WO2016151859A1 - 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート - Google Patents
銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート Download PDFInfo
- Publication number
- WO2016151859A1 WO2016151859A1 PCT/JP2015/059482 JP2015059482W WO2016151859A1 WO 2016151859 A1 WO2016151859 A1 WO 2016151859A1 JP 2015059482 W JP2015059482 W JP 2015059482W WO 2016151859 A1 WO2016151859 A1 WO 2016151859A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silver
- copper powder
- dendritic
- coated
- coated copper
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- 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
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/627—Copper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/66—Copper alloys, e.g. bronze
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/066—Treatment or coating resulting in a free metal containing surface-region
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
- 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
- C09D5/32—Radiation-absorbing paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
-
- 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
-
- 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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- 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
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/26—Electron or ion microscopes; Electron or ion diffraction tubes
- H01J37/28—Electron or ion microscopes; Electron or ion diffraction tubes with scanning beams
Definitions
- the present invention relates to a copper powder (silver coated copper powder) coated with silver on the surface, and more specifically, a new dendritic shape that can improve conductivity by using as a material such as a conductive paste.
- the present invention relates to a silver-coated copper powder and a copper paste, a conductive paint, and a conductive sheet using the same.
- metal fillers such as silver powder and silver-coated copper powder, such as resin pastes, fired pastes, and electromagnetic shielding paints.
- a metal filler paste of silver powder or silver-coated copper is applied or printed on various substrates, and is subjected to heat curing or heat baking treatment to form a conductive film that becomes a wiring layer, an electrode, or the like.
- a resin-type conductive paste is made of a metal filler, a resin, a curing agent, a solvent, etc., printed on a conductor circuit pattern or terminal, and cured by heating at 100 ° C. to 200 ° C. An electrode is formed.
- the resin-type conductive paste since the thermosetting resin is cured and contracted by heat, when the metal filler is pressed and brought into contact, the metal filler overlaps and an electrically connected current path is formed. Since this resin-type conductive paste is processed at a curing temperature of 200 ° C. or less, it is used for a substrate using a heat-sensitive material such as a printed wiring board.
- the fired conductive paste is made of a metal filler, glass, solvent, etc., printed on a conductor circuit pattern or terminal, and heated and fired at 600 ° C. to 800 ° C. to form a conductive film.
- the fired conductive paste is processed at a high temperature to sinter the metal fillers to ensure conductivity. Since this fired conductive paste is processed at such a high firing temperature, it cannot be used for a printed wiring board using a resin material, but the metal filler is sintered by high temperature processing. Low resistance can be realized. Therefore, the fired conductive paste is used for an external electrode of a multilayer ceramic capacitor.
- electromagnetic wave shields are used to prevent the generation of electromagnetic noise from electronic equipment.
- personal computers and mobile phone cases have been made of resin, so that the case is made conductive.
- a method of forming a thin metal film by a vapor deposition method or a sputtering method a method of applying a conductive paint, a method of attaching a conductive sheet to a necessary place and shielding an electromagnetic wave, etc. Proposed.
- special methods are required in the processing process for the method of applying the metal filler dispersed in the resin and the method of dispersing the metal filler in the resin and processing it into a sheet and attaching it to the housing. It has excellent flexibility and is widely used.
- Patent Document 2 discloses a method for obtaining a flaky copper powder suitable for a filler of a conductive paste. Specifically, a spherical copper powder having an average particle size of 0.5 ⁇ m to 10 ⁇ m is used as a raw material, and it is mechanically processed into a flat plate shape by a mechanical energy of a medium loaded in the mill using a ball mill or a vibration mill. is there.
- Patent Document 3 discloses a technique relating to a copper powder for conductive paste, more specifically, a disk-shaped copper powder having high performance as a copper paste for through holes and external electrodes, and a method for producing the same. Specifically, the granular atomized copper powder is put into a medium agitating mill, and a steel ball having a diameter of 1/8 inch to 1/4 inch is used as a grinding medium. % To 1% and processed into a flat plate shape by pulverization in air or in an inert atmosphere.
- silver powder is often used as the metal filler used for these conductive pastes and electromagnetic wave shields, but the surface of copper powder that is cheaper than silver powder is coated with silver due to the trend of cost reduction. There is a tendency to use silver-coated copper powder in which the amount of silver used is reduced.
- a method of coating silver on the surface of copper powder there are a method of coating silver on the copper surface by a substitution reaction and a method of coating silver in an electroless plating solution containing a reducing agent.
- Patent Document 4 discloses a manufacturing method in which a silver film is formed on a copper surface by a substitution reaction between copper and silver ions by introducing copper powder into a solution containing silver ions.
- the method based on this substitution reaction has a problem in that when a silver film is formed on the copper surface, further dissolution of copper does not proceed, so that the silver coating amount cannot be controlled.
- Patent Document 5 proposes a method for producing copper powder coated with silver by a reaction between copper powder and silver nitrate in a solution in which a reducing agent is dissolved.
- dendritic shape electrolytic copper powder deposited in dendritic shape called dendritic shape is known, and since the shape is dendritic, it is characterized by a large surface area. Due to the dendritic shape as described above, when this is used for a conductive film or the like, the dendritic branches are overlapped with each other, conduction is easy, and the number of contact points between particles is larger than that of spherical particles. Therefore, there is an advantage that the amount of the conductive filler in the conductive paste or the like can be reduced.
- Patent Documents 6 and 7 propose a silver-coated copper powder in which silver is coated on a dendrite-like copper powder surface.
- Patent Documents 6 and 7 disclose a dendrite characterized by a long branch branched from the main axis as further grown in a dendrite shape, and the silver-coated copper powder has a particle size larger than that of a conventional dendrite.
- Patent Document 9 also points out that a problem occurs in that the resin does not uniformly disperse in the resin and that the viscosity of the paste increases due to agglomeration, resulting in a problem in wiring formation by printing.
- dendritic copper powder as a metal filler such as a conductive paste, which is a cause of difficulty in improving the conductivity of the paste.
- a dendritic shape having a three-dimensional shape is easier to secure a contact than a granular one, and high conductivity can be expected as a conductive paste or electromagnetic wave shield.
- the conventional silver-coated copper powder having a dendrite-like shape is a dendrite characterized by a long branch branched from the main axis, and has a long and narrow branch-like shape. And the structure is simple, and it is not an ideal shape as a shape that effectively secures a contact point using less silver-coated copper powder.
- JP 2003-258490 A Japanese Patent Laid-Open No. 2005-200734 JP 2002-15622 A JP 2000-248303 A JP 2006-161081 A JP 2013-89576 A JP 2013-100592 A Japanese Patent No. 46976643 JP 2011-58027 A
- the present invention has been proposed in view of such circumstances and prevents aggregation while increasing the number of contacts when the dendritic copper powders coated with silver are in contact with each other to ensure excellent conductivity.
- An object of the present invention is to provide a dendritic silver-coated copper powder that can be suitably used as a conductive paste, electromagnetic wave shield or the like.
- the inventors of the present invention have intensively studied to solve the above-described problems.
- tabular copper particles having a dendritic shape having a main trunk grown into a dendritic shape and a plurality of branches separated from the main trunk and having a cross-sectional average thickness within a specific range gather, and silver is formed on the surface thereof.
- Is coated silver powder, and the average particle diameter (D50) of the copper powder is in a specific range, so that excellent conductivity is ensured, for example, uniformly mixed with resin
- the present invention has been completed by finding that it can be suitably used for applications such as conductive paste. That is, the present invention provides the following.
- copper particles having a dendritic shape having a main trunk that grows linearly and a plurality of branches separated from the main trunk are aggregated, and the surface is coated with silver.
- It is silver coat copper powder Comprising: The cross-sectional average thickness of the main trunk and branch of the said copper particle exceeds 1.0 micrometer, and is 5.0 micrometers or less, The said silver coat copper powder overlapped one layer or more.
- a silver-coated copper powder characterized by being a flat plate composed of a laminated structure and having an average particle diameter (D50) of 1.0 ⁇ m to 100 ⁇ m.
- the ratio obtained by dividing the cross-sectional average thickness of the copper particles coated with silver by the average particle diameter (D50) of the silver-coated copper powder is It is silver coat copper powder characterized by being in the range of more than 0.01 and 5.0 or less.
- the silver coating amount is 1% by mass to 50% by mass with respect to 100% by mass of the total silver-coated copper powder coated with silver. It is the silver coat copper powder characterized by this.
- a fourth invention of the present invention is characterized in that, in any one of the first to third inventions, the bulk density is in the range of 0.5 g / cm 3 to 5.0 g / cm 3. Coated copper powder.
- the silver in the first to fourth invention of any one of, the BET specific surface area characterized in that a 0.2m 2 /g ⁇ 3.0m 2 / g Coated copper powder.
