WO2016121558A1 - 銀被覆粒子及びその製造方法 - Google Patents

銀被覆粒子及びその製造方法 Download PDF

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Publication number
WO2016121558A1
WO2016121558A1 PCT/JP2016/051303 JP2016051303W WO2016121558A1 WO 2016121558 A1 WO2016121558 A1 WO 2016121558A1 JP 2016051303 W JP2016051303 W JP 2016051303W WO 2016121558 A1 WO2016121558 A1 WO 2016121558A1
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WIPO (PCT)
Prior art keywords
silver
particles
coated
resin
mass
Prior art date
Application number
PCT/JP2016/051303
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English (en)
French (fr)
Inventor
寛人 赤池
山崎　和彦
Original Assignee
三菱マテリアル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2015244052A external-priority patent/JP6665514B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to CN202010810748.3A priority Critical patent/CN111951996B/zh
Priority to CN201680007251.XA priority patent/CN107210090A/zh
Priority to US15/545,861 priority patent/US10590540B2/en
Priority to EP16743162.6A priority patent/EP3252780B1/en
Priority to KR1020177020855A priority patent/KR102226646B1/ko
Publication of WO2016121558A1 publication Critical patent/WO2016121558A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1233—Organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/168—Control of temperature, e.g. temperature of bath, substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a silver-coated particle suitable as a conductive filler contained in a conductive adhesive, a conductive film, and a conductive spacer, and a method for producing the same. More specifically, when a shear stress is applied to the mixture of the core particles and the binder resin in order to produce a conductive adhesive or the like, the silver coating layer is cracked or cracked or the silver coating layer is peeled off from the core particles.
  • the present invention relates to silver-coated particles that are difficult to improve and can further improve the conductivity of a conductive adhesive or the like.
  • the conductive adhesive is a mixture of resin and metal conductive particles, and representative examples include a conductive paste and a conductive ink.
  • Conductive pastes and conductive inks are excellent in workability such as stress absorption, low temperature mounting, fine pitch conduction, insulation and no use of flux, and have been used for connecting electrodes of liquid crystal displays, touch panel substrates, keyboards and the like.
  • metal-coated resin particles in which metal particles are coated on core particles of resin particles have been developed as conductive particles. Such metal-coated resin particles have the advantage of reducing manufacturing costs and weight.
  • a conductive electroless-plated powder in which the core particles of the resin particles are electrolessly plated with nickel and the upper surface thereof is coated with gold is disclosed (for example, see Patent Document 1).
  • This conductive electroless plating powder is said to provide high conductive performance by Ni or Ni—Au coating as a plating layer being firmly adhered to resin particles as core particles.
  • it comprises a core particle of spherical resin, a tin adsorption layer provided on the surface of the core particle, and silver coated on the surface of the tin adsorption layer.
  • a silver-coated spherical resin in which the amount of silver is 5 to 80 parts by mass and the crystallite diameter of the silver measured by X-ray diffraction method is in the range of 18 to 24 nm is disclosed (for example, patent document) 2).
  • the spherical resin core particles are catalyzed with tin, and then electrolessly plated with silver to enhance the adhesion of the silver coating.
  • the resin particle in the case of forming a Ni—Au multilayer coating on the core particle of the resin particle, the resin particle is obtained by electrolessly plating the gold after electrolessly plating the core particle of the resin particle.
  • the adhesion between the core particles and gold is improved.
  • nickel plating and gold plating must be performed, and the plating process is complicated.
  • materials, base materials, and time required for the plating are required.
  • silver electroless plating is performed, and the crystallite diameter is as small as 18 to 24 nm.
  • the silver film is made dense and the adhesion is improved.
  • the coated spherical resin obtained by the method of Patent Document 2 has insufficient film strength due to its small crystallite diameter.
  • the silver coating layer is cracked by grain boundary fracture. There was a possibility that cracking occurred, resulting in peeling of the silver coating layer from the core particles, resulting in a decrease in the conductivity of the conductive adhesive.
  • an anisotropic conductive adhesive the peeled-off plated piece becomes a foreign substance and may enter a gap that should be insulated and cause a malfunction.
  • the purpose of the present invention is to produce a conductive adhesive or the like, when a shear stress is applied to a mixture of silver-coated core particles and a binder resin, the silver coating layer is cracked or cracked by grain boundary fracture or It is an object of the present invention to provide a silver-coated particle and a method for producing the same, in which peeling of the silver coating layer from the core particle is less likely to occur and the conductivity of the conductive adhesive or the like can be further improved.
  • a first aspect of the present invention is a silver-coated particle comprising core particles made of resin particles or inorganic particles, and a silver coating layer formed on the surface of the core particle, and is included in the silver coating layer
  • the amount of silver is 5 to 90 parts by mass with respect to 100 parts by mass of the silver-coated particles.
  • the silver-coated particles have a silver crystallite diameter in the range of 35 to 200 nm, which is calculated from the obtained diffraction lines.
  • the crystallite diameter measured by a predetermined X-ray diffraction method is as large as 35 to 200 nm. Excellent.
  • the silver-coated layer is broken due to grain boundary destruction. Cracks or cracks or peeling of the silver coating layer from the core particles hardly occur, and the conductivity of the conductive adhesive or the like can be further improved.
  • a core particle composed of resin particles or inorganic particles is added to an aqueous solution of a tin compound to form a tin adsorption layer on the surface of the core particle;
  • a step of producing a silver-coated particle precursor having a silver coating layer on the surface of the core particles by performing electroless silver plating on the tin adsorption layer using a reducing agent, and washing and drying the silver-coated particle precursor Later, the crystallites of silver constituting the silver coating layer are sintered by heat treatment at a temperature of 100 ° C. or higher and lower than 250 ° C. in the air or immediately after washing with water at a temperature of 100 ° C. or higher and lower than 250 ° C. for 0.5 to 10 hours. And a step of bringing the silver crystallite diameter measured by an X-ray diffraction method into a range of 35 to 200 nm.
  • a silver-coated particle precursor is prepared, washed with water and dried, and then at a temperature of 100 ° C. or more and less than 250 ° C. in the atmosphere or immediately after washing with water 100
  • the crystallites in the silver coating layer are sintered by heat treatment at a temperature of not lower than 250 ° C. and lower than 250 ° C. for 0.5 to 10 hours.
  • the crystallite diameter of silver is increased, the crystallinity of the crystallite is increased, and the crystallite diameter range measured by the X-ray diffraction method is 35 to 200 nm.
  • the silver coating layer coats the core particles more uniformly and securely adheres to the core particles by heat treatment, silver coated particles with improved conductivity can be obtained.
  • the third aspect of the present invention is a method for producing a conductive adhesive by mixing silver-coated particles and a binder resin based on the first aspect.
  • the conductive adhesive produced by the method according to the third aspect of the present invention is excellent in conductivity.
  • a fourth aspect of the present invention is a method for producing a conductive film by applying a resin composition obtained by mixing silver-coated particles and a binder resin based on the first aspect to the surface of a support film.
  • the conductive film produced by the method according to the fourth aspect of the present invention is excellent in conductivity.
  • the resin composition obtained by mixing the silver-coated particles and the binder resin based on the first aspect is applied to the surface of either or both of the two substrates, and then the two sheets. This is a method for manufacturing a conductive spacer by bonding the substrates.
  • the conductive spacer manufactured by the method according to the fifth aspect of the present invention is excellent in conductivity.
  • the silver coating layer is less likely to crack or crack or peel from the core particles of the silver coating layer.
  • a silver-coated spherical resin that can further improve the electrical conductivity of a conductive adhesive or the like and a method for producing the same can be provided.
  • FIG. 1 is a diagram showing a TEM image (magnification of 500,000 times) of the cross section of the silver coating layer of the silver-coated particles P1 of Example 2.
  • FIG. The core particle 2 and the silver coating layer 1 of the silver coating particle P1 of the present invention are shown together with the hardened resin 3.
  • FIG. 2 is a view showing a TEM image (magnification of 500,000 times) of a cross section of the silver coating layer of the silver-coated particles P2 of Comparative Example 2.
  • the core particle 12 and the silver coating layer 11 of the silver coating particle P2 of the comparative example are shown together with the hardened resin 13.
  • the silver-coated particle P ⁇ b> 1 of the present embodiment includes a core particle 2 (mother particle) and a silver coating layer 1 formed on the surface of the core particle 2.
  • the silver crystallite diameter calculated from the obtained diffraction line is in the range of 35 to 200 nm, preferably in the range of 40 to 80 nm, and the silver coating layer 1 covers the core particle 2 without gaps. If the crystallite diameter of silver is less than 35 nm, the silver coating layer 1 does not cover the core particles 2 without any gaps, and the coverage, adhesion and coating strength of the silver coating layer 1 to the core particles 2 are poor. If it exceeds 200 nm, the silver coating layer 1 shrinks due to oversintering during production, and silver aggregates on the core particles 2, and the coverage of the silver coating layer 1 tends to decrease, and the core particles 2 become resin particles. In this case, the appearance of the silver-coated particles P1 is impaired by deformation, and the silver coating layer 1 may be peeled off.
  • the method for producing silver-coated particles of the present embodiment includes the step of adding the core particles 2 to an aqueous solution of a tin compound kept at 25 to 45 ° C. to form a tin adsorption layer on the surface of the core particles 2; A step of producing a silver-coated particle precursor having a silver coating layer 1 on the surface of the core particle 2 by performing electroless silver plating on the tin adsorption layer formed on the surface of the core particle 2 using a reducing agent; The method includes a step of heat-treating the coated particle precursor after being washed with water and dried at a temperature of 100 ° C. or more and less than 250 ° C. in the atmosphere or immediately after washing with water at a temperature of 100 ° C. or more and less than 250 ° C. for 0.5 to 10 hours.
  • the core particle 2 serving as a base of the silver-coated particle P1 includes spherical particles having a high degree of circularity or irregularly shaped particles having a low degree of circularity.
  • the spherical particles may be substantially spherical particles, and include, for example, perfect spherical particles, particles having an almost spherical shape such as an ellipse, and particles having a slight unevenness on the surface. Examples of irregularly shaped particles include rod-like, plate-like, and scale-like particles.
  • the core particle 2 is made of resin particles or inorganic particles in terms of material.
