WO2014007238A1 - 絶縁性粒子付き導電性粒子、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、導電材料及び接続構造体 Download PDF

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WO2014007238A1
WO2014007238A1 PCT/JP2013/068116 JP2013068116W WO2014007238A1 WO 2014007238 A1 WO2014007238 A1 WO 2014007238A1 JP 2013068116 W JP2013068116 W JP 2013068116W WO 2014007238 A1 WO2014007238 A1 WO 2014007238A1
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Prior art keywords
particles
conductive
insulating particles
insulating
conductive particles
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PCT/JP2013/068116
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English (en)
French (fr)
Japanese (ja)
Inventor
茂雄 真原
沙織 上田
伸也 上野山
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積水化学工業株式会社
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Priority to CN201380032489.4A priority Critical patent/CN104380392B/zh
Priority to JP2013535614A priority patent/JP6480661B2/ja
Priority to KR1020147029846A priority patent/KR102095826B1/ko
Publication of WO2014007238A1 publication Critical patent/WO2014007238A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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

Definitions

  • the present invention relates to conductive particles with insulating particles that can be used for electrical connection between electrodes, for example. 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 materials conductive particles are dispersed in a binder resin.
  • the anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.
  • Patent Document 1 includes an insulating particle including a particle having a conductive metal surface and an insulating particle covering the surface of the particle having the conductive metal surface. Conductive particles are disclosed. Patent Document 1 describes that when two or more kinds of insulating particles having different particle diameters are used in combination, small insulating particles enter a gap covered with large insulating particles, thereby improving the coating density. .
  • the conductive metal surface is covered with insulating particles, and therefore, between the vertically adjacent electrodes that should not be connected after the upper and lower conductive connections. Electrical connection can be suppressed. That is, the insulation reliability in the conductively connected connection structure can be improved.
  • the small insulating particles are inserted into the gaps covered with the large insulating particles, thereby increasing the coating density, thereby increasing the insulation reliability. be able to.
  • Patent Document 1 only describes that small insulating particles are allowed to enter a gap covered with large insulating particles.
  • the insulating particles are easily detached from the surface of the conductive particles unintentionally before the conductive connection.
  • the insulating particles may be easily detached from the surface of the conductive particles to expose the surface of the conductive particles. As a result, there is a problem that the insulation reliability is lowered.
  • An object of the present invention is to provide conductive particles with insulating particles that can increase insulation reliability when electrodes are connected, and a conductive material and a connection structure using the conductive particles with insulating particles. It is to be.
  • a limited object of the present invention is to provide conductive particles with insulating particles that are difficult to insulate from the surface of the conductive particles even if an impact is applied before the conductive connection, and the insulating property. It is to provide a conductive material and a connection structure using conductive particles with particles.
  • conductive particles having at least a conductive portion on the surface, a plurality of first insulating particles disposed on the surface of the conductive particles, and on the surface of the conductive particles A plurality of second insulating particles arranged, wherein an average particle diameter of the second insulating particles is smaller than an average particle diameter of the first insulating particles, and the second insulating particles
  • the conductive particles with insulating particles are provided on the surface of the conductive particles so that 50% or more of the total number of the conductive particles does not come into contact with the first insulating particles.
  • the 70% or more of the total number of the second insulating particles is not in contact with the first insulating particles. It is arrange
  • 50% or more of the total number of the second insulating particles does not contact the first insulating particles and It arrange
  • the first insulating particles are attached to the surface of the conductive particles through a chemical bond.
  • the second insulating particles are attached to the surface of the conductive particles through a chemical bond.
  • the first insulating particles and the second insulating particles are respectively disposed on the surfaces of the conductive particles by a hybridization method. It has not been.
  • the conductive particles have protrusions on the outer surface of the conductive part.
  • 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 connecting portion connecting the second connection target member, wherein the connecting portion is formed of the above-described conductive particles with insulating particles, or the conductive particles with insulating particles and a binder resin.
  • a connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. Is provided.
  • the conductive particles with insulating particles according to the present invention include conductive particles having at least a conductive portion on the surface, a plurality of first insulating particles disposed on the surface of the conductive particles, and the conductive particles. Second insulating particles disposed on the surface of the first insulating particles, and the average particle size of the second insulating particles is smaller than the average particle size of the first insulating particles. Since 50% or more of the total number of the insulating particles is arranged on the surface of the conductive particles so as not to contact the first insulating particles, the insulating particles according to the present invention are attached. Insulating reliability can be improved when the electrodes are connected using conductive particles.
  • 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 front cross-sectional view schematically showing a connection structure using the conductive particles with insulating particles shown in FIG.
  • FIG. 5 is a schematic diagram for explaining a method for evaluating the coverage.
  • FIG. 1 is a sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.
