WO2022191402A1 - 낮은 휨 변형을 갖는 저조도 표면처리동박, 이를 포함하는 동박적층판 및 프린트 배선판 - Google Patents
낮은 휨 변형을 갖는 저조도 표면처리동박, 이를 포함하는 동박적층판 및 프린트 배선판 Download PDFInfo
- Publication number
- WO2022191402A1 WO2022191402A1 PCT/KR2022/000439 KR2022000439W WO2022191402A1 WO 2022191402 A1 WO2022191402 A1 WO 2022191402A1 KR 2022000439 W KR2022000439 W KR 2022000439W WO 2022191402 A1 WO2022191402 A1 WO 2022191402A1
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- Prior art keywords
- copper foil
- treated
- treated copper
- foil
- less
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000011889 copper foil Substances 0.000 title claims abstract description 99
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 238000005452 bending Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000011888 foil Substances 0.000 claims abstract description 25
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000005540 biological transmission Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000010410 layer Substances 0.000 description 24
- 238000004381 surface treatment Methods 0.000 description 24
- 238000000635 electron micrograph Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 9
- 239000002335 surface treatment layer Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 241001572347 Lycaena hermes Species 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- 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
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- 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
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- 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
- B32B15/04—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
- B32B15/085—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 comprising polyolefins
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary 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
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- 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
-
- 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
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
-
- 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
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
-
- 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
Definitions
- the present invention relates to a surface-treated copper foil, and more particularly, to a surface-treated copper foil having excellent adhesive strength with a resin substrate, exhibiting low flexural deformation after adhesion to a resin substrate, and low transmission loss, suitable as a high-frequency foil, and a copper foil comprising the same It relates to a laminated board and a printed wiring board.
- the printed circuit formed on the substrate is being miniaturized, highly integrated, and miniaturized, and accordingly, the copper foil used in the printed circuit board is also required to have various physical properties.
- the composite material for a substrate used in the manufacture of flexible substrates, high-density mounting multilayer substrates, high-frequency circuit boards, etc. (hereinafter collectively referred to as 'circuit board' or 'printed wiring board') used therein is a conductor (copper foil). ) and an insulating substrate (including a film) supporting it, the insulating substrate secures insulation between conductors and has a strength sufficient to support components.
- the thickness of the insulator is getting thinner according to the trend of thinning and high integration of electronic product substrates in recent years.
- bending deformation occurs in the copper clad laminate (CCL) after lamination. Depending on the load, it can become more serious.
- U.S. Patent Publication No. 6194056 suggests a method of manufacturing a high-strength copper foil using various additives in order to minimize the change in physical properties of the copper foil, but the copper foil manufactured in this way still has high surface roughness. It is difficult to be used for high-frequency foil, and there is no consideration for reduction in bending deformation after lamination.
- the inventors of the present invention have discovered that the change in physical properties of the copper foil before and after lamination affects the warpage of the copper clad laminate after lamination.
- an object of the present invention is to provide a surface-treated copper foil suitable as a high-frequency foil that has excellent adhesive strength with a resin substrate and suppresses warpage before and after lamination press, a copper clad laminate including the same, and a printed wiring board including the same.
- the present invention provides a surface-treated copper foil comprising a surface-treated layer formed on at least one surface of the copper foil and an antioxidant layer formed on the surface-treated layer, wherein at least one surface of the surface-treated copper foil has an average particle diameter
- Surface-treated copper foil comprising fine copper particles of 100 nm or less, wherein the surface-treated copper foil has a deformation value (Y) of 5 or less expressed by the following formula;
- T1 (T1-T2)/(kgf/mm 2 )
- Y2 (E2-E1)/%
- T2 and E2 are measured after heat treatment at a pressure of 4.9 Mpa and a temperature of 220 ° C. for 90 minutes, respectively.
- tensile strength and elongation and T1 and E1 are tensile strength and elongation measured at room temperature, respectively).
- the surface-treated copper foil is manufactured as a copper clad laminate by bonding with a low dielectric resin (low DK Prepreg), polyimide (PI), hydrocarbon or polytetrafluoroethylene (PTFE) film.
- a low dielectric resin low DK Prepreg
- PI polyimide
- PTFE polytetrafluoroethylene
- the bending deformation may be 0.5 mm or less.
- the 10-point average roughness of at least one side of the surface-treated copper foil may be 0.5 ⁇ m or less, and the glossiness may be 200 or more.
- the surface-treated copper foil may have an adhesive strength of 0.5 kgf/cm or more with a low-k resin, polyimide, hydrocarbon or polytetrafluoroethylene film.