  • the resin core particles 2 include silicone-based, acrylic-based, phenol-based, and styrene-based resins. These resins have characteristics required when the silver-coated particles P1 are used in anisotropic conductive adhesives or conductive films, for example, how to collapse the filler when a load is applied to the filler. This is because the recovery rate is high when the load is unloaded.
  • the silicone resin include silicone resin, silicone rubber, silicone resin-coated silicone rubber, and the like.
  • acrylic resins include methyl methacrylate resin (PMMA resin), acrylic-styrene copolymer resin (AS resin), modified acrylic resin, etc.
  • phenolic resins include phenol resin and phenol / formaldehyde resin.
  • Phenol / furfural resin examples include polystyrene resin, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), and the like.
  • examples of the inorganic core particle 2 include talc (talc), silica, mica, alumina, or boron nitride.
  • the average particle size of the core particles 2 is desirably in the range of 0.5 to 40 ⁇ m.
  • the average particle diameter of the core particle 2 is less than 0.5 ⁇ m, the surface area of the core particle 2 becomes large, and it is necessary to increase the amount of silver for obtaining the necessary conductivity as the conductive filler or conductive particle.
  • the average particle diameter of the core particles 2 is larger than 40 ⁇ m, it is difficult to apply the silver-coated particles P1 to the fine pattern.
  • the average particle size of the core particles 2 is 300 core particles at a magnification of 2000 times using a scanning electron microscope (model number: S-4300SE) manufactured by Hitachi High-Technologies Corporation and using software (product name: PC SEM). The particle size of 2 is measured. And the average value of this measured value is calculated and an average particle diameter is obtained. In addition, in the core particle 2 having a shape other than a true sphere, a value obtained by averaging long sides is referred to as an average particle diameter.
  • a silver coating layer 1 is provided on the surface of the core particle 2.
  • a nonconductor such as an organic material or an inorganic material
  • a treatment for providing a tin adsorption layer on the surface of the core particle 2 is performed as a catalyst treatment, and then an electroless silver plating treatment is performed to form the silver coating layer 1.
  • the silver coating layer 1 of the present embodiment is prepared by adding the core particle 2 to an aqueous solution of a tin compound kept at 25 to 45 ° C. to form a tin adsorption layer on the surface of the core particle 2.
  • the tin adsorption layer is formed on the surface of the core particle 2 by performing electroless silver plating using a reducing agent.
  • a material in which the silver coating layer 1 is formed on the surface of the core particle 2 by electroless silver plating is referred to as a silver-coated particle precursor, and a material obtained by heat-treating this precursor is referred to as a silver-coated particle P1.
  • the core particles 2 are added to an aqueous solution of a tin compound and stirred, and then the core particles 2 are separated by filtration and washed with water.
  • the stirring time is appropriately determined depending on the temperature of the following tin compound aqueous solution and the content of the tin compound, and is preferably 0.5 to 24 hours.
  • the temperature of the aqueous solution of the tin compound is preferably 25 to 45 ° C. If the temperature of the aqueous solution of the tin compound is less than 25 ° C., the temperature is too low and the activity of the aqueous solution becomes low, and the tin compound does not adhere sufficiently to the core particles 2.
  • tin compound examples include stannous chloride, stannous fluoride, stannous bromide, stannous iodide, and the like.
  • the content of tin in the aqueous solution when the above tin compound is used is preferably 20 g / dm 3 or more, and can be contained in the aqueous solution until a saturated concentration is reached.
  • electroless silver plating is performed on the tin adsorption layer using a reducing agent, thereby forming a silver coating layer 1 on the surface of the core particle 2 to form a silver coated particle precursor. Get the body.
  • (I) a method of immersing the core particle 2 having a tin adsorption layer formed on the surface thereof in an aqueous solution containing a complexing agent, a reducing agent, etc., and dropping a silver salt aqueous solution
  • (II) A method of immersing the core particle 2 having a tin adsorption layer formed on the surface thereof in an aqueous solution containing a silver salt and a complexing agent and dropping the aqueous solution of the reducing agent
  • a method in which the core particles 2 having a tin adsorption layer formed on the surface thereof are immersed in the aqueous solution and a caustic aqueous solution is dropped is used.
  • silver salt silver nitrate or silver nitrate dissolved in nitric acid
  • Complexing agents include ammonia, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid tetrasodium, nitrotriacetic acid, triethylenetetraamminehexaacetic acid, sodium thiosulfate, succinate, succinimide, citrate or iodide salts, etc.
  • reducing agent formalin, glucose, imidazole, Rochelle salt (sodium potassium tartrate), hydrazine and its derivatives, hydroquinone, L-ascorbic acid or formic acid can be used.
  • formaldehyde is preferable because of its strong reducing power, a mixture of two or more reducing agents containing at least formaldehyde is more preferable, and a mixture of reducing agent containing formaldehyde and glucose is most preferable.
  • a substitution reaction between tin and silver ions in the tin adsorption layer starts, and metallic silver as a nucleus is deposited on the surface of the core particle 2.
  • a silver coating layer having a predetermined crystallite diameter is formed on the surface of the core particle 2 to obtain a silver-coated particle precursor.
  • Drying is performed by putting the silver-coated particle precursor washed with water into a container such as a stainless bat and maintaining the temperature at 50 to 80 ° C. using a vacuum dryer.
  • the dried silver-coated particle precursor is put in a container similar to that at the time of drying, the bulk thickness is set to 1 cm or less, and the temperature is 100 ° C. or more and less than 250 ° C. in the air using a blow dryer or an electric muffle furnace. For 0.5 to 10 hours.
  • the suspension is stirred at a rotational speed of 100 to 300 rpm in an autoclave.
  • the cake obtained by filtering the suspension is dried at a temperature of 50 to 80 ° C. using a vacuum dryer. Done.
  • the treatment in the air has an advantage that the treatment can be easily performed without requiring special equipment, and the treatment in the water has an advantage that a uniform heat treatment is possible.
  • heat treatment may be performed in the air using an apparatus such as an airflow dryer or a spray dryer.
  • an apparatus such as an airflow dryer or a spray dryer.
  • the heat treatment temperature is less than 100 ° C. and the heat treatment time is less than 0.5 hours, the silver of the silver coating layer 1 is not thermally diffused and sintering hardly occurs, so that the crystallinity is low.
  • the heat treatment temperature exceeds 250 ° C. or more, or the heat treatment time exceeds 10 hours, peeling of the silver coating layer 1 due to thermal stress between the silver coating layer 1 and the core particles and aggregation of silver accompanying the peeling proceed. This causes problems.
  • a preferable heat treatment temperature is 120 to 200 ° C., and a heat treatment time is 1 to 5 hours.
  • the size of the silver crystallite diameter of the silver coating layer 1 can be controlled within the range of 35 to 200 nm. Specifically, as the heat treatment temperature is increased or the heat treatment time is increased, the silver of the silver coating layer 1 is sintered and the crystallite diameter of the silver is increased, so that the heat treatment temperature is lowered or the heat treatment time is shortened. The more the silver sinter of the silver coating layer 1 progresses, the smaller the silver crystallite diameter.
  • the amount of silver contained in the silver coating layer 1 formed on the surface of the silver-coated particles P1 is 5 to 90 parts by mass with respect to 100 parts by mass of the silver-coated particles.
  • the silver coating amount (content) is determined by the average particle size of the resin and the required conductivity.
  • the silver content is less than 5 parts by mass with respect to 100 parts by mass of the silver-coated particles, the silver coating layer 1 does not cover the core particles 2 without any gaps even when the heat treatment described above is performed.
  • the silver-coated particles P1 are dispersed as the conductive particles, it is difficult to obtain a contact point between silver and sufficient conductivity cannot be imparted.
  • specific gravity will become large and cost will become high, and conductivity will be saturated.
  • the silver content is preferably 28 to 80 parts by mass, more preferably 28 to 70 parts by mass.
  • the silver-coated particle P1 of this embodiment is excellent as a conductive filler or conductive particle, and can be optimally applied to a conductive adhesive, a conductive adhesive, a conductive film, or a conductive spacer, in particular.
  • the conductive adhesive is classified into an isotropic conductive adhesive (ICA) and an anisotropic conductive adhesive (ACA). Moreover, it has a paste form, a film form, or an ink form depending on the form of the binder.
  • ICA isotropic conductive adhesive
  • ACA anisotropic conductive adhesive
  • the binder shrinks when the binder is cured, so that the fillers are in contact with each other in the vertical direction, the horizontal direction, and the diagonal direction. can get. It is also possible to form a sheet with an isotropic conductive adhesive.
  • the anisotropic conductive adhesive the anisotropic conductive adhesive is sandwiched between conductive materials in which a filler is dispersed in a binder and the conductive materials to be connected are connected.
  • the conductive material to be connected to the filler between the conductive materials to be connected comes into contact in the vertical direction, and conductivity is obtained.
  • the fillers are arranged in the lateral direction via a binder which is an insulator, and the conductivity is not obtained because they do not contact each other.
  • the conductive adhesive examples include anisotropic or isotropic conductive paste, anisotropic or isotropic conductive ink, and the like.
  • the conductive adhesive is prepared by uniformly mixing the conductive particles made of the silver-coated particles P1 of the present embodiment and the insulating binder resin using a kneader such as a planetary mixer or a three-roll mill. .
  • the conductive particles are uniformly dispersed in the insulating binder resin.
  • the content of the silver-coated particles P1 is not particularly limited and is appropriately determined depending on the application and the like.
  • the insulating binder resin in the conductive adhesive is not particularly limited, and examples thereof include a composition that is cured by heat and light, such as a thermoplastic resin and a curable resin composition.
  • a thermoplastic resin include a styrene-butadiene block copolymer, an acrylate resin, and an ethylene-vinyl acetate resin.
  • the curable resin composition include a resin composition containing an epoxy monomer or oligomer having a glycidyl group and a curing agent such as isocyanate.
  • the conductive film there is an anisotropic or isotropic conductive film formed into a film shape.
  • the conductive film is prepared by first preparing a resin composition in which conductive particles made of the silver-coated particles P1 of the present embodiment are dispersed in an insulating binder resin, and then applying this resin composition to the surface of a support film such as PET. It is produced by applying to.
  • This resin composition is prepared by uniformly mixing conductive particles and an insulating binder resin using a kneader such as a planetary mixer or a three-roll mill. In the conductive film, the conductive particles are uniformly dispersed in the insulating binder resin on the support film.
