JP6276351B2 - Conductive particles, conductive materials, and connection structures - Google Patents
Conductive particles, conductive materials, and connection structures Download PDFInfo
- Publication number
- JP6276351B2 JP6276351B2 JP2016172462A JP2016172462A JP6276351B2 JP 6276351 B2 JP6276351 B2 JP 6276351B2 JP 2016172462 A JP2016172462 A JP 2016172462A JP 2016172462 A JP2016172462 A JP 2016172462A JP 6276351 B2 JP6276351 B2 JP 6276351B2
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- Prior art keywords
- conductive layer
- conductive
- particles
- weight
- nickel
- Prior art date
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- 239000002245 particle Substances 0.000 title claims description 433
- 239000004020 conductor Substances 0.000 title claims description 34
- 239000010410 layer Substances 0.000 claims description 299
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 190
- 229920005989 resin Polymers 0.000 claims description 115
- 239000011347 resin Substances 0.000 claims description 115
- 229910052759 nickel Inorganic materials 0.000 claims description 92
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 66
- 229910052750 molybdenum Inorganic materials 0.000 claims description 66
- 239000011733 molybdenum Substances 0.000 claims description 66
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 65
- 229910052721 tungsten Inorganic materials 0.000 claims description 65
- 239000010937 tungsten Substances 0.000 claims description 65
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 45
- 229910052796 boron Inorganic materials 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 238000007747 plating Methods 0.000 claims description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 29
- 239000011574 phosphorus Substances 0.000 claims description 29
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 241000135309 Processus Species 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 49
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- 239000011162 core material Substances 0.000 description 46
- 239000002585 base Substances 0.000 description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 239000010408 film Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 24
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- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- -1 polyethylene Polymers 0.000 description 12
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- 239000011684 sodium molybdate Substances 0.000 description 11
- 235000015393 sodium molybdate Nutrition 0.000 description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- 238000007373 indentation Methods 0.000 description 10
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- IJIMPXOIJZHGTP-UHFFFAOYSA-N boranylidynemolybdenum nickel Chemical compound [Ni].B#[Mo] IJIMPXOIJZHGTP-UHFFFAOYSA-N 0.000 description 9
- IGLTYURFTAWDMX-UHFFFAOYSA-N boranylidynetungsten nickel Chemical compound [Ni].B#[W] IGLTYURFTAWDMX-UHFFFAOYSA-N 0.000 description 9
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000011246 composite particle Substances 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002923 metal particle Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 150000002739 metals Chemical class 0.000 description 4
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical group [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- 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
-
- 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
- B22F1/16—Metallic particles coated with a non-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
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- 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
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Description
本発明は、基材粒子の表面上に導電層が配置されている導電性粒子に関し、より詳細には、例えば、電極間の電気的な接続に用いることができる導電性粒子に関する。また、本発明は、上記導電性粒子を用いた導電材料及び接続構造体に関する。 The present invention relates to conductive particles in which a conductive layer is arranged on the surface of base particles, and more particularly to conductive particles that can be used for electrical connection between electrodes, for example. The present invention also relates to a conductive material and a connection structure using the conductive particles.
異方性導電ペースト及び異方性導電フィルム等の異方性導電材料が広く知られている。該異方性導電材料では、バインダー樹脂中に導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin.
上記異方性導電材料は、ＩＣチップとフレキシブルプリント回路基板との接続、及びＩＣチップとＩＴＯ電極を有する回路基板との接続等に用いられている。例えば、ＩＣチップの電極と回路基板の電極との間に異方性導電材料を配置した後、加熱及び加圧することにより、これらの電極を電気的に接続できる。 The anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.
上記導電性粒子の一例として、下記の特許文献１には、平均粒径１〜２０μｍの球状の基材粒子の表面に、無電解めっき法によりニッケル導電層又はニッケル合金導電層が形成された導電性粒子が開示されている。この導電性粒子は、導電層の最表層に０．０５〜４μｍの微小な突起を有する。該導電層と該突起とは実質的に連続的に連なっている。
As an example of the conductive particles, the following
特許文献１に記載の導電性粒子を用いて電極間を接続した場合には、電極間の接続抵抗が高くなることがある。特許文献１の実施例では、ニッケルとリンとを含む導電層が形成されている。導電性粒子により接続される電極、及び導電性粒子の導電層の表面には、酸化被膜が形成されていることが多い。ニッケルとリンとを含む導電層を有する導電性粒子を用いて電極間を接続した場合には、ニッケルとリンとを含む導電層が比較的柔らかいので、電極及び導電性粒子の表面の酸化被膜を十分に排除できず、接続抵抗が高くなることがある。
When the electrodes are connected using the conductive particles described in
また、接続抵抗を低くするために、特許文献１に記載のようなニッケルとリンとを含む導電層の厚みを厚くすると、導電性粒子により接続対象部材又は基板が傷つくことがある。
Moreover, when the thickness of the conductive layer containing nickel and phosphorus as described in
さらに、導電性粒子により電極間が接続された接続構造体は、高温高湿下に晒されることがある。特許文献１に記載のような従来の導電性粒子では、高温高湿下で酸などの影響で導電層が変性し、電極間の接続抵抗が高くなることがある。すなわち、接続構造体が高温高湿下に晒されたときに、電極間の接続抵抗が高くなることがあり、低い接続抵抗を長期間維持できないことがある。
Furthermore, the connection structure in which the electrodes are connected by the conductive particles may be exposed to high temperature and high humidity. In the conventional conductive particles as described in
本発明の目的は、電極間を接続して接続構造体を得た場合に、電極間の接続抵抗を低くすることができ、更に高温高湿下での接続抵抗の上昇を抑制できる導電性粒子、並びに該導電性粒子を用いた導電材料及び接続構造体を提供することである。 An object of the present invention is to provide a conductive particle capable of reducing the connection resistance between electrodes when the electrodes are connected to obtain a connection structure, and further suppressing an increase in connection resistance under high temperature and high humidity. And providing a conductive material and a connection structure using the conductive particles.
本発明の広い局面によれば、基材粒子と、該基材粒子の表面上に配置された導電層とを有し、上記導電層が、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含み、上記導電層の全体１００重量％中、ニッケルの含有量が６０重量％以上であり、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量が５重量％を超える、導電性粒子が提供される。 According to a wide aspect of the present invention, the substrate has a base particle and a conductive layer disposed on the surface of the base particle, and the conductive layer is at least one of nickel, tungsten, and molybdenum. A conductive layer portion 100 having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction. Conductive particles are provided in which the total content of tungsten and molybdenum exceeds 5% by weight.
本発明に係る導電性粒子のある特定の局面では、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量が１０重量％以上である。 In a specific aspect of the conductive particle according to the present invention, the total content of tungsten and molybdenum is 10% in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. % By weight or more.
本発明に係る導電性粒子の他の特定の局面では、上記導電層の厚み方向で、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の上記金属成分が偏在しており、上記導電層の外側部分が、上記導電層の内側部分よりも上記金属成分を多く含む。 In another specific aspect of the conductive particle according to the present invention, nickel and at least one metal component of tungsten and molybdenum are unevenly distributed in the thickness direction of the conductive layer, and the outside of the conductive layer. The portion contains more metal component than the inner portion of the conductive layer.
本発明に係る導電性粒子の別の特定の局面では、上記導電層の全体１００重量％中、タングステン及びモリブデンの合計の含有量が５重量％を超える。 In another specific aspect of the conductive particles according to the present invention, the total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the entire conductive layer.
本発明に係る複数の導電性粒子１０重量部を５重量％クエン酸水溶液１００重量部に２５℃で１分間浸漬したときに、溶出するニッケルイオン濃度が、導電性粒子の単位表面積当たり１００ｐｐｍ／ｃｍ２以下であることが好ましい。 When 10 parts by weight of a plurality of conductive particles according to the present invention are immersed in 100 parts by weight of a 5% by weight citric acid aqueous solution at 25 ° C. for 1 minute, the concentration of nickel ions eluted is 100 ppm / cm per unit surface area of the conductive particles. It is preferable that it is 2 or less.
本発明に係る導電性粒子の他の特定の局面では、上記導電層は、還元剤を用いる無電解ニッケルめっきにより形成されており、上記導電層が上記還元剤に由来する成分を含まないか、又は上記還元剤に由来する成分を含みかつ上記導電層の全体１００重量％中の上記還元剤に由来する成分の含有量が５重量％以下である。 In another specific aspect of the conductive particles according to the present invention, the conductive layer is formed by electroless nickel plating using a reducing agent, and the conductive layer does not include a component derived from the reducing agent, Or content of the component derived from the said reducing agent in the 100 weight% of the whole of the said conductive layer containing the component derived from the said reducing agent is 5 weight% or less.
本発明に係る導電性粒子の他の特定の局面では、上記導電層はボロンを含む。上記導電層の全体１００重量％中、ボロンの含有量は０．０５重量％以上、４重量％以下であることが好ましい。 In another specific aspect of the conductive particle according to the present invention, the conductive layer includes boron. The boron content is preferably 0.05% by weight or more and 4% by weight or less in 100% by weight of the entire conductive layer.
本発明に係る導電性粒子の別の特定の局面では、上記導電層がリンを含まないか、又は上記導電層がリンを含みかつ上記導電層の全体１００重量％中のリンの含有量が０．５重量％未満である。 In another specific aspect of the conductive particles according to the present invention, the conductive layer does not contain phosphorus, or the conductive layer contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer is 0. Less than 5% by weight.
本発明に係る導電性粒子の他の特定の局面では、上記導電層は外表面に突起を有する。 In another specific aspect of the conductive particle according to the present invention, the conductive layer has a protrusion on the outer surface.
本発明に係る導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。 The conductive material according to the present invention includes the conductive particles described above and a binder resin.
本発明に係る接続構造体は、第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を接続している接続部とを備えており、該接続部が、上述した導電性粒子により形成されているか、又は該導電性粒子とバインダー樹脂とを含む導電材料により形成されている。 The connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection The part is formed of the above-described conductive particles, or is formed of a conductive material containing the conductive particles and a binder resin.
本発明に係る導電性粒子では、基材粒子の表面上に導電層が配置されており、上記導電層が、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含み、上記導電層の全体１００重量％中、ニッケルの含有量が６０重量％以上であり、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量が５重量％を超えるので、本発明に係る導電性粒子を用いて電極間を接続して接続構造体を得た場合に、電極間の接続抵抗を低くすることができる。さらに、接続構造体が高温高湿下に晒されても、接続抵抗が高くなり難い。 In the conductive particles according to the present invention, a conductive layer is disposed on the surface of the base particle, and the conductive layer contains nickel and at least one metal component of tungsten and molybdenum, In 100% by weight of the entire layer, the nickel content is 60% by weight or more, and in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer, tungsten and molybdenum Since total content exceeds 5 weight%, when connecting between electrodes using the electroconductive particle which concerns on this invention and obtaining a connection structure, the connection resistance between electrodes can be made low. Furthermore, even when the connection structure is exposed to high temperature and high humidity, the connection resistance is unlikely to increase.
以下、本発明の詳細を説明する。 Details of the present invention will be described below.
本発明に係る導電性粒子は、基材粒子と、該基材粒子の表面上に配置された導電層とを有する。上記導電層は、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含む。上記導電層の全体１００重量％中、ニッケルの含有量は６０重量％以上である。上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量は５重量％を超える。 The electroconductive particle which concerns on this invention has a base material particle and the electroconductive layer arrange | positioned on the surface of this base material particle. The conductive layer includes nickel and at least one metal component of tungsten and molybdenum. In 100% by weight of the entire conductive layer, the nickel content is 60% by weight or more. The total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer.
本発明に係る導電性粒子では、上記導電層が特定の上記組成を有するので、本発明に係る導電性粒子を電極間の接続に用いた場合に、電極間の接続抵抗を低くすることができる。また、特定の上記組成を有する導電層は比較的硬い。従って、電極間の接続時に、電極及び導電性粒子の表面の酸化被膜を効果的に排除できることによっても、電極間の接続抵抗が低くなる。 In the conductive particles according to the present invention, since the conductive layer has a specific composition, when the conductive particles according to the present invention are used for connection between electrodes, the connection resistance between the electrodes can be lowered. . Moreover, the conductive layer having the specific composition is relatively hard. Therefore, the connection resistance between the electrodes can be reduced by effectively eliminating the oxide film on the surfaces of the electrodes and the conductive particles when connecting the electrodes.
さらに、本発明に係る導電性粒子では、外側の表面近傍におけるタングステン及びモリブデンの合計の含有量が比較的多い。このため、例えば、導電層の耐酸性が高くなる。従って、上記接続構造体が高温高湿下に晒されても、酸等の影響が低減される。この結果、電極間の接続抵抗が上昇し難くなり、低い接続抵抗を長期間に渡り維持できる。 Furthermore, in the conductive particles according to the present invention, the total content of tungsten and molybdenum in the vicinity of the outer surface is relatively large. For this reason, for example, the acid resistance of the conductive layer is increased. Therefore, even if the connection structure is exposed to high temperature and high humidity, the influence of acid or the like is reduced. As a result, the connection resistance between the electrodes hardly increases, and a low connection resistance can be maintained over a long period of time.
これに対して、特に上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量が５重量％以下であると、上記接続構造体が高温高湿下に晒されたときに、電極間の接続抵抗が次第に高くなる。 On the other hand, when the total content of tungsten and molybdenum is 5% by weight or less in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer, When the connection structure is exposed to high temperature and high humidity, the connection resistance between the electrodes gradually increases.
高温高湿下での電極間の接続抵抗の上昇をより一層抑制する観点からは、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量は多いほどよい。従って、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量は好ましくは１０重量％以上、より好ましくは１５重量％以上、更に好ましくは２０重量％以上、特に好ましくは２５重量％以上、最も好ましくは３０重量％以上である。初期の接続抵抗をより一層低くする観点からは、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量は好ましくは６０重量％以下、より好ましくは５０重量％以下、更に好ましくは４０重量％以下である。 From the viewpoint of further suppressing the increase in the connection resistance between the electrodes under high temperature and high humidity, tungsten and 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. The higher the total content of molybdenum, the better. Accordingly, the total content of tungsten and molybdenum is preferably 10% by weight or more, more preferably 15% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm inward from the outer surface of the conductive layer. More preferably, it is 20% by weight or more, particularly preferably 25% by weight or more, and most preferably 30% by weight or more. From the viewpoint of further reducing the initial connection resistance, the total content of tungsten and molybdenum is preferably 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. 60% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.
