WO2014054572A1 - Conductive particle, conductive material and connecting structure - Google Patents

Conductive particle, conductive material and connecting structure Download PDF

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Publication number
WO2014054572A1
WO2014054572A1 PCT/JP2013/076515 JP2013076515W WO2014054572A1 WO 2014054572 A1 WO2014054572 A1 WO 2014054572A1 JP 2013076515 W JP2013076515 W JP 2013076515W WO 2014054572 A1 WO2014054572 A1 WO 2014054572A1
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Prior art keywords
conductive
particles
conductive layer
layer
particle
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PCT/JP2013/076515
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French (fr)
Japanese (ja)
Inventor
敬三 西岡
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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 KR1020147033188A priority Critical patent/KR102095823B1/en
Priority to CN201380037610.2A priority patent/CN104471650A/en
Priority to JP2013546501A priority patent/JP5636118B2/en
Publication of WO2014054572A1 publication Critical patent/WO2014054572A1/en

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    • H—ELECTRICITY
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    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • H—ELECTRICITY
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    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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    • 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
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    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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    • 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
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    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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    • H05K3/361—Assembling flexible printed circuits with other printed circuits

Definitions

  • the present invention relates to conductive particles in which a conductive material is arranged on the surface of base particles.
  • this invention relates to the electroconductive particle which can be used for the electrical connection between electrodes, for example.
  • the present invention also relates to a conductive material and a connection structure using the conductive particles.
  • Conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known.
  • anisotropic conductive materials conductive particles are dispersed in a binder resin.
  • the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), 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.
  • FOG Glass
  • COF Chip on Film
  • Patent Document 1 discloses conductive particles including composite particles and a metal plating layer covering the composite particles.
  • the composite particles include a plastic core and non-conductive inorganic particles adsorbed on the plastic core by chemical bonding.
  • Patent Document 2 a plastic core, a polymer electrolyte layer covering the plastic core, metal particles adsorbed on the plastic core through the polymer electrolyte layer, and the metal particles are covered.
  • surroundings of the said plastic core is disclosed.
  • Patent Document 2 describes that the metal particles to be adsorbed on the plastic core are, for example, metal particles selected from gold, silver, copper, palladium, and nickel.
  • Patent Document 3 discloses conductive particles in which a multilayer conductive layer of a metal plating film layer containing nickel and phosphorus and a gold layer is formed on the surface of a base material particle.
  • a core substance is disposed on the surface of the base particle, and the core substance is covered with a conductive layer.
  • the conductive layer is raised by the core material, and protrusions are formed on the surface of the conductive layer.
  • the conductive material constituting the core material is a metal
  • examples of the metal include nickel, copper, gold, silver, platinum, zinc, iron, lead, tin, aluminum, cobalt, Consists of metals such as indium, chromium, titanium, antimony, bismuth, germanium and cadmium, and two or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy and tin-lead-silver alloy Alloys and the like are mentioned.
  • Patent Documents 1 to 3 described above disclose conductive particles having protrusions on the outer surface of the conductive layer.
  • an oxide film is formed on the surfaces of the electrodes connected by the conductive particles and the conductive layer of the conductive particles.
  • the protrusion of the conductive layer is formed so as to contact the conductive layer and the electrode by eliminating the oxide film on the surface of the electrode and the conductive particle when the electrodes are pressure-bonded via the conductive particle. .
  • connection resistance may increase. Further, the oxide film on the surface of the electrode and the conductive particles cannot be sufficiently removed, and the connection resistance tends to be relatively high.
  • An object of the present invention is to provide conductive particles capable of reducing the connection resistance between electrodes when the electrodes are connected, and a conductive material and a connection structure using the conductive particles.
  • the method includes a base particle and a conductive material disposed in a partial region on the surface of the base particle, and the material of the conductive material has a Mohs hardness higher than that of nickel.
  • a conductive particle which is a material, is provided.
  • the conductive particle includes the base particle and the conductive material disposed in a partial region on the surface of the base particle,
  • the material of the conductive material is molybdenum, tungsten carbide, tungsten, titanium carbide, or tantalum carbide.
  • the conductive particle includes a plurality of the conductive materials.
  • this electroconductive particle is on the surface of the said base material particle, the electroconductive layer arrange
  • the conductive material disposed in a part of the region, and the conductive material is embedded in the conductive layer.
  • the conductive layer has a protrusion on an outer surface, and the conductive material is disposed inside the protrusion of the conductive layer.
  • the conductive layer has a nickel layer.
  • the conductive layer has a nickel layer on the base particle side and a palladium layer on the side opposite to the base particle side.
  • the conductive particle further includes an insulating substance attached to the surface of the conductive layer.
  • the conductive material is a particle.
  • the conductive particle includes the base particle and the conductive material disposed in a partial region on the surface of the base particle,
  • the material of the conductive material is molybdenum, tungsten carbide, tungsten, or tantalum carbide.
  • a conductive material including the above-described conductive particles 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 connection portion is formed of the conductive particles described above or formed of a conductive material including the conductive 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 particles.
  • the conductive material is disposed in a partial region on the surface of the base particle, and the material of the conductive material is higher in Mohs hardness than nickel.
  • the connection resistance can be lowered.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
  • the electroconductive particle which concerns on this invention is equipped with a base material particle and the electrically conductive material arrange
  • the conductive material is a material having a Mohs hardness higher than that of nickel.
  • the material of the conductive material is preferably molybdenum, tungsten, tungsten carbide, titanium carbide, or tantalum carbide, and is preferably molybdenum, tungsten, tungsten carbide, or tantalum carbide. These materials have high Mohs hardness. When the electrodes are connected using conductive particles including the conductive material of these materials, connection failure between the electrodes hardly occurs, and the connection resistance between the electrodes can be effectively reduced.
  • the electroconductive particle which concerns on this invention is the said base material particle, the electroconductive layer arrange
  • connection resistance can be further reduced.
  • the conductive layer has a protrusion on the outer surface, and the conductive material is disposed inside the protrusion of the conductive layer. It is preferable that the protrusion is formed by the conductive material.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the outer surface of the conductive layer.
  • the oxide film is eliminated by the protrusions by placing the conductive particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle can be contacted still more reliably and the connection resistance between electrodes can be made still lower.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • a conductive particle 1 shown in FIG. 1 includes a base particle 2, a conductive layer 3, a plurality of conductive materials 4, and a plurality of insulating substances 5.
  • the conductive layer 3 is disposed on the surface of the base particle 2. In the conductive particles 1, a single conductive layer 3 is formed.
  • the conductive layer 3 covers the base particle 2.
  • the conductive layer 3 also covers the conductive material 4.
  • the conductive layer 3 has a plurality of protrusions 3a on the outer surface.
  • the conductive particle 1 includes a plurality of conductive materials 4.
  • a plurality of conductive materials 4 are arranged in a partial region on the surface of the base particle 2 and are embedded in the conductive layer 3.
  • the conductive material 4 is not disposed in all regions on the surface of the base particle 2.
  • the conductive material 4 does not cover the entire surface of the base particle 2. Since the conductive material 4 is disposed in a partial region on the surface of the base material particle 2, the base material particle 2 has a surface region that is not in contact with the conductive material 4.
  • the conductive material 4 is disposed inside the protrusion 3a.
  • One conductive material 4 is arranged inside one protrusion 3a.
  • the outer surface of the conductive layer 3 is raised by the plurality of conductive materials 4, and a plurality of protrusions 3a are formed.
  • the conductive material 4 is a particle. Since the conductive material 4 is a particle, the conductive material 4 is arranged in a partial region on the surface of the substrate particle 2.
  • the conductive material 4 is in contact with the substrate particles 2.
  • a conductive layer may be disposed between the surface of the base particle and the surface of the conductive material.
  • the conductive material may not be in contact with the base material particle, and the surface of the base material particle and the surface of the conductive material may be separated from each other.
  • the insulating substance 5 is disposed on the surface of the conductive layer 3.
  • the insulating substance 5 is an insulating particle.
  • the insulating substance 5 is made of an insulating material.
  • the conductive particles do not necessarily include an insulating substance.
  • the conductive particles may include an insulating layer that covers the outer surface of the conductive layer as an insulating substance instead of the insulating particles.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • a conductive particle 11 shown in FIG. 2 includes a base particle 2, a first conductive layer 12, a second conductive layer 13, a plurality of conductive materials 4, and a plurality of insulating substances 5.
  • the conductive particle 1 has a single-layered conductive layer
  • the conductive particle 11 has a two-layered first conductive layer 12 and second conductive layer 13 formed. Yes.
  • the conductive material 4 is embedded in the first conductive layer 11 and the conductive layer 13.
  • the first conductive layer 12 is disposed on the surface of the base particle 2.
  • the first conductive layer 12 is disposed between the base particle 2 and the second conductive layer 13.
  • the first conductive layer 12 is located on the base particle 2 side and is a conductive layer in contact with the base particle 2.
  • the second conductive layer 13 is located on the side opposite to the base particle 2 side and is not in contact with the base particle 2. Therefore, the first conductive layer 12 is disposed on the surface of the base particle 2, and the second conductive layer 13 is disposed on the surface of the first conductive layer 12.
  • the second conductive layer 13 has a plurality of protrusions 13a on the outer surface.
  • the conductive particles 11 have a plurality of protrusions 11a on the conductive surface.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • a conductive particle 21 shown in FIG. 3 includes a base particle 2, a conductive layer 22, and a plurality of conductive materials 4.
  • the conductive layer 22 is disposed on the surface of the base particle 2.
  • the conductive material 4 is embedded in the conductive layer 22.
  • the conductive particles 21 do not have protrusions on the surface.
  • the conductive particles 21 are spherical.
  • the conductive layer 22 does not have a protrusion on the outer surface.
  • the electroconductive particle which concerns on this invention does not need to have a litigation
  • the conductive particles 21 do not have an insulating material.
  • the conductive particles 21 may include an insulating material disposed on the surface of the conductive layer 22.
  • Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. Of these, substrate particles excluding metal particles are preferable, and resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles are more preferable.
  • 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, polyethylene terephthalate, Polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamid Imide, polyether ether ketone, polyether sulfone, divinyl benzene polymer, and diviny
  • polyolefin resins such as polyethylene, polypropylene,
  • 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 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 includes a non-crosslinkable monomer and 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; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate
  • 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 glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure Silane-
  • 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 metal particles are preferably copper particles.
  • the substrate particles are preferably not metal particles.
  • the particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 1.5 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and even more preferably. Is not more than 300 ⁇ m, more preferably not more than 50 ⁇ m, particularly preferably not more than 30 ⁇ m, and most preferably not more than 5 ⁇ m.
  • the particle diameter of the substrate particles is equal to or greater than the above lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased, and the electrodes are connected via the conductive particles. The connection resistance between them becomes even lower.
  • the particle diameter of the base particle indicates a diameter when the base particle is a true sphere, and indicates a maximum diameter when the base particle is not a true sphere.
  • the particle diameter of the substrate particles is particularly preferably 2 ⁇ m or more and 5 ⁇ m or less. When the particle diameter of the substrate particles is in the range of 2 to 5 ⁇ m, even when the distance between the electrodes is small and the conductive layer is thick, small conductive particles can be obtained.
  • the particle diameter of the substrate particles is also preferably 3 ⁇ m or less.
  • the electroconductive particle which concerns on this invention has the electroconductive layer arrange
  • the metal for forming the conductive layer is not particularly limited.
  • 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.
  • the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
  • 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 a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver. Is preferable, and a palladium layer or a gold layer is more preferable.
  • the outermost layer is preferably a palladium layer, and is preferably a gold layer.
  • the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.
  • the nickel layer contains 50% by weight or more of nickel.
  • the palladium layer or the gold layer contains 50% by weight or more of palladium or gold.
  • the conductive layer in contact with the substrate particles contains nickel.
  • the conductive layer is a single layer like the conductive particles 1 and 21, the conductive layer preferably contains nickel.
  • the first conductive layer (base The conductive layer in contact with the material particles preferably contains nickel.
  • the conductive layer and the first conductive layer preferably contain nickel as a main component. The conductivity of the conductive layer containing nickel is relatively high. Therefore, when the electrodes are connected by conductive particles having a conductive layer containing nickel, the connection resistance between the electrodes is further reduced.
  • the nickel content is preferably 50% by weight or more.
  • the content of nickel is preferably 50% by weight or more in 100% by weight of the conductive layer.
  • the conductive layer includes the first and second conductive layers, the content of nickel in 100% by weight of the first conductive layer is preferably 50% by weight or more.
  • the connection resistance between the electrodes is considerably low.
  • the nickel content is more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
  • the content of nickel in the conductive layer or 100% by weight of the first conductive layer may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more. Good.
  • the content of nickel in the conductive layer or 100% by weight of the first conductive layer is preferably 99.85% by weight or less, more preferably 99.7% by weight or less, and still more preferably less than 99.45% by weight. .
  • the connection resistance between the electrodes is further reduced.
  • there are few oxide films in the surface of an electrode or a conductive layer there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.
  • the conductive layer or the first conductive layer preferably contains nickel and at least one of boron and phosphorus.
  • nickel and at least one of boron and phosphorus may be alloyed.
  • components other than nickel, boron, and phosphorus may be used.
  • the connection structure when the connection structure is exposed to the presence of an acid, the connection resistance between the electrodes may increase. Therefore, the conductive layer or the first conductive layer has a high phosphorus content in the nickel layer on the base particle side and a low phosphorus content in the nickel layer on the side opposite to the base particle. May be good.
  • the total content of boron and phosphorus in the conductive layer or 100% by weight of the first conductive layer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1%. % By weight or more, preferably 5% by weight or less, more preferably 4% by weight or less, further preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less.
  • the total content of boron and phosphorus is not less than the above lower limit, the conductive layer or the first conductive layer becomes harder, and the oxide film on the surface of the electrode and conductive particles is more effectively removed.
  • the connection resistance between the electrodes can be further reduced.
  • the total content of boron and phosphorus is not more than the above upper limit, the content of nickel is relatively increased, so that the connection resistance between the electrodes is reduced.
  • the boron content in the conductive layer or 100% by weight of the first conductive layer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably Is 5% by weight or less, more preferably 4% by weight or less, further preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less.
  • the boron content is not less than the above lower limit, the conductive layer or the first conductive layer becomes harder, and the oxide film on the surface of the electrode and the conductive particles can be more effectively removed.
  • the connection resistance can be further reduced. If the boron content is less than or equal to the above upper limit, the nickel content is relatively increased, so that the connection resistance between the electrodes is reduced.
  • the conductive layer or the first conductive layer does not contain phosphorus or contains phosphorus, and the content of phosphorus in 100% by weight of the conductive layer or the first conductive layer is less than 10.0% by weight. Is preferred.
  • the content of phosphorus in 100% by weight of the conductive layer is more preferably less than 0.5% by weight, still more preferably 0.3% by weight or less, and particularly preferably 0.1% by weight or less. It is particularly preferable that the conductive layer or the first conductive layer does not contain phosphorus.
  • the method for measuring each content of nickel, boron, phosphorus, etc. in the conductive layer or the first conductive layer is not particularly limited, and various known analytical methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer, or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.
  • ICP emission spectrometer When measuring the content of nickel, boron, phosphorus, etc. in the conductive layer or the first conductive layer, it is preferable to use an ICP emission spectrometer.
  • ICP emission analyzers include ICP emission analyzers manufactured by HORIBA.
  • the conductive layer preferably has a nickel layer on the base particle side and a second conductive layer on the side opposite to the base particle side.
  • the second conductive layer is preferably a palladium layer or a gold layer, more preferably a palladium layer, and more preferably a gold layer.
  • the method for forming the conductive layer or the first conductive layer on the surface of the substrate particles and the method for forming the second conductive layer on the surface of the first conductive layer are 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 paste containing metal powder or metal powder and a binder is used for base particles or other conductive layers.
  • a method of coating the surface for example, since formation of a conductive layer is simple, the method by electroless plating is preferable.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • 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 20 ⁇ m or less.
  • the particle diameter of the conductive particles is not less than the above 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 electrode is sufficiently large, and the conductive layer is formed. Aggregated conductive particles are less likely to be formed during formation. 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 particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
  • the total thickness of the conductive layer in the conductive particles and the thickness of the conductive layer when the conductive layer is a single layer are preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably It is 1 ⁇ m or less, 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. To do.
  • the thickness of the conductive layer (first conductive layer) in contact with the substrate particles is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, and still more preferably. It is 0.05 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less, and still more preferably 0.1 ⁇ m or less.
  • the thickness of the conductive layer in contact with the substrate particles is not less than the above lower limit and not more than the above upper limit, the coating with the conductive layer can be made uniform and the connection resistance between the electrodes becomes sufficiently low.
  • the thickness of the entire conductive layer in the conductive particles and the thickness of the conductive layer when the conductive layer is a single layer are particularly preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less. Furthermore, when the particle diameter of the substrate particles is 2 ⁇ m or more and 5 ⁇ m or less, and the thickness of the entire conductive layer in the conductive particles and the conductive layer is a single layer, the thickness of the conductive layer is 0.05 ⁇ m or more, 0. It is particularly preferable that the thickness is 3 ⁇ m or less. In this case, the conductive particles can be suitably used for applications in which a large current flows. Furthermore, when the conductive particles are compressed to connect the electrodes, it is possible to further suppress the electrodes from being damaged.
  • the thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • a method for controlling the contents of nickel, boron and phosphorus in the conductive layer and the first conductive layer for example, a method of controlling the pH of the nickel plating solution when forming the conductive layer by electroless nickel plating
  • a method of adjusting the concentration of the boron-containing reducing agent when forming the conductive layer by electroless nickel plating, a method of adjusting the concentration of the phosphorus-containing reducing agent when forming the conductive layer by electroless nickel plating, and A method for adjusting the nickel concentration in the nickel plating solution is exemplified.
  • a catalytic step and an electroless plating step are performed.
  • an example of a method for forming an alloy plating layer containing nickel and boron on the surface of resin particles by electroless plating will be described.
  • a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
  • the surface of the resin particles is activated with an acid solution or an alkali solution
  • the reducing agent a boron-containing reducing agent is preferably used.
  • a conductive layer containing phosphorus can be formed by using a phosphorus-containing reducing agent as the reducing agent.
  • a nickel plating bath containing a nickel-containing compound and the boron-containing reducing agent is preferably used.
  • nickel By immersing the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and a conductive layer containing nickel and boron can be formed.
  • nickel-containing compound examples include nickel sulfate and nickel chloride.
  • the nickel-containing compound is preferably a nickel salt.
  • Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, potassium borohydride, and the like.
  • Examples of the phosphorus-containing reducing agent include sodium hypophosphite.
  • the electroconductive particle which concerns on this invention is equipped with the electrically conductive material arrange
  • the conductive material is made of molybdenum (Mo) (Mohs hardness 5.5), tungsten (W) (Mohs hardness 7.5), tungsten carbide (WC) (Mohs hardness 9), titanium carbide (TiC) (Mohs hardness). 9) or tantalum carbide (TaC) (Mohs hardness 9).
  • the Mohs hardness of the material of the conductive material is higher than the Mohs hardness of nickel (Ni) (Mohs hardness 5.0).
  • the material of the conductive material is preferably tungsten carbide or tantalum carbide.
  • the material of the conductive material is preferably molybdenum, preferably tungsten, preferably tungsten carbide, preferably titanium carbide, and preferably tantalum carbide.
  • the value of the powder resistivity of the conductive material is preferably 0.1 ⁇ ⁇ cm or less.
  • the conductive particles according to the present invention preferably have protrusions on the conductive surface.
  • the conductive layer preferably has a protrusion on the outer surface. It is preferable that there are a plurality of the protrusions.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive layer of the conductive particles.
  • an electrode and electroconductive particle can be contacted still more reliably and the connection resistance between electrodes can be made low.
  • the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles are projected between the conductive particles and the electrodes by the protrusions of the conductive particles. Can be effectively eliminated. For this reason, the conduction
  • the conductive layer It is easy for the conductive layer to have a plurality of protrusions on the outer surface by embedding the conductive material in the conductive layer.
  • the conductive material may or may not be in contact with the base material particles.
  • a part of the conductive layer may be disposed between the base particle and the conductive material.
  • the conductive particles according to the present invention preferably include a plurality of the conductive materials.
  • the conductive part of the conductive particles can be hardened at a place where the plurality of conductive materials are arranged inside the conductive layer. Moreover, it is easy to form a plurality of protrusions on the surfaces of the conductive particles and the conductive layer.
  • the conductive material is preferably particles.
  • the conductive part of the conductive particles can be effectively hardened due to the shape of the conductive material that is the particles disposed inside the conductive layer. Moreover, it is easy to form a plurality of protrusions on the surfaces of the conductive particles and the conductive layer.
  • the shape of the conductive material that is a particle is preferably a lump.
  • Examples of the conductive material that is a particle include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
  • the maximum diameter of the conductive material is preferably 0.005D or more, more preferably 0.015D or more, preferably 0.25D or less, more preferably 0.15D or less. It is.
  • the size of the conductive material in the thickness direction of the conductive layer is preferably 0.005D or more, more preferably 0.015D or more, preferably 0.00. 25D or less, more preferably 0.15D or less.
  • the conductive material is attached to the surface of the base particle, and then the conductive layer is formed by electroless plating, and the conductive layer is formed by electroless plating on the surface of the base particle. Then, the method of making the said conductive material adhere and forming a conductive layer by electroless plating etc. is mentioned.
  • the first conductive layer is formed on the surface of the base particle, and then the conductive material is disposed on the first conductive layer, and then the second conductive layer is formed. Examples thereof include a method of forming a layer, and a method of adding the conductive material in the middle of forming a conductive layer on the surface of the base particle.
  • the number of the conductive material and the number of the protrusions per one conductive particle are preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of the conductive materials and the number of the protrusions is not particularly limited. The upper limit of the number of the conductive materials and the number of the protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
  • the conductive particles according to the present invention preferably include an insulating substance disposed on the surface of the conductive layer.
  • an insulating substance disposed on the surface of the conductive layer.
  • an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes.
  • the insulating substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes.
  • the insulating substance between the conductive layer of the conductive particles and the electrode can be easily excluded.
  • the insulating substance is preferably an insulating particle because the insulating substance can be more easily removed during crimping between the electrodes.
  • the conductive material according to the present invention includes the conductive particles described above and a binder resin.
  • the conductive 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.
  • As the binder resin a known insulating resin is used.
  • 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, a heat stabilizer, and a light stabilizer.
  • a filler for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
  • the method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used.
  • Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse
  • distributing is mentioned.
  • 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 the conductive film that includes the conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, 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 are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
  • the content of the conductive 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, it is 10 weight% or less.
  • the content of the conductive 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 can be obtained by connecting the connection target members using the conductive particles of the present invention or using a conductive material containing the conductive particles and a binder resin.
  • connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member.
  • the connection structure is preferably formed of the conductive particles of the present invention or formed of a conductive material containing the conductive particles and a binder resin.
  • the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
  • FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
  • connection portion 54 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 that connects the first and second connection target members 52 and 53.
  • the connection portion 54 is formed by curing a conductive material including the conductive particles 1.
  • the conductive particles 1 are schematically shown for convenience of illustration.
  • the first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
  • the first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
  • 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 pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • 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 preferably a conductive material for connecting electronic components.
  • the conductive material is a paste-like conductive paste, and is preferably applied on the connection target member in a paste-like state.
  • 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.
  • the conductive particles can be used as a conductive material for electrical connection between the upper and lower substrates constituting the liquid crystal display element.
  • Conductive particles are mixed with thermosetting resin or thermosetting resin combined with heat UV, dispersed, applied in a dot pattern on one side of the substrate, and bonded to the counter substrate, and the conductive particles are mixed with the peripheral sealant.
  • thermosetting resin or thermosetting resin combined with heat UV, dispersed, applied in a dot pattern on one side of the substrate, and bonded to the counter substrate
  • the conductive particles are mixed with the peripheral sealant
  • the electroconductive particle which concerns on this invention is applicable also to such a usage form.
  • the powder resistivity of the conductive material used in the following examples showed a value of 0.1 ⁇ ⁇ cm or less.
  • the powder resistivity of the conductive material is molybdenum (Mo) (0.001 ⁇ ⁇ cm), tungsten (W) (0.001 ⁇ ⁇ cm), tungsten carbide (WC) (0.005 ⁇ ⁇ cm).
  • Mo molybdenum
  • W tungsten
  • WC tungsten carbide
  • TiC titanium carbide
  • TaC tantalum carbide
  • the powder resistivity was determined by a powder resistivity measurement system “Lorestar GP” manufactured by Mitsubishi Chemical Corporation using 2.5 g of a conductive material and a powder resistivity at a load of 20 kN at 23 ° C. .
  • Example 1 Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to remove the particles, washed with water, and dried to obtain conductive particles having a nickel layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles to which the conductive material is attached. Obtained.
  • the content of nickel in 100% by weight of the nickel layer was 98.9% by weight, and the content of boron was 1.1% by weight.
  • the obtained conductive particles have a plurality of conductive materials embedded in the conductive layer, have a plurality of protrusions on the outer surface of the conductive layer, and the conductive material is disposed inside the protrusions of the conductive layer. It was.
  • Example 2 Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to tungsten particles (average particle size 100 nm).
  • Example 3 Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to tantalum carbide particles (average particle size 100 nm).
  • Example 4 Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to molybdenum particles (average particle size 100 nm).
  • Example 5 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
  • Step of attaching insulating particles The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of insulating particles.
  • Example 2 10 g of the conductive particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
  • Example 6 Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 2. .
  • Example 7 Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 3. .
  • Example 8 Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 4. .
  • Example 9 10 g of the conductive particles obtained in Example 1 were added to 500 mL of ion-exchanged water and sufficiently dispersed with an ultrasonic processor to obtain a suspension. While stirring the suspension at 50 ° C., 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.06 mol / L of sodium formate as a reducing agent, and pH 10.0 containing a crystal modifier. An electroless plating solution was prepared.
  • the electroless plating solution was gradually added to the obtained suspension, and electroless palladium plating was performed. When the thickness of the palladium layer reached 0.03 ⁇ m, the electroless palladium plating was finished. Next, by washing and vacuum drying, conductive particles having a palladium layer (thickness: 0.03 ⁇ m) laminated on the surface of the nickel layer were obtained.
  • Example 10 Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 2.
  • Example 11 Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 3.
  • Example 12 Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 4.
  • Divinylbenzene resin particles having a particle size of 3.0 ⁇ m (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) and divinylbenzene resin particles having a particle size of 2.5 ⁇ m (“Micropearl SP manufactured by Sekisui Chemical Co., Ltd.) are used. Conductive particles were obtained in the same manner as in Example 1 except for changing to -2025 ").
  • Example 14 (1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • Electroless nickel plating step A nickel plating solution (pH 9.0) containing nickel sulfate 0.25 mol / L, sodium hypophosphite 0.25 mol / L and sodium citrate 0.15 mol / L was prepared.
  • the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-phosphorous conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles.
  • Example 15 (1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating.
  • a nickel plating solution (pH 10.0) containing nickel sulfate 0.25 mol / L, sodium hypophosphite 0.25 mol / L and sodium citrate 0.15 mol / L was gradually added dropwise to the suspension. Electroless nickel plating was performed. Thereafter, the suspension was filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-phosphorous conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles.
  • Example 16 (1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • Nickel plating solution containing 0.23 mol / L nickel sulfate, 0.92 mol / L dimethylamine borane, 0.5 mol / L sodium citrate and 0.01 mol / L sodium tungstate (pH 8. 5) 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 obtain conductive particles having a nickel-tungsten-boron conductive layer (thickness of about 0.1 ⁇ m) on the surface of the resin particles. Obtained.
  • Example 1 Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to copper particles (average particle size 100 nm).
  • Example 2 Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to silica particles (average particle size 100 nm).
  • Example 17 (1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
  • connection resistance Fabrication of connection structure 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP” manufactured by HX3941) and 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight.
  • a resin composition was obtained by dispersing.
  • the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
  • the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
  • the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
  • a two-layer flexible printed board width 2 cm, length 1 cm having the same aluminum electrode was bonded after being aligned so that the electrodes overlap each other.
  • the laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
  • a two-layer flexible printed board in which an aluminum electrode is directly formed on a polyimide film was used.
  • connection resistance measurement The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Further, the connection resistance was determined according to the following criteria.
  • connection resistance ⁇ : Less than 90% of connection resistance when using conductive particles of Reference Example 1 ⁇ : 90% or more and less than 95% of connection resistance when using conductive particles of Reference Example 1 ⁇ : Reference Example 1 95% or more of connection resistance when using conductive particles of less than 105% ⁇ : 105% or more of connection resistance when using conductive particles of Reference Example 1

