WO2019194134A1 - 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 - Google Patents

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 Download PDF

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WO2019194134A1
WO2019194134A1 PCT/JP2019/014484 JP2019014484W WO2019194134A1 WO 2019194134 A1 WO2019194134 A1 WO 2019194134A1 JP 2019014484 W JP2019014484 W JP 2019014484W WO 2019194134 A1 WO2019194134 A1 WO 2019194134A1
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Prior art keywords
particles
conductive
insulating particles
insulating
functional group
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PCT/JP2019/014484
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English (en)
French (fr)
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 KR1020207027727A priority Critical patent/KR20200140808A/ko
Priority to CN201980021514.6A priority patent/CN111902884B/zh
Priority to JP2019528593A priority patent/JP7312109B2/ja
Publication of WO2019194134A1 publication Critical patent/WO2019194134A1/ja

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    • 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
    • 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
    • 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
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • 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 conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles, and a method for producing conductive particles with insulating particles. Moreover, this invention relates to the electrically-conductive material and connection structure using the said electroconductive particle with an insulating particle.
  • 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.
  • conductive particles in which the surface of the conductive layer is insulated may be used as the conductive particles.
  • the anisotropic conductive material is used for obtaining various connection structures.
  • Examples of the connection using the anisotropic conductive material include a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a 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)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • conductive particles conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles may be used. Further, coated conductive particles in which an insulating layer is disposed on the surface of the conductive layer may be used.
  • Patent Document 1 discloses resin particles that are present on the surface of the conductive particles and insulate the conductive particles.
  • the resin particles include a copolymer of a polymerizable component containing at least an alkyl (meth) acrylate and a polyvalent (meth) acrylate as essential components.
  • the polyvalent (meth) acrylate is a compound in which each (meth) acryl group is bonded to each other via three or more carbon atoms.
  • Patent Document 2 discloses insulating coated conductive particles having conductive particles whose surface has conductivity and insulating fine particles adhering to the surface of the conductive particles.
  • the surface of the core particle containing the polymer component derived from the crosslinkable monomer is coated with a coating layer containing the polymer component derived from the crosslinkable monomer.
  • the degree of cross-linking defined by the following formula (1) of the core particles is 7 or more.
  • the degree of crosslinking defined by the following formula (1) of the core particle is higher than the degree of crosslinking defined by the following formula (1) of the coating layer.
  • Crosslinking degree polymerizable functional group number of crosslinkable monomer ⁇ (number of moles of crosslinkable monomer / number of moles of all monomers) ⁇ 100 Formula (1)
  • the insulating particles are detached from the surface of the conductive particles when the conductive particles with insulating particles and the binder resin are mixed to produce an anisotropic conductive material.
  • a crosslinkable monomer crosslinking agent
  • the content of the crosslinkable monomer increases, the solvent resistance of the resulting insulating particles can be improved.
  • the obtained insulating particles are hard and lack flexibility, it is difficult to sufficiently improve the adhesion of the conductive particles to the surface, and the insulating particles are not detached from the surface of the conductive particles. It can be difficult to prevent.
  • the conductive particles may not be arranged in a highly uniform state between the upper and lower electrodes to be connected.
  • the agglomerated conductive particles may cause a short circuit between laterally adjacent electrodes that should not be connected.
  • conventional conductive particles with insulating particles it may be difficult to significantly improve the conduction reliability between the upper and lower electrodes to be connected and the insulation reliability between laterally adjacent electrodes that should not be connected. .
  • An object of the present invention is to provide a conductive particle with insulating particles and a method for producing conductive particles with insulating particles, which can effectively increase the insulation reliability when the electrodes are electrically connected. It is. Another object of the present invention is to provide a conductive material and a connection structure using the conductive particles with insulating particles.
  • the present invention comprises conductive particles having at least a conductive portion on the surface, and a plurality of insulating particles arranged on the surface of the conductive particles, wherein the insulating particles are polymerizable compounds.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group, and the polymer includes the first functional group.
  • Conductive particles with insulating particles having one functional group and the second functional group are provided.
  • the polymerizable compound does not contain a cross-linking agent, or the cross-linking agent is 10 wt% or less in 100 wt% of the polymerizable compound. Including.
  • the first functional group and the second functional group have a property capable of reacting upon stimulation.
  • the stimulus is heating or light irradiation.
  • the present invention comprises conductive particles having at least a conductive portion on the surface, and a plurality of insulating particles arranged on the surface of the conductive particles, wherein the insulating particles are polymerizable compounds.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group, and the polymer includes the first functional group.
  • a conductive particle with insulating particles which includes a structure in which one functional group and the second functional group are reacted.
  • the polymerizable compound does not contain a cross-linking agent, or the cross-linking agent is 10 wt% or less in 100 wt% of the polymerizable compound. Including.
  • the degree of crosslinking of the insulating particles obtained by the following formula (1) is 10 or more.
  • A is the number of polymerizable functional groups of the crosslinking agent
  • B is the number of moles of the crosslinking agent
  • C is the compound having the first functional group and the compound having the second functional group.
  • D is the total number of moles of the polymerizable compound.
  • the first functional group is a cyclic ether group, an isocyanate group, an aldehyde group, or a nitrile group.
  • the cyclic ether group is an epoxy group or an oxetanyl group.
  • the second functional group is an amide group, a hydroxyl group, a carboxyl group, an imide group, or an amino group.
  • the conductive particles have a particle diameter of 1 ⁇ m or more and 5 ⁇ m or less.
  • the method includes an arrangement step of arranging the insulating particles on the surface of the conductive particles using conductive particles having at least a conductive portion on the surface and a plurality of insulating particles.
  • the insulating particles are a polymer of a polymerizable compound, and the polymerizable compound has a compound having a first functional group and a compound having a second functional group different from the first functional group;
  • the manufacturing method of the electroconductive particle with an insulating particle containing is provided.
  • the polymerizable compound does not contain a crosslinking agent, or 10% by weight of the crosslinking agent in 100% by weight of the polymerizable compound. % Included.
  • positioning process is less than 50 degreeC
  • the said polymer is a said 1st functional group and a said 2nd functional. Conductive particles with insulating particles having a group are obtained.
  • a heating step of heating the conductive particles with insulating particles is provided after the arranging step, and the heating temperature of the heating step is Conductivity with insulating particles, which is 70 ° C. or higher, the heating time of the heating step is 1 hour or longer, and the polymer includes a structure in which the first functional group and the second functional group are reacted. Get particles.
  • a conductive material including the conductive particles with insulating particles described above and a binder resin.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member A connection portion connecting the second connection target member, and the material of the connection portion is the above-described conductive particles with insulating particles, or the conductive particles with insulating particles and a binder resin.
  • a connection structure is provided in which the first electrode and the second electrode are electrically connected by the conductive portion of the conductive particles with insulating particles. .
