CN102089454B - 表面处理铜箔 - Google Patents
表面处理铜箔 Download PDFInfo
- Publication number
- CN102089454B CN102089454B CN2009801265223A CN200980126522A CN102089454B CN 102089454 B CN102089454 B CN 102089454B CN 2009801265223 A CN2009801265223 A CN 2009801265223A CN 200980126522 A CN200980126522 A CN 200980126522A CN 102089454 B CN102089454 B CN 102089454B
- Authority
- CN
- China
- Prior art keywords
- copper foil
- surface treatment
- binding face
- treatment
- aforementioned
- 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.)
- Expired - Fee Related
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000011889 copper foil Substances 0.000 title claims abstract description 164
- 238000011282 treatment Methods 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000004381 surface treatment Methods 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 47
- 239000003870 refractory metal Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 238000007788 roughening Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 33
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002335 surface treatment layer Substances 0.000 abstract 3
- 238000005253 cladding Methods 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 24
- 239000011651 chromium Substances 0.000 description 20
- 229910052804 chromium Inorganic materials 0.000 description 19
- 238000012545 processing Methods 0.000 description 15
- 238000005530 etching Methods 0.000 description 13
- 238000005240 physical vapour deposition Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- -1 argon ion Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 238000013459 approach Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- 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
- B32B15/04—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
- 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
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
-
- 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
