CN1681373A - 层叠板用铜合金箔 - Google Patents
层叠板用铜合金箔 Download PDFInfo
- Publication number
- CN1681373A CN1681373A CNA2005100726067A CN200510072606A CN1681373A CN 1681373 A CN1681373 A CN 1681373A CN A2005100726067 A CNA2005100726067 A CN A2005100726067A CN 200510072606 A CN200510072606 A CN 200510072606A CN 1681373 A CN1681373 A CN 1681373A
- Authority
- CN
- China
- Prior art keywords
- copper
- copper alloy
- alloy foil
- quality
- tunicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 64
- 239000011888 foil Substances 0.000 title claims abstract description 63
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 72
- 239000010949 copper Substances 0.000 claims description 38
- 239000011889 copper foil Substances 0.000 claims description 38
- 239000004922 lacquer Substances 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 abstract description 44
- 239000004642 Polyimide Substances 0.000 abstract description 36
- 239000000758 substrate Substances 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000003746 surface roughness Effects 0.000 abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002966 varnish Substances 0.000 abstract description 4
- 238000007788 roughening Methods 0.000 abstract 2
- 230000003449 preventive effect Effects 0.000 abstract 1
- 239000004020 conductor Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000005266 casting Methods 0.000 description 17
- 239000010936 titanium Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011133 lead Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 229910052738 indium Inorganic materials 0.000 description 10
- 239000011120 plywood Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 230000037303 wrinkles Effects 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
- Y10T428/12507—More than two components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12882—Cu-base component alternative to Ag-, Au-, or Ni-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12896—Ag-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
本发明提供一种在以含聚酰胺酸的漆作为原料而形成树脂基板的双层印刷电路布线板上,与漆的润湿性良好、不进行粗糙化处理而可直接与聚酰亚胺接合的、表面粗糙度小的层叠板用的铜合金箔。提供这样一种层叠板用的铜合金箔,即含有特定元素的铜合金,将防锈被膜的厚度设为从表面起为5nm以下,则与漆的润湿性良好,强度和导电性优良,并且在不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后形成的被膜的180度剥离强度为8.0N/cm以上。
Description
技术领域
本发明涉及用于印刷电路布线板用的层叠板的铜合金箔。
背景技术
在电子设备的电子电路上大多使用印刷电路布线板。
印刷电路布线板根据成为基体材料的树脂的种类,大体分为硬质层叠板(硬的基板)和挠性层叠板(挠性基板)。挠性基板以具有挠性为特征,除了用于可动部的布线以外,还可在电子设备内的弯曲状态收放,故也可以用作节省空间的布线材料。另外,由于基板自身薄,故也可作为半导体组件的插入式选择指用途或液晶显示器的IC磁带载体使用。挠性基板上成为基体材料的树脂大多使用聚酰亚胺,关于导电材料,从导电性出发一般使用铜。挠性基板根据其构成有三层挠性基板和双层挠性基板。三层挠性基板是用环氧树脂和丙烯树脂等粘结剂将聚酰亚胺等树脂薄膜和成为导电材料的铜箔粘合而成的。另外,双层挠性基板是将聚酰亚胺等树脂和成为导电材料的铜直接接合而成的。