- a sixth aspect of the present invention is a metal filler characterized by containing the silver-coated copper powder according to any one of the first to fifth aspects in a proportion of 20% by mass or more of the total. It is.
- a seventh invention of the present invention is a conductive paste characterized in that a metal filler according to the sixth invention is mixed with a resin.
- An eighth invention of the present invention is a conductive paint for electromagnetic wave shielding, characterized by using the metal filler according to the sixth invention.
- a ninth invention of the present invention is an electromagnetic wave shielding conductive sheet characterized by using the metal filler according to the sixth invention.
- the silver-coated copper powder according to the present invention it is possible to ensure sufficient contact when the copper powders are in contact with each other while ensuring excellent electrical conductivity, and to prevent aggregation and be uniform with the resin and the like. It can be mixed and can be used suitably for uses, such as an electrically conductive paste and an electromagnetic wave shield.
- the present embodiment a specific embodiment of the copper powder according to the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings.
- the present invention is limited to the following embodiments.
- various modifications are possible without departing from the scope of the present invention.
- the notation “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less”.
- the silver-coated copper powder according to the present embodiment is a silver coat in which copper particles having a shape having a main trunk grown in a dendritic shape and a plurality of branches separated from the main trunk are aggregated, and the surface thereof is coated with silver. Copper powder.
- FIG. 1 is a schematic view showing a specific shape of copper particles coated with silver constituting the silver-coated copper powder according to the present embodiment.
- the copper particles 1 coated with silver (hereinafter simply referred to as “copper particles 1”) have a dendritic shape that is a two-dimensional or three-dimensional form. More specifically, the copper particle 1 has a shape having a main trunk 2 grown in a dendritic shape and a plurality of branches 3 separated from the main trunk 2, and the copper particle 1 has an average cross-sectional thickness. It is a flat plate having a thickness of more than 1.0 ⁇ m and not more than 5.0 ⁇ m.
- the branch 3 in the copper particle 1 means both a branch 3a branched from the main trunk 2 and a branch 3b further branched from the branch 3a.
- the silver-coated copper powder according to the present embodiment is a dendritic copper powder (dendritic copper powder) having a main trunk and a plurality of branches, which is configured by aggregating such flat copper particles 1.
- This is a silver-coated copper powder (hereinafter also referred to as “dendritic silver-coated copper powder”) having a surface coated with silver, and is a flat plate composed of one or a plurality of laminated structures (FIG. 3 or FIG. 4 (see SEM image of copper powder).
- the average particle diameter (D50) of the dendritic silver-coated copper powder composed of the flat copper particles 1 is 1.0 ⁇ m to 100 ⁇ m.
- the silver coating amount of the dendritic silver-coated copper powder according to the present embodiment is 1% by mass to 50% by mass with respect to 100% by mass of the silver-coated copper coated copper powder as a whole.
- the thickness of silver (coating thickness) is an extremely thin film of about 0.15 ⁇ m or less. Therefore, the dendritic silver-coated copper powder has a shape that retains the shape of the dendritic copper powder before silver coating. Therefore, both the shape of the dendritic copper powder before coating silver and the shape of the dendritic silver-coated copper powder after coating silver on the copper powder are both dendritic in two-dimensional or three-dimensional forms. And is a flat plate composed of one or a plurality of stacked layers.
- the dendritic silver-coated copper powder according to the present embodiment is electrolyzed by, for example, immersing an anode and a cathode in a sulfuric acid electrolytic solution containing copper ions and passing a direct current.
- FIG. 2 to FIG. 4 are photographic diagrams showing examples of observation images when the dendritic copper powder before being coated with silver is observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- 2 shows the dendritic copper powder observed at a magnification of 5,000 times
- FIGS. 3 and 4 show the dendritic copper powder observed at a magnification of 10,000 times
- FIG. 5 is a photograph showing an example of an observation image when the dendritic silver-coated copper powder obtained by coating the dendritic copper powder of FIG. 2 with silver is observed with an SEM.
- FIG. 6 is a photograph figure which shows an example of an observation image when similarly observing another location of the dendritic silver coat copper powder which coat
- 5 shows the dendritic silver-coated copper powder observed at a magnification of 1,000 times
- FIG. 6 shows the dendritic silver-coated copper powder observed at a magnification of 10,000 times.
- the dendritic copper powder constituting the silver-coated copper powder according to the present embodiment has a main trunk and a branch branched from the main trunk. It shows a dendritic precipitation state. Moreover, the main trunk and the branch are flat and are composed of copper particles 1 having a dendritic shape (see the schematic diagram of FIG. 1), and the copper particles 1 are fine on the surface. Has a convex part.
- the flat copper particles 1 constituting the dendritic copper powder and having the main trunk 2 and the branches 3 have a cross-sectional average thickness of more than 1.0 ⁇ m and 5.0 ⁇ m or less.
- the main part and branch of dendritic copper powder are constituted by tabular copper particles 1 having an average cross-sectional thickness of 5.0 ⁇ m or less, so that copper particles 1 and dendritic silver-coated copper constituted thereby are formed.
- a large area where the powders come into contact with each other can be secured. And since the contact area becomes large, low resistance, that is, high conductivity can be realized.
- the dendritic copper powder is composed of the flat copper particles 1, it can contribute to thinning of the wiring material and the like.
- the lower limit of the cross-sectional average thickness of the flat copper particles 1 is not particularly limited, but in the method of depositing on the cathode by electrolysis from a sulfuric acid-containing electrolytic solution containing copper ions described later, The tabular copper particles 1 having a cross-sectional average thickness exceeding 0 ⁇ m can be obtained.
- the average particle size (D50) is 1.0 ⁇ m to 100 ⁇ m.
- an average particle diameter (D50) can be measured by the laser diffraction scattering type particle size distribution measuring method, for example.
- the metal filler in the resin is dendritic. Due to the shape developed into a shape, dendritic copper powders are entangled with each other to cause agglomeration and are not uniformly dispersed in the resin. In addition, the agglomeration increases the viscosity of the paste and causes problems in wiring formation by printing. This occurs because the shape (particle diameter) of the dendritic silver-coated copper powder is large.
- the dendritic silver-coated copper powder It is necessary to reduce the shape of the. However, if the particle diameter of the dendritic silver-coated copper powder is too small, the dendritic shape cannot be secured. Therefore, the effect of being in a dendritic shape, that is, a three-dimensional shape, has a large surface area and excellent moldability and sinterability, and can be molded with high strength by being firmly connected via a branch-like portion. In order to secure the effect, it is necessary that the dendritic silver-coated copper powder is larger than a predetermined size.
- the dendritic silver-coated copper powder according to the present embodiment has an average particle size of 1.0 ⁇ m to 100 ⁇ m, which increases the surface area and ensures good moldability and sinterability. Can do.
- the dendritic shape having the main trunk 2 and the branches 3 and the copper particles 1 having a flat plate shape are assembled and configured. More contact points between the copper powders can be secured by the three-dimensional effect of being dendritic and the effect that the copper particles 1 constituting the dendritic shape are flat.
- Patent Document 2 and Patent Document 3 when spherical copper powder is formed into a flat plate shape by a mechanical method, it is necessary to prevent copper oxidation during mechanical processing. It is processed into a flat plate shape by adding a fatty acid and pulverizing it in air or in an inert atmosphere. However, it cannot be completely prevented from oxidation, and the fatty acid added during processing may affect dispersibility when it is made into a paste, so it is necessary to remove it after the end of processing, The fatty acid may be firmly fixed to the copper surface due to the pressure during machining, which causes a problem that it cannot be completely removed.
- the flat copper particles 1 constituting the dendritic silver-coated copper powder according to the present embodiment are produced by directly growing into a dendritic copper powder shape without performing mechanical processing. Therefore, it is not necessary to generate oxidation or remove fatty acids, which is a problem in machining, and the electrical conductivity characteristics can be made extremely good.
- the dendritic silver coat copper powder which concerns on this Embodiment is not specifically limited, the cross-sectional average thickness of the flat copper particle 1 mentioned above was remove
- the ratio (average cross-sectional thickness / average particle diameter) is preferably in the range of more than 0.01 and 5.0 or less.
- the ratio (aspect ratio) expressed by “average cross-sectional thickness / average particle diameter” is, for example, the degree of aggregation and dispersibility when processed as a conductive copper paste, and the retention of the appearance shape when the copper paste is applied. It becomes an indicator such as.
- this aspect ratio exceeds 5.0, it comes close to a copper powder made of spherical copper particles, and the effect of surface contact is lost.
- the aspect ratio is 0.01 or less, the viscosity increases during paste formation, and the external shape retention and surface smoothness during application of the copper paste may deteriorate.