  • the conductive particle 1 includes a conductive particle 2, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.
  • the conductive particles 2 have at least a conductive portion 12 on the surface.
  • the first insulating particles 3 are disposed on the surface of the conductive particles 2.
  • the second insulating particles 4 are disposed on the surface of the conductive particles 2.
  • 50% or more of the total number of the second insulating particles 4 is arranged on the surface of the conductive particles 2 so as not to contact the first insulating particles 3. All of the second insulating particles 4 may be disposed on the surface of the conductive particles 2 so as not to contact the first insulating particles 3. A part of the second insulating particles 4 may be arranged on the surface of the conductive particles 2 so as to be in contact with the first insulating particles 3.
  • the plurality of first insulating particles 3 are in contact with the surface of the conductive particles 2 and are attached to the surface of the conductive particles 2.
  • the plurality of first insulating particles 3 are in contact with the outer surface of the conductive part 12 in the conductive particle 2 and are attached to the outer surface of the conductive part 12.
  • the plurality of second insulating particles 4 are in contact with the surface of the conductive particles 2 and are attached to the surface of the conductive particles 2.
  • the plurality of second insulating particles 4 are in contact with the outer surface of the conductive portion 12 in the conductive particles 2 and are attached to the outer surface of the conductive portion 12.
  • 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 part 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 first insulating particles 3 and the second insulating particles 4 are each formed of an insulating material.
  • the average particle diameter of the second insulating particles 4 is smaller than the average particle diameter of the first insulating particles 3.
  • FIG. 2 is a sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.
  • 2 includes conductive particles 22, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.
  • the conductive particles 22 have at least a conductive portion 26 on the surface.
  • the first insulating particles 3 are disposed on the surface of the conductive particles 22.
  • the second insulating particles 4 are disposed on the surface of the conductive particles 22.
  • 50% or more of the total number of the second insulating particles 4 is arranged on the surface of the conductive particles 22 so as not to contact the first insulating particles 3.
  • the conductive particles 1 with insulating particles and the conductive particles 21 with insulating particles differ only in the conductive particles 2 and 22.
  • the conductive particle 22 includes the base particle 11 and a conductive portion 26 disposed on the surface of the base particle 11.
  • the conductive particle 22 has a plurality of core substances 27 on the surface of the base particle 11.
  • the conductive portion 26 covers the base particle 11 and the core material 27. By covering the core material 27 with the conductive portion 26, the conductive particles 22 have a plurality of protrusions 28 on the surface.
  • the surface of the conductive portion 26 is raised by the core material 27, and a plurality of protrusions 28 are formed.
  • FIG. 3 is a sectional view showing conductive particles with insulating particles according to the third embodiment of the present invention.
  • 3 includes conductive particles 32, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.
  • the conductive particles 32 have at least a conductive portion 36 on the surface.
  • the first insulating particles 3 are disposed on the surface of the conductive particles 32.
  • the second insulating particles 4 are disposed on the surface of the conductive particles 32.
  • 50% or more of the total number of the second insulating particles 4 is arranged on the surface of the conductive particles 32 so as not to contact the first insulating particles 3.
  • the conductive particles 1 with insulating particles and the conductive particles 31 with insulating particles differ only in the conductive particles 2 and 32.
  • the conductive particle 32 includes the base particle 11 and a conductive portion 36 disposed on the surface of the base particle 11.
  • the conductive particles 22 have a core material 27, but the conductive particles 32 do not have a core material.
  • the conductive portion 36 has a first portion and a second portion that is thicker than the first portion.
  • the conductive particles 32 have a plurality of protrusions 37 on the surface. A portion excluding the plurality of protrusions 37 is the first portion in the conductive portion 36.
  • the plurality of protrusions 37 are the second portion in which the conductive portion 36 is thick.
  • the average particle diameter of the second insulating particles 4 is smaller than the average particle diameter of the first insulating particles 3, and the second insulating particles 4 50% or more of the total number of particles is arranged on the surfaces of the conductive particles 2, 22, and 32 so as not to contact the first insulating particles 3. Since the second insulating particles 4 are not in contact with the first insulating particles 3, the interval between the exposed surfaces of the conductive particles 2 is narrowed. For this reason, when the upper and lower electrodes are electrically connected using the conductive particles 1, 21, 31 with insulating particles, the electrodes adjacent in the lateral direction that should not be connected are electrically connected. Can be suppressed. That is, insulation reliability can be improved.
  • the first insulating particles can be prevented from being detached from the surface of the conductive particles.
  • the first insulating particles are hardly detached from the surface of the conductive particles due to an impact at the time of contact.
  • the first insulating particles are not intended. Since desorption is suppressed, it is possible to suppress electrical connection between adjacent electrodes, and to ensure sufficient insulation reliability.