上記導電層の厚み方向で、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の上記金属成分が偏在しており、上記導電層の外側部分が、上記導電層の内側部分よりも上記金属成分を多く含むことが好ましい。この場合には、電極間の初期の接続抵抗を効果的に低くし、更に高温高湿下での接続抵抗の上昇をより一層効果的に抑制できる。上記導電層の外側部分は、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分であることが好ましい。上記導電層の内側部分は、上記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分よりも内側部分であることが好ましい。なお、本発明に係る導電性粒子では、導電層全体で、上記金属成分の含有量は濃度勾配を有していなくてもよい。導電層全体で、上記金属成分の含有量は略均一であってもよい。従って、全ての導電層部分で、タングステン及びモリブデンの合計の含有量が５重量％を超えていてもよい。 In the thickness direction of the conductive layer, nickel and at least one metal component of tungsten and molybdenum are unevenly distributed, and the outer portion of the conductive layer has the metal component more than the inner portion of the conductive layer. It is preferable to include many. In this case, it is possible to effectively reduce the initial connection resistance between the electrodes and further effectively suppress the increase in the connection resistance under high temperature and high humidity. The outer portion of the conductive layer is preferably a conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inner side in the thickness direction. The inner portion of the conductive layer is preferably an inner portion of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. In addition, in the electroconductive particle which concerns on this invention, content of the said metal component does not need to have a concentration gradient in the whole electroconductive layer. The content of the metal component may be substantially uniform throughout the conductive layer. Therefore, the total content of tungsten and molybdenum may exceed 5% by weight in all the conductive layer portions.
本発明に係る複数の導電性粒子１０重量部を５重量％クエン酸水溶液１００重量部に２５℃で１分間浸漬したときに、溶出するニッケルイオン濃度が、導電性粒子の単位表面積当たり１００ｐｐｍ／ｃｍ２以下であることが好ましい。この場合には、電極間の接続抵抗が効果的に低くなり、電極に接する導電性粒子が耐えられる電流容量がより一層高くなる。 When 10 parts by weight of a plurality of conductive particles according to the present invention are immersed in 100 parts by weight of a 5% by weight citric acid aqueous solution at 25 ° C. for 1 minute, the concentration of nickel ions eluted is 100 ppm / cm per unit surface area of the conductive particles. It is preferable that it is 2 or less. In this case, the connection resistance between the electrodes is effectively reduced, and the current capacity that the conductive particles in contact with the electrodes can withstand is further increased.
上記導電層は、還元剤を用いる無電解ニッケルめっきにより形成されており、上記導電層が上記還元剤に由来する成分を含まないか、又は上記還元剤に由来する成分を含みかつ上記導電層の全体１００重量％中の上記還元剤に由来する成分の含有量が５重量％以下であることが好ましい。この場合には、電極間の接続抵抗を効果的に低くし、更に高温高湿下での接続抵抗の上昇を効果的に抑制できる。上記導電層の全体１００重量％中の上記還元剤に由来する成分の含有量は、より好ましくは４重量％以下、より一層好ましくは３重量％以下、更に一層好ましくは１重量％以下、特に好ましくは０．３重量％以下、最も好ましくは０．１重量％以下である。 The conductive layer is formed by electroless nickel plating using a reducing agent, and the conductive layer does not include a component derived from the reducing agent or includes a component derived from the reducing agent and The content of the component derived from the reducing agent in 100% by weight as a whole is preferably 5% by weight or less. In this case, it is possible to effectively reduce the connection resistance between the electrodes and further effectively suppress the increase in the connection resistance under high temperature and high humidity. The content of the component derived from the reducing agent in 100% by weight of the entire conductive layer is more preferably 4% by weight or less, still more preferably 3% by weight or less, still more preferably 1% by weight or less, particularly preferably. Is 0.3% by weight or less, most preferably 0.1% by weight or less.
上記還元剤に由来する成分としては、リンやホウ素が挙げられる。上記還元剤は、リン含有還元剤又はホウ素含有還元剤であることが好ましく、ホウ素含有還元剤であることがより好ましい。上記還元剤に由来する成分は、リン又はホウ素であることが好ましく、ホウ素であることがより好ましい。 Examples of the component derived from the reducing agent include phosphorus and boron. The reducing agent is preferably a phosphorus-containing reducing agent or a boron-containing reducing agent, and more preferably a boron-containing reducing agent. The component derived from the reducing agent is preferably phosphorus or boron, and more preferably boron.
以下、図面を参照しつつ、本発明の具体的な実施形態及び実施例を説明することにより、本発明を明らかにする。 Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.
図１は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。 FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
図１に示すように、導電性粒子１は、基材粒子２と、導電層３と、複数の芯物質４と、複数の絶縁物質５とを有する。
As shown in FIG. 1, the
導電層３は、基材粒子２の表面上に配置されている。導電性粒子１は、基材粒子２の表面が導電層３により被覆された被覆粒子である。
The
導電性粒子１は表面に、複数の突起１ａを有する。導電層３は外表面に、複数の突起３ａを有する。複数の芯物質４が、基材粒子２の表面上に配置されている。複数の芯物質４は導電層３内に埋め込まれている。芯物質４は、突起１ａ，３ａの内側に配置されている。導電層３は、複数の芯物質４を被覆している。複数の芯物質４により導電層３の外表面が***されており、突起１ａ，３ａが形成されている。
The
導電性粒子１は、導電層３の外表面上に配置された絶縁物質５を有する。導電層３の外表面の少なくとも一部の領域が、絶縁物質５により被覆されている。絶縁物質５は絶縁性を有する材料により形成されており、絶縁性粒子である。このように、本発明に係る導電性粒子は、導電層の外表面上に配置された絶縁物質を有していてもよい。但し、本発明に係る導電性粒子は、絶縁物質を必ずしも有していなくてもよい。
The
図２は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。 FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
図２に示す導電性粒子１１は、基材粒子２と、第２の導電層１２（他の導電層）と、導電層１３（第１の導電層）と、複数の芯物質４と、複数の絶縁物質５とを有する。
The
導電性粒子１と導電性粒子１１とでは、導電層のみが異なっている。すなわち、導電性粒子１では、１層構造の導電層が形成されているのに対し、導電性粒子１１では、２層構造の第２の導電層１２及び導電層１３が形成されている。
Only the conductive layer is different between the
導電層１３は、基材粒子２の表面上に配置されている。基材粒子２と導電層１３との間に、第２の導電層１２（他の導電層）が配置されている。従って、基材粒子２の表面上に第２の導電層１２が配置されており、第２の導電層１２の表面上に導電層１３が配置されている。導電層１３は外表面に、複数の突起１３ａを有する。導電性粒子１１は表面に、複数の突起１１ａを有する。
The
図３は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。 FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
図３に示す導電性粒子２１は、基材粒子２と、導電層２２とを有する。導電層２２は、基材粒子２の表面上に配置されている。
The
導電性粒子２１は、芯物質を有さない。導電性粒子２１は表面に突起を有さない。導電性粒子２１は球状である。導電層２２は表面に突起を有さない。このように、本発明に係る導電性粒子は突起を有していなくてもよく、球状であってもよい。また、導電性粒子２１は、絶縁物質を有さない。但し、導電性粒子２１は、導電層２２の表面上に配置された絶縁物質を有していてもよい。
The
［基材粒子］
上記基材粒子としては、樹脂粒子、金属を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。上記基材粒子は、金属粒子を除く基材粒子であることが好ましく、樹脂粒子、金属を除く無機粒子又は有機無機ハイブリッド粒子であることがより好ましい。
[Base material particles]
Examples of the substrate particles include resin particles, inorganic particles excluding metals, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal, or organic-inorganic hybrid particles.
上記基材粒子は、樹脂により形成された樹脂粒子であることが好ましい。上記導電性粒子を用いて電極間を接続する際には、上記導電性粒子を電極間に配置した後、圧着することにより上記導電性粒子を圧縮させる。基材粒子が樹脂粒子であると、上記圧着の際に上記導電性粒子が変形しやすく、導電性粒子と電極との接触面積が大きくなる。このため、電極間の導通信頼性が高くなる。 The substrate particles are preferably resin particles formed of a resin. When connecting between electrodes using the said electroconductive particle, after arrange | positioning the said electroconductive particle between electrodes, the said electroconductive particle is compressed by crimping | bonding. When the substrate particles are resin particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction | electrical_connection reliability between electrodes becomes high.
上記樹脂粒子を形成するための樹脂として、種々の有機物が好適に用いられる。上記樹脂粒子を形成するための樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリプロピレン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂；ポリメチルメタクリレート及びポリメチルアクリレート等のアクリル樹脂；ポリアルキレンテレフタレート、ポリカーボネート、ポリアミド、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ポリスルホン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、及び、エチレン性不飽和基を有する種々の重合性単量体を１種もしくは２種以上重合させて得られる重合体等が挙げられる。導電材料に適した任意の圧縮時の物性を有する樹脂粒子を設計及び合成することができ、かつ基材粒子の硬度を好適な範囲に容易に制御できるので、上記樹脂粒子を形成するための樹脂は、エチレン性不飽和基を複数有する重合性単量体を１種又は２種以上重合させた重合体であることが好ましい。 Various organic materials are suitably used as the resin for forming the resin particles. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate. Polyalkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone , Polyphenylene oxide, polyacetal, polyimide, polyamideimide, poly Ether ketone, polyether sulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. Resin for forming the resin particles can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range, which is suitable for conductive materials and having physical properties at the time of compression. Is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.
上記樹脂粒子を、エチレン性不飽和基を有する単量体を重合させて得る場合、上記エチレン性不飽和基を有する単量体としては、非架橋性の単量体と架橋性の単量体とが挙げられる。 When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And so on.
上記非架橋性の単量体としては、例えば、スチレン、α−メチルスチレン等のスチレン系単量体；（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート類；２−ヒドロキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート類；（メタ）アクリロニトリル等のニトリル含有単量体；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル等のビニルエーテル類；酢酸ビニル、酪酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の酸ビニルエステル類；エチレン、プロピレン、イソプレン、ブタジエン等の不飽和炭化水素；トリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート、塩化ビニル、フッ化ビニル、クロルスチレン等のハロゲン含有単量体等が挙げられる。 Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.
上記架橋性の単量体としては、例えば、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、（ポリ）テトラメチレンジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート等の多官能（メタ）アクリレート類；トリアリル（イソ）シアヌレート、トリアリルトリメリテート、ジビニルベンゼン、ジアリルフタレート、ジアリルアクリルアミド、ジアリルエーテル、γ−（メタ）アクリロキシプロピルトリメトキシシラン、トリメトキシシリルスチレン、ビニルトリメトキシシラン等のシラン含有単量体等が挙げられる。 Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanurate, tria Rutorimeriteto, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, .gamma. (meth) acryloxy propyl trimethoxy silane, trimethoxy silyl styrene, include silane-containing monomers such as vinyltrimethoxysilane.
上記エチレン性不飽和基を有する重合性単量体を、公知の方法により重合させることで、上記樹脂粒子を得ることができる。この方法としては、例えば、ラジカル重合開始剤の存在下で懸濁重合する方法、並びに非架橋の種粒子を用いてラジカル重合開始剤とともに単量体を膨潤させて重合する方法等が挙げられる。 The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
上記基材粒子が金属粒子を除く無機粒子又は有機無機ハイブリッド粒子である場合に、上記基材粒子を形成するための無機物としては、シリカ及びカーボンブラック等が挙げられる。上記シリカにより形成された粒子としては特に限定されないが、例えば、加水分解性のアルコキシシル基を２つ以上持つケイ素化合物を加水分解して架橋重合体粒子を形成した後に、必要に応じて焼成を行うことにより得られる粒子が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。 In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles, examples of the inorganic material for forming the substrate particles include silica and carbon black. Although it does not specifically limit as the particle | grains formed with the said silica, For example, after hydrolyzing the silicon compound which has two or more hydrolysable alkoxysil groups, and forming a crosslinked polymer particle, it calcinates as needed. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
上記基材粒子が金属粒子である場合に、該金属粒子を形成するための金属としては、銀、銅、ニッケル、ケイ素、金及びチタン等が挙げられる。但し、上記基材粒子は金属粒子ではないことが好ましい。 When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, the substrate particles are preferably not metal particles.
上記基材粒子の粒子径は、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上、より一層好ましくは１μｍ以上、更に好ましくは１．５μｍ以上、特に好ましくは２μｍ以上、好ましくは１０００μｍ以下、より好ましくは５００μｍ以下、より一層好ましくは３００μｍ以下、更に好ましくは５０μｍ以下、更に一層好ましくは３０μｍ以下、特に好ましくは５μｍ以下、最も好ましくは３μｍ以下である。基材粒子の粒子径が上記下限以上であると、導電性粒子と電極との接触面積が大きくなるため、電極間の導通信頼性がより一層高くなり、導電性粒子を介して接続された電極間の接続抵抗がより一層低くなる。さらに、基材粒子の表面に導電層を無電解めっきにより形成する際に凝集し難くなり、凝集した導電性粒子が形成されにくくなる。粒子径が上記上限以下であると、導電性粒子が充分に圧縮されやすく、電極間の接続抵抗がより一層低くなり、更に電極間の間隔が小さくなる。上記基材粒子の粒子径は、基材粒子が真球状である場合には、直径を示し、基材粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the substrate particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm or less, More preferably, it is 500 μm or less, still more preferably 300 μm or less, still more preferably 50 μm or less, still more preferably 30 μm or less, particularly preferably 5 μm or less, and most preferably 3 μm or less. When the particle diameter of the substrate particles is equal to or greater than the above lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased, and the electrodes are connected via the conductive particles. The connection resistance between them becomes even lower. Further, when forming the conductive layer on the surface of the base particle by electroless plating, it becomes difficult to aggregate and the aggregated conductive particles are hardly formed. When the particle diameter is not more than the above upper limit, the conductive particles are easily compressed, the connection resistance between the electrodes is further reduced, and the distance between the electrodes is further reduced. The particle diameter of the base particle indicates a diameter when the base particle is a true sphere, and indicates a maximum diameter when the base particle is not a true sphere.
上記基材粒子の粒子径は、０．１μｍ以上、５μｍ以下であることが特に好ましい。上記基材粒子の粒子径が０．１〜５μｍの範囲内であると、電極間の間隔が小さくなり、かつ導電層の厚みを厚くしても、小さい導電性粒子が得られる。電極間の間隔をより一層小さくしたり、導電層の厚みを厚くしても、より一層小さい導電性粒子を得たりする観点からは、上記基材粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは２μｍ以上、好ましくは３μｍ以下である。 The particle diameter of the substrate particles is particularly preferably 0.1 μm or more and 5 μm or less. When the particle diameter of the substrate particles is in the range of 0.1 to 5 μm, even when the distance between the electrodes is small and the thickness of the conductive layer is increased, small conductive particles can be obtained. From the viewpoint of obtaining even smaller conductive particles even when the distance between the electrodes is further reduced or the conductive layer is thickened, the particle diameter of the base particles is preferably 0.5 μm or more. More preferably, it is 2 μm or more, preferably 3 μm or less.