- the bulk density of the dendritic silver-coated copper powder according to the present embodiment is not particularly limited, but is preferably in the range of 0.5 g / cm 3 to 5.0 g / cm 3 . If the bulk density is less than 0.5 g / cm 3 , there is a possibility that sufficient contact between the silver-coated copper powders cannot be ensured. On the other hand, when the bulk density exceeds 5.0 g / cm 3 , the average particle diameter of the silver-coated copper powder also increases, and the surface area may decrease and the moldability and sinterability may deteriorate.
- the dendritic silver coat copper powder of the shape as mentioned above is occupied in a predetermined ratio in the obtained silver coat copper powder when observed with an electron microscope, copper of other shapes Even if powder is mixed, the same effect as the silver coat copper powder which consists only of the dendritic silver coat copper powder can be acquired.
- the dendritic silver-coated copper powder having the shape described above is 80% by number or more, preferably 90% of the total silver-coated copper powder. As long as it occupies a ratio of several percent or more, silver-coated copper powder of other shapes may be included.
- the dendritic silver-coated copper powder according to the present embodiment is a flat plate having a cross-sectional average thickness of more than 1.0 ⁇ m and 5.0 ⁇ m or less, and the surface of which is coated with silver. 1 is a dendritic structure. Below, the silver coating
- the dendritic silver-coated copper powder according to the present embodiment is preferably 1% by mass to 50% by mass with respect to 100% by mass of the total silver-coated copper powder coated with silver on the dendritic copper powder before silver coating. This is a very thin film having a silver thickness (coating thickness) of 0.15 ⁇ m or less.
- the dendritic silver-coated copper powder has a shape that retains the shape of the dendritic copper powder before silver coating.
- the silver coating amount in the dendritic silver-coated copper powder is preferably in the range of 1% by mass to 50% by mass with respect to 100% by mass of the total silver-coated copper powder coated with silver.
- the silver coating amount is preferably as small as possible from the viewpoint of cost.
- the coating amount of silver is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more with respect to 100% by mass of the total silver-coated copper powder coated with silver. More preferably.
- the silver coating amount when the silver coating amount increases, it is not preferable from the viewpoint of cost, and the silver coating amount is preferably 50% by mass or less with respect to 100% by mass of the silver-coated copper coated copper powder as a whole, It is more preferably 30% by mass or less, and further preferably 20% by mass or less.
- the average thickness of silver coated on the surface of the dendritic copper powder is about 0.0003 ⁇ m to 0.15 ⁇ m, and 0.005 ⁇ m to 0.05 ⁇ m. Preferably there is. If the silver coating thickness is less than 0.0003 ⁇ m on average, a uniform silver coating cannot be secured on the surface of the copper powder, and this causes a decrease in conductivity. On the other hand, when the silver coating thickness exceeds 0.15 ⁇ m on average, it is not preferable from the viewpoint of cost.
- the average thickness of the silver coated on the surface of the dendritic copper powder is about 0.0003 ⁇ m to 0.15 ⁇ m, and the cross-sectional average thickness of the tabular copper particles 1 constituting the dendritic copper powder (0. 5 ⁇ m to 5.0 ⁇ m). Therefore, before and after coating the surface of the dendritic copper powder with silver, the cross-sectional average thickness of the flat copper particles 1 does not substantially change.
- the dendritic silver-coated copper powder according to the present embodiment is not particularly limited, it is preferable the value of the BET specific surface area of 0.2m 2 /g ⁇ 3.0m 2 / g.
- the BET specific surface area value is less than 0.2 m 2 / g, the copper particles 1 coated with silver may not have the desired shape as described above, and high conductivity may not be obtained.
- the BET specific surface area value exceeds 3.0 m 2 / g, the silver coating on the surface of the dendritic silver-coated copper powder becomes non-uniform and high conductivity may not be obtained.
- the copper particles 1 constituting the silver-coated copper powder may become too fine, and the silver-coated copper powder may be in a fine whisker-like state, resulting in a decrease in conductivity.
- the BET specific surface area can be measured in accordance with JIS Z8830: 2013.
- the dendritic copper powder before being coated with silver can be produced, for example, by a predetermined electrolytic method using a sulfuric acid acidic solution containing copper ions as an electrolytic solution.
- electrolysis for example, a sulfuric acid electrolytic solution containing copper ions is accommodated in an electrolytic cell in which metallic copper is used as an anode (anode) and a stainless steel plate or titanium plate is used as a cathode (cathode). Electrolysis is performed by passing a direct current through the liquid at a predetermined current density. Thereby, a dendritic copper powder can be deposited (electrodeposition) on a cathode with electricity supply.
- the tabular copper particles 1 are assembled only by electrolysis without mechanically deforming the granular copper powder obtained by electrolysis using a medium such as a ball.
- the dendritic copper powder having a dendritic shape can be deposited on the cathode surface.
- the electrolytic solution for example, a solution containing a water-soluble copper salt, sulfuric acid, an additive such as an amine compound, and chloride ions can be used.
- the water-soluble copper salt is a copper ion source that supplies copper ions, and examples thereof include copper sulfate such as copper sulfate pentahydrate, copper chloride, and copper nitrate, but are not particularly limited.
- the copper ion concentration in the electrolytic solution can be about 1 g / L to 20 g / L, preferably about 2 g / L to 10 g / L.
- Sulfuric acid is for making sulfuric acid electrolyte.
- concentration of sulfuric acid in the electrolyte can be about 20 g / L to 300 g / L, preferably about 50 g / L to 200 g / L, as the free sulfuric acid concentration. Since the sulfuric acid concentration affects the conductivity of the electrolyte, it affects the uniformity of the copper powder obtained on the cathode.
- an amine compound can be used as the additive.
- This amine compound together with chloride ions described later, contributes to shape control of the deposited copper powder, and the copper powder deposited on the cathode surface has a dendritic shape and is a flat plate having a predetermined average cross-sectional thickness.
- a dendritic copper powder composed of copper particles and having a main trunk and a plurality of branches can be obtained.
- amine compounds examples include safranin O (3,7-diamino-2,8-dimethyl-5-phenyl-5-phenazinium chloride, C 20 H 19 N 4 Cl, CAS number: 477-73-64). Can be used. In addition, as an amine compound, you may add individually by 1 type and may add it in combination of 2 or more types. The amount of amine compound added is preferably such that the concentration in the electrolyte exceeds 50 mg / L and is not more than 500 mg / L, and is in the range of 100 mg / L to 400 mg / L. More preferably.
- chloride ions compounds that supply chloride ions such as hydrochloric acid and sodium chloride (chloride ion source) can be added to the electrolyte solution.
- a chloride ion contributes to shape control of the copper powder to precipitate with additives, such as an amine compound mentioned above.
- the chloride ion concentration in the electrolytic solution is not particularly limited, but can be about 1 mg / L to 1000 mg / L, preferably about 10 mg / L to 500 mg / L.
- the copper powder is deposited on the cathode by electrolysis using the electrolytic solution having the above-described composition.
- the electrolysis method a known method can be used.
- the current density is preferably in the range of 5 A / dm 2 to 30 A / dm 2 in electrolysis using a sulfuric acid electrolytic solution, and the electrolytic solution is energized while stirring.
- the liquid temperature (bath temperature) of the electrolytic solution can be, for example, about 20 ° C. to 60 ° C.
- the dendritic silver-coated copper powder according to the present embodiment is coated on the surface of the dendritic copper powder prepared by the above-described electrolytic method using, for example, a reduction electroless plating method or a substitutional electroless plating method. Can be manufactured.
- the dendritic copper powder is dispersed in a cleaning solution and washed while stirring. it can.
- This washing treatment is preferably carried out in an acidic solution, more preferably a polyvalent carboxylic acid that is also used for a reducing agent described later.
- filtration and separation of the dendritic copper powder and washing with water are repeated as appropriate to obtain a water slurry in which the dendritic copper powder is dispersed in water.
- what is necessary is just to use a well-known method about filtration, isolation
- the surface of the dendritic copper powder is obtained by adding a reducing agent and a silver ion solution to the water slurry obtained after washing the dendritic copper powder.
- a reducing agent to the water slurry in advance and dispersing it
- the silver ion solution is continuously added to the water slurry containing the reducing agent and the dendritic copper powder, thereby adding to the surface of the dendritic copper powder.
- Silver can be coated more uniformly.
- the reducing agent various reducing agents can be used, but it is preferable that the reducing agent has a low reducing power and cannot reduce copper complex ions.
- a reducing organic compound can be used.
- carbohydrates, polyvalent carboxylic acids and salts thereof, aldehydes, and the like can be used. More specifically, glucose (glucose), lactic acid, oxalic acid, tartaric acid, malic acid, malonic acid, glycolic acid, sodium potassium tartrate, formalin and the like can be mentioned.
- the reducing agent After adding the reducing agent to the water slurry containing the dendritic copper powder, it is preferable to perform stirring or the like in order to sufficiently disperse the reducing agent. Moreover, in order to adjust a water slurry to desired pH, an acid or an alkali can be added suitably. Further, the dispersion of the reducing organic compound as the reducing agent may be promoted by adding a water-soluble organic solvent such as alcohol.
