the polymerizable monomer is a crosslinkable monomer A coated particle is provided in which the content of the crosslinkable monomer is 10.0% by weight or more in 100% by weight of the polymerizable monomer.
  • the crosslinkable monomer contains divinylbenzene.
  • the polymerizable monomer contains a compound represented by the following formula (1).
  • X1 represents a hydroxyl group, an alkoxy group or an alkyl group having 1 to 12 carbon atoms
  • X2 represents an organic group containing an unsaturated bond
  • the organic group containing the unsaturated bond is (meth)acryloyl. including groups.
  • the polymerizable monomer contains a non-crosslinking monomer, and the non-crosslinking monomer contains styrene.
  • the insulating particles are resin particles.
  • the insulating particles contain a polymer.
  • the ratio of the thickness of the coated portion to the particle diameter of the insulating particles is 1/2 or less.
  • the area of the portion covered with the coating part is 80% or more of 100% of the total surface area of the conductive particles with insulating particles.
  • the material of the coating portion is polymerized to obtain the A method for producing coated particles, comprising the step of forming the coating portion on the surface of the conductive portion of the conductive particles and on the surface of the insulating particles to obtain coated particles.
  • the method for producing coated particles comprises the steps of: obtaining conductive particles by arranging the conductive portion on the surface of the substrate particle; a step of disposing a plurality of the insulating particles on the surface of the conductive portion of the insulating particles to obtain conductive particles with insulating particles.
  • a broad aspect of the present invention provides a resin composition containing the coated particles described above and a binder resin.
  • a first member to be connected having a first electrode on its surface
  • a second member to be connected having a second electrode on its surface
  • the first member to be connected a connecting portion connecting the second member to be connected, wherein the material of the connecting portion contains the above-described coated particles, and the first electrode and the second electrode are electrically conductive.
  • a connection structure is provided that is electrically connected by the particles.
  • the coated particles according to the present invention include conductive particles with insulating particles and a coating portion.
  • the conductive particles with insulating particles have conductive particles and a plurality of insulating particles arranged on the surfaces of the conductive particles.
  • the conductive particle according to the present invention has a base particle and a conductive portion arranged on the surface of the base particle.
  • the coating portion coats at least a portion of the surface of the conductive portion and at least a portion of the surface of the insulating particle.
  • the material of the coating portion contains a polymerizable monomer
  • the polymerizable monomer contains a crosslinkable monomer
  • 100% by weight of the polymerizable monomer and the content of the crosslinkable monomer is 10.0% by weight or more. Since the coated particles according to the present invention have the above configuration, aggregation of the particles can be suppressed, and when the electrodes are electrically connected, the reliability of conduction can be improved, and Insulation reliability can be improved.
  • FIG. 1 is a cross-sectional view showing coated particles according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing coated particles according to a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing coated particles according to a third embodiment of the invention.
  • FIG. 4 is a cross-sectional view schematically showing a connected structure using coated particles according to the first embodiment of the present invention.
  • a coated particle according to the present invention comprises a conductive particle with insulating particles and a coating portion.
  • the conductive particles with insulating particles have conductive particles and a plurality of insulating particles arranged on the surfaces of the conductive particles.
  • the conductive particle according to the present invention has a base particle and a conductive portion arranged on the surface of the base particle.
  • the coating portion coats at least a portion of the surface of the conductive portion and at least a portion of the surface of the insulating particle.
  • the material of the coating portion contains a polymerizable monomer, and the polymerizable monomer contains a crosslinkable monomer.
  • the content of the crosslinkable monomer is 10.0% by weight or more in 100% by weight of the polymerizable monomer.
  • a non-crosslinkable monomer is used as a coating material, so when forming a coating on the surface of the conductive particles with insulating particles, the particles (conductive particles with insulating particles) is apt to aggregate in the dispersion, and may not sufficiently coat the surface of the conductive particles with insulating particles. As a result, the insulating particles are detached from the surfaces of the conductive particles, and it may be difficult to improve the insulation reliability when the electrodes are electrically connected by the conductive particles. In addition, when the particles aggregate during the formation of the coating, the resulting coated particles are also in an aggregated state.
  • anisotropic conductive material produced by using agglomerated conductive particles with insulating particles or agglomerated coated particles and a binder resin
  • the anisotropic conductive material is coated and then connected. Particles are not evenly distributed between the upper and lower electrodes, and as a result, it may be difficult to sufficiently improve conduction reliability.
  • agglomerated particles tend to cause short circuits between laterally adjacent electrodes that should not be connected, and may reduce the insulation reliability between laterally adjacent electrodes.
  • the coated particles according to the present invention have the above configuration, aggregation of the particles can be suppressed, and when the electrodes are electrically connected, the reliability of conduction can be improved. And insulation reliability can be improved.
  • FIG. 1 is a cross-sectional view showing coated particles according to the first embodiment of the present invention.
  • the coated particle 1 shown in FIG. 1 includes a conductive particle 2 with insulating particles and a coating portion 3.
  • the electrically conductive particles 2 with insulating particles have the electrically conductive particles 11 and the plurality of insulating particles 12 arranged on the surfaces of the electrically conductive particles 11 .
  • conductive particles 11 have substrate particles 21 and conductive portions 22 arranged on the surfaces of substrate particles 21 .
  • the coating portion 3 covers the surfaces of the conductive particles 11 (the surfaces of the conductive portions 22 ) and the insulating particles 12 .
  • the coating portion 3 is arranged on the surface of the conductive particle 11 (the surface of the conductive portion 22) and on the surface of the insulating particle 12, and the conductive particle 11 (conductive portion 22) and It is in contact with insulating particles 12 .
  • the coating portion 3 covers the surface of the conductive particles 2 with insulating particles.
  • the insulating particles 12 are arranged on the surfaces of the conductive particles 11 .
  • the insulating particles 12 are arranged on the surface of the conductive portion 22 and are in contact with the conductive portion 22 .
  • the conductive portion 22 covers the surfaces of the base particles 21 .
  • the surfaces of the base particles 21 are covered with the conductive parts 22 .