- the surface-treated copper foil may have a transmission loss (S21) at 20 GHz of 3.0 dB/100 mm or less.
- the antioxidant layer may contain at least one element selected from the group consisting of nickel, cobalt, zinc, nickel, tin and phosphorus, and may preferably include nickel and phosphorus.
- the present invention provides a copper clad laminate in which the above-described surface-treated copper foil is laminated on a resin substrate.
- the present invention provides a printed wiring board formed using the above-described copper clad laminate.
- a surface-treated copper foil, a copper clad laminate including the same, and a printed wiring board including the same which is suitable as a high-frequency foil that has excellent adhesive strength with a resin substrate and suppresses warpage before and after pressing.
- 1a and 1b are electron micrographs of observing the surfaces of the surface-treated copper foil specimens prepared in Examples before and after surface treatment (after formation of an antioxidant layer), respectively.
- FIGS. 2A and 2B are electron micrographs of grain changes in the cross section of the specimen with a focused ion beam (FIB) device before and after hot pressing of the surface-treated copper foil specimen prepared in Examples, respectively.
- FIB focused ion beam
- 3A and 3B are electron micrographs of observations of the surface of the surface-treated copper foil specimen prepared in Comparative Example 1 before and after surface treatment, respectively.
- 4A and 4B are electron micrographs of grain changes in the cross section of the specimen prepared in Comparative Example 1, respectively, with a focused ion beam device before and after hot pressing.
- 5A and 5B are electron micrographs of observing the surface of the surface-treated copper foil specimen prepared in Comparative Example 2 before and after surface treatment, respectively.
- the surface-treated copper foil of the present invention includes an original foil, a surface-treated layer on at least one surface of the original foil, and an antioxidant layer on the surface-treated layer.
- an original foil a surface-treated layer on at least one surface of the original foil
- an antioxidant layer on the surface-treated layer.
- the untreated copper foil may be an electrodeposited copper foil or a rolled copper foil.
- the thickness of the original foil is not particularly limited, but when the surface-treated copper foil is used for a printed wiring board, the thickness of the original foil may be, for example, 6 to 35 ⁇ m, preferably 7 to 17 ⁇ m.
- the original foil is 35kgf/mm 2 to 60kgf/mm 2 , 35kgf/mm 2 to 50kgf/mm 2 , or 35kgf/mm 2 to 45kgf/mm 2 It is preferable to have a tensile strength.
- the mechanical properties of the raw foil are kept constant before and after hot pressing in the bonding process with a prepreg for forming a copper clad laminate or a printed wiring board.
- the change in crystal grains before and after pressing is very small in the original foil.
- the rate of change of the tensile strength value after heat treatment at a pressure of 4.9 Mpa and a temperature of 220 ° C. for the original foil at room temperature may be less than 5%, or less than 3%.
- the rate of change of elongation after heat treatment for a predetermined time at a pressure of 4.9Mpa and a temperature of 220° C. with respect to elongation at room temperature may be less than 5% or less than 3%.
- the surface treatment layer may be formed on one or both surfaces of the original foil.
- the surface treatment method for forming the surface treatment layer of the present invention is not particularly limited, but may be formed by, for example, electrolytic plating of an original foil.
- an aqueous solution containing 5 to 60 g/L of copper salt and 50 to 200 g/L of additives may be used, for example, adjusted to pH 1 to 8 (eg, 6 to 7).
- the copper salt examples include copper sulfate (CuSO 4 ), copper nitrate (Cu(NO 3 ) 2 ), copper chloride (CuCl 2 ), copper acetate (Cu(CH 3 COO) 2 ), and the like, and as an additive, citric acid (C6H8O7), ethylenediaminetetraacetic acid (C 10 H 16 N 2 O 8 ), nitrilotriacetic acid (C 6 H 9 NO 6 ), sodium citrate (C 6 H 5 Na 3 O 7 ), tartaric acid (C 4 ) At least one selected from the group consisting of H 6 O 6 ) may be used, but is not limited thereto.
- Electrolytic plating for example, is immersed in an electrolyte using an insoluble electrode as an anode and an untreated raw foil as a cathode, and at a liquid temperature of 25 to 45° C. and a current density of 0.5 to 10 A/dm 2 , for example, 5 to 20 seconds. It may be carried out by electrolysis during the time, but is not limited thereto.
- an antioxidant layer may be formed on the surface treatment layer.
- the antioxidant layer may include nickel (Ni) and phosphorus (P).
- the antioxidant layer may further include zinc (Zn), cobalt (Co), titanium (Ti), tin (Sn), or the like, if necessary.
