JP5887305B2 - 電磁波シールド用金属箔、電磁波シールド材、及びシールドケーブル - Google Patents
電磁波シールド用金属箔、電磁波シールド材、及びシールドケーブル Download PDFInfo
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- JP5887305B2 JP5887305B2 JP2013140287A JP2013140287A JP5887305B2 JP 5887305 B2 JP5887305 B2 JP 5887305B2 JP 2013140287 A JP2013140287 A JP 2013140287A JP 2013140287 A JP2013140287 A JP 2013140287A JP 5887305 B2 JP5887305 B2 JP 5887305B2
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- Prior art keywords
- alloy layer
- layer
- metal foil
- electromagnetic wave
- wave shielding
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- 239000000463 material Substances 0.000 title claims description 50
- 239000011888 foil Substances 0.000 title claims description 46
- 229910052751 metal Inorganic materials 0.000 title claims description 42
- 239000002184 metal Substances 0.000 title claims description 42
- 229910045601 alloy Inorganic materials 0.000 claims description 114
- 239000000956 alloy Substances 0.000 claims description 114
- 239000010949 copper Substances 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000010944 silver (metal) Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 152
- 238000007747 plating Methods 0.000 description 50
- 238000005260 corrosion Methods 0.000 description 34
- 230000007797 corrosion Effects 0.000 description 34
- 239000011135 tin Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 22
- 239000010408 film Substances 0.000 description 19
- 239000011889 copper foil Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018100 Ni-Sn Inorganic materials 0.000 description 3
- 229910018532 Ni—Sn Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011104 metalized film Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910019043 CoSn Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910005382 FeSn Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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Description