  • the conductive particles with insulating particles according to the present invention include 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 insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group.
  • the polymer has the first functional group and the second functional group. Since the conductive particles with insulating particles according to the present invention have the above-described configuration, the insulation reliability can be effectively increased when the electrodes are electrically connected.
  • the conductive particles with insulating particles according to the present invention include 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 insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group.
  • the polymer includes a structure in which the first functional group and the second functional group are reacted. Since the conductive particles with insulating particles according to the present invention have the above-described configuration, the insulation reliability can be effectively increased when the electrodes are electrically connected.
  • the method for producing conductive particles with insulating particles according to the present invention uses the conductive particles having at least a conductive portion on the surface and a plurality of insulating particles, and the insulating particles are formed on the surface of the conductive particles.
  • positioning process which arranges is provided.
  • the insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group. including.
  • FIG. 1 is a cross-sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing conductive particles with insulating particles according to the third embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing a connection structure using conductive particles with insulating particles according to the first embodiment of the present invention.
  • the conductive particles with insulating particles according to the present invention include conductive particles having a conductive portion on at least a surface thereof, and a plurality of insulating particles arranged on the surface of the conductive particles.
  • the insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group.
  • the polymer has the first functional group and the second functional group.
  • the conductive particles with insulating particles according to the present invention have the above-described configuration, the insulation reliability can be effectively increased when the electrodes are electrically connected.
  • both of the particles before the first functional group and the second functional group react with each other and the particles after the first functional group and the second functional group react with each other. Is disclosed.
  • the polymer has the first functional group and the second functional group, and the first functional group and the second functional group. Has not reacted.
  • the conductive particles with insulating particles are particles before the first functional group and the second functional group react with each other.
  • the degree of cross-linking of the insulating particles is low and has flexibility. The adhesion between the insulating particles and the surface of the conductive particles can be improved.
  • the conductive particles with insulating particles according to the present invention include 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 insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group.
  • the polymer includes a structure in which the first functional group and the second functional group are reacted.
  • the conductive particles with insulating particles according to the present invention have the above-described configuration, the insulation reliability can be effectively increased when the electrodes are electrically connected.
  • the polymer includes a structure in which the first functional group and the second functional group are reacted.
  • the conductive particles with insulating particles are particles after the first functional group and the second functional group have reacted.
  • the conductive particles with insulating particles are preferably obtained by reacting the first functional group with the second functional group before blending in the binder resin. In the conductive particles with insulating particles before being blended in the binder resin, it is preferable that the first functional group and the second functional group are reacted.
  • the degree of crosslinking of the insulating particles can be increased. Solvent resistance can be improved.
  • the insulating particles are detached from the surface of the conductive particles when the conductive particles with insulating particles and the binder resin are mixed to produce an anisotropic conductive material.
  • a crosslinkable monomer crosslinking agent
  • crosslinking agent may be used to improve solvent resistance.
  • conventional insulating particles are hard and lack flexibility, it is difficult to sufficiently enhance the adhesion between the insulating particles and the surface of the conductive particles, and the insulating particles are detached from the surface of the conductive particles. It may be difficult to prevent separation.
  • it may be difficult to greatly increase the insulation reliability between laterally adjacent electrodes that should not be connected.
  • the present inventors have found that both the adhesion to the surface of the conductive particles and the solvent resistance can be made compatible with the insulating particles by using the specific conductive particles with insulating particles. .
  • the present invention since the above-described configuration is provided, it is possible to prevent the insulating particles from being detached from the surface of the conductive particles. As a result, it is possible to effectively increase the insulation reliability between adjacent lateral electrodes that should not be connected.
  • the degree of crosslinking of the insulating particles can be increased, it is possible to prevent the conductive particles with insulating particles from sticking or agglomerating with each other, and the conductive property with insulating particles in the anisotropic conductive material can be prevented.
  • the dispersibility of the particles can be increased. As a result, a sufficient amount of conductive particles arranged between the upper and lower electrodes to be connected can be ensured, and the conduction reliability between the upper and lower electrodes to be connected can be effectively increased.
  • the coefficient of variation (CV value) of the particle diameter of the conductive particles with insulating 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 diameter of conductive particles with insulating particles Dn: Average value of particle diameter of conductive particles with insulating particles
  • the shape of the conductive particles with insulating particles is not particularly limited.
  • the shape of the conductive particles with insulating particles may be spherical, non-spherical, flat or the like.
  • the conductive particles with insulating particles are dispersed in a binder resin and are preferably used for obtaining a conductive material.
  • FIG. 1 is a cross-sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.
  • the 1 includes a conductive particle 2 and a plurality of insulating particles 3 arranged on the surface of the conductive particle 2.
  • the insulating particles 3 are made of an insulating material.
  • the conductive particles 2 have base material particles 11 and conductive portions 12 arranged on the surface of the base material particles 11.
  • the conductive portion 12 is a conductive layer.
  • the conductive part 12 covers the surface of the base particle 11.
  • the conductive particle 2 is a coated particle in which the surface of the base particle 11 is coated with the conductive portion 12.
  • the conductive particle 2 has a conductive portion 12 on the surface.
  • the conductive part may cover the entire surface of the base particle, or the conductive part may cover a part of the surface of the base particle.
  • the insulating particles are preferably disposed on the surface of the conductive portion.
  • FIG. 2 is a cross-sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.
  • conductive particles 22 includes conductive particles 22 and a plurality of insulating particles 3 arranged on the surface of the conductive particles 22.
  • the conductive particle 22 includes the base particle 11 and a conductive portion 31 disposed on the surface of the base particle 11.
  • the conductive portion 31 is a conductive layer.
  • the conductive particles 22 have a plurality of core substances 32 on the surface of the substrate particles 11.
  • the conductive portion 31 covers the base particle 11 and the core substance 32.
  • the conductive particles 22 have a plurality of protrusions 33 on the surface.
  • the surface of the conductive portion 31 is raised by the core substance 32, and a plurality of protrusions 33 are formed.
  • the conductive part may cover the entire surface of the base particle, or the conductive part may cover a part of the surface of the base particle.
  • the insulating particles are preferably disposed on the surface of the conductive portion.
  • FIG. 3 is a cross-sectional view showing conductive particles with insulating particles according to the third embodiment of the present invention.
  • 3 includes a conductive particle 42 and a plurality of insulating particles 3 arranged on the surface of the conductive particle 42.
  • the conductive particle 42 includes the base particle 11 and a conductive part 51 disposed on the surface of the base particle 11.
  • the conductive portion 51 is a conductive layer.
  • the conductive particles 42 do not have a core substance like the conductive particles 22.
  • the conductive portion 51 has a first portion and a second portion that is thicker than the first portion.