  • the coverage Z which is an area of, is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more, and particularly preferably 70%. Above, most preferably 80% or more.
  • the coverage which is the total area of the portions covered with the first insulating particles and the second insulating particles occupying the entire surface area of the conductive particles, is obtained as follows.
  • the conductive particle coverage Z (%) of the conductive particles with insulating particles (attachment rate Z (%)) (Also called).
  • the said coverage is a total area (projected area) of the part coat
  • the coverage ratio is the surface of the conductive particles of the conductive particles with insulating particles in the observation image.
  • the total area of the first and second insulating particles in the circle of the outer peripheral edge portion of the surface of the conductive particles occupying the entire area of the outer peripheral edge circle (the hatched portion in FIG. 5A) (see FIG. 5 (b) shaded portion).
  • the average particle size of the second insulating particles is 9/10 or less of the average particle size of the first insulating particles. Preferably, it is 4/5 or less, more preferably 2/3 or less, and particularly preferably 1/2 or less.
  • the average particle diameter of the second insulating particles is preferably 1/30 or more, more preferably 1/20 or more, and more preferably 1/10 or more of the average particle diameter of the first insulating particles. More preferably.
  • the “average particle diameter” of the first and second insulating particles represents a number average particle diameter.
  • the average particle diameter of the first and second insulating particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
  • the second insulating particles may be disposed on the surface of the conductive particles so as to be in contact with the first insulating particles.
  • the number of the second insulating particles arranged on the surface of the conductive particles so as to be in contact with the first insulating particles is large.
  • 10% or more of the total number of the second insulating particles is arranged on the surface of the conductive particles so as to be in contact with the first insulating particles. Preferably it is.
  • the ratio X1 of the number of second insulating particles arranged on the surface of the conductive particles so as to come into contact with the first insulating particles is more preferably 20% or more, and further preferably 30% or more. .
  • the second insulating particles are in contact with the first insulating particles when the first insulating particles are detached during the conductive connection. Insulating particles are also easily detached. As a result, the conduction reliability is further enhanced.
  • the total number of second insulating particles indicates the number of second insulating particles that one conductive particle has.
  • the number of second insulating particles arranged on the surface of the conductive particles so as to be in contact with the first insulating particles is the number of the second insulating particles in contact with the conductive particles. Both the number and the number of second insulating particles not in contact with the conductive particles are included.
  • a method of surface-treating the first insulating particles so that the second insulating particles are easily attached, the first insulation A method of surface-treating the second insulating particles so that the conductive particles are likely to adhere, and the second insulating particles after the second insulating particles are attached to the surface of the first insulating particles
  • a method of attaching the first insulating particles to which the particles adhere to the surface of the conductive particles For example, there may be mentioned a method of attaching the first insulating particles to which the particles adhere to the surface of the conductive particles.
  • 50% or more of the total number of the second insulating particles should not be in contact with the first insulating particles on the surface of the conductive particles. Is arranged.
  • the ratio X2 of the number of the second insulating particles arranged on the surface of the conductive particles so as not to contact the first insulating particles is more preferably more than 50%, still more preferably 55% or more. More preferably, it is 60% or more, still more preferably 65% or more, particularly preferably 70% or more, and most preferably more than 80%.
  • the total number of second insulating particles indicates the number of second insulating particles that one conductive particle has.
  • the number of the second insulating particles arranged on the surface of the conductive particles so as not to contact the first insulating particles is the number of the second insulating particles in contact with the conductive particles. Both the number and the number of second insulating particles not in contact with the conductive particles are included.
  • the ratio X3 of the number of second insulating particles arranged on the surface of the conductive particles so as not to contact the first insulating particles and so as to contact the conductive particles is more preferably 70%. Above, more preferably 75% or more, particularly preferably 80% or more, preferably 100% or less. The ratio of the number may be 99% or less, 95% or less, or 90% or less.
  • the total number of second insulating particles indicates the number of second insulating particles that one conductive particle has.
  • a method of surface-treating the first insulating particles so that the second insulating particles are less likely to adhere, the first insulation A method of surface-treating the second insulating particles so that the conductive particles are less likely to adhere, and the second so that the second insulating particles are more likely to adhere to the conductive particles than the first insulating particles.
  • the average number Y1 is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 5 or more, most preferably 10 or more, preferably 100 or less, more preferably 50 or less. More preferably, it is 20 or less.
  • the average number Y1 may be less than 10.
  • the average number of the first insulating particles arranged on the surface of the conductive particles per one of the conductive particles is the number of the first insulating particles included in the one conductive particle. Is the average.
  • the second insulating particles arranged on the surface of the conductive particles per one of the conductive particles is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 10 or more, most preferably 20 or more, preferably 1000 or less, more preferably 500 or less. More preferably, the number is 100 or less.