Abstract

Provided are: a conductive particle whereby connection resistance can be reduced in the cases where electrodes are connected to each other; and a conductive material using the conductive particle. A conductive particle (1) of the present invention is provided with a base material particle (2), and a conductive material (4) that is disposed on a region of the base material particle (2), said region being a part of the surface of the base material particle, and the conductive material (4) is a material having a Mohs hardness higher than that of nickel.

Description

導電性粒子、導電材料及び接続構造体Conductive particles, conductive materials, and connection structures
　本発明は、基材粒子の表面上に導電材が配置されている導電性粒子に関する。より詳細には、本発明は、例えば、電極間の電気的な接続に用いることができる導電性粒子に関する。また、本発明は、上記導電性粒子を用いた導電材料及び接続構造体に関する。 The present invention relates to conductive particles in which a conductive material is arranged on the surface of base particles. In more detail, this invention relates to the electroconductive particle which can be used for the electrical connection between electrodes, for example. The present invention also relates to a conductive material and a connection structure using the conductive particles.
　異方性導電ペースト及び異方性導電フィルム等の導電材料が広く知られている。これらの異方性導電材料では、バインダー樹脂中に導電性粒子が分散されている。 Conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In these anisotropic conductive materials, conductive particles are dispersed in a binder resin.
　上記異方性導電材料は、各種の接続構造体を得るために、例えば、フレキシブルプリント基板とガラス基板との接続（ＦＯＧ（Ｆｉｌｍ　ｏｎ　Ｇｌａｓｓ））、半導体チップとフレキシブルプリント基板との接続（ＣＯＦ（Ｃｈｉｐ　ｏｎ　Ｆｉｌｍ））、半導体チップとガラス基板との接続（ＣＯＧ（Ｃｈｉｐ　ｏｎ　Ｇｌａｓｓ））、並びにフレキシブルプリント基板とガラスエポキシ基板との接続（ＦＯＢ（Ｆｉｌｍ　ｏｎ　Ｂｏａｒｄ））等に使用されている。 In order to obtain various connection structures, for example, the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), 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.
　上記導電性粒子の一例として、下記の特許文献１には、複合粒子と、該複合粒子を覆う金属めっき層とを備える導電性粒子が開示されている。上記複合粒子は、プラスチック核体と、該プラスチック核体に化学結合により吸着した非導電性無機粒子とを有する。 As an example of the conductive particles, Patent Document 1 below discloses conductive particles including composite particles and a metal plating layer covering the composite particles. The composite particles include a plastic core and non-conductive inorganic particles adsorbed on the plastic core by chemical bonding.
　下記の特許文献２には、プラスチック核体と、該プラスチック核体を覆う高分子電解質層と、該高分子電解質層を介して上記プラスチック核体に吸着した金属粒子と、該金属粒子を覆うように上記プラスチック核体の周囲に形成された無電解金属めっき層とを備える導電性粒子が開示されている。特許文献２では、上記プラスチック核体に吸着させる金属粒子が、例えば、金、銀、銅、パラジウム及びニッケルから選ばれる金属の粒子であることが記載されている。 In Patent Document 2 below, a plastic core, a polymer electrolyte layer covering the plastic core, metal particles adsorbed on the plastic core through the polymer electrolyte layer, and the metal particles are covered. The electroconductive particle provided with the electroless metal plating layer formed in the circumference | surroundings of the said plastic core is disclosed. Patent Document 2 describes that the metal particles to be adsorbed on the plastic core are, for example, metal particles selected from gold, silver, copper, palladium, and nickel.
　下記の特許文献３には、基材粒子の表面に、ニッケル及びリンを含有する金属めっき被膜層と金層との多層の導電層が形成されている導電性粒子が開示されている。該導電性粒子では、基材粒子の表面上に芯物質が配置されており、該芯物質は導電層により被覆されている。芯物質により導電層が隆起されており、導電層の表面に突起が形成されている。特許文献３では、上記芯物質を構成する導電性物質が金属である場合に、該金属としては、例えば、ニッケル、銅、金、銀、白金、亜鉛、鉄、鉛、錫、アルミニウム、コバルト、インジウム、クロム、チタン、アンチモン、ビスマス、ゲルマニウム及びカドミウム等の金属、並びに錫－鉛合金、錫－銅合金、錫－銀合金及び錫－鉛－銀合金等の２種類以上の金属で構成される合金等が挙げられている。 The following Patent Document 3 discloses conductive particles in which a multilayer conductive layer of a metal plating film layer containing nickel and phosphorus and a gold layer is formed on the surface of a base material particle. In the conductive particles, a core substance is disposed on the surface of the base particle, and the core substance is covered with a conductive layer. The conductive layer is raised by the core material, and protrusions are formed on the surface of the conductive layer. In Patent Document 3, when the conductive material constituting the core material is a metal, examples of the metal include nickel, copper, gold, silver, platinum, zinc, iron, lead, tin, aluminum, cobalt, Consists of metals such as indium, chromium, titanium, antimony, bismuth, germanium and cadmium, and two or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy and tin-lead-silver alloy Alloys and the like are mentioned.
特開２０１１－２９１７９号公報JP2011-29179A 特開２０１１－１０８４４６号公報JP 2011-108446 A 特開２００６－２２８４７５号公報JP 2006-228475 A
　上述した特許文献１～３には、導電層の外側の表面に突起を有する導電性粒子が開示されている。導電性粒子により接続される電極、及び導電性粒子の導電層の表面には、酸化被膜が形成されていることが多い。上記導電層の突起は、導電性粒子を介して電極間を圧着する際に、電極及び導電性粒子の表面の酸化被膜を排除して、導電層と電極とを接触させるために形成されている。 Patent Documents 1 to 3 described above disclose conductive particles having protrusions on the outer surface of the conductive layer. In many cases, an oxide film is formed on the surfaces of the electrodes connected by the conductive particles and the conductive layer of the conductive particles. The protrusion of the conductive layer is formed so as to contact the conductive layer and the electrode by eliminating the oxide film on the surface of the electrode and the conductive particle when the electrodes are pressure-bonded via the conductive particle. .
　しかしながら、特許文献１～３に記載のような従来の導電性粒子を用いて電極間を接続した場合には、接続抵抗が高くなることがある。また、電極及び導電性粒子の表面の酸化被膜を十分に排除できずに、接続抵抗が比較的高くなりやすい。 However, when the electrodes are connected using conventional conductive particles as described in Patent Documents 1 to 3, the connection resistance may increase. Further, the oxide film on the surface of the electrode and the conductive particles cannot be sufficiently removed, and the connection resistance tends to be relatively high.
　また、近年、電極間の接続抵抗をより一層低くすることを可能にする導電性粒子が望まれている。 In recent years, conductive particles that can further reduce the connection resistance between electrodes have been desired.
　本発明の目的は、電極間を接続した場合に、電極間の接続抵抗を低くすることができる導電性粒子、並びに該導電性粒子を用いた導電材料及び接続構造体を提供することである。 An object of the present invention is to provide conductive particles capable of reducing the connection resistance between electrodes when the electrodes are connected, and a conductive material and a connection structure using the conductive particles.
　本発明の広い局面によれば、基材粒子と、前記基材粒子の表面上の一部の領域に配置された導電材とを備え、前記導電材の材質が、ニッケルよりもモース硬度が高い材質である、導電性粒子が提供される。 According to a wide aspect of the present invention, the method includes a base particle and a conductive material disposed in a partial region on the surface of the base particle, and the material of the conductive material has a Mohs hardness higher than that of nickel. A conductive particle, which is a material, is provided.
　本発明に係る導電性粒子のある特定の局面では、前記導電性粒子は、前記基材粒子と、前記基材粒子の表面上の一部の領域に配置された前記導電材とを備え、前記導電材の材質が、モリブデン、炭化タングステン、タングステン、炭化チタン又は炭化タンタルである。 In a specific aspect of the conductive particle according to the present invention, the conductive particle includes the base particle and the conductive material disposed in a partial region on the surface of the base particle, The material of the conductive material is molybdenum, tungsten carbide, tungsten, titanium carbide, or tantalum carbide.
　本発明に係る導電性粒子のある特定の局面では、該導電性粒子は、複数の前記導電材を備える。 In a specific aspect of the conductive particle according to the present invention, the conductive particle includes a plurality of the conductive materials.
　本発明に係る導電性粒子のある特定の局面では、該導電性粒子は、前記基材粒子と、前記基材粒子の表面上に配置されている導電層と、前記基材粒子の表面上の一部の領域に配置されている前記導電材とを備え、前記導電材が、前記導電層内に埋め込まれている。 On the specific situation with the electroconductive particle which concerns on this invention, this electroconductive particle is on the surface of the said base material particle, the electroconductive layer arrange | positioned on the surface of the said base material particle, and the said base material particle The conductive material disposed in a part of the region, and the conductive material is embedded in the conductive layer.
　本発明に係る導電性粒子のある特定の局面では、前記導電層が外側の表面に突起を有し、前記導電層の前記突起の内側に前記導電材が配置されている。 In a specific aspect of the conductive particle according to the present invention, the conductive layer has a protrusion on an outer surface, and the conductive material is disposed inside the protrusion of the conductive layer.
　本発明に係る導電性粒子のある特定の局面では、前記導電層がニッケル層を有する。 In a specific aspect of the conductive particles according to the present invention, the conductive layer has a nickel layer.
　本発明に係る導電性粒子のある特定の局面では、前記導電層が、前記基材粒子側にニッケル層と、前記基材粒子側とは反対側にパラジウム層とを有する。 In a specific aspect of the conductive particles according to the present invention, the conductive layer has a nickel layer on the base particle side and a palladium layer on the side opposite to the base particle side.
　本発明に係る導電性粒子のある特定の局面では、該導電性粒子は、前記導電層の表面に付着している絶縁性物質をさらに備える。 In a specific aspect of the conductive particle according to the present invention, the conductive particle further includes an insulating substance attached to the surface of the conductive layer.
　本発明に係る導電性粒子のある特定の局面では、前記導電材が粒子である。 In a specific aspect of the conductive particle according to the present invention, the conductive material is a particle.
　本発明に係る導電性粒子のある特定の局面では、前記導電性粒子は、前記基材粒子と、前記基材粒子の表面上の一部の領域に配置された前記導電材とを備え、前記導電材の材質が、モリブデン、炭化タングステン、タングステン又は炭化タンタルである。 In a specific aspect of the conductive particle according to the present invention, the conductive particle includes the base particle and the conductive material disposed in a partial region on the surface of the base particle, The material of the conductive material is molybdenum, tungsten carbide, tungsten, or tantalum carbide.
　本発明の広い局面によれば、上述した導電性粒子と、バインダー樹脂とを含む、導電材料が提供される。 According to a wide aspect of the present invention, there is provided a conductive material including the above-described conductive particles and a binder resin.
　本発明の広い局面によれば、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、前記第１の接続対象部材と前記第２の接続対象部材を接続している接続部とを備え、前記接続部が、上述した導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されており、前記第１の電極と前記第２の電極とが前記導電性粒子により電気的に接続されている、接続構造体が提供される。 According to a wide aspect of the present invention, 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, and the A connection portion connecting the second connection target member, wherein the connection portion is formed of the conductive particles described above or formed of a conductive material including the conductive particles and a binder resin. In addition, a connection structure is provided in which the first electrode and the second electrode are electrically connected by the conductive particles.
　本発明に係る導電性粒子は、基材粒子の表面上の一部の領域に導電材が配置されており、上記導電材の材質が、ニッケルよりもモース硬度が高い材質であるので、本発明に係る導電性粒子を用いて電極間を接続した場合に、接続抵抗を低くすることができる。 In the conductive particles according to the present invention, the conductive material is disposed in a partial region on the surface of the base particle, and the material of the conductive material is higher in Mohs hardness than nickel. When the electrodes are connected using the conductive particles according to the above, the connection resistance can be lowered.
図１は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. 図２は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention. 図３は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention. 図４は、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体を模式的に示す正面断面図である。FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
　以下、本発明の詳細を説明する。 Hereinafter, the details of the present invention will be described.
　（導電性粒子）
　本発明に係る導電性粒子は、基材粒子と、該基材粒子の表面上の一部の領域に配置された導電材とを備える。上記導電材の材質が、ニッケルよりもモース硬度が高い材質である。 (Conductive particles)
The electroconductive particle which concerns on this invention is equipped with a base material particle and the electrically conductive material arrange | positioned in the one part area | region on the surface of this base material particle. The conductive material is a material having a Mohs hardness higher than that of nickel.
　本発明に係る導電性粒子における上述した構成の採用によって、本発明に係る導電性粒子を用いて電極間を接続した場合に、電極間の接続不良が生じ難くなり、更に電極間の接続抵抗を効果的に低くすることができる。 By adopting the above-described configuration in the conductive particles according to the present invention, when the electrodes are connected using the conductive particles according to the present invention, poor connection between the electrodes is less likely to occur, and the connection resistance between the electrodes is further reduced. It can be effectively lowered.
　上記導電材の材質は、モリブデン、タングステン、炭化タングステン、炭化チタン又は炭化タンタルであることが好ましく、モリブデン、タングステン、炭化タングステン、又は炭化タンタルであることも好ましい。これらの材質のモース硬度は高い。これらの材質の導電材を備える導電性粒子を用いて電極間を接続した場合には、電極間の接続不良が生じ難くなり、更に電極間の接続抵抗を効果的に低くすることができる。 The material of the conductive material is preferably molybdenum, tungsten, tungsten carbide, titanium carbide, or tantalum carbide, and is preferably molybdenum, tungsten, tungsten carbide, or tantalum carbide. These materials have high Mohs hardness. When the electrodes are connected using conductive particles including the conductive material of these materials, connection failure between the electrodes hardly occurs, and the connection resistance between the electrodes can be effectively reduced.
　本発明に係る導電性粒子は、上記基材粒子と、上記基材粒子の表面上に配置されている導電層と、上記基材粒子の表面上の一部の領域に配置されている上記導電材とを備えることが好ましい。この場合に、上記導電材は、上記導電層内に埋め込まれていることが好ましい。上記導電層の一部の領域が、上記基材粒子と接していることが好ましい。 The electroconductive particle which concerns on this invention is the said base material particle, the electroconductive layer arrange | positioned on the surface of the said base material particle, and the said electroconductivity arrange | positioned in the one part area | region on the surface of the said base material particle. It is preferable to provide a material. In this case, it is preferable that the conductive material is embedded in the conductive layer. It is preferable that a partial region of the conductive layer is in contact with the base material particles.
　上記導電層内に上記導電材が埋め込まれている導電性粒子を用いることによって、導電性粒子を用いて電極間を接続した場合に、電極間の接続不良がより一層生じ難くなり、更に電極間の接続抵抗をより一層低くすることができる。 By using the conductive particles in which the conductive material is embedded in the conductive layer, when the electrodes are connected using the conductive particles, poor connection between the electrodes is further less likely to occur. The connection resistance can be further reduced.
　本発明に係る導電性粒子では、上記導電層が外側の表面に突起を有し、上記導電層の上記突起の内側に上記導電材が配置されていることが好ましい。上記導電材によって、上記突起が形成されていることが好ましい。 In the conductive particles according to the present invention, it is preferable that the conductive layer has a protrusion on the outer surface, and the conductive material is disposed inside the protrusion of the conductive layer. It is preferable that the protrusion is formed by the conductive material.
　導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。さらに、上記導電層の外側の表面には、酸化被膜が形成されていることが多い。上記導電層が外側の表面に複数の突起を有することにより、電極間に導電性粒子を配置した後、圧着させることにより、突起により酸化被膜が排除される。このため、電極と導電性粒子とをより一層確実に接触させることができ、電極間の接続抵抗を更に一層低くすることができる。 An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the outer surface of the conductive layer. When the conductive layer has a plurality of protrusions on the outer surface, the oxide film is eliminated by the protrusions by placing the conductive particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle can be contacted still more reliably and the connection resistance between electrodes can be made still lower.
　以下、図面を参照しつつ本発明の具体的な実施形態及び実施例を説明することにより、本発明を明らかにする。 Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.
　図１は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。 FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
　図１に示す導電性粒子１は、基材粒子２と、導電層３と、複数の導電材４と、複数の絶縁性物質５とを備える。導電層３は、基材粒子２の表面上に配置されている。導電性粒子１では、単層の導電層３が形成されている。導電層３は、基材粒子２を被覆している。導電層３は、導電材４も被覆している。導電層３は、外側の表面に複数の突起３ａを有する。
A conductive particle 1 shown in FIG. 1 includes a base particle 2, a conductive layer 3, a plurality of conductive materials 4, and a plurality of insulating substances 5. The conductive layer 3 is disposed on the surface of the base particle 2. In the conductive particles 1, a single conductive layer 3 is formed. The conductive layer 3 covers the base particle 2. The conductive layer 3 also covers the conductive material 4. The conductive layer 3 has a plurality of protrusions 3a on the outer surface.