  • the conductive particles 11 have conductive portions 22 on their surfaces.
  • the conductive portion 22 is a conductive layer.
  • the conductive portion 22 is a single-layer conductive layer. In the conductive particles, the conductive portion may cover the entire surface of the substrate particle, or the conductive portion may cover a portion of the surface of the substrate particle.
  • the material of the coating portion 3 is dispersed in the dispersion liquid. It can be obtained by forming the covering portion 3 by polymerizing. Polymerization can be carried out in a dispersion liquid in which the conductive particles 2 with insulating particles are dispersed in a dispersion medium. Coated particles 1A and 1B, which will be described later, can also be obtained in the same manner as the coated particles 1.
  • FIG. 2 is a cross-sectional view showing coated particles according to the second embodiment of the present invention.
  • a coated particle 1A shown in FIG. 2 includes a conductive particle 2A with insulating particles and a coating portion 3A.
  • conductive particles 2A with insulating particles have conductive particles 11A and a plurality of insulating particles 12A arranged on the surfaces of the conductive particles 11A.
  • conductive particle 11A has substrate particle 21A and conductive portion 22A arranged on the surface of substrate particle 21A.
  • the coating portions 3A cover the surfaces of the conductive particles 11A (the surfaces of the conductive portions 22A) and the insulating particles 12A.
  • the coating portion 3A is arranged on the surface of the conductive particle 11A (the surface of the conductive portion 22A) and on the surface of the insulating particle 12A, and the conductive particle 11A (conductive portion 22A) and It is in contact with the insulating particles 12A.
  • the coating portions 3A cover the surfaces of the conductive particles 2A with insulating particles.
  • the insulating particles 12A are arranged on the surface of the conductive particles 11A. In the coated particle 1A, the insulating particles 12A are arranged on the surface of the conductive portion 22A and are in contact with the conductive portion 22A.
  • the conductive portion 22A is a two-layered conductive layer.
  • the conductive portion 22A includes a first conductive portion 22AA and a second conductive portion 22AB.
  • the first conductive portion 22AA is laminated on the surface of the substrate particle 21A
  • the second conductive portion 22AB is laminated on the surface of the first conductive portion 22AA.
  • the configuration of the conductive portion is different between the coated particles 1 and 1A.
  • the conductive portion may be a single conductive layer or multiple conductive layers.
  • FIG. 3 is a cross-sectional view showing coated particles according to the third embodiment of the present invention.
  • a coated particle 1B shown in FIG. 3 includes a conductive particle 2B with insulating particles and a coating portion 3B.
  • conductive particles 2B with insulating particles have conductive particles 11B and a plurality of insulating particles 12B arranged on the surface of conductive particles 11B.
  • the conductive particles 11B are composed of base particles 21B, conductive portions 22B arranged on the surfaces of the base particles 21B, and a plurality of core substances 23B arranged on the surfaces of the base particles 21B.
  • the coated portions 3B cover the surfaces of the conductive particles 11B (the surfaces of the conductive portions 22B) and the surfaces of the insulating particles 12B.
  • the coating portion 3B is arranged on the surface of the conductive particle 11B (the surface of the conductive portion 22B) and on the surface of the insulating particle 12B, and the conductive particle 11B (conductive portion 22B) and It is in contact with insulating particles 12B.
  • the coating portions 3B cover the surfaces of the conductive particles 2B with insulating particles.
  • the insulating particles 12B are arranged on the surfaces of the conductive particles 11B. In the coated particle 1B, the insulating particles 12B are arranged on the surface of the conductive portion 22B and are in contact with the conductive portion 22B.
  • the conductive part 22B covers the base particle 21B and the core substance 23B. Since the conductive portion 22B covers the core substance 23B, the coated particles 1B, the conductive particles 2B with insulating particles, and the conductive particles 11B have a plurality of projections 11Ba on their surfaces. The surface of the conductive portion 22B is raised by the core substance 23B, and a plurality of projections 11Ba are formed.
  • coated particles 1 and coated particles 1B differ in the presence or absence of the use of a core substance and the presence or absence of projections.
  • the coated particles may or may not have projections on the surface.
  • (meth)acrylate indicates acrylate and methacrylate.
  • (Meth)acryl indicates acryl and methacryl.
  • (Meth)acryloyl indicates acryloyl and methacryloyl.
  • the particle diameter of the coated particles is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, still more preferably 2.0 ⁇ m or more, and preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 5.0 ⁇ m. It is below.
  • the particle diameter of the coated particles is equal to or more than the lower limit and equal to or less than the upper limit, when the electrodes are connected using the coated particles, the contact area between the coated particles and the electrodes is sufficiently large, and the conductive portion It becomes difficult to form agglomerated coated particles when forming the. Also, the distance between the electrodes connected via the coating particles does not become too large, and the conductive portion is less likely to peel off from the surface of the substrate particles.
  • the particle size of the coated particles is preferably the average particle size.
  • the average particle size means the number average particle size.
  • the particle size of the coated particles can be determined, for example, by observing 50 arbitrary coated particles with an electron microscope or an optical microscope and calculating the average particle size of each coated particle, or performing laser diffraction particle size distribution measurement. It is required by
  • the coefficient of variation (CV value) of the particle size of the coated particles is preferably 10% or less, more preferably 5% or less.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ /Dn) ⁇ 100 ⁇ : standard deviation of particle size of coated particles Dn: average value of particle size of coated particles
  • the shape of the coated particles is not particularly limited.
  • the shape of the coated particles may be spherical, may be other than spherical, or may be flat.
  • the coated particles are dispersed in a binder resin and suitably used to obtain a resin composition.
  • the substrate particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably substrate particles other than metal particles, and more preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles.
  • the substrate particles may be core-shell particles comprising a core and a shell arranged on the surface of the core.
  • the core may be an organic core and the shell may be an inorganic shell.
  • Materials for the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate, polyamide, and phenol formaldehyde.
  • polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene
  • acrylic resins such as polymethyl methacrylate and polymethyl acrylate
  • polycarbonate polyamide
  • phenol formaldehyde phenol formaldehyde
  • Resin melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenolic resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, Examples include polyamideimide, polyetheretherketone, polyethersulfone, and divinylbenzene polymer.
  • the divinylbenzene polymer may be a divinylbenzene copolymer.
  • the divinylbenzene copolymer examples include a divinylbenzene-styrene copolymer and a divinylbenzene-(meth)acrylate copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the material of the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. is preferred.
  • the polymerizable monomer having an ethylenically unsaturated group may be a non-crosslinking monomer. and crosslinkable monomers.
  • non-crosslinkable monomers examples include styrene and styrene-based monomers such as ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; methyl ( meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl ( Alkyl (meth)acrylate compounds such as meth)acrylate and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and glycidyl (meth)acrylate, etc.
  • carboxyl group-containing monomers
  • crosslinkable monomer examples include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, (poly)ethylene glycol Polyfunctional (meth)acrylate compounds such as di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, and 1,4-butanedio
  • the crosslinkable monomers include (poly)ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta Erythritol tetra(meth)acrylate or dipentaerythritol poly(meth)acrylate is preferred.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having the ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using uncrosslinked seed particles.
  • inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, carbon black, and the like. .
  • the inorganic substance is not a metal.
  • the particles formed of silica can be obtained, for example, by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, followed by firing as necessary. particles that can be used.
  • the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed from a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core. It is preferred that the core is an organic core. Preferably, the shell is an inorganic shell. From the viewpoint of effectively reducing the connection resistance between electrodes, the substrate particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
  • Examples of the material for the organic core include the materials for the resin particles described above.
  • the material for the inorganic shell examples include the inorganic substances listed above as the material for the substrate particles.
  • the inorganic shell material is preferably silica.
  • the inorganic shell is preferably formed by forming a metal alkoxide into a shell-like material on the surface of the core by a sol-gel method, and then firing the shell-like material.
  • the metal alkoxide is preferably silane alkoxide.
  • the inorganic shell is preferably made of silane alkoxide.
  • the substrate particles are metal particles
  • examples of metals that are materials of the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the particle diameter of the substrate particles is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less.
  • the particle size of the substrate particles is equal to or more than the lower limit and equal to or less than the upper limit, the distance between the electrodes becomes small, and small conductive particles (coated particles) can be obtained even if the thickness of the conductive portion is increased. .
  • the conductive portion is formed on the surface of the substrate particles and the coating portion is arranged, aggregation is less likely to occur, and the formation of aggregated conductive particles with insulating particles and coated particles is less likely.
  • the shape of the substrate particles is not particularly limited.
  • the shape of the substrate particles may be spherical, may be other than spherical, or may be flat.
  • the particle size of the base material particles indicates the number average particle size.
  • the particle size of the substrate particles is determined using a particle size distribution analyzer or the like.
  • the particle diameter of the substrate particles is preferably determined by observing 50 arbitrary substrate particles with an electron microscope or an optical microscope and calculating the average value. In the case of measuring the particle diameter of the substrate particles of the coated particles, the measurement can be performed, for example, as follows.
  • the coated particles have projections on the outer surface of the conductive portion. It is preferable that the protrusion is plural.
  • the conductive particles preferably have protrusions on the outer surface of the conductive portion. It is preferable that the protrusion is plural.
  • an oxide film is often formed on the surface of the electrode that comes into contact with the coated particles. When coating particles having protrusions on their surfaces are used, the oxide film can be effectively removed by the protrusions at the time of conductive connection. As a result, the electrode and the coated particles can be brought into contact with each other more reliably, the contact area between the coated particles and the electrode can be sufficiently increased, and the connection resistance can be reduced more effectively.
  • the coated particles are dispersed in a binder resin and used as a resin composition or a conductive material
  • the projections of the coated particles can more effectively remove the binder resin between the coated particles and the electrode. Therefore, the contact area between the coated particles and the electrode can be sufficiently increased, and the connection resistance can be reduced more effectively.
  • Methods for forming protrusions on the surface of the coated particles and the conductive particles include a method of depositing a core substance on the surface of the substrate particles and then forming the conductive portions by electroless plating, and a method of forming the conductive portions on the surfaces of the substrate particles.
  • a method of forming a conductive portion by electroplating, adhering a core substance, and further forming a conductive portion by electroless plating may be used.
  • the core substance is added to the dispersion liquid of the substrate particles, and the core substance is accumulated on the surface of the substrate particles by, for example, Van der Waals force. and a method of adding the core substance to a container containing the base particles and attaching the core substance to the surface of the base particles by mechanical action such as rotation of the container.
  • the method of accumulating and attaching the core substance to the surface of the substrate particles in the dispersion liquid is preferable because the amount of the core substance to be adhered can be easily controlled.
  • the conductive particles may have a first conductive portion on the surface of the substrate particles and a second conductive portion on the surface of the first conductive portion.
  • the core substance may be adhered to the surface of the substrate particles, or the core substance may be adhered to the surface of the first conductive portion.
  • the core substance is preferably covered with the second conductive portion, and more preferably covered with the first conductive portion and the second conductive portion. After the core substance is adhered to the surface of the base particle, the conductive particles form the first conductive portion on the surface of the base particle and the core substance, and then form the first conductive portion on the surface of the first conductive portion. It is preferably obtained by forming a second conductive portion on the .
  • Conductive substances and non-conductive substances can be mentioned as substances that constitute the core substance.
  • the conductive substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers. Polyacetylene etc. are mentioned as said conductive polymer. Silica, alumina, zirconia, and the like are mentioned as the non-conductive substance.
  • the substance constituting the core substance is preferably a metal.
  • the core substance is preferably metal particles.
  • metals examples include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and alloys composed of two or more metals such as tungsten carbide. Among them, nickel, copper, silver or gold is preferable.
  • the metal forming the core substance may be the same as or different from the metal forming the conductive portion (conductive layer).
  • the shape of the core substance is not particularly limited.
  • the shape of the core substance is preferably massive.