印刷电路布线板是将包铜层叠板的铜箔腐蚀而形成各种布线图形的,用软钎料将电子部件连接起来进行装配,但印刷电路布线板用的材料反复经受这种高温条件,故要求具有耐热性。近年来,从对环境的影响考虑,广泛使用铅游离软钎料,但与以往的铅软钎料相比,熔点高,故对挠性基板的耐热性要求更加严格。因此,双层挠性基板的有机材料只使用耐热性良好的聚酰亚胺,故与用耐热性差的环氧树脂和丙烯树脂等粘结剂的三层挠性基板相比更容易提高耐热性,其使用量增加。
将聚酰亚胺树脂作为基体材料的双层挠性基板的主要制造方法有:①金属喷镀法,②层叠法,③铸造法。①的金属喷镀法是用阴极真空喷镀法等将Cr等金属薄薄地蒸镀在聚酰亚胺薄膜上,再用阴极真空喷镀法或镀层法等将成为印刷电路布线板的导电材料的铜形成必要的厚度的方法,不使用铜箔。②的层叠法是将成为印刷电路布线板的导电材料的铜箔直接层叠在聚酰亚胺薄膜上的方法。③的铸造法是将成为基体材料的聚酰亚胺树脂的先身即含聚酰胺(ポリアミツク)酸的清漆涂敷在成为印刷电路布线板的导电材料的铜箔上面、通过加热硬化而形成的聚酰亚胺被膜作为树脂基板的方法。
近年来,随着电子设备的小型化、轻量化、高功能化,对于印刷电路布线板高密度装配的要求提高,向缩小电子电路的布线宽度和布线间隔的微小间距方向发展。若导电材料使用表面粗糙度大的铜箔或通过粗糙化处理形成凹凸形状的铜箔,则在以腐蚀方式形成电路时,产生铜残留在树脂中的腐蚀残留,或腐蚀直线性降低,容易使电路宽度不均匀。因此,为了使电子电路微小间距化,铜箔的表面粗糙度小比较理想。另外,在个人计算机和移动通信等电子设备上,电信号高频率化,但若电信号的频率为1GHz以上,则电流只在导体表面流动的集肤效应的影响显著,不能无视因表面凹凸使传送路线变化的影响。因此,尝试了像金属喷镀法那样在平滑的聚酰亚胺薄膜上形成金属膜、使层叠法和铸造法所用的铜箔的表面粗糙度减小。
但是,成为印刷电路布线板的导电材料的铜箔,按其制造方法的不同分为电解铜箔和轧制铜箔。电解铜箔是从硫酸铜电镀液中将铜电解析出到钛和不锈钢滚筒上制成的,在电镀液中加入添加剂或调节电解析出条件,可以制造表面粗糙度小的铜箔,所谓表面平整箔。轧制铜箔是用轧辊进行塑性加工制造的,故可以得到轧辊的表面形状复印在箔表面上的平滑表面。所谓箔,一般系指厚度为100μm以下的薄板。
为了改善用于印刷电路布线板的铜箔与树脂的粘结性,进行在表面上电镀铜粒子而形成铜箔的粗糙化处理。这是通过铜箔的表面形成凹凸、使铜箔深入树脂、而获得机械性粘结强度的所谓固定效果来改善粘结性的,但根据上述原因,不进行粗糙化处理的表面粗糙度小的铜箔与树脂薄膜粘合在一起比较理想,在不进行粗糙化处理的情况下,必须确保粘结强度。三层挠性基板,为了改善金属即铜箔与有机物即粘结剂的粘结强度,尝试了在铜箔上涂敷有机硅烷偶合剂等。但是,双层挠性基板的制造温度为300℃~400℃,比三层挠性基板的100℃~200℃要高,故容易引起偶合剂的热分解,不能改善粘结性。
作为导电材料用的铜箔的原材料,采用纯铜和含有少量添加元素的铜合金。随着电子电路的微小间距化,作为导体的铜箔变薄,并且电路宽度变窄,故对铜箔的特性要求是直流电阻损失小,导电率高。铜是导电性优良的材料,在重视导电性的上述领域,一般采用纯度99.9%以上的纯铜。但是,提高铜的纯度,其强度降低,故铜箔薄时,搬运性差,因此最好铜箔的强度大。另外,双层挠性基板,像铸造法那样由聚酰胺酸合成聚酰亚胺时在300℃~400℃高温下,必须进行10分钟至1小时左右的加热处理,使铜箔软化,搬运性差,因此,最好通过在300℃温度下加热处理1小时左右就不会软化。
在这种状况下,试验了用铸造法制作将聚酰亚胺树脂作为基体材料的双层挠性基板。不是在铜合金箔上粘结聚酰亚胺薄膜,而是将聚酰亚胺的前身即含聚酰胺酸的漆涂敷在铜合金箔上,然后进行加热硬化,形成聚酰亚胺被膜。结果表明,根据铜合金箔的表面状态的不同,有时与含有聚酰胺酸的漆的润湿性差,产生漆的附着量不均的现象,难以使加热硬化后的聚酰亚胺被膜厚度均匀。
发明内容
提供一种层叠板用的铜合金箔,在用铸造法制造以聚酰亚胺为基体材料的双层印刷电路布线板时,改善铜合金箔与含有聚酰胺酸的漆的润湿性,消除漆附着量的不均匀现象,可使加热硬化后的聚酰亚胺被膜厚度均匀,并且在不进行粗糙化处理之类的特别处理的情况下,可获得180°剥离强度为8.0N/cm以上的粘接强度,这种铜合金箔的强度高且搬运性优艮。
本发明者们对于在铜合金箔上涂敷含有聚酰胺酸的漆时产生漆附着量不均的原因进行了调查,结果发现,其原因在于铜合金箔与漆的润湿性差,润湿性差的原因是为防止铜合金箔变色而涂敷的防锈被膜。在纯铜和铜合金的变色防止剂中大多使用苯并三唑和咪唑等有机物,通过限制这些防锈被膜的厚度,来改善与含有聚酰胺酸的漆的润湿性,可以使加热硬化后的聚酰亚胺被膜厚度均匀。另外,还发现,与以聚酰胺酸作为原料时的聚酰亚胺的粘接性,利用以导电性优良的纯铜作为基础、加入少量的添加元素的铜合金,可以得到改善,即使不进行粗糙化处理,也可与将聚酰胺酸进行热硬化后的被膜具有充分的粘接强度。具体地说,关于各种添加元素对防锈被膜与聚酰胺酸的润湿性和与将该酸加热硬化后的聚酰亚胺的粘接性等的影响反复进行研究的结果,得到本发明:
(1)层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Ag 0.02质量%~1.0质量%、In 0.01质量%~0.5质量%各成分中的一种以上,其余部分由铜及不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则导电率为80%IACS以上,与含有聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后形成的被膜的180度剥离强度为8.0N/cm以上。