　導電性粒子１は、複数の導電材４を備える。複数の導電材４が、基材粒子２の表面上の一部の領域に配置されており、導電層３内に埋め込まれている。導電材４は、基材粒子２の表面上の全ての領域に配置されていない。導電材４は、基材粒子２の表面全体を被覆していない。導電材４が基材粒子２の表面上の一部の領域に配置されているので、基材粒子２は、導電材４に接していない表面の領域を有する。導電材４は、突起３ａの内側に配置されている。１つの突起３ａの内側に１つの導電材４が配置されている。複数の導電材４により導電層３の外側の表面が隆起されており、複数の突起３ａが形成されている。導電性粒子が複数の導電材を備えることで、導電性粒子の外側の表面に複数の突起を形成することが容易である。
The conductive particle 1 includes a plurality of conductive materials 4. A plurality of conductive materials 4 are arranged in a partial region on the surface of the base particle 2 and are embedded in the conductive layer 3. The conductive material 4 is not disposed in all regions on the surface of the base particle 2. The conductive material 4 does not cover the entire surface of the base particle 2. Since the conductive material 4 is disposed in a partial region on the surface of the base material particle 2, the base material particle 2 has a surface region that is not in contact with the conductive material 4. The conductive material 4 is disposed inside the protrusion 3a. One conductive material 4 is arranged inside one protrusion 3a. The outer surface of the conductive layer 3 is raised by the plurality of conductive materials 4, and a plurality of protrusions 3a are formed. By providing the conductive particles with a plurality of conductive materials, it is easy to form a plurality of protrusions on the outer surface of the conductive particles.

　導電材４は粒子である。導電材４が粒子であるため、基材粒子２の表面上の一部の領域に、導電材４が配置されている。
The conductive material 4 is a particle. Since the conductive material 4 is a particle, the conductive material 4 is arranged in a partial region on the surface of the substrate particle 2.

　導電材４は、基材粒子２に接している。基材粒子の表面と導電材の表面との間に、導電層が配置されていてもよい。導電材が基材粒子に接しておらず、基材粒子の表面と導電材の表面とが距離を隔てていてもよい。
The conductive material 4 is in contact with the substrate particles 2. A conductive layer may be disposed between the surface of the base particle and the surface of the conductive material. The conductive material may not be in contact with the base material particle, and the surface of the base material particle and the surface of the conductive material may be separated from each other.

　絶縁性物質５は、導電層３の表面上に配置されている。絶縁性物質５は絶縁性粒子である。絶縁性物質５は、絶縁性を有する材料により形成されている。導電性粒子は絶縁性物質を、必ずしも備えていなくてもよい。また、導電性粒子は、絶縁性物質として、絶縁粒子にかえて導電層の外側の表面を被覆している絶縁層を備えていてもよい。
The insulating substance 5 is disposed on the surface of the conductive layer 3. The insulating substance 5 is an insulating particle. The insulating substance 5 is made of an insulating material. The conductive particles do not necessarily include an insulating substance. In addition, the conductive particles may include an insulating layer that covers the outer surface of the conductive layer as an insulating substance instead of the insulating particles.

　図２は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。
FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.

　図２に示す導電性粒子１１は、基材粒子２と、第１の導電層１２と、第２の導電層１３と、複数の導電材４と、複数の絶縁性物質５とを備える。
A conductive particle 11 shown in FIG. 2 includes a base particle 2, a first conductive layer 12, a second conductive layer 13, a plurality of conductive materials 4, and a plurality of insulating substances 5.

　導電性粒子１と導電性粒子１１とでは、導電層のみが異なっている。すなわち、導電性粒子１では、１層構造の導電層が形成されているのに対し、導電性粒子１１では、２層構造の第１の導電層１２及び第２の導電層１３が形成されている。導電材４は、第１の導電層１１及び導電層１３内に埋め込まれている。
Only the conductive layer is different between the conductive particles 1 and the conductive particles 11. That is, the conductive particle 1 has a single-layered conductive layer, whereas the conductive particle 11 has a two-layered first conductive layer 12 and second conductive layer 13 formed. Yes. The conductive material 4 is embedded in the first conductive layer 11 and the conductive layer 13.

　第１の導電層１２は、基材粒子２の表面上に配置されている。基材粒子２と第２の導電層１３との間に、第１の導電層１２が配置されている。第１の導電層１２は、基材粒子２側に位置しており、基材粒子２に接する導電層である。第２の導電層１３は、基材粒子２側とは反対側に位置しており、基材粒子２に接していない。従って、基材粒子２の表面上に第１の導電層１２が配置されており、第１の導電層１２の表面上に第２の導電層１３が配置されている。第２の導電層１３は外表面に、複数の突起１３ａを有する。導電性粒子１１は導電性の表面に、複数の突起１１ａを有する。
The first conductive layer 12 is disposed on the surface of the base particle 2. The first conductive layer 12 is disposed between the base particle 2 and the second conductive layer 13. The first conductive layer 12 is located on the base particle 2 side and is a conductive layer in contact with the base particle 2. The second conductive layer 13 is located on the side opposite to the base particle 2 side and is not in contact with the base particle 2. Therefore, the first conductive layer 12 is disposed on the surface of the base particle 2, and the second conductive layer 13 is disposed on the surface of the first conductive layer 12. The second conductive layer 13 has a plurality of protrusions 13a on the outer surface. The conductive particles 11 have a plurality of protrusions 11a on the conductive surface.

　図３は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。
FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.

　図３に示す導電性粒子２１は、基材粒子２と、導電層２２と、複数の導電材４とを備える。導電層２２は、基材粒子２の表面上に配置されている。導電材４は、導電層２２内に埋め込まれている。
A conductive particle 21 shown in FIG. 3 includes a base particle 2, a conductive layer 22, and a plurality of conductive materials 4. The conductive layer 22 is disposed on the surface of the base particle 2. The conductive material 4 is embedded in the conductive layer 22.

　導電性粒子２１は表面に突起を有さない。導電性粒子２１は球状である。導電層２２は外側の表面に突起を有さない。このように、本発明に係る導電性粒子は突起を有していなくてもよく、球状であってもよい。また、導電性粒子２１は、絶縁性物質を有さない。但し、導電性粒子２１は、導電層２２の表面上に配置された絶縁性物質を備えていてもよい。
The conductive particles 21 do not have protrusions on the surface. The conductive particles 21 are spherical. The conductive layer 22 does not have a protrusion on the outer surface. Thus, the electroconductive particle which concerns on this invention does not need to have a processus | protrusion, and may be spherical. Further, the conductive particles 21 do not have an insulating material. However, the conductive particles 21 may include an insulating material disposed on the surface of the conductive layer 22.

　以下、導電性粒子をより詳細に説明する。
Hereinafter, the conductive particles will be described in more detail.

　［基材粒子］

　上記基材粒子としては、樹脂粒子、金属粒子を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。なかでも、金属粒子を除く基材粒子が好ましく、樹脂粒子、金属粒子を除く無機粒子又は有機無機ハイブリッド粒子がより好ましい。
[Base material particles]

Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. Of these, substrate particles excluding metal particles are preferable, and resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles are more preferable.

　上記樹脂粒子を形成するための樹脂として、種々の有機物が好適に用いられる。上記樹脂粒子を形成するための樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂；ポリメチルメタクリレート及びポリメチルアクリレート等のアクリル樹脂；ポリアルキレンテレフタレート、ポリカーボネート、ポリアミド、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ポリエチレンテレフタレート、ポリスルホン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ジビニルベンゼン重合体、並びにジビニルベンゼン系共重合体等が挙げられる。上記ジビニルベンゼン系共重合体等としては、ジビニルベンゼン－スチレン共重合体及びジビニルベンゼン－（メタ）アクリル酸エステル共重合体等が挙げられる。上記樹脂粒子の硬度を好適な範囲に容易に制御できるので、上記樹脂粒子を形成するための樹脂は、エチレン性不飽和基を有する重合性単量体を１種又は２種以上重合させた重合体であることが好ましい。
Various organic materials are suitably used as the resin for forming the resin particles. Examples of 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, polyethylene terephthalate, Polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamid Imide, polyether ether ketone, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer, and the like. Examples of the divinylbenzene copolymer 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 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.

　上記樹脂粒子を、エチレン性不飽和基を有する単量体を重合させて得る場合には、該エチレン性不飽和基を有する単量体としては、非架橋性の単量体と架橋性の単量体とが挙げられる。
When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having the ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And a polymer.

　上記非架橋性の単量体としては、例えば、スチレン、α－メチルスチレン等のスチレン系単量体；（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート類；２－ヒドロキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート類；（メタ）アクリロニトリル等のニトリル含有単量体；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル等のビニルエーテル類；酢酸ビニル、酪酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の酸ビニルエステル類；エチレン、プロピレン、イソプレン、ブタジエン等の不飽和炭化水素；トリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート、塩化ビニル、フッ化ビニル、クロルスチレン等のハロゲン含有単量体等が挙げられる。
Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-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; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.