  • the core substance includes, for example, particulate lumps, agglomerates in which a plurality of microparticles are aggregated, irregular lumps, and the like.
  • the average height of the plurality of projections is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
  • the connection resistance between the electrodes can be effectively lowered.
  • the conductive particles have conductive portions on their surfaces.
  • the conductive portion is arranged on the surface of the substrate particle.
  • the conductive portion preferably contains a metal.
  • the metal forming the conductive portion is not particularly limited. Examples of the metals include gold, silver, copper, tin, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium, and alloys thereof. Alternatively, tin-doped indium oxide (ITO) may be used as the metal. Only one of the above metals may be used, or two or more thereof may be used in combination.
  • ITO tin-doped indium oxide
  • the conductive portion preferably contains tin, nickel, palladium, copper or gold, more preferably tin or nickel, and still more preferably nickel.
  • the conductive portion preferably contains nickel as a main metal.
  • the content of nickel in 100% by weight of the conductive portion is preferably 15% by weight or more, more preferably 20% by weight or more, still more preferably 25% by weight or more, and particularly preferably 25% by weight or more. is 30% by weight or more.
  • the content of nickel in 100% by weight of the conductive portion may be 100% by weight (total amount) or may be 90% by weight or less.
  • the conductive portion may be formed of one layer.
  • the conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers.
  • the metal constituting the outermost layer is preferably tin, nickel, palladium, copper or gold, and is tin, nickel, palladium or nickel. is more preferred, and palladium or gold is even more preferred.
  • the connection resistance between the electrodes is even lower. Further, when the metal forming the outermost layer is gold, the corrosion resistance is further enhanced.
  • the area of the portion covered with the conductive portion is preferably 80% or more, more preferably 90% or more.
  • the upper limit of the coverage by the conductive portion is not particularly limited. A coverage rate of the conductive portion may be 99% or less. When the coverage by the conductive portion is equal to or more than the lower limit and equal to or less than the upper limit, the reliability of conduction can be more effectively improved when the electrodes are electrically connected.
  • the thickness of the conductive portion is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive portion is equal to or more than the lower limit and equal to or less than the upper limit, the reliability of conduction is further effectively improved, and the conductive particles do not become too hard, so that the conductive particles can be electrically conductive when connecting between electrodes. Particles can be sufficiently deformed.
  • the thickness of the conductive portion in the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, and preferably 0.5 ⁇ m or less, and more preferably. is 0.3 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is equal to or more than the lower limit and equal to or less than the upper limit, the conductive portion of the outermost layer is uniform, the corrosion resistance is sufficiently high, and the connection resistance between electrodes is sufficiently low. can do.
  • the thickness of the innermost conductive portion is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and preferably 0.5 ⁇ m or less, more preferably. is 0.3 ⁇ m or less.
  • the thickness of the conductive portion of the innermost layer is equal to or more than the lower limit and equal to or less than the upper limit, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes can be further reduced.
  • the thickness of the conductive portion can be measured, for example, by observing the cross section of the coated particles using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the method of forming the conductive portion on the surface of the substrate particles is not particularly limited.
  • Methods for forming the conductive portion include, for example, a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, and metal powder or Examples thereof include a method of coating the surface of the substrate particles with a paste containing a metal powder and a binder.
  • the method of forming the conductive portion is preferably electroless plating, electroplating, or a method using physical collision. Methods such as vacuum deposition, ion plating, and ion sputtering can be used as the method by physical vapor deposition. Also, in the method using physical collision, for example, a sheeter composer (manufactured by Tokuju Kosakusho Co., Ltd.) or the like is used.
  • the coated particles according to the present invention comprise a plurality of insulating particles arranged on the surface of the conductive particles. Since the coated particles have the above structure, short-circuiting between adjacent electrodes can be prevented when the coated particles are used to connect electrodes. Specifically, when a plurality of coating particles come into contact with each other, the insulating particles are present between the plurality of electrodes, so short-circuiting can be prevented not between the upper and lower electrodes but between the laterally adjacent electrodes. Insulating particles between the conductive particles and the electrodes can be easily eliminated by pressing the coated particles with two electrodes when the electrodes are connected. Furthermore, when the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, the insulating particles between the conductive particles and the electrode can be removed more easily.
  • the insulating particles are preferably polymers of polymerizable compounds.
  • the polymerizable compound is not particularly limited. Examples of the polymerizable compound include the materials for the resin particles described above.
  • the insulating particles are preferably resin particles from the viewpoint of more effectively increasing the reliability of conduction and the reliability of insulation when the electrodes are electrically connected. Moreover, the insulating particles preferably contain a polymer from the viewpoint of more effectively improving the reliability of conduction and the reliability of insulation when the electrodes are electrically connected.
  • the molecular weight of the polymer is preferably 10,000 or more, more preferably 50,000 or more, and still more preferably, from the viewpoint of more effectively improving conduction reliability and insulation reliability. is 100,000 or more, preferably 2,000,000 or less, more preferably 1,500,000 or less, and still more preferably 1,000,000 or less.
  • the material of the insulating particles preferably contains a divinylbenzene-styrene copolymer from the viewpoint of more effectively improving the reliability of conduction and insulation when the electrodes are electrically connected.
  • the content of divinylbenzene in 100% by weight of the material of the insulating particles is preferably 1. % by weight or more, more preferably 2% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less.
  • Methods for arranging the insulating particles on the surface of the conductive portion include chemical methods and physical or mechanical methods.
  • the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, an emulsion polymerization method, and the like.
  • the physical or mechanical methods include spray drying, hybridization, electrostatic adhesion, atomization, dipping and vacuum deposition. From the viewpoint of more effectively improving the conduction reliability and insulation reliability when the electrodes are electrically connected, the method of arranging the insulating particles on the surface of the conductive portion is a physical method. Preferably.
  • the particle size of the insulating particles can be appropriately selected depending on the particle size of the coated particles, the application of the coated particles, and the like.