(2)层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Ag 0.02质量%~1.0质量%、In 0.01质量%~0.5质量%各成分中的一种以上,还含有Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti和Zn各成分中的一种以上,总量为0.005~2.5质量%,其余部分由铜和不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则抗拉强度为500N/mm2以上,导电率为60%IACS以上,与含有聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后形成的被膜的180度剥离强度为8.0N/cm以上。
(3)层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Sn 0.01质量%~0.5质量%,其余部分由铜和不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则导电率为70%IACS以上,与含聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后而形成的被膜的180度剥离强度为8.0N/cm以上。
(4)层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Sn 0.01质量%~0.5质量%,还含有Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti和Zn各成分中的一种以上,总量为0.005质量%~2.5质量%,其余部分由铜和不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则抗拉强度为500N/mm2以上,导电率为60%IACS以上,与含聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后形成的被膜的180度剥离强度为8.0N/cm以上。
(5)(1)~(4)所记载的层叠板用铜合金箔,其特征在于,加热1小时后的抗拉强度成为加热前的抗拉强度与软化后的抗拉强度的中间值时的温度为300℃以上。
本发明的铜合金箔用于以聚酰亚胺作为基体材料的印刷电路布线板用的层叠板时,即使表面粗糙度小,与树脂也具有良好的粘接性,而且具有高的导电性,该聚酰亚胺是以含聚酰胺酸的漆为原料进行加热硬化后形成的。另外,由于强度大,箔的搬运性良好。因此,很适合于作为需要微细布线的电子电路的导电材料的用途。
发明的实施形式
对在本发明中上述限定表面状态和合金成分的原因进行说明。
(1)防锈被膜:纯铜和铜合金的防止变色用苯并三唑和咪唑等含有氮的有机物,在表面上形成与铜的螯合物而成为防锈被膜,这种方法已被广泛采用。另一方面,这些防锈被膜有防水性,还有这样的作用,即,使含聚酰胺酸的漆与不调和的液体的润湿性变差。因此,对防锈被膜的厚度限制为从表面起5nm以下,可以使漆的涂敷厚度均匀,对聚酰胺酸进行加热,通过聚酰亚胺化反应得到的聚酰亚胺的厚度波动可以减小。为了减小防锈被膜的厚度,例如有降低防锈剂浓度的方法,防锈剂采用苯并三唑的情况下,其浓度为5000ppm以下比较理想。防锈被膜从表面起的厚度,通过俄歇电子光谱分析进行测定可以定量化。即,通过俄歇电子光谱分析,对深度方向进行分析,构成防锈剂的元素即氮的检测强度是通过测定从表面直至与本底相同为止的深度、按SiO2换算求出的。
(2)Ag、In、Sn:众所周知,Ag、In在制造树脂时作为促进聚合的催化剂而起作用。因此,添加在铜中成为合金箔,便可促进金属与聚酰亚胺树脂的结合,强化了界面的结合。若Ag、In的添加量过少,则不能充分起到催化剂的作用,故金属与树脂的结合不充分,改善粘接性的效果小。作为印刷电路布线板,必须赋予在实用上不产生故障的180°剥离强度即8.0N/cm以上。已经判明,为了获得这样的特性,Ag、In的添加量按重量比分别为0.02质量%以上、0.01质量%以上。
另外,Ag、In固溶在铜中,改善耐热性,Ag、In对导电率的影响小,含少量银的铜合金箔适用于导电材料。但是,添加在铜中的Ag、In量多,则导电率降低,不适合作为电路用的导电材料。因此,对印刷电路布线板的层叠板用铜合金箔的合适成分进行了研究,结果表明,按重量比为Ag、In为0.02~1.0质量%,最好为0.04~0.5质量%,In为0.01~0.5质量%,最好为0.02~0.3质量%。判明Sn也有同样的作用,故作为印刷电路布线板的层叠板用铜合金箔的合适的成分,按重量比为Sn 0.01~0.5质量%,最好为0.02~0.2质量%。
(3)抗拉强度和导电性:一般,强度和导电性有相反的关系,强度越高的材料,导电性有降低的倾向。
因此,对于要求导电率高的材料,即使强度差,也规定导电率必须高,故导电率规定为80%IACS。另外,由于抗拉强度小于500N/mm2时,搬运等操作易产生折皱,故提高抗拉强度,导电率便降低,导电率为60%IACS以下的情况下,作为层叠板用的导电材料不理想。适合于高强度、搬运性良好的层叠板用的铜合金箔的条件,规定为抗拉强度500N/mm2以上、导电率60%IACS以上。
(4)Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti及Zn:Ag虽然具有提高铜合金的强度的效果,尤其从搬运性这一点出发需要高强度的情况下,添加第3种元素是有效的。Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti和Zn都主要由于固溶强化而具有提高铜合金强度的效果,根据需要,添加1种以上的元素。其含量,若总量小于0.005质量%,则上述作用不能获得所希望的效果,另一方面,总量超过2.5质量%的情况下,使导电性、软钎焊性、加工性显著降低。因此,Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti和Zn的含量范围规定为总量0.005质量%~2.5重量%。