  • the insulating binder resin in the conductive film examples include a resin composition containing a thermosetting resin such as an epoxy resin or a phenoxy resin as a main component.
  • the content of the silver-coated particles P1 in the resin composition in the conductive film is not particularly limited, and is appropriately determined depending on the application and the like, but is 0.5 to 10 parts by mass relative to 100 parts by mass of the binder resin A range is preferred.
  • the conductive spacer is used by electrically connecting the wiring portions of the two upper and lower substrates sandwiching the liquid crystal substance vertically and holding the gap between the substrates at a predetermined dimension.
  • the conductive spacer is obtained by first adding conductive particles made of the silver-coated particles P1 of the present embodiment to an insulating binder resin such as a thermosetting resin or an ultraviolet light curable adhesive, and then the conductive particles and the binder resin.
  • an insulating binder resin such as a thermosetting resin or an ultraviolet light curable adhesive
  • the conductive particles and the binder resin are prepared by uniformly mixing using a kneader such as a planetary mixer or a three-roll mill, and then applying the above resin composition to one or both of the wiring portions of the upper and lower two substrates to prepare two sheets. It is manufactured by bonding the substrates.
  • the content of the silver-coated particles P1 is not particularly limited and is appropriately determined depending on the application and the like, but is preferably in the range of 2 to 10 parts by mass
  • the conductive adhesive, the conductive film or the conductive spacer including the conductive particles made of the silver-coated particles P1 of the present embodiment has a high shearing force when kneading the mixture of the conductive particles and the insulating binder resin. Even if it is over, the silver coating layer 1 is hardly cracked or cracked or peeled off from the core particles 2 of the silver coating layer 1, and the conductivity is further improved. Thereby, when the silver covering particle P1 of this invention is used for an anisotropic conductive adhesive, for example, the short circuit of anisotropic conduction (lateral direction) can be avoided and reliability improves.
  • Example 1 First, 20 g of stannous chloride and 15 cm 3 of hydrochloric acid having a concentration of 35% were diluted to 1 dm 3 with water using a 1 dm 3 volumetric flask and kept at 30 ° C. To this aqueous solution, 50 g of a spherical acrylic-styrene copolymer resin having an average particle size of 10 ⁇ m as core particles serving as a base is added and stirred for 1 hour, and then the acrylic-styrene copolymer resin is filtered off and washed with water. The pretreatment was performed.
  • a silver coating layer was formed by electroless plating on the surface of the acrylic-styrene copolymer resin having a tin adsorption layer formed on the surface by the pretreatment.
  • 40 g of sodium ethylenediaminetetraacetate as a complexing agent, 20.0 g of sodium hydroxide as a pH adjusting agent, and 15 ml of formalin (formaldehyde concentration 37% by mass) as a reducing agent are added to 2 dm 3 of water.
  • a slurry was prepared by immersing the pretreated acrylic-styrene copolymer resin in this aqueous solution.
  • This silver-coated particle precursor is loosened from the aggregated particles using a 325 mesh stainless steel plain weave wire mesh and a vibrating sieve, and then the loose silver-coated particle precursor is spread on a stainless steel bat so that the thickness is 1 mm. After heating up to 140 ° C. in 30 minutes in the furnace, the same temperature was maintained for 4 hours and heat treatment was performed to sinter the silver crystallites of the silver coating layer. Silver-coated particles having an amount of 45% by mass were obtained.
  • Example 2 As a core particle serving as a base material, a spherical acrylic-styrene copolymer resin having an average particle diameter of 3 ⁇ m was used to adjust the mass of silver to be plated. The temperature during the heat treatment was 150 ° C. and the holding time was 3 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle
  • FIG. 1 shows a TEM image (magnification of 500,000 times) of a cross section of the silver coating layer of the silver-coated particles.
  • the inner side of the silver coating layer 1 is a core particle 2 as a base, and the outer side of the silver coating layer is a solidified resin 3.
  • Example 3 As a core particle serving as a base, a spherical acrylic-styrene copolymer resin having an average particle diameter of 1 ⁇ m was used to adjust the mass of silver to be plated. The temperature during the heat treatment was 120 ° C. and the holding time was 7 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 90 mass% with respect to 100 mass% of silver covering particles.
  • Example 1 was carried out in the same manner as Example 1 except that the mass of silver to be plated was adjusted using a spherical acrylic-styrene copolymer resin having an average particle diameter of 20 ⁇ m as the core particle serving as a base. It carried out similarly and obtained the silver covering particle
  • Example 5 As a core particle serving as a base, a spherical acrylic-styrene copolymer resin having an average particle diameter of 40 ⁇ m was used to adjust the mass of silver to be plated. The temperature during the heat treatment was 160 ° C. and the holding time was 1.5 hours. Other than that, it carried out similarly to Example 1 and obtained the silver covering particle whose quantity of silver is 15 mass% with respect to 100 mass% of silver covering particles.
  • Example 6 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base, and the mass of silver to be plated was adjusted. The temperature during the heat treatment was 130 ° C. and the holding time was 4 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 20 mass% with respect to 100 mass% of silver covering particles.
  • Example 7 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base, and the mass of silver to be plated was adjusted. The temperature during the heat treatment was 160 ° C. and the holding time was 6 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle
  • Example 8> The same acrylic-styrene copolymer resin as in Example 5 was used as the core particle serving as a base, and the mass of silver to be plated was adjusted. Other than that was carried out similarly to Example 5, and obtained the silver covering particle whose quantity of silver is 5 mass% with respect to 100 mass% of silver covering particles.
  • Example 9 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed at 100 ° C. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 10 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material.
  • the heat treatment in the atmosphere of Example 1 was performed at 200 ° C.
  • Example 11 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed for 0.5 hour. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 12 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed for 10 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 13> The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material.
  • a silver-coated particle precursor was obtained in the same manner as in Example 1 except that Example 1 was not dried.
  • the obtained silver-coated particle precursor was heat-treated in water. Specifically, after suspending the silver-coated particle precursor in ion-exchanged water so as to be 10% by mass, the suspension is stirred at a rotation speed of 150 rpm in an autoclave at a temperature of 150 ° C. After heat treatment by holding for 3 hours to sinter the silver crystallites of the silver coating layer, the cake obtained by filtering the suspension was dried at a temperature of 60 ° C. using a vacuum dryer. Thereby, the silver covering particle
  • Example 14 A spherical phenol resin having an average particle diameter of 10 ⁇ m was used as the core particle serving as a base, the temperature during heat treatment was 160 ° C., and the holding time was 1 hour. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 15 A spherical polystyrene resin having an average particle diameter of 10 ⁇ m was used as the core particle serving as a base, and the temperature during the heat treatment was 120 ° C. and the holding time was 8 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 17 As a core particle serving as a base, a silicone resin atomized in a rod shape having an average particle diameter of 10 ⁇ m was used, and the mass of silver to be plated was adjusted. The temperature during the heat treatment was 130 ° C. and the holding time was 5 hours. Other than that was carried out similarly to Example 1, and obtained silver covering particle
  • Example 18 A plate-like boron nitride powder having an average particle diameter of 8 ⁇ m was used as the core particle as a base, and the mass of silver to be plated was adjusted. Other than that was carried out similarly to Example 1, and obtained the silver covering particle
  • Example 19 As the core particle serving as a base, scaly talc powder having an average particle diameter of 5 ⁇ m was used, and the mass of silver to be plated was adjusted. The temperature during the heat treatment was 150 ° C. and the holding time was 3 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 70 mass% with respect to 100 mass% of silver covering particles.
  • Example 20 Spherical silicone rubber particles having an average particle diameter of 10 ⁇ m were used as core particles serving as a base, and the mass of silver to be plated was prepared. The temperature during the heat treatment was 245 ° C., and the holding time was 1 hour. Other than that was carried out similarly to Example 1, and obtained the silver covering particle
  • Example 1 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. A silver-coated particle precursor was obtained in the same manner as in Example 1. The obtained silver-coated particle precursor was not heat-treated. As a result, silver-coated particles having a silver content of 45% by mass with respect to 100% by mass of the silver-coated particles were obtained.
  • Example 2 The same acrylic-styrene copolymer resin as in Example 2 was used as the core particle as a base material. In the same manner as in Example 2, a silver-coated particle precursor was obtained. The obtained silver-coated particle precursor was not heat-treated. As a result, silver-coated particles having 65% by mass of silver with respect to 100% by mass of silver-coated particles were obtained. The silver-coated particles were solidified with an epoxy resin and sliced in the same manner as in Example 2 and then observed with a TEM. FIG. 2 shows a TEM image (magnification of 500,000 times) of the cross section of the silver coating layer of the silver coating particle P2. In FIG. 2, the inner side of the silver coating layer 11 is a core particle 12 that becomes a base, and the outer side of the silver coating layer is a solidified resin 13.
  • Example 3 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed for 0.25 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 4 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed for 11 hours. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 5 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed at 90 ° C. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • Example 6 The same acrylic-styrene copolymer resin as in Example 1 was used as the core particle as a base material. The heat treatment in the atmosphere of Example 1 was performed at 255 ° C. Other than that was carried out similarly to Example 1, and obtained the silver covering particle whose quantity of silver is 45 mass% with respect to 100 mass% of silver covering particles.
  • ⁇ Comparative Example 7> A scale-like talc powder having an average particle diameter of 3 ⁇ m was used as the core particle as a base, and the mass of silver to be plated was adjusted. Otherwise, a silver-coated particle precursor was obtained in the same manner as in Example 1. The obtained silver-coated particle precursor was not heat-treated. As a result, silver coated particles having an amount of silver of 78% by mass with respect to 100% by mass of the silver coated particles were obtained.
  • Table 1 shows the material of the core particles, the average particle diameter, the amount of silver in the silver-coated particles, the heat treatment atmosphere, the heat treatment temperature and the heat treatment time when producing the silver-coated particles in Examples 1 to 19 and Comparative Examples 1 to 7.
  • AS resin means “acryl-styrene copolymer resin”.
  • Average film thickness of silver coating layer The average film thickness of the silver coating layer is the average film thickness d, the value obtained by dividing the average particle diameter of the core particles by 2, r, the core particle specific gravity dcore, and the silver specific gravity. DAg, and the ratio of the mass of silver in the silver-coated particles to the mass of the silver-coated particles was calculated from the following equation.