- a known silver plating solution can be used, and among these, a silver nitrate solution is preferably used.
- the silver nitrate solution is more preferably added as an ammoniacal silver nitrate solution because complex formation is easy.
- the ammonia used in the ammoniacal silver nitrate solution is added to the silver nitrate solution, previously added to the water slurry together with the reducing agent, or added to the water slurry at the same time as an ammonia solution separate from the silver nitrate solution. Any method including these combinations may be used.
- the silver ion solution when added to the water slurry containing the dendritic copper powder and the reducing agent, it is preferable to gradually add the silver ion solution at a relatively slow rate. It can be formed on the surface of copper powder. Moreover, in order to improve the uniformity of the thickness of the coating, it is more preferable to keep the addition rate constant. Further, a reducing agent or the like previously added to the water slurry may be adjusted with another solution and gradually added together with the silver ion solution.
- the water slurry to which the silver ion solution or the like has been added is filtered, separated, washed with water, and then dried to obtain a dendritic silver-coated copper powder.
- the processing means after the filtration is not particularly limited, and a known method may be used.
- the silver coating method using the substitutional electroless plating method utilizes the difference in ionization tendency between copper and silver, and the silver ions in the solution are converted by the electrons generated when copper is dissolved in the solution. It is reduced and deposited on the copper surface. Therefore, the substitutional electroless silver plating solution can be coated with silver as a silver ion source, a complexing agent, and a conductive salt as main components. In order to do so, surfactants, brighteners, crystal modifiers, pH adjusters, precipitation inhibitors, stabilizers and the like can be added as necessary. Even in the production of the silver-coated copper powder according to the present embodiment, the plating solution is not particularly limited.
- the silver salt silver nitrate, silver iodide, silver sulfate, silver formate, silver acetate, silver lactate or the like can be used, and can be reacted with the dendritic copper powder dispersed in the water slurry.
- the silver ion concentration in the plating solution can be about 1 g / L to 10 g / L.
- the complexing agent forms a complex with silver ions
- representative examples include citric acid, tartaric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediamine, glycine, hydantoin, pyrrolidone, succinimide and the like.
- N-containing compounds, hydroxyethylidene diphosphonic acid, aminotrimethylenephosphonic acid, mercaptopropionic acid, thioglycol, thiosemicarbazide and the like can be used.
- the concentration of the complexing agent in the plating solution can be about 10 g / L to 100 g / L.
- the conductive salt inorganic acids such as nitric acid, boric acid and phosphoric acid, organic acids such as citric acid, maleic acid, tartaric acid and phthalic acid, or sodium, potassium and ammonium salts thereof can be used.
- concentration of the conductive salt in the plating solution can be about 5 g / L to 50 g / L.
- the control of the coating amount when the surface of the dendritic copper powder is coated with silver can be controlled by changing the amount of silver in the substitutional electroless plating solution, for example. Moreover, in order to improve the uniformity of the thickness of the coating, it is preferable to keep the addition rate constant.
- the slurry after the reaction is filtered, separated, washed with water, and then dried to obtain a dendritic silver-coated copper powder.
- the processing means after the filtration is not particularly limited, and a known method may be used.
- the dendritic silver-coated copper powder according to the present embodiment is a resinous silver-coated copper powder having a main trunk and a plurality of branches branched from the main trunk, as shown in the schematic diagram of FIG. And a silver-coated flat plate having a main trunk 2 grown in a dendritic shape and a plurality of branches 3 separated from the main trunk 2 and having an average cross-sectional thickness of more than 1.0 ⁇ m and 5.0 ⁇ m or less.
- the copper particles are assembled to form a structure.
- the average particle diameter (D50) of the dendritic silver-coated copper powder is 1.0 ⁇ m to 100 ⁇ m.
- the dendritic shape increases the surface area, makes the moldability and sinterability excellent, and flat copper particles having a predetermined cross-sectional average thickness A large number of contacts can be ensured by gathering and forming a dendritic shape, and exhibits excellent conductivity.
- the dendritic silver-coated copper powder having such a predetermined structure even when it is a copper paste or the like, aggregation can be suppressed and it can be uniformly dispersed in the resin. In addition, it is possible to suppress the occurrence of poor printability due to an increase in the viscosity of the paste. Therefore, according to this dendritic silver coat copper powder, it can be used conveniently for uses, such as a conductive paste and a conductive paint.
- the conductive paste (copper paste) is not limited to use under particularly limited conditions.
- the dendritic silver-coated copper powder according to the present embodiment is used as a metal filler, a binder resin, a solvent, and further necessary. Depending on the case, it can be prepared by kneading with additives such as a curing agent, an antioxidant, a coupling agent, and a corrosion inhibitor.
- the binder resin is not particularly limited, and those conventionally used can be used.
- an epoxy resin, a phenol resin, an unsaturated polyester resin, or the like can be used.
- organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, terpineol, ethyl carbitol, carbitol acetate, and butyl cellosolve can be used.
- the amount of the organic solvent added is not particularly limited, but should be adjusted in consideration of the particle size of the dendritic silver-coated copper powder so as to have a viscosity suitable for a conductive film forming method such as screen printing or dispenser. Can do.
- resin components can be added to adjust the viscosity.
- a cellulose-based resin typified by ethyl cellulose can be used, and it can be added as an organic vehicle dissolved in an organic solvent such as terpineol.
- an antioxidant or the like can be added in order to improve the conductivity after firing.
- an antioxidant for example, a hydroxycarboxylic acid etc. can be mentioned. More specifically, hydroxycarboxylic acids such as citric acid, malic acid, tartaric acid, and lactic acid are preferable, and citric acid or malic acid having a high adsorptive power to copper is particularly preferable.
- the addition amount of the antioxidant can be set to, for example, about 1% to 15% by weight in consideration of the antioxidant effect, the viscosity of the paste, and the like.
- conventionally used 2-ethyl 4-methylimidazole can be used.
- conventionally used benzothiazole, benzimidazole, and the like can also be used for the corrosion inhibitor.
- the metal which has electroconductivity such as copper powder of another shape, silver coat copper powder, and nickel and tin A filler can be mixed and used.
- the gap between the dendritic silver-coated copper powder is mixed with a metal filler such as copper powder of other shapes together with the dendritic silver-coated copper powder according to the present embodiment.
- a metal filler such as copper powder of other shapes
- copper powder of another shape is filled, and this makes it possible to secure more contacts for ensuring conductivity.
- the total amount of dendritic silver-coated copper powder and other shapes of copper powder can be reduced.
- the dendritic silver-coated copper powder is less than 20% by mass of the total amount of copper powder used as the metal filler, the contacts between the dendritic silver-coated copper powders are reduced and mixed with copper powder of other shapes. Even if the increase in the contact due to is taken into account, the conductivity of the metal filler is lowered.
- Various electric circuits can be formed using the conductive paste prepared using the metal filler described above. Even in this case, the circuit pattern forming method or the like conventionally used can be used without being limited to use under particularly limited conditions. For example, a conductive paste produced using the metal filler is applied or printed on a fired substrate or an unfired substrate, heated, and then pressed and cured and baked as necessary, so that a printed wiring board or Electrical circuits and external electrodes for various electronic components can be formed.
- the above-described metal filler is used as an electromagnetic wave shielding material, it is not limited to use under particularly limited conditions, and a general method, for example, using the metal filler mixed with a resin can be used. it can.
- a general method for example, mixing the metal filler with a resin and a solvent, and further adding an antioxidant, a thickener as necessary. It can be used as a conductive paint by mixing and kneading with an agent, an anti-settling agent and the like.
- the binder resin and solvent used at this time are not particularly limited, and those conventionally used can be used.
- the binder resin vinyl chloride resin, vinyl acetate resin, acrylic resin, polyester resin, fluorine resin, silicon resin, phenol resin, or the like can be used.
- the solvent conventionally used alcohols such as isopropanol, aromatic hydrocarbons such as toluene, esters such as methyl acetate, ketones such as methyl ethyl ketone, and the like can be used.
- the antioxidant conventionally used fatty acid amides, higher fatty acid amines, phenylenediamine derivatives, titanate coupling agents, and the like can be used.
- the resin used for forming the electromagnetic wave shielding layer of the conductive sheet for electromagnetic wave shielding is not particularly limited. Conventionally used ones can be used. For example, various polymers and copolymers such as vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, acrylic resin, polyurethane resin, polyester resin, olefin resin, chlorinated olefin resin, polyvinyl alcohol resin, alkyd resin, phenol resin, etc. A thermoplastic resin, a thermosetting resin, a radiation curable resin, and the like can be appropriately used.
- the method for producing the electromagnetic shielding material is not particularly limited.