上記の複合材料としては、銅又は銅合金箔からなる基材の一方の面に樹脂層又はフィルムを積層し、他の面にSnめっき被膜を形成した構造が用いられている(特許文献1参照)。
又、プラズマディスプレイ用の電磁波シールド体として、銅箔の回路を透明基材上に形成し、銅箔の表示画面側の面に錫とニッケルとモリブデンとからなる合金めっきを施すことで、反射率を低減した技術が報告されている(特許文献2参照)。
本発明は上記課題を解決するためになされたものであり、従来のSnめっきよりも耐食性、耐熱性に優れた電磁波シールド用金属箔、電磁波シールド材、及びシールドケーブルの提供を目的とする。
前記合金層がさらに、P、Wの群から選ばれる1種以上のC元素群を含み、前記合金層全体に対する前記C元素群の合計含有率が40質量%以下であることが好ましい。
前記合金層に含まれるCu、Al及びZnの合計含有率が10質量%以下であることが好ましい。
前記合金層の表面に、酸化物が形成されていることが好ましい。
前記基材が金、銀、白金、ステンレス、鉄、ニッケル、亜鉛、銅、銅合金、アルミニウム、又はアルミニウム合金からなることが好ましい。
前記基材がアルミニウムまたはアルミニウム合金であって、前記基材と前記下地層の間に、Zn層が形成されていることが好ましい。
前記樹脂層は樹脂フィルムであることが好ましい。
(基材)
基材1は、電磁波シールド効果を発揮する導電性の高い金属であればなんでもよい。基材1としては金、銀、白金、ステンレス、鉄、ニッケル、亜鉛、銅、銅合金、アルミニウム、又はアルミニウム合金などの箔が挙げられるが、銅又はアルミニウムの箔が一般的である。
基材1の形成方法は特に限定されず、例えば圧延して製造してもよく、電気めっきで箔を形成してもよい。また、後述する電磁波シールド材の樹脂層又は樹脂フィルムの表面に、乾式めっきして基材1を成膜してもよい。
基材1の厚みを4μmを超えたものとする。基材1の厚みが4μm以下であると数十MHzの低周波に対するシールド性能が劣ると共に、圧延や電解で基材1を製造しにくく、さらにハンドリング性に劣る。基材1の厚みは好ましくは5〜100μm、より好ましくは6〜50μmである。基材1の厚みが100μmより厚くなると柔軟性が劣り、後工程で加工しにくくなると共に、原料コストも増加する場合がある。
圧延銅箔としては、純度99.9%以上の無酸素銅(JIS-H3100(C1020))又はタフピッチ銅(JIS-H3100(C1100))を用いることができる。又、銅合金箔としては要求される強度や導電性に応じて公知の銅合金を用いることができる。公知の銅合金としては、例えば、0.01〜0.3%の錫入り銅合金や0.01〜0.05%の銀入り銅合金が挙げられ、特に、導電性に優れたものとしてCu-0.12%Sn、Cu-0.02%Agがよく用いられる。例えば、圧延銅箔として導電率が5%以上のものを用いることができる。電解銅箔としては、公知のものを用いることができる。
又、アルミニウム箔としては、純度99.0%以上のアルミニウム箔を用いることができる。又、アルミニウム合金箔としては、要求される強度や導電率に応じて公知のアルミニウム合金を用いることができる。公知のアルミニウム合金としては、例えば、0.01〜0.15%のSiと0.01〜1.0%のFe入りのアルミニウム合金、1.0〜1.5%のMn入りアルミニウム合金が挙げられる。
合金層2は、SnからなるA元素と、Ag、Ni、Fe及びCoの群から選ばれる1種以上のB元素群とからなる。
Snめっき被膜は耐食性に優れるとされているが、NOXやSOXといった腐食ガスに対する耐性が必ずしも高くない。
そこで、純Snの代わりに、Snと、所定の元素とからなる合金層2を形成することで、耐食性、耐熱性を向上させることができる。
合金層2は金属間化合物であることが好ましい。金属間化合物としては例えばAg3Sn、Ni3Sn4、FeSn2、CoSnなどが挙げられる。金属間化合物は非平衡合金層と比較して耐食性が良好である。