- H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
-
- 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
- H05K2201/0302—Properties and characteristics in general
- H05K2201/0317—Thin film conductor layer; Thin film passive component
-
- 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
- H05K2201/032—Materials
- H05K2201/0323—Carbon
-
- 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
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
-
- 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
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
-
- 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
- Y10T428/12625—Free carbon containing component
-
- 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.]
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Abstract
本发明的目的在于,提供一种表面处理铜箔,其在表面处理层中不含有铬,且在加工成印刷线路板后的电路的剥离强度、该剥离强度的耐药品性劣化率等方面表现优良。为了达到该目的,采用了一种表面处理铜箔,其在与绝缘树脂基材相贴合而制造覆铜层压板时所使用的铜箔的贴合面上,设置有表面处理层,其特征在于,所述表面处理层,是采用干式成膜法,在实施了净化处理的前述铜箔的贴合面上,附着熔点为1400℃以上的高熔点金属成分,进而附着碳成分而形成。
Description
技术领域
本发明涉及一种表面处理铜箔。特别是,涉及一种采用干式成膜法形成表面处理铜箔的表面处理层而得到的印刷线路板制造用的表面处理铜箔。
背景技术
在由覆铜层压板加工成印刷线路板的工艺中,一直以来多数采用借助于溶液的蚀刻工艺。因此,要求在覆铜层压板阶段具有铜箔对绝缘树脂基板的良好的粘附性,并且在加工成印刷线路板后的电路与绝缘树脂基板之间还具有良好的粘附性。
为了满足该要求,在用于制造印刷线路板的铜箔的粘接面上,施以各种表面处理,以提高其与绝缘树脂基材之间的粘附性。并且,作为以往的印刷线路板用铜箔中的防锈元素、表面改性元素,广泛使用铬成分,以进行镀铬或铬酸盐处理等。特别是,近年来市售的铜箔几乎都采用了铬酸盐处理。
作为采用铬成分作为表面处理成分的示例,例如,在专利文献1中,公开了一种印刷线路板用铜箔,其与基材的粘附性(基材与铜箔之间的粘接强度)、耐湿性、耐药品性、耐热性优良,其中,有一种的特征在于在铜箔的单面或双面上具有经蒸镀形成的金属铬层,例如采用溅射法进行蒸镀而形成的金属铬层;还有一种的特征在于将铜箔的单面通过剥离层保持于载体上,并具有经蒸镀形成于该铜箔的相反面上的金属铬层,例如采用溅射法蒸镀而形成的金属铬层。
此外,在专利文献2中,作为可最大限度地发挥以增大与制造印刷线路板用的铜箔的基材之间的粘接强度为目的而使用的硅烷偶联剂性能的铜箔,公开了一种印刷线路板用表面处理铜箔,其是由下述方式获得:作为防锈处理,在铜箔表面上形成锌或锌合金层,在该锌或锌合金层的表面形成电解铬酸盐层,在无需对该电解铬酸盐层进行干燥的情况下,在该电解铬酸盐层上形成硅烷偶联剂吸附层并使之干燥,由此获得了印刷线路板用的表面处理铜箔。
如此作为表面处理成分使用的铬成分,在作为铬化合物存在的情况下,氧化值为三价或六价。并且,六价铬对生物的毒性远远高于三价铬对生物的毒性,而且,六价铬化合物在土壌中的迁移性也比三价铬大,对环境的负荷高。
关于含有如铬等对人体带来影响的有害物质的废弃物,从二十世纪七十年代开始在世界上就出现跨越国境的转移现象。其结果是,在发展中国家存放了来自发达国家的有害废弃物,从而引起环境污染等问题。因此,二十世纪八十年代,制订了《控制危险废物越境转移及其处置的巴塞尔公约(有害廃棄物の国境を越える移動及びその処分の規制に関するバ一ゼル条約)》,该条约规定了一些废弃物越境转移等规则的国际框架和手续等,并1993年开始也在日本国内生效。