［導電層］
本発明に係る導電性粒子は、基材粒子の表面上に配置されている導電層を有する。上記導電層は、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含む。以下、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含む導電層を、導電層Ｘと記載することがある。上記導電層Ｘの全体１００重量％中、ニッケルの含有量は６０重量％以上である。上記導電層Ｘの外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量は５重量％を超える。
[Conductive layer]
The electroconductive particle which concerns on this invention has the electroconductive layer arrange | positioned on the surface of base material particle. The conductive layer includes nickel and at least one metal component of tungsten and molybdenum. Hereinafter, a conductive layer containing nickel and at least one metal component of tungsten and molybdenum may be referred to as a conductive layer X. In 100 weight% of the whole conductive layer X, the nickel content is 60 weight% or more. The total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer X toward the inside in the thickness direction.
導電層Ｘは、基材粒子の表面に直接積層されていてもよく、他の導電層などを介して基材粒子の表面上に配置されていてもよい。さらに、上記導電層Ｘの表面上に他の導電層が配置されていてもよい。導電性粒子の外表面が導電層Ｘであることが好ましい。導電層Ｘを外表面に有する導電性粒子により電極間を接続することにより、接続抵抗が十分に低くなる。 The conductive layer X may be directly laminated on the surface of the base particle, or may be disposed on the surface of the base particle via another conductive layer or the like. Furthermore, another conductive layer may be disposed on the surface of the conductive layer X. The outer surface of the conductive particles is preferably the conductive layer X. By connecting the electrodes with conductive particles having the conductive layer X on the outer surface, the connection resistance is sufficiently low.
電極間の初期の接続抵抗を効果的に低くする観点からは、上記導電層Ｘの全体１００重量％中の上記ニッケルの含有量は多いほどよい。従って、上記導電層Ｘの全体１００重量％中、上記ニッケルの含有量は好ましくは６５重量％以上、より好ましくは７０重量％以上、より一層好ましくは７５重量％以上、更に好ましくは８０重量％以上、更に一層好ましくは８５重量％以上、特に好ましくは９０重量％以上、最も好ましくは９５重量％以上である。上記導電層Ｘの全体１００重量％中のニッケルの含有量は９７重量％以上であってもよく、９７．５重量％以上であってもよく、９８重量％以上であってもよい。 From the viewpoint of effectively reducing the initial connection resistance between the electrodes, it is better that the content of nickel in the entire 100 wt% of the conductive layer X is larger. Therefore, the content of nickel is preferably 65% by weight or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, and further preferably 80% by weight or more in the total 100% by weight of the conductive layer X. Even more preferably, it is 85% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. The content of nickel in 100% by weight of the entire conductive layer X may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
ニッケルの含有量の上限は、タングステン、モリブデン及びボロンなどの含有量により適宜変更できる。上記導電層Ｘの全体１００重量％中のニッケルの含有量は好ましくは９９．８５重量％以下、より好ましくは９９．７重量％以下、更に好ましくは９９．４５重量％未満である。上記ニッケルの含有量が上記下限以上であると、電極間の接続抵抗がより一層低くなる。また、電極や導電層の表面における酸化被膜が少ない場合には、上記ニッケルの含有量が多いほど電極間の接続抵抗が低くなる傾向がある。 The upper limit of the nickel content can be appropriately changed depending on the contents of tungsten, molybdenum, boron, and the like. The content of nickel in 100% by weight of the entire conductive layer X is preferably 99.85% by weight or less, more preferably 99.7% by weight or less, and still more preferably less than 99.45% by weight. When the nickel content is not less than the lower limit, the connection resistance between the electrodes is further reduced. Moreover, when there are few oxide films in the surface of an electrode or a conductive layer, there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.
上記導電層Ｘは、ニッケルに加えて、タングステン及びモリブデンの内の少なくとも１種の金属成分を含む。すなわち、上記導電層Ｘは、ニッケルとタングステン及びモリブデンの内の少なくとも１種の金属成分とを含むニッケル−タングステン／モリブデン導電層である。導電層Ｘでは、ニッケルとタングステン及びモリブデンの内の少なくとも１種の金属成分とが合金化していてもよい。また、導電層Ｘでは、タングステン及びモリブデン以外に、クロム、シーボーギウムを用いてもよい。 The conductive layer X includes at least one metal component of tungsten and molybdenum in addition to nickel. That is, the conductive layer X is a nickel-tungsten / molybdenum conductive layer containing nickel and at least one metal component of tungsten and molybdenum. In the conductive layer X, nickel and at least one metal component of tungsten and molybdenum may be alloyed. In the conductive layer X, chromium or seaborgium may be used in addition to tungsten and molybdenum.
また、タングステン及びモリブデンの双方を含まない導電層を有する導電性粒子では、該タングステン及びモリブデンの双方を含まないニッケル導電層が圧縮初期段階で硬さが比較的低くなりやすい。このため、電極間の接続時に、電極及び導電性粒子の表面の酸化被膜を排除する効果が小さくなり、接続抵抗が低くなる傾向がある。 In the case of conductive particles having a conductive layer that does not contain both tungsten and molybdenum, the nickel conductive layer that does not contain both tungsten and molybdenum tends to have a relatively low hardness in the initial compression stage. For this reason, at the time of connection between electrodes, the effect which excludes the oxide film on the surface of an electrode and electroconductive particle becomes small, and there exists a tendency for connection resistance to become low.
一方で、接続抵抗を低くする効果をより一層得るために、又は大きな電流が流れる用途に適するように、タングステン及びモリブデンの双方を含まないニッケル導電層の厚みを厚くすると、導電性粒子により接続対象部材又は基板が傷つきやすくなる傾向がある。この結果、接続構造体における電極間の導通信頼性が低くなる傾向がある。 On the other hand, if the thickness of the nickel conductive layer that does not contain both tungsten and molybdenum is increased in order to obtain the effect of lowering the connection resistance further, or to be suitable for applications in which a large current flows, conductive objects may cause connection. The member or the substrate tends to be easily damaged. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
これに対して、導電性粒子が導電層Ｘを有することにより、電極間の接続抵抗が効果的に低くなる。また、上記導電層Ｘに適度に割れが生じるようにすることが容易である。適度に圧縮されたときに割れが発生することによって電極の損傷がより一層生じ難くなり、従って電極間の接続抵抗がより一層低くなる。 On the other hand, when the conductive particles have the conductive layer X, the connection resistance between the electrodes is effectively reduced. Moreover, it is easy to cause a moderate crack in the conductive layer X. When cracks occur when compressed appropriately, damage to the electrodes is less likely to occur, and therefore the connection resistance between the electrodes is further reduced.
さらに、導電層Ｘは適度な硬さを有するので、導電性粒子を圧縮して電極間を接続したとき、電極に適度な圧痕を形成できる。なお、電極に形成される圧痕は、導電性粒子が電極を押してできた電極の凹部である。 Furthermore, since the conductive layer X has an appropriate hardness, an appropriate indentation can be formed on the electrodes when the conductive particles are compressed to connect the electrodes. The indentation formed on the electrode is a concave portion of the electrode formed by pressing the electrode with conductive particles.
上記導電層Ｘの全体１００重量％中のタングステン及びモリブデンの合計の含有量（金属成分の含有量）は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、より一層好ましくは０．２重量％以上、更に好ましくは０．５重量％以上、更に一層好ましくは１重量％以上、特に好ましくは５重量％を超え、最も好ましくは１０重量％以上である。タングステン及びモリブデンの合計の含有量が上記下限以上であると、導電層の外表面の硬さがより一層高くなる。このため、電極や導電層の表面に酸化被膜が形成されている場合に、電極及び導電性粒子の表面の酸化被膜を効果的に排除でき、接続抵抗を低くすることができ、かつ得られる接続構造体の耐衝撃性を高めることができる。さらに、タングステン及びモリブデンの合計の含有量が上記下限以上であると、導電層の外表面の磁性が弱くなり、複数の導電性粒子が凝集し難くなる。このため、電極間の短絡を効果的に抑制できる。 The total content of tungsten and molybdenum (content of metal component) in 100% by weight of the entire conductive layer X is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably. Is 0.2% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably more than 5% by weight, most preferably 10% by weight or more. When the total content of tungsten and molybdenum is not less than the above lower limit, the hardness of the outer surface of the conductive layer is further increased. For this reason, when the oxide film is formed on the surface of the electrode or the conductive layer, the oxide film on the surface of the electrode and the conductive particles can be effectively eliminated, the connection resistance can be lowered, and the obtained connection The impact resistance of the structure can be increased. Furthermore, when the total content of tungsten and molybdenum is equal to or greater than the above lower limit, the magnetism of the outer surface of the conductive layer becomes weak, and a plurality of conductive particles are difficult to aggregate. For this reason, the short circuit between electrodes can be suppressed effectively.
上記導電層Ｘの全体１００重量％中のタングステン及びモリブデンの合計の含有量の上限は、ニッケル及びボロンなどの含有量により適宜変更できる。上記導電層Ｘの全体１００重量％中のタングステン及びモリブデンの合計の含有量は、好ましくは４０重量％以下、より好ましくは３０重量％以下、更に好ましくは２５重量％以下、特に好ましくは２０重量％以下である。 The upper limit of the total content of tungsten and molybdenum in 100% by weight of the entire conductive layer X can be appropriately changed depending on the contents of nickel, boron, and the like. The total content of tungsten and molybdenum in 100% by weight of the entire conductive layer X is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight. It is as follows.
上記導電層Ｘは、ニッケルに加えて、ボロンを含むことが好ましい。上記導電層Ｘは、ニッケルと、タングステン及びモリブデンの内の少なくとも１種と、ボロンとを含むことが好ましい。すなわち、上記導電層Ｘは、ニッケルとタングステン及びモリブデンの内の少なくとも１種とボロンとを含むニッケル−タングステン／モリブデン−ボロン導電層であることが好ましい。上記導電層Ｘでは、ニッケルとボロンとが合金化していてもよく、タングステン及びモリブデンの内の少なくとも１種とボロンとが合金化していてもよい。また、上記導電層Ｘでは、タングステン、モリブデン及びボロン以外に、クロム、シーボーギウムを用いてもよい。 The conductive layer X preferably contains boron in addition to nickel. The conductive layer X preferably contains nickel, at least one of tungsten and molybdenum, and boron. That is, the conductive layer X is preferably a nickel-tungsten / molybdenum-boron conductive layer containing at least one of nickel, tungsten, and molybdenum and boron. In the conductive layer X, nickel and boron may be alloyed, or at least one of tungsten and molybdenum and boron may be alloyed. In the conductive layer X, chromium or seaborgium may be used in addition to tungsten, molybdenum, and boron.
また、ボロンを含まないニッケル導電層を有する導電性粒子では、該ボロンを含まないニッケル導電層が圧縮初期段階で比較的柔らかく、電極間の接続時に、電極及び導電性粒子の表面の酸化被膜を排除する効果が小さくなり、接続抵抗を低くする効果が小さくなる傾向がある。また、導電層は、ボロンではなくリンを含むことがある。ニッケルとリンとを含む導電層を有する導電性粒子では、電極及び導電性粒子の表面の酸化被膜を排除する効果が小さくなり、接続抵抗を低くする効果が小さくなりやすい傾向がある。 Moreover, in the conductive particles having a nickel conductive layer that does not contain boron, the nickel conductive layer that does not contain boron is relatively soft at the initial stage of compression, and an oxide film on the surface of the electrode and the conductive particles is formed when the electrodes are connected. The effect of eliminating tends to be small, and the effect of reducing the connection resistance tends to be small. In addition, the conductive layer may contain phosphorus instead of boron. In the conductive particles having a conductive layer containing nickel and phosphorus, the effect of eliminating the oxide film on the surface of the electrode and the conductive particles tends to be small, and the effect of reducing the connection resistance tends to be small.
一方で、接続抵抗を低くする効果をより一層得るために、又は大きな電流が流れる用途に適するように、ボロンを含まない導電層の厚みを厚くしたり、ニッケルとリンとを含む導電層の厚みを厚くしたりすると、導電性粒子により接続対象部材又は基板が傷つきやすくなる傾向がある。この結果、接続構造体における電極間の導通信頼性が低くなる傾向がある。 On the other hand, the thickness of the conductive layer not containing boron or the thickness of the conductive layer containing nickel and phosphorus is increased in order to obtain the effect of lowering the connection resistance or to be suitable for applications in which a large current flows. If the thickness is increased, the connection target member or the substrate tends to be easily damaged by the conductive particles. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
これに対して、上記導電層Ｘがボロンを含む場合には、導電層が適度な硬さを有するので、電極の損傷がより一層生じ難くなり、従って電極間の接続抵抗がより一層低くなる。 On the other hand, when the conductive layer X contains boron, the conductive layer has an appropriate hardness, so that the electrodes are more unlikely to be damaged, and therefore the connection resistance between the electrodes is further reduced.
さらに、上記導電層Ｘがニッケル−タングステン／モリブデン−ボロン導電層である場合には、該ニッケル−タングステン／モリブデン−ボロン導電層は適度な硬さを有するので、導電性粒子を圧縮して電極間を接続したとき、電極に適度な圧痕を形成できる。なお、電極に形成される圧痕は、導電性粒子が電極を押してできた電極の凹部である。 Further, in the case where the conductive layer X is a nickel-tungsten / molybdenum-boron conductive layer, the nickel-tungsten / molybdenum-boron conductive layer has an appropriate hardness. When is connected, an appropriate indentation can be formed on the electrode. The indentation formed on the electrode is a concave portion of the electrode formed by pressing the electrode with conductive particles.
上記導電層Ｘの全体１００重量％中のボロンの含有量は好ましくは０．０１重量％以上、より好ましくは０．０５重量％以上、更に好ましくは０．１重量％以上、好ましくは５重量％以下、より好ましくは４重量％以下、更に好ましくは３重量％以下、特に好ましくは２．５重量％以下、最も好ましくは２重量％以下である。ボロンの含有量が上記下限以上であると、導電層Ｘがより一層硬くなり、電極及び導電性粒子の表面の酸化被膜をより一層効果的に除去でき、電極間の接続抵抗がより一層低くなる。ボロンの含有量が上記上限以下であると、ニッケル、タングステン及びモリブデンなどの含有量が相対的に多くなるので、電極間の接続抵抗がより一層低くなる。 The content of boron in 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably 5% by weight. Below, more preferably 4% by weight or less, still more preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less. When the boron content is not less than the above lower limit, the conductive layer X becomes harder, the oxide film on the surface of the electrode and the conductive particles can be more effectively removed, and the connection resistance between the electrodes is further reduced. . If the boron content is less than or equal to the above upper limit, the contents of nickel, tungsten, molybdenum, and the like are relatively increased, so that the connection resistance between the electrodes is further reduced.