(5)180°剥离强度:180°剥离强度小时,会产生从层叠板上剥离的现象,故必须具有8.0N/cm以上的粘接强度。
对本发明的铜合金箔的制造方法进行说明。在熔化的纯铜中添加规定量的合金元素,在铸模内铸造成为铸锭。为了抑制氧化物等的生成,铜合金的熔化铸造最好在真空中或惰性气体氛围中进行。另外,原料最好使用含氧量少的电解铜或无氧铜。铸锭通过热轧减薄到一定程度的厚度后,进行剥皮,然后,反复进行冷轧和退火,最后进行冷轧,精加工成为箔材。轧制后的材料附着有轧制油,故用丙酮和石油系溶剂等进行脱脂处理。
若在退火中产生氧化层,则含妨碍后工序的进行,故退火必须在真空中或惰性气体氛围中进行,或在退火后必须去除氧化层。例如,为用酸洗法去除氧化层,最好使用硫酸+过氧化氢、硝酸+过氧化氢、或硫酸+过氧化氢+氟化物。
具体实施方式
以下,对本发明的实施例加以说明。
铜合金的制作,用高频真空感应熔化炉在Ar氛围中、在高纯度石墨制坩埚内熔化主原料无氧铜,将从银、铟、铝、铜铍基合金、钴、铜铁基合金、镁、锰、镍、铜磷基合金、铅、铜硅基合金、钛及锌中选择的添加元素作为辅助原料添加到溶化的无氧铜中,然后注入铸铁制的铸模内进行铸造。用该方法得到厚30mm、宽50mm、长150mm、重量约2kg的铜合金铸锭。将该铸锭加热到900℃,用热轧方法轧制到8mm厚,去除氧化铁皮后反复进行冷轧和热处理,得到厚度35μm的轧制铜合金箔。
用上述方法得到的厚度35μm的铜合金箔附着有轧制油,故浸渍在丙酮中去除油分。再将它浸渍在含硫酸10质量%和过氧化氢1质量%的水溶液中,去除表面的氧化层和防锈被膜。为了调查防锈被膜的厚度的影响,将它浸渍在调整苯并三唑的浓度后的水溶液中,并立即进行干燥。除此以外,不进行粗糙化处理和硅烷偶合处理等改善粘接性的特别的表面处理。将这样制作的铜合金箔固定在油漆工盘上,用给液器涂敷含聚酰胺酸和作为溶剂的N-甲基吡咯烷酮的漆。将它放在真空干燥机内,使溶剂挥发以后,最终在350℃温度下保持10分钟,对聚酰胺酸进行加热硬化而成为聚酰亚胺被膜,得到由聚酰亚胺和铜合金2层构成的包铜层叠板。这里,聚酰亚胺被膜的厚度约50μm。
这样得到的铜合金箔的“抗拉强度”、“导电率”、“耐热性”“防锈被膜的厚度”、“漆的涂敷性”及与聚酰亚胺被膜的“粘接强度”用以下方法进行评价。
(1)抗拉强度:抗拉强度是通过抗拉试验测定了室温下的抗拉强度。测定试样是用精密刀具将加工成厚35μm的铜箔切断成宽12.7mm、长150mm的长方形而得到的。以评点间距离50mm、拉伸速度50mm/分对试样进行测定。
(2)导电率:用双电桥的直流器端子法求20℃温度下的电阻。测定试样是将加工成厚35μm的铜箔切断成宽12.7mm而得到的。对该试样测定评点间长50mm的电阻,求出导电率。
(3)耐热性:加热1小时后在室温下测定抗拉强度,将成为加热前的抗拉强度与软化后的抗拉强度的中间值的加热温度作为软化温度,对耐热性进行了评价。
(4)防锈被膜的厚度:如上所述,进行俄歇电子光谱分析的深度方向分析,构成防锈剂的元素即氮的检测强度,是测定从表面直至与本底相同为止的深度,并按SiO2换算而求出的。
(5)漆的涂敷性:将含聚酰胺酸的漆涂敷在铜箔上时,观察漆的状态,将未看到凹陷的用○表示,看到有凹陷的用×表示。
(6)粘接强度:粘接强度是依据JIS C 5016所记载的方法对180°剥离强度进行测定的。测定时用双面带将聚酰亚胺一侧固定在拉伸试验机侧,将铜合金箔向180度方向弯曲剥离。剥离宽度为5.0mm,在拉伸速度为50mm/分的条件下进行测定。
(1)实施例1
表示本发明技术方案1和技术方案5的实施例。表1是铜合金箔的成分,表2是其特性评价结果。
No.1~No.9实施例是本发明技术方案1和技术方案5的铜合金箔的发明例。如表2所示,本发明的铜合金箔,导电率为80%IACS以上,粘接聚酰亚胺后的180度剥离强度为8.0N/cm以上。具有优良的耐照性,漆的涂敷性良好,而且与聚酰亚胺具有高的粘接强度。
【表1】
No. | 化学成分(质量%) | ||||||||||||||
Ag | In | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
1 | 0.03 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
2 | 0.096 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
3 | 0.41 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
4 | 0.83 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
5 | - | 0.013 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
6 | - | 0.052 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
7 | - | 0.24 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
8 | - | 0.44 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
9 | 0.22 | 0.2 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
【表2】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
1 | 410 | 99 | 300 | 1 | ○ | 8.1 |