近年来,在EU(欧盟)的ELV指令中,采纳了从2003年7月1日后对EU市场上所注册的新车禁止使用环境荷载物质即铅、六价铬、汞、镉的方案,提倡积极使用三价铬。此外,在电气、电子行业中,欧州的WEEE(WasteElectrical and Electronic Equipment)指令和RoHS(Restriction on HazardousSubstances)指令最终达成一致,作为用于废旧电气、电子设备中的特定有害物质,将以六价铬(Cr6+)为代表的6种物质,规定为即使分别回收也存在环境风险的物质而予以限制使用,印刷线路板也成为了该规定的对象。
而且,近年来人们对环境问题的意识在提高,由此担心即使采用了三价铬,但若错误地进行其废弃处理则会转化为六价铬,或者若弄错分析方法则会断定为六价铬之虑。鉴于这样的考虑,人们已在探讨采用不使用铬成分本身的印刷线路板用铜箔。
例如,在专利文献3中,公开了一种包括不使用铬的铜箔的概念,其是在至少一个面上具有粘接性促进层的金属箔,其特征在于,该粘接性促进层含有至少一种硅烷偶联剂并且不含有铬,而且,其特征还在于,在该粘接性促进层的下面所形成的该金属箔的基底表面上,不施加表面粗糙处理、或不存在附着于该基底表面的锌层或者铬层。并公开了金属箔,其中,在前述金属箔的前述基底表面与前述粘接性促进层之间设置有金属层,该金属层中的金属选自由铟、锡、镍、钴、黄铜、青铜或两种以上这些金属的混合物所构成的组中,此外,在前述金属箔的前述基底表面与前述粘接性促进层之间设 置有金属层,该金属层中的金属选自由锡、铬-锌混合物、镍、钼、铝以及两种以上这些金属的混合物所构成的组中。
现有技术文献
专利文献1:日本特开2000-340911号公报
专利文献2:日本特开2001-177204号公报
专利文献3:日本特开平7-170064号公报
发明内容
发明要解决的课题
一般而言,防锈处理层是为了从大气氧化中保护铜箔、并确保长期保存性而使用。然而,与基材树脂之间的粘附性会基于该防锈处理层的种类而发生变化,特别是,对加工成印刷线路板以后的电路的剥离强度、该剥离强度的耐药品性劣化率、耐吸湿劣化率等带来较大的影响。
基于以上所述,人们一直希望表面处理铜箔在电解铜箔的表面处理层中不使用铬,并满足加工成印刷线路板后的电路的剥离强度、该剥离强度的耐药品性劣化率、耐吸湿劣化率等基本的必要条件。
解决课题的方法
因此,本发明人经过精心研究,结果发现,通过使用下述无铬的表面处理铜箔,能够获得与绝缘树脂基材的良好粘附性。下面,针对本发明的表面处理铜箔进行说明。
本发明的表面处理铜箔,在与绝缘树脂基材相贴合而制造覆铜层压板时所使用的铜箔的贴合面上,设置有表面处理层,其特征在于,所述表面处理层,是在实施了净化处理的前述铜箔的贴合面上,采用干式成膜法,附着熔点为1400℃以上的高熔点金属成分,进而附着碳成分而形成。
对于构成本发明的设置于表面处理铜箔的铜箔贴合面上的表面处理层的、熔点为1400℃以上的高熔点金属成分而言,优选采用物理蒸镀法附着1nm~10nm的换算厚度的量。
对于构成本发明的设置于表面处理铜箔的贴合面上的表面处理层的碳成分而言,优选采用物理蒸镀法附着1nm~5nm的换算厚度的量。
在本发明的表面处理铜箔中,作为前述熔点为1400℃以上的高熔点金属成分,优选使用钛成分。
对于本发明的表面处理铜箔所使用的铜箔,优选使用其贴合面没有实施粗化处理而且表面粗糙度(Rzjis)为2.0μm以下的铜箔。
本发明的表面处理铜箔中实施的净化处理,优选为去除铜箔表面的铜氧化物的处理。
本发明的表面处理铜箔中实施的净化处理,也优选为在铜箔表面物理蒸镀铜的处理,所述铜箔表面是采用干式成膜法形成铜层的铜箔表面。
发明的效果
本发明的表面处理铜箔,是在作为对绝缘树脂基材的贴合面使用的铜箔的贴合面上施以净化处理,并依次附着熔点为1400℃以上的高熔点金属成分、碳成分的各种成分而得到的表面处理铜箔。并且,在附着该熔点为1400℃以上的高熔点金属成分、碳成分的各种成分时,积极应用干式成膜法(包括物理蒸镀法)。基于采用干式成膜法,不同于采用电化学方法的情况,可形成同一平面内的膜厚均匀性优良、且在组成上没有偏差的表面处理层。因此,通过积极采用不同于一直以来所用的电化学方法的干式成膜法形成表面处理层,由此,能够形成完全不同于以往电解铜箔的表面处理的表面处理层。基于使用本发明的表面处理铜箔,即使得不到对铜箔的贴合面上施以粗化处理而带来的对绝缘树脂基材的固着效果,也能够使加工成覆铜层压板时的铜箔的粘附性以及加工成印刷线路板时的电路的粘附性,达到实用上无障碍的剥离强度。