  • the average number of the second insulating particles arranged on the surface of the conductive particles per one of the conductive particles is the number of second insulating particles included in the one conductive particle. Is the average.
  • the ratio of the second insulating particles arranged on the surface of the conductive particles to the average number Y2 is preferably 0.001 or more, more preferably 0.00. 005 or more, more preferably 0.05 or more, preferably 1 or less, more preferably 0.5 or less.
  • the ratio (average number Y1 / average number Y2) may exceed 0.5.
  • the number of the first and second insulating particles arranged on the surface of the conductive particles is the number of the first and second insulating particles not in contact with the conductive particles. included.
  • the second insulating particles adhere to the surface of the conductive particles through a chemical bond.
  • the first particles are bonded to the surface of the conductive particles via a chemical bond. It is preferable that the insulating particles adhere. In addition, when the first insulating particles adhere to the surface of the conductive particles through chemical bonds, the insulation reliability of the connection structure is further increased.
  • the conductive particles preferably have protrusions on the outer surface of the conductive part.
  • the insulation reliability tends to decrease as the protrusions increase.
  • the conductive particles with insulating particles according to the present invention since the first and second insulating particles are provided, insulation reliability can be sufficiently ensured even if the protrusions are large.
  • the said electroconductive particle should just have an electroconductive part on the surface at least.
  • the conductive part is preferably a conductive layer.
  • the conductive particles may be base particles and conductive particles having a conductive layer disposed on the surface of the base particles, or may be metal particles whose entirety is a conductive portion.
  • the base particles and the conductive material disposed on the surface of the base particles are used. Conductive particles having a portion are preferred.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the base particles may be core-shell particles.
  • the said base particle is a base particle except a metal particle, and it is more preferable that it is an inorganic particle or an organic inorganic hybrid particle except a resin particle, a metal particle.
  • the base material particles are preferably resin particles formed of a resin.
  • the conductive particles with insulating particles are compressed by placing the conductive particles with insulating particles between the electrodes and then pressing them.
  • the substrate particles are resin particles, the conductive particles are likely to be deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction
  • the resin for forming 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; Alkylene terephthalate, 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, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylene
  • the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
  • the monomer having the ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.
  • 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; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; acids such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate Atom
  • 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) acrylates such as acrylate, (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanurate, tri Lil
  • 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.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal
  • examples of inorganic substances for forming the substrate particles include silica and carbon black.
  • grains formed with the said silica For example, after hydrolyzing the silicon compound which has two or more hydrolysable alkoxysil groups, and forming a crosslinked polymer particle, it calcinates as needed.
  • grains obtained by performing are mentioned.
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the substrate particles are preferably not metal particles.
  • the metal for forming the conductive part is not particularly limited. Furthermore, in the case where the conductive particles are metal particles that are conductive parts as a whole, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and these. And the like. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
  • the melting point of the conductive part is preferably 300 ° C. or higher, more preferably 450 ° C. or higher.
  • the conductive part may be a conductive part that is not solder.
  • 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.
  • the first insulating particles can be attached to the surface of the conductive part having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.
  • the second insulating particles can be attached to the surface of the conductive portion having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.
  • the conductive layer may be formed of a single layer.
  • the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers.
  • the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable.
  • the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced.
  • the outermost layer is a gold layer, the corrosion resistance is further enhanced.
  • the method for forming the conductive layer on the surface of the substrate particles is not particularly limited.
  • a method for forming the conductive layer for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc.
  • the method by electroless plating is preferable.
  • the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • the average particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles with insulating particles. And it becomes difficult to form aggregated conductive particles when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
  • the “average particle size” of the conductive particles indicates a number average particle size.
  • the average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
  • the thickness of the conductive layer 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 even more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .
  • the thickness of the outermost conductive layer is preferably 0.001 ⁇ m or more, more preferably the thickness of the gold layer when the outermost layer is a gold layer. It is 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
  • the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficiently high. Lower. Further, the thinner the gold layer when the outermost layer is a gold layer, the lower the cost.
  • the thickness of the conductive layer can be measured by observing the cross section of the conductive particles or the conductive particles with insulating particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the conductive particles preferably have protrusions on the outer surface of the conductive part, and the protrusions are preferably plural.
  • 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
  • the core substance is added to the dispersion of the base particle, and the core substance is accumulated on the base particle surface by, for example, van der Waals force.
  • 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 mechanical action such as rotation of the container is preferable.
  • the conductive particles may have a first conductive layer on the surface of the base particle, and may have a second conductive layer on the first conductive layer.
  • a core substance may be attached to the surface of the first conductive layer.
  • the core substance is preferably covered with a second conductive layer.
  • the thickness of the first conductive layer is preferably 0.05 ⁇ m or more, and preferably 0.5 ⁇ m or less.