　上記架橋性の単量体としては、例えば、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、（ポリ）テトラメチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート等の多官能（メタ）アクリレート類；トリアリル（イソ）シアヌレート、トリアリルトリメリテート、ジビニルベンゼン、ジアリルフタレート、ジアリルアクリルアミド、ジアリルエーテル、γ－（メタ）アクリロキシプロピルトリメトキシシラン、トリメトキシシリルスチレン、ビニルトリメトキシシラン等のシラン含有単量体等が挙げられる。
Examples of the crosslinkable monomer 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 glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure Silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.
　上記エチレン性不飽和基を有する重合性単量体を、公知の方法により重合させることで、上記樹脂粒子を得ることができる。この方法としては、例えば、ラジカル重合開始剤の存在下で懸濁重合する方法、並びに非架橋の種粒子を用いてラジカル重合開始剤とともに単量体を膨潤させて重合する方法等が挙げられる。 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.
　上記基材粒子が金属を除く無機粒子又は有機無機ハイブリッド粒子である場合には、基材粒子を形成するための無機物としては、シリカ及びカーボンブラック等が挙げられる。上記シリカにより形成された粒子としては特に限定されないが、例えば、加水分解性のアルコキシシル基を２つ以上有するケイ素化合物を加水分解して架橋重合体粒子を形成した後に、必要に応じて焼成を行うことにより得られる粒子が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。 In the case where 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. Although it does not specifically limit as the particle | 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. The particle | 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.
　上記基材粒子が金属粒子である場合に、該金属粒子を形成するための金属としては、銀、銅、ニッケル、ケイ素、金及びチタン等が挙げられる。上記基材粒子が金属粒子である場合に、該金属粒子は銅粒子であることが好ましい。但し、上記基材粒子は金属粒子ではないことが好ましい。 When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium. When the base material particles are metal particles, the metal particles are preferably copper particles. However, the substrate particles are preferably not metal particles.
　上記基材粒子の粒子径は、好ましくは０．１μｍ以上、より好ましくは１μｍ以上、更に好ましくは１．５μｍ以上、特に好ましくは２μｍ以上、好ましくは１０００μｍ以下、より好ましくは５００μｍ以下、より一層好ましくは３００μｍ以下、更に好ましくは５０μｍ以下、特に好ましくは３０μｍ以下、最も好ましくは５μｍ以下である。基材粒子の粒子径が上記下限以上であると、導電性粒子と電極との接触面積が大きくなるため、電極間の導通信頼性がより一層高くなり、導電性粒子を介して接続された電極間の接続抵抗がより一層低くなる。さらに、基材粒子の表面に導電層を無電解めっきにより形成する際に凝集し難くなり、凝集した導電性粒子が形成されにくくなる。粒子径が上記上限以下であると、導電性粒子が充分に圧縮されやすく、電極間の接続抵抗がより一層低くなり、更に電極間の間隔が小さくなる。上記基材粒子の粒子径は、基材粒子が真球状である場合には、直径を示し、基材粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the substrate particles is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably. Is not more than 300 μm, more preferably not more than 50 μm, particularly preferably not more than 30 μm, and most preferably not more than 5 μm. When the particle diameter of the substrate particles is equal to or greater than the above lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased, and the electrodes are connected via the conductive particles. The connection resistance between them becomes even lower. Further, when forming the conductive layer on the surface of the base particle by electroless plating, it becomes difficult to aggregate and the aggregated conductive particles are hardly formed. When the particle diameter is not more than the above upper limit, the conductive particles are easily compressed, the connection resistance between the electrodes is further reduced, and the distance between the electrodes is further reduced. The particle diameter of the base particle indicates a diameter when the base particle is a true sphere, and indicates a maximum diameter when the base particle is not a true sphere.
　上記基材粒子の粒子径は、２μｍ以上、５μｍ以下であることが特に好ましい。上記基材粒子の粒子径が２～５μｍの範囲内であると、電極間の間隔が小さくなり、かつ導電層の厚みを厚くしても、小さい導電性粒子が得られる。上記基材粒子の粒子径は、３μｍ以下であることも好ましい。 The particle diameter of the substrate particles is particularly preferably 2 μm or more and 5 μm or less. When the particle diameter of the substrate particles is in the range of 2 to 5 μm, even when the distance between the electrodes is small and the conductive layer is thick, small conductive particles can be obtained. The particle diameter of the substrate particles is also preferably 3 μm or less.
　［導電層］
　本発明に係る導電性粒子は、基材粒子の表面上に配置されている導電層を有する。 [Conductive layer]
The electroconductive particle which concerns on this invention has the electroconductive layer arrange | positioned on the surface of base material particle.
　上記導電層を形成するための金属は特に限定されない。該金属としては、例えば、金、銀、パラジウム、銅、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、タリウム、ゲルマニウム、カドミウム、ケイ素及びこれらの合金等が挙げられる。また、上記金属としては、錫ドープ酸化インジウム（ＩＴＯ）及びはんだ等が挙げられる。なかでも、電極間の接続抵抗をより一層低くすることができるので、錫を含む合金、ニッケル、パラジウム、銅又は金が好ましく、ニッケル又はパラジウムが好ましい。 The metal for forming the conductive layer 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 can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
　導電性粒子１，２１のように、上記導電層は、１つの層により形成されていてもよい。導電性粒子１１のように、導電層は、複数の層により形成されていてもよい。すなわち、導電層は、２層以上の積層構造を有していてもよい。導電層が複数の層により形成されている場合には、最外層（第２の導電層など）は、金層、ニッケル層、パラジウム層、銅層又は錫と銀とを含む合金層であることが好ましく、パラジウム層又は金層であることがより好ましい。最外層は、パラジウム層であることが好ましく、金層であることも好ましい。最外層がこれらの好ましい導電層である場合には、電極間の接続抵抗がより一層低くなる。また、最外層が金層である場合には、耐腐食性がより一層高くなる。ニッケル層はニッケルを５０重量％以上含む。パラジウム層又は金層は、パラジウム又は金を５０重量％以上含む。 Like the conductive particles 1 and 21, the conductive layer may be formed of a single layer. Like the conductive particles 11, 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. When the conductive layer is formed of a plurality of layers, the outermost layer (second conductive layer, etc.) is a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver. Is preferable, and a palladium layer or a gold layer is more preferable. The outermost layer is preferably a palladium layer, and is preferably a gold layer. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced. The nickel layer contains 50% by weight or more of nickel. The palladium layer or the gold layer contains 50% by weight or more of palladium or gold.
　上記基材粒子に接する導電層が、ニッケルを含むことが好ましい。導電性粒子１，２１のように上記導電層が単層である場合に、上記導電層はニッケルを含むことが好ましい。導電性粒子１１のように導電層が基材粒子側の第１の導電層と、基材粒子側とは反対側の第２の導電層とを有する場合に、上記第１の導電層（基材粒子に接する導電層）が、ニッケルを含むことが好ましい。上記導電層及び上記第１の導電層は、ニッケルを主成分として含むことが好ましい。ニッケルを含む導電層の導電性は比較的高い。従って、ニッケルを含む導電層を備える導電性粒子により電極間を接続した場合に、電極間の接続抵抗がより一層低くなる。 It is preferable that the conductive layer in contact with the substrate particles contains nickel. In the case where the conductive layer is a single layer like the conductive particles 1 and 21, the conductive layer preferably contains nickel. When the conductive layer has a first conductive layer on the substrate particle side and a second conductive layer on the opposite side to the substrate particle side, like the conductive particles 11, the first conductive layer (base The conductive layer in contact with the material particles preferably contains nickel. The conductive layer and the first conductive layer preferably contain nickel as a main component. The conductivity of the conductive layer containing nickel is relatively high. Therefore, when the electrodes are connected by conductive particles having a conductive layer containing nickel, the connection resistance between the electrodes is further reduced.
　上記基材粒子に接する導電層１００重量％中、ニッケルの含有量は５０重量％以上であることが好ましい。上記導電層が単層である場合に、上記導電層１００重量％中、ニッケルの含有量は５０重量％以上であることが好ましい。上記導電層が上記第１，第２の導電層を備える場合に、上記第１の導電層１００重量％中のニッケルの含有量は５０重量％以上であることが好ましい。ニッケルの含有量が５０重量％以上であると、電極間の接続抵抗がかなり低くなる。上記導電層又は上記第１の導電層１００重量％中、ニッケルの含有量はより好ましくは６０重量％以上、更に好ましくは７０重量％以上、特に好ましくは９０重量％以上である。上記導電層又は上記第１の導電層１００重量％中のニッケルの含有量は９７重量％以上であってもよく、９７．５重量％以上であってもよく、９８重量％以上であってもよい。上記導電層又は上記第１の導電層１００重量％中のニッケルの含有量は好ましくは９９．８５重量％以下、より好ましくは９９．７重量％以下、更に好ましくは９９．４５重量％未満である。上記ニッケルの含有量が上記下限以上であると、電極間の接続抵抗がより一層低くなる。また、電極や導電層の表面における酸化被膜が少ない場合には、上記ニッケルの含有量が多いほど電極間の接続抵抗が低くなる傾向がある。 In 100% by weight of the conductive layer in contact with the substrate particles, the nickel content is preferably 50% by weight or more. When the conductive layer is a single layer, the content of nickel is preferably 50% by weight or more in 100% by weight of the conductive layer. When the conductive layer includes the first and second conductive layers, the content of nickel in 100% by weight of the first conductive layer is preferably 50% by weight or more. When the nickel content is 50% by weight or more, the connection resistance between the electrodes is considerably low. In 100% by weight of the conductive layer or the first conductive layer, the nickel content is more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. The content of nickel in the conductive layer or 100% by weight of the first conductive layer may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more. Good. The content of nickel in the conductive layer or 100% by weight of the first conductive layer is preferably 99.85% by weight or less, more preferably 99.7% by weight or less, and still more preferably less than 99.45% by weight. . When the nickel content is not less than the lower limit, the connection resistance between the electrodes is further reduced. Moreover, when there are few oxide films in the surface of an electrode or a conductive layer, there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.
　上記導電層又は上記第１の導電層は、ニッケルと、ボロン及びリンの内の少なくとも１種とを含むことが好ましい。上記導電層又は上記第１の導電層では、ニッケルとボロン及びリンの内の少なくとも１種とは合金化していてもよい。また、上記導電層又は上記第１の導電層では、ニッケル、ボロン及びリン以外の成分を用いてもよい。 The conductive layer or the first conductive layer preferably contains nickel and at least one of boron and phosphorus. In the conductive layer or the first conductive layer, nickel and at least one of boron and phosphorus may be alloyed. In the conductive layer or the first conductive layer, components other than nickel, boron, and phosphorus may be used.
　また、接続構造体が酸の存在下に晒されたときに、電極間の接続抵抗が上昇することがある。このため、上記導電層又は上記第１の導電層は、基材粒子側でニッケル層中のリンの含有量が高く、基材粒子とは反対側でニッケル層中のリンの含有量が低い方がよい場合がある。 Also, when the connection structure is exposed to the presence of an acid, the connection resistance between the electrodes may increase. Therefore, the conductive layer or the first conductive layer has a high phosphorus content in the nickel layer on the base particle side and a low phosphorus content in the nickel layer on the side opposite to the base particle. May be good.
　上記導電層又は上記第１の導電層１００重量％中のボロンとリンとの合計の含有量は好ましくは０．０１重量％以上、より好ましくは０．０５重量％以上、更に好ましくは０．１重量％以上、好ましくは５重量％以下、より好ましくは４重量％以下、更に好ましくは３重量％以下、特に好ましくは２．５重量％以下、最も好ましくは２重量％以下である。ボロンとリンとの合計の含有量が上記下限以上であると、上記導電層又は上記第１の導電層がより一層硬くなり、電極及び導電性粒子の表面の酸化被膜をより一層効果的に除去でき、電極間の接続抵抗をより一層低くすることができる。ボロンとリンとの合計の含有量が上記上限以下であると、ニッケルの含有量が相対的に多くなるので、電極間の接続抵抗が低くなる。 The total content of boron and phosphorus in the conductive layer or 100% by weight of the first conductive layer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1%. % By weight or more, preferably 5% by weight or less, more preferably 4% by weight or less, further preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less. When the total content of boron and phosphorus is not less than the above lower limit, the conductive layer or the first conductive layer becomes harder, and the oxide film on the surface of the electrode and conductive particles is more effectively removed. In addition, the connection resistance between the electrodes can be further reduced. When the total content of boron and phosphorus is not more than the above upper limit, the content of nickel is relatively increased, so that the connection resistance between the electrodes is reduced.
　上記導電層又は上記第１の導電層１００重量％中のボロンの含有量は好ましくは０．０１重量％以上、より好ましくは０．０５重量％以上、更に好ましくは０．１重量％以上、好ましくは５重量％以下、より好ましくは４重量％以下、更に好ましくは３重量％以下、特に好ましくは２．５重量％以下、最も好ましくは２重量％以下である。ボロンの含有量が上記下限以上であると、上記導電層又は上記第１の導電層がより一層硬くなり、電極及び導電性粒子の表面の酸化被膜をより一層効果的に除去でき、電極間の接続抵抗をより一層低くすることができる。ボロンの含有量が上記上限以下であると、ニッケルの含有量が相対的に多くなるので、電極間の接続抵抗が低くなる。 The boron content in the conductive layer or 100% by weight of the first conductive layer is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably Is 5% by weight or less, more preferably 4% by weight or less, further preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less. When the boron content is not less than the above lower limit, the conductive layer or the first conductive layer becomes harder, and the oxide film on the surface of the electrode and the conductive particles can be more effectively removed. The connection resistance can be further reduced. If the boron content is less than or equal to the above upper limit, the nickel content is relatively increased, so that the connection resistance between the electrodes is reduced.
　上記導電層又は上記第１の導電層は、リンを含まないか又は含み、かつ上記導電層又は上記第１の導電層１００重量％中のリンの含有量が１０．０重量％未満であることが好ましい。上記導電層１００重量％中のリンの含有量はより好ましくは０．５重量％未満、更に好ましくは０．３重量％以下、特に好ましくは０．１重量％以下である。上記導電層又は上記第１の導電層はリンを含まないことが特に好ましい。 The conductive layer or the first conductive layer does not contain phosphorus or contains phosphorus, and the content of phosphorus in 100% by weight of the conductive layer or the first conductive layer is less than 10.0% by weight. Is preferred. The content of phosphorus in 100% by weight of the conductive layer is more preferably less than 0.5% by weight, still more preferably 0.3% by weight or less, and particularly preferably 0.1% by weight or less. It is particularly preferable that the conductive layer or the first conductive layer does not contain phosphorus.
　上記導電層又は上記第１の導電層におけるニッケル、ボロン及びリンなどの各含有量の測定方法は、既知の種々の分析法を用いることができ特に限定されない。この測定方法として、吸光分析法又はスペクトル分析法等が挙げられる。上記吸光分析法では、フレーム吸光光度計及び電気加熱炉吸光光度計等を用いることができる。上記スペクトル分析法としては、プラズマ発光分析法及びプラズマイオン源質量分析法等が挙げられる。 The method for measuring each content of nickel, boron, phosphorus, etc. in the conductive layer or the first conductive layer is not particularly limited, and various known analytical methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer, or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.
　上記導電層又は上記第１の導電層におけるニッケル、ボロン及びリンなどの各含有量を測定する際には、ＩＣＰ発光分析装置を用いることが好ましい。ＩＣＰ発光分析装置の市販品としては、ＨＯＲＩＢＡ社製のＩＣＰ発光分析装置等が挙げられる。 When measuring the content of nickel, boron, phosphorus, etc. in the conductive layer or the first conductive layer, it is preferable to use an ICP emission spectrometer. Examples of commercially available ICP emission analyzers include ICP emission analyzers manufactured by HORIBA.
　電極間の接続抵抗をより一層低くする観点からは、上記導電層が、上記基材粒子側にニッケル層と、上記基材粒子側とは反対側に第２の導電層とを有することが好ましい。この場合に、第２の導電層が、パラジウム層又は金層であることが好ましく、パラジウム層であることがより好ましく、金層であることがより好ましい。 From the viewpoint of further reducing the connection resistance between the electrodes, the conductive layer preferably has a nickel layer on the base particle side and a second conductive layer on the side opposite to the base particle side. . In this case, the second conductive layer is preferably a palladium layer or a gold layer, more preferably a palladium layer, and more preferably a gold layer.