另外,本发明的表面处理铜箔,在作为对绝缘树脂基材的贴合面使用的铜箔的贴合面上施以净化处理。并且,此后,依次附着熔点为1400℃以上的高熔点金属成分和碳成分的各种成分。通过如此操作,大幅度提高了铜箔表面与熔点为1400℃以上的高熔点金属成分以及碳成分之间的粘附性。
具体实施方式
下面,针对本发明表面处理铜箔的实施方式进行说明。
本发明表面处理铜箔的实施方式:本发明的表面处理铜箔,在与绝缘树 脂基材相贴合而制造覆铜层压板时所使用的铜箔的贴合面上,设有表面处理层。从而,有必要至少在铜箔的贴合面上具备表面处理层,但为了确保作为表面处理铜箔的长期保存性,可在其相反面上也设置用于获得防锈效果的表面处理层。作为此时设置于相反面上的表面处理层,可设置与贴合面相同的表面处理层。但是,对于该相反面的表面处理,若仅期待防锈效果时,则从成本的角度考虑,可采用含锌的无机防锈,使用苯并三唑或咪唑等的有机防锈等。
并且,本发明的表面处理铜箔,是使用不具备表面处理层的未处理铜箔得到的。在此所述的铜箔,可使用电解铜箔、压延铜箔中的任意一种,而不论其制造方法如何。此外,对于此时的铜箔厚度,并没有特别限制,可根据用途使用任意厚度的铜箔。通常可使用厚度为6μm~300μm范围的铜箔。并且,对于低于6μm厚度的铜箔,优选作为以下状态的超薄铜箔(带有载体箔的铜箔)使用:载体箔与超薄铜箔通过接合界面形成暂时的贴合状态,从而支撑于载体箔状态的超薄铜箔(带有载体箔的铜箔)。
针对在以上所述铜箔的与绝缘树脂基材的贴合面上设置的表面处理层进行说明。本发明的表面处理铜箔的情况下,在形成表面处理层之前,对形成表面处理层的铜箔的贴合面施以净化处理。该净化处理,是为了在铜箔表面形成尽可能没有铜氧化物的状态,使其接近露出金属铜的状态而实施的处理。即:由于形成于铜箔表面的氧化层或污染,会引起铜箔与表面处理层之间的粘附性降低,但通过实施该净化处理,成为在铜箔表面没有多余铜氧化物的状态,防止粘附性的降低。此外,净化处理至少可以在铜箔与绝缘树脂基材的贴合面一侧(即,形成表面处理层的侧)实施,也可以在成为基底的铜箔的双面上实施。
作为净化处理,通过采用去除铜氧化物的方法以及以干式成膜法使新生铜附着于铜箔表面的方法中的任意一种,可获得尽可能接近于露出金属铜的表面的铜箔表面。
针对从作为基底的铜箔表面去除铜氧化物的净化处理进行说明。作为此时的净化处理方法,可以举出溅射处理、等离子处理等。当采用溅射处理时,在真空腔室内,用离子枪等对氩离子、氮离子等进行加速,从而使其碰撞于铜箔表面,使存在于铜箔表面的铜氧化物发生离子化而赶出去,从而主要去 除铜氧化物而使金属铜尽可能显露于铜箔表面,以进行铜箔表面的净化。此时,组合使用溅射处理和电子簇射,也能够进行良好的净化。此外,当使用等离子处理时,通过采用电容耦合型等离子源等使铜箔表面的铜氧化物瞬间得到升华,去除铜箔表面的铜氧化物,进行铜箔表面的净化。
接着,说明对铜箔表面采用干式成膜法而获得露出金属铜的状态的净化处理。此时的净化处理方法所使用的干式成膜法,除了称作所谓物理蒸镀法的溅射蒸镀法、真空蒸镀法、EB蒸镀法等之外,还包括化学气相沉积法等气相反应法。在此,举出一个例子进行说明,当使用溅射蒸镀法时,采用铜靶材料,在真空腔室内使铜原子附着于铜箔表面上,成为露出新生的金属铜的状态。如此,当采用物理蒸镀法对作为基底的铜箔表面进行净化处理时,为了减少偏差,铜箔表面上形成的铜膜厚度优选为10nm以上。
当铜箔的贴合面的净化处理结束后,进行表面处理层的形成。首先,使熔点为1400℃以上的高熔点金属成分附着于铜箔的贴合面上。若只使后述的碳附着于铜箔表面而不使该高熔点金属成分附着于铜箔表面上,则表面处理铜箔与绝缘树脂基材之间的粘附状态中容易出现偏差,特别是,在覆铜层压板的同一平面内检测位置上的偏差大,因此不优选。并且,在此所述的熔点为1400℃以上的高熔点金属成分,优选使用钛、镍、钴、锆、钨中的任意一种。但是,考虑到印刷线路板的制造工艺以及以蚀刻进行去除等各种条件时,更加优选使用钛。此时的熔点为1400℃以上的高熔点金属成分,优选采用干式成膜法使其附着成膜。其中,若考虑到成膜效率,则优选使用溅射蒸镀法、真空蒸镀、EB蒸镀法等物理蒸镀法。进而,若从成膜效率、成膜厚度的稳定性、工序控制的简易度等各种控制要素以及对它们的控制简易度考虑时,则最优选使用溅射蒸镀法。
并且,对于熔点为1400℃以上的高熔点金属成分(下面,简称为“高熔点金属成分”),优选使其附着1nm~10nm的换算厚度的量。当高熔点金属成分附着量为小于1nm时,得不到附着高熔点金属成分的效果,得不到表面处理铜箔与绝缘树脂基材之间良好的粘附性。另一方面,当高熔点金属成分量为超过10nm时,由于高熔点金属成分附着量过多,加工成印刷线路板时难以通过蚀刻液等进行溶解去除,因此,蚀刻时间变长,难以形成具备良好蚀刻因子的微距间电路。此外,在此所述的换算厚度,是指将表面处理铜箔 溶解于化学药品中并通过ICP装置等进行检测,对所得到的值进行换算而得到的厚度。通过如上所述操作,使高熔点金属成分附着于铜箔表面上。