2 | 430 | 97 | 350 | 1 | ○ | 9.1 |
3 | 470 | 92 | 370 | 2 | ○ | 10.3 |
4 | 480 | 83 | 380 | 1 | ○ | 10.6 |
5 | 410 | 99 | 320 | 1 | ○ | 8.3 |
6 | 460 | 97 | 350 | 2 | ○ | 9.9 |
7 | 490 | 88 | 380 | 1 | ○ | 11.7 |
8 | 510 | 82 | 390 | 1 | ○ | 12.9 |
9 | 500 | 86 | 380 | 1 | ○ | 11.9 |
下面,表示本发明的技术方案2和技术方案5的发明例。表3是铜合金箔的成分,表4是其特性评价结果。
No.10~No.14实施例是本发明技术方案2和技术方案5的铜合金箔的发明例。如表4所示,本发明的铜合金箔,导电率为60%IACS以上,抗拉强度为500N/mm2以上,粘接聚酰亚胺后的180度剥离强度为8.0N/cm以上。具有优良的耐热性和强度,漆的涂敷性良好,而且与聚酰亚胺具有高的粘接强度。
【表3】
No. | 化学成分(质量%) | ||||||||||||||
Ag | In | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
10 | 0.1 | - | 0.1 | 0.096 | 0.2 | - | - | - | - | - | - | - | - | - | 其余 |
11 | 0.1 | - | - | - | - | - | 0.046 | 0.048 | - | - | - | - | - | - | 其余 |
12 | 0.2 | - | - | - | - | - | - | - | - | - | 0.056 | - | 0.21 | - | 其余 |
13 | - | 0.2 | - | - | - | 0.2 | - | - | 0.15 | - | 0.043 | - | - | 0.1 | 其余 |
14 | - | 0.2 | - | - | - | - | - | - | - | 0.06 | - | 0.11 | - | - | 其余 |
【表4】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
10 | 650 | 74 | 390 | 1 | ○ | 10.7 |
11 | 550 | 83 | 440 | 2 | ○ | 13.4 |
12 | 680 | 65 | 450 | 2 | ○ | 10.3 |
13 | 600 | 72 | 450 | 1 | ○ | 12.8 |
14 | 540 | 84 | 370 | 2 | ○ | 11.1 |
表5是比较例的铜合金箔的成分,表6是其特性评价结果。No.15~No.19是本发明技术方案1和技术方案5的比较例。No.15是不添加本发明的合金成分的轧制铜箔。将无氧铜在Ar氛围中进行熔化铸造成铸锭,将该铸锭加工成箔材,与聚酰亚胺粘结。由于原料是纯铜,故导电性虽好,但180度剥离强度为7.5N/cm,不能获得充分的粘接强度,故作为印刷电路布线板时有可能产生剥离。
【表5】
No. | 化学成分(质量%) | ||||||||||||||
Ag | In | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
15 | - | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
16 | 0.015 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
17 | 1.3 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
18 | - | 0.008 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
19 | - | 0.55 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
20 | 0.19 | - | - | - | - | - | - | - | 0.2 | 2.7 | - | - | - | - | 其余 |
21 | - | 0.19 | - | - | - | - | - | - | - | - | - | - | 2.8 | - | 其余 |
22 | 0.41 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
【表6】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
15 | 400 | 99 | 140 | 2 | ○ | 7.5 |
16 | 400 | 99 | 220 | 1 | ○ | 7.6 |
17 | 480 | 77 | 380 | 2 | ○ | 13 |
18 | 400 | 99 | 280 | 1 | ○ | 7.8 |
19 | 530 | 78 | 390 | 1 | ○ | 13.1 |
20 | 690 | 35 | 450 | 1 | ○ | 7.8 |
21 | 910 | 14 | 450 | 1 | ○ | 13.8 |
22 | 430 | 97 | 350 | 7 | × | - |
No.16~No.19比较例,添加Ag或In,采用与发明例一样的方法加工成箔。No.16比较例,Ag的浓度小,故导电率大,但改善耐热性和粘接性的效果不充分。180度剥离强度小,加工成层叠板后会产生剥离。另外,No.17比较例,Ag的浓度按重量比大于1.0质量%进行添加,故耐热性和180度剥离强度高,但导电率低,小于80%IACS,作为要求导电率高的印刷电路布线板的导电材料是不合适的。同样,No.18比较例,因In的浓度小,故导电率大,但改善耐热性和粘接性的效果不充分,No.19实施例,In的浓度按重量比大于0.5质量%进行添加,故导电率低,小于80%IACS,不适合用作要求导电率高的印刷电路布线板的导电材料。