さらに、上記導電層Ｘがボロンを含むことによって、上記導電層がかなり硬くなる結果、導電性粒子により電極間を接続した接続構造体に衝撃が与えられても、導通不良が生じ難くなる。すなわち、接続構造体の耐衝撃性を高めることもできる。 Furthermore, when the conductive layer X contains boron, the conductive layer is considerably hardened. As a result, even when an impact is applied to the connection structure connecting the electrodes by the conductive particles, it is difficult to cause poor conduction. That is, the impact resistance of the connection structure can be increased.
また、ニッケルとボロンとを含む上記導電層の表面の磁性は高く、電極間を電気的に接続した場合に、磁性により凝集した導電性粒子の影響で、横方向に隣接する電極間が接続されやすい傾向がある。上記導電層Ｘがニッケルとタングステン及びモリブデンの内の少なくとも１種とボロンとを含むことにより、上記導電層Ｘの表面の磁性がかなり低くなる。このため、複数の導電性粒子が凝集するのを抑制できる。従って、電極間を電気的に接続した場合に、凝集した導電性粒子により横方向に隣接する電極間が接続されるのを抑制できる。すなわち、隣り合う電極間の短絡をより一層防止できる。 In addition, the surface of the conductive layer containing nickel and boron has high magnetism, and when the electrodes are electrically connected, the electrodes adjacent to each other in the lateral direction are connected due to the influence of the conductive particles aggregated by magnetism. It tends to be easy. When the conductive layer X contains nickel, at least one of tungsten and molybdenum, and boron, the magnetic property of the surface of the conductive layer X is considerably reduced. For this reason, it can suppress that several electroconductive particle aggregates. Therefore, when the electrodes are electrically connected, it is possible to prevent the electrodes adjacent in the lateral direction from being connected by the aggregated conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.
上記導電層Ｘはリンを含まないか、又は上記導電層Ｘはリンを含みかつ上記導電層Ｘの全体１００重量％中のリンの含有量が０．５重量％未満であることが好ましい。上記導電層Ｘの全体１００重量％中のリンの含有量はより好ましくは０．３重量％以下、更に好ましくは０．１重量％以下である。上記導電層Ｘはリンを含まないことが特に好ましい。 It is preferable that the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer X is less than 0.5% by weight. The content of phosphorus in the total 100% by weight of the conductive layer X is more preferably 0.3% by weight or less, and still more preferably 0.1% by weight or less. It is particularly preferable that the conductive layer X does not contain phosphorus.
上記導電層Ｘにおけるニッケル、タングステン、モリブデン、ボロン及びリンの各含有量の測定方法は、既知の種々の分析法を用いることができ特に限定されない。この測定方法として、吸光分析法又はスペクトル分析法等が挙げられる。上記吸光分析法では、フレーム吸光光度計及び電気加熱炉吸光光度計等を用いることができる。上記スペクトル分析法としては、プラズマ発光分析法及びプラズマイオン源質量分析法等が挙げられる。 The method for measuring the contents of nickel, tungsten, molybdenum, boron and phosphorus in the conductive layer X is not particularly limited, and various known analysis methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer, or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.
上記導電層Ｘにおけるニッケル、タングステン、モリブデン、ボロン及びリンの各含有量を測定する際には、ＩＣＰ発光分析装置を用いることが好ましい。ＩＣＰ発光分析装置の市販品としては、ＨＯＲＩＢＡ社製のＩＣＰ発光分析装置等が挙げられる。 When measuring the contents of nickel, tungsten, molybdenum, boron, and phosphorus in the conductive layer X, it is preferable to use an ICP emission spectrometer. Examples of commercially available ICP emission analyzers include ICP emission analyzers manufactured by HORIBA.
上記導電層Ｘの厚み方向におけるニッケル、タングステン、モリブデン、ボロン及びリンの各含有量を測定する際には、ＦＥ−ＴＥＭ装置を用いることが好ましい。ＦＥ−ＴＥＭ装置の市販品としては、日本電子社製のＪＥＭ−２０１０等が挙げられる。 When measuring each content of nickel, tungsten, molybdenum, boron, and phosphorus in the thickness direction of the conductive layer X, it is preferable to use an FE-TEM apparatus. Examples of commercially available FE-TEM devices include JEM-2010 manufactured by JEOL Ltd.
上記他の導電層（第２の導電層）を形成するための金属は特に限定されない。該金属としては、例えば、金、銀、銅、パラジウム、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、タリウム、ゲルマニウム、カドミウム、ケイ素、タングステン、モリブデン及びこれらの合金等が挙げられる。また、上記金属としては、錫ドープ酸化インジウム（ＩＴＯ）及びはんだ等が挙げられる。なかでも、電極間の接続抵抗がより一層低くなるので、錫を含む合金、ニッケル、パラジウム、銅又は金が好ましく、ニッケル又はパラジウムがより好ましい。上記導電層を構成する金属はニッケルを含むことが好ましい。 The metal for forming the other conductive layer (second conductive layer) is not particularly limited. Examples of the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable. The metal constituting the conductive layer preferably contains nickel.
上記基材粒子の表面上に導電層（他の導電層及び導電層Ｘ）を形成する方法は特に限定されない。導電層を形成する方法としては、例えば、無電解めっきによる方法、電気めっきによる方法、物理的蒸着による方法、並びに金属粉末もしくは金属粉末とバインダーとを含むペーストを基材粒子又は他の導電層の表面にコーティングする方法等が挙げられる。なかでも、導電層の形成が簡便であるので、無電解めっきによる方法が好ましい。上記物理的蒸着による方法としては、真空蒸着、イオンプレーティング及びイオンスパッタリング等の方法が挙げられる。 The method for forming a conductive layer (another conductive layer and conductive layer X) on the surface of the substrate particle is not particularly limited. As a method for forming the conductive layer, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a paste containing metal powder or metal powder and a binder is used for base particles or other conductive layers. For example, a method of coating the surface. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
上記導電性粒子の粒子径は、好ましくは０．１１μｍ以上、より好ましくは０．５μｍ以上、更に好ましくは０．５１μｍ以上、特に好ましくは１μｍ以上、好ましくは１００μｍ以下、より好ましくは２０μｍ以下、更に好ましくは５．６μｍ以下、特に好ましくは３．６μｍ以下である。導電性粒子の粒子径が上記下限以上及び上記上限以下であると、導電性粒子を用いて電極間を接続した場合に、導電性粒子と電極との接触面積が充分に大きくなり、かつ導電層を形成する際に凝集した導電性粒子が形成されにくくなる。また、導電性粒子を介して接続された電極間の間隔が大きくなりすぎず、かつ導電層が基材粒子の表面から剥離し難くなる。 The particle diameter of the conductive particles is preferably 0.11 μm or more, more preferably 0.5 μm or more, further preferably 0.51 μm or more, particularly preferably 1 μm or more, preferably 100 μm or less, more preferably 20 μm or less, and further Preferably it is 5.6 micrometers or less, Most preferably, it is 3.6 micrometers or less. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
上記導電性粒子の粒子径は、導電性粒子が真球状である場合には、直径を示し、導電性粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
上記導電層Ｘの厚みは好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上、更に好ましくは０．０５μｍ以上、好ましくは１μｍ以下、より好ましくは０．３μｍ以下である。上記導電層Ｘの厚みが上記下限以上及び上記上限以下であると、充分な導電性が得られ、かつ導電性粒子が硬くなりすぎずに、電極間の接続の際に導電性粒子が充分に変形する。 The thickness of the conductive layer X is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, preferably 1 μm or less, more preferably 0.3 μm or less. When the thickness of the conductive layer X is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Deform.
導電層が２層以上の積層構造である場合に、導電層Ｘの厚みは、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上、更に好ましくは０．０５μｍ以上、好ましくは０．５μｍ以下、より好ましくは０．３μｍ以下、更に好ましくは０．１μｍ以下である。上記導電層Ｘの厚みが上記下限以上及び上記上限以下であると、導電層Ｘによる被覆を均一にでき、かつ電極間の接続抵抗が充分に低くなる。 When the conductive layer has a laminated structure of two or more layers, the thickness of the conductive layer X is preferably 0.001 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, preferably 0.5 μm or less. More preferably, it is 0.3 μm or less, and further preferably 0.1 μm or less. When the thickness of the conductive layer X is not less than the above lower limit and not more than the above upper limit, the coating with the conductive layer X can be made uniform, and the connection resistance between the electrodes becomes sufficiently low.
導電層が２層以上の積層構造である場合に、導電層全体の厚みは、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上、更に好ましくは０．０５μｍ以上、特に好ましくは０．１μｍ以上、好ましくは１μｍ以下、より好ましくは０．５μｍ以下、より一層好ましくは０．３μｍ以下、更に好ましくは０．１μｍ以下である。上記導電層全体の厚みが上記下限以上及び上記上限以下であると、導電層全体による被覆を均一にでき、かつ電極間の接続抵抗が充分に低くなる。 When the conductive layer has a laminated structure of two or more layers, the total thickness of the conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and particularly preferably 0.1 μm. The thickness is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less, and still more preferably 0.1 μm or less. When the thickness of the entire conductive layer is not less than the above lower limit and not more than the above upper limit, the covering of the entire conductive layer can be made uniform, and the connection resistance between the electrodes becomes sufficiently low.
上記導電層Ｘの厚みは、０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。さらに、基材粒子の粒子径が０．１μｍ以上（より好ましくは０．５μｍ以上、更に好ましくは２μｍ以上）、５μｍ以下（より好ましくは３μｍ以下）であり、かつ、上記導電層Ｘの厚みが０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。上記導電層全体の厚みは、０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。さらに、基材粒子の粒子径が０．１μｍ以上（より好ましくは０．５μｍ以上、更に好ましくは２μｍ以上）、５μｍ以下（より好ましくは３μｍ以下）であり、かつ、上記導電層全体の厚みが０．０５μｍ以上、０．３μｍ以下であることが特に好ましい。これらの場合には、導電性粒子を大きな電流が流れる用途により好適に用いることができる。さらに、導電性粒子を圧縮して電極間を接続した場合に、電極が損傷するのをより一層抑制できる。 The thickness of the conductive layer X is particularly preferably 0.05 μm or more and 0.3 μm or less. Furthermore, the particle diameter of the base particles is 0.1 μm or more (more preferably 0.5 μm or more, more preferably 2 μm or more), 5 μm or less (more preferably 3 μm or less), and the thickness of the conductive layer X is It is particularly preferably 0.05 μm or more and 0.3 μm or less. The total thickness of the conductive layer is particularly preferably 0.05 μm or more and 0.3 μm or less. Furthermore, the particle diameter of the substrate particles is 0.1 μm or more (more preferably 0.5 μm or more, more preferably 2 μm or more), 5 μm or less (more preferably 3 μm or less), and the thickness of the entire conductive layer is It is particularly preferably 0.05 μm or more and 0.3 μm or less. In these cases, the conductive particles can be suitably used for applications in which a large current flows. Furthermore, when the conductive particles are compressed to connect the electrodes, it is possible to further suppress the electrodes from being damaged.
上記導電層Ｘの厚み及び上記導電層全体の厚みは、例えば透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより測定できる。 The thickness of the conductive layer X and the thickness of the entire conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
上記導電層Ｘにおけるニッケル、タングステン、モリブデン及びボロンの各含有量を制御する方法としては、例えば、無電解ニッケルめっきにより導電層Ｘを形成する際に、ニッケルめっき液のｐＨを制御する方法、無電解ニッケルめっきにより導電層Ｘを形成する際に、ボロン含有還元剤の濃度を調整する方法、ニッケルめっき液中のタングステン濃度を調整する方法、ニッケルめっき液中のモリブデン濃度を調整する方法並びにニッケルめっき液中のニッケル塩濃度を調整する方法等が挙げられる。 Examples of a method for controlling the contents of nickel, tungsten, molybdenum and boron in the conductive layer X include, for example, a method for controlling the pH of a nickel plating solution when the conductive layer X is formed by electroless nickel plating. When forming the conductive layer X by electrolytic nickel plating, a method of adjusting the concentration of the boron-containing reducing agent, a method of adjusting the tungsten concentration in the nickel plating solution, a method of adjusting the molybdenum concentration in the nickel plating solution, and nickel plating Examples include a method of adjusting the nickel salt concentration in the liquid.
また、導電層Ｘにおけるニッケル、タングステン、モリブデン又はボロンが濃度勾配を有するようにする方法としては、無電解ニッケルめっきの形成時期によって、ニッケル、タングステン、モリブデン又はボロンを含む配合成分の配合量を調整する方法等が挙げられる。 In addition, as a method for making nickel, tungsten, molybdenum or boron in the conductive layer X have a concentration gradient, the compounding amount of the compounding component containing nickel, tungsten, molybdenum or boron is adjusted depending on the formation time of the electroless nickel plating. And the like.
無電解めっきにより形成する方法では、一般的に、触媒化工程と、無電解めっき工程とが行われる。以下、無電解めっきにより、樹脂粒子の表面に、ニッケルとタングステン及びモリブデンの内の少なくとも１種とボロンと含む合金めっき層を形成する方法の一例を説明する。 In the method of forming by electroless plating, generally, a catalyzing step and an electroless plating step are performed. Hereinafter, an example of a method for forming an alloy plating layer containing at least one of nickel, tungsten, and molybdenum and boron on the surface of the resin particles by electroless plating will be described.
上記触媒化工程では、無電解めっきによりめっき層を形成するための起点となる触媒を、樹脂粒子の表面に形成させる。 In the catalyzing step, a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
上記触媒を樹脂粒子の表面に形成させる方法としては、例えば、塩化パラジウムと塩化スズとを含む溶液に、樹脂粒子を添加した後、酸溶液又はアルカリ溶液により樹脂粒子の表面を活性化させて、樹脂粒子の表面にパラジウムを析出させる方法、並びに硫酸パラジウムとアミノピリジンとを含有する溶液に、樹脂粒子を添加した後、還元剤を含む溶液により樹脂粒子の表面を活性化させて、樹脂粒子の表面にパラジウムを析出させる方法等が挙げられる。上記還元剤として、ボロン含有還元剤が好適に用いられる。但し、上記還元剤として、次亜リン酸ナトリウム等のリン含有還元剤を用いてもよい。 As a method of forming the catalyst on the surface of the resin particles, for example, after adding the resin particles to a solution containing palladium chloride and tin chloride, the surface of the resin particles is activated with an acid solution or an alkali solution, A method of depositing palladium on the surface of the resin particles, and after adding the resin particles to a solution containing palladium sulfate and aminopyridine, the surface of the resin particles is activated by a solution containing a reducing agent. Examples thereof include a method of depositing palladium on the surface. As the reducing agent, a boron-containing reducing agent is preferably used. However, a phosphorus-containing reducing agent such as sodium hypophosphite may be used as the reducing agent.