下地層3はB元素群からなる。下地層3は基材1から合金層2に基材の構成元素が拡散するのを防止するので、高温環境に曝されても接触抵抗が増加し難くなる。たとえば基材に銅箔を使用した場合、合金層2にCuが拡散すると、大気により合金層2中のCuが酸化され、接触抵抗が増加する。また、基材にアルミニウム箔を使用した場合、基材上に合金層2をめっきしようとすると、基材上にまずZnを置換めっきする必要がある。このため、Znめっき層からZnが合金層2に拡散する。この場合、塩水に対する耐食性が低下する。また、大気により合金層2中のZnが酸化され、接触抵抗が増加する。そこで、Znめっき層と合金層2の間に下地層3を設け、Znの拡散を防止する。
すなわち、基材1がCu、Al、Znを含む場合(例えば、基材1が銅箔の場合)、下地層3を形成することにより基材1から合金層2に拡散するCu、Al、Znの量を低減することができる。
下地層3は、B元素群とC元素群とからなる合金層から構成されていてもよい。
上記A元素の総付着量が10〜300μmol/dm2であり、20〜200μmol/dm2であることが好ましく、30〜90μmol/dm2であることがさらに好ましい。
A元素の総付着量が10μmol/dm2未満であると、合金層2が十分に形成されず、合金層2の耐食性が低下する。一方、A元素の総付着量が300μmol/dm2を超えると、電磁波シールド材が例えば自動車用ケーブル等に用いられたときに、製造工程や自動車への組み付け時に屈曲などの変形が加わって合金層2表面にクラックを生じ、耐食性が低下する。また、コストアップに繋がる。
B元素群の総付着量が40μmol/dm2未満であると、合金層2が十分に形成されず、合金層2の耐食性が低下する。B元素群の総付着量が900μmol/dm2を超えると、屈曲などの変形が加わった時に下地層3にクラックを生じ、耐食性が低下する。また、コストアップに繋がる。
酸化物は、層となっていなくてもよく、合金層2の表面に存在すればよいが、1〜50nm、より好ましくは3〜30nm、さらに好ましくは5〜20nmの厚みとするのがよい。酸化物は合金層2と比較すると接触抵抗が高いため、層の厚みが50nmを超えると接触抵抗が増加する。
合金層2は、合金めっき(湿式めっき)、合金層を構成する合金のターゲットを用いたスパッタ、合金層を構成する成分を用いた蒸着等によって形成することができる。
又、図1(a)に示すように、例えば、基材1の片面にまずB元素群からなる第1めっき層21を形成し、第1めっき層21の表面にA元素からなる第2めっき層22を形成した後、熱処理して第1めっき層21の元素を第2めっき層22中に拡散させ、図1(b)に示す合金層2を形成することもできる。この際、第1めっき層21の厚みを厚くし、熱処理後に第1めっき層21の一部を下地層3として残存させる。又、図1(a)に示すように、加熱により合金層2を形成する場合、第2めっき層22を形成したときに自然酸化で酸化物が第2めっき層22上に形成され、その後の加熱による合金化によっても合金層2表面に酸化物が残存する。この酸化物は、耐食性といった特性を向上させる効果がある。
熱処理が不十分であると金属間化合物が形成されず、A元素とB元素の濃度が厚み方向に段階的に変化した非平衡合金層が形成される。
勿論、基材1の表面に、熱処理せずに直接下地層3、合金層2をこの順にめっき等で形成してもよい。又、下地層3、合金層2は、湿式めっきの他、蒸着、PVD、CVD等によって形成することもできる。
なお、C元素群は、合金層2を形成する際に合金層2自体に含有させてもよい。又、下地層3にC元素群を含ませ、下地層3の表面に合金層2を形成した後、熱処理でC元素群を合金層2中に拡散させてもよい。
樹脂層としては例えばポリイミド等の樹脂を用いることができ、樹脂フィルムとしては例えばPET(ポリエチレンテレフタラート)、PEN(ポリエチレンナフタレート)のフィルムを用いることができる。樹脂層や樹脂フィルムは、接着剤により金属箔に接着されてもよいが、接着剤を用いずに溶融樹脂を金属箔上にキャスティングしたり、フィルムを金属箔に熱圧着させてもよい。また、樹脂フィルムにPVDやCVDで直接銅やアルミニウムの層を基材として形成したフィルムや、樹脂フィルムにPVDやCVDで銅やアルミニウムの薄い層を導電層として形成した後、この導電層上に湿式めっきで金属層を厚く形成したメタライズドフィルムを用いてもよい。