　上記基材粒子の表面上に上記導電層又は上記第１の導電層を形成する方法並びに上記第１の導電層の表面上に上記第２の導電層を形成する方法は特に限定されない。導電層を形成する方法としては、例えば、無電解めっきによる方法、電気めっきによる方法、物理的蒸着による方法、並びに金属粉末もしくは金属粉末とバインダーとを含むペーストを基材粒子又は他の導電層の表面にコーティングする方法等が挙げられる。なかでも、導電層の形成が簡便であるので、無電解めっきによる方法が好ましい。上記物理的蒸着による方法としては、真空蒸着、イオンプレーティング及びイオンスパッタリング等の方法が挙げられる。 The method for forming the conductive layer or the first conductive layer on the surface of the substrate particles and the method for forming the second conductive layer on the surface of the first conductive layer are not particularly limited. As 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 paste containing metal powder or metal powder and a binder is used for base particles or other conductive layers. For example, a method of coating the surface. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
　上記導電性粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上、好ましくは１００μｍ以下、より好ましくは２０μｍ以下である。導電性粒子の粒子径が上記下限以上及び上限以下であると、導電性粒子を用いて電極間を接続した場合に、導電性粒子と電極との接触面積が充分に大きくなり、かつ導電層を形成する際に凝集した導電性粒子が形成されにくくなる。また、導電性粒子を介して接続された電極間の間隔が大きくなりすぎず、かつ導電層が基材粒子の表面から剥離し難くなる。 The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 20 μm or less. When the particle diameter of the conductive particles is not less than the above 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 electrode is sufficiently large, and the conductive layer is formed. Aggregated conductive particles are less likely to be formed during formation. 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.
　上記導電性粒子の粒子径は、導電性粒子が真球状である場合には、直径を示し、導電性粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
　導電性粒子における導電層全体の厚み及び導電層が単層である場合の導電層の厚みは、好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上、更に好ましくは０．０５μｍ以上、好ましくは１μｍ以下、より好ましくは０．３μｍ以下である。上記導電層の厚みが上記下限以上及び上記上限以下であると、充分な導電性が得られ、かつ導電性粒子が硬くなりすぎずに、電極間の接続の際に導電性粒子が充分に変形する。 The total thickness of the conductive layer in the conductive particles and the thickness of the conductive layer when the conductive layer is a single layer are preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, preferably It is 1 μm or less, more preferably 0.3 μm or less. When 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. To do.
　導電層が２層以上の積層構造である場合に、基材粒子に接する導電層（第１の導電層）の厚みは、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上、更に好ましくは０．０５μｍ以上、好ましくは０．５μｍ以下、より好ましくは０．３μｍ以下、更に好ましくは０．１μｍ以下である。基材粒子に接する導電層の厚みが上記下限以上及び上記上限以下であると、導電層による被覆を均一にでき、かつ電極間の接続抵抗が充分に低くなる。 When the conductive layer has a laminated structure of two or more layers, the thickness of the conductive layer (first conductive layer) in contact with the substrate particles is preferably 0.001 μm or more, more preferably 0.01 μm or more, and still more preferably. It is 0.05 μm or more, preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.1 μm or less. When the thickness of the conductive layer in contact with the substrate particles is not less than the above lower limit and not more than the above upper limit, the coating with the conductive layer can be made uniform and the connection resistance between the electrodes becomes sufficiently low.
　導電性粒子における導電層全体の厚み及び導電層が単層である場合の導電層の厚みは、０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。さらに、基材粒子の粒子径が２μｍ以上、５μｍ以下であり、かつ、導電性粒子における導電層全体の厚み及び導電層が単層である場合の導電層の厚みが０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。この場合には、導電性粒子を大きな電流が流れる用途により好適に用いることができる。さらに、導電性粒子を圧縮して電極間を接続した場合に、電極が損傷するのをより一層抑制できる。 The thickness of the entire conductive layer in the conductive particles and the thickness of the conductive layer when the conductive layer is a single layer are particularly preferably 0.05 μm or more and 0.3 μm or less. Furthermore, when the particle diameter of the substrate particles is 2 μm or more and 5 μm or less, and the thickness of the entire conductive layer in the conductive particles and the conductive layer is a single layer, the thickness of the conductive layer is 0.05 μm or more, 0. It is particularly preferable that the thickness is 3 μm or less. In this case, the conductive particles can be suitably used for applications in which a large current flows. Furthermore, when the conductive particles are compressed to connect the electrodes, it is possible to further suppress the electrodes from being damaged.
　上記導電層の厚みは、例えば透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより測定できる。 The thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
　上記導電層及び上記第１の導電層におけるニッケル、ボロン及びリンの含有量を制御する方法としては、例えば、無電解ニッケルめっきにより導電層を形成する際に、ニッケルめっき液のｐＨを制御する方法、無電解ニッケルめっきにより導電層を形成する際に、ボロン含有還元剤の濃度を調整する方法、無電解ニッケルめっきにより導電層を形成する際に、リン含有還元剤の濃度を調整する方法、並びにニッケルめっき液中のニッケル濃度を調整する方法等が挙げられる。 As a method for controlling the contents of nickel, boron and phosphorus in the conductive layer and the first conductive layer, for example, a method of controlling the pH of the nickel plating solution when forming the conductive layer by electroless nickel plating A method of adjusting the concentration of the boron-containing reducing agent when forming the conductive layer by electroless nickel plating, a method of adjusting the concentration of the phosphorus-containing reducing agent when forming the conductive layer by electroless nickel plating, and A method for adjusting the nickel concentration in the nickel plating solution is exemplified.
　無電解めっきにより形成する方法では、一般的に、触媒化工程と、無電解めっき工程とが行われる。以下、無電解めっきにより、樹脂粒子の表面に、ニッケルとボロンとを含む合金めっき層を形成する方法の一例を説明する。 In the method of forming by electroless plating, generally, a catalytic step and an electroless plating step are performed. Hereinafter, an example of a method for forming an alloy plating layer containing nickel and boron on the surface of resin particles by electroless plating will be described.
　上記触媒化工程では、無電解めっきによりめっき層を形成するための起点となる触媒を、樹脂粒子の表面に形成させる。 In the catalyzing step, a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
　上記触媒を樹脂粒子の表面に形成させる方法としては、例えば、塩化パラジウムと塩化スズとを含む溶液に、樹脂粒子を添加した後、酸溶液又はアルカリ溶液により樹脂粒子の表面を活性化させて、樹脂粒子の表面にパラジウムを析出させる方法、並びに硫酸パラジウムとアミノピリジンとを含有する溶液に、樹脂粒子を添加した後、還元剤を含む溶液により樹脂粒子の表面を活性化させて、樹脂粒子の表面にパラジウムを析出させる方法等が挙げられる。上記還元剤として、ボロン含有還元剤が好適に用いられる。また、上記還元剤として、リン含有還元剤を用いることで、リンを含む導電層を形成できる。 As a method of forming the catalyst on the surface of the resin particles, for example, after adding the resin particles to a solution containing palladium chloride and tin chloride, the surface of the resin particles is activated with an acid solution or an alkali solution, A method of depositing palladium on the surface of the resin particles, and after adding the resin particles to a solution containing palladium sulfate and aminopyridine, the surface of the resin particles is activated by a solution containing a reducing agent. Examples thereof include a method of depositing palladium on the surface. As the reducing agent, a boron-containing reducing agent is preferably used. In addition, a conductive layer containing phosphorus can be formed by using a phosphorus-containing reducing agent as the reducing agent.
　上記無電解めっき工程では、ニッケル含有化合物及び上記ボロン含有還元剤を含むニッケルめっき浴が好適に用いられる。ニッケルめっき浴中に樹脂粒子を浸漬することにより、触媒が表面に形成された樹脂粒子の表面に、ニッケルを析出させることができ、ニッケルとボロンとを含む導電層を形成できる。 In the electroless plating step, a nickel plating bath containing a nickel-containing compound and the boron-containing reducing agent is preferably used. By immersing the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and a conductive layer containing nickel and boron can be formed.
　上記ニッケル含有化合物としては、硫酸ニッケル及び塩化ニッケル等が挙げられる。上記ニッケル含有化合物は、ニッケル塩であることが好ましい。 Examples of the nickel-containing compound include nickel sulfate and nickel chloride. The nickel-containing compound is preferably a nickel salt.
　上記ボロン含有還元剤としては、ジメチルアミンボラン、水素化ホウ素ナトリウム及び水素化ホウ素カリウム等が挙げられる。上記リン含有還元剤としては、次亜リン酸ナトリウム等が挙げられる。 Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, potassium borohydride, and the like. Examples of the phosphorus-containing reducing agent include sodium hypophosphite.
　［導電材］
　本発明に係る導電性粒子は、基材粒子の表面上に配置された導電材を備える。該導電材の材質は、モリブデン（Ｍｏ）（モース硬度５．５）、タングステン（Ｗ）（モース硬度７．５）、炭化タングステン（ＷＣ）（モース硬度９）、炭化チタン（ＴｉＣ）（モース硬度９）、又は炭化タンタル（ＴａＣ）（モース硬度９）であることが好ましい。導電性粒子が、この特定の材質の導電材を備えることで、導電性粒子の導電性の表面が十分に硬くなって、電極間の接続抵抗をかなり低くすることができる。上記導電材の材質のモース硬度は、ニッケル（Ｎｉ）（モース硬度５．０）のモース硬度よりも高い。上記導電材の材質は、炭化タングステン又は炭化タンタルであることが好ましい。上記導電材の材質は、モリブデンであることが好ましく、タングステンであることが好ましく、炭化タングステンであることが好ましく、炭化チタンであることが好ましく、炭化タンタルであることが好ましい。 [Conductive material]
The electroconductive particle which concerns on this invention is equipped with the electrically conductive material arrange | positioned on the surface of base material particle. The conductive material is made of molybdenum (Mo) (Mohs hardness 5.5), tungsten (W) (Mohs hardness 7.5), tungsten carbide (WC) (Mohs hardness 9), titanium carbide (TiC) (Mohs hardness). 9) or tantalum carbide (TaC) (Mohs hardness 9). When the conductive particles include the conductive material of this specific material, the conductive surface of the conductive particles becomes sufficiently hard, and the connection resistance between the electrodes can be considerably reduced. The Mohs hardness of the material of the conductive material is higher than the Mohs hardness of nickel (Ni) (Mohs hardness 5.0). The material of the conductive material is preferably tungsten carbide or tantalum carbide. The material of the conductive material is preferably molybdenum, preferably tungsten, preferably tungsten carbide, preferably titanium carbide, and preferably tantalum carbide.
　上記導電材の粉体抵抗率の値は、０．１Ω・ｃｍ以下であることが好ましい。 The value of the powder resistivity of the conductive material is preferably 0.1 Ω · cm or less.
　本発明に係る導電性粒子は、導電性の表面に突起を有することが好ましい。上記導電層は外側の表面に突起を有することが好ましい。該突起は複数であることが好ましい。導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。さらに、導電性粒子の導電層の表面には、酸化被膜が形成されていることが多い。突起を有する導電性粒子の使用により、電極間に導電性粒子を配置した後、圧着させることにより、突起により酸化被膜が効果的に排除される。上記突起の内側に特定の材質の上記導電材が存在することで、突起により酸化被膜がかなり排除されやすくなる。このため、電極と導電性粒子とをより一層確実に接触させることができ、電極間の接続抵抗を低くすることができる。さらに、導電性粒子が表面に絶縁性物質を有する場合、又は導電性粒子がバインダー樹脂中に分散されて導電材料として用いられる場合に、導電性粒子の突起によって、導電性粒子と電極との間の樹脂を効果的に排除できる。このため、電極間の導通信頼性を高めることができる。 The conductive particles according to the present invention preferably have protrusions on the conductive surface. The conductive layer preferably has a protrusion on the outer surface. It is preferable that there are a plurality of the protrusions. An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive layer of the conductive particles. By using the conductive particles having protrusions, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and then pressing them. The presence of the conductive material of a specific material inside the protrusion makes it easier to remove the oxide film by the protrusion. For this reason, an electrode and electroconductive particle can be contacted still more reliably and the connection resistance between electrodes can be made low. Further, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles are projected between the conductive particles and the electrodes by the protrusions of the conductive particles. Can be effectively eliminated. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.
　上記導電材が上記導電層中に埋め込まれていることによって、上記導電層が外側の表面に複数の突起を有するようにすることが容易である。 It is easy for the conductive layer to have a plurality of protrusions on the outer surface by embedding the conductive material in the conductive layer.
　上記導電性粒子が上記導電層を備える場合に、上記導電材は、上記基材粒子に接していてもよく、接していなくてもよい。上記基材粒子と上記導電材との間に、上記導電層の一部が配置されていてもよい。 When the conductive particles include the conductive layer, the conductive material may or may not be in contact with the base material particles. A part of the conductive layer may be disposed between the base particle and the conductive material.
　本発明に係る導電性粒子は、複数の上記導電材を備えることが好ましい。この場合には、導電層の内側に複数の上記導電材が配置されている箇所で、導電性粒子の導電部を硬くすることができる。また、導電性粒子及び導電層の表面に複数の突起を形成することが容易である。 The conductive particles according to the present invention preferably include a plurality of the conductive materials. In this case, the conductive part of the conductive particles can be hardened at a place where the plurality of conductive materials are arranged inside the conductive layer. Moreover, it is easy to form a plurality of protrusions on the surfaces of the conductive particles and the conductive layer.
　上記導電材は粒子であることが好ましい。この場合には、導電層の内側に配置された粒子である導電材の形状に由来して、導電性粒子の導電部を効果的に硬くすることができる。また、導電性粒子及び導電層の表面に複数の突起を形成することが容易である。 The conductive material is preferably particles. In this case, the conductive part of the conductive particles can be effectively hardened due to the shape of the conductive material that is the particles disposed inside the conductive layer. Moreover, it is easy to form a plurality of protrusions on the surfaces of the conductive particles and the conductive layer.
　粒子である上記導電材の形状は塊状であることが好ましい。粒子である上記導電材としては、例えば、粒子状の塊、複数の微小粒子が凝集した凝集塊、及び不定形の塊等が挙げられる。 The shape of the conductive material that is a particle is preferably a lump. Examples of the conductive material that is a particle include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
　上記基材粒子の粒子径をＤとしたときに、上記導電材の最大径は好ましくは０．００５Ｄ以上、より好ましくは０．０１５Ｄ以上、好ましくは０．２５Ｄ以下、より好ましくは０．１５Ｄ以下である。 When the particle diameter of the substrate particles is D, the maximum diameter of the conductive material is preferably 0.005D or more, more preferably 0.015D or more, preferably 0.25D or less, more preferably 0.15D or less. It is.
　また、上記基材粒子の粒子径をＤとしたときに、上記導電層の厚み方向における上記導電材の大きさは、好ましくは０．００５Ｄ以上、より好ましくは０．０１５Ｄ以上、好ましくは０．２５Ｄ以下、より好ましくは０．１５Ｄ以下である。 In addition, when the particle diameter of the base material particle is D, the size of the conductive material in the thickness direction of the conductive layer is preferably 0.005D or more, more preferably 0.015D or more, preferably 0.00. 25D or less, more preferably 0.15D or less.
　上記突起を形成する方法としては、基材粒子の表面に上記導電材を付着させた後、無電解めっきにより導電層を形成する方法、並びに基材粒子の表面に無電解めっきにより導電層を形成した後、上記導電材を付着させて、更に無電解めっきにより導電層を形成する方法等が挙げられる。上記突起を形成する他の方法としては、基材粒子の表面上に、第１の導電層を形成した後、該第１の導電層上に上記導電材を配置し、次に第２の導電層を形成する方法、並びに基材粒子の表面上に導電層を形成する途中段階で、上記導電材を添加する方法等が挙げられる。 As the method for forming the protrusions, the conductive material is attached to the surface of the base particle, and then the conductive layer is formed by electroless plating, and the conductive layer is formed by electroless plating on the surface of the base particle. Then, the method of making the said conductive material adhere and forming a conductive layer by electroless plating etc. is mentioned. As another method for forming the protrusions, the first conductive layer is formed on the surface of the base particle, and then the conductive material is disposed on the first conductive layer, and then the second conductive layer is formed. Examples thereof include a method of forming a layer, and a method of adding the conductive material in the middle of forming a conductive layer on the surface of the base particle.