  • the particle diameter of the insulating particles is preferably 10 nm or more, more preferably 100 nm or more, still more preferably 200 nm or more, particularly preferably 300 nm or more, preferably 2000 nm or less, more preferably 1000 nm or less, and still more preferably 800 nm or less. , and particularly preferably 500 nm or less.
  • the particle diameter of the insulating particles is equal to or greater than the lower limit, the plurality of coated particles are less likely to agglomerate when the coated particles are dispersed in the binder resin.
  • the particle diameter of the insulating particles is equal to or less than the upper limit, there is no need to increase the pressure too much in order to remove the insulating particles between the electrodes and the conductive particles when connecting the electrodes. , without the need to heat to high temperatures.
  • the particle size of the insulating particles is preferably the average particle size, preferably the number average particle size.
  • the particle size of the insulating particles is determined using a particle size distribution analyzer or the like.
  • the particle diameter of the insulating particles is preferably obtained by observing 50 arbitrary insulating particles with an electron microscope or an optical microscope and calculating the average value, or by performing laser diffraction particle size distribution measurement. When measuring the particle diameter of the insulating particles in the coated particles, the measurement can be performed, for example, as follows.
  • the coating particles are added to "Technovit 4000” manufactured by Kulzer so that the content is 30% by weight, and dispersed to prepare an embedded resin body for inspection containing the coating particles.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • a cross section of the insulating particles is cut out so as to pass through the vicinity of the center of the insulating particles in the coated particles dispersed in the embedding resin body for inspection.
  • FE-SEM field emission scanning electron microscope
  • the image magnification is set to 50,000 times, 50 insulating particles are randomly selected, and the insulating particles are observed.
  • the circle-equivalent diameter of the insulating particles is measured as the particle diameter, and the arithmetic mean of these values is taken as the particle diameter of the insulating particles.
  • two or more kinds of insulating particles having different particle sizes may be used together.
  • the insulating particles with a small particle size enter the gaps covered with the insulating particles with a large particle size, and the insulating particles are formed on the surface of the conductive particles. Particles can be arranged much more efficiently.
  • the coefficient of variation (CV value) of the particle diameter of the insulating particles is preferably 20% or less.
  • the coefficient of variation of the particle diameter of the insulating particles is equal to or less than the upper limit, the thickness of the insulating particles in the resulting coated particles becomes more uniform, and uniform pressure is more easily applied during conductive connection. It is possible to further reduce the connection resistance between the electrodes.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ /Dn) ⁇ 100 ⁇ : standard deviation of particle size of insulating particles Dn: average value of particle size of insulating particles
  • the shape of the insulating particles is not particularly limited.
  • the insulating particles may have a spherical shape, a shape other than a spherical shape, or a flat shape.
  • the portion covered with the insulating particles out of 100% of the total surface area of the conductive portion is preferably 30% or more, more preferably 40% or more, and preferably 70% or less, more preferably 60% or less.
  • the coverage rate of the insulating particles can be measured, for example, by the following method.
  • Conductive particles with insulating particles are observed from one direction with a scanning electron microscope (SEM), and the outer peripheral edge portion of the surface of the conductive portion occupies the entire area within the circle of the outer peripheral edge portion of the surface of the conductive portion in the observed image.
  • the coverage by the insulating particles is preferably calculated as an average coverage by observing 20 conductive particles with insulating particles and averaging the measurement results of each conductive particle with insulating particles.
  • the coverage by the insulating particles can also be measured by mapping analysis such as EDX accompanying SEM.
  • the coverage of the insulating particles can be adjusted by, for example, the amount of the insulating particles added to the base particles, the mixing time, etc. Therefore, the method of adjusting the coverage of the insulating particles is not particularly limited. .
  • the coating portion coats at least a portion of the surface of the conductive portion and at least a portion of the surface of the insulating particle.
  • the covering portion covers at least part of the surface of the conductive particles with the insulating particles.
  • the coated portion is arranged on at least a portion of the surface of the conductive portion and at least a portion of the surface of the insulating particle.
  • the coated portion is arranged on at least a portion of the surface of the conductive portion and at least a portion of the surface of the insulating particle.
  • the covering portion may be a coating.
  • the covering portion may not be arranged between the conductive portion and the insulating particles. From the viewpoint of exhibiting the effect of the present invention more effectively, it is preferable that the covering portion is arranged in a region of the surface of the conductive portion where the insulating particles are not arranged. In this case, the covering portion may or may not be arranged between the conductive portion and the insulating particles. The conductive portion and the insulating particles may be in direct contact with each other without the coating portion interposed therebetween.
  • the coating portion covers the entire surface of the conductive particles with the insulating particles. From the viewpoint of exhibiting the effect of the present invention more effectively, it is preferable that the covering portion covers the surface of the conductive portion and the surface of the insulating particles.
  • the material of the covering portion contains a polymerizable monomer, and the polymerizable monomer contains a crosslinkable monomer.
  • the material of the covering portion contains a polymerizable component, and the polymerizable component contains a crosslinkable monomer.
  • the covering portion preferably contains a skeleton derived from a polymerizable monomer, and preferably contains a skeleton derived from a crosslinkable monomer.
  • crosslinkable monomer examples include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, (poly)ethylene glycol Polyfunctional (meth)acrylate compounds such as di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, and 1,4-butanedio
  • the crosslinkable monomer is divinylbenzene or (poly ) preferably contains ethylene glycol di(meth)acrylate, more preferably divinylbenzene.
  • the molecular weight of the crosslinkable monomer is preferably 50 or more. , more preferably 100 or more, preferably 500 or less, more preferably 300 or less.
  • the content of the crosslinkable monomer is 10.0% by weight or more in 100% by weight of the polymerizable monomer.
  • the crosslinkable The monomer content is preferably 12% by weight or more, more preferably 15% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less, and even more preferably 25% by weight or less.
  • the polymerizable monomer may contain a non-crosslinkable monomer.
  • the covering portion may contain a skeleton derived from a non-crosslinkable monomer.