No.20和No.21是本发明技术方案2和技术方案5的比较例。No.20除了添加Ag以外还添加P和Ni,No.21除了添加Ag以外还添加Ti、采用与发明例一样的方法加工成箔材。P或Ti的添加量按重量比超过2.5质量%进行添加,故导电率低,小于70%IACS,作为印刷电路布线板的导电材料不合适。
No.22比较例使用No.2发明例的合金箔,浸渍在将苯并三唑的浓度调整为7000ppm的水溶液中进行处理。其结果,防锈被膜厚,为7nm、故与含聚酰胺酸的漆的润湿性差,可以看到漆的凹坠陷。因此,不能得到均匀的聚酰亚胺被膜,不能测定180度剥离强度。
(2)实施例2
表示本发明技术方案3和技术方案5的实施例。表7是铜合金箔的成分,表8是其特性评价结果。
No.23~No.26实施例是本发明技术方案3和技术方案5的铜合金箔的发明例。如表8所示,本发明的铜合金箔,导电率为70%IACS以上,粘接聚酰亚胺后的180度剥离强度为8.0N/cm以上。由此可知,具有优良的耐热性,漆的涂敷性良好,并且与聚酰亚胺具有高的粘接强度。
【表7】
No. | 化学成分(质量%) | |||||||||||||
Sn | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
23 | 0.015 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
24 | 0.050 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
25 | 0.18 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
26 | 0.40 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
【表8】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
23 | 420 | 98 | 300 | 1 | ○ | 8.4 |
24 | 460 | 95 | 360 | 1 | ○ | 10.0 |
25 | 480 | 82 | 380 | 1 | ○ | 11.3 |
26 | 490 | 73 | 390 | 1 | ○ | 12.1 |
下面,表示本发明的技术方案4和技术方案5的发明例。表9是铜合金箔的成分,表10是其特性评价结果。
No.27~No.31实施例是本发明技术方案2和技术方案5的铜合金箔的发明例。如表10所示,本发明的铜合金箔,导电率为60%IACS以上,抗拉强度为500N/mm2以上,粘接聚酰亚胺后的180度剥离强度8.0N/cm以上。由此可知,具有优良的耐热性和强度,漆的涂敷性良好,而且与聚酰亚胺具有高的粘接强度。
【表9】
No. | 化学成分(质量%) | |||||||||||||
Sn | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
27 | 0.10 | - | 0.11 | 0.21 | - | - | - | - | - | - | - | - | - | 其余 |
28 | 0.40 | 0.015 | - | - | - | - | 0.091 | - | 0.045 | - | 0.1 | - | 0.10 | 其余 |
29 | 0.21 | - | - | - | - | 0.094 | - | - | - | - | - | 0.31 | - | 其余 |
30 | 0.19 | - | - | - | 0.20 | - | - | 0.11 | - | 0.029 | - | - | 0.19 | 其余 |
31 | 0.20 | - | - | - | - | - | - | - | 0.050 | - | 0.091 | - | - | 其余 |
【表10】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
27 | 650 | 75 | 390 | 1 | ○ | 12.7 |
28 | 580 | 60 | 450 | 1 | ○ | 13.6 |
29 | 690 | 63 | 450 | 2 | ○ | 10.5 |
30 | 620 | 70 | 400 | 1 | ○ | 12.1 |
31 | 550 | 82 | 360 | 1 | ○ | 11.0 |
表11是比较例的铜合金箔的成分,表12是其特性评价结果。No.32~No.34是本发明技术方案1和技术方案5的比较例。No.32是不添加本发明的合金成分的轧制铜箔。将无氧铜在Ar氛围中进行熔化并铸造成铸锭,将该铸锭加工成箔材,与聚酰亚胺粘结。由于原料是铜,故导电性好,但180度剥离强度为7.5N/cm,不能获得足够的粘接强度,因此,作为印刷电路布线板时会产生剥离。
【表11】
No. | 化学成分(质量%) | |||||||||||||
Sn | Al | Be | Co | Fe | Mg | Mn | Ni | P | Pb | Si | Ti | Zn | Cu及不可避免的杂质 | |
32 | - | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
33 | 0.008 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
34 | 0.59 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