- the adhesion amount of the antioxidant layer for example, 30 to 300 mg/m 2 , for example 50 to 120 mg/m 2 , but may be, but is not limited thereto.
- the method for forming the antioxidant layer in the present invention is not particularly limited, but may be formed by, for example, electrolytic plating of a copper foil containing a surface treatment layer.
- an aqueous solution containing 3 to 15 g/L of nickel salt and 15 to 60 g/L of phosphoric acid (H 3 PO 4 ) may be used as the electrolyte.
- Electrolytic plating is, for example, immersed in an electrolyte using an insoluble electrode as an anode and a copper foil containing a surface treatment layer as a cathode, and at a liquid temperature of 25 to 45° C.
- nickel salt examples include nickel sulfate (NiSO4), nickel nitrate (Ni(NO 3 ) 2 ), nickel chloride (NiCl2), nickel acetate (C 4 H 6 NiO 4 ), and the like, but are not limited thereto.
- the surface-treated copper foil comprising a surface-treated layer formed on at least one surface of the copper original foil and an antioxidant layer formed on the surface-treated layer.
- the surface-treated layer-forming surface of the surface-treated copper foil contains fine copper particles having an average particle diameter of 100 nm or less.
- the fine copper particles on the surface of the surface-treated copper foil may have an average particle diameter of 10 to 100 nm, 20 to 100 nm, or 50 to 100 nm.
- the average particle diameter of the copper particles can be calculated by obtaining a Scanning Electron Microscope (SEM) image of the surface treatment layer and measuring the particle diameter of the copper particles through image analysis. It can be calculated by averaging. When the average particle diameter of the fine copper particles of the surface treatment layer is within this range, the adhesive strength with the resin substrate is excellent and the transmission loss is small, so that it can be suitable as a high-frequency foil.
- SEM Scanning Electron Microscope
- the surface-treated copper foil preferably has a deformation value (Y) of 5 or less expressed by Equation 1 below.
- T1 and E1 are tensile strength and elongation measured at room temperature, respectively. Therefore, the deformation value Y is unitless.
- the tensile strength and elongation of the surface-treated copper foil can be measured using a tensile tester according to the IPC-TM-650 2.4.18B standard.
- the surface-treated copper foil of the present invention has little change in grains before and after pressing, so that it is possible to achieve the effect of suppressing the bending deformation that occurs during adhesion to the thin prepreg. More preferably, the deformation value (Y) may be 4.5 or less, 4.0 or less, or 3.5 or less.
- the surface-treated copper foil when the surface-treated copper foil is manufactured as a copper clad laminate by bonding with a low-k resin, polyimide, hydrocarbon or polytetrafluoroethylene film, its bending deformation is 0.5 mm or less, more preferably 0.4 mm or less do it with At this time, the bending deformation can be evaluated by measuring the degree (mm) of the copper foil being rolled up after cutting a 50mm*50mm cross at the center of the copper clad laminate with a steel ruler.
- the 10-point average roughness Rz of the surface-treated copper foil may be 0.4 ⁇ m or less, 0.5 ⁇ m or less, 0.6 ⁇ m or less, or 0.7 ⁇ m or less.
- the 10-point average roughness Rz may be 0.2 ⁇ m or more or 0.3 ⁇ m or more.
- the gloss (Gs 60°) of the surface-treated copper foil may be 200 or more, 250 or more, 300 or more, and may be less than 400 or less than 500.
- '10-point average roughness Rz' may mean the 10-point average roughness Rz specified in 5.1 Definition of ten point average roughness of JIS B 0601-1994 'Definition and display of surface roughness'
- ' Gloss (Gs 60°)' may mean a value obtained by irradiating measurement light to the surface of the copper foil at an incident angle of 60° and measuring the intensity of light reflected at a reflection angle of 60° according to JIS Z 874.
- the 10-point average roughness Rz of the surface-treated copper foil may be 0.25 to 0.5 ⁇ m, for example, 0.3 to 0.45 ⁇ m
- the gloss (Gs 60°) is, for example, 200 to 400, other examples For example, it may be 220 to 380, but is not limited thereto.
- the surface-treated copper foil may have an adhesive strength of 0.5 kgf/cm or more with a low-k resin, polyimide, hydrocarbon, or polytetrafluoroethylene film.
- the adhesive strength may be an adhesive strength measured based on the JIS C6481 standard.