樹脂層や樹脂フィルムとしては公知のものを用いることができる。樹脂層や樹脂フィルムの厚みは特に制限されないが、例えば1〜100μm、より好ましくは3〜50μmのものを好適に用いることができる。又、接着剤を用いた場合、接着層の厚みは例えば10μm以下とすることができる。
材料の軽薄化の観点から、電磁波シールド材100の厚みは1.0mm以下、より好ましくは0.01〜0.5mmであることが好ましい。
(基材)
圧延銅箔としては、所定の厚さに調整した圧延銅箔(JX日鉱日石金属製の型番C1100)を用いた。
電解銅箔としては、厚さ8μmの無粗化処理の電解銅箔(JX日鉱日石金属製の型番JTC箔)を用いた。
Cuメタライズドフィルムとしては、厚さ8μmのメタライジングCCL(日鉱金属製の製品名「マキナス」)を用いた。
アルミニウム箔としては、厚さ12μmのアルミニウム箔(サン・アルミニウム工業社製)を用いた。
Alメタライズドフィルムとしては、厚さ12μmのPETフィルム(東洋紡績社製)に真空蒸着でアルミニウムを6μm形成したものを用いた。
合金層を、上記基材の片面に形成した。表1に、合金層の形成方法を示す。
表1において「めっき」とは、図1(a)に示す方法で第1めっき層21、第2めっき層22をこの順でめっきした後、表1に示す条件で熱処理したものである。表1において「合金めっき」は、基材上にめっきにより下地層を形成した後、合金めっきにより合金層を下地層の表面に形成したものである。
なお、Ni、Sn、Ag、Co、Fe、Cu、Zn、各種Ni合金の各めっきは、以下の条件で形成した。
Snめっき:フェノールスルホン酸Sn浴(Sn濃度:40g/L、電流密度:2〜10A/dm2)
Agめっき:シアン化Ag浴(Ag濃度:10g/L、電流密度:0.2〜4A/dm2)
Coめっき:シアン化Ag浴(Co濃度:20g/L、電流密度:1〜8A/dm2)
Feめっき:硫酸Fe浴(Fe濃度:20g/L、電流密度:2〜10A/dm2)
Cuめっき:硫酸Cu浴(Cu濃度:20g/L、電流密度:2〜10A/dm2)
Znめっき:硫酸Zn浴(Zn濃度:20g/L、電流密度:1〜5A/dm2)
Ni−Snめっき:ピロリン酸塩浴(Ni濃度10g/L、Sn濃度10g/L、電流密度:0.1〜2A/dm2)
Ni−Pめっき:硫酸浴(Ni濃度:20g/L、P濃度:20g/L、電流密度:2〜4A/dm2)
Ni−Wめっき:硫酸浴(Ni濃度:20g/L、W濃度:20g/L、電流密度:0.1〜2A/dm2)
Ni−Feめっき:硫酸浴(Ni濃度:20g/L、Fe濃度:10g/L、電流密度:0.1〜2A/dm2)
Ni−Coめっき:硫酸浴(Ni濃度:20g/L、Co濃度:10g/L、電流密度:0.1〜2A/dm2)
表1において「合金スパッタ」は、基材上にNiをスパッタして下地層を形成した後、対応する合金のターゲット材を用いてスパッタして合金層を形成したものである。なお、合金スパッタで成膜される層は合金層そのものの組成であるので、熱処理は行わなかった。
なお、スパッタ、合金スパッタは以下の条件で行った。
スパッタ装置:バッチ式スパッタリング装置(アルバック社、型式MNS−6000)
スパッタ条件:到達真空度1.0×10-5Pa、スパッタリング圧0.2Pa、スパッタリング電力:50W
ターゲット:Ni(純度3N)、Sn(純度3N)、Ni−Sn(Ni:Sn=30:70質量%)
蒸着装置:真空蒸着装置(アルバック社、型式MB05−1006)
蒸着条件:到達真空度5.0×10-3Pa、電子ビーム加速電圧6kV
蒸着源:Ni(純度3N)、In(純度3N)、Sn(純度3N)
得られた電磁波シールド用金属箔を50mm×50mmに切り出し、表面の皮膜をHNO3(2重量%)とHCl(5重量%)を混合した溶液に溶解した。そして、溶液中の金属濃度をICP発光分光分析装置(エスアイアイ・ナノテクノロジー株式会社製、SFC−3100)にて定量し、単位面積当たりの金属重量から付着量(μmol/dm2)を算出した。