  • the conductive particles form a first conductive layer on the surface of the base particle, and then a core material is deposited on the surface of the first conductive layer, and then the first conductive layer and the core material are formed. It is preferably obtained by forming a second conductive layer on the surface.
  • the material constituting the core material there may be mentioned a conductive material and a non-conductive material.
  • 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. Among them, metal is preferable because of high conductivity.
  • the metal examples 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. Of these, nickel, copper, silver or gold is preferable.
  • the metal constituting the core substance 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 is effectively reduced.
  • the “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter).
  • the average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
  • the number of the protrusions per conductive particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
  • the average particle diameter of the second insulating particles is preferably 0.7 times or more, more preferably 1 time the average height of the protrusions. Above, preferably 5 times or less, more preferably 3 times or less.
  • the average height of the protrusions indicates the average value of the heights of the plurality of protrusions, and the height of the protrusions is on a line (dashed line L1 shown in FIG. 2) connecting the center of the conductive particles and the tips of the protrusions. Shows the distance from the imaginary line (broken line L2 shown in FIG. 2) of the conductive layer (on the outer surface of the spherical conductive particles assuming no protrusion) to the tip of the protrusion when it is assumed that there is no protrusion. . That is, in FIG. 2, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the protrusion is shown.
  • the first and second insulating particles are particles having insulating properties. Each of the first and second insulating particles is smaller than the conductive particles.
  • the first and second insulating particles can prevent a short circuit between adjacent electrodes. Specifically, when the conductive particles with a plurality of insulating particles come into contact with each other, the first and second insulating particles exist between the conductive particles in the conductive particles with a plurality of insulating particles. It is possible to prevent a short circuit between electrodes adjacent in the horizontal direction, not between the upper and lower electrodes.
  • the first and second insulating particles between the conductive portion and the electrode can be easily removed by pressurizing the conductive particles with insulating particles with two electrodes. .
  • protrusions are provided on the surface of the conductive particles, the first and second insulating particles between the conductive portion and the electrode can be more easily eliminated.
  • Examples of the material constituting the first and second insulating particles include an insulating resin and an insulating inorganic substance.
  • As said insulating resin the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned.
  • As said insulating inorganic substance the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.
  • the insulating resin that is the material of the first and second insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, and thermoplastics. Examples include cross-linked resins, thermosetting resins, and water-soluble resins.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
  • each of the first and second insulating particles is preferably an inorganic particle, and is preferably a silica particle. It is preferable.
  • examples of the inorganic particles include shirasu particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, and silica particles.
  • examples of the silica particles include pulverized silica and spherical silica. Spherical silica is preferably used.
  • the silica particles preferably have a functional group capable of chemical bonding such as a carboxyl group and a hydroxyl group on the surface, and more preferably have a hydroxyl group.
  • Inorganic particles are relatively hard, especially silica particles are relatively hard.
  • the surface of the conductive particles has a hard insulating property. There is a tendency for particles to be easily detached.
  • the conductive particles with insulating particles according to the present invention are used, the first insulating particles are removed during the kneading even if the hard first insulating particles are used. Even if they are separated, insulation reliability can be ensured as a result of the second insulating particles remaining.
  • the second insulating particles adhere to the surface of the first insulating particles through a chemical bond. It is preferable that the first insulating particles are attached to the surface of the conductive particles through a chemical bond.
  • This chemical bond includes a covalent bond, a hydrogen bond, an ionic bond, a coordination bond, and the like. Of these, a covalent bond is preferable, and a chemical bond using a reactive functional group is preferable.
  • Examples of the reactive functional group that forms the chemical bond include a vinyl group, (meth) acryloyl group, silane group, silanol group, carboxyl group, amino group, ammonium group, nitro group, hydroxyl group, carbonyl group, thiol group, Examples thereof include a sulfonic acid group, a sulfonium group, a boric acid group, an oxazoline group, a pyrrolidone group, a phosphoric acid group, and a nitrile group.
  • a vinyl group and a (meth) acryloyl group are preferable.
  • the insulating particles having a reactive functional group on the surface as the first insulating particles are preferably used.
  • the first insulating particles were subjected to a surface treatment using a compound having a reactive functional group. It is preferable to use the first insulating particles.
  • Examples of the reactive functional group that can be introduced on the surfaces of the first and second insulating particles include a (meth) acryloyl group, a glycidyl group, a hydroxyl group, a vinyl group, and an amino group.
  • the reactive functional group on the surface of the first and second insulating particles is at least one kind of reactivity selected from the group consisting of (meth) acryloyl group, glycidyl group, hydroxyl group, vinyl group and amino group. It is preferably a functional group.
  • Examples of the compound (surface treatment substance) for introducing the reactive functional group include a compound having a (meth) acryloyl group, a compound having an epoxy group, a compound having a vinyl group, and the like.