  • the crystallite diameter of silver in the silver coating layer is obtained by filling the obtained powdery silver-coated particles in the sample holder attached to this apparatus using an X-ray diffraction apparatus Empirean manufactured by PANalytical.
  • This method is the method used to measure the crystallite diameter of silver in Patent Document 2 described above (see paragraph [0021] of Patent Document 2).
  • an average value of crystallite diameters in the (111) plane, (200) plane, (220) plane, and (311) plane of the silver crystal is calculated as the crystallite diameter value.
  • the “silver crystallite diameter in the range of 18 to 24 nm” obtained is determined by the measurement method of the present invention to be “silver crystallite diameter in the range of 26 to 34 nm”.
  • a shear stress test is performed by the following method. 80 parts by mass of silver-coated particles are made into a paste-like mixture using 20 parts by mass of ethylene glycol and a planetary mixer (Shinky Co., Ltd. Awatori Netaro). This paste-like mixture was kneaded 10 times in a three-roll mill (EXACT M-80E) to apply shear stress to the silver-coated particles. The rotation speed of the three rolls at this time was set to 30 rpm, 55 rpm, and 100 rpm, and the interval between the rolls was set to a value that is five times the particle diameter of the silver-coated particles.
  • appearance A is a state in which the silver-coated particles having cracks, cracks, or peeling from the core particles of the silver coating layer are 5% or less of the total
  • appearance B is a state of 5 to 20%.
  • 20% to 100% is the appearance C.
  • the shear stress test is performed on the silver-coated particles by the method described in (3) above.
  • a compression test of the silver-coated particles is performed before and after the shear stress test. This compression test is performed in a state where one silver-coated particle is compressed in the vertical direction using a micro compression tester (manufactured by Shimadzu Corporation, MCT-W200J).
  • the compression ratio was 20% in the case of spherical particles, and 5% in the case of particles having an aspect ratio of 2 or more, such as plate-like particles.
  • the electrical resistance value of the silver-coated particles when compressed is measured by energizing with the same apparatus. The average of the resistance values when 10 silver-coated particles are measured per condition is taken as a measured value.
  • Example 3 in which the amount of silver in the silver-coated particles was the upper limit, although the cost increased due to the increase in the amount of silver, the plating appearance and compression before and after the application of shear stress were the same as above. There was almost no change in the resistance value at the time, and silver coated particles suitable for applications such as adhesives and conductive spacers were obtained.
  • Example 6 in which the crystallite diameter of silver was the lower limit and Example 7 in which the upper limit was reached, the resistance value during compression before and after applying shear stress was slightly changed, but good silver coating including appearance Became particles.
  • Example 8 in which the amount of silver in the silver-coated particles became the lower limit, although the initial resistance value was slightly high, the change before and after the application of the shear stress was small, and the silver-coated particles were good including the appearance.
  • Example 9 in which the heat treatment was performed at a relatively low temperature
  • Example 11 in which the heat treatment was performed with a relatively short heat treatment time
  • the crystallite diameter became a smaller value depending on the treatment.
  • the resistance value during compression before and after applying the shear stress it was a good silver-coated particle including the appearance.
  • Example 19 in which talc, which is an inorganic substance, was used as the core particle, although the resistance value at the time of compression was relatively high, the change before and after the application of shear stress was small, and the silver-coated particle having good appearance and appearance It became.
  • the silver-coated particles of Comparative Examples 1, 2, and 7 that were not heat-treated the silver-coated particles of Comparative Example 3 with a heat treatment time of less than 0.5 hours, and the silver-coated particles of Comparative Example 5 with a heat treatment temperature of less than 100 ° C Since the crystallite diameter of the particles was less than 35 nm, the silver peeled off after application of shear stress, the appearance was impaired, and the resistance value during compression showed a high value of 1000 or more, which is not suitable as conductive particles. It became.
  • the crystallite diameter exceeded 200 nm because the heat treatment time was too long.
  • the silver-coated particles are deformed by the shrinkage of the silver-coated layer due to staking, and partial peeling of the silver is observed both before and after application of shear stress, and the appearance is impaired, and the resistance values during compression are as high as 820 ⁇ and 1000 ⁇ or more, respectively. It showed a value and became an unsuitable state as conductive particles.