- an electromagnetic shielding layer is formed by applying or printing a coating material in which a metal filler and a resin are dispersed or dissolved in a solvent on a substrate, and the surface is solidified. It can manufacture by making it dry to such an extent.
- a metal filler containing the dendritic silver-coated copper powder according to the present embodiment can also be used.
- the average particle size (D50) was measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., HRA9320 X-100).
- the obtained silver-coated copper powder was embedded in an epoxy resin to produce a measurement sample, the sample was cut and polished, and observed with a scanning electron microscope to observe the cross section of the silver-coated copper powder. More specifically, 20 copper powders are observed, the average thickness (cross-sectional average thickness) of the copper powder is obtained, and the value of the cross-sectional average thickness is obtained with a laser diffraction / scattering particle size distribution analyzer. From the ratio to the average particle diameter (D50), the aspect ratio (average cross-sectional thickness / D50) was determined.
- BET specific surface area The BET specific surface area was measured using a specific surface area / pore distribution measuring device (manufactured by Cantachrome, QUADRASORB SI).
- the specific resistance value of the film was determined by measuring the sheet resistance value by a four-terminal method using a low resistivity meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation), and measuring the surface roughness profile (Tokyo Seimitsu Co., Ltd.).
- the film thickness of the coating film was measured by SURFCO M130A), and the sheet resistance value was obtained by dividing by the film thickness.
- the electromagnetic shielding characteristics were evaluated by measuring the attenuation rate of the samples obtained in the examples and comparative examples using an electromagnetic wave having a frequency of 1 GHz. Specifically, the level in Comparative Example 4 in which no dendritic silver-coated copper powder is used is “ ⁇ ”, and the level worse than that in Comparative Example 4 is “ ⁇ ”. The case where it was better than the level was evaluated as “ ⁇ ”, and the case where it was superior was evaluated as “ ⁇ ”.
- Example 1 Manufacture of dendritic copper powder>
- An electrolytic cell with a capacity of 100 L is used with a titanium electrode plate having an electrode area of 200 mm ⁇ 200 mm as a cathode and a copper electrode plate with an electrode area of 200 mm ⁇ 200 mm as an anode, and an electrolytic solution is charged into the electrolytic cell. Then, a direct current was applied thereto to deposit copper powder (dendritic copper powder) on the cathode plate.
- an electrolytic solution having a copper ion concentration of 5 g / L and a sulfuric acid concentration of 150 g / L was used.
- safranin O manufactured by Kanto Chemical Co., Inc.
- a hydrochloric acid solution manufactured by Wako Pure Chemical Industries, Ltd.
- concentration in a liquid is added so that it might become 10 mg / L as a chloride ion (chlorine ion) density
- the current density of the cathode is 25 A / dm 2 under the condition that the temperature is maintained at 25 ° C.
- Current was applied to deposit copper powder on the cathode plate.
- the electrolytic copper powder deposited on the cathode plate was recovered by mechanically scraping it off the bottom of the electrolytic cell using a scraper, and the recovered copper powder was washed with pure water and then put in a vacuum dryer and dried. .
- the deposited copper powder As a result of observing the shape of the copper powder thus obtained by the method using the above-mentioned scanning electron microscope (SEM), in the deposited copper powder, at least 90% by number or more of the copper powder is a linearly grown main trunk, A dendritic copper powder having a two-dimensional or three-dimensional dendritic shape in which copper particles having a plurality of branches linearly branched from the main trunk and a branch further branched from the branch are assembled. Met. Moreover, copper powder was flat form comprised by the laminated structure which 1 layer or several overlapped.
- the powder was filtered, washed with water and dried through ethanol.
- a dendritic silver-coated copper powder having a surface coated with silver was obtained.
- the dendritic silver coat copper powder was flat form comprised by the laminated structure which 1 layer or several overlapped.
- the dendritic silver-coated copper powder was recovered and the amount of silver coating was measured, it was 26.2% by mass based on 100% by mass of the silver-coated silver-coated copper powder.
- the surface of the dendritic copper powder before silver coating was uniformly coated with silver, two-dimensional or three-dimensional Dendritic silver-coated copper having a dendritic shape having a dendritic shape having a main trunk grown in a dendritic form, a plurality of branches branched from the main trunk, and a branch further branched from the branch It was powder.
- at least 90% by number or more of the obtained silver-coated copper powder was the dendritic silver-coated copper powder having the shape described above.
- the copper particles constituting the main trunk and branches of the dendritic silver-coated copper powder have a flat cross-sectional thickness of 3.4 ⁇ m on average, and the average particle diameter (D50) of the dendritic silver-coated copper powder is It was 58.9 ⁇ m.
- the aspect ratio (cross-sectional average thickness / average particle diameter) calculated from the average cross-sectional thickness of the copper particles constituting the dendritic silver-coated copper powder and the average particle diameter of the dendritic silver-coated copper powder was 0.006. It was.
- the bulk density of the obtained copper powder was 3.0 g / cm 3 .
- the BET specific surface area was 1.1 m 2 / g.
- the prepared dendritic silver-coated copper powder was mixed with 20 g of a phenolic resin (manufactured by Gunei Chemical Co., Ltd., PL-2211) and 10 g of butyl cellosolve (manufactured by Kanto Chemical Co., Ltd., deer special grade).
- a kneader manufactured by Nippon Seiki Seisakusho Co., Ltd., non-bubbling kneader NBK-1
- kneading at 1500 rpm for 3 minutes was repeated four times to form a paste.
- the copper powder was uniformly dispersed in the resin without agglomeration.
- the obtained conductive paste was printed on glass with a metal squeegee and cured in air at 150 ° C. and 200 ° C. for 30 minutes.
- Example 2 ⁇ Manufacture of dendritic copper powder>
- a composition having a copper ion concentration of 7 g / L and a sulfuric acid concentration of 150 g / L is used, and safranin O as an additive is added to the electrolytic solution so that the concentration in the electrolytic solution is 150 mg / L.
- a hydrochloric acid solution was added so that the chlorine ion concentration in the electrolytic solution was 25 mg / L.
- the current density of the cathode is set to 20 A / dm 2 under the condition that the temperature is maintained at 25 ° C.
- the electrolytic copper powder deposited on the cathode plate was recovered by mechanically scraping it off the bottom of the electrolytic cell using a scraper, and the recovered copper powder was washed with pure water and then put in a vacuum dryer and dried. .
- a substitution type electroless plating solution a solution having a composition in which 20 g of silver nitrate, 20 g of citric acid, and 10 g of ethylenediamine are dissolved in 1 liter of ion-exchanged water is added, and 100 g of dendritic copper powder is put into the solution and stirred for 60 minutes. Reacted. The bath temperature at this time was 25 ° C.
- the powder was filtered, washed with water, and dried through ethanol.
- a dendritic silver-coated copper powder having a surface coated with silver was obtained.
- the dendritic silver coat copper powder was flat form comprised by the laminated structure which 1 layer or several overlapped. When the dendritic silver-coated copper powder was recovered and the silver coating amount was measured, it was 10.6% by mass relative to 100% by mass of the silver-coated silver-coated copper powder.
- silver silver having a two-dimensional or three-dimensional dendritic shape which is made of coated copper powder and has a main trunk grown in a dendritic shape, a plurality of branches branched from the main trunk, and a branch further branched from the branch It was a coated copper powder.
- at least 90% by number or more of the obtained silver-coated copper powder was the dendritic silver-coated copper powder having the shape described above.
- the copper particle which comprises the main trunk and branch of the dendritic silver coat copper powder was a flat form whose cross-sectional thickness is 1.2 micrometers on average, and had a fine convex part on the surface.
- the average particle diameter (D50) of this dendritic silver coat copper powder was 44.6 micrometers.
- the aspect ratio (cross-sectional average thickness / average particle diameter) calculated from the cross-sectional average thickness of the copper particles and the average particle diameter of the dendritic copper powder was 0.03.
- the bulk density of the obtained copper powder was 1.6 g / cm 3 .
- the BET specific surface area was 1.7 m 2 / g.
- the prepared dendritic silver-coated copper powder was mixed with 20 g of a phenolic resin (manufactured by Gunei Chemical Co., Ltd., PL-2211) and 10 g of butyl cellosolve (manufactured by Kanto Chemical Co., Ltd., deer special grade).
- a kneader manufactured by Nippon Seiki Seisakusho Co., Ltd., non-bubbling kneader NBK-1
- kneading at 1500 rpm for 3 minutes was repeated four times to form a paste.
- the copper powder was uniformly dispersed in the resin without agglomeration.
- the obtained conductive paste was printed on glass with a metal squeegee and cured in air at 150 ° C. and 200 ° C. for 30 minutes.
- Example 3 The dendritic silver-coated copper powder produced in Example 1 was dispersed in a resin to obtain an electromagnetic wave shielding material.