  • the non-crosslinkable monomers include styrene and styrene-based monomers such as ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; methyl ( meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl ( Alkyl (meth)acrylate compounds such as meth)acrylate and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, g
  • the polymerizable monomer is a non-crosslinking monomer. and the non-crosslinkable monomer preferably contains styrene.
  • the molecular weight of the non-crosslinking monomer is preferably 50. Above, more preferably 100 or more, preferably 500 or less, more preferably 300 or less.
  • the content of the non-crosslinkable monomer in 100% by weight of the polymerizable monomer is preferably 50% by weight. Above, it is more preferably 70% by weight or more, still more preferably 75% by weight or more, preferably 90% by weight or less, and more preferably 85% by weight or less.
  • the content of the non-crosslinkable monomer is at least the lower limit and at most the upper limit, the aggregation of particles is further suppressed when forming the coating portion, and the surface of the conductive particles with insulating particles can be coated well.
  • the polymerizable monomer preferably contains a compound represented by the following formula (1).
  • X1 represents a hydroxyl group, an alkoxy group or an alkyl group having 1 to 12 carbon atoms
  • X2 represents an organic group containing an unsaturated bond
  • the organic group containing the unsaturated bond is (meth)acryloyl including groups.
  • X1 is preferably a hydroxyl group. That is, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1A). In this case, the effects of the present invention can be exhibited more effectively.
  • X2 represents an organic group containing an unsaturated bond
  • the organic group containing an unsaturated bond includes a (meth)acryloyl group
  • Examples of the compound represented by the above formula (1A) include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol methacrylate, and acid phosphooxypolyoxypropylene glycol methacrylate. Only one kind of the compound represented by the above formula (1A) may be used, or two or more kinds thereof may be used in combination.
  • the compound represented by the above formula (1A) is preferably acid phosphooxyethyl methacrylate or acid phosphooxypolyoxyethylene glycol methacrylate, more preferably acid phosphooxypolyoxyethylene glycol methacrylate.
  • aggregation of the particles can be further suppressed when forming the coating portion, and the surfaces of the conductive particles with insulating particles can be well coated.
  • the thickness of the covering portion is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and preferably 500 nm or less, more preferably It is 200 nm or less, more preferably 150 nm or less.
  • the thickness of the coating portion can be measured, for example, by observing the cross section of the coated particles using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the ratio of the thickness of the coating portion to the particle diameter of the insulating particles is referred to as the ratio (thickness of the coating portion/particle diameter of the insulating particles).
  • the ratio (thickness of the coating portion/particle diameter of the insulating particles) is preferably 1/20 or more, more preferably 1/10 or more, It is preferably 1/2 or less, more preferably 1/3 or less.
  • the area of the portion covered by the covering portion (coverage by the covering portion) in 100% of the total surface area of the conductive particles with insulating particles is , preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably 100%.
  • the coverage by the covering portion can be measured by the following method.
  • Conductive particles with insulating particles are observed from one direction with a scanning electron microscope (SEM), and the outer peripheral edge portion of the surface of the conductive portion occupies the entire area within the circle of the outer peripheral edge portion of the surface of the conductive portion in the observed image. Calculated from the total area of the covered portion within the circle of It is preferable to calculate the coverage by the coating part as an average coverage by observing 20 coated particles and averaging the measurement results of each coated particle.
  • SEM scanning electron microscope
  • the content of the coated part in 100% by weight of the coated particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 10% by weight or less, more preferably 5.0% by weight. % by weight or less, more preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less.
  • the content of the coating portion is at least the lower limit and at most the upper limit, aggregation of the coated particles can be more effectively suppressed.
  • the material of the coating portion is polymerized in a dispersion liquid in which the conductive particles with insulating particles are dispersed in a dispersion medium, and the surface of the conductive portion of the conductive particle is A step of forming a coating portion on the top and on the surface of the insulating particles to obtain coated particles is provided.
  • the dispersion medium examples include solvents.
  • examples of the dispersion medium include water, methanol, ethanol, and 2-propanol. Only one kind of the dispersion medium may be used, or two or more kinds thereof may be used in combination.
  • the dispersion medium is preferably water from the viewpoint of further suppressing the aggregation of the particles when forming the coating portion and satisfactorily covering the surfaces of the conductive particles with insulating particles. After forming the coating portion on the surface of the conductive portion of the conductive particles with insulating particles and on the surface of the insulating particles, the dispersion medium is removed as necessary.
  • the coating portion can be formed by polymerizing the material of the coating portion by a known method.
  • this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using uncrosslinked seed particles.
  • the method for producing a coated particle according to the present invention includes a step of arranging the conductive portion on the surface of the base particle to obtain a conductive particle; (1) disposing the insulating particles to obtain conductive particles with insulating particles. In this case, when the electrodes are electrically connected, reliability of conduction and reliability of insulation can be improved more effectively.
  • the resin composition according to the present invention contains the coated particles described above and a binder resin.
  • the coated particles are preferably dispersed in a binder resin for use.
  • the coated particles are preferably dispersed in a binder resin and used as a resin composition.
  • the resin composition is preferably a conductive material, more preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is preferably a conductive material for circuit connection. Since the above-described coated particles are used in the resin composition and the conductive material, the reliability of conduction and the reliability of insulation can be more effectively improved when the electrodes are electrically connected.
  • the binder resin is not particularly limited.
  • a known insulating resin is used as the binder resin.
  • the binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component.
  • the curable component include photocurable components and thermosetting components.
  • the photocurable component preferably contains a photocurable compound and a photopolymerization initiator.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
  • binder resin examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers. Only one kind of the binder resin may be used, or two or more kinds thereof may be used in combination.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin and styrene resin.
  • examples of the thermoplastic resins include polyolefin resins, ethylene-vinyl acetate copolymers and polyamide resins.
  • examples of the curable resin include epoxy resin, urethane resin, polyimide resin and unsaturated polyester resin.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymers examples include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated products of styrene-butadiene-styrene block copolymers, and styrene-isoprene. - hydrogenated products of styrene block copolymers;
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the resin composition includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer. It may contain various additives such as agents, UV absorbers, lubricants, antistatic agents and flame retardants.