　上記導電性粒子１個当たりの上記導電材の数及び上記突起の数はそれぞれ、好ましくは３個以上、より好ましくは５個以上である。上記導電材の数及び上記突起の数の上限は特に限定されない。上記導電材の数及び上記突起の数の上限は導電性粒子の粒子径等を考慮して適宜選択できる。 The number of the conductive material and the number of the protrusions per one conductive particle are preferably 3 or more, more preferably 5 or more. The upper limit of the number of the conductive materials and the number of the protrusions is not particularly limited. The upper limit of the number of the conductive materials and the number of the protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
　［絶縁性物質］
　本発明に係る導電性粒子は、上記導電層の表面上に配置された絶縁性物質を備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡をより一層防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁性物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、２つの電極で導電性粒子を加圧することにより、導電性粒子の導電層と電極との間の絶縁性物質を容易に排除できる。導電性粒子が導電層の外側の表面に複数の突起を有する場合には、導電性粒子の導電層と電極との間の絶縁性物質を容易に排除できる。 [Insulating material]
The conductive particles according to the present invention preferably include an insulating substance disposed on the surface of the conductive layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be further prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. In addition, the insulating substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes. In the case where the conductive particles have a plurality of protrusions on the outer surface of the conductive layer, the insulating substance between the conductive layer of the conductive particles and the electrode can be easily excluded.
　電極間の圧着時に上記絶縁性物質をより一層容易に排除できることから、上記絶縁性物質は、絶縁性粒子であることが好ましい。 The insulating substance is preferably an insulating particle because the insulating substance can be more easily removed during crimping between the electrodes.
　上記絶縁性物質の材料である絶縁性樹脂の具体例としては、ポリオレフィン類、（メタ）アクリレート重合体、（メタ）アクリレート共重合体、ブロックポリマー、熱可塑性樹脂、熱可塑性樹脂の架橋物、熱硬化性樹脂及び水溶性樹脂等が挙げられる。 Specific examples of the insulating resin that is the material of the insulating material include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable resins and water-soluble resins.
　（導電材料）
　本発明に係る導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。本発明に係る導電性粒子は、バインダー樹脂中に分散され、導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。 (Conductive material)
The conductive material according to the present invention includes the conductive particles described above and a binder resin. The conductive 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.
　上記バインダー樹脂は特に限定されない。上記バインダー樹脂として、公知の絶縁性の樹脂が用いられる。 The binder resin is not particularly limited. As the binder resin, a known insulating resin is used.
　上記バインダー樹脂としては、例えば、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体及びエラストマー等が挙げられる。上記バインダー樹脂は１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of 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.
　上記ビニル樹脂としては、例えば、酢酸ビニル樹脂、アクリル樹脂及びスチレン樹脂等が挙げられる。上記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、エチレン－酢酸ビニル共重合体及びポリアミド樹脂等が挙げられる。上記硬化性樹脂としては、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂及び不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂又は湿気硬化型樹脂であってもよい。上記硬化性樹脂は、硬化剤と併用されてもよい。上記熱可塑性ブロック共重合体としては、例えば、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、及びスチレン－イソプレン－スチレンブロック共重合体の水素添加物等が挙げられる。上記エラストマーとしては、例えば、スチレン－ブタジエン共重合ゴム、及びアクリロニトリル－スチレンブロック共重合ゴム等が挙げられる。 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. Examples of the thermoplastic block copolymer 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. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
　上記導電材料は、上記導電性粒子及び上記バインダー樹脂の他に、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 In addition to the conductive particles and the binder resin, the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer. Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
　上記バインダー樹脂中に上記導電性粒子を分散させる方法は、従来公知の分散方法を用いることができ特に限定されない。上記バインダー樹脂中に上記導電性粒子を分散させる方法としては、例えば、上記バインダー樹脂中に上記導電性粒子を添加した後、プラネタリーミキサー等で混練して分散させる方法、上記導電性粒子を水又は有機溶剤中にホモジナイザー等を用いて均一に分散させた後、上記バインダー樹脂中に添加し、プラネタリーミキサー等で混練して分散させる方法、並びに上記バインダー樹脂を水又は有機溶剤等で希釈した後、上記導電性粒子を添加し、プラネタリーミキサー等で混練して分散させる方法等が挙げられる。 The method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse | distributing is mentioned.
　本発明に係る導電材料は、導電ペースト及び導電フィルム等として使用され得る。本発明に係る導電材料が、導電フィルムである場合には、該導電性粒子を含む導電フィルムに、導電性粒子を含まないフィルムが積層されていてもよい。上記導電ペーストは異方性導電ペーストであることが好ましい。上記導電フィルムは、異方性導電フィルムであることが好ましい。 The conductive material according to the present invention can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film that does not include conductive particles may be laminated on the conductive film that includes the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
　上記導電材料１００重量％中、上記バインダー樹脂の含有量は好ましくは１０重量％以上、より好ましくは３０重量％以上、更に好ましくは５０重量％以上、特に好ましくは７０重量％以上、好ましくは９９．９９重量％以下、より好ましくは９９．９重量％以下である。上記バインダー樹脂の含有量が上記下限以上及び上記上限以下であると、電極間に導電性粒子が効率的に配置され、導電材料により接続された接続対象部材の接続信頼性がより一層高くなる。 In 100% by weight of the conductive material, 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. When 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 increased.
　上記導電材料１００重量％中、上記導電性粒子の含有量は好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、好ましくは４０重量％以下、より好ましくは２０重量％以下、更に好ましくは１０重量％以下である。上記導電性粒子の含有量が上記下限以上及び上記上限以下であると、電極間の導通信頼性がより一層高くなる。 In 100% by weight of the conductive material, the content of the conductive 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, it is 10 weight% or less. When the content of the conductive 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.
　（接続構造体）
　本発明の導電性粒子を用いて、又は該導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 (Connection structure)
A connection structure can be obtained by connecting the connection target members using the conductive particles of the present invention or using a conductive material containing the conductive particles and a binder resin.
　上記接続構造体は、第１の接続対象部材と、第２の接続対象部材と、第１の接続対象部材と第２の接続対象部材を接続している接続部とを備え、該接続部が本発明の導電性粒子により形成されているか、又は該導電性粒子とバインダー樹脂とを含む導電材料により形成されている接続構造体であることが好ましい。導電性粒子が用いられた場合には、接続部自体が導電性粒子である。すなわち、第１，第２の接続対象部材が導電性粒子により接続される。 The connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member. The connection structure is preferably formed of the conductive particles of the present invention or formed of a conductive material containing the conductive particles and a binder resin. In the case where conductive particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
　図４に、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体を模式的に正面断面図で示す。 FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
　図４に示す接続構造体５１は、第１の接続対象部材５２と、第２の接続対象部材５３と、第１，第２の接続対象部材５２，５３を接続している接続部５４とを備える。接続部５４は、導電性粒子１を含む導電材料を硬化させることにより形成されている。なお、図４では、導電性粒子１は、図示の便宜上、略図的に示されている。 4 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 that connects the first and second connection target members 52 and 53. Prepare. The connection portion 54 is formed by curing a conductive material including the conductive particles 1. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration.
　第１の接続対象部材５２は表面（上面）に、複数の第１の電極５２ａを有する。第２の接続対象部材５３は表面（下面）に、複数の第２の電極５３ａを有する。第１の電極５２ａと第２の電極５３ａとが、１つ又は複数の導電性粒子１により電気的に接続されている。従って、第１，第２の接続対象部材５２，５３が導電性粒子１により電気的に接続されている。 The first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface). The first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
　上記接続構造体の製造方法は特に限定されない。接続構造体の製造方法の一例としては、第１の接続対象部材と第２の接続対象部材との間に上記導電材料を配置し、積層体を得た後、該積層体を加熱及び加圧する方法等が挙げられる。上記加圧の圧力は９．８×１０４～４．９×１０６Ｐａ程度である。上記加熱の温度は、１２０～２２０℃程度である。 The manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of the connection structure, 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 pressurizing pressure is about 9.8 × 10 4 to 4.9 × 10 6 Pa. The heating temperature is about 120 to 220 ° C.
　上記接続対象部材としては、具体的には、半導体チップ、コンデンサ及びダイオード等の電子部品、並びにプリント基板、フレキシブルプリント基板、ガラスエポキシ基板及びガラス基板等の回路基板などの電子部品等が挙げられる。上記導電材料は、電子部品を接続するための導電材料であることが好ましい。上記導電材料はペースト状の導電ペーストであり、ペースト状の状態で接続対象部材上に塗工されることが好ましい。 Specific examples of the connection target member 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 preferably a conductive material for connecting electronic components. The conductive material is a paste-like conductive paste, and is preferably applied on the connection target member in a paste-like state.
　上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、錫電極、アルミニウム電極、銅電極、モリブデン電極及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、錫電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 Examples of the electrode provided on the connection target member 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. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When 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. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of 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.
　本発明に係る導電性粒子の別の使用形態を挙げると、液晶表示素子を構成する上下基板間の電気的な接続をするための導通材料として導電性粒子を使用することもできる。導電性粒子を熱硬化性樹脂又は熱ＵＶ併用硬化性樹脂に混合し、分散させて、片側基板上に点状に塗布し、対向基板と貼り合わせる方法、並びに導電性粒子を周辺シール剤に混合し分散させて線状に塗布して、封止シールと上下基板の電気接続を兼用する方法等がある。このような使用形態にも、本発明に係る導電性粒子は適用できる。 As another use form of the conductive particles according to the present invention, the conductive particles can be used as a conductive material for electrical connection between the upper and lower substrates constituting the liquid crystal display element. Conductive particles are mixed with thermosetting resin or thermosetting resin combined with heat UV, dispersed, applied in a dot pattern on one side of the substrate, and bonded to the counter substrate, and the conductive particles are mixed with the peripheral sealant For example, there is a method in which the sealing seal and the upper and lower substrates are electrically connected to each other by applying them in a linear form. The electroconductive particle which concerns on this invention is applicable also to such a usage form.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　以下の実施例で用いた導電材の粉体抵抗率は０．１Ω・ｃｍ以下の値を示した。導電材の粉体抵抗率は、具体的には、モリブデン（Ｍｏ）（０．００１Ω・ｃｍ）、タングステン（Ｗ）（０．００１Ω・ｃｍ）、炭化タングステン（ＷＣ）（０．００５Ω・ｃｍ）、炭化チタン（ＴｉＣ）（０．００５Ω・ｃｍ）、炭化タンタル（ＴａＣ）（０．００３Ω・ｃｍ）であった。 The powder resistivity of the conductive material used in the following examples showed a value of 0.1 Ω · cm or less. Specifically, the powder resistivity of the conductive material is molybdenum (Mo) (0.001 Ω · cm), tungsten (W) (0.001 Ω · cm), tungsten carbide (WC) (0.005 Ω · cm). And titanium carbide (TiC) (0.005 Ω · cm) and tantalum carbide (TaC) (0.003 Ω · cm).
　上記粉体抵抗率は、三菱化学社製の製粉体抵抗率測定システム「ロレスターＧＰ」にて、導電材２．５ｇを用いて、２３℃にて荷重２０ｋＮのときの粉体抵抗率で求めた。 The powder resistivity was determined by a powder resistivity measurement system “Lorestar GP” manufactured by Mitsubishi Chemical Corporation using 2.5 g of a conductive material and a powder resistivity at a load of 20 kN at 23 ° C. .
　（実施例１）
　（１）パラジウム付着工程
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０５」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着した樹脂粒子を得た。 (Example 1)
(1) Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles with palladium attached.
　（２）導電材付着工程
　パラジウムが付着した樹脂粒子をイオン交換水４００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、炭化タングステン粒子（平均粒子径１００ｎｍ）を５重量％含むスラリー４００ｇを、得られた分散液に３分間かけて添加し、導電材が付着した樹脂粒子を含む懸濁液を得た。 (2) Conductive Material Adhering Step The resin particles to which palladium was attached were stirred and dispersed in 400 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 400 g of a slurry containing 5% by weight of tungsten carbide particles (average particle size 100 nm) was added to the obtained dispersion over 3 minutes to obtain a suspension containing resin particles to which a conductive material adhered.
　（３）無電解ニッケルめっき工程
　硫酸ニッケル０．２３ｍｏｌ／Ｌ、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、及びクエン酸ナトリウム０．５ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ８．５）を用意した。 (3) Electroless nickel plating step A nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, and 0.5 mol / L of sodium citrate was prepared.
　得られた懸濁液を６０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解ニッケルめっきを行った。その後、懸濁液を濾過することにより、粒子を取り出し、水洗し、乾燥することにより、導電材が付着した樹脂粒子の表面上にニッケル層（厚み０．１μｍ）が配置された導電性粒子を得た。ニッケル層１００重量％中のニッケルの含有量は９８．９重量％、ボロンの含有量は１．１重量％であった。得られた導電性粒子は、導電層内に埋め込まれた複数の導電材を備えており、導電層の外側の表面に複数の突起を有し、導電層の突起の内側に導電材が配置されていた。 While stirring the obtained suspension at 60 ° C., the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to remove the particles, washed with water, and dried to obtain conductive particles having a nickel layer (thickness: 0.1 μm) disposed on the surface of the resin particles to which the conductive material is attached. Obtained. The content of nickel in 100% by weight of the nickel layer was 98.9% by weight, and the content of boron was 1.1% by weight. The obtained conductive particles have a plurality of conductive materials embedded in the conductive layer, have a plurality of protrusions on the outer surface of the conductive layer, and the conductive material is disposed inside the protrusions of the conductive layer. It was.
　（実施例２）
　炭化タングステン粒子（平均粒子径１００ｎｍ）を、タングステン粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Example 2)
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to tungsten particles (average particle size 100 nm).
　（実施例３）
　炭化タングステン粒子（平均粒子径１００ｎｍ）を、炭化タンタル粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Example 3)
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to tantalum carbide particles (average particle size 100 nm).
　（実施例４）
　炭化タングステン粒子（平均粒子径１００ｎｍ）をを、モリブデン粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 Example 4
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to molybdenum particles (average particle size 100 nm).
　（実施例５）
　（１）絶縁性粒子の作製
　４ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた１０００ｍＬのセパラブルフラスコに、メタクリル酸メチル１００ｍｍｏｌと、Ｎ，Ｎ，Ｎ－トリメチル－Ｎ－２－メタクリロイルオキシエチルアンモニウムクロライド１ｍｍｏｌと、２，２’－アゾビス（２－アミジノプロパン）二塩酸塩１ｍｍｏｌとを含むモノマー組成物を固形分率が５重量％となるようにイオン交換水に秤取した後、２００ｒｐｍで攪拌し、窒素雰囲気下７０℃で２４時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径２２０ｎｍ及びＣＶ値１０％の絶縁性粒子を得た。 (Example 5)
(1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
　（２）絶縁性粒子の付着工程
　絶縁性粒子を超音波照射下でイオン交換水に分散させ、絶縁性粒子の１０重量％水分散液を得た。 (2) Step of attaching insulating particles The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of insulating particles.
　実施例１で得られた導電性粒子１０ｇをイオン交換水５００ｍＬに分散させ、絶縁性粒子の水分散液４ｇを添加し、室温で６時間攪拌した。３μｍのメッシュフィルターでろ過した後、更にメタノールで洗浄し、乾燥し、絶縁性粒子が付着した導電性粒子を得た。 10 g of the conductive particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
　走査型電子顕微鏡（ＳＥＭ）により観察したところ、導電性粒子の表面に絶縁性粒子による被覆層が１層のみ形成されていた。画像解析により導電性粒子の中心より２．５μｍの面積に対する絶縁性粒子の被覆面積（即ち絶縁性粒子の粒子径の投影面積）を算出したところ、被覆率は３５％であった。 When observed with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles by image analysis (that is, the projected area of the particle diameter of the insulating particles) was calculated to be 35%.