  • the conductive particles 42 have a plurality of protrusions 52 on the surface. A portion excluding the plurality of protrusions 52 is the first portion of the conductive portion 51.
  • the plurality of protrusions 52 are the second portions where the conductive portion 51 is thick.
  • the conductive part may cover the entire surface of the base particle, or the conductive part may cover a part of the surface of the base particle.
  • the insulating particles are preferably disposed on the surface of the conductive portion.
  • the method for producing conductive particles with insulating particles according to the present invention uses the conductive particles having at least a conductive portion on the surface and a plurality of insulating particles, and the insulating particles are formed on the surface of the conductive particles.
  • positioning is provided.
  • the insulating particles are a polymer of a polymerizable compound.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group. including.
  • the obtained conductive particles with insulating particles are preferably particles before the first functional group and the second functional group react with each other.
  • the insulation reliability can be effectively increased when the electrodes are electrically connected.
  • the temperature of the arranging step is preferably less than 50 ° C., and the temperature of the arranging step is more preferably 40 ° C. or less.
  • the polymer in the conductive particles with insulating particles after the placing step, the polymer has the first functional group and the second functional group. It is preferable to have.
  • the first functional group and the second functional group are not reacted in the conductive particles with insulating particles after the placing step. It is preferable.
  • the first functional group and the second functional group are not reacted in the conductive particles with insulating particles after the placing step. Therefore, the degree of crosslinking of the insulating particles is low and has flexibility, and the adhesion between the insulating particles and the surface of the conductive particles can be improved.
  • the heating temperature in the heating step is preferably 70 ° C. or higher, and more preferably 90 ° C. or higher.
  • the heating time in the heating step is preferably 1 hour or longer, and more preferably 2 hours or longer in the heating step.
  • the polymer in the conductive particles with insulating particles after the heating step, includes the first functional group and the second functional group.
  • the first functional group and the second functional group are reacted. It is preferable.
  • the conductive particles with insulating particles after the heating step are preferably particles after the first functional group and the second functional group have reacted.
  • the first functional group and the second functional group are reacted. Therefore, the degree of crosslinking of the insulating particles can be increased, and the solvent resistance of the insulating particles can be increased.
  • the heating step is provided after the arranging step, adhesion to the surface of the conductive particles and solvent resistance with respect to the insulating particles. Both can be made compatible with sex. As a result, when the electrodes are electrically connected using the conductive particles with insulating particles, the insulation reliability between the adjacent lateral electrodes that should not be connected can be more effectively increased. .
  • the degree of cross-linking of the insulating particles can be increased, so that the adhesion and aggregation of the conductive particles with insulating particles can be prevented and anisotropic. Dispersibility of the conductive particles with insulating particles in the conductive material can be improved. As a result, the conduction reliability between the upper and lower electrodes to be connected can be further improved effectively.
  • the said electroconductive particle has a base material particle and the electroconductive part arrange
  • the conductive portion may have a single layer structure or a multilayer structure of two or more layers.
  • the particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, particularly preferably. Is 5 ⁇ m or less.
  • the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes is sufficiently large, And it becomes difficult to form the aggregated conductive particles when forming the conductive portion. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion is difficult to peel from the surface of the base particle.
  • the particle diameter of the conductive particles is preferably an average particle diameter, and more preferably a number average particle diameter.
  • the particle diameter of the conductive particles may be determined by, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value of the particle diameter of each conductive particle, or measuring a laser diffraction particle size distribution. It is calculated by doing. In observation with an electron microscope or an optical microscope, the particle diameter of each conductive particle is determined as a particle diameter in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter at an equivalent circle diameter of any 50 conductive particles is almost equal to the average particle diameter at a sphere equivalent diameter. In the laser diffraction particle size distribution measurement, the particle diameter of each conductive particle is obtained as a particle diameter in a sphere equivalent diameter.
  • the particle diameter of the conductive particles is preferably calculated by laser diffraction particle size distribution measurement.
  • the coefficient of variation (CV value) of the particle diameter of the conductive particles is preferably 10% or less, more preferably 5% or less.
  • the variation coefficient of the particle diameter of the conductive particles is not more than the above upper limit, the conduction reliability and the insulation reliability between the electrodes can be further effectively improved.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the conductive particles may have a spherical shape, a non-spherical shape, or a flat shape.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the base particle may be a core-shell particle including a core and a shell disposed on the surface of the core.
  • the core may be an organic core, and the shell may be an inorganic shell.
  • the material 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, Phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, Polyimide, polyamideimide, polyetheretherketone, poly Polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer, and the like.
  • polyolefin resins such as polyethylene, polypropy
  • the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester 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 includes a non-crosslinkable monomer and And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -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, Alkyl (meth) acrylate compounds such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meta Oxyl
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate; triallyl (iso) Silane-containing
  • (meth) acrylate indicates acrylate and methacrylate.
  • (meth) acryl refers to acrylic and methacrylic.
  • (meth) acryloyl refers to acryloyl and methacryloyl.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an 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 non-crosslinked seed particles.
  • examples of inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the inorganic substance is preferably not a metal.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of 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.
  • the core is preferably an organic core.
  • the shell is preferably an inorganic shell.
  • the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
  • the material for the organic core includes the material for the resin particles described above.
  • the material for the inorganic shell examples include the inorganic materials listed above as the material for the base material particles.
  • the material of the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of a silane alkoxide.
  • the substrate particles are metal particles
  • examples of the metal that is a material 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 ⁇ m or more, further preferably 2 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the particle diameter of the substrate particles is not less than the above lower limit and not more than the above upper limit, even when the distance between the electrodes is small and the thickness of the conductive layer is increased, small conductive particles can be obtained. Further, when forming the conductive portion on the surface of the base particle, it becomes difficult to aggregate and it becomes difficult to form the aggregated conductive particles.
  • the particle diameter of the substrate particles is particularly preferably 2 ⁇ m or more and 50 ⁇ m or less.
  • the particle diameter of the substrate particles is in the range of 2 ⁇ m or more and 50 ⁇ m or less, it is difficult to aggregate when forming the conductive portion on the surface of the substrate particles, and aggregated conductive particles are difficult to be formed.
  • the particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
  • the particle diameter of the base material particles indicates a number average particle diameter.
  • the particle diameter of the substrate particles is determined using a particle size distribution measuring device 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 an average value. In observation with an electron microscope or an optical microscope, the particle diameter of the base particle per particle is obtained as a particle diameter in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter at an equivalent circle diameter of any 50 base particles is substantially equal to the average particle diameter at a sphere equivalent diameter. In the particle size distribution measuring apparatus, the particle diameter of the base material particle per particle is obtained as a particle diameter in a sphere equivalent diameter.
  • the particle diameter of the substrate particles is preferably calculated by a particle size distribution measuring device. In the case of measuring the particle diameter of the substrate particles in the conductive particles, for example, it can be measured as follows.