35 | 0.22 | - | - | - | 2.9 | - | - | - | - | - | - | - | - | 其余 |
36 | 0.20 | - | - | - | - | - | - | - | - | - | - | 2.7 | - | 其余 |
37 | 0.05 | - | - | - | - | - | - | - | - | - | - | - | - | 其余 |
【表12】
No. | 抗拉强度(N/mm2) | 导电率(%IACS) | 耐热性(℃) | 防锈被膜的厚度(nm) | 漆的涂敷性 | 180度剥离强度(N/cm) |
32 | 400 | 99 | 140 | 2 | ○ | 7.5 |
33 | 400 | 99 | 250 | 1 | ○ | 7.7 |
34 | 550 | 67 | 380 | 1 | ○ | 12.3 |
35 | 540 | 30 | 450 | 1 | ○ | 13.1 |
36 | 890 | 15 | 450 | 1 | ○ | 12.0 |
37 | 450 | 95 | 360 | 7 | × | - |
No.33和No.34添加Sn,采用与发明例同样的方法加工成箔材。No.33的Sn浓度小,故导电率高,但改善耐热性和粘接性的效果不充分。180度剥离强度小,加工成层叠板后会产生剥离。另外,No.34的Sn浓度是按重量比大于0.5质量%进行添加的,故耐热性和180度剥离强度高,但导电率低,小于70%IACS,作为需要导电率高的印刷电路布线板的导电材料不合适。
No.35和No.36是本发明技术方案2和技术方案5的比较例。除了分别添加Sn以外,No.35添加Fe,No.36添加Ti,采用与发明例一样的方法加工成箔材。Fe或Ti的添加量按重量比大于2.5质量%进行添加,故抗拉强度、耐热性及粘接性高,但导电率低,小于60%IACS,作为印刷电路布线板的导电材料不合适。
No.37比较例采用No.24发明例的合金箔,浸渍在将苯并三唑浓度调整为7000ppm的水溶液中进行处理。其结果,防锈被膜变厚,为7nm,故与含聚酰胺酸的漆的润湿性差,可以看到漆的凹陷。因此,不能得到均匀的聚酰亚胺被膜,不能对180度剥离强度进行测定。
Claims (3)
1.一种层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Sn 0.01质量%~0.5质量%,其余部分由铜和不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则导电率为70%IACS以上,与含聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后而形成的被膜的180度剥离强度为8.0N/cm以上。
2.一种层叠板用铜合金箔,其特征在于,添加元素的成分按重量比例为含有Sn 0.01质量%~0.5质量%,还含有Al、Be、Co、Fe、Mg、Mn、Ni、P、Pb、Si、Ti和Zn各成分中的一种以上,总量为0.005质量%~2.5质量%,其余部分由铜和不可避免的杂质构成,在铜合金箔表面上形成有苯并三唑和咪唑等含氮的有机物的防锈被膜,将防锈被膜的厚度设为从表面起5nm以下,则抗拉强度为500N/mm2以上,导电率为60%IACS以上,与含聚酰胺酸的漆的润湿性良好,在实施了防绣被膜的铜箔表面上不进行粗糙化处理的情况下,与将聚酰胺酸热硬化后形成的被膜的180度剥离强度为8.0N/cm以上。
3.根据权利要求1或2所述的层叠板用铜合金箔,其特征在于,加热1小时后的抗拉强度成为加热前的抗拉强度与软化后的抗拉强度的中间值时的温度为300℃以上。
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JP244874/2001 | 2001-08-10 | ||
JP2001244874A JP2003055722A (ja) | 2001-08-10 | 2001-08-10 | 積層板用銅合金箔 |
JP2001249609A JP2003064430A (ja) | 2001-08-20 | 2001-08-20 | 積層板用銅合金箔 |
JP249609/2001 | 2001-08-20 |
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CNB021286558A Division CN1229001C (zh) | 2001-08-10 | 2002-08-09 | 层叠板用铜合金箔 |
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KR100491385B1 (ko) * | 2001-07-04 | 2005-05-24 | 닛꼬 긴조꾸 가꼬 가부시키가이샤 | 적층판용 구리합금박 |
TW200404484A (en) * | 2002-09-02 | 2004-03-16 | Furukawa Circuit Foil | Copper foil for soft circuit board package module, for plasma display, or for radio-frequency printed circuit board |
US6727467B1 (en) * | 2003-01-31 | 2004-04-27 | W.E.T. Automotive Systems Ag | Heated handle and method of forming same |
US8123927B1 (en) | 2003-09-23 | 2012-02-28 | Rockstar Bidco, LP | Reduced circuit trace roughness for improved signal performance |