得られた電磁波シールド用金属箔について、STEM(走査透過型電子顕微鏡、日本電子株式会社製JEM−2100F)による線分析を行い、層構成を判定した。分析した指定元素は、A元素、B元素群、C元素群、C、S及びOである。また、上記した指定元素の合計を100%として、各元素の濃度(質量%)を分析した(加速電圧:200kV、測定間隔:2nm)。
A元素の合計量及びB元素群の合計量を、それぞれ5質量%以上含む層を合金層2とした。例えば、B元素が2元素を含む場合、各元素の合計値を採用する。
合金層2よりも表層側に位置し、A元素の合計を5質量%以上含むと共に、Oが5質量%以上である層を酸化物とし、合金層2よりも下層側に位置し、B元素群の元素の合計を5質量%以上含むと共に、A元素の合計が5質量%未満の層を下地層3とした。
上記定義による合金層2におけるCu、Al、Zn、およびC元素の割合の平均値をCu、Al、ZnおよびC元素の含有率とした。
(耐熱性)
又、得られた電磁波シールド用金属箔の合金層側の面について、それぞれ120℃で500時間大気加熱後、合金層側の最表面の接触抵抗を測定した。
接触抵抗の測定は山崎精機株式会社製の電気接点シミュレーターCRS−1を使用して四端子法で測定した。プローブ:金プローブ、接触荷重:20gf、バイアス電流:10mA、摺動距離:1mm
◎:接触抵抗が20mΩ未満
○:接触抵抗が20mΩ以上100mΩ未満
×:接触抵抗が100mΩ以上
大気加熱後の接触抵抗の評価が◎又は○であれば、耐熱性が良好といえる。
又、得られた電磁波シールド用金属箔の合金層側の面について、大気加熱せずに耐食性試験(塩水噴霧試験、及びガス腐食試験)を行ったのち、合金層側の最表面の接触抵抗を測定した。
接触抵抗の測定は上記耐熱性の試験と同様とした。
塩水噴霧試験は、JIS−Z2371(温度:35℃、塩水成分:塩化ナトリウム、塩水濃度:5質量%、噴霧圧力:98±10kPa、噴霧時間:48h)に従った。
◎:接触抵抗が20mΩ未満
○:接触抵抗が20mΩ以上100mΩ未満
×:接触抵抗が100mΩ以上
◎:接触抵抗が20mΩ未満
○:接触抵抗が20mΩ以上100mΩ未満
×:接触抵抗が100mΩ以上
塩水噴霧試験、及びガス腐食試験の評価が◎又は○であれば、耐食性が良好といえる。
又、得られた電磁波シールド用金属箔の電磁波シールド効果を、測定周波数50〜1000MHzの範囲で、KEC(関西電子工業振興センター)法で行った。KEC法は、装置内に試料が存在しない状態を基準とし、装置内に試料を挿入した時の減衰量(電磁波シールド効果)をデシベル表示で評価する方法であり、値が大きいほど電磁波シールド効果が優れている。
信号発生器:SIGNAL GENERATOR SML02(ROHDE&SCHWARZ社製)
スペクトラムアナライザー:R3132 SPECTRUM ANALYZER(ADVANTEST社製)
各試料につき、上記KEC法で3回ずつ測定し、その値を平均化したものを、以下の基準で判定した。電磁波シールド効果の評価が○又は△であれば実用上、問題はない。
○:減衰量が80dBを超える
△:減衰量が40dBを超え、80dB以下
×:減衰量が40dB未満
特に、A元素の融点以下の温度で熱処理をして合金層を形成した実施例1〜5、7〜15、18、20〜23の場合、熱処理をしなかった実施例6、16、17、19および融点以上の温度で熱処理した実施例24に比べて耐食性がさらに優れていた。これは後述するように合金層が金属間化合物であるためである。
なお、図3、4は、それぞれ実施例4の試料のSTEMによる断面像、及びSTEMによる線分析の結果を示す。断面像におけるX層、Y層は、線分析の結果から、それぞれNi−Sn合金層、Ni層であることがわかる。
又、TEM(日本電子社製、JEM−2100F)により、各実施例及び比較例の合金層の電子回折パターンを解析した結果、実施例1〜5、7〜15、18、20〜23、比較例1、3、5、9の合金層はいずれも金属間化合物であることが確認された。
A元素の総付着量が10μmol/dm2未満である比較例2の場合、耐熱性、耐食性が劣った。
B元素群の付着量が40μmol/dm2未満である比較例4の場合、耐熱性、耐食性が劣った。