  • FIG. 1 which showed the TEM image (magnification 500,000 times) of the silver coating layer cross section of the silver coating particle of Example 2, since silver in a silver coating layer sintered and the crystallite diameter became large, silver coating The layer covered the core particles without gaps. As a result, the silver coating layer did not peel even after the application of shear stress, and a smooth coating layer was maintained.
  • FIG. 2 which shows the TEM image (magnification 500,000 times) of the silver coating layer cross section of the silver coating particle of the comparative example 2, since the silver crystallite in a silver coating layer is small, a silver coating layer is a core particle without a gap. Was not coated. As a result, silver was peeled off by grain boundary fracture when shear stress was applied.
  • the silver-coated particles of the present invention can be used as conductive fillers or conductive particles for anisotropic or isotropic conductive adhesives, anisotropic or isotropic conductive films, and conductive spacers. .
  • Silver coating particle 1 Silver coating layer 2 Core particle (mother particle) 3 Solidified resin P2 Silver coated particles (comparative example) 11 Silver coating layer (comparative example) 12 Core particles (mother particles, comparative example) 13 Hardened resin (comparative example)

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Abstract

　無機又は樹脂粒子からなるコア粒子（２）と、このコア粒子（２）の表面に形成された銀被覆層（１）とを備えた銀被覆粒子（Ｐ１）であって、銀被覆層（１）中の銀の量が銀被覆粒子１００質量部に対して５～９０質量部であり、Ｘ線回折装置に付属する試料ホルダーに前記銀被覆粒子（Ｐ１）を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から算出される銀の結晶子径が３５～２００ｎｍの範囲にある銀被覆粒子（Ｐ１）を提供する。

Description

銀被覆粒子及びその製造方法
　本発明は、導電性接着剤、導電性フィルム、導電性スペーサに含まれる導電性フィラーとして好適な銀被覆粒子及びその製造方法に関する。更に詳しくは、導電性接着剤等を作製するために、コア粒子とバインダ樹脂との混合物にせん断応力を加えた際に銀被覆層に亀裂若しくは割れ又は銀被覆層のコア粒子からの剥離が生じにくく、導電性接着剤等の導電性をより向上し得る銀被覆粒子に関するものである。
　本願は、２０１５年１月２８日に日本に出願された特願２０１５－０１３９８４号、および２０１５年１２月１５日に日本に出願された特願２０１５－２４４０５２号に基づき優先権を主張し、その内容をここに援用する。
　鉛はんだの各種代替材料として導電性接着剤が検討されている。導電性接着剤は樹脂と金属の導電性粒子が混合したもので、代表的なものとして導電性ペースト及び導電性インキがある。導電性ペースト及び導電性インキは、応力吸収、低温実装、微小ピッチの導電、絶縁及びフラックスを使用しない等の作業性に優れ、液晶ディスプレイ、タッチパネル基板、キーボード等の電極接続に使用されてきた。このような導電性ペースト、導電性インキを更に使いやすくするために、導電性粒子として樹脂粒子のコア粒子に金属を被覆した金属被覆樹脂粒子が開発されている。こうした金属被覆樹脂粒子は製造コストや重量を低減する特長がある。金属被覆樹脂粒子として、樹脂粒子のコア粒子にニッケルを無電解めっきし、その上面に金を被覆した導電性無電解めっき粉体が開示されている（例えば、特許文献１参照）。この導電性無電解めっき粉体は、コア粒子である樹脂粒子にめっき層であるＮｉ又はＮｉ－Ａｕ被膜が強固に密着して高い導電性能性を付与するとされている。その一方、球状樹脂のコア粒子と、このコア粒子の表面に設けられた錫吸着層と、この錫吸着層の表面に被覆された銀とを具備し、銀被覆球状樹脂１００質量部に対して前記銀の量が５～８０質量部であり、かつＸ線回折法により測定される前記銀の結晶子径が１８～２４ｎｍの範囲にある銀被覆球状樹脂が開示されている（例えば、特許文献２参照）。この銀被覆球状樹脂は、球状樹脂のコア粒子に、錫で触媒化処理を行い、次いで銀の無電解めっきを施し、銀の被膜の密着性を高めている。
日本国特開平０８－３１１６５５号公報（Ａ）（請求項１、段落［００１５］、［００１６］） ＷＯ２０１２／０２３５６６（Ａ）（請求項１）
　特許文献１の方法では、樹脂粒子のコア粒子にＮｉ－Ａｕ複層被膜を形成する場合、樹脂粒子のコア粒子にニッケルの無電解めっきをした後で金の無電解めっきをすることで樹脂粒子のコア粒子と金との密着性を向上させている。しかしこの方法ではニッケルめっき、金めっきをそれぞれしなければならずめっき処理が煩雑である上、そのために必要とされる材料、基材、時間を要していた。一方、特許文献２の方法では、錫で前処理をして球状樹脂のコア粒子の表面に錫吸着層を設けた後、銀の無電解めっきを施し、結晶子径を１８～２４ｎｍという小さな値に制御することで銀の皮膜を緻密にし、密着性を高めている。しかし、この特許文献２の方法で得られる被覆球状樹脂では、その結晶子径が小さいことにより皮膜の強度が十分でなかった。この場合、例えば、導電性接着剤を作製するために、銀を被覆した球状樹脂のコア粒子とバインダ樹脂との混合物に高いせん断力を加えた際に銀の被覆層に粒界破壊により亀裂や割れが生じ、これに起因して銀被覆層のコア粒子からの剥離が発生して、導電性接着剤の導電性の低下を招くおそれがあった。また、異方性の導電性接着剤の場合には剥がれためっき片が異物となり、本来絶縁されるべき隙間に入り込み誤動作を起こすおそれがあった。
　本願発明の目的は、導電性接着剤等を作製するために、銀を被覆したコア粒子とバインダ樹脂との混合物にせん断応力を加えた際に、銀被覆層に粒界破壊による亀裂若しくは割れ又は銀被覆層のコア粒子からの剥離が生じにくく、導電性接着剤等の導電性をより向上し得る銀被覆粒子及びその製造方法を提供することにある。
　本願発明の第１の態様は、樹脂粒子又は無機粒子からなるコア粒子と、このコア粒子の表面に形成された銀被覆層とを備えた銀被覆粒子であって、この銀被覆層に含まれる銀の量が銀被覆粒子１００質量部に対して５～９０質量部であり、Ｘ線回折装置に付属する試料ホルダーに前記銀被覆粒子を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から算出される前記銀の結晶子径が３５～２００ｎｍの範囲にある銀被覆粒子である。
　本発明の第１の態様の銀被覆粒子では、所定のＸ線回折法により測定されるその結晶子径が３５～２００ｎｍと大きいため、銀被覆層によるコア粒子に対する被覆性、密着性及び皮膜強度に優れる。この結果、この銀被覆粒子を用いて導電性接着剤等を作製するために、銀を被覆したコア粒子とバインダ樹脂との混合物に高いせん断力を加えても、銀被覆層に粒界破壊による亀裂若しくは割れ又は銀被覆層のコア粒子からの剥離が生じにくく、導電性接着剤等の導電性をより向上することができる。
　本願発明の第２の態様は、樹脂粒子又は無機粒子からなるコア粒子を錫化合物の水溶液に添加して前記コア粒子の表面に錫吸着層を形成する工程と、前記コア粒子の表面に形成された錫吸着層に還元剤を用いて無電解銀めっきを行って前記コア粒子の表面に銀被覆層を有する銀被覆粒子前駆体を作製する工程と、前記銀被覆粒子前駆体を水洗し乾燥した後で大気中１００℃以上２５０℃未満の温度又は水洗直後に水中１００℃以上２５０℃未満の温度で０．５～１０時間熱処理して前記銀被覆層を構成する銀の結晶子を焼結させ、Ｘ線回折法により測定される前記銀の結晶子径を３５～２００ｎｍの範囲にする工程とを含む銀被覆粒子の製造方法である。
　本願発明の第２の態様の銀被覆粒子の製造方法では、銀被覆粒子前駆体を作製し、これを水洗し乾燥した後で、大気中１００℃以上２５０℃未満の温度又は水洗直後に水中１００℃以上２５０℃未満の温度で０．５～１０時間熱処理することにより、銀被覆層内の結晶子を焼結させる。これにより銀の結晶子径が増大し、その結晶子の結晶化度が高まり、Ｘ線回折法により測定される結晶子径の範囲が３５～２００ｎｍになる。この結果、熱処理により銀被覆層がコア粒子をより均一に被覆しかつコア粒子により確実に密着するため、導電性をより向上した銀被覆粒子が得られる。
　本願発明の第３の態様は、第１の態様に基づく銀被覆粒子とバインダ樹脂とを混合することにより導電性接着剤を製造する方法である。
　本願発明の第３の態様に基づく方法で製造された導電性接着剤は導電性に優れる。
　本願発明の第４の態様は、第１の態様に基づく銀被覆粒子とバインダ樹脂とを混合してなる樹脂組成物を支持フィルム表面に塗布することにより導電性フィルムを製造する方法である。
　本態様発明の第４の態様に基づく方法で製造された導電性フィルムは導電性に優れる。
　本願発明の第５の態様は、第１の観点に基づく銀被覆粒子とバインダ樹脂とを混合してなる樹脂組成物を２枚の基板のいずれか又は双方の表面に塗布した後、前記２枚の基板を貼り合わせることにより導電性スペーサを製造する方法である。
　本願発明の第５の態様に基づく方法で製造された導電性スペーサは導電性に優れる。
　導電性接着剤等を作製するために、コア粒子とバインダ樹脂との混合物にせん断応力を加えた際に、銀被覆層に亀裂若しくは割れ又は銀被覆層のコア粒子からの剥離が生じにくく、導電性接着剤等の導電性をより向上し得る銀被覆球状樹脂及びその製造方法を提供することができる。
図１は実施例２の銀被覆粒子Ｐ１の銀被覆層断面のＴＥＭ像（倍率５０万倍）を示す図である。本願発明の銀被覆粒子Ｐ１のコア粒子２と銀被覆層１とが、固めた樹脂３とともに示されている。 図２は比較例２の銀被覆粒子Ｐ２の銀被覆層断面のＴＥＭ像（倍率５０万倍）を示す図である。比較例の銀被覆粒子Ｐ２のコア粒子１２と銀被覆層１１とが、固めた樹脂１３とともに示されている。
　次に本願発明を実施するための形態を説明する。
〔銀被覆粒子〕