  • An embedded resin for inspecting conductive particles is prepared by adding to and dispersing in “Technobit 4000” manufactured by Kulzer so that the content of the conductive particles is 30% by weight.
  • a cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-SEM field emission scanning electron microscope
  • the image magnification is set to 25000 times, 50 conductive particles are randomly selected, and the base particles of each conductive particle are observed. To do.
  • the particle diameter of the base particle in each conductive particle is measured, and arithmetically averaged to obtain the particle diameter of the base particle.
  • the conductive particles have at least a conductive portion on the surface.
  • the conductive part preferably contains a metal.
  • the metal which comprises the said electroconductive part is not specifically limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together. From the viewpoint of further reducing the connection resistance between the electrodes, the metal is preferably an alloy containing tin, nickel, palladium, copper, or gold, and more preferably nickel or palladium.
  • the conductive portion and the outer surface portion of the conductive portion contain nickel.
  • the content of nickel in 100% by weight of the conductive part containing nickel is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more.
  • the content of nickel in 100% by weight of the conductive part containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
  • hydroxyl groups are present on the surface of the conductive part due to oxidation.
  • a hydroxyl group exists on the surface of a conductive portion formed of nickel by oxidation.
  • Insulating particles can be disposed on the surface of the conductive part having such a hydroxyl group (the surface of the conductive particles) via a chemical bond.
  • the conductive part may be formed of one layer.
  • the conductive part may be formed of a plurality of layers. That is, the conductive part may have a laminated structure of two or more layers.
  • the metal constituting the outermost layer is preferably gold, nickel, palladium, copper, or an alloy containing tin and silver, and is gold. More preferred.
  • the connection resistance between electrodes becomes still lower. Further, when the metal constituting the outermost layer is gold, the corrosion resistance is further enhanced.
  • the method for forming the conductive portion on the surface of the substrate particle is not particularly limited.
  • Examples of the method for forming the conductive part include 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 a 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 for forming the conductive part is preferably a method by electroless plating, electroplating or physical collision.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like is used.
  • the thickness of the conductive part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive part is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Can be deformed.
  • the thickness of the conductive part of the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably Is 0.1 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the conductive portion of the outermost layer becomes uniform, corrosion resistance is sufficiently high, and connection resistance between the electrodes is sufficiently low. can do.
  • the thickness of the conductive part can be measured, for example, by observing a cross section of the conductive particles using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the conductive particles preferably have a plurality of protrusions on the outer surface of the conductive part.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles.
  • the oxide film is effectively applied by the protrusions by placing conductive particles with insulating particles between the electrodes and pressing them. Can be eliminated. For this reason, an electrode and an electroconductive part contact more reliably and the connection resistance between electrodes becomes still lower.
  • the insulating particles between the conductive particles and the electrodes can be effectively eliminated by the protrusions of the conductive particles. For this reason, the conduction
  • a conductive part is formed by electroless plating, and a conductive part is formed by electroless plating on the surface of the base particle. Thereafter, a method of attaching a core substance and further forming a conductive portion by electroless plating can be used.
  • a first conductive part is formed on the surface of the base particle, and then a core substance is disposed on the first conductive part, and then the second conductive part.
  • the conductive material is formed on the base particle by electroless plating without using the core material, and then plating is deposited on the surface of the conductive portion in the form of a protrusion.
  • a method of forming a conductive portion may be used.
  • the core substance is added to the dispersion of the base particle, and the core substance is accumulated on the surface of the base particle by van der Waals force.
  • Examples thereof include a method of adhering, and a method of adding a core substance to a container containing base particles and causing the core substance to adhere to the surface of the base particles by a mechanical action such as rotation of the container.
  • the method of causing the core material to adhere to the surface of the base material particles is a method of accumulating and attaching the core material to the surface of the base material particles in the dispersion. preferable.
  • the materials constituting the core material include conductive materials and non-conductive materials.
  • the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers.
  • the conductive polymer include polyacetylene.
  • the nonconductive material include silica, alumina, and zirconia. From the viewpoint of further improving the conduction reliability between the electrodes, the core substance is preferably a metal.
  • the metal is not particularly limited.
  • the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead.
  • examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide.
  • the metal is preferably nickel, copper, silver or gold.
  • the metal may be the same as or different from the metal constituting the conductive part (conductive layer).
  • the shape of the core substance is not particularly limited.
  • the shape of the core substance is preferably a lump.
  • Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
  • the average diameter (average particle diameter) of the core substance 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 reduced.
  • the average particle diameter of the core substance is preferably a number average particle diameter.
  • the average particle diameter of the core substance is, for example, by observing 50 arbitrary core substances with an electron microscope or an optical microscope, calculating the average value of the particle diameter of each core substance, or performing laser diffraction particle size distribution measurement. Is required. In observation with an electron microscope or an optical microscope, the particle diameter of each core substance is determined as a particle diameter in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter at an equivalent circle diameter of any 50 core substances is substantially equal to the average particle diameter at a sphere equivalent diameter. In the laser diffraction particle size distribution measurement, the particle diameter of the core material per particle is obtained as a particle diameter in a sphere equivalent diameter.
  • the average particle diameter of the core substance is preferably calculated by laser diffraction particle size distribution measurement.
  • the conductive particles with insulating particles according to the present invention include a plurality of insulating particles arranged on the surface of the conductive particles.
  • a short circuit between adjacent electrodes can be prevented.
  • insulating particles exist between the plurality of electrodes, preventing short-circuiting between adjacent electrodes in the horizontal direction instead of between the upper and lower electrodes. it can.
  • the insulating particle between the electroconductive part of an electroconductive particle and an electrode can be easily excluded by pressurizing the electroconductive particle with an insulating particle with two electrodes in the case of the connection between electrodes.
  • the insulating particles between the conductive part of the conductive particle and the electrode can be more easily eliminated.
  • the insulating particles are a polymer of a polymerizable compound.
  • the insulating particles are preferably a polymer of a polymerizable component containing a plurality of types of polymerizable compounds.
  • the polymerizable compound is not particularly limited. Examples of the polymerizable compound include the resin particle materials described above.
  • the insulating particles may be the resin particles described above.
  • the polymerizable compound may contain a polymerizable compound having a homopolymer having a glass transition temperature of less than 100 ° C.
  • the polymerizable component may contain a polymerizable compound whose homopolymer has a glass transition temperature of less than 100 ° C.
  • the polymerizable compound may contain 10% by weight or more of a polymerizable compound having a glass transition temperature of less than 100 ° C. in a homopolymer in 100% by weight of the polymerizable compound.
  • the polymerizable component may contain 10% by weight or more of a polymerizable compound having a glass transition temperature of less than 100 ° C. in a homopolymer in 100% by weight of the polymerizable component.