上記無電解めっき工程では、ニッケル塩と、タングステン含有化合物及びモリブデン含有化合物の内の少なくとも１種と、上記ボロン含有還元剤とを含むニッケルめっき浴が用いられる。ニッケルめっき浴中に樹脂粒子を浸漬することにより、触媒が表面に形成された樹脂粒子の表面に、ニッケルを析出させることができ、ニッケルとタングステン及びモリブデンの内の少なくとも１種とボロンとを含む導電層を形成できる。 In the electroless plating step, a nickel plating bath containing a nickel salt, at least one of a tungsten-containing compound and a molybdenum-containing compound, and the boron-containing reducing agent is used. By immersing the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and includes at least one of nickel, tungsten, and molybdenum and boron. A conductive layer can be formed.
上記タングステン含有化合物としては、ホウ化タングステン及びタングステン酸ナトリウム等が挙げられる。 Examples of the tungsten-containing compound include tungsten boride and sodium tungstate.
上記モリブデン含有化合物としては、ホウ化モリブデン及びモリブデン酸ナトリウム等が挙げられる。 Examples of the molybdenum-containing compound include molybdenum boride and sodium molybdate.
上記ボロン含有還元剤としては、ジメチルアミンボラン、水素化ホウ素ナトリウム及び水素化ホウ素カリウム等が挙げられる。 Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, and potassium borohydride.
本発明に係る導電性粒子は、表面に突起を有することが好ましい。上記導電層は、外表面に突起を有することが好ましい。導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。さらに、導電性粒子の導電層の表面には、酸化被膜が形成されていることが多い。突起を有する導電性粒子の使用により、電極間に導電性粒子を配置した後、圧着させることにより、突起により酸化被膜が効果的に排除される。このため、電極と導電性粒子とをより一層確実に接触させることができ、電極間の接続抵抗を低くすることができる。さらに、導電性粒子が表面に絶縁物質を有する場合、又は導電性粒子が樹脂中に分散されて導電材料として用いられる場合に、導電性粒子の突起によって、導電性粒子と電極との間の絶縁物質又は樹脂を効果的に排除できる。このため、電極間の導通信頼性を高めることができる。 The conductive particles according to the present invention preferably have protrusions on the surface. The conductive layer preferably has a protrusion on the outer surface. An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive layer of the conductive particles. By using the conductive particles having protrusions, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle can be contacted still more reliably and the connection resistance between electrodes can be made low. Further, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in the resin and used as a conductive material, the conductive particles and the electrodes are insulated by the protrusions of the conductive particles. Substances or resins can be effectively excluded. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.
上記突起は複数であることが好ましい。上記導電性粒子１個当たりの上記導電層の外表面の突起は、好ましくは３個以上、より好ましくは５個以上である。上記突起の数の上限は特に限定されない。突起の数の上限は導電性粒子の粒子径等を考慮して適宜選択できる。 It is preferable that there are a plurality of protrusions. The number of protrusions on the outer surface of the conductive layer per one conductive particle is preferably 3 or more, more preferably 5 or more. The upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
複数の上記突起の平均高さは、好ましくは０．００１μｍ以上、より好ましくは０．０５μｍ以上、好ましくは０．９μｍ以下、より好ましくは０．２μｍ以下である。上記突起の平均高さが上記下限以上及び上記上限以下であると、電極間の接続抵抗を効果的に低くすることができる。 The average height of the plurality of protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. When the average height of the protrusions is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively lowered.
［芯物質］
上記芯物質が上記導電層中に埋め込まれていることによって、上記導電層が外表面に複数の突起を有するようにすることが容易である。但し、導電性粒子及び導電層の表面に突起を形成するために、芯物質を必ずしも用いなくてもよい。
[Core material]
Since the core substance is embedded in the conductive layer, it is easy for the conductive layer to have a plurality of protrusions on the outer surface. However, in order to form protrusions on the surfaces of the conductive particles and the conductive layer, the core substance is not necessarily used.
上記突起を形成する方法としては、基材粒子の表面に芯物質を付着させた後、無電解めっきにより導電層を形成する方法、並びに基材粒子の表面に無電解めっきにより導電層を形成した後、芯物質を付着させ、更に無電解めっきにより導電層を形成する方法等が挙げられる。 As the method for forming the protrusions, a core material is attached to the surface of the base particle, and then a conductive layer is formed by electroless plating, and a conductive layer is formed on the surface of the base particle by electroless plating. Thereafter, a method of attaching a core substance and further forming a conductive layer by electroless plating may be used.
上記基材粒子の表面上に芯物質を配置する方法としては、例えば、基材粒子の分散液中に、芯物質を添加し、基材粒子の表面に芯物質を、例えば、ファンデルワールス力により集積させ、付着させる方法、並びに基材粒子を入れた容器に、芯物質を添加し、容器の回転等による機械的な作用により基材粒子の表面に芯物質を付着させる方法等が挙げられる。なかでも、付着させる芯物質の量を制御しやすいため、分散液中の基材粒子の表面に芯物質を集積させ、付着させる方法が好ましい。 As a method of disposing the core substance on the surface of the base particle, for example, the core substance is added to the dispersion of the base particle, and the core substance is applied to the surface of the base particle, for example, van der Waals force. And a method in which a core substance is added to a container containing base particles, and a core substance is attached to the surface of the base particles by mechanical action such as rotation of the container. . Especially, since the quantity of the core substance to adhere is easy to control, the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.
上記芯物質を構成する物質としては、導電性物質及び非導電性物質が挙げられる。上記導電性物質としては、例えば、金属、金属の酸化物、黒鉛等の導電性非金属及び導電性ポリマー等が挙げられる。上記導電性ポリマーとしては、ポリアセチレン等が挙げられる。上記非導電性物質としては、シリカ、アルミナ、チタン酸バリウム及びジルコニア等が挙げられる。なかでも、導電性を高めることができ、更に接続抵抗を効果的に低くすることができるので、金属が好ましい。上記芯物質は金属粒子であることが好ましい。 Examples of the material constituting the core material include conductive materials and non-conductive materials. Examples of the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Examples of the non-conductive substance include silica, alumina, barium titanate, zirconia, and the like. Among them, metal is preferable because conductivity can be increased and connection resistance can be effectively reduced. The core substance is preferably metal particles.
上記金属としては、例えば、金、銀、銅、白金、亜鉛、鉄、鉛、錫、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、ゲルマニウム及びカドミウム等の金属、並びに錫−鉛合金、錫−銅合金、錫−銀合金、錫−鉛−銀合金及び炭化タングステン等の２種類以上の金属で構成される合金等が挙げられる。なかでも、ニッケル、銅、銀又は金が好ましい。上記芯物質を構成する金属は、上記導電層を構成する金属と同じであってもよく、異なっていてもよい。上記芯物質を構成する金属は、上記導電層を構成する金属を含むことが好ましい。上記芯物質を構成する金属は、ニッケルを含むことが好ましい。上記芯物質を構成する金属は、ニッケルを含むことが好ましい。 Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide. Of these, nickel, copper, silver or gold is preferable. The metal constituting the core material may be the same as or different from the metal constituting the conductive layer. The metal constituting the core material preferably includes a metal constituting the conductive layer. It is preferable that the metal which comprises the said core substance contains nickel. It is preferable that the metal which comprises the said core substance contains nickel.
上記芯物質の形状は特に限定されない。芯物質の形状は塊状であることが好ましい。芯物質としては、例えば、粒子状の塊、複数の微小粒子が凝集した凝集塊、及び不定形の塊等が挙げられる。 The shape of the core material is not particularly limited. The shape of the core substance is preferably a lump. Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
上記芯物質の平均径（平均粒子径）は、好ましくは０．００１μｍ以上、より好ましくは０．０５μｍ以上、好ましくは０．９μｍ以下、より好ましくは０．２μｍ以下である。上記芯物質の平均径が上記下限以上及び上記上限以下であると、電極間の接続抵抗を効果的に低くすることができる。 The average diameter (average particle diameter) of the core substance is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. When the average diameter of the core substance is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.
上記芯物質の「平均径（平均粒子径）」は、数平均径（数平均粒子径）を示す。芯物質の平均径は、任意の芯物質５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することにより求められる。 The “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
上記芯物質の表面上に、無機粒子が配置されていてもよい。芯物質の表面上に配置された無機粒子は複数であることが好ましい。芯物質の表面に、無機粒子が付着していてもよい。このような無機粒子と芯物質とを備える複合粒子を用いてもよい。無機粒子の大きさ（平均径）は、芯物質の大きさ（平均径）よりも小さいことが好ましく、上記無機粒子は、無機微粒子であることが好ましい。 Inorganic particles may be disposed on the surface of the core substance. It is preferable that there are a plurality of inorganic particles arranged on the surface of the core substance. Inorganic particles may be attached to the surface of the core substance. You may use the composite particle provided with such an inorganic particle and a core substance. The size (average diameter) of the inorganic particles is preferably smaller than the size (average diameter) of the core substance, and the inorganic particles are preferably inorganic fine particles.
上記芯物質の表面上に配置される上記無機粒子の材料としては、シリカ（二酸化珪素、モース硬度６〜７）、ジルコニア（モース硬度８〜９）、アルミナ（モース硬度９）、炭化タングステン（モース硬度９）及びダイヤモンド（モース硬度１０）等が挙げられる。上記無機粒子は、シリカ、ジルコニア、アルミナ、炭化タングステン又はダイヤモンドであることが好ましく、シリカ、ジルコニア、アルミナ又はダイヤモンドであることも好ましい。上記無機粒子のモース硬度は好ましくは５以上、より好ましくは６以上である。上記無機粒子のモース硬度は上記導電層のモース硬度よりも大きいことが好ましい。上記無機粒子のモース硬度は上記第２の導電層のモース硬度よりも大きいことが好ましい。上記無機粒子のモース硬度と上記導電層のモース硬度との差の絶対値、並びに上記無機粒子のモース硬度と上記第２の導電層のモース硬度との差の絶対値は、好ましくは０．１以上、より好ましくは０．２以上、更に好ましくは０．５以上、特に好ましくは１以上である。また、導電層が複数の層により形成されていている場合には、複数の層を構成する全ての金属よりも無機粒子の方が硬いことが、接続抵抗の低減効果がより一層効果的に発揮される。 Examples of the material of the inorganic particles arranged on the surface of the core substance include silica (silicon dioxide, Mohs hardness 6-7), zirconia (Mohs hardness 8-9), alumina (Mohs hardness 9), tungsten carbide (Mohs). Hardness 9), diamond (Mohs hardness 10), and the like. The inorganic particles are preferably silica, zirconia, alumina, tungsten carbide or diamond, and are also preferably silica, zirconia, alumina or diamond. The Mohs hardness of the inorganic particles is preferably 5 or more, more preferably 6 or more. The Mohs hardness of the inorganic particles is preferably larger than the Mohs hardness of the conductive layer. The Mohs hardness of the inorganic particles is preferably larger than the Mohs hardness of the second conductive layer. The absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the conductive layer, and the absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the second conductive layer are preferably 0.1. Above, more preferably 0.2 or more, still more preferably 0.5 or more, particularly preferably 1 or more. In addition, when the conductive layer is formed of a plurality of layers, the inorganic particles are harder than all the metals constituting the plurality of layers, so that the effect of reducing the connection resistance is more effectively exhibited. Is done.
上記無機粒子の平均粒子径は、好ましくは０．０００１μｍ以上、より好ましくは０．００５μｍ以上、好ましくは０．５μｍ以下、より好ましくは０．１μｍ以下である。上記無機粒子の平均粒子径が上記下限以上及び上記上限以下であると、電極間の接続抵抗を効果的に低くすることができる。 The average particle size of the inorganic particles is preferably 0.0001 μm or more, more preferably 0.005 μm or more, preferably 0.5 μm or less, more preferably 0.1 μm or less. When the average particle size of the inorganic particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.
上記無機粒子の「平均粒子径」は、数平均粒子径を示す。無機粒子の平均粒子径は、任意の無機粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することにより求められる。 The “average particle diameter” of the inorganic particles indicates a number average particle diameter. The average particle diameter of the inorganic particles is obtained by observing 50 arbitrary inorganic particles with an electron microscope or an optical microscope and calculating an average value.
上記芯物質の表面上に無機粒子が配置されている複合粒子を用いる場合に、上記複合粒子の平均径（平均粒子径）は、好ましくは０．００１２μｍ以上、より好ましくは０．０５０２μｍ以上、好ましくは１．９μｍ以下、より好ましくは１．２μｍ以下である。上記複合粒子の平均径が上記下限以上及び上記上限以下であると、電極間の接続抵抗を効果的に低くすることができる。 When using composite particles in which inorganic particles are arranged on the surface of the core substance, the average diameter of the composite particles (average particle diameter) is preferably 0.0012 μm or more, more preferably 0.0502 μm or more, preferably Is 1.9 μm or less, more preferably 1.2 μm or less. When the average diameter of the composite particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.
上記複合粒子の「平均径（平均粒子径）」は、数平均径（数平均粒子径）を示す。上記複合粒子の平均径は、任意の複合粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することにより求められる。 The “average diameter (average particle diameter)” of the composite particles indicates a number average diameter (number average particle diameter). The average diameter of the composite particles is determined by observing 50 arbitrary composite particles with an electron microscope or an optical microscope and calculating an average value.
［絶縁物質］
本発明に係る導電性粒子は、上記導電層の表面上に配置された絶縁物質を備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、２つの電極で導電性粒子を加圧することにより、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。導電性粒子が導電層の外表面に複数の突起を有するので、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。
[Insulating material]
The conductive particles according to the present invention preferably include an insulating material disposed on the surface of the conductive layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. Note that when the conductive particles are pressurized with the two electrodes at the time of connection between the electrodes, the insulating substance between the conductive layer of the conductive particles and the electrodes can be easily excluded. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be easily excluded.
電極間の圧着時に上記絶縁物質をより一層容易に排除できることから、上記絶縁物質は、絶縁性粒子であることが好ましい。 It is preferable that the insulating material is an insulating particle because the insulating material can be more easily removed when the electrodes are pressed.