- the preparation of the dendritic copper powder for producing the dendritic silver-coated copper powder, and the conditions until the dendritic copper-coated copper powder was coated with silver to produce the dendritic silver-coated copper powder were as described in Example 1.
- the dendritic silver-coated copper powder having a silver coating amount of 26.2% by mass with respect to 100% by mass of the total silver-coated copper powder coated with silver was used.
- a 40 g of this dendritic silver-coated copper powder was mixed with 100 g of vinyl chloride resin and 200 g of methyl ethyl ketone, and paste was made by repeating kneading at 1500 rpm for 3 minutes four times using a small kneader. During pasting, the copper powder was uniformly dispersed in the resin without agglomeration. This was coated and dried using a Mayer bar on a substrate made of a transparent polyethylene terephthalate sheet having a thickness of 100 ⁇ m to form an electromagnetic wave shielding layer having a thickness of 25 ⁇ m.
- the characteristics of the electromagnetic wave shield were evaluated by measuring the attenuation rate using an electromagnetic wave having a frequency of 1 GHz. Table 1 shows the results.
- Example 1 Copper powder was deposited on the cathode plate in the same manner as in Example 1 except that safranin O as an additive and chlorine ions were not added to the electrolytic solution. Thereafter, the surface of the obtained copper powder was coated with silver in the same manner as in Example 1 to obtain a silver-coated copper powder.
- the silver coating amount of the silver-coated copper powder was 26.1% by mass with respect to 100% by mass of the entire silver-coated silver-coated copper powder.
- FIG. 7 shows the results of observing the shape of the obtained silver-coated copper powder with a SEM field of view at a magnification of 5,000 times.
- the shape of the obtained silver-coated copper powder is a dendritic shape in which particulate copper is gathered, and the surface of the copper powder is in a state where silver is coated.
- the average particle diameter (D50) of the silver-coated copper powder was 45.3 ⁇ m. Further, no minute convex portion was formed on the dendritic portion.
- 40 g of silver-coated copper powder produced by the method described above is mixed with 20 g of a phenolic resin (manufactured by Gunei Chemical Co., Ltd., PL-2211) and 10 g of butyl cellosolve (manufactured by Kanto Chemical Co., Ltd., deer special grade).
- a kneader manufactured by Nippon Seiki Seisakusho Co., Ltd., non-bubbling kneader NBK-1
- kneading at 1500 rpm for 3 minutes was repeated four times to form a paste.
- the viscosity increased every time kneading was repeated.
- the obtained conductive paste was printed on glass with a metal squeegee and cured in air at 150 ° C. and 200 ° C. for 30 minutes.
- the specific resistance of the film obtained by curing As a result of measuring the specific resistance of the film obtained by curing, it was 670 ⁇ 10 ⁇ 6 ⁇ ⁇ cm (curing temperature 150 ° C.) and 310 ⁇ 10 ⁇ 6 ⁇ ⁇ cm (curing temperature 200 ° C.), respectively. Compared with the conductive paste obtained in the examples, the specific resistance value was high and the conductivity was inferior.
- the temperature is maintained at 45 ° C. so that the current density of the cathode becomes 20 A / dm 2. Current was applied to deposit copper powder on the cathode plate.
- FIG. 8 shows the result of observing the shape of the obtained silver-coated copper powder with a SEM field of view at a magnification of 5,000 times.
- the shape of the obtained electrolytic copper powder was a dendritic copper powder formed by collecting granular copper particles.
- the dendritic main trunks and branches are rounded and not in the form of a flat plate composed of one or a plurality of laminated structures like the copper powder obtained in the examples.
- the obtained dendritic silver-coated copper powder was collected and the amount of silver coating was measured. Moreover, as a result of observing the obtained dendritic silver-coated copper powder with a field of view of 5,000 times by SEM, the surface of the dendritic copper powder before silver coating was uniformly coated with silver, two-dimensional or three-dimensional It was a dimensional dendritic shape, and was not a flat plate composed of one or a plurality of laminated structures, like the silver-coated copper powder obtained in the examples.
- the prepared dendritic silver-coated copper powder was mixed with 20 g of a phenolic resin (manufactured by Gunei Chemical Co., Ltd., PL-2211) and 10 g of butyl cellosolve (manufactured by Kanto Chemical Co., Ltd., deer special grade).
- a kneader manufactured by Nippon Seiki Seisakusho Co., Ltd., non-bubbling kneader NBK-1
- kneading at 1500 rpm for 3 minutes was repeated four times to form a paste.
- the copper powder was uniformly dispersed in the resin without agglomeration.
- the obtained conductive paste was printed on glass with a metal squeegee and cured in air at 150 ° C. and 200 ° C. for 30 minutes.
- the flat copper powder was prepared by mechanically flattening granular electrolytic copper powder. Specifically, 5 g of stearic acid was added to 500 g of granular atomized copper powder (manufactured by Mekin Metal Powders Co., Ltd.) having an average particle diameter of 7.9 ⁇ m, and flattened with a ball mill. The ball mill was charged with 5 kg of 3 mm zirconia beads and flattened by rotating for 60 minutes at a rotation speed of 500 rpm.
- the obtained flat copper powder was coated with silver in the same manner as in Example 1.
- the silver coating amount of the produced flat silver-coated copper powder was 26.4% by mass with respect to 100% by mass of the entire silver-coated silver-coated copper powder.
- the plate-like silver-coated copper powder thus produced was measured with a laser diffraction / scattering particle size distribution measuring instrument.
- the average particle size (D50) was 24.1 ⁇ m, and as a result of observation with an SEM, the thickness was 0.6 ⁇ m, the surface was smooth, and no minute protrusions were formed.
- the aspect-ratio (cross-sectional average thickness / average particle diameter) computed from the cross-sectional average thickness and average particle diameter was 0.02.
- Comparative Example 4 Similar to the one used in Comparative Example 3, a silver coated copper powder in which silver is coated on a flat copper powder prepared by mechanically flattening a granular electrolytic copper powder is prepared, and the silver coated copper powder is used. The characteristics of the electromagnetic wave shield were evaluated, and the effect of the dendritic shape was examined in comparison with the electromagnetic wave shield produced using the dendritic silver-coated copper powder in the examples.
- the flat silver coated copper powder used was coated with silver in the same manner as in Example 1. The silver coating amount of the produced flat silver-coated copper powder was 26.1% by mass with respect to 100% by mass of the entire silver-coated silver-coated copper powder.
- a 40 g of this flat silver-coated copper powder was mixed with 100 g of vinyl chloride resin and 200 g of methyl ethyl ketone, and paste was made by repeating kneading at 1500 rpm for 3 minutes four times using a small kneader. During pasting, the copper powder was uniformly dispersed in the resin without agglomeration. This was coated and dried using a Mayer bar on a substrate made of a transparent polyethylene terephthalate sheet having a thickness of 100 ⁇ m to form an electromagnetic wave shielding layer having a thickness of 25 ⁇ m.