  • the homopolymer in the polymerizable compound having a glass transition temperature of less than 100 ° C. means a homopolymer obtained by homopolymerizing the polymerizable compound.
  • the polymerizable compound (the polymerizable component) contains a polymerizable compound having a glass transition temperature of a homopolymer of less than 100 ° C.
  • the insulating particles can be made more flexible, and the insulating particles and the conductive particles can be made conductive. Adhesion with the surface of the conductive particles can be further enhanced.
  • the polymerizable compound includes a compound having a first functional group and a compound having a second functional group different from the first functional group.
  • the first functional group and the second functional group are preferably reactive functional groups.
  • the compound having the first functional group and the compound having the second functional group are preferably polymerizable compounds.
  • the polymerizable compound preferably includes a polymerizable compound having a first reactive functional group and a polymerizable compound having a second reactive functional group different from the first reactive functional group.
  • the polymerizable component preferably includes a polymerizable compound having a first reactive functional group and a polymerizable compound having a second reactive functional group different from the first reactive functional group.
  • the first functional group is preferably a cyclic ether group, an isocyanate group, an aldehyde group or a nitrile group, more preferably a cyclic ether group, an isocyanate group or a nitrile group, and a cyclic ether group or a nitrile group. More preferably.
  • the cyclic ether group is preferably an epoxy group or an oxetanyl group, and more preferably an epoxy group.
  • Examples of the compound having an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • the compound which has the said epoxy group only 1 type may be used and 2 or more types may be used together.
  • the compound having an epoxy group is preferably glycidyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate glycidyl ether.
  • Examples of the compound having the cyclic ether group include (3-ethyloxetane-3-yl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and cyclic trimethylolpropane formal (meth). An acrylate etc. are mentioned.
  • the compound which has the said cyclic ether group except the said epoxy group, only 1 type may be used and 2 or more types may be used together.
  • the compound having the cyclic ether group (excluding the epoxy group) is preferably (3-ethyloxetane-3-yl) methyl (meth) acrylate.
  • Examples of the compound having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, 2-[(3,5 -Dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 2-propylene isocyanate, 1-phenyl-2-propylene isocyanate, 4,4-dimethylpentene- 5-isocyanate, 2,4,4-trimethylpentene-5-isocyanate, 3,3-dimethylpentene-5-isocyanate, 2-allyl-2-isocyanatomethyl-malonic acid diethyl ester, 1-phenyl-3-methyl- 3-Butene isocyania Over DOO, 4-vinyl benzene is
  • the compound having an isocyanate group is preferably 2- (meth) acryloyloxyethyl isocyanate or 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate.
  • Examples of the compound having an aldehyde group include acrolein.
  • Examples of the compound having a nitrile group include (meth) acrylonitrile.
  • the second functional group is different from the first functional group.
  • the second functional group is preferably an amide group, a hydroxyl group, a carboxyl group, an imide group or an amino group, more preferably an amide group, a carboxyl group or an amino group, and an amide group or a carboxyl group. Is more preferable.
  • the insulation reliability is further effectively improved when the electrodes are electrically connected using the conductive particles with insulating particles. be able to.
  • Examples of the compound having an amide group include (meth) acrylamide, N-substituted (meth) acrylamide, and N, N-substituted (meth) acrylamide.
  • the N-substituted (meth) acrylamide is not particularly limited.
  • Examples of the N-substituted (meth) acrylamide include N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, and N-methoxymethyl (meth) acrylamide.
  • N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. are mentioned.
  • the N, N-substituted (meth) acrylamide is not particularly limited.
  • N, N-substituted (meth) acrylamide examples include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and (meth) acryloylmorpholine.
  • the compound which has the said amide group only 1 type may be used and 2 or more types may be used together.
  • the compound having an amide group is preferably (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N, N-dimethyl (meth) acrylamide, and more preferably (meth) acrylamide.
  • Examples of the compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate , Vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, pentaerythritol tri (meth) Acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid ethylene oxide modified di (meth) acrylate, 2-hydroxy
  • the compound having a hydroxyl group is preferably 2-hydroxyethyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate.
  • Examples of the compound having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, itaconic acid, succinic acid, fumaric acid and citraconic acid, And salts and anhydrides thereof.
  • unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid
  • unsaturated dicarboxylic acids such as maleic acid, itaconic acid, succinic acid, fumaric acid and citraconic acid
  • salts and anhydrides thereof As for the compound which has the said carboxyl group, only 1 type may be used and 2 or more types may be used together.
  • the compound having a carboxyl group is preferably (meth) acrylic acid.
  • Examples of the compound having an imide group include imide (meth) acrylate and maleimide.
  • imide (meth) acrylate and maleimide As for the compound which has the said imide group, only 1 type may be used and 2 or more types may be used together.
  • the compound having an imide group is preferably imide (meth) acrylate.
  • Examples of the compound having an amino group include N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl methacrylate.
  • the compound which has the said amino group only 1 type may be used and 2 or more types may be used together.
  • the compound having an amino group is preferably N, N-dimethylaminoethyl (meth) acrylate.
  • the polymerizable compound does not contain a crosslinking agent, or contains 100% by weight or less of the crosslinking compound in 100% by weight of the polymerizable compound.
  • the polymerizable component does not contain a crosslinking agent, or contains 100% by weight or less of the crosslinking agent in 100% by weight of the polymerizable component.
  • the polymerizable compound is contained in 100% by weight of the polymerizable compound from the viewpoint of increasing the insulation reliability more effectively.
  • the crosslinking agent is preferably contained at 7% by weight or less, and more preferably at 6% by weight or less in 100% by weight of the polymerizable compound.
  • the polymerizable component is contained in 100% by weight of the polymerizable component from the viewpoint of further effectively improving the insulation reliability.
  • the crosslinking agent is preferably contained in an amount of 7% by weight or less, more preferably 6% by weight or less in 100% by weight of the polymerizable component.
  • the polymerizable compound is contained in 100% by weight of the polymerizable compound from the viewpoint of increasing the insulation reliability more effectively.
  • the crosslinking agent is contained at 5% by weight or less, and it is further preferable that the crosslinking agent is contained at less than 5% by weight in 100% by weight of the polymerizable compound.
  • the polymerizable component is contained in 100% by weight of the polymerizable component from the viewpoint of further effectively improving the insulation reliability. It is more preferable that the crosslinking agent is contained at 5% by weight or less, and it is further preferable that the crosslinking agent is contained at less than 5% by weight in 100% by weight of the polymerizable component.
  • the polymerizable compound does not contain a cross-linking agent from the viewpoint of further effectively increasing the insulation reliability.
  • the polymerizable component does not contain a crosslinking agent from the viewpoint of further increasing the insulation reliability more effectively.
  • the degree of crosslinking of the insulating particles obtained by the following formula (1) is preferably 10 or more, and more preferably 14 or more.