上記絶縁物質の材料である絶縁性樹脂の具体例としては、ポリオレフィン類、（メタ）アクリレート重合体、（メタ）アクリレート共重合体、ブロックポリマー、熱可塑性樹脂、熱可塑性樹脂の架橋物、熱硬化性樹脂及び水溶性樹脂等が挙げられる。 Specific examples of the insulating resin that is the material of the insulating material include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, and thermosetting. Resin, water-soluble resin, and the like.
上記ポリオレフィン類としては、ポリエチレン、エチレン−酢酸ビニル共重合体及びエチレン−アクリル酸エステル共重合体等が挙げられる。上記（メタ）アクリレート重合体としては、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート及びポリブチル（メタ）アクリレート等が挙げられる。上記ブロックポリマーとしては、ポリスチレン、スチレン−アクリル酸エステル共重合体、ＳＢ型スチレン−ブタジエンブロック共重合体、及びＳＢＳ型スチレン−ブタジエンブロック共重合体、並びにこれらの水素添加物等が挙げられる。上記熱可塑性樹脂としては、ビニル重合体及びビニル共重合体等が挙げられる。上記熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂及びメラミン樹脂等が挙げられる。上記水溶性樹脂としては、ポリビニルアルコール、ポリアクリル酸、ポリアクリルアミド、ポリビニルピロリドン、ポリエチレンオキシド及びメチルセルロース等が挙げられる。なかでも、水溶性樹脂が好ましく、ポリビニルアルコールがより好ましい。 Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
上記導電層の表面上に絶縁物質を配置する方法としては、化学的方法、及び物理的もしくは機械的方法等が挙げられる。上記化学的方法としては、例えば、界面重合法、粒子存在下での懸濁重合法及び乳化重合法等が挙げられる。上記物理的もしくは機械的方法としては、スプレードライ、ハイブリダイゼーション、静電付着法、噴霧法、ディッピング及び真空蒸着による方法等が挙げられる。なかでも、絶縁物質が脱離し難いことから、上記導電層の表面に、化学結合を介して上記絶縁物質を配置する方法が好ましい。 Examples of a method for disposing an insulating material on the surface of the conductive layer include a chemical method and a physical or mechanical method. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. In particular, since the insulating substance is difficult to be detached, a method of disposing the insulating substance on the surface of the conductive layer through a chemical bond is preferable.
上記絶縁物質の平均径（平均粒子径）は、導電性粒子の粒子径及び導電性粒子の用途等によって適宜選択できる。上記絶縁物質の平均径（平均粒子径）は好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上、好ましくは１μｍ以下、より好ましくは０．５μｍ以下である。絶縁物質の平均径が上記下限以上であると、導電性粒子がバインダー樹脂中に分散されたときに、複数の導電性粒子における導電層同士が接触し難くなる。絶縁性粒子の平均径が上記上限以下であると、電極間の接続の際に、電極と導電性粒子との間の絶縁物質を排除するために、圧力を高くしすぎる必要がなくなり、高温に加熱する必要もなくなる。 The average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles, the use of the conductive particles, and the like. The average diameter (average particle diameter) of the insulating material is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 1 μm or less, more preferably 0.5 μm or less. When the average diameter of the insulating material is not less than the above lower limit, the conductive layers of the plurality of conductive particles are difficult to contact when the conductive particles are dispersed in the binder resin. When the average diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating material between the electrodes and the conductive particles when the electrodes are connected. There is no need for heating.
上記絶縁物質の「平均径（平均粒子径）」は、数平均径（数平均粒子径）を示す。絶縁物質の平均径は、粒度分布測定装置等を用いて求められる。 The “average diameter (average particle diameter)” of the insulating material indicates a number average diameter (number average particle diameter). The average diameter of the insulating material is obtained using a particle size distribution measuring device or the like.
（導電材料）
本発明に係る導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。上記導電性粒子は、バインダー樹脂中に分散され、導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。
(Conductive material)
The conductive material according to the present invention includes the conductive particles described above and a binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material.
上記バインダー樹脂は特に限定されない。上記バインダー樹脂として、公知の絶縁性の樹脂が用いられる。 The binder resin is not particularly limited. As the binder resin, a known insulating resin is used.
上記バインダー樹脂としては、例えば、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体及びエラストマー等が挙げられる。上記バインダー樹脂は１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.
上記ビニル樹脂としては、例えば、酢酸ビニル樹脂、アクリル樹脂及びスチレン樹脂等が挙げられる。上記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、エチレン−酢酸ビニル共重合体及びポリアミド樹脂等が挙げられる。上記硬化性樹脂としては、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂及び不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂又は湿気硬化型樹脂であってもよい。上記硬化性樹脂は、硬化剤と併用されてもよい。上記熱可塑性ブロック共重合体としては、例えば、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体の水素添加物、及びスチレン−イソプレン−スチレンブロック共重合体の水素添加物等が挙げられる。上記エラストマーとしては、例えば、スチレン−ブタジエン共重合ゴム、及びアクリロニトリル−スチレンブロック共重合ゴム等が挙げられる。 Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated product of a styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
上記導電材料は、上記導電性粒子及び上記バインダー樹脂の他に、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 In addition to the conductive particles and the binder resin, the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer. Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
上記バインダー樹脂中に上記導電性粒子を分散させる方法は、従来公知の分散方法を用いることができ特に限定されない。上記バインダー樹脂中に上記導電性粒子を分散させる方法としては、例えば、上記バインダー樹脂中に上記導電性粒子を添加した後、プラネタリーミキサー等で混練して分散させる方法、上記導電性粒子を水又は有機溶剤中にホモジナイザー等を用いて均一に分散させた後、上記バインダー樹脂中に添加し、プラネタリーミキサー等で混練して分散させる方法、並びに上記バインダー樹脂を水又は有機溶剤等で希釈した後、上記導電性粒子を添加し、プラネタリーミキサー等で混練して分散させる方法等が挙げられる。 The method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse | distributing is mentioned.
本発明に係る導電材料は、導電ペースト及び導電フィルム等として使用され得る。本発明に係る導電材料が、導電フィルムである場合には、導電性粒子を含む導電フィルムに、導電性粒子を含まないフィルムが積層されていてもよい。上記導電ペーストは、異方性導電ペーストであることが好ましい。上記導電フィルムは、異方性導電フィルムであることが好ましい。 The conductive material according to the present invention can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
上記導電材料１００重量％中、上記バインダー樹脂の含有量は好ましくは１０重量％以上、より好ましくは３０重量％以上、更に好ましくは５０重量％以上、特に好ましくは７０重量％以上、好ましくは９９．９９重量％以下、より好ましくは９９．９重量％以下である。上記バインダー樹脂の含有量が上記下限以上及び上記上限以下であると、電極間に導電性粒子が効率的に配置され、導電材料により接続された接続対象部材の接続信頼性がより一層高くなる。 In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
上記導電材料１００重量％中、上記導電性粒子の含有量は好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、好ましくは４０重量％以下、より好ましくは２０重量％以下、更に好ましくは１０重量％以下である。上記導電性粒子の含有量が上記下限以上及び上記上限以下であると、電極間の導通信頼性がより一層高くなる。 In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 weight% or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
（接続構造体）
本発明の導電性粒子を用いて、又は該導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。
(Connection structure)
A connection structure can be obtained by connecting the connection target members using the conductive particles of the present invention or using a conductive material containing the conductive particles and a binder resin.
上記接続構造体は、第１の接続対象部材と、第２の接続対象部材と、第１，第２の接続対象部材を接続している接続部とを備え、該接続部が本発明の導電性粒子により形成されているか、又は該導電性粒子とバインダー樹脂とを含む導電材料（異方性導電材料など）により形成されている接続構造体であることが好ましい。導電性粒子が用いられた場合には、接続部自体が導電性粒子である。すなわち、第１，第２の接続対象部材が導電性粒子により接続される。 The connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection portion is a conductive member of the present invention. The connection structure is preferably formed of conductive particles or formed of a conductive material (such as an anisotropic conductive material) containing the conductive particles and a binder resin. In the case where conductive particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
図４に、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体を模式的に正面断面図で示す。 In FIG. 4, the connection structure using the electroconductive particle which concerns on the 1st Embodiment of this invention is typically shown with front sectional drawing.
図４に示す接続構造体５１は、第１の接続対象部材５２と、第２の接続対象部材５３と、第１，第２の接続対象部材５２，５３を接続している接続部５４とを備える。接続部５４は、導電性粒子１を含む導電材料を硬化させることにより形成されている。なお、図４では、導電性粒子１は、図示の便宜上、略図的に示されている。
4 includes a first
第１の接続対象部材５２は上面５２ａ（表面）に、複数の電極５２ｂを有する。第２の接続対象部材５３は下面５３ａ（表面）に、複数の電極５３ｂを有する。電極５２ｂと電極５３ｂとが、１つ又は複数の導電性粒子１により電気的に接続されている。従って、第１，第２の接続対象部材５２，５３が導電性粒子１により電気的に接続されている。
The first
上記接続構造体の製造方法は特に限定されない。接続構造体の製造方法の一例としては、第１の接続対象部材と第２の接続対象部材との間に上記導電材料を配置し、積層体を得た後、該積層体を加熱及び加圧する方法等が挙げられる。 The manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of the connection structure, the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
上記加圧の圧力は９．８×１０４〜４．９×１０６Ｐａ程度である。上記加熱の温度は、１２０〜２２０℃程度である。 The pressure of the said pressurization is about 9.8 * 10 < 4 > -4.9 * 10 < 6 > Pa. The temperature of the said heating is about 120-220 degreeC.
上記接続対象部材としては、具体的には、半導体チップ、コンデンサ及びダイオード等の電子部品、並びにプリント基板、フレキシブルプリント基板及びガラス基板等の回路基板などの電子部品等が挙げられる。上記接続対象部材は電子部品であることが好ましい。上記導電性粒子は、電子部品における電極の電気的な接続に用いられることが好ましい。 Specific examples of the connection target member include electronic components such as a semiconductor chip, a capacitor, and a diode, and circuit components such as a printed board, a flexible printed board, and a glass board. The connection target member is preferably an electronic component. The conductive particles are preferably used for electrical connection of electrodes in an electronic component.
上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、錫電極、アルミニウム電極、銅電極、モリブデン電極及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、錫電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.
（実施例１）
粒子径が３．０μｍであるジビニルベンゼン共重合体樹脂粒子（積水化学工業社製「ミクロパールＳＰ−２０３」）を用意した。
Example 1
Divinylbenzene copolymer resin particles having a particle size of 3.0 μm (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) were prepared.
パラジウム触媒液を５重量％含むアルカリ溶液１００重量部に、上記樹脂粒子１０重量部を、超音波分散器を用いて分散させた後、溶液をろ過することにより、樹脂粒子を取り出した。次いで、樹脂粒子をジメチルアミンボラン１重量％溶液１００重量部に添加し、樹脂粒子の表面を活性化させた。表面が活性化された樹脂粒子を十分に水洗した後、蒸留水５００重量部に加え、分散させることにより、懸濁液を得た。 After dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, the resin particles were taken out by filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
また、硫酸ニッケル０．２３ｍｏｌ／Ｌ、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、クエン酸ナトリウム０．５ｍｏｌ／Ｌ及びタングステン酸ナトリウム０．０１ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ８．５）を用意した。得られた懸濁液を６０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解めっき前期工程を行った。 Further, a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium tungstate was prepared. While stirring the obtained suspension at 60 ° C., the above nickel plating solution was gradually added dropwise to the suspension, and an electroless plating first step was performed.
続いて、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、タングステン酸ナトリウム０．０１ｍｏｌ／Ｌを含むめっき液（ｐＨ１１．０）を徐々に滴下し、無電解めっき後期工程を行った。その後、懸濁液をろ過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。 Subsequently, a plating solution (pH 11.0) containing dimethylamine borane 0.92 mol / L and sodium tungstate 0.01 mol / L was gradually dropped to perform the latter stage of electroless plating. Thereafter, by filtering the suspension, the particles are taken out, washed with water, and dried to obtain conductive particles in which a nickel-tungsten-boron conductive layer (thickness 0.1 μm) is arranged on the surface of the resin particles. It was.
（実施例２）
前期工程及び後期工程において、タングステン酸ナトリウム濃度を０．１２ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 2)
A nickel-tungsten-boron conductive layer (thickness: 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.12 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例３）
前期工程及び後期工程において、タングステン酸ナトリウム濃度を０．２３ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 3)
A nickel-tungsten-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.23 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例４）
前期工程及び後期工程において、タングステン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
Example 4
A nickel-tungsten-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例５）
前期工程及び後期工程において、ジメチルアミンボラン濃度を２．７６ｍｏｌ／Ｌに変更したこと、並びにタングステン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 5)
In the first step and the second step, the resin particles were prepared in the same manner as in Example 1 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium tungstate concentration was changed to 0.35 mol / L. Conductive particles having a nickel-tungsten-boron conductive layer (thickness 0.1 μm) disposed on the surface were obtained.
（実施例６）
（１）パラジウム付着工程
粒子径が５．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ−２０５」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
(Example 6)
(1) Palladium adhesion process The divinylbenzene resin particle ("Micropearl SP-205" by Sekisui Chemical Co., Ltd.) whose particle diameter is 5.0 micrometers was prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles to which palladium was attached.
（２）芯物質付着工程
パラジウムが付着された樹脂粒子をイオン交換水３００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー（平均粒子径１００ｎｍ）１ｇを３分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
(2) Core substance adhesion step The resin particles to which palladium was adhered were stirred and dispersed in 300 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 1 g of metallic nickel particle slurry (average particle diameter 100 nm) was added to the dispersion over 3 minutes to obtain resin particles to which the core substance was adhered.
（３）無電解ニッケルめっき工程
実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(3) Electroless nickel plating step In the same manner as in Example 1, conductive particles in which a nickel-tungsten-boron conductive layer (thickness: 0.1 μm) was disposed on the surface of the resin particles were obtained.