  • Examples of the compound (surface treatment substance) for introducing a vinyl group include a silane compound having a vinyl group, a titanium compound having a vinyl group, and a phosphate compound having a vinyl group.
  • the surface treatment substance is preferably a silane compound having a vinyl group.
  • Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyltriisopropoxysilane.
  • a compound (surface treatment substance) for introducing a (meth) acryloyl group a silane compound having a (meth) acryloyl group, a titanium compound having a (meth) acryloyl group, and a phosphoric acid having a (meth) acryloyl group Compounds and the like.
  • the surface treatment substance is also preferably a silane compound having a (meth) acryloyl group.
  • silane compound having a (meth) acryloyl group examples include (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltridimethoxysilane, and the like.
  • Examples of the method for attaching the first and second insulating particles to the surfaces of the conductive particles and 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 a spray drying method, a hybridization method, an electrostatic adhesion method, a spray method, a dipping method, and a vacuum deposition method.
  • the method of arranging the first and second insulating particles is a method other than the hybridization method.
  • the first insulating particles are not arranged on the surface of the conductive particles by the hybridization method.
  • the second insulating particles are preferably not arranged on the surface of the conductive particles by the hybridization method. Since the first insulating particles are more difficult to desorb, a method of arranging the first insulating particles on the surface of the conductive particles through a chemical bond is preferable. Since the second insulating particles are more difficult to desorb, a method of arranging the second insulating particles on the surface of the conductive particles through a chemical bond is preferable.
  • the conductive particles are put in 3 L of a solvent such as water, and the first and second insulating particles are gradually added while stirring. After sufficiently stirring, the conductive particles with insulating particles are separated and dried by a vacuum dryer or the like to obtain conductive particles with insulating particles.
  • a solvent such as water
  • the conductive part preferably has a reactive functional group capable of reacting with the first insulating particles on the surface.
  • the first insulating particles preferably have a reactive functional group capable of reacting with the conductive part on the surface. By introducing a chemical bond with these reactive functional groups, it becomes difficult for the first insulating particles to be unintentionally detached from the surface of the conductive particles. In addition, the insulation reliability and the insulation reliability against impact are further enhanced.
  • the conductive part has a reactive functional group capable of reacting with the second insulating particles on the surface.
  • the second insulating particles have a reactive functional group capable of reacting with the conductive portion on the surface. By introducing a chemical bond with these reactive functional groups, it becomes difficult for the second insulating particles to be unintentionally detached from the surface of the conductive particles. In addition, the insulation reliability and the insulation reliability against impact are further enhanced.
  • the reactive functional group an appropriate group is selected in consideration of reactivity.
  • the reactive functional group include a hydroxyl group, a vinyl group, and an amino group. Since the reactivity is excellent, the reactive functional group is preferably a hydroxyl group.
  • the conductive particles preferably have a hydroxyl group on the surface.
  • the conductive part preferably has a hydroxyl group on the surface.
  • the insulating particles preferably have a hydroxyl group on the surface.
  • the adhesion between the first and second insulating particles and the conductive particles is appropriately increased by the dehydration reaction.
  • Examples of the compound having a hydroxyl group include a P—OH group-containing compound and a Si—OH group-containing compound.
  • Examples of the compound having a hydroxyl group for introducing a hydroxyl group on the surface of the insulating particles include a P—OH group-containing compound and a Si—OH group-containing compound.
  • P—OH group-containing compound examples include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monomethacrylate. Only one type of P—OH group-containing compound may be used, or two or more types may be used in combination.
  • Si—OH group-containing compound examples include vinyltrihydroxysilane and 3-methacryloxypropyltrihydroxysilane.
  • said Si-OH group containing compound only 1 type may be used and 2 or more types may be used together.
  • insulating particles having a hydroxyl group on the surface can be obtained by a treatment using a silane coupling agent.
  • silane coupling agent include hydroxytrimethoxysilane.
  • the conductive material according to the present invention includes the conductive particles with insulating particles according to the present invention and a binder resin.
  • the conductive particles with insulating particles according to the present invention are dispersed in the binder resin, the first and second insulating particles are hardly detached from the surface of the conductive particles.
  • the conductive particles with insulating particles according to the present invention are preferably dispersed in a binder resin and used as a conductive material.
  • the conductive material is preferably an anisotropic conductive material.
  • the binder resin is not particularly limited. In general, an insulating resin is used as the binder resin.
  • the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for 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 is not particularly limited, and a conventionally known dispersion method can be used.
  • Examples of a method for dispersing conductive particles with insulating particles in a binder resin include, for example, a method in which conductive particles with insulating particles are added to a binder resin and then kneaded and dispersed with a planetary mixer or the like.