  • the degree of crosslinking of the insulating particles is not less than the above lower limit, the insulating reliability can be further effectively improved when the electrodes are electrically connected using the conductive particles with insulating particles. .
  • A is the number of polymerizable functional groups of the crosslinking agent
  • B is the number of moles of the crosslinking agent
  • C is the compound having the first functional group and the compound having the second functional group.
  • D is the total number of moles of the polymerizable compound.
  • the cross-linking agent is not particularly limited.
  • the crosslinking agent is preferably a polymerizable compound having two or more ethylenically unsaturated groups in one molecule.
  • Examples of the cross-linking agent include cross-linkable monomers that are the materials of the resin particles described above. From the viewpoint of easily controlling the reaction of the polymerizable compound, the crosslinking agent is preferably ethylene glycol di (meth) acrylate or tetramethylolmethane tetra (meth) acrylate.
  • the polymer has a configuration (first configuration) in which the polymer has the first functional group and the second functional group, or the polymer. Includes a structure (second structure) that includes a structure in which the first functional group and the second functional group are reacted.
  • the polymer has the first functional group and the second functional group, and the first 1 functional group and the second functional group are not reacted.
  • the first functional group and the second functional group do not react with each other. Is low and has flexibility, and can improve the adhesion between the insulating particles and the surface of the conductive particles.
  • the first functional group and the second functional group have a property capable of reacting by stimulation.
  • the stimulation is preferably heating or light irradiation, and more preferably heating.
  • the property which can react means the property which can form a chemical bond.
  • the first functional group and the second functional group form a chemical bond by stimulation (heating or light irradiation).
  • the polymer When the conductive particles with insulating particles according to the present invention have the second configuration, the polymer includes a structure in which the first functional group and the second functional group are reacted. The first functional group and the second functional group are reacted. In the case where the conductive particles with insulating particles according to the present invention have the second configuration, the first functional group and the second functional group are reacted with each other. And the solvent resistance of the insulating particles can be improved.
  • the conductive particles with insulating particles having the second configuration can be obtained by heating or irradiating the conductive particles with insulating particles having the first configuration. It is preferred to obtain particles.
  • the conductive particles with insulating particles having the second configuration are more preferably obtained by heating the conductive particles with insulating particles having the first configuration.
  • Examples of the method for disposing the insulating particles on the surface of the conductive part include a chemical method and a physical or mechanical method.
  • Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
  • Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. Since the insulating particles are difficult to be detached, a method in which the insulating particles are arranged on the surface of the conductive portion via a chemical bond is preferable.
  • the conductive particles with insulating particles according to the present invention it is preferable that a hydroxyl group or the like existing on the surface of the conductive part and the compound having the first functional group are chemically bonded, and the surface of the conductive part It is preferable that the hydroxyl group and the like existing in the compound and the compound having the second functional group are chemically bonded.
  • the hydroxyl group and the like present on the surface of the conductive part may be chemically bonded to the first functional group, and the hydroxyl group present on the surface of the conductive part. And the first functional group may not be chemically bonded.
  • a hydroxyl group or the like present on the surface of the conductive part may be chemically bonded to the second functional group, and a hydroxyl group present on the surface of the conductive part.
  • the second functional group may not be chemically bonded.
  • the outer surface of the conductive part and the outer surface of the insulating particle may each be coated with a compound having a reactive functional group.
  • the outer surface of the conductive part and the outer surface of the insulating particle may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the outer surface of the insulating particle through a polymer electrolyte such as polyethyleneimine.
  • the particle diameter of the insulating particles can be appropriately selected depending on the particle diameter of the conductive particles with insulating particles and the use of the conductive particles with insulating particles.
  • the particle diameter of the insulating particles is preferably 10 nm or more, more preferably 100 nm or more, further preferably 200 nm or more, particularly preferably 300 nm or more, preferably 4000 nm or less, more preferably 2000 nm or less, and further preferably 1500 nm or less. Especially preferably, it is 1000 nm or less.
  • the particle diameter of the insulating particles is equal to or greater than the lower limit, when the conductive particles with insulating particles are dispersed in a binder resin, the conductive portions in the plurality of conductive particles with insulating particles are It becomes difficult to touch.
  • the particle diameter of the insulating particles is not more than the above upper limit, it is not necessary to increase the pressure too much in order to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes. Also, there is no need to heat to high temperature.
  • the particle diameter of the insulating particles indicates a number average particle diameter.
  • the particle diameter of the insulating particles is determined using a particle size distribution measuring device 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 an average value. In observation with an electron microscope or an optical microscope, the particle diameter of each insulating particle is obtained as a particle diameter in a circle-equivalent diameter. In observation with an electron microscope or an optical microscope, the average particle diameter at an equivalent circle diameter of any 50 insulating particles is substantially equal to the average particle diameter at a sphere equivalent diameter.
  • the particle diameter of the insulating particles per particle is obtained as the particle diameter in a sphere equivalent diameter.
  • the particle diameter of the insulating particles is preferably calculated by a particle size distribution measuring device. When measuring the particle diameter of the insulating particles in the conductive particles with insulating particles, for example, the measurement can be performed as follows.
  • the conductive particles with insulating particles are added to and dispersed in “Technobit 4000” manufactured by Kulzer so that the content is 30% by weight, and an embedded resin for inspecting conductive particles is produced.
  • an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) to pass through the vicinity of the center of the dispersed conductive particles with insulating particles in the embedded resin for inspection, the cross section of the conductive particles with insulating particles is cut. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 50 conductive particles with insulating particles were randomly selected, and each conductive particle with insulating particles was selected. Observe the insulating particles. The particle diameter of the insulating particles in each conductive particle with insulating particles is measured, and arithmetically averaged to obtain the particle diameter of the insulating particles.
  • the conductive particles with insulating particles according to the present invention may be used in combination of two or more insulating particles having different particle diameters.
  • the insulating particles having a small particle diameter enter the gaps covered with the insulating particles having a large particle diameter, and the above coverage is more effectively achieved. Can be increased.
  • the insulating particles include a first insulating particle having a particle diameter of 0.1 ⁇ m or more and less than 0.25 ⁇ m, and a particle diameter of 0.25 ⁇ m. It is preferable to include the second insulating particles of 0.8 ⁇ m or less. It is preferable that the particle size distribution of the first insulating particles does not overlap with the particle size distribution of the second insulating particles.
  • the average particle diameter of the first insulating particles is preferably different from the average particle diameter of the second insulating particles.
  • 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 not more than the above upper limit, the thickness of the insulating particles of the obtained conductive particles with insulating particles becomes even more uniform, and the pressure is more uniformly applied during conductive connection. It can be applied more easily, and the connection resistance between the electrodes can be further reduced.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of insulating particles Dn: Average value of particle diameter of insulating particles
  • the shape of the insulating particles is not particularly limited.