B元素群の付着量が900μmol/dm2を超えた比較例5の場合、合金層にクラックが発生したため、耐熱性、耐食性が劣った。
下地層3を形成しなかった比較例6の場合、めっき後の熱処理で基材のCuが合金層に拡散し、合金層中のCu濃度が10%を超えたため、耐熱性、耐食性が劣った。
A元素の融点を超える温度で熱処理をした比較例7の場合、局所的に合金化が過度に進行したため、もともと下地層となる図1の層21の一部が下地層3として残存せず、合金層の一部が基材上に直接形成された。このため、熱処理時に基材のCuが合金層中に拡散し、合金層中のCu濃度が10%を超えたため、耐熱性、耐食性が劣った。
下地層3を形成しなかった比較例8の場合、耐熱試験後に基材のCuが合金層に拡散したため、耐熱性が劣った。但し、比較例8の場合、合金層形成時に熱処理をしなかったために合金層にCuは拡散せず、合金層中のCu濃度は10%未満であったため、耐食性は良好であった。
基材の厚さが4μm以下である比較例9例の場合、電磁波シールド効果が劣った。
B元素群の代わりにCuを用いた比較例10の場合、耐熱性、耐食性が劣った。
A元素の代わりにZnを用いた比較例11の場合、耐熱性、耐食性が劣った。
2 合金層
3 下地層
4 樹脂層又は樹脂フィルム
10 電磁波シールド用金属箔
100 電磁波シールド材
Claims (10)
- 厚み4μmを超える金属箔からなる基材の片面又は両面に、SnからなるA元素と、Ag、Ni、Fe、及びCoの群から選ばれる1種以上のB元素群とからなる合金層が形成され、前記合金層と前記基材の間に前記B元素群からなる下地層が形成され、
前記基材の片面の前記A元素の付着量が10〜300μmol/dm2、かつ前記B元素群の総付着量が40〜900μmol/dm2であり、
前記合金層の表面に前記A元素群からなる金属層が存在せず、かつ前記合金層をSEMで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径0.1〜2.0μmの複数の針状又は柱状の突起を有しない電磁波シールド用金属箔。 - 前記合金層が金属間化合物である請求項1に記載の電磁波シールド用金属箔。
- 前記合金層がさらに、P、Wの群から選ばれる1種以上のC元素群を含み、
前記合金層全体に対する前記C元素群の合計含有率が40質量%以下である請求項1又は2に記載の電磁波シールド用金属箔。 - 前記合金層に含まれるCu、Al及びZnの合計含有率が10質量%以下である請求項1〜3のいずれかに記載の電磁波シールド用金属箔。
- 前記合金層の表面に、酸化物が形成されている請求項1〜4のいずれかに記載の電磁波シールド用金属箔。
- 前記基材が金、銀、白金、ステンレス、鉄、ニッケル、亜鉛、銅、銅合金、アルミニウム、又はアルミニウム合金からなる請求項1〜5のいずれかに記載の電磁波シールド用金属箔。
- 前記基材がアルミニウムまたはアルミニウム合金であって、前記基材と前記下地層の間に、Zn層が形成されている請求項1〜6のいずれかに記載の電磁波シールド用金属箔。
- 請求項1〜7のいずれかに記載の電磁波シールド用金属箔の片面に、樹脂層が積層されている電磁波シールド材。
- 前記樹脂層は樹脂フィルムであることを特徴とする請求項8に記載の電磁波シールド材。
- 請求項8又は9に記載の電磁波シールド材でシールドされたシールドケーブル。
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CN201480035687.0A CN105309061B (zh) | 2013-07-04 | 2014-06-30 | 电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆 |
US14/902,198 US10842058B2 (en) | 2013-07-04 | 2014-06-30 | Metal foil for electromagnetic shielding, electromagnetic shielding material, and shielding cable |
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