（実施例７）
前期工程及び後期工程において、タングステン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例６と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 7)
A nickel-tungsten-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 6 except that the sodium tungstate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例８）
（１）絶縁性粒子の作製
４ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた１０００ｍＬのセパラブルフラスコに、メタクリル酸メチル１００ｍｍｏｌと、Ｎ，Ｎ，Ｎ−トリメチル−Ｎ−２−メタクリロイルオキシエチルアンモニウムクロライド１ｍｍｏｌと、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩１ｍｍｏｌとを含むモノマー組成物を固形分率が５重量％となるようにイオン交換水に秤取した後、２００ｒｐｍで攪拌し、窒素雰囲気下７０℃で２４時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径２２０ｎｍ及びＣＶ値１０％の絶縁性粒子を得た。
(Example 8)
(1) Production of insulating particles A 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe was charged with 100 mmol methyl methacrylate and N, N, N-trimethyl. Ion-exchanged water containing a monomer composition containing 1 mmol of -N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
絶縁性粒子を超音波照射下でイオン交換水に分散させ、絶縁性粒子の１０重量％水分散液を得た。 The insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
実施例６で得られた導電性粒子１０ｇをイオン交換水５００ｍＬに分散させ、絶縁性粒子の水分散液４ｇを添加し、室温で６時間攪拌した。３μｍのメッシュフィルターでろ過した後、更にメタノールで洗浄し、乾燥し、絶縁性粒子が付着した導電性粒子を得た。 10 g of the conductive particles obtained in Example 6 were dispersed in 500 mL of ion exchange water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
走査電子顕微鏡（ＳＥＭ）により観察したところ、導電性粒子の表面に絶縁性粒子による被覆層が１層のみ形成されていた。画像解析により導電性粒子の中心より２．５μｍの面積に対する絶縁性粒子の被覆面積（即ち絶縁性粒子の粒子径の投影面積）を算出したところ、被覆率は３０％であった。 When observed with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles by image analysis (that is, the projected area of the particle diameter of the insulating particles) was calculated to be 30%.
（実施例９）
前期工程及び後期工程において、タングステン酸ナトリウム濃度を０．４６ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
Example 9
A nickel-tungsten-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.46 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例１０）
前期工程及び後期工程において、ジメチルアミンボラン濃度を４．６０ｍｏｌ／Ｌに変更したこと以外は実施例３と同様にして、樹脂粒子の表面にニッケル−タングステン−ボロン導電層（厚み約０．１μｍ）が配置された導電性粒子を得た。
(Example 10)
A nickel-tungsten-boron conductive layer (thickness of about 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 3 except that the dimethylamine borane concentration was changed to 4.60 mol / L in the first and second steps. The electroconductive particle by which was arrange | positioned was obtained.
（比較例１）
前期工程において、ニッケルめっき液におけるジメチルアミンボラン０．９２ｍｏｌ／Ｌを、次亜リン酸ナトリウム０．５ｍｏｌ／Ｌに変更したこと以外は実施例１と同様にして、樹脂粒子の表面にニッケルとタングステンとリンとを含む導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Comparative Example 1)
In the previous step, nickel and tungsten were formed on the surfaces of the resin particles in the same manner as in Example 1 except that 0.92 mol / L of dimethylamine borane in the nickel plating solution was changed to 0.5 mol / L of sodium hypophosphite. Conductive particles in which conductive layers (thickness: 0.1 μm) containing phosphorus and phosphorus were arranged were obtained.
（比較例２）
前期工程及び後期工程において、ニッケルめっき液におけるタングステン酸ナトリウム０．０１ｍｏｌ／Ｌを用いなかったこと以外は実施例１と同様にして、樹脂粒子の表面にニッケルとボロンとを含む導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Comparative Example 2)
A conductive layer (thickness 0) containing nickel and boron on the surface of the resin particles in the same manner as in Example 1 except that sodium tungstate 0.01 mol / L in the nickel plating solution was not used in the first step and the second step. .1 μm) was obtained.
（実施例１１）
粒子径が３．０μｍであるジビニルベンゼン共重合体樹脂粒子（積水化学工業社製「ミクロパールＳＰ−２０３」）を用意した。
(Example 11)
Divinylbenzene copolymer resin particles having a particle size of 3.0 μm (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) were prepared.
パラジウム触媒液を５重量％含むアルカリ溶液１００重量部に、上記樹脂粒子１０重量部を、超音波分散器を用いて分散させた後、溶液をろ過することにより、樹脂粒子を取り出した。次いで、樹脂粒子をジメチルアミンボラン１重量％溶液１００重量部に添加し、樹脂粒子の表面を活性化させた。表面が活性化された樹脂粒子を十分に水洗した後、蒸留水５００重量部に加え、分散させることにより、懸濁液を得た。 After dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, the resin particles were taken out by filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
また、硫酸ニッケル０．２３ｍｏｌ／Ｌ、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、クエン酸ナトリウム０．５ｍｏｌ／Ｌ及びモリブデン酸ナトリウム０．０１ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ８．５）を用意した。 Further, a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium molybdate was prepared.
得られた懸濁液を６０℃にて攪拌しながら、上記ニッケルめっき液を懸濁液に徐々に滴下し、無電解めっき前期工程を行った。 While stirring the obtained suspension at 60 ° C., the above nickel plating solution was gradually added dropwise to the suspension, and an electroless plating first step was performed.
続いて、ジメチルアミンボラン０．９２ｍｏｌ／Ｌ、モリブデン酸ナトリウム０．０１ｍｏｌ／Ｌを含むめっき液（ｐＨ１１．０）を徐々に滴下し、無電解めっき後期工程を行った。その後、懸濁液をろ過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。 Subsequently, a plating solution (pH 11.0) containing dimethylamine borane 0.92 mol / L and sodium molybdate 0.01 mol / L was gradually dropped to perform the latter stage of electroless plating. Thereafter, by filtering the suspension, the particles are taken out, washed with water, and dried to obtain conductive particles in which a nickel-molybdenum-boron conductive layer (thickness 0.1 μm) is disposed on the surface of the resin particles. It was.
（実施例１２）
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を０．１２ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 12)
A nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.12 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例１３）
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を０．２３ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 13)
A nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.23 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例１４）
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 14)
A nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例１５）
前期工程及び後期工程において、ジメチルアミンボラン濃度を２．７６ｍｏｌ／Ｌに変更したこと、並びにモリブデン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 15)
Resin particles were prepared in the same manner as in Example 11 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Conductive particles having a nickel-molybdenum-boron conductive layer (thickness 0.1 μm) disposed on the surface were obtained.
（実施例１６）
（１）パラジウム付着工程
粒子径が５．０μｍであるジビニルベンゼン樹脂粒子（積水化学工業社製「ミクロパールＳＰ−２０５」）を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を８重量％含むパラジウム触媒化液１００ｍＬ中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。ｐＨ６の０．５重量％ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
(Example 16)
(1) Palladium adhesion process The divinylbenzene resin particle ("Micropearl SP-205" by Sekisui Chemical Co., Ltd.) whose particle diameter is 5.0 micrometers was prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Resin particles were added to 0.5 wt% dimethylamine borane solution at pH 6 to obtain resin particles to which palladium was attached.
（２）芯物質付着工程
パラジウムが付着された樹脂粒子をイオン交換水３００ｍＬ中で３分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー（平均粒子径１００ｎｍ）１ｇを３分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
(2) Core substance adhesion step The resin particles to which palladium was adhered were stirred and dispersed in 300 mL of ion exchange water for 3 minutes to obtain a dispersion. Next, 1 g of metallic nickel particle slurry (average particle diameter 100 nm) was added to the dispersion over 3 minutes to obtain resin particles to which the core substance was adhered.
（３）無電解ニッケルめっき工程
実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(3) Electroless nickel plating step In the same manner as in Example 11, conductive particles were obtained in which a nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was disposed on the surface of the resin particles.
（実施例１７）
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を０．３５ｍｏｌ／Ｌに変更したこと以外は実施例１６と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 17)
A nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 16 except that the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例１８）
（１）絶縁性粒子の作製
４ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた１０００ｍＬのセパラブルフラスコに、メタクリル酸メチル１００ｍｍｏｌと、Ｎ，Ｎ，Ｎ−トリメチル−Ｎ−２−メタクリロイルオキシエチルアンモニウムクロライド１ｍｍｏｌと、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩１ｍｍｏｌとを含むモノマー組成物を固形分率が５重量％となるようにイオン交換水に秤取した後、２００ｒｐｍで攪拌し、窒素雰囲気下７０℃で２４時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径２２０ｎｍ及びＣＶ値１０％の絶縁性粒子を得た。
(Example 18)
(1) Production of insulating particles A 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe was charged with 100 mmol methyl methacrylate and N, N, N-trimethyl. Ion-exchanged water containing a monomer composition containing 1 mmol of -N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
絶縁性粒子を超音波照射下でイオン交換水に分散させ、絶縁性粒子の１０重量％水分散液を得た。 The insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
実施例１６で得られた導電性粒子１０ｇをイオン交換水５００ｍＬに分散させ、絶縁性粒子の水分散液４ｇを添加し、室温で６時間攪拌した。３μｍのメッシュフィルターでろ過した後、更にメタノールで洗浄し、乾燥し、絶縁性粒子が付着した導電性粒子を得た。 10 g of the conductive particles obtained in Example 16 were dispersed in 500 mL of ion exchange water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
走査電子顕微鏡（ＳＥＭ）により観察したところ、導電性粒子の表面に絶縁性粒子による被覆層が１層のみ形成されていた。画像解析により導電性粒子の中心より２．５μｍの面積に対する絶縁性粒子の被覆面積（即ち絶縁性粒子の粒子径の投影面積）を算出したところ、被覆率は３０％であった。 When observed with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles by image analysis (that is, the projected area of the particle diameter of the insulating particles) was calculated to be 30%.
（実施例１９）
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を０．４６ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Example 19)
A nickel-molybdenum-boron conductive layer (thickness 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.46 mol / L in the first and second steps. Arranged conductive particles were obtained.
（実施例２０）
前期工程及び後期工程において、ジメチルアミンボラン濃度を４．６０ｍｏｌ／Ｌに変更したこと以外は実施例１３と同様にして、樹脂粒子の表面にニッケル−モリブデン−ボロン導電層（厚み約０．１μｍ）が配置された導電性粒子を得た。
(Example 20)
A nickel-molybdenum-boron conductive layer (thickness of about 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 13 except that the dimethylamine borane concentration was changed to 4.60 mol / L in the first and second steps. The electroconductive particle by which was arrange | positioned was obtained.
（比較例３）
ニッケルめっき液におけるジメチルアミンボラン０．９２ｍｏｌ／Ｌを、次亜リン酸ナトリウム０．５ｍｏｌ／Ｌに変更したこと以外は実施例１１と同様にして、樹脂粒子の表面にニッケルとモリブデンとリンとを含む導電層（厚み０．１μｍ）が配置された導電性粒子を得た。
(Comparative Example 3)
In the same manner as in Example 11 except that 0.92 mol / L of dimethylamine borane in the nickel plating solution was changed to 0.5 mol / L of sodium hypophosphite, nickel, molybdenum and phosphorus were added to the surface of the resin particles. The electroconductive particle by which the electroconductive layer (thickness 0.1 micrometer) containing was arrange | positioned was obtained.
（実施例２１）
前期工程及び後期工程において、モリブデン酸ナトリウム０．０１ｍｏｌ／Ｌを追加したこと以外は実施例６と同様にして、樹脂粒子の表面にニッケル−タングステン−モリブデン−ボロン導電層（厚み約０．１μｍ）が配置された導電性粒子を得た。
(Example 21)
A nickel-tungsten-molybdenum-boron conductive layer (thickness of about 0.1 μm) was formed on the surface of the resin particles in the same manner as in Example 6 except that 0.01 mol / L of sodium molybdate was added in the first and second steps. The electroconductive particle by which was arrange | positioned was obtained.
（比較例４）
前期工程及び後期工程において、モリブデン酸ナトリウム０．０１ｍｏｌ／Ｌを追加したこと以外は比較例１と同様にして、樹脂粒子の表面にニッケル−タングステン−モリブデン−ボロン導電層（厚み約０．１μｍ）が配置された導電性粒子を得た。
(Comparative Example 4)
A nickel-tungsten-molybdenum-boron conductive layer (thickness: about 0.1 μm) was formed on the surface of the resin particles in the same manner as in Comparative Example 1 except that 0.01 mol / L of sodium molybdate was added in the first and second steps. The electroconductive particle by which was arrange | positioned was obtained.
（評価）
（１）導電層の全体１００重量％中のニッケル、ボロン、タングステン及びモリブデンの含有量
６０％硝酸５ｍＬと３７％塩酸１０ｍＬとの混合液に、導電性粒子５ｇを加え、導電層を完全に溶解させ、溶液を得た。得られた溶液を用いて、ニッケル、ボロン、タングステン及びモリブデンの含有量をＩＣＰ−ＭＳ分析器（日立製作所社製）により分析した。なお、実施例の導電性粒子における導電層はリンを含んでいなかった。
(Evaluation)
(1) Content of nickel, boron, tungsten and molybdenum in 100% by weight of the total conductive layer Add 5g of conductive particles to a mixture of 5mL of 60% nitric acid and 10mL of 37% hydrochloric acid to completely dissolve the conductive layer. To give a solution. Using the obtained solution, the contents of nickel, boron, tungsten and molybdenum were analyzed with an ICP-MS analyzer (manufactured by Hitachi, Ltd.). In addition, the electroconductive layer in the electroconductive particle of an Example did not contain phosphorus.
（２）導電層の厚み方向におけるタングステン及びモリブデンの合計の含有量
導電層の厚み方向における各成分の含有量の分布を測定した。導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分において、ニッケル、ボロン、タングステン及びモリブデンの各含有量を評価した。
(2) Total content of tungsten and molybdenum in the thickness direction of the conductive layer The distribution of the content of each component in the thickness direction of the conductive layer was measured. Each content of nickel, boron, tungsten and molybdenum was evaluated in the conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction.
導電層の厚み方向における各成分の含有量の分布（導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分における各成分の含有量）については、以下のようにして評価した。 The distribution of the content of each component in the thickness direction of the conductive layer (the content of each component in the conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction) is evaluated as follows. did.
集束イオンビームを用いて、得られた導電性粒子の薄膜切片を作製した。透過型電子顕微鏡ＦＥ−ＴＥＭ（日本電子社製「ＪＥＭ−２０１０ＦＥＦ」）を用いて、エネルギー分散型Ｘ線分析装置（ＥＤＳ）により、導電層におけるニッケル、ボロン、タングステン及びモリブデンの各含有量を測定した。 Using a focused ion beam, a thin film slice of the obtained conductive particles was prepared. Using a transmission electron microscope FE-TEM (“JEM-2010FEF” manufactured by JEOL Ltd.), each content of nickel, boron, tungsten and molybdenum in the conductive layer is measured by an energy dispersive X-ray analyzer (EDS). did.
（３）溶出したニッケルイオン濃度
複数の導電性粒子１０重量部を５重量％クエン酸水溶液１００重量部に２５℃で１分間浸漬した。ＩＣＰ発光分析装置（ＨＯＲＩＢＡ社製「ＵＬＴＩＭＡ２」）を用いて、浸漬後の液中に溶出したニッケルイオン濃度を測定した。導電性粒子の単位表面積当たりの溶出したニッケルイオン濃度（ｐｐｍ／ｃｍ２）を求めた。
(3) Eluted nickel ion concentration 10 parts by weight of a plurality of conductive particles were immersed in 100 parts by weight of a 5% by weight citric acid aqueous solution at 25 ° C. for 1 minute. The concentration of nickel ions eluted in the liquid after immersion was measured using an ICP emission spectrometer (“ULTIMA2” manufactured by HORIBA). The eluted nickel ion concentration (ppm / cm 2 ) per unit surface area of the conductive particles was determined.