  • the shape of the insulating particles may be spherical, non-spherical, flat or the like.
  • the conductive material according to the present invention includes the above-described conductive particles with insulating particles and a binder resin.
  • the conductive particles with insulating particles are preferably used by being dispersed in a binder resin, and are preferably used as a conductive material by being dispersed in a binder resin.
  • the conductive material is 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 conductive particles with insulating particles described above are used in the conductive material, the conductive particles with insulating particles before the conductive connection such as dispersing the conductive particles with insulating particles in a binder resin are used. Insulating particles can be prevented from being unintentionally detached from the surface, and the insulation reliability between the electrodes can be further enhanced.
  • the binder resin is not particularly limited.
  • the binder resin a known insulating resin is used.
  • the binder resin preferably includes a thermoplastic component (thermoplastic compound) or a curable component, and more preferably includes a curable component.
  • the curable component include a photocurable component and a thermosetting component. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator.
  • 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.
  • vinyl resins examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers.
  • the said binder resin only 1 type may be used and 2 or more types may be used together.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
  • examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
  • examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an 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 copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and heat stability.
  • Various additives such as an agent, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
  • the method for dispersing the conductive particles with insulating particles in the binder resin may be any conventionally known dispersion method and is not particularly limited.
  • Examples of the method for dispersing the conductive particles with insulating particles in the binder resin include the following methods. A method in which the conductive particles with insulating particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. A method in which the conductive particles with insulating particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, and kneaded and dispersed by a planetary mixer or the like. A method in which the binder resin is diluted with water or an organic solvent, and then the conductive particles with insulating particles are added and kneaded and dispersed by a planetary mixer or the like.
  • the viscosity ( ⁇ 25) at 25 ° C. of the conductive material is preferably 30 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, preferably 400 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
  • the viscosity of the conductive material at 25 ° C. is not less than the above lower limit and not more than the above upper limit, the insulation reliability between the electrodes can be further effectively increased, and the conduction reliability between the electrodes can be further effectively improved. Can be increased.
  • the said viscosity ((eta) 25) can be suitably adjusted with the kind and compounding quantity of a compounding component.
  • the viscosity ( ⁇ 25) can be measured under conditions of 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
  • the conductive material according to the present invention can be used as a conductive paste and a conductive film.
  • the conductive material according to the present invention is a conductive film
  • a film that does not include conductive particles may be laminated on a conductive film that includes 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 in 100% by weight of the conductive material 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. Is 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further enhanced. Can do.
  • the content of the conductive particles with insulating particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 80% by weight or less. It is preferably 60% by weight or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • the content of the conductive particles with insulating particles is not less than the above lower limit and not more than the above upper limit, conduction reliability and insulation reliability between the electrodes can be further enhanced.
  • connection structure includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connecting portion connecting the second connection target members.
  • the material of the connection portion is the above-described conductive particles with insulating particles or a conductive material including the conductive particles with insulating particles and a binder resin.
  • the first electrode and the second electrode are electrically connected by the conductive portion in the conductive particles with insulating particles.
  • connection structure includes a step of arranging the conductive particles with insulating particles or the conductive material between the first connection target member and the second connection target member, and thermocompression bonding. It can be obtained through a conductive connection step. It is preferable that the insulating particles are detached from the conductive particles with insulating particles during the thermocompression bonding.
  • FIG. 4 is a cross-sectional view schematically showing a connection structure using conductive particles with insulating 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 connecting portion 84 is formed of a conductive material including the conductive particles 1 with insulating particles.
  • the connecting portion 84 is preferably formed by curing a conductive material including a plurality of conductive particles 1 with insulating particles.
  • the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, the conductive particles 21 or 41 with insulating particles may be used.
  • the first connection target member 82 has a plurality of first electrodes 82a on the surface (upper surface).
  • the second connection target member 83 has a plurality of second electrodes 83a on the surface (lower surface).
  • the 1st electrode 82a and the 2nd electrode 83a are electrically connected by the electroconductive particle 2 in the electroconductive particle 1 with one or some insulating particle. Therefore, the 1st connection object member 82 and the 2nd connection object member 83 are electrically connected by the electroconductive part in the electroconductive particle 1 with an insulating particle.
  • the manufacturing method of the connection structure is not particularly limited.
  • the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
  • the pressure for the thermocompression bonding is preferably 40 MPa or more, more preferably 60 MPa or more, preferably 90 MPa or less, more preferably 70 MPa or less.
  • the heating temperature of the thermocompression bonding is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 140 ° C. or lower, more preferably 120 ° C. or lower.
  • the insulating particles can be easily detached from the surface of the conductive particles with insulating particles during conductive connection, and the conduction reliability between the electrodes can be improved. It can be further increased.
  • the insulating particles existing between the conductive particles, the first electrode, and the second electrode can be eliminated.
  • the insulating particles existing between the conductive particles and the first electrode and the second electrode are electrically conductive with the insulating particles. Easily desorbs 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 part may be partially exposed. The portion where the surface of the conductive portion is exposed contacts the first electrode and the second electrode, thereby electrically connecting the first electrode and the second electrode via the conductive particles. be able to.
  • the first connection target member and the second connection target member are not particularly limited.
  • electronic components such as a semiconductor chip, a semiconductor package, a LED chip, a LED package, a capacitor
  • the first connection target member and the second connection target member are preferably electronic components.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode.
  • 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 formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material 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 element include Sn, Al, and Ga.
  • Example 1 Production of conductive particles Resin particles formed of a copolymer resin of tetramethylolmethane tetraacrylate and divinylbenzene having a particle diameter of 3 ⁇ m were prepared. After dispersing 10 parts by weight of base material particles in 100 parts by weight of an alkaline solution containing 5% by weight of palladium catalyst solution using an ultrasonic disperser, the base material particles were taken out by filtering the solution. Next, the base particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the base particles. The substrate particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a dispersion. Next, 1 g of nickel particle slurry (average particle size 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing base particles to which the core substance was adhered.
  • nickel particle slurry average particle size 100 nm
  • a nickel plating solution (pH 8.5) containing 0.35 mol / L of nickel sulfate, 1.38 mol / L of dimethylamine borane and 0.5 mol / L of sodium citrate was prepared.
  • the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, by filtering the suspension, the particles are taken out, washed with water, and dried to form a nickel-boron conductive layer (thickness 0.15 ⁇ m) on the surface of the base particles, and have a conductive part on the surface. Conductive particles were obtained.
  • the above composition consists of 500 mL of distilled water, 0.2 part by weight (0.5 mmol) of acid phosphooxypolyoxyethylene glycol methacrylate, 2,2′-azobis ⁇ 2- [N- (2-carboxyethyl) amidino] propane ⁇ 0.2 part by weight (0.5 mmol) and a polymerizable compound are included.