　本実施形態の銀被覆粒子Ｐ１は、コア粒子２（母粒子）と、このコア粒子２の表面に形成された銀被覆層１とを備える。この銀被覆層１に含まれる銀の量は銀被覆粒子１００質量部に対して５～９０質量部であり、かつＸ線回折装置に付属する試料ホルダーに前記銀被覆粒子Ｐ１を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から算出される銀の結晶子径が３５～２００ｎｍの範囲、好ましくは４０～８０ｎｍの範囲にあって、銀被覆層１が隙間なくコア粒子２を被覆する。銀の結晶子径が３５ｎｍ未満であると、銀被覆層１が隙間なくコア粒子２を被覆せず、コア粒子２に対する銀被覆層１の被覆性、密着性と皮膜強度に劣る。２００ｎｍを超えると、製造時の過焼結により銀被覆層１が収縮し、コア粒子２上で銀が凝集し、銀被覆層１の被覆率が低下しやすくなるとともに、コア粒子２が樹脂粒子の場合は変形することで銀被覆粒子Ｐ１の外観が損なわれるとともに、銀被覆層１が剥離するおそれがある。
〔銀被覆粒子の製造方法〕
　本実施形態の銀被覆粒子の製造方法は、上記コア粒子２を２５～４５℃に保温された錫化合物の水溶液に添加して上記コア粒子２の表面に錫吸着層を形成する工程と、上記コア粒子２の表面に形成された錫吸着層に還元剤を用いて無電解銀めっきを行ってコア粒子２の表面に銀被覆層１を有する銀被覆粒子前駆体を作製する工程と、上記銀被覆粒子前駆体を水洗し乾燥した後で大気中１００℃以上２５０℃未満の温度又は水洗直後に水中１００℃以上２５０℃未満の温度で０．５～１０時間熱処理する工程を含む方法である。
〔コア粒子〕
　銀被覆粒子Ｐ１の母体となるコア粒子２は、形状的には円形度の高い球状粒子又は円形度の低い異形粒子を含む。球状粒子は実質的に球状の粒子であればよく、例えば、完全な球形の粒子、楕円のような球形に近い形状の粒子、表面に若干の凹凸がある粒子が含まれる。異形粒子としては、棒状、板状、鱗片状の粒子が挙げられる。またコア粒子２は、材質的には樹脂粒子又は無機粒子からなる。
　樹脂のコア粒子２としては、シリコーン系、アクリル系、フェノール系又はスチレン系樹脂が挙げられる。これらの樹脂は、銀被覆粒子Ｐ１が異方性の導電性接着剤や導電性フィルム等で使用される際に要求される特性、例えばフィラーに荷重による負荷を与えたときのフィラーの潰れ方、及び荷重を除荷したときの回復率が高いためである。シリコーン系の樹脂としては、シリコーン樹脂、シリコーンゴム、シリコーン樹脂被覆シリコーンゴム等が挙げられる。アクリル系の樹脂としては、メタクリル酸メチル樹脂（ＰＭＭＡ樹脂）、アクリルースチレン共重合体樹脂（ＡＳ樹脂）、変性アクリル樹脂等が挙げられ、フェノール系の樹脂としては、フェノール樹脂、フェノール・ホルムアルデヒド樹脂、フェノール・フルフラール樹脂等が挙げられ、スチレン系の樹脂としてポリスチレン樹脂、スチレン・アクリロニトリル共重合体、アクリロニトリル・ブタジエン・スチレン共重合体樹脂（ＡＢＳ樹脂）等が挙げられる。無機のコア粒子２としては、タルク（滑石）、シリカ、マイカ、アルミナ、又は窒化ホウ素が挙げられる。
　コア粒子２の平均粒径は、０．５～４０μｍの範囲内であることが望ましい。コア粒子２の平均粒径が０．５μｍ未満ではコア粒子２の表面積が大きくなり、導電性フィラー又は導電性粒子として必要な導電性を得るための銀の量を多くする必要がある。コア粒子２の平均粒径が４０μｍより大きいと銀被覆粒子Ｐ１を微細パターンに適用することが困難になる。
　コア粒子２の平均粒径は、株式会社日立ハイテクノロジーズ製走査型電子顕微鏡（型番：Ｓ－４３００ＳＥ）を用いて、ソフトウェア（品名：ＰＣ ＳＥＭ）により、倍率：２０００倍で、３００個のコア粒子２の粒径を測定する。そしてこの測定値の平均値を算出して平均粒径が得られる。なお、真球以外の形状をもつコア粒子２においては長辺を平均した値を平均粒径という。
〔無電解銀めっきによる銀被覆層の形成方法／銀被覆粒子前駆体の作製方法〕
　コア粒子２の表面には、銀被覆層１が設けられる。一般に、有機質材料や無機質材料などの不導体の表面に無電解めっきを実施する際には、予め不導体の表面に対して触媒化処理を行う必要がある。本実施形態では、触媒化処理としてコア粒子２の表面に錫吸着層が設ける処理を行い、その後で無電解銀めっき処理を行って銀被覆層１を形成する。具体的には、本実施形態の銀被覆層１は、コア粒子２を２５～４５℃に保温された錫化合物の水溶液に添加してこのコア粒子２の表面に錫吸着層を形成した後、この錫吸着層に還元剤を用いて無電解銀めっきを行うことにより、コア粒子２の表面に形成する。本明細書では、無電解銀めっきによるコア粒子２の表面に銀被覆層１が形成されたものを銀被覆粒子前駆体といい、この前駆体を熱処理したものを銀被覆粒子Ｐ１という。
　上記錫吸着層を形成するためには、錫化合物の水溶液にコア粒子２を添加し攪拌した後、コア粒子２を濾別して水洗する。攪拌時間は、以下の錫化合物の水溶液の温度及び錫化合物の含有量によって適宜決定されるが、好ましくは、０．５～２４時間である。錫化合物の水溶液の温度は、好ましくは２５～４５℃である。錫化合物の水溶液の温度が２５℃未満であると、温度が低く過ぎて水溶液の活性が低くなり、コア粒子２に錫化合物が十分に付着しない。一方、錫化合物の水溶液の温度が４５℃を超えると、錫化合物が酸化するため、水溶液が不安定となり、コア粒子２に錫化合物が十分に付着しない。この処理によりを２５～４５℃の水溶液で実施すると、錫の２価イオンがコア粒子２の表面に付着し錫吸着層が形成される。
　上記錫化合物としては、塩化第一錫、フッ化第一錫、臭化第一錫、ヨウ化第一錫等が挙げられる。上記錫化合物を用いたときの水溶液中の錫の含有量は、２０ｇ／ｄｍ３以上が好ましく、飽和濃度となるまで水溶液に含有させることができる。なお、錫化合物の溶解性を向上するために、水溶液中の錫１ｇに対して塩酸０．８ｃｍ３以上を含有することが好ましい。
　コア粒子２の表面に錫吸着層を形成した後、この錫吸着層に還元剤を用いて無電解銀めっきを行うことによりコア粒子２の表面に銀被覆層１を形成して銀被覆粒子前駆体を得る。無電解銀めっき法としては、（Ｉ）錯化剤、還元剤等を含む水溶液中に、表面に錫吸着層を形成したコア粒子２を浸漬し、銀塩水溶液を滴下する方法、（ＩＩ）銀塩、錯化剤を含む水溶液中に、表面に錫吸着層を形成したコア粒子２を浸漬し、還元剤水溶液を滴下する方法、（ＩＩＩ）銀塩、錯化剤、還元剤等を含む水溶液に、表面に錫吸着層を形成したコア粒子２を浸漬し、苛性アルカリ水溶液を滴下する方法が挙げられる。
　銀塩としては、硝酸銀或いは銀を硝酸に溶解したもの等を用いることができる。錯化剤としては、アンモニア、エチレンジアミン四酢酸、エチレンジアミン四酢酸四ナトリウム、ニトロ三酢酸、トリエチレンテトラアンミン六酢酸、チオ硫酸ナトリウム、コハク酸塩、コハク酸イミド、クエン酸塩又はヨウ化物塩等の塩類を用いることができる。還元剤としては、ホルマリン、ブドウ糖、イミダゾール、ロッシェル塩（酒石酸ナトリウムカリウム）、ヒドラジン及びその誘導体、ヒドロキノン、Ｌ－アスコルビン酸又はギ酸等を用いることができる。還元剤としては、還元力の強さから、ホルムアルデヒドが好ましく、少なくともホルムアルデヒドを含む２種以上の還元剤の混合物がより好ましく、ホルムアルデヒドとブドウ糖を含む還元剤の混合物が最も好ましい。
　無電解銀めっき処理工程において、最初に錫吸着層の錫と銀イオンとの置換反応が開始し、コア粒子２の表面に核となる金属銀が析出する。上記の置換反応と自己触媒的還元反応によって、コア粒子２の表面に所定の結晶子径を有する銀の被覆層が形成され、銀被覆粒子前駆体が得られる。
〔銀被覆粒子前駆体の熱処理／銀被覆粒子の作製〕
　得られた銀被覆粒子前駆体を水洗し乾燥した後で大気中１００℃以上２５０℃未満の温度又は水洗直後に水中１００℃以上２５０℃未満の温度で０．５～１０時間熱処理することにより、銀被覆粒子Ｐ１を作製する。具体的には、水洗は、銀被覆粒子前駆体をイオン交換水中でデカンテーションと、上澄み水の除去を電気伝導度が１０μＳ／ｃｍ以下となるまで繰り返す。また乾燥は、水洗した銀被覆粒子前駆体をステンレスバットのような容器に入れ、真空乾燥機を用いて５０～８０℃の温度に維持して行われる。大気中での熱処理の場合、乾燥した銀被覆粒子前駆体を乾燥時と同様な容器に入れ、かさ厚みを１ｃｍ以下として送風乾燥機や電気マッフル炉で大気中、１００℃以上２５０℃未満の温度で０．５～１０時間保持することにより、行われる。水中での熱処理の場合、イオン交換水中に乾燥前の銀被覆粒子前駆体を１～２０質量％となるように懸濁した後、オートクレーブにてこの懸濁液を１００～３００ｒｐｍの回転速度で撹拌しながら、１００℃以上２５０℃未満の温度で０．５～１０時間、好ましくは保持した後、懸濁液をろ過したケーキを真空乾燥機を用いて５０～８０℃の温度で乾燥することにより行われる。大気中での処理は、特殊な設備を必要とせず簡便に処理が可能という利点があり、水中での処理は、均一な熱処理が可能という利点がある。この他に、設備は必要となるが、気流式乾燥機やスプレードライヤーといった装置を用いて大気中で熱処理を行ってもよい。この熱処理により、銀被覆層１の銀の結晶子が焼結する。これにより銀の結晶子径が増大し、その結晶化度が高まる。
　熱処理温度が１００℃未満及び熱処理時間が０．５時間未満では、銀被覆層１の銀が熱拡散せず、焼結が殆ど生じないため結晶化度が低い。また熱処理温度が２５０℃以上、を超えるもしくは、熱処理時間が１０時間を超えると、銀被覆層１とコア粒子間の熱応力による銀被覆層１の剥離や、剥離に伴う銀の凝集が進行するといった不具合を生じる。好ましい熱処理温度は１２０～２００℃であり、熱処理時間は１～５時間である。この熱処理温度及び/又は時間を上記範囲内で変えることにより、銀被覆層１の銀の結晶子径の大きさを制御して３５～２００ｎｍの範囲内にすることができる。具体的には、熱処理温度を高くするか、熱処理時間を長くするほど、銀被覆層１の銀が焼結して銀の結晶子径が大きくなり、熱処理温度を低くするか、熱処理時間を短くするほど、銀被覆層１の銀の焼結が進行せず、銀の結晶子径が小さくなる。
　銀被覆粒子Ｐ１の表面に形成された銀被覆層１に含まれる銀の量は、銀被覆粒子１００質量部に対して５～９０質量部である。銀の被覆量（含有量）は樹脂の平均粒径と必要とされる導電性により決められる。銀被覆粒子１００質量部に対して、銀の含有量が５質量部未満であると、上述した熱処理を行っても銀被覆層１が隙間なくコア粒子２を被覆しないため、導電性フィラー又は導電性粒子として銀被覆粒子Ｐ１が分散したときに、銀同士の接点が取り難く十分な導電性を付与できない。一方、銀の含有量が９０質量部を超えると比重が大きくなりコストも高くなるとともに導電性が飽和してしまう。この銀の含有量は好ましくは２８～８０質量部、より好ましくは２８～７０質量部である。
〔導電性接着剤、導電性フィルム、導電性スペーサ〕
　本実施形態の銀被覆粒子Ｐ１は、導電性フィラー又は導電性粒子として優れており、特に、導電性接着剤、導電性接着剤、導電性フィルム又は導電性スペーサに最適に適用できる。
〔導電性接着剤〕
　導電性接着剤は、等方性の導電性接着剤（ＩＣＡ：Isotropic Conductive Adhesive）と異方性の導電性接着剤（ＡＣＡ：Anisotropic Conductive Adhesive）に区分される。また、バインダの形態によってペースト状、フィルム状、インク状の形態を有する。等方性の導電性接着剤は、バインダ硬化時にバインダが収縮することで、縦方向、横方向、斜方向ともにフィラーが互いに接触し、これにより接続したい導電物とフィラーが接触して導電性が得られる。等方性の導電性接着剤にてシートを形成することも可能である。異方性の導電性接着剤は、バインダ中にフィラーが分散していて接続したい導電物同士の間に異方性の導電性接着剤を挟み込む。これを縦方向に加圧することで、接続したい導電物の間のフィラーと接続したい導電物が縦方向に接触し導電性が得られる。一方、加圧されていない部分は絶縁物であるバインダを介してフィラー同士が横方向に配置され、互いに接触しないので導電性は得られない。
　導電性接着剤としては、例えば、異方性又は等方性の導電性ペースト、異方性又は等方性の導電性インキなどが挙げられる。導電性接着剤は、本実施形態の銀被覆粒子Ｐ１からなる導電性粒子と絶縁性のバインダ樹脂とを遊星混合機や三本ロールミルのような混練機を用いて均一に混合して調製される。導電性接着剤では、絶縁性のバインダ樹脂中に導電性粒子が均一に分散する。銀被覆粒子Ｐ１の含有量は、特に限定されず、用途などに応じて適宜決定されるが、バインダ樹脂１００質量部に対して０．５～５質量部の範囲が好ましい。