US7383629B2 (en) * | 2004-11-19 | 2008-06-10 | Endicott Interconnect Technologies, Inc. | Method of making circuitized substrates utilizing smooth-sided conductive layers as part thereof |
JP4857594B2 (ja) * | 2005-04-26 | 2012-01-18 | 大日本印刷株式会社 | 回路部材、及び回路部材の製造方法 |
CN101428304B (zh) * | 2007-11-05 | 2012-04-18 | 江苏鸿尔有色合金实业有限公司 | 银铜板(排、棒、管)生产工艺 |
JP5325175B2 (ja) * | 2010-07-15 | 2013-10-23 | Jx日鉱日石金属株式会社 | 銅箔複合体、及び成形体の製造方法 |
JP5705311B2 (ja) | 2011-05-13 | 2015-04-22 | Jx日鉱日石金属株式会社 | 銅箔複合体及びそれに使用される銅箔、並びに成形体及びその製造方法 |
WO2013105265A1 (ja) | 2012-01-13 | 2013-07-18 | Jx日鉱日石金属株式会社 | 銅箔複合体、並びに成形体及びその製造方法 |
US9955574B2 (en) | 2012-01-13 | 2018-04-24 | Jx Nippon Mining & Metals Corporation | Copper foil composite, formed product and method of producing the same |
CN110501263B (zh) * | 2018-05-16 | 2022-06-28 | 宝山钢铁股份有限公司 | 一种镀锡板表面润湿性评价方法 |
CN114765081A (zh) * | 2021-01-14 | 2022-07-19 | 日立金属株式会社 | 铜合金线、镀线、电线及电缆 |
WO2023129408A1 (en) * | 2021-12-28 | 2023-07-06 | Graphenix Development, Inc. | Anodes for lithium-based energy storage devices |
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US4908275A (en) * | 1987-03-04 | 1990-03-13 | Nippon Mining Co., Ltd. | Film carrier and method of manufacturing same |
US4731128A (en) * | 1987-05-21 | 1988-03-15 | International Business Machines Corporation | Protection of copper from corrosion |
JPH0819499B2 (ja) * | 1987-06-10 | 1996-02-28 | 古河電気工業株式会社 | フレキシブルプリント用銅合金 |
JP2505480B2 (ja) * | 1987-08-27 | 1996-06-12 | 日鉱金属株式会社 | フレキシブル回路基板用銅合金箔 |
JP2726939B2 (ja) * | 1989-03-06 | 1998-03-11 | 日鉱金属 株式会社 | 加工性,耐熱性の優れた高導電性銅合金 |
JPH04290286A (ja) * | 1991-03-19 | 1992-10-14 | Tatsuta Electric Wire & Cable Co Ltd | 電磁波遮蔽付きフレキシブルプリント板 |
JPH05226833A (ja) * | 1992-02-17 | 1993-09-03 | Toshiba Corp | 配線板の製造方法 |
JPH08293654A (ja) * | 1995-04-21 | 1996-11-05 | World Metal:Kk | セラミックへの金属被膜形成方法及び金属被覆セラミック構造体 |
US6221176B1 (en) * | 1999-03-17 | 2001-04-24 | Gould Electronics, Inc. | Surface treatment of copper to prevent microcracking in flexible circuits |
CN1195395C (zh) * | 2001-01-30 | 2005-03-30 | 日鉱金属股份有限公司 | 积层板用铜合金箔 |
JP4309602B2 (ja) * | 2001-04-25 | 2009-08-05 | メック株式会社 | 銅または銅合金と樹脂との接着性を向上させる方法、ならびに積層体 |
JP2003027162A (ja) * | 2001-07-13 | 2003-01-29 | Nippon Mining & Metals Co Ltd | 積層板用銅合金箔 |
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US6808825B2 (en) | 2004-10-26 |
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KR20030014168A (ko) | 2003-02-15 |
CN1406105A (zh) | 2003-03-26 |
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