- the characteristics of the electromagnetic wave shield were evaluated by measuring the attenuation rate using an electromagnetic wave having a frequency of 1 GHz. Table 1 shows the results.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本実施の形態に係る銀コート銅粉は、樹枝状に成長した主幹とその主幹から分かれた複数の枝とを有する形状の銅粒子が集合してなり、その表面に銀が被覆された銀コート銅粉である。
本実施の形態に係る樹枝状銀コート銅粉は、上述したように、断面平均厚さが1.0μmを超えて5.0μm以下の平板状である、表面に銀が被覆されている銅粒子1によって樹枝状に構成されたものである。以下に、銀コート銅粉の表面に対する銀被覆について説明する。
次に、本実施の形態に係る樹枝状銀コート銅粉の製造方法について説明する。以下では、先ず、樹枝状銀コート銅粉を構成する樹枝状銅粉の製造方法について説明し、続いて、その樹枝状銅粉に対して銀を被覆して樹枝状銀コート銅粉を得る方法について説明する。
銀を被覆する前の樹枝状銅粉は、例えば、銅イオンを含有する硫酸酸性溶液を電解液として用いて所定の電解法により製造することができる。
本実施の形態に係る樹枝状銀コート銅粉は、上述した電解法により作製した樹枝状銅粉の表面に、例えば、還元型無電解めっき法や置換型無電解めっき法を用いて銀を被覆することにより製造することができる。
本実施の形態に係る樹枝状銀コート銅粉は、上述したように、主幹とその主幹から分岐した複数の枝を有する樹脂状の銀コート銅粉であり、図1の模式図に示したように、樹枝状に成長した主幹2とその主幹2から分かれた複数の枝3とを有する形状であって且つ断面平均厚さが1.0μmを超えて5.0μm以下の銀被覆された平板状の銅粒子が集合して構成されている。そして、当該樹枝状銀コート銅粉の平均粒子径(D50)は、1.0μm~100μmである。このような樹枝状銀コート銅粉では、樹枝状の形状であることにより表面積が大きくなり、成形性や焼結性が優れたものとなり、また所定の断面平均厚さの平板状の銅粒子が集合して樹枝状に構成されていることにより、接点の数を多く確保することができ、優れた導電性を発揮する。
下記の実施例、比較例に得られた銀コート銅粉について、以下の方法により、形状の観察、平均粒子径の測定等を行った。
走査型電子顕微鏡(日本電子株式会社製,JSM-7100F型)により、所定の倍率の視野で任意に20視野を観察し、その視野内に含まれる銅粉の外観を観察した。
平均粒子径(D50)は、レーザー回折・散乱法粒度分布測定器(日機装株式会社製,HRA9320 X-100)を用いて測定した。
得られた銀コート銅粉をエポキシ樹脂に埋め込んで測定試料を作製し、その試料に対して切断・研磨を行い、走査型電子顕微鏡で観察することによって銀コート銅粉の断面を観察した。より具体的には、銅粉を20個観察して、その銅粉の平均厚さ(断面平均厚さ)を求め、その断面平均厚さの値とレーザー回折・散乱法粒度分布測定器で求めた平均粒子径(D50)との比から、アスペクト比(断面平均厚さ/D50)を求めた。
BET比表面積は、比表面積・細孔分布測定装置(カンタクローム社製,QUADRASORB SI)を用いて測定した。
被膜の比抵抗値は、低抵抗率計(三菱化学株式会社製,Loresta-GP MCP-T600)を用いて四端子法によりシート抵抗値を測定し、表面粗さ形状測定器(東京精密株式会社製,SURFCO M130A)により被膜の膜厚を測定して、シート抵抗値を膜厚で除することによって求めた。
電磁波シールド特性の評価は、各実施例及び比較例にて得られた試料について、周波数1GHzの電磁波を用いて、その減衰率を測定して評価した。具体的には、樹枝状銀コート銅粉を使用していない比較例4の場合のレベルを『△』として、その比較例4のレベルよりも悪い場合を『×』とし、その比較例4のレベルよりも良好な場合を『○』とし、さらに優れている場合を『◎』として評価した。
[実施例1]
<樹枝状銅粉の製造>
容量が100Lの電解槽に、電極面積が200mm×200mmのチタン製の電極板を陰極とし、電極面積が200mm×200mmの銅製の電極板を陽極として用い、その電解槽中に電解液を装入し、これに直流電流を通電して銅粉(樹枝状銅粉)を陰極板上に析出させた。
次に、上述した方法で作製した樹枝状銅粉を用いて銀コート銅粉を作製した。
次に、上述した方法で作製した樹枝状銀コート銅粉をペースト化して導電性ペーストを作製した。
<樹枝状銅粉の製造>
電解液として、銅イオン濃度が7g/L、硫酸濃度が150g/Lの組成のものを用い、その電解液に、添加剤としてサフラニンOを電解液中の濃度として150mg/Lとなるように添加し、さらに塩酸溶液を電解液中の塩素イオン濃度として25mg/Lとなるように添加した。そして、上述のように濃度調整した電解液を、ポンプを用いて15L/minの流量で循環しながら、温度を25℃に維持した条件で、陰極の電流密度が20A/dm2になるように通電して陰極板上に銅粉を析出させた。陰極板上に析出した電解銅粉を、スクレーパーを用いて機械的に電解槽の槽底に掻き落として回収し、回収した銅粉を純水で洗浄した後、減圧乾燥器に入れて乾燥した。
得られた樹枝状銅粉100gを用いて、置換型無電解めっき液によりその銅粉表面に銀被覆を行った。
次に、上述した方法で作製した樹枝状銀コート銅粉をペースト化して導電性ペーストを作製した。
実施例1にて作製した樹枝状銀コート銅粉を樹脂に分散して電磁波シールド材とした。なお、樹枝状銀コート銅粉を作製するための樹枝状銅粉の作製、及び、その樹枝状銅粉に銀を被覆して樹枝状銀コート銅粉を作製するまでの条件は、実施例1と同様とし、銀被覆量が銀被覆した銀コート銅粉全体の質量100%に対して26.2質量%の樹枝状銀コート銅粉を使用した。
電解液中に、添加剤としてのサフラニンOと、塩素イオンとを添加しない条件としたこと以外は、実施例1と同様にして銅粉を陰極板上に析出させた。その後、得られた銅粉を実施例1と同様にしてその銅粉表面に銀を被覆し、銀コート銅粉を得た。その銀コート銅粉の銀被覆量は、銀被覆した銀コート銅粉全体の質量100%に対して26.1質量%であった。
<樹枝状銅粉の製造>
電解液として、銅イオン濃度が10g/L、硫酸濃度が150g/Lの組成のものを用いた。また、この電解液に、添加剤としてサフラニンO(関東化学工業株式会社製)を電解液中の濃度として50mg/Lとなるように添加し、さらに塩酸溶液(和光純薬工業株式会社製)を電解液中の塩化物イオン(塩素イオン)濃度として10mg/Lとなるように添加した。そして、上述したような濃度に調整した電解液を、定量ポンプを用いて15L/minの流量で循環しながら、温度を45℃に維持し、陰極の電流密度が20A/dm2になるように通電して陰極板上に銅粉を析出させた。
次に、得られた樹枝状銅粉を用い、実施例1と同様にして銀コート銅粉を作製した。
次に、上述した方法で作製した樹枝状銀コート銅粉をペースト化して導電性ペーストを作製した。
従来の平板状銅粉に銀を被覆させた銀コート銅粉による導電性ペーストの特性を評価し、実施例における樹枝状銀コート銅粉を用いて作製した導電性ペーストと比較した。
比較例3にて用いたものと同様に粒状の電解銅粉を機械的に扁平化させて作製した平板状銅粉に銀を被覆させた銀コート銅粉を作製し、その銀コート銅粉による電磁波シールドの特性を評価し、実施例における樹枝状銀コート銅粉を用いて作製した電磁波シールドと比較して、樹枝状形状の効果を調べた。なお、使用した平板状の銀コート銅粉は、実施例1と同じ方法で銀を被覆した。作製した平板状銀コート銅粉の銀被覆量は、銀被覆した銀コート銅粉全体の質量100%に対して26.1質量%であった。
2 (銅粒子の)主幹
3,3a,3b (銅粒子の)枝
Claims (9)
- 直線的に成長した主幹と該主幹から分かれた複数の枝とを有する樹枝状の形状の銅粒子が集合してなり、表面に銀が被覆された銀コート銅粉であって、
前記銅粒子の主幹及び枝の断面平均厚さが1.0μmを超えて5.0μm以下の平板状であり、
当該銀コート銅粉は1層又は複数の重なった積層構造で構成された平板状であって平均粒子径(D50)が1.0μm~100μmである
ことを特徴とする銀コート銅粉。 - 前記銀が被覆されている銅粒子の断面平均厚さを当該銀コート銅粉の平均粒子径(D50)で除した比が0.01を超えて5.0以下の範囲である
ことを特徴とする請求項1に記載の銀コート銅粉。 - 銀被覆量が銀被覆した当該銀コート銅粉全体の質量100%に対して1質量%~50質量%である
ことを特徴とする請求項1又は2に記載の銀コート銅粉。 - 嵩密度が0.5g/cm3~5.0g/cm3の範囲である
ことを特徴とする請求項1乃至3のいずれか1項に記載の銀コート銅粉。 - BET比表面積値が0.2m2/g~3.0m2/gである
ことを特徴とする請求項1乃至4のいずれか1項に記載の銀コート銅粉。 - 請求項1乃至5のいずれかに記載の銀コート銅粉を、全体の20質量%以上の割合で含有していることを特徴とする金属フィラー。
- 請求項6に記載の金属フィラーを樹脂に混合させてなることを特徴とする導電性ペースト。
- 請求項6に記載の金属フィラーを用いてなることを特徴とする電磁波シールド用導電性塗料。
- 請求項6に記載の金属フィラーを用いてなることを特徴とする電磁波シールド用導電性シート。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15886411.6A EP3275571A4 (en) | 2015-03-26 | 2015-03-26 | Silver-coated copper powder and conductive paste, conductive material, and conductive sheet using same |
CN201580077852.3A CN107427912A (zh) | 2015-03-26 | 2015-03-26 | 覆银铜粉及使用该覆银铜粉的导电性膏、导电性涂料、导电性片 |
PCT/JP2015/059482 WO2016151859A1 (ja) | 2015-03-26 | 2015-03-26 | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート |
US15/560,721 US20180079000A1 (en) | 2015-03-26 | 2015-03-26 | Silver-coated copper powder and conductive paste, conductive material, and conductive sheet using same |
KR1020177030444A KR20170130530A (ko) | 2015-03-26 | 2015-03-26 | 은 코팅 동분 및 그것을 이용한 도전성 페이스트, 도전성 도료, 도전성 시트 |
JP2015540389A JP5920541B1 (ja) | 2015-03-26 | 2015-03-26 | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2015/059482 WO2016151859A1 (ja) | 2015-03-26 | 2015-03-26 | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016151859A1 true WO2016151859A1 (ja) | 2016-09-29 |
Family
ID=55974086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/059482 WO2016151859A1 (ja) | 2015-03-26 | 2015-03-26 | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート |
Country Status (6)
Country | Link |
---|---|
US (1) | US20180079000A1 (ja) |
EP (1) | EP3275571A4 (ja) |
JP (1) | JP5920541B1 (ja) |
KR (1) | KR20170130530A (ja) |
CN (1) | CN107427912A (ja) |
WO (1) | WO2016151859A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3530706A1 (en) | 2018-02-27 | 2019-08-28 | Fundación Cetena | Method for producing a conductive ink for offset printing and conductive ink thus produced |
WO2021142750A1 (zh) * | 2020-01-17 | 2021-07-22 | 深圳市首骋新材料科技有限公司 | 一种改性环氧丙烯酸树脂导电胶及其制备方法和应用 |