- the adhesive strength of the surface-treated copper foil with a low-k resin, polyimide, hydrocarbon or polytetrafluoroethylene film is 0.5 to 1.0 kgf/cm, 0.5 to 2.0 kgf/cm, 0.5 to 3.0 kgf/cm, It may be 0.5 to 4.0 kgf/cm, or 0.5 to 7.0 kgf/cm, but is not limited thereto.
- the surface-treated copper foil may have a transmission loss (S21) at 20 GHz of 3.0 dB/100 mm or less.
- the transmission loss (S21) at '20 GHz is obtained by attaching the surface-treated copper foil to the polytetrafluoroethylene resin on both sides, forming a microstrip line so that the characteristic impedance is 50 ⁇ , and then using a network analyzer. It may mean the measured transmission loss at 20 GHz.
- the transmission loss (S21) at 20 GHz of the surface-treated copper foil may be 0.5 to 3.0 dB/100 mm, 1.0 to 3.0 dB/100 mm, or 1.5 to 2.5 dB/100 mm.
- the above-mentioned surface-treated copper foil can be used as a copper-clad laminate by being laminated on a resin substrate, and this copper-clad laminate can be used to manufacture a printed wiring board.
- an electrolytic cell system with a capacity of 2L that can be circulated at 20L/min was prepared.
- the temperature of the copper electrolyte was kept constant at 45°C
- the anode was 10 mm thick and a DSE (Dimentionally Stable Electrode) plate with a size of 10 cm x 10 cm was used, and the cathode had the same size and thickness as the anode.
- an 11 ⁇ m thick raw foil was first prepared before surface treatment. Copper 100g/L, sulfuric acid 150g/L, chloride ion 30ppm, polyethylene glycol 30ppm, bis-(3-sulfopropyl)-disulfide 40ppm, 3-(benzothiazoli-2-mercapto)-propyl-sulfonic acid sodium salt 40ppm, Using a copper electrolyte consisting of 2 ppm of diethyl thiourea, the current density was 35 A/dm 2 A raw foil was prepared before surface treatment.
- the surface treatment was immersed in an aqueous solution containing copper 5g/L and disodium ethylenediaminetetraacetic acid 200g/L, and plating was performed for 10 seconds under the conditions of a solution temperature of 25°C, pH 7, and a current density of 3A/dm 2 .
- an antioxidant layer was formed on the surface-treated copper foil in an aqueous solution composed of 5 g/L of nickel and 20 g/L of phosphoric acid under the conditions of a liquid temperature of 40° C., pH 4, and a current density of 1 A/dm 2 .
- Example 2 In the production of the raw foil before surface treatment, the same as in Example 1, except that the raw foil was prepared before surface treatment by plating in a copper electrolyte consisting of only 250 to 400 g/L of copper, 80 to 150 g/L of sulfuric acid, and 1 ppm of chlorine ions. A surface-treated copper foil was prepared using the method.
- Example 2 The same method as in Example 1 was used, except that the surface was treated by plating for 10 seconds under the conditions of an electrolyte temperature of 30° C. and a current density of 15 A/dm 2 in a copper electrolyte consisting of 25 g/L of copper and 150 g/L of sulfuric acid. A treated copper foil was prepared.
- the tensile strength and elongation were measured using a tensile tester according to the IPC-TM-650 2.4.18B standard.
- the 10-point average roughness R z was measured after surface treatment of the copper foil using a surface roughness meter.
- An SEM image was taken of the surface of the copper foil after surface treatment using a scanning electron microscope, and the particle size of 100 copper particles in an area of 100 ⁇ m ⁇ 100 ⁇ m was measured, and the average value thereof was obtained.
- Adhesive strength (unit: kgf/cm)
- Adhesive strength of surface-treated copper foil was measured according to JIS C6481 standard.
- the insulator used was a product with a thickness of 40 ⁇ m, a product name of Panasonic Corporation, MEGTRON (R-5785).
- a transmission loss of 20 GHz was obtained using S21 is suitable for high-speed transmission because the closer the value is to 0, the less transmission loss.
- Occurrence was classified into occurrence (O) and non-occurrence (X).
- 1A and 1B are electron micrographs of observations of the surface of the surface-treated copper foil specimen prepared in Examples before and after surface treatment and oxidation prevention layer formation, respectively.
- the surface of the specimen of the example shows a smooth surface before surface treatment (1a), and after surface treatment (1b), it can be seen that fine copper particles of 100 nm or less are generated on the surface of the specimen. have.
- Figures 2a and 2b are electron micrographs of the crystal grain change of the cross section of the specimen with FIB before and after hot pressing of the surface-treated copper foil specimen prepared in Examples, respectively.