　導電性接着剤における絶縁性のバインダ樹脂としては、特に限定されず、例えば、熱可塑性樹脂や、硬化性樹脂組成物などの熱や光によって硬化する組成物などが挙げられる。熱可塑性樹脂としては、スチレン－ブタジエンブロック共重合体、アクリレート樹脂、エチレン－酢酸ビニル樹脂などが挙げられる。硬化性樹脂組成物としては、グリシジル基を有するエポキシ系モノマーやオリゴマーと、イソシアネートなどの硬化剤とを含有する樹脂組成物が挙げられる。
〔導電性フィルム〕
　導電性フィルムとしては、フィルム状に成形された異方性又は等方性の導電性フィルムがある。導電性フィルムは、先ず本実施形態の銀被覆粒子Ｐ１からなる導電性粒子が絶縁性のバインダ樹脂中に分散された樹脂組成物を作製し、次いでこの樹脂組成物をＰＥＴ等の支持フィルムの表面に塗布することにより作製される。この樹脂組成物は導電性粒子と絶縁性のバインダ樹脂とを遊星混合機や三本ロールミルのような混練機を用いて均一に混合して調製される。導電性フィルムでは、支持体フィルム上で絶縁性のバインダ樹脂中に導電性粒子が均一に分散する。導電性フィルムにおける絶縁性のバインダ樹脂としては、エポキシ樹脂、フェノキシ樹脂などの熱硬化性樹脂を主成分として含む樹脂組成物が挙げられる。導電性フィルムにおける樹脂組成物中の銀被覆粒子Ｐ１の含有量は、特に限定されず、用途などに応じて適宜決定されるが、バインダ樹脂１００質量部に対して０．５～１０質量部の範囲が好ましい。
〔導電性スペーサ〕
　導電性スペーサは、液晶表示装置において、液晶物質を挟む上下２枚の基板の配線部分を電気的に上下に接続し、かつ基板の間隙を所定の寸法に保持して使用される。導電性スペーサは、先ず本実施形態の銀被覆粒子Ｐ１からなる導電性粒子を熱硬化性樹脂や紫外光硬化型接着剤などの絶縁性のバインダ樹脂に添加した後、導電性粒子とバインダ樹脂とを遊星混合機や三本ロールミルのような混練機を用いて均一に混合して調製し、次いで上下２枚の基板の配線部分のいずれか一方又は双方に上記樹脂組成物を塗布して２枚の基板を貼り合わせることにより作製される。銀被覆粒子Ｐ１の含有量は、特に限定されず、用途などに応じて適宜決定されるが、バインダ樹脂１００質量部に対して２～１０質量部の範囲が好ましい。
　本実施形態の銀被覆粒子Ｐ１からなる導電性粒子を含む導電性接着剤、導電性フィルム又は導電性スペーサは、導電性粒子と絶縁性のバインダ樹脂との混合物を混練するときに高いせん断力をかけても、銀被覆層１に亀裂若しくは割れ又は銀被覆層１のコア粒子２からの剥離が生じにくく、その導電性をより向上する。これにより、本願発明の銀被覆粒子Ｐ１を例えば異方性の導電性接着剤に用いた場合、異方導電（横方向）の短絡を回避でき、信頼性が向上する。
　次に本願発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
　先ず、塩化第一錫２０ｇと、濃度が３５％の塩酸１５ｃｍ３を、容量１ｄｍ３のメスフラスコを用いて水で１ｄｍ３に希釈（メスアップ）し、３０℃に保温した。この水溶液に、母体となるコア粒子として平均粒径が１０μｍである球状のアクリルースチレン共重合体樹脂５０ｇを添加して、１時間撹拌し、その後、アクリルースチレン共重合体樹脂を濾別して水洗することにより前処理を行った。
　次に、上記前処理により表面に錫吸着層が形成されたアクリルースチレン共重合体樹脂の表面に、無電解めっきにより銀被覆層を形成した。具体的には、先ず、水２ｄｍ３に、錯化剤としてエチレンジアミン四酢酸ナトリウム４０ｇ、ｐＨ調整剤として水酸化ナトリウム２０．０ｇ、還元剤としてホルマリン（ホルムアルデヒド濃度３７質量％）１５ｍｌを添加し、これらを溶解させることにより、錯化剤及び還元剤を含む水溶液を調製した。次に、この水溶液に、上記前処理後のアクリルースチレン共重合体樹脂を浸漬させることによりスラリーを調製した。
　次いで、硝酸銀３０ｇ、２５％アンモニア水３５ｍｌ、水５０ｍｌを混合して硝酸銀含有水溶液を調製し、上記スラリーを攪拌しながら、この硝酸銀含有水溶液を滴下した。更に、硝酸銀含有水溶液滴下後のスラリーに、水酸化ナトリウム水溶液を滴下してｐＨを１２に調整し、２５℃の温度に保持しながら撹拌することにより、銀を樹脂表面上に析出させた。その後、洗浄、濾過を行い、最後に真空乾燥機を用いて６０℃の温度で乾燥させ、銀被覆粒子前駆体を得た。この銀被覆粒子前駆体を３２５メッシュのステンレス平織り金網と振動篩を用いて塊状となった粒子をほぐした後、ほぐれた銀被覆粒子前駆体をステンレスバットに厚み１ｍｍとなるように敷き詰め、電気マッフル炉内にて３０分で１４０℃まで昇温した後、同温度を４時間保持して熱処理し、銀被覆層の銀の結晶子を焼結させ、銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例２＞
　母体となるコア粒子として、平均粒径が３μｍである球状のアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。また熱処理時の温度を１５０℃、保持時間を３時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が６５質量％である銀被覆粒子を得た。この銀被覆粒子をエポキシ樹脂で固めてスライスした後、ＴＥＭ(Transmission Electron Microscope)で観察した。この銀被覆粒子の銀被覆層断面のＴＥＭ像（倍率５０万倍）を図１に示す。図１において銀被覆層１の内側が母体となるコア粒子２であり、銀被覆層の外側が固めた樹脂３である。
＜実施例３＞
　母体となるコア粒子として、平均粒径が１μｍである球状のアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。また熱処理時の温度を１２０℃、保持時間を７時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が９０質量％である銀被覆粒子を得た。
＜実施例４＞
　母体となるコア粒子として、平均粒径が２０μｍである球状のアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整したこと以外、実施例１と同様に行って実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が２５質量％である銀被覆粒子を得た。
＜実施例５＞
　母体となるコア粒子として、平均粒径が４０μｍである球状のアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。また熱処理時の温度を１６０℃、保持時間を１．５時間とした。それ以外、実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が１５質量％である銀被覆粒子を得た。
＜実施例６＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。また熱処理時の温度を１３０℃、保持時間を４時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が２０質量％である銀被覆粒子を得た。
＜実施例７＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。また熱処理時の温度を１６０℃、保持時間を６時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が８０質量％である銀被覆粒子を得た。
＜実施例８＞
　母体となるコア粒子として実施例５と同じアクリルースチレン共重合体樹脂を用いて、めっきする銀の質量を調整した。それ以外は実施例５と同様に行って銀被覆粒子１００質量％に対して銀の量が５質量％である銀被覆粒子を得た。
＜実施例９＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を１００℃で行った。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１０＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を２００℃で行った。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１１＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を０．５時間行った。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１２＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を１０時間行った。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１３＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の乾燥を行わない以外、実施例１と同様にして銀被覆粒子前駆体を得た。得られた銀被覆粒子前駆体を水中で熱処理した。具体的には、この銀被覆粒子前駆体をイオン交換水中に１０質量％となるように懸濁した後、オートクレーブにてこの懸濁液を１５０ｒｐｍの回転速度で撹拌しながら、１５０℃の温度で３時間保持して熱処理し、銀被覆層の銀の結晶子を焼結させた後、懸濁液をろ過したケーキを真空乾燥機を用いて６０℃の温度で乾燥した。これにより、銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１４＞
　母体となるコア粒子として、平均粒径が１０μｍである球状のフェノール樹脂を用い、熱処理時の温度を１６０℃、保持時間を１時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１５＞
　母体となるコア粒子として、平均粒径が１０μｍである球状のポリスチレン樹脂を用い、熱処理時の温度を１２０℃、保持時間を８時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜実施例１６＞
　母体となるコア粒子として、平均粒径が２μｍである球状のシリコーン樹脂を用い、めっきする銀の質量を調整した。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が８０質量％である銀被覆粒子を得た。
＜実施例１７＞
　母体となるコア粒子として、平均粒径が１０μｍである棒状にアトマイズされたシリコーン樹脂を用い、めっきする銀の質量を調整した。また熱処理時の温度を１３０℃、保持時間を５時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が５０質量％である銀被覆粒子を得た。
＜実施例１８＞
　母体となるコア粒子として、平均粒径が８μｍである板状の窒化ホウ素粉末を用い、めっきする銀の質量を調整した。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が６０質量％である銀被覆粒子を得た。
＜実施例１９＞
　母体となるコア粒子として、平均粒径が５μｍである鱗片状のタルク粉末を用い、めっきする銀の質量を調整した。また熱処理時の温度を１５０℃、保持時間を３時間とした。それ以外は実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が７０質量％である銀被覆粒子を得た。
＜実施例２０＞
　母体となるコア粒子として、平均粒径が１０μｍである球状のシリコーンゴム粒子を用い、めっきする銀の質量を調製した。また熱処理時の温度を２４５℃、保持時間を１時間とした。それ以外は実施例１と同様に行って、銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例１＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１と同様にして銀被覆粒子前駆体を得た。得られた銀被覆粒子前駆体を熱処理しなかった。これにより銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例２＞