  • the polymerizable compound is a compound having 90 parts by weight (0.9 mol) of methyl methacrylate, 7 parts by weight (0.05 mol) of glycidyl methacrylate which is a compound having a first functional group, and a compound having a second functional group. Contains 4 parts by weight (0.05 mol) of some methacrylamide. After completion of the reaction, the mixture was freeze-dried to obtain insulating particles (particle diameter: 300 nm) having amide groups derived from methacrylamide and epoxy groups derived from glycidyl methacrylate on the surface.
  • conductive material anisotropic conductive paste 7 parts by weight of the obtained conductive particles with insulating particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, and phenol novolac A conductive material (anisotropic conductive paste) was obtained by blending 30 parts by weight of type epoxy resin and SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) and defoaming and stirring for 3 minutes.
  • SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
  • a transparent glass substrate having an IZO electrode pattern (first electrode, metal Vickers hardness of 100 Hv on the electrode surface) having an L / S of 10 ⁇ m / 10 ⁇ m was prepared. Further, a semiconductor chip was prepared in which an Au electrode pattern (second electrode, metal Vickers hardness of 50 Hv on the electrode surface) having L / S of 10 ⁇ m / 10 ⁇ m was formed on the lower surface.
  • the obtained anisotropic conductive paste was applied on the transparent glass substrate so as to have a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face 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 form the anisotropic conductive paste layer. It hardened
  • Example 2 In the production of the conductive particles with insulating particles, after obtaining the conductive particles with insulating particles, the mixture is further heated at 90 ° C. for 2 hours, and amide groups and epoxy groups on the surface of the insulating particles. Conductive particles with insulating particles (including the structure in which the insulating particles are reacted with an amide group and an epoxy group) were obtained. A conductive material and a connection structure were obtained in the same manner as in Example 1 except that the obtained conductive particles with insulating particles were used.
  • Example 3 When producing insulating particles, the amount of methyl methacrylate is changed to 80 parts by weight (0.8 mol) for the polymerizable compound, and the amount of glycidyl methacrylate, which is a compound having the first functional group, is changed. Was changed to 14 parts by weight (0.1 mol), and the amount of methacrylamide as the compound having the second functional group was changed to 9 parts by weight (0.1 mol). Except for the above changes, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2.
  • Example 4 During the production of the insulating particles, the amount of methyl methacrylate was changed to 80 parts by weight (0.8 mol) with respect to the polymerizable compound. Furthermore, instead of 7 parts by weight (0.05 mol) of glycidyl methacrylate which is a compound having the first functional group, 7 parts by weight (0.1 mol) of methacrylonitrile which is a compound having the first functional group is used. It was. Furthermore, instead of 4 parts by weight (0.05 mol) of methacrylamide which is a compound having the second functional group, 9 parts by weight (0.1 mol) of methacrylic acid which is a compound having the second functional group was used. Except for the above changes, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2.
  • Example 5 When producing insulating particles, the amount of methyl methacrylate is changed to 92 parts by weight (0.92 mol) with respect to the polymerizable compound, and the amount of glycidyl methacrylate, which is a compound having the first functional group, is changed. Was changed to 4 parts by weight (0.03 mol), and the amount of methacrylamide as the compound having the second functional group was changed to 3 parts by weight (0.03 mol). Furthermore, 4 parts by weight (0.02 mol) of ethylene glycol dimethacrylate as a crosslinking agent was added. Except for the above changes, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2.
  • Example 6 When producing insulating particles, the amount of methyl methacrylate is changed to 58 parts by weight (0.58 mol) with respect to the polymerizable compound, and the amount of glycidyl methacrylate, which is a compound having the first functional group, is changed. Was changed to 14 parts by weight (0.1 mol), and the amount of methacrylamide as the compound having the second functional group was changed to 9 parts by weight (0.1 mol). Furthermore, 35 parts by weight (0.2 mol) of benzyl methacrylate was added, and 6 parts by weight (0.02 mol) of trimethylolpropane triacrylate as a crosslinking agent was added. Except for the above changes, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2.
  • Example 7 When producing insulating particles, the amount of methyl methacrylate is changed to 56 parts by weight (0.56 mol) with respect to the polymerizable compound, and the amount of glycidyl methacrylate, which is a compound having the first functional group, is changed. Was changed to 14 parts by weight (0.1 mol), and the amount of methacrylamide as the compound having the second functional group was changed to 9 parts by weight (0.1 mol). Furthermore, 35 parts by weight (0.2 mol) of benzyl methacrylate was added, and 8 parts by weight (0.04 mol) of ethylene glycol dimethacrylate as a crosslinking agent was added. Except for the above changes, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2.
  • Adhesiveness of insulating particles was evaluated as follows. The adhesion of the insulating particles was determined according to the following criteria.
  • Evaluation method of adhesion of insulating particles Arbitrary 50 conductive particles with insulating particles were observed using a scanning electron microscope (SEM) immediately after the production. Moreover, after preparing the electroconductive particle dispersion liquid with insulating particles using the obtained electroconductive material, arbitrary 50 electroconductive particles with insulating particles were observed using SEM. From the results of these SEM observations, the number of coatings of insulating particles on the conductive particles with insulating particles immediately after production is compared with the number of coatings of insulating particles on the conductive particles with insulating particles after the dispersion is adjusted. did. In SEM observation, the total number of insulating particles observed was defined as the coating number.
  • the ratio of the coating number of the insulating particles in the conductive particles with insulating particles after the dispersion adjustment to the coating number of the insulating particles in the conductive particles with insulating particles is 50% or more and less than 70%.
  • the ratio of the number of coatings of insulating particles in the conductive particles with insulating particles after dispersion adjustment to the number of coatings of insulating particles in the conductive particles with conductive particles is less than 50%
  • Connection resistance is 1.5 ⁇ or less ⁇ : 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 ⁇ 10 ⁇ or less ⁇ : Connection resistance exceeds 10 ⁇
  • Insulation reliability between adjacent electrodes in the horizontal direction
  • the presence or absence of leakage between adjacent electrodes was evaluated by measuring the resistance value with a tester.
  • the insulation reliability was evaluated according to the following criteria.
  • connection structures having a resistance value of 10 8 ⁇ or more is 20 ⁇ : The number of connection structures having a resistance value of 10 8 ⁇ or more is 18 or more and less than 20 ⁇ : The resistance value is The number of connection structures with 10 8 ⁇ or more is 15 or more and less than 18 ⁇ : The number of connection structures with a resistance value of 10 8 ⁇ or more is 10 or more and less than 15 ⁇ : The resistance value is 10 8 ⁇ or more The number of connection structures of 5 or more and less than 10 XX: The number of connection structures having a resistance value of 10 8 ⁇ or more is less than 5

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