　（実施例６）
　絶縁性粒子を付着させる前の実施例１で得られた導電性粒子を、実施例２で得られた導電性粒子に変更したこと以外は実施例５と同様にして、導電性粒子を得た。 (Example 6)
Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 2. .
　（実施例７）
　絶縁性粒子を付着させる前の実施例１で得られた導電性粒子を、実施例３で得られた導電性粒子に変更したこと以外は実施例５と同様にして、導電性粒子を得た。 (Example 7)
Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 3. .
　（実施例８）
　絶縁性粒子を付着させる前の実施例１で得られた導電性粒子を、実施例４で得られた導電性粒子に変更したこと以外は実施例５と同様にして、導電性粒子を得た。 (Example 8)
Conductive particles were obtained in the same manner as in Example 5 except that the conductive particles obtained in Example 1 before attaching the insulating particles were changed to the conductive particles obtained in Example 4. .
　（実施例９）
　実施例１で得られた導電性粒子１０ｇを、イオン交換水５００ｍＬに添加し、超音波処理機により充分に分散させて、懸濁液を得た。この懸濁液を５０℃で攪拌しながら、硫酸パラジウム０．０２ｍｏｌ／Ｌ、錯化剤としてエチレンジアミン０．０４ｍｏｌ／Ｌ、還元剤として蟻酸ナトリウム０．０６ｍｏｌ／Ｌ及び結晶調整剤を含むｐＨ１０．０の無電解めっき液を用意した。 Example 9
10 g of the conductive particles obtained in Example 1 were added to 500 mL of ion-exchanged water and sufficiently dispersed with an ultrasonic processor to obtain a suspension. While stirring the suspension at 50 ° C., 0.02 mol / L of palladium sulfate, 0.04 mol / L of ethylenediamine as a complexing agent, 0.06 mol / L of sodium formate as a reducing agent, and pH 10.0 containing a crystal modifier. An electroless plating solution was prepared.
　得られた懸濁液に、上記無電解めっき液を徐々に添加し、無電解パラジウムめっきを行った。パラジウム層の厚みが０．０３μｍになった時点で無電解パラジウムめっきを終了した。次に、洗浄し、真空乾燥することにより、ニッケル層の表面にパラジウム層（厚み０．０３μｍ）が積層された導電性粒子を得た。 The electroless plating solution was gradually added to the obtained suspension, and electroless palladium plating was performed. When the thickness of the palladium layer reached 0.03 μm, the electroless palladium plating was finished. Next, by washing and vacuum drying, conductive particles having a palladium layer (thickness: 0.03 μm) laminated on the surface of the nickel layer were obtained.
　（実施例１０）
　パラジウム層を形成する前の実施例１で得られた導電性粒子を、実施例２で得られた導電性粒子に変更したこと以外は実施例９と同様にして、導電性粒子を得た。 (Example 10)
Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 2.
　（実施例１１）
　パラジウム層を形成する前の実施例１で得られた導電性粒子を、実施例３で得られた導電性粒子に変更したこと以外は実施例９と同様にして、導電性粒子を得た。 (Example 11)
Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 3.
　（実施例１２）
　パラジウム層を形成する前の実施例１で得られた導電性粒子を、実施例４で得られた導電性粒子に変更したこと以外は実施例９と同様にして、導電性粒子を得た。 Example 12
Conductive particles were obtained in the same manner as in Example 9, except that the conductive particles obtained in Example 1 before forming the palladium layer were changed to the conductive particles obtained in Example 4.
　（実施例１３）
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０３」）を、粒子径が２．５μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０２５」）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Example 13)
Divinylbenzene resin particles having a particle size of 3.0 μm (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) and divinylbenzene resin particles having a particle size of 2.5 μm (“Micropearl SP manufactured by Sekisui Chemical Co., Ltd.) are used. Conductive particles were obtained in the same manner as in Example 1 except for changing to -2025 ").
　（実施例１４）
　（１）パラジウム付着工程
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０３」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着した樹脂粒子を得た。 (Example 14)
(1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles with palladium attached.
　（２）導電材付着工程
　パラジウムが付着した樹脂粒子をイオン交換水４００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、炭化タングステン粒子（平均粒子径１００ｎｍ）を５重量％含むスラリー４００ｇを、得られた分散液に３分間かけて添加し、導電材が付着した樹脂粒子を含む懸濁液を得た。 (2) Conductive Material Adhering Step The resin particles to which palladium was attached were stirred and dispersed in 400 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 400 g of a slurry containing 5% by weight of tungsten carbide particles (average particle size 100 nm) was added to the obtained dispersion over 3 minutes to obtain a suspension containing resin particles to which a conductive material adhered.
　（３）無電解ニッケルめっき工程
　硫酸ニッケル０．２５ｍｏｌ／Ｌ、次亜リン酸ナトリウム０．２５ｍｏｌ／Ｌ及びクエン酸ナトリウム０．１５ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ９．０）を用意した。 (3) Electroless nickel plating step A nickel plating solution (pH 9.0) containing nickel sulfate 0.25 mol / L, sodium hypophosphite 0.25 mol / L and sodium citrate 0.15 mol / L was prepared.
　得られた懸濁液を７０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解ニッケルめっきを行った。その後、懸濁液を濾過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル－リン導電層（厚み０．１μｍ）配置された導電性粒子を得た。 While stirring the obtained suspension at 70 ° C., the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension was filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-phosphorous conductive layer (thickness 0.1 μm) disposed on the surface of the resin particles.
　（実施例１５）
　（１）パラジウム付着工程
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０３」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着した樹脂粒子を得た。 (Example 15)
(1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles with palladium attached.
　（２）導電材付着工程
　パラジウムが付着した樹脂粒子をイオン交換水４００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、炭化タングステン粒子（平均粒子径１００ｎｍ）を５重量％含むスラリー４００ｇを、得られた分散液に３分間かけて添加し、導電材が付着した樹脂粒子を含む懸濁液を得た。 (2) Conductive Material Adhering Step The resin particles to which palladium was attached were stirred and dispersed in 400 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 400 g of a slurry containing 5% by weight of tungsten carbide particles (average particle size 100 nm) was added to the obtained dispersion over 3 minutes to obtain a suspension containing resin particles to which a conductive material adhered.
　（３）無電解ニッケルめっき工程
　硫酸ニッケル０．２５ｍｏｌ／Ｌ、次亜リン酸ナトリウム０．２５ｍｏｌ／Ｌ及びクエン酸ナトリウム０．１５ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ６．０）を用意した。 (3) Electroless nickel plating step A nickel plating solution (pH 6.0) containing nickel sulfate 0.25 mol / L, sodium hypophosphite 0.25 mol / L and sodium citrate 0.15 mol / L was prepared.
　得られた懸濁液を６０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解ニッケルめっきを行った。続いて、硫酸ニッケル０．２５ｍｏｌ／Ｌ、次亜リン酸ナトリウム０．２５ｍｏｌ／Ｌ及びクエン酸ナトリウム０．１５ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ１０．０）を懸濁液に徐々に滴下し、無電解ニッケルめっきを行った。その後、懸濁液を濾過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル－リン導電層（厚み０．１μｍ）配置された導電性粒子を得た。 While stirring the obtained suspension at 60 ° C., the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Subsequently, a nickel plating solution (pH 10.0) containing nickel sulfate 0.25 mol / L, sodium hypophosphite 0.25 mol / L and sodium citrate 0.15 mol / L was gradually added dropwise to the suspension. Electroless nickel plating was performed. Thereafter, the suspension was filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-phosphorous conductive layer (thickness 0.1 μm) disposed on the surface of the resin particles.
　（実施例１６）
　（１）パラジウム付着工程
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０３」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着した樹脂粒子を得た。 (Example 16)
(1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles with palladium attached.
　（２）導電材付着工程
　パラジウムが付着した樹脂粒子をイオン交換水４００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、炭化タングステン粒子（平均粒子径１００ｎｍ）を５重量％含むスラリー４００ｇを、得られた分散液に３分間かけて添加し、導電材が付着した樹脂粒子を含む懸濁液を得た。 (2) Conductive Material Adhering Step The resin particles to which palladium was attached were stirred and dispersed in 400 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 400 g of a slurry containing 5% by weight of tungsten carbide particles (average particle size 100 nm) was added to the obtained dispersion over 3 minutes to obtain a suspension containing resin particles to which a conductive material adhered.
　（３）無電解ニッケルめっき工程
　硫酸ニッケル０．２３ｍｏｌ／Ｌ、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、クエン酸ナトリウム０．５ｍｏｌ／Ｌ及びタングステン酸ナトリウム０．０１ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ８．５）を用意した。 (3) Electroless nickel plating step Nickel plating solution containing 0.23 mol / L nickel sulfate, 0.92 mol / L dimethylamine borane, 0.5 mol / L sodium citrate and 0.01 mol / L sodium tungstate (pH 8. 5) was prepared.
　得られた懸濁液を６０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解ニッケルめっきを行った。その後、懸濁液を濾過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル－タングステン－ボロン導電層（厚み約０．１μｍ）が設けられた導電性粒子を得た。 While stirring the obtained suspension at 60 ° C., 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 obtain conductive particles having a nickel-tungsten-boron conductive layer (thickness of about 0.1 μm) on the surface of the resin particles. Obtained.
　（参考例１）
　炭化タングステン粒子（平均粒子径１００ｎｍ）を、ニッケル粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Reference Example 1)
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to nickel particles (average particle size 100 nm).
　（比較例１）
　炭化タングステン粒子（平均粒子径１００ｎｍ）を、銅粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Comparative Example 1)
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to copper particles (average particle size 100 nm).
　（比較例２）
　炭化タングステン粒子（平均粒子径１００ｎｍ）を、シリカ粒子（平均粒子径１００ｎｍ）に変更したこと以外は実施例１と同様にして、導電性粒子を得た。 (Comparative Example 2)
Conductive particles were obtained in the same manner as in Example 1 except that the tungsten carbide particles (average particle size 100 nm) were changed to silica particles (average particle size 100 nm).
　（実施例１７）
　（１）パラジウム付着工程
　粒子径が３．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ－２０３」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着した樹脂粒子を得た。 (Example 17)
(1) Palladium adhesion step Divinylbenzene resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 μm were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles with palladium attached.
　（２）導電材付着工程
　パラジウムが付着した樹脂粒子をイオン交換水４００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、炭化タングステン粒子（平均粒子径１００ｎｍ）を５重量％含むスラリー４００ｇを、得られた分散液に３分間かけて添加し、導電材が付着した樹脂粒子を含む懸濁液を得た。 (2) Conductive Material Adhering Step The resin particles to which palladium was attached were stirred and dispersed in 400 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 400 g of a slurry containing 5% by weight of tungsten carbide particles (average particle size 100 nm) was added to the obtained dispersion over 3 minutes to obtain a suspension containing resin particles to which a conductive material adhered.
　（３）無電解銅めっき工程
　硫酸銅０．２３ｍｏｌ／Ｌ、エチレンジアミン四酢酸塩２．３ｍｏｌ／Ｌ、ホルマリン０．５ｍｏｌ／Ｌを含む銅めっき液（ｐＨ１２．５）を用意した。得られた懸濁液を６０℃にて攪拌しながら、上記銅めっき液を懸濁液に徐々に滴下し、無電解銅めっきを行った。その後、懸濁液を濾過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面上に銅導電層（厚み０．１μｍ）配置された導電性粒子を得た。 (3) Electroless copper plating step A copper plating solution (pH 12.5) containing 0.23 mol / L copper sulfate, 2.3 mol / L ethylenediaminetetraacetate, and 0.5 mol / L formalin was prepared. While stirring the obtained suspension at 60 ° C., the copper plating solution was gradually added dropwise to the suspension to perform electroless copper plating. Thereafter, by filtering the suspension, the particles were taken out, washed with water, and dried to obtain conductive particles in which a copper conductive layer (thickness: 0.1 μm) was disposed on the surface of the resin particles.
　（評価）
　（１）接続抵抗
　接続構造体の作製：
　ビスフェノールＡ型エポキシ樹脂（三菱化学社製「エピコート１００９」）１０重量部と、アクリルゴム（重量平均分子量約８０万）４０重量部と、メチルエチルケトン２００重量部と、マイクロカプセル型硬化剤（旭化成ケミカルズ社製「ＨＸ３９４１ＨＰ」）５０重量部と、シランカップリング剤（東レダウコーニングシリコーン社製「ＳＨ６０４０」）２重量部とを混合し、導電性粒子を含有量が３重量％となるように添加し、分散させ、樹脂組成物を得た。 (Evaluation)
(1) Connection resistance Fabrication of connection structure:
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP" manufactured by HX3941) and 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight. A resin composition was obtained by dispersing.
　得られた樹脂組成物を、片面が離型処理された厚さ５０μｍのＰＥＴ（ポリエチレンテレフタレート）フィルムに塗布し、７０℃の熱風で５分間乾燥し、異方性導電フィルムを作製した。得られた異方性導電フィルムの厚さは１２μｍであった。 The obtained resin composition was applied to a 50 μm-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film. The thickness of the obtained anisotropic conductive film was 12 μm.
　得られた異方性導電フィルムを５ｍｍ×５ｍｍの大きさに切断した。切断された異方性導電フィルムを、一方に抵抗測定用の引き回し線を有するアルミニウム電極（高さ０．２μｍ、Ｌ／Ｓ＝２０μｍ／２０μｍ）を有するガラス基板（幅３ｃｍ、長さ３ｃｍ）のアルミニウム電極側のほぼ中央に貼り付けた。次いで、同じアルミニウム電極を有する２層フレキシブルプリント基板（幅２ｃｍ、長さ１ｃｍ）を、電極同士が重なるように位置合わせをしてから貼り合わせた。このガラス基板と２層フレキシブルプリント基板との積層体を、１０Ｎ、１８０℃、及び２０秒間の圧着条件で熱圧着し、接続構造体を得た。なお、ポリイミドフィルムにアルミニウム電極が直接形成されている２層フレキシブルプリント基板を用いた。 The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. The cut anisotropic conductive film is formed of a glass substrate (width 3 cm, length 3 cm) having an aluminum electrode (height 0.2 μm, L / S = 20 μm / 20 μm) having a lead wire for resistance measurement on one side. Affixed almost at the center on the aluminum electrode side. Next, a two-layer flexible printed board (width 2 cm, length 1 cm) having the same aluminum electrode was bonded after being aligned so that the electrodes overlap each other. The laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure. A two-layer flexible printed board in which an aluminum electrode is directly formed on a polyimide film was used.
　接続抵抗の測定：
　得られた接続構造体の対向する電極間の接続抵抗を４端子法により測定した。また、接続抵抗を下記の基準で判定した。 Connection resistance measurement:
The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Further, the connection resistance was determined according to the following criteria.
　［接続抵抗の評価基準］
　○○：参考例１の導電性粒子を用いた場合の接続抵抗の９０％未満
　○：参考例１の導電性粒子を用いた場合の接続抵抗の９０％以上、９５％未満
　△：参考例１の導電性粒子を用いた場合の接続抵抗の９５％以上、１０５％未満
　×：参考例１の導電性粒子を用いた場合の接続抵抗の１０５％以上 [Evaluation criteria for connection resistance]
◯: Less than 90% of connection resistance when using conductive particles of Reference Example 1 ○: 90% or more and less than 95% of connection resistance when using conductive particles of Reference Example 1 Δ: Reference Example 1 95% or more of connection resistance when using conductive particles of less than 105% ×: 105% or more of connection resistance when using conductive particles of Reference Example 1
　結果を下記の表１，２に示す。 The results are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　１…導電性粒子
　１ａ…突起
　２…基材粒子
　３…導電層
　３ａ…突起
　４…導電材
　５…絶縁性物質
　１１…導電性粒子
　１１ａ…突起
　１２…第１の導電層
　１３…第２の導電層
　１３ａ…突起
　２１…導電性粒子
　２２…導電層
　５１…接続構造体
　５２…第１の接続対象部材
　５２ａ…第１の電極
　５３…第２の接続対象部材
　５３ａ…第２の電極
　５４…接続部 DESCRIPTION OF SYMBOLS 1 ... Conductive particle 1a ... Protrusion 2 ... Base material particle 3 ... Conductive layer 3a ... Protrusion 4 ... Conductive material 5 ... Insulating substance 11 ... Conductive particle 11a ... Protrusion 12 ... 1st conductive layer 13 ... 2nd electroconductivity Layer 13a ... Protrusion 21 ... Conductive particle 22 ... Conductive layer 51 ... Connection structure 52 ... First connection object member 52a ... First electrode 53 ... Second connection object member 53a ... Second electrode 54 ... Connection part