然后,使碳成分附着于该高熔点金属成分的表面上。如此,通过使碳成分与高熔点金属成分一起进行附着,表面处理铜箔与绝缘树脂层之间的粘附性变得良好且达到稳定化。并且,对于该碳成分的附着,优选采用物理蒸镀法来进行。对于此时的方法,并没有特别限制,但在采用溅射蒸镀法时,是使氩离子等碰撞于碳靶材上,并使碳成分附着于铜箔的表面上。
并且,对于此时的碳成分,优选使其附着1nm~5nm的换算厚度的量。当碳成分附着量为小于1nm时,得不到附着碳的效果,而成为仅附着高熔点金属成分的状态,得不到表面处理铜箔与绝缘树脂基材之间良好的粘附性。另一方面,当碳成分量为超过5nm时,碳成分附着量过多,从而加工成印刷线路板时,在铜箔电路下侧的面上增加致使导体电阻增大的碳成分,因此不优选。此外,碳成分的换算厚度的检测方法如下:将本发明的表面处理铜箔的试片,置于气体分析装置的高温氧气流中,使该气流中的氧与碳成分发生反应,转变成一氧化碳和二氧化碳气体,对该一氧化碳和二氧化碳的气体量进行检测,计算出每单位面积的碳成分量,进而换算成每单位面积的厚度。
以上所述的表面处理层,适用于不施加粗化处理而与绝缘树脂基板贴合的用途的表面处理铜箔中。通常的铜箔在进行表面处理之前,对表面施以粗化处理。若铜箔的贴合面上存在凹凸状态的粗化处理,则该粗化处理的凹凸状态通过加压加工,嵌入绝缘树脂基材的内部,发挥固着效果,从而提高粘附性。但是,若存在这种粗化处理,则即使经蚀刻加工,对表面处理铜箔的主体部分的溶解结束,也不能去除嵌入绝缘树脂基材内部的粗化处理部,因此,还需要蚀刻时间(过蚀刻时间)。若该过蚀刻时间变长,已结束蚀刻的铜箔电路的溶解还要进行,因此会使铜箔电路的蚀刻因子变差。对此,在本发明的表面处理铜箔中,即使将未处理铜箔用于表面处理铜箔的制造中,也能够获得与绝缘树脂层之间良好的粘附性。并且,若该未处理铜箔的表面粗糙度(Rzjis)为2.0μm以下,则蚀刻加工时的过蚀刻时间能够大幅度缩短,可容易地提高所形成的铜箔电路的蚀刻因子。其原因在于,虽然在此将表面粗糙度作为未处理铜箔的贴合面的值来表示,但即使形成本发明所述的表面处理层,只要是采用触针式粗糙度仪进行检测,则表面粗糙度的值在表面处 理的前后没有大的变化的缘故。
接着,针对本发明的表面处理铜箔的制造方法进行说明。上述表面处理铜箔的制造方法,包括下述工序A和工序B。下面,针对每个工序进行陈述。
工序A:在该工序中进行铜箔表面的净化处理。在此所述的净化处理,是指使金属铜露出在形成表面处理层的基底即铜箔表面上的处理。对于净化处理已经陈述过,因此省略说明。
工序B:采用干式成膜法,对净化过的铜箔形成由熔点为1400℃以上的高熔点金属成分与碳层构成的表面处理层,以作为表面处理铜箔。
并且,当在该熔点为1400℃以上的高熔点金属成分的覆膜形成中,采用属于干式成膜法的物理蒸镀法时,也优选采用溅射蒸镀法。对于该溅射蒸镀条件,并没有特别限制,可使用钛靶、镍靶等,采用极限真空度Pu为1×10-3Pa以下、溅射压PAr为0.1Pa~3.0Pa、溅射电功率密度为0.1W/cm2~3W/cm2、溅射时间为5秒~20秒、溅射种子采用氩离子的条件等。
进而,对于此后进行的碳的物理蒸镀法,并不局限于特别的制造方法。可采用通常所知悉的所有的物理蒸镀法。下面,为了更容易理解本发明的内容,对实施例和比较例进行陈述。
实施例
作为实施例,调整钛成分以及碳成分的附着量以成为表1所示换算厚度,制作实施例1~实施例5的表面处理铜箔。然后,涂布聚醚砜系树脂而形成带树脂铜箔,并与FR-4基材进行贴合后,评价与该FR-4基材的贴合面的粘附性。
净化处理:作为净化处理,举出采用溅射蒸镀法,获得金属铜露出于铜箔表面的状态的实施例。首先,准备贴合面的表面粗糙度为Rzjis=1.3μm、厚度为18μm的电解铜箔的卷筒(roll)。作为溅射装置,采用水冷式DC磁控管溅射装置。使用150mm×300mm尺寸的铜靶,作为溅射条件采用极限真空度Pu为低于1×10-4Pa、溅射压PAr为0.1Pa、溅射电功率为1500W下处理10秒的条件,由此附着50nm厚度的铜成分。
钛成分的附着:钛成分对铜箔贴合面的附着,通过水冷式DC磁控管溅射装置,使用150mm×300mm尺寸的钛靶,并作为溅射条件采用极限真空度 Pu为1×10-3Pa以下,溅射压PAr为0.1Pa~1Pa、溅射电功率为100W~1000W下处理10秒的条件,由此附着钛成分。