  • the method for dispersing the coated particles in the binder resin may be a conventionally known dispersing method, and is not particularly limited.
  • Examples of the method for dispersing the coated particles in the binder resin include the following methods. A method of adding the coated particles to the binder resin and then kneading and dispersing them with a planetary mixer or the like. A method in which the coated particles are uniformly dispersed in water or an organic dispersion medium using a homogenizer or the like, and then added to the binder resin and kneaded with a planetary mixer or the like for dispersion. A method of diluting the above binder resin with water or an organic dispersion medium or the like, adding the above coated particles, and kneading and dispersing the mixture with a planetary mixer or the like.
  • the viscosity ( ⁇ 25) of the resin composition at 25°C is preferably 30 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, and preferably 400 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
  • the viscosity ( ⁇ 25) can be appropriately adjusted depending on the types and amounts of ingredients to be blended.
  • the viscosity ( ⁇ 25) can be measured, for example, using an E-type viscometer ("TVE22L” manufactured by Toki Sangyo Co., Ltd.) under conditions of 25°C and 5 rpm.
  • E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) under conditions of 25°C and 5 rpm.
  • the conductive material can be used as a conductive paste, a conductive film, and the like.
  • the conductive material is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more, It is preferably 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder resin is the lower limit or more and the upper limit or less, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target members connected by the resin composition is further increased. be able to.
  • the content of the coated particles in 100% by weight of the resin composition is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 80% by weight or less, more preferably 60% by weight. %, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • content of the coated particles is equal to or more than the lower limit and equal to or less than the upper limit, reliability of electrical connection and reliability of insulation between electrodes can be further enhanced.
  • connection structure includes a first connection object member having a first electrode on the surface, a second connection object member having a second electrode on the surface, the first connection object member, and a connecting portion connecting the second member to be connected.
  • the material of the connecting portion contains the coated particles described above.
  • the first electrode and the second electrode are electrically connected by the conductive particles.
  • connection structure is obtained through a step of disposing the coated particles between the first member to be connected and the second member to be connected, and a step of conducting conductive connection by thermocompression bonding. be able to. It is preferable that the covering portion and the insulating particles are detached from the covering particles during the thermocompression bonding. Further, instead of the coated particles, the resin composition may be arranged.
  • FIG. 4 is a cross-sectional view schematically showing a connected structure using coated particles according to the first embodiment of the present invention.
  • a connection structure 81 shown in FIG. 4 includes a first connection target member 82, a second connection target member 83, and a connection portion that connects the first connection target member 82 and the second connection target member 83. 84.
  • the material of the connecting portion 84 contains the coated particles 1 .
  • the connecting portion 84 may be made of a resin composition containing the coating particles 1 .
  • the connecting portion 84 is preferably formed by curing a resin composition containing a plurality of coating particles 1 .
  • the coated particles 1 are schematically shown for convenience of illustration. Instead of the coated particles 1, coated particles 1A or 1B may be used.
  • the first connection target member 82 has a plurality of first electrodes 82a on its surface (upper surface).
  • the second connection target member 83 has a plurality of second electrodes 83a on its surface (lower surface).
  • the first electrode 82a and the second electrode 83a are electrically connected by the conductive particles 11 (not shown in FIG. 4) in one or more coated particles 1.
  • FIG. Therefore, the first connection target member 82 and the second connection target member 83 are electrically connected by the conductive portions 22 (not shown in FIG. 4) of the conductive particles 11 (not shown in FIG. 4).
  • the manufacturing method of the connection structure is not particularly limited.
  • the coated particles or the resin composition is arranged between a first member to be connected and a second member to be connected to obtain a laminate, and then the laminate and a method of heating and pressurizing.
  • the pressure of the thermocompression bonding is preferably 40 MPa or higher, more preferably 60 MPa or higher, and preferably 90 MPa or lower, more preferably 70 MPa or lower.
  • the temperature (heating temperature) of the thermocompression bonding is preferably 80° C. or higher, more preferably 100° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower.
  • the coating portion and the insulating particles can be easily detached from the surface of the coating particles at the time of conductive connection, and the reliability of conduction between electrodes is improved. can be further enhanced.
  • the coating portion and the insulating particles existing between the conductive particles and the first electrode and the second electrode can be eliminated.
  • the conductive particles, the insulating particles present between the first electrode and the second electrode, the conductive particles with the insulating particles easily detached from the surface of the particles.
  • some of the insulating particles may be detached from the surface of the conductive particles with insulating particles, and the surface of the conductive portion may be partially exposed. The exposed portion of the conductive portion is in contact with the first electrode and the second electrode, thereby electrically connecting the first electrode and the second electrode via the conductive particles. can do.
  • the first member to be connected and the second member to be connected are not particularly limited.
  • the first connection target member and the second connection target member include electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors and diodes, resin films, printed circuit boards, Examples include electronic components such as circuit boards such as flexible printed boards, flexible flat cables, rigid flexible boards, glass epoxy boards and glass boards.
  • the first member to be connected and the second member to be connected are preferably electronic components.
  • the electrodes provided on the connection target members include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode.
  • the electrode When the electrode is an aluminum electrode, it may be an electrode made of only aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer.
  • materials for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal elements include Sn, Al and Ga.
  • Example 1 Preparation of conductive particles with insulating particles Conductive particles having a conductive portion in which a nickel plating layer is formed on the surface of divinylbenzene resin particles (base particles) (average particle diameter 3.0 ⁇ m, conductive portion thickness of 0.15 ⁇ m) was prepared.
  • Composition A was prepared in a 1000 mL separable flask equipped with a 4-neck separable cover, a stirring blade, a three-way cock, a cooling tube, and a temperature probe.
  • Composition A contains 97 parts by weight of styrene, 3 parts by weight of divinylbenzene, 0.5 parts by weight of acid phosphooxypolyoxyethylene glycol methacrylate, and 2,2′-azobis ⁇ 2-[N-(2-carboxyethyl)amidino ] Propane ⁇ 0.1 parts by weight. After that, the composition A was weighed into distilled water so that the solid content was 10% by weight, and the mixture was stirred at 200 rpm and polymerized at 60° C. for 24 hours under a nitrogen atmosphere.