Claims (12)

  1. 　基材粒子と、
    　前記基材粒子の表面上の一部の領域に配置された導電材とを備え、
    　前記導電材の材質が、ニッケルよりもモース硬度が高い材質である、導電性粒子。     Substrate particles,
    A conductive material disposed in a partial region on the surface of the substrate particles,
    The electroconductive particle whose material of the said electrically conductive material is a material whose Mohs hardness is higher than nickel.
  2. 　前記基材粒子と、
    　前記基材粒子の表面上の一部の領域に配置された前記導電材とを備え、
    　前記導電材の材質が、モリブデン、炭化タングステン、タングステン、炭化チタン又は炭化タンタルである、請求項１に記載の導電性粒子。     The substrate particles;
    The conductive material disposed in a partial region on the surface of the substrate particles,
    The conductive particles according to claim 1, wherein a material of the conductive material is molybdenum, tungsten carbide, tungsten, titanium carbide, or tantalum carbide.
  3. 　複数の前記導電材を備える、請求項１又は２に記載の導電性粒子。 The conductive particles according to claim 1, comprising a plurality of the conductive materials.
  4. 　前記基材粒子と、
    　前記基材粒子の表面上に配置されている導電層と、
    　前記基材粒子の表面上の一部の領域に配置されている前記導電材とを備え、
    　前記導電材が、前記導電層内に埋め込まれている、請求項１～３のいずれか１項に記載の導電性粒子。     The substrate particles;
    A conductive layer disposed on the surface of the substrate particles;
    The conductive material disposed in a partial region on the surface of the substrate particles,
    The conductive particle according to any one of claims 1 to 3, wherein the conductive material is embedded in the conductive layer.
  5. 　前記導電層が外側の表面に突起を有し、前記導電層の前記突起の内側に前記導電材が配置されている、請求項４に記載の導電性粒子。 The conductive particle according to claim 4, wherein the conductive layer has a protrusion on an outer surface, and the conductive material is disposed inside the protrusion of the conductive layer.
  6. 　前記導電層がニッケル層を有する、請求項４又は５に記載の導電性粒子。 The conductive particles according to claim 4 or 5, wherein the conductive layer has a nickel layer.
  7. 　前記導電層が、前記基材粒子側にニッケル層と、前記基材粒子側とは反対側にパラジウム層とを有する、請求項４～６のいずれか１項に記載の導電性粒子。 The conductive particles according to any one of claims 4 to 6, wherein the conductive layer has a nickel layer on the substrate particle side and a palladium layer on the opposite side to the substrate particle side.
  8. 　前記導電層の表面に付着している絶縁性物質をさらに備える、請求項４～７のいずれか１項に記載の導電性粒子。 The conductive particles according to any one of claims 4 to 7, further comprising an insulating substance attached to a surface of the conductive layer.
  9. 　前記導電材が粒子である、請求項１～８のいずれか１項に記載の導電性粒子。 The conductive particle according to any one of claims 1 to 8, wherein the conductive material is a particle.
  10. 　前記基材粒子と、
    　前記基材粒子の表面上の一部の領域に配置された前記導電材とを備え、
    　前記導電材の材質が、モリブデン、炭化タングステン、タングステン又は炭化タンタルである、請求項１～９のいずれか１項に記載の導電性粒子。     The substrate particles;
    The conductive material disposed in a partial region on the surface of the substrate particles,
    The conductive particles according to any one of claims 1 to 9, wherein a material of the conductive material is molybdenum, tungsten carbide, tungsten, or tantalum carbide.
  11. 　請求項１～１０のいずれか１項に記載の導電性粒子と、バインダー樹脂とを含む、導電材料。 A conductive material comprising the conductive particles according to any one of claims 1 to 10 and a binder resin.
  12. 　第１の電極を表面に有する第１の接続対象部材と、
    　第２の電極を表面に有する第２の接続対象部材と、
    　前記第１の接続対象部材と前記第２の接続対象部材を接続している接続部とを備え、
    　前記接続部が、請求項１～１０のいずれか１項に記載の導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されており、
    　前記第１の電極と前記第２の電極とが前記導電性粒子により電気的に接続されている、接続構造体。     A first connection object member having a first electrode on its surface;
    A second connection target member having a second electrode on its surface;
    A connecting portion connecting the first connection target member and the second connection target member;
    The connection portion is formed of the conductive particles according to any one of claims 1 to 10, or is formed of a conductive material including the conductive particles and a binder resin.
    A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.
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