（４）めっき状態
得られた導電性粒子５０個のめっき状態を、走査型電子顕微鏡により観察した。めっき割れ又はめっき剥がれ等のめっきむらの有無を観察した。めっきむらが確認された導電性粒子が４個以下の場合を「良好」、めっきむらが確認された導電性粒子が５個以上の場合を「不良」と判定した。
(4) Plating state The plating state of 50 conductive particles obtained was observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or plating peeling was observed. The case where the number of conductive particles in which plating unevenness was confirmed was 4 or less was judged as “good”, and the case where the number of conductive particles in which plating unevenness was confirmed was 5 or more was judged as “bad”.
（５）凝集状態
ビスフェノールＡ型エポキシ樹脂（三菱化学社製「エピコート１００９」）１０重量部と、アクリルゴム（重量平均分子量約８０万）４０重量部と、メチルエチルケトン２００重量部と、マイクロカプセル型硬化剤（旭化成ケミカルズ社製「ＨＸ３９４１ＨＰ」）５０重量部と、シランカップリング剤（東レダウコーニングシリコーン社製「ＳＨ６０４０」）２重量部とを混合し、導電性粒子を含有量が３重量％となるように添加し、分散させ、異方性導電材料を得た。
(5) Aggregation state 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and microcapsule type curing 50 parts by weight of the agent (“HX3941HP” manufactured by Asahi Kasei Chemicals Co., Ltd.) and 2 parts by weight of the silane coupling agent (“SH6040” manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed to give a conductive particle content of 3% by weight. Thus, an anisotropic conductive material was obtained.
得られた異方性導電材料を２５℃で７２時間保管した。保管後に、異方性導電材料において凝集した導電性粒子が沈降しているか否かを評価した。凝集した導電性粒子が沈降していない場合を「良好」、凝集した導電性粒子が沈降している場合を「不良」と判定した。 The obtained anisotropic conductive material was stored at 25 ° C. for 72 hours. After storage, it was evaluated whether or not the conductive particles aggregated in the anisotropic conductive material were settled. The case where the aggregated conductive particles were not settled was judged as “good”, and the case where the aggregated conductive particles were settled was judged as “bad”.
（６）初期の接続抵抗
接続構造体の作製：
ビスフェノールＡ型エポキシ樹脂（三菱化学社製「エピコート１００９」）１０重量部と、アクリルゴム（重量平均分子量約８０万）４０重量部と、メチルエチルケトン２００重量部と、マイクロカプセル型硬化剤（旭化成ケミカルズ社製「ＨＸ３９４１ＨＰ」）５０重量部と、シランカップリング剤（東レダウコーニングシリコーン社製「ＳＨ６０４０」）２重量部とを混合し、導電性粒子を含有量が３重量％となるように添加し、分散させ、樹脂組成物を得た。
(6) Initial connection resistance Fabrication of connection structure:
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP" manufactured by HX3941) and 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight. A resin composition was obtained by dispersing.
得られた樹脂組成物を、片面が離型処理された厚さ５０μｍのＰＥＴ（ポリエチレンテレフタレート）フィルムに塗布し、７０℃の熱風で５分間乾燥し、異方性導電フィルムを作製した。得られた異方性導電フィルムの厚さは１２μｍであった。 The obtained resin composition was applied to a 50 μm-thick PET (polyethylene terephthalate) film whose one surface was released from the mold, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film. The thickness of the obtained anisotropic conductive film was 12 μm.
得られた異方性導電フィルムを５ｍｍ×５ｍｍの大きさに切断した。切断された異方性導電フィルムを、一方に抵抗測定用の引き回し線を有するアルミニウム電極（高さ０．２μｍ、Ｌ／Ｓ＝２０μｍ／２０μｍ）を有するガラス基板（幅３ｃｍ、長さ３ｃｍ）のアルミニウム電極側のほぼ中央に貼り付けた。次いで、同じアルミニウム電極を有する２層フレキシブルプリント基板（幅２ｃｍ、長さ１ｃｍ）を、電極同士が重なるように位置合わせをしてから貼り合わせた。このガラス基板と２層フレキシブルプリント基板との積層体を、１０Ｎ、１８０℃、及び２０秒間の圧着条件で熱圧着し、接続構造体を得た。なお、ポリイミドフィルムにアルミニウム電極が直接形成されている２層フレキシブルプリント基板を用いた。
The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. The cut anisotropic conductive film is formed of a glass substrate (
接続抵抗の測定：
得られた接続構造体の対向する電極間の接続抵抗を４端子法により測定した。また、初期の接続抵抗を下記の基準で判定した。
Connection resistance measurement:
The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. The initial connection resistance was determined according to the following criteria.
〔初期の接続抵抗の評価基準〕
○○：接続抵抗が２．０Ω以下
○：接続抵抗が２．０Ωを超え、３．０Ω以下
△：接続抵抗が３．０Ωを超え、５．０Ω以下
×：接続抵抗が５．０Ωを超える
[Evaluation criteria for initial connection resistance]
○○: Connection resistance is 2.0Ω or less ○: Connection resistance exceeds 2.0Ω, 3.0Ω or less △: Connection resistance exceeds 3.0Ω, 5.0Ω or less ×: Connection resistance exceeds 5.0Ω
（７）高温高湿試験後の接続抵抗
上記（６）初期の接続抵抗の評価で得られた接続構造体を、８５℃及び湿度８５％の条件で１００時間放置した。放置後の接続構造体の電極間の接続抵抗を四端子法により測定し、得られた測定値を高温高湿試験後の接続抵抗とした。また、高温高湿試験後の接続抵抗を下記の基準で判定した。
(7) Connection resistance after high-temperature and high-humidity test The connection structure obtained by the above (6) evaluation of the initial connection resistance was allowed to stand for 100 hours under the conditions of 85 ° C. and 85% humidity. The connection resistance between the electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measured value was used as the connection resistance after the high temperature and high humidity test. Moreover, the connection resistance after a high temperature, high humidity test was determined according to the following criteria.
〔高温高湿試験後の接続抵抗の評価基準〕
○○：接続抵抗が２．０Ω以下
○：接続抵抗が２．０Ωを超え、３．０Ω以下
△：接続抵抗が３．０Ωを超え、５．０Ω以下
×：接続抵抗が５．０Ωを超える
[Evaluation criteria for connection resistance after high temperature and high humidity test]
○○: Connection resistance is 2.0Ω or less ○: Connection resistance exceeds 2.0Ω, 3.0Ω or less △: Connection resistance exceeds 3.0Ω, 5.0Ω or less ×: Connection resistance exceeds 5.0Ω
（８）耐衝撃性
上記（６）初期の接続抵抗の評価で得られた接続構造体を高さ７０ｃｍの位置から落下させ、導通を確認することにより耐衝撃性の評価を行った。初期抵抗値からの抵抗値の上昇率が５０％以下の場合を「良好」、初期抵抗値からの抵抗値の上昇率が５０％を超える場合を「不良」と判定した。
(8) Impact resistance The impact resistance was evaluated by dropping the connection structure obtained in the above (6) evaluation of the initial connection resistance from a position having a height of 70 cm and confirming conduction. The case where the rate of increase in resistance value from the initial resistance value was 50% or less was determined as “good”, and the case where the rate of increase in resistance value from the initial resistance value exceeded 50% was determined as “bad”.
（９）圧痕の形成の有無
微分干渉顕微鏡を用いて、上記（６）の評価の接続構造体の作製で得られた接続構造体のガラス基板側から、ガラス基板に設けられた電極を観察し、導電性粒子が接触した電極の圧痕の形成の有無を下記の判定基準で評価した。なお、電極の圧痕の形成の有無について、電極面積が０．０２ｍｍ２となるように、微分干渉顕微鏡にて観察し、電極０．０２ｍｍ２あたりの圧痕の個数を算出した。任意の１０箇所を微分干渉顕微鏡にて観察し、電極０．０２ｍｍ２あたりの圧痕の個数の平均値を算出した。
(9) Presence or absence of formation of indentation Using a differential interference microscope, the electrodes provided on the glass substrate were observed from the glass substrate side of the connection structure obtained in the production of the connection structure evaluated in (6) above. The presence or absence of indentation of the electrode in contact with the conductive particles was evaluated according to the following criteria. In addition, the presence or absence of the formation of the impression of the electrode was observed with a differential interference microscope so that the electrode area was 0.02 mm 2, and the number of impressions per electrode of 0.02 mm 2 was calculated. Arbitrary ten places were observed with the differential interference microscope, and the average value of the number of impressions per electrode 0.02 mm 2 was calculated.
〔圧痕の形成の有無の判定基準〕
○○：電極０．０２ｍｍ２あたりの圧痕が２５個以上
○：電極０．０２ｍｍ２あたりの圧痕が２０個以上、２５個未満
△：電極０．０２ｍｍ２あたりの圧痕が５個以上、２０個未満
×：電極０．０２ｍｍ２あたりの圧痕が５個未満
[Criteria for the presence or absence of indentation]
○: 25 or more indentations per electrode 0.02 mm 2 ○: 20 or more indentations per electrode 0.02 mm 2 , less than 25 Δ: 5 or more indentations per electrode 0.02 mm 2 , 20 Less than x: Less than 5 impressions per electrode 0.02 mm 2
結果を下記の表１〜３に示す。下記の表１〜３において、５ｎｍの導電層部分は、導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分を示す。溶出したニッケルイオン濃度は、導電性粒子の単位表面積当たりの溶出したニッケルイオン濃度を示す。 The results are shown in Tables 1 to 3 below. In the following Tables 1 to 3, a 5 nm conductive layer portion indicates a conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction. The eluted nickel ion concentration indicates the eluted nickel ion concentration per unit surface area of the conductive particles.
１…導電性粒子
１ａ…突起
２…基材粒子
３…導電層
３ａ…突起
４…芯物質
５…絶縁物質
１１…導電性粒子
１１ａ…突起
１２…第２の導電層
１３…導電層
１３ａ…突起
２１…導電性粒子
２２…導電層
５１…接続構造体
５２…第１の接続対象部材
５２ａ…上面
５２ｂ…電極
５３…第２の接続対象部材
５３ａ…下面
５３ｂ…電極
５４…接続部
DESCRIPTION OF
Claims (11)
前記導電層は、前記基材粒子の表面上に配置されており、
前記導電層が、１層構造であり、
前記導電層の全体１００重量％中、ニッケルの含有量が６０重量％以上であり、
前記導電層の外表面から厚み方向に内側に向かって５ｎｍの厚みの導電層部分１００重量％中、タングステン及びモリブデンの合計の含有量が５重量％を超え、
前記導電層の厚み方向で、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の前記金属成分が偏在している、導電性粒子（但し、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含む導電層の内表面が、銅粒子に接している導電性粒子を除く、かつ、ニッケルと、タングステン及びモリブデンの内の少なくとも１種の金属成分とを含む導電層の内表面が、銅層に接している導電性粒子を除く）。 A conductive layer comprising base particles, nickel, and at least one metal component of tungsten and molybdenum;
The conductive layer is disposed on the surface of the base particle,
The conductive layer has a single layer structure,
In 100% by weight of the entire conductive layer, the nickel content is 60% by weight or more,
In 100 wt% of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer, the total content of tungsten and molybdenum exceeds 5 wt% ,
Conductive particles in which at least one metal component of nickel and tungsten and molybdenum is unevenly distributed in the thickness direction of the conductive layer (however, at least one metal of nickel, tungsten and molybdenum) The inner surface of the conductive layer containing the component excludes the conductive particles in contact with the copper particles, and the inner surface of the conductive layer containing nickel and at least one metal component of tungsten and molybdenum, Excluding conductive particles in contact with the copper layer).
前記導電層が前記還元剤に由来する成分を含まないか、又は前記還元剤に由来する成分を含みかつ前記導電層の全体１００重量％中の前記還元剤に由来する成分の含有量が５重量％以下である、請求項１〜４のいずれか１項に記載の導電性粒子。 The conductive layer is formed by electroless nickel plating using a reducing agent,
The conductive layer does not contain a component derived from the reducing agent, or contains a component derived from the reducing agent, and the content of the component derived from the reducing agent in 100% by weight of the whole conductive layer is 5%. The electroconductive particle of any one of Claims 1-4 which is% or less.
前記接続部が、請求項１〜９のいずれか１項に記載の導電性粒子により形成されているか、又は該導電性粒子とバインダー樹脂とを含む導電材料により形成されている、接続構造体。 A first connection target member, a second connection target member, and a connection part connecting the first and second connection target members;
A connection structure in which the connection part is formed of the conductive particles according to any one of claims 1 to 9, or is formed of a conductive material including the conductive particles and a binder resin.
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| CN102474025B (en) * | 2010-01-08 | 2014-05-07 | 日立化成株式会社 | Circuit connecting adhesion film and circuit connecting structure |
| WO2011108342A1 (en) * | 2010-03-01 | 2011-09-09 | 新日鐵化学株式会社 | Metal nanoparticle composite and process for production thereof |
| JP5534891B2 (en) * | 2010-03-26 | 2014-07-02 | 積水化学工業株式会社 | Conductive particle, method for producing conductive particle, anisotropic conductive material, and connection structure |
| JP2012164454A (en) * | 2011-02-04 | 2012-08-30 | Sony Chemical & Information Device Corp | Conductive particle and anisotropic conductive material using the same |
| CN103650063B (en) * | 2011-07-28 | 2016-01-20 | 积水化学工业株式会社 | Electroconductive particle, electric conducting material and connection structural bodies |
| JP5952553B2 (en) * | 2011-12-14 | 2016-07-13 | 株式会社日本触媒 | Conductive fine particles and anisotropic conductive material containing the same |
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| CN103748635B (en) | 2016-08-31 |
| JP2013232408A (en) | 2013-11-14 |
| CN103748635A (en) | 2014-04-23 |
| JP6004983B2 (en) | 2016-10-12 |
| TWI553658B (en) | 2016-10-11 |
| JP5297569B1 (en) | 2013-09-25 |
| WO2013094637A1 (en) | 2013-06-27 |
| KR101941721B1 (en) | 2019-01-23 |
| TW201337951A (en) | 2013-09-16 |
| JP2016219438A (en) | 2016-12-22 |
| KR20140106385A (en) | 2014-09-03 |
| JPWO2013094637A1 (en) | 2015-04-27 |
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