  • Conductive particles with particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, kneaded and dispersed with a planetary mixer, etc., and the binder resin is water or organic Examples include a method of adding conductive particles with insulating particles after diluting with a solvent or the like, and kneading and dispersing with a planetary mixer or the like.
  • 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 conductive material according to the present invention is preferably a conductive paste.
  • the conductive paste is excellent in handleability and circuit fillability. Although a relatively large force is applied to the conductive particles with insulating particles when obtaining the conductive paste, the insulating particles are detached from the surface of the conductive particles due to the presence of the second insulating particles. Can be suppressed.
  • the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 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 with insulating particles are efficiently arranged between the electrodes, and the conduction reliability of the connection target member connected by the conductive material is further increased. Get higher.
  • 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, preferably 40% by weight or less, more preferably 20%. % By weight or less, more preferably 15% 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, the conduction reliability between the electrodes is further enhanced.
  • connection structure By using the conductive particles with insulating particles described above, or by using a conductive material including the conductive particles with insulating particles and a binder resin, a connection structure can be obtained by connecting the connection target members. it can.
  • the connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion.
  • the first connection target member preferably has a first electrode on the surface.
  • the second connection object member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles.
  • the connection portion itself is formed of conductive particles with insulating particles. That is, the first and second connection target members are electrically connected by the conductive particles in the conductive particles with insulating particles.
  • FIG. 4 is a cross-sectional view schematically showing a connection structure using the conductive particles 1 with insulating particles shown in FIG.
  • the connection structure 81 shown in FIG. 4 is a connection that connects the first connection target member 82, the second connection target member 83, and the first connection target member 82 and the second connection target member 83.
  • the connecting portion 84 is formed of a conductive material including the conductive particles 1 with insulating particles and a binder resin.
  • the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, conductive particles 21 and 31 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 first and second connection target members 82 and 83 are electrically connected by the conductive particles 2 in the conductive particles 1 with insulating particles.
  • the manufacturing method of the connection structure is not particularly limited.
  • a method of manufacturing a connection structure a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • the first and second insulating particles 3 and 4 existing between the conductive particles 2 and the first and second electrodes 82a and 83a can be eliminated.
  • the first and second insulating particles 3 and 4 existing between the conductive particles 2 and the first and second electrodes 82a and 83a are melted. Or the surface of the conductive particles 2 is partially exposed.
  • some of the first and second insulating particles 3 and 4 are detached from the surface of the conductive particles 2 and the conductive particles.
  • the surface of 2 may be partially exposed. The portion where the surface of the conductive particle 2 is exposed contacts the first and second electrodes 82a and 83a, so that the first and second electrodes 82a and 83a are electrically connected through the conductive particle 2. it can.
  • connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
  • the conductive material is in a paste form, and is preferably applied on the connection target member in a paste state.
  • the conductive particles with insulating particles and the conductive material are preferably used for connection of a connection target member that is an electronic component.
  • the connection target member is preferably an electronic component.
  • the conductive particles with insulating particles are preferably used for electrical connection of electrodes in an electronic component.
  • the conductive particles with insulating particles according to the present invention are particularly suitable for COG having a glass substrate and a semiconductor chip as connection target members, or FOG having a glass substrate and a flexible printed circuit board (FPC) as connection target members. Is done.
  • the conductive particles with insulating particles according to the present invention may be used for COG or FOG.
  • the first and second connection target members are preferably a glass substrate and a semiconductor chip, or a glass substrate and a flexible printed board.
  • the first and second connection target members may be a glass substrate and a semiconductor chip, or may be a glass substrate and a flexible printed board.
  • bumps are provided on a semiconductor chip used in a COG having a glass substrate and a semiconductor chip as connection target members.
  • the bump size is preferably an electrode area of 1000 ⁇ m 2 or more and 10,000 ⁇ m 2 or less.
  • the electrode space in the semiconductor chip provided with the bump (electrode) is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the conductive particles with insulating particles according to the present invention are preferably used.
  • the electrode space is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • 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, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum 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. Examples of the trivalent metal element include Sn, Al, and Ga.
  • Example 1 Electroless plating pretreatment process
  • resin particles Average particle size 3 ⁇ m formed from a copolymer resin of tetramethylolmethanetetraacrylate and divinylbenzene, alkali degreasing with sodium hydroxide aqueous solution, acid neutralization, and sensitizing in tin dichloride solution are performed. It was.
  • the resin particles were treated with an ion adsorbent for 5 minutes and then added to an aqueous palladium sulfate solution. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.
  • a nickel plating solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared.
  • the slurry adjusted to pH 5 was heated to 80 ° C., and then the nickel plating solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.
  • a late nickel plating solution containing 20% by weight of nickel sulfate, 5% by weight of dimethylamine borane and 5% by weight of sodium hydroxide was prepared.