　母体となるコア粒子として実施例２と同じアクリルースチレン共重合体樹脂を用いた。実施例２と同様にして銀被覆粒子前駆体を得た。得られた銀被覆粒子前駆体を熱処理しなかった。これにより銀被覆粒子１００質量％に対して銀の量が６５質量％である銀被覆粒子を得た。実施例２と同様にこの銀被覆粒子をエポキシ樹脂で固めてスライスした後、ＴＥＭで観察した。この銀被覆粒子Ｐ２の銀被覆層断面のＴＥＭ像（倍率５０万倍）を図２に示す。図２において銀被覆層１１の内側が母体となるコア粒子１２であり、銀被覆層の外側が固めた樹脂１３である。
＜比較例３＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を０．２５時間行った。それ以外は、実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例４＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を１１時間行った。それ以外は、実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例５＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を９０℃で行った。それ以外は、実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例６＞
　母体となるコア粒子として実施例１と同じアクリルースチレン共重合体樹脂を用いた。実施例１の大気中での熱処理を２５５℃で行った。それ以外は、実施例１と同様に行って銀被覆粒子１００質量％に対して銀の量が４５質量％である銀被覆粒子を得た。
＜比較例７＞
母体となるコア粒子として平均粒径が３μｍである鱗片状のタルク粉末を用い、めっきする銀の質量を調整した。それ以外は、実施例１と同様にして銀被覆粒子前駆体を得た。得られた銀被覆粒子前駆体を熱処理しなかった。これにより銀被覆粒子１００質量％に対して銀の量が７８質量％である銀被覆粒子を得た。
　実施例１～１９及び比較例１～７のコア粒子の材質、平均粒径、銀被覆粒子の銀の量、銀被覆粒子を製造するときの熱処理雰囲気、熱処理温度及び熱処理時間を表１に示す。表１において「ＡＳ樹脂」は「アクリル-スチレン共重合体樹脂」をそれぞれ意味する。
Figure JPOXMLDOC01-appb-T000001
　　＜比較試験及び評価＞
　実施例１～２０及び比較例１～７で得られた銀被覆粒子について、銀被覆層の平均膜厚、銀被覆層の銀の結晶子径、せん断応力印加前後の銀被覆層の外観及び２０％圧縮した時のせん断応力印加前後の銀被覆粒子の抵抗値を、以下に示す方法でそれぞれ評価した。これらの結果を表２に示す。
　（１）銀被覆層の平均膜厚
　銀被覆層の平均膜厚は、平均膜厚をｄ、コア粒子の平均粒径を２で除した値をｒ、コア粒子の比重をｄｃｏｒｅ、銀の比重をｄＡｇ、銀被覆粒子中の銀の質量と銀被覆粒子の質量の比をａとして以下の式より算出した。
Figure JPOXMLDOC01-appb-M000002
　（２）銀被覆層の銀の結晶子径
　銀被覆層の銀の結晶子径は、Ｘ線回折装置に付属する試料ホルダーに前記銀被覆粒子を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から算出される。この実施の形態では、銀被覆層の銀の結晶子径は、ＰＡＮａｌｙｔｉｃａｌ社製、Ｘ線回折装置Ｅｍｐｙｒｅａｎを用いて、この装置に付属する試料ホルダーに、得られた粉末状の銀被覆粒子を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から解析ソフトであるＴＯＰＡＳ（ＢｒｕｋｅｒＡＸＳ社製）を使用し、プロファイル関数としてＦＰを用いたＰａｗｌｅｙ法にて解析し、ローレンツ関数成分の半値幅から算出される。測定は、Ｃｕ管球を用い、４０ｋＶ、４０ｍＡとし、特性Ｘ線（波長１．５４Å）でステップ間隔を０．０２５ｄｅｇとして行う。このＰａｗｌｅｙ法による解析から銀被覆層の銀の結晶子径を求める。なお、参考となる銀の結晶子径の測定法としてシェラーの式を用いた方法がある。この方法は前述した特許文献２において銀の結晶子径を測定するのに用いられた方法である（特許文献２の段落[００２１]参照。）。この方法では、銀結晶の（１１１）面、（２００）面、（２２０）面及び（３１１）面における結晶子径の平均値を結晶子径の値として算出する。なおシェラーの式は、Ｄｈｋｌ＝Ｋλ／βｃｏｓθ（但し、Ｄｈｋｌ：結晶子の大きさ［ｍ］、λ：測定Ｘ線波長［ｍ］、Ｋ：定数＝０．９、β：半価幅［ｒａｄ］、θ：回折線のブラッグ角［ｒａｄ］で表される。本願発明の測定法による測定値と参考となるシェラーの式を用いた方法により求められる特許文献２の請求項１に記載された「銀の結晶子径が１８～２４ｎｍの範囲」は、本願発明の測定法により求めると「銀の結晶子径が２６～３４ｎｍの範囲」になる。
　（３）せん断応力印加前後の銀被覆層の外観評価
　せん断応力試験を次の方法により行う。銀被覆粒子８０質量部をエチレングリコール２０質量部と遊星混合機（シンキー社あわとり練太郎）を用いてペースト状の混合物とする。このペースト状混合物を三本ロールミル（ＥＸＡＣＴ社Ｍ－８０Ｅ）にて１０回混練を繰り返し、銀被覆粒子にせん断応力を加えた。この時の三本のロールの回転速度は３０ｒｐｍ、５５ｒｐｍ、１００ｒｐｍ、ロール間の間隔は銀被覆粒子の粒子径の５倍の値に設定した。このせん断応力を銀被覆粒子に印加する前後で、株式会社日立ハイテクノロジーズ製走査型電子顕微鏡（型番：Ｓ－４３００ＳＥ）により、銀被覆粒子の外観を観察して評価する。このとき、銀被覆層に亀裂、割れ又は銀被覆層のコア粒子からの剥離がある銀被覆粒子が全体の５％以下である状態を外観Ａとし、５～２０％である状態を外観Ｂとし、２０～１００％の割合である状態を外観Ｃとする。
　（４）圧縮した時のせん断応力印加前後の銀被覆粒子の抵抗値
　上記（３）に記載した方法でせん断応力試験を銀被覆粒子に対して行う。せん断応力試験の前後で、銀被覆粒子の圧縮試験を行う。この圧縮試験は、微小圧縮試験機（島津製作所製、ＭＣＴ－Ｗ２００Ｊ）を用いて銀被覆粒子１つを上下方向に圧縮した状態で行う。圧縮率は、球状粒子の場合は２０％とし、板状粒子などの長辺と短辺のアスペクト比が２以上の粒子に関しては５％とした。圧縮したときの銀被覆粒子の電気的抵抗値を同装置にて通電することにより測定する。これを一条件につき銀被覆粒子１０個を測定した際の抵抗値の平均を測定値とする。
Figure JPOXMLDOC01-appb-T000003
　表２から明らかなように、適切な熱処理を施して結晶子径を制御した実施例１～２、実施例４～５、実施例１３～１８の銀被覆粒子については、せん断応力印加前後でめっき外観及び圧縮時の抵抗値に変化がほとんど見られなく、導電性接着剤や導電スペーサといった用途に適した銀被覆粒子となった。また、銀被覆粒子中の銀の量を上限値とした実施例３については、銀の量が増加したことでコストは上昇しているものの、上記と同様にせん断応力印加前後でめっき外観及び圧縮時の抵抗値に変化がほとんど見られなく、接着剤や導電性スペーサといった用途に適した銀被覆粒子となった。
　銀の結晶子径が下限値となった実施例６、上限値となった実施例７においては、せん断応力印加前後の圧縮時の抵抗値に多少変化があるものの、外観も含め良好な銀被覆粒子となった。
　銀被覆粒子の銀の量が下限値となった実施例８おいては、初期抵抗値はやや高いものの、せん断応力印加前後の変化は小さく、外観も含め良好な銀被覆粒子となった。
　熱処理温度が比較的低温で処理を行った実施例９と、熱処理時間を比較的短めに処理を行った実施例１１においては、結晶子径が処理に応じて小さめの値となった。また、せん断応力印加前後で圧縮時の抵抗値の変化はある程度あったものの、外観を含めて良好な銀被覆粒子となった。
　熱処理温度が比較的高温である実施例１０及び実施例２０、熱処理時間が比較的長めである実施例１２においては、結晶子径が大きく増大したものの、外観、抵抗値ともに良好な銀被覆粒子となった。
　コア粒子として無機物であるタルクを用いた実施例１９においては、圧縮時の抵抗値が比較的高めとなったものの、せん断応力印加前後でのその変化は小さく、外観を含めて良好な銀被覆粒子となった。
　一方、熱処理を施さなかった比較例１、２及び７の銀被覆粒子、熱処理時間が０．５時間未満の比較例３の銀被覆粒子、及び熱処理温度が１００℃未満の比較例５の銀被覆粒子についてはその結晶子径が３５ｎｍを下回ったため、せん断応力印加後では銀が剥離し、外観が損なわれるとともに、圧縮時の抵抗値が１０００以上と高い値を示し、導電性粒子として不適な状態となった。
　熱処理時間が１０時間を超過した比較例４の銀被覆粒子及び熱処理温度を２５０℃以上とした比較例６の銀被覆粒子では、熱処理時間が長すぎるために結晶子径が２００ｎｍを上回り、過焼結による銀被覆層の収縮によって銀被覆粒子が変形し、せん断応力の印加前後両方で部分的な銀の剥離が認められ外観が損なわれるとともに、圧縮時の抵抗値がそれぞれ８２０Ω、１０００Ω以上と高い値を示し、導電性粒子として不適な状態となった。
　実施例２の銀被覆粒子の銀被覆層断面のＴＥＭ像（倍率５０万倍）を示した図１から、銀被覆層中の銀が焼結し結晶子径が大きくなったことにより、銀被覆層が隙間なくコア粒子を被覆した。この結果、せん断応力印加後も銀被覆層が剥離せず、平滑な被覆層を保持していた。一方、比較例２の銀被覆粒子の銀被覆層断面のＴＥＭ像（倍率５０万倍）を示す図２から、銀被覆層中の銀の結晶子が小さいため、銀被覆層が隙間なくコア粒子を被覆しなかった。この結果、せん断応力印加時に粒界破壊によって銀が剥離した。
　本願発明の銀被覆粒子は、異方性又は等方性の導電性接着剤、異方性又は等方性の導電性フィルム及び導電性スペーサの導電性フィラー又は導電性粒子として利用することができる。
　Ｐ１　　銀被覆粒子
　１　　銀被覆層
　２　　コア粒子（母粒子）
　３　　固めた樹脂
　Ｐ２　　銀被覆粒子（比較例）
　１１　　銀被覆層（比較例）
　１２　　コア粒子（母粒子、比較例）
　１３　　固めた樹脂（比較例）

Claims (5)

  1. 　樹脂粒子又は無機粒子からなるコア粒子と、このコア粒子の表面に形成された銀被覆層とを備えた銀被覆粒子であって、
    　前記銀被覆層に含まれる銀の量が銀被覆粒子１００質量部に対して５～９０質量部であり、Ｘ線回折装置に付属する試料ホルダーに前記銀被覆粒子を充填して２θ／θ＝３０～１２０ｄｅｇの範囲でＸ線を照射し、得られた回折線から算出される前記銀の結晶子径が３５～２００ｎｍの範囲にある銀被覆粒子。
  2. 　樹脂粒子又は無機粒子からなるコア粒子を錫化合物の水溶液に添加して前記コア粒子の表面に錫吸着層を形成する工程と、
    　前記コア粒子の表面に形成された錫吸着層に還元剤を用いて無電解銀めっきを行って前記コア粒子の表面に銀被覆層を有する銀被覆粒子前駆体を作製する工程と、
    　前記銀被覆粒子前駆体を水洗し乾燥した後で大気中１００℃以上２５０℃未満の温度又は水洗直後に水中１００℃以上２５０℃未満の温度で０．５～１０時間熱処理して前記銀被覆層を構成する銀を焼結させ、Ｘ線回折法により測定される前記銀の結晶子径を３５～２００ｎｍの範囲にする工程とを含む銀被覆粒子の製造方法。
  3. 　請求項１記載の銀被覆粒子とバインダ樹脂とを混合することにより導電性接着剤を製造する方法。
  4. 　請求項１記載の銀被覆粒子とバインダ樹脂とを混合してなる樹脂組成物を支持フィルム表面に塗布することにより導電性フィルムを製造する方法。
  5. 　請求項１記載の銀被覆粒子とバインダ樹脂とを混合してなる樹脂組成物を２枚の基板のいずれか又は双方の表面に塗布した後、前記２枚の基板を貼り合わせることにより導電性スペーサを製造する方法。
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