  • insulating particles (divinylbenzene-styrene copolymer, average particle size 300 nm), then dispersed in 30 mL of pure water under ultrasonic irradiation, 10 weight of insulating particles % dispersion was obtained.
  • the mixture was stirred at 200 rpm and polymerized at 60° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, the particles were filtered through a 10 ⁇ m mesh filter, washed with methanol, and dried to obtain coated particles in which the surfaces of the conductive particles with insulating particles were coated with the coating portion.
  • resin composition anisotropic conductive paste 7 parts by weight of the obtained coated particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, and 30 parts by weight of phenol novolac type epoxy resin Parts by weight and SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) were blended, defoamed and stirred for 3 minutes to obtain a resin composition (anisotropic conductive paste).
  • SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
  • a transparent glass substrate was prepared on the upper surface of which an IZO electrode pattern (first electrode, Vickers hardness of electrode surface metal: 100 Hv) with L/S of 10 ⁇ m/10 ⁇ m was formed.
  • a semiconductor chip having an Au electrode pattern with L/S of 10 ⁇ m/10 ⁇ m (second electrode, Vickers hardness of electrode surface metal 50 Hv) formed on the lower surface was prepared.
  • the obtained resin composition (anisotropic conductive paste) was applied onto the transparent glass substrate so as to have a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chip was laminated on the anisotropic conductive paste layer so that the electrodes faced each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 60 MPa is applied to the anisotropic conductive paste layer. It was cured at 100° C. to obtain a connected structure.
  • Example 2 to 10 and Comparative Example 2 Coated particles, a resin composition, and a bonded structure were obtained in the same manner as in Example 1, except that the configuration of the coated particles was changed as shown in Tables 1 to 3 below.
  • Ratio thickness of coating/particle diameter of insulating particles
  • the thickness of the coating portion and the particle diameter of the insulating particles were measured by the above method, and the ratio of the thickness of the coating portion to the particle size of the insulating particles (thickness of the coating portion/insulating particle particle diameter) was determined.
  • the residual rate of insulating particles is 100% ⁇ : residual rate of insulating particles is 80% or more and less than 100% ⁇ : residual rate of insulating particles is 70% or more and less than 80% ⁇ : residual rate of insulating particles is less than 70%
  • the number of aggregated particles is 4 or less ⁇ : The number of aggregated particles is 5 or more and 6 or less ⁇ : The number of aggregated particles is 7 or more and 9 Below ⁇ : The number of aggregated particles is 10 or more
  • Connection resistance exceeds 1.5 ⁇ and 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ and 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇ and 10 ⁇ or less ⁇ : Connection resistance exceeds 10 ⁇ surpass
  • Insulation reliability (between laterally adjacent electrodes) The presence or absence of leakage between adjacent electrodes in the obtained 20 connection structures was evaluated by measuring the resistance value with a tester. Insulation reliability was evaluated according to the following criteria.
  • connection structures with a resistance value of 10 8 ⁇ or more are 20 ⁇ : The number of connection structures with a resistance value of 10 8 ⁇ or more is 18 or more and 19 or less ⁇ : The resistance value is The number of connection structures with a resistance value of 10 8 ⁇ or more is 15 or more and 17 or less ⁇ : The number of connection structures with a resistance value of 10 8 ⁇ or more is 14 or less
  • compositions and results of the conductive particles with coated particles and insulating particles are shown in Tables 1 to 3 below.

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Abstract

La présente invention concerne des particules enrobées avec lesquelles il est possible de supprimer l'agrégation de particules, et d'augmenter la fiabilité de conduction et d'augmenter la fiabilité d'isolation lors de la connexion électrique d'électrodes.　Les particules enrobées selon la présente invention comprennent chacune une particule conductrice comprenant des particules isolantes, et une partie d'enrobage. Chaque particule conductrice comprenant des particules isolantes est composée d'une particule conductrice et d'une pluralité de particules isolantes disposées sur la surface de la particule conductrice. Chaque particule conductrice est composée d'une particule de base et d'une partie conductrice disposée sur la surface de la particule de base. La partie d'enrobage recouvre au moins une partie de la surface de la partie conductrice et au moins une partie de la surface des particules isolantes. Le matériau formant la partie d'enrobage comprend des monomères polymérisables, et les monomères polymérisables comprennent des monomères réticulables. La teneur en monomère réticulable représente 10,0 % en poids ou plus de 100 % en poids de tous les monomères polymérisables.
PCT/JP2022/023409 2021-06-11 2022-06-10 Particules enrobées, procédé de production de particules enrobées, composition de résine et structure de connexion WO2022260159A1 (fr)

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JP2022538342A JPWO2022260159A1 (fr) 2021-06-11 2022-06-10
KR1020237029689A KR20240019751A (ko) 2021-06-11 2022-06-10 피복 입자, 피복 입자의 제조 방법, 수지 조성물 및 접속 구조체

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268303A (ja) * 1995-03-13 1995-10-17 Soken Kagaku Kk 異方導電性接着剤組成物
JP2013030479A (ja) * 2011-06-22 2013-02-07 Sekisui Chem Co Ltd 絶縁性粒子付き導電性粒子、異方性導電材料及び接続構造体

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5476168B2 (ja) 2010-03-09 2014-04-23 積水化学工業株式会社 導電性粒子、異方性導電材料及び接続構造体
JP6564302B2 (ja) 2014-10-28 2019-08-21 積水化学工業株式会社 絶縁性粒子付き導電性粒子、絶縁性粒子付き導電性粒子の製造方法、導電材料及び接続構造体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268303A (ja) * 1995-03-13 1995-10-17 Soken Kagaku Kk 異方導電性接着剤組成物
JP2013030479A (ja) * 2011-06-22 2013-02-07 Sekisui Chem Co Ltd 絶縁性粒子付き導電性粒子、異方性導電材料及び接続構造体

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