  • the late nickel plating solution was continuously added dropwise to the solution that had undergone the plating reaction with the previous nickel plating solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles, and conductive particles A were obtained.
  • the nickel layer had a thickness of 0.1 ⁇ m.
  • Distilled water was added to the monomer composition so that the solid content was 10% by weight, and the mixture was stirred at 150 rpm and polymerized at 60 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was freeze-dried to obtain first insulating particles (average particle diameter 400 nm) having P—OH groups derived from acid phosphooxypolyoxyethylene glycol methacrylate on the surface.
  • second insulating particles (average particle size 180 nm) were obtained in the same manner except that the stirring speed was changed to 300 rpm and the polymerization temperature was changed to 80 ° C.
  • the insulating particles obtained above were each dispersed in distilled water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
  • 10 g of the obtained conductive particles A were dispersed in 500 mL of distilled water, 3 g of an aqueous dispersion of first insulating particles was added, and the mixture was stirred at room temperature for 3 hours. Further, 2 g of an aqueous dispersion of second insulating particles was added and stirred at room temperature for 3 hours. After filtration through a 3 ⁇ m mesh filter, the product was further washed with methanol and dried to obtain conductive particles with insulating particles.
  • the conductive particles with insulating particles had a coating layer of insulating particles formed on the surface of the conductive particles having protrusions.
  • Example 2 to 4 and Comparative Examples 1 to 3 Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the addition amount of the aqueous dispersion of the first and second insulating particles was changed as shown in Table 1 below.
  • Coverage ratio Z which is the total area of the portions covered with the first and second insulating particles in the entire surface area of the conductive particles
  • the coverage which is the total projected area of the portions covered with the first and second insulating particles occupying the entire surface area of the conductive particles, was determined.
  • the average value of the 20 coverages was defined as the coverage Z.
  • the second insulating material disposed on the surface of the conductive particles so as not to contact the first insulating particles out of the total number of the second insulating particles.
  • the ratio X2 (%) of the number of the functional particles was determined.
  • the number ratio X2 was determined according to the following criteria.
  • the surface of the conductive particles so as not to contact the first insulating particles and to contact the conductive particles out of the total number of the second insulating particles.
  • the ratio X3 (%) of the number of the second insulating particles arranged above was determined.
  • the number ratio X3 was determined according to the following criteria.
  • the average number Y1 of the first insulating particles arranged on the surface of the conductive particles per conductive particle was determined.
  • the average number Y1 was determined according to the following criteria.
  • the average number Y2 of second insulating particles arranged on the surface of the conductive particles per conductive particle was determined.
  • the average number Y2 was determined according to the following criteria.
  • the average number Y1 of the first insulating particles arranged on the surface of the conductive particles per conductive particle is arranged on the surface of the conductive particles per conductive particle.
  • Ratio of the second insulating particles to the average number Y2 (average number Y1 / average number Y2)
  • the ratio (average number Y1 / average number Y2) to the average number Y2 of the second insulating particles arranged on the surface of the conductive particles was determined.
  • the ratio (average number Y1 / average number Y2) was determined according to the following criteria.
  • Ratio (average number Y1 / average number Y2) ratio is 0.005 or more and 0.5 or less
  • C Ratio The ratio of (average number Y1 / average number Y2) exceeds 1.
  • a transparent glass substrate on which an ITO electrode pattern with L / S of 30 ⁇ m / 30 ⁇ m was formed was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 ⁇ m / 30 ⁇ 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 1 MPa is applied to form the anisotropic conductive paste layer. It hardened
  • the conductivity was determined according to the following criteria.
  • ⁇ The ratio of the number of connection structures having a resistance value of 5 ⁇ or less is 80% or more.
  • ⁇ The ratio of the number of connection structures having a resistance value of 5 ⁇ or less is 60% or more and less than 80%.
  • X The resistance value is 5 ⁇ or less. Less than 60% of the number of connection structures
  • Insulation between adjacent electrodes in the horizontal direction
  • conductivity evaluation the presence or absence of leakage between adjacent electrodes was evaluated by measuring resistance with a tester. Insulation was judged according to the following criteria.
  • ⁇ The ratio of the number of connection structures having a resistance value of 10 8 ⁇ or more is 90% or more.
  • ⁇ The ratio of the number of connection structures having a resistance value of 10 8 ⁇ or more is 80% or more and less than 90%.
  • the ratio of the number of connection structures having a value of 10 8 ⁇ or more is 60% or more and less than 80%.
  • X The ratio of the number of connection structures having a resistance value of 10 8 ⁇ or more is less than 60%. Show.

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PCT/JP2013/068116 2012-07-03 2013-07-02 絶縁性粒子付き導電性粒子、導電材料及び接続構造体 WO2014007238A1 (ja)

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