WO2021142752A1 (zh) * | 2020-01-17 | 2021-07-22 | 深圳市首骋新材料科技有限公司 | 一种有机硅树脂导电胶及其制备方法和应用 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5907302B1 (ja) * | 2015-05-15 | 2016-04-26 | 住友金属鉱山株式会社 | 銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銅粉の製造方法 |
JP5907301B1 (ja) * | 2015-05-15 | 2016-04-26 | 住友金属鉱山株式会社 | 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法 |
JP7150273B2 (ja) * | 2017-12-21 | 2022-10-11 | 国立大学法人北海道大学 | 銅酸化物粒子組成物、導電性ペースト及び導電性インク |
JP7003668B2 (ja) * | 2018-01-05 | 2022-02-04 | 住友電気工業株式会社 | 銅ナノインクの製造方法及び銅ナノインク |
CN110842190B (zh) * | 2019-10-11 | 2021-10-15 | 云南大学 | 一种银包覆铜粉的制备方法 |
TWI718819B (zh) * | 2019-12-19 | 2021-02-11 | 財團法人工業技術研究院 | 導電纖維及其製造方法 |
CN111462935A (zh) * | 2020-05-12 | 2020-07-28 | 无锡市伍豪机械设备有限公司 | 导电性颗粒及其制造方法 |
KR102460883B1 (ko) * | 2020-12-07 | 2022-11-02 | 덕산하이메탈(주) | 전도성 입자 |
CN114628058B (zh) * | 2022-05-16 | 2022-09-13 | 西安宏星电子浆料科技股份有限公司 | 一种多层片式陶瓷电容器用铜端电极浆料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011214032A (ja) * | 2010-03-31 | 2011-10-27 | Jx Nippon Mining & Metals Corp | ブレーキパッド用銅粉 |
JP2013053347A (ja) * | 2011-09-05 | 2013-03-21 | Mitsui Mining & Smelting Co Ltd | デンドライト状銅粉 |
JP2013100592A (ja) * | 2011-10-21 | 2013-05-23 | Mitsui Mining & Smelting Co Ltd | 銀被覆銅粉 |
JP5503813B1 (ja) * | 2012-08-02 | 2014-05-28 | 三井金属鉱業株式会社 | 導電性フィルム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1049622A (zh) * | 1990-03-06 | 1991-03-06 | 北京市印刷技术研究所 | 导电铜粉的表面处理方法 |
TWI329534B (en) * | 2003-07-09 | 2010-09-01 | Fry Metals Inc | Coating metal particles |
CN1876282A (zh) * | 2006-07-07 | 2006-12-13 | 清华大学 | 一种铜粉表面化学镀银的方法 |
JP6166012B2 (ja) * | 2011-01-28 | 2017-07-19 | 三井金属鉱業株式会社 | 導電性粉末及び導電性ペースト |
JP5320442B2 (ja) * | 2011-07-13 | 2013-10-23 | 三井金属鉱業株式会社 | デンドライト状銅粉 |
JP5631841B2 (ja) * | 2011-10-21 | 2014-11-26 | 三井金属鉱業株式会社 | 銀被覆銅粉 |
JP6264731B2 (ja) * | 2012-03-06 | 2018-01-24 | 東洋インキScホールディングス株式会社 | 導電性樹脂組成物、導電性シート、電磁波シールドシートおよびこれらの製造方法、並びに導電性微粒子の製造方法 |
JP2014019877A (ja) * | 2012-07-12 | 2014-02-03 | Furukawa Electric Co Ltd:The | 銅微粒子の製造方法 |
JP2014159646A (ja) * | 2014-06-11 | 2014-09-04 | Mitsui Mining & Smelting Co Ltd | 銀被覆銅粉 |
-
2015
- 2015-03-26 US US15/560,721 patent/US20180079000A1/en not_active Abandoned
- 2015-03-26 KR KR1020177030444A patent/KR20170130530A/ko not_active Application Discontinuation
- 2015-03-26 JP JP2015540389A patent/JP5920541B1/ja not_active Expired - Fee Related
- 2015-03-26 CN CN201580077852.3A patent/CN107427912A/zh active Pending
- 2015-03-26 EP EP15886411.6A patent/EP3275571A4/en not_active Withdrawn
- 2015-03-26 WO PCT/JP2015/059482 patent/WO2016151859A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011214032A (ja) * | 2010-03-31 | 2011-10-27 | Jx Nippon Mining & Metals Corp | ブレーキパッド用銅粉 |
JP2013053347A (ja) * | 2011-09-05 | 2013-03-21 | Mitsui Mining & Smelting Co Ltd | デンドライト状銅粉 |
JP2013100592A (ja) * | 2011-10-21 | 2013-05-23 | Mitsui Mining & Smelting Co Ltd | 銀被覆銅粉 |
JP5503813B1 (ja) * | 2012-08-02 | 2014-05-28 | 三井金属鉱業株式会社 | 導電性フィルム |
Non-Patent Citations (1)
Title |
---|
See also references of EP3275571A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3530706A1 (en) | 2018-02-27 | 2019-08-28 | Fundación Cetena | Method for producing a conductive ink for offset printing and conductive ink thus produced |
WO2021142750A1 (zh) * | 2020-01-17 | 2021-07-22 | 深圳市首骋新材料科技有限公司 | 一种改性环氧丙烯酸树脂导电胶及其制备方法和应用 |
WO2021142752A1 (zh) * | 2020-01-17 | 2021-07-22 | 深圳市首骋新材料科技有限公司 | 一种有机硅树脂导电胶及其制备方法和应用 |
CN113412321A (zh) * | 2020-01-17 | 2021-09-17 | 深圳市首骋新材料科技有限公司 | 一种有机硅树脂导电胶及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016151859A1 (ja) | 2017-04-27 |
KR20170130530A (ko) | 2017-11-28 |
JP5920541B1 (ja) | 2016-05-18 |
US20180079000A1 (en) | 2018-03-22 |
EP3275571A4 (en) | 2018-11-21 |
CN107427912A (zh) | 2017-12-01 |
EP3275571A1 (en) | 2018-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5920541B1 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
WO2016038914A1 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
WO2016031286A1 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP5907301B1 (ja) | 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法 | |
JP5858201B1 (ja) | 銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート | |
JP5920540B1 (ja) | 銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート | |
JP2016139598A (ja) | 銀コート銅粉、及びそれを用いた銅ペースト、導電性塗料、導電性シート | |
JP2017071819A (ja) | 銀粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP6274076B2 (ja) | 銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート | |
JP5790900B1 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP6332125B2 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP2016139597A (ja) | 樹枝状銀コート銅粉の製造方法 | |
JP2016060966A (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP5858202B1 (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP6332124B2 (ja) | 銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP6332058B2 (ja) | 銅粉、及びそれを用いた銅ペースト、導電性塗料、導電性シート | |
JP2017066462A (ja) | 銀コート銅粉の製造方法、及びそれを用いた導電性ペーストの製造方法 | |
TWI553661B (zh) | Silver powder and its use of conductive paste, conductive paint, conductive film | |
JP2016094658A (ja) | 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート | |
JP6056901B2 (ja) | 樹枝状銀コート銅粉の製造方法、及びその樹枝状銀コート銅粉を用いた銅ペースト、導電性塗料、導電性シート | |
JP2017066463A (ja) | Niコート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート、並びにNiコート銅粉の製造方法 | |
JP2017066444A (ja) | Niコート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート、並びにNiコート銅粉の製造方法 | |
JP2017066442A (ja) | Niコート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート、並びにNiコート銅粉の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015540389 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15886411 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15560721 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015886411 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20177030444 Country of ref document: KR Kind code of ref document: A |