碳成分的附着:接着,在结束了钛成分附着的铜箔的贴合面上,进行碳成分的附着。采用与钛成分的附着相同的溅射装置,使用150mm×300mm尺寸的碳靶,并作为溅射条件,采用极限真空度Pu为低于1×10-4Pa、溅射压PAr为0.1Pa~1Pa、溅射电功率为500W~3000W的条件,由此附着碳成分。
对于钛成分以及碳成分的附着,是调整电功率密度以使各附着量成为表1的实施例1~实施例5中所示的换算厚度来进行附着。
针对如上述操作所得到的实施例1~5的表面处理铜箔,涂布由70重量份聚醚砜树脂(SUMIKAEXCEL(スミカェクセル)PES-5003P,住友化学株式会社制造)和30重量份环氧树脂(EPPN-502,日本化药株式会社制造)构成的树脂,并风干后,在140℃的加热环境中进行干燥处理,得到涂布有半固化状态的厚度为2μm的树脂的带树脂铜箔。
粘附性评价:对使用实施例1~5的表面处理铜箔的带树脂铜箔与FR-4等级的半固化片进行180℃×60分钟的热压加工,制造出覆铜层压板。并且,采用蚀刻法,制备印刷线路板试片(具备宽度为0.4mm的剥离强度检测用直线电路),进行剥离强度的评价。关于剥离强度,分别针对常态、锡焊后、盐酸浸渍后和高压锅试验(下面记为“PCT”)后,进行了检测。将这些评价结果汇总于表1中。
锡焊后的剥离强度,是将印刷线路板试片漂浮于260℃的焊浴中10分钟后冷却至室温后再检测的剥离强度。
盐酸浸渍后的剥离强度,是将印刷线路板试片浸渍于按盐酸∶水=1∶2的比例混合的60℃的溶液中90分钟后进行水洗、干燥后直接检测的剥离强度。通过检测盐酸浸渍后的剥离强度,可评价电路的耐盐酸性。
所谓PCT,是一种印刷线路板的层间连接可靠性试验。PCT后的剥离强度,是将印刷线路板试片保持在121℃×100%RH的高温高压环境中24小时后所检测的剥离强度。即:基于检测PCT后的剥离强度,能够评价电路的耐湿性。
比较例
作为比较例,显示作为高熔点金属成分的钛成分附着量为偏离本发明范围的0.4nm的表面处理铜箔。从表1可知,相比于比较例1的表面处理铜箔,实施例1~实施例5的表面处理铜箔的剥离强度的值均变大。
表1
工业实用性
本发明的表面处理铜箔,在作为对绝缘树脂基材的贴合面使用的铜箔的表面上施以净化处理,并主要采用物理蒸镀法,依次附着熔点为1400℃以上的高熔点金属成分和碳成分。基于采用该构成,不同于采用电化学方法来形成表面处理层的铜箔,可使表面处理层的同一平面内的膜厚均匀性优良,可形成没有组成上的偏差的表面处理层。其结果,当加工成覆铜层压板时,可减小铜箔与绝缘树脂层之间的粘附性在不同检测部位的偏差。并且,本发明的表面处理铜箔,可具备适于使未粗化的铜箔以保持良好的粘附性的状态贴合于绝缘树脂基材的表面处理层。
Claims (7)
1.一种表面处理铜箔,在与绝缘树脂基材贴合而制造覆铜层压板时所使用的铜箔的贴合面上设置有表面处理层,其特征在于,
在实施了净化处理的前述铜箔的贴合面具有由熔点为1400℃以上的高熔点金属成分和碳成分构成的表面处理层。
2.如权利要求1所述的表面处理铜箔,其中,构成设置于前述铜箔的贴合面上的表面处理层的熔点1400℃以上的高熔点金属成分的厚度是以换算厚度计为1nm~10nm。
3.如权利要求1所述的表面处理铜箔,其中,构成设置于前述铜箔的贴合面上的表面处理层的碳成分的厚度是以换算厚度计为1nm~5nm。
4.如权利要求1所述的表面处理铜箔,其中,前述熔点为1400℃以上的高熔点金属成分是钛成分。
5.如权利要求1所述的表面处理铜箔,其中,前述铜箔的贴合面没有实施粗化处理、且表面粗糙度Rzjis为2.0μm以下。
6.如权利要求1~5中任一项所述的表面处理铜箔,其中,前述铜箔的贴合面是通过前述净化处理去除了铜箔表面的铜氧化物的贴合面。
7.如权利要求1~5中任一项所述的表面处理铜箔,其中,前述铜箔的贴合面是通过前述净化处理在铜箔表面上露出净化后铜层的贴合面。
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JP2007146289A (ja) * | 2005-10-31 | 2007-06-14 | Mitsui Mining & Smelting Co Ltd | 電解銅箔の製造方法、該製造方法で得られる電解銅箔、該電解銅箔を用いて得られる表面処理銅箔及び該電解銅箔又は該表面処理銅箔を用いて得られる銅張積層板 |
TW200738913A (en) * | 2006-03-10 | 2007-10-16 | Mitsui Mining & Smelting Co | Surface treated elctrolytic copper foil and process for producing the same |
WO2007125994A1 (ja) * | 2006-04-28 | 2007-11-08 | Mitsui Mining & Smelting Co., Ltd. | 電解銅箔、その電解銅箔を用いた表面処理銅箔及びその表面処理銅箔を用いた銅張積層板並びにその電解銅箔の製造方法 |
JP4754402B2 (ja) * | 2006-05-17 | 2011-08-24 | 三井金属鉱業株式会社 | キャリア箔付銅箔、キャリア箔付銅箔の製造方法、キャリア箔付表面処理銅箔及びそのキャリア箔付表面処理銅箔を用いた銅張積層板 |
JP5024930B2 (ja) * | 2006-10-31 | 2012-09-12 | 三井金属鉱業株式会社 | 表面処理銅箔、極薄プライマ樹脂層付表面処理銅箔及びその表面処理銅箔の製造方法並びに極薄プライマ樹脂層付表面処理銅箔の製造方法 |
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2008
- 2008-07-11 JP JP2008181266A patent/JP5255349B2/ja not_active Expired - Fee Related
-
2009
- 2009-06-26 WO PCT/JP2009/061710 patent/WO2010004885A1/ja active Application Filing
- 2009-06-26 KR KR1020117000305A patent/KR101599511B1/ko not_active IP Right Cessation
- 2009-06-26 CN CN2009801265223A patent/CN102089454B/zh not_active Expired - Fee Related
- 2009-06-26 US US13/002,394 patent/US8394509B2/en not_active Expired - Fee Related
- 2009-06-30 TW TW098121954A patent/TWI434637B/zh not_active IP Right Cessation
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WO2002031065A3 (de) * | 2000-10-11 | 2002-06-27 | Chemetall Gmbh | Verfahren zur vorbehandlung und anschliessenden beschichtung von metallischen oberflächen vor der umformung mit einem lackähnlichen überzug und verwendung der derart beschichteten substrate |
JP2007081274A (ja) * | 2005-09-16 | 2007-03-29 | Oike Ind Co Ltd | フレキシブル回路用基板 |
WO2007135972A1 (ja) * | 2006-05-19 | 2007-11-29 | Mitsui Mining & Smelting Co., Ltd. | キャリアシート付銅箔、キャリアシート付銅箔の製造方法、キャリアシート付表面処理銅箔及びそのキャリアシート付表面処理銅箔を用いた銅張積層板 |
Also Published As
Publication number | Publication date |
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WO2010004885A1 (ja) | 2010-01-14 |
CN102089454A (zh) | 2011-06-08 |
KR20110039237A (ko) | 2011-04-15 |
KR101599511B1 (ko) | 2016-03-03 |
JP5255349B2 (ja) | 2013-08-07 |
US20110189503A1 (en) | 2011-08-04 |
TWI434637B (zh) | 2014-04-11 |
US8394509B2 (en) | 2013-03-12 |
TW201016090A (en) | 2010-04-16 |
JP2010018855A (ja) | 2010-01-28 |
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