- FIGS. 3A and 3B are electron micrographs of observing the surface of the surface-treated copper foil specimen prepared in Comparative Example 1 before the surface treatment and after the surface treatment and the formation of the antioxidant layer, respectively, FIGS. 4A and 4B are respectively in Comparative Example 1 It is an electron micrograph of the grain change of the cross section of the specimen with FIB before and after hot pressing of the prepared surface-treated copper foil specimen.
- the specimen of Comparative Example 1 shows a relatively high roughness compared to that of Example (FIG. 1A) before surface treatment (FIG. 3A), and after surface treatment (FIG. 3B) ) It can be seen that fine copper particles are formed.
- FIGS. 4A and 4B it can be seen that, in the specimen of Comparative Example 1, the grain size after pressing ( FIG. 4B ) was significantly increased compared to before pressing ( FIG. 4A ).
- FIG. 5A and 5B are electron micrographs of observations of the surface of the surface-treated copper foil specimen prepared in Comparative Example 2 before (FIG. 5A) and after the surface treatment and the formation of the antioxidant layer (FIG. 5B), respectively. As shown, it can be seen that the specimen of Comparative Example 2 has coarse copper particles formed on the surface after the surface treatment and the formation of the antioxidant layer (FIG. 5b).
- Table 1 is a table summarizing the change value (Y) calculation results for the specimens prepared in Example 1 and Comparative Examples 1 to 2
- Table 2 is the specimen prepared in Examples and Comparative Examples 1 to 2 This is a table summarizing the results of physical property evaluation of
- Example 1 3.4 0.34 67 307 0.57 1.9 0.4 Comparative Example 1 51.1 0.89 54 69 0.32 2.7 5.8 Comparative Example 2 1.8 0.79 1224 63 0.71 3.8 0.6
- the specimen of Comparative Example 1 exhibits a phenomenon in which the surface-treated surface roughness is higher than that of the specimen of Example, but the adhesive strength decreases due to a decrease in strength after pressing.
- Comparative Example 2 showed a higher adhesive strength than that of Example, but it was confirmed that the transmission loss characteristics were deteriorated due to relatively large copper particles and high roughness.
- the present invention can be applied to an electrodeposited copper foil, a copper clad laminate, and a printed wiring board.
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Abstract
Description
구분 | 인장강도(kgf/mm2) | 연신율(%) | 변화수치 Y | ||||
T1 | T2 | T1-T2 | E1 | E2 | E2-E1 | ||
실시예1 | 43.3 | 41.9 | 1.4 | 10.5 | 12.5 | 2 | 3.4 |
비교예1 | 53.3 | 23.9 | 29.4 | 5.2 | 16.9 | 11.7 | 51.1 |
비교예2 | 41.9 | 40.3 | 1.6 | 11.9 | 12.1 | 0.2 | 1.8 |
구분 | 변화수치 (Y) |
표면처리면 Rz (㎛) |
구리입자크기 (nm) |
광택도 (Gs 60도) |
접착강도 (kgf/cm) |
S21@20Ghz (dB/100mm) |
동박 휨 변형 (mm) |
실시예1 | 3.4 | 0.34 | 67 | 307 | 0.57 | 1.9 | 0.4 |
비교예1 | 51.1 | 0.89 | 54 | 69 | 0.32 | 2.7 | 5.8 |
비교예2 | 1.8 | 0.79 | 1224 | 63 | 0.71 | 3.8 | 0.6 |
Claims (10)
- 구리 원박의 적어도 한 면에 형성된 표면처리층과 상기 표면처리층 상에 형성된 산화방지층을 포함하는 표면처리동박에 있어서,표면처리동박의 적어도 한 면은 평균입경이 100 nm 이하인 미세 구리 입자를 포함하고,상기 표면처리동박은 아래의 수식으로 표현되는 변형 수치(Y)가 5 이하인 것을 특징으로 하는 표면처리동박;변형수치(Y) = 인장강도 변형수치(Y1) + 연신율 변형수치(Y2)(여기서, Y1 = (T1-T2)/(kgf/mm2)이고, Y2 = (E2-E1)/%이며, T2 및 E2는 각각 4.9Mpa의 압력 및 220℃의 온도에서 90 분간 열처리 후 측정한 인장강도와 연신율이고, T1과 E1은 각각 상온에서 측정한 인장강도와 연신율임).
- 제1항에 있어서,상기 표면처리동박은, 저유전 수지(low DK Prepreg), 폴리이미드(PI), 하이드로카본(Hydrocarbon) 또는 폴리테트라플루오로에틸렌(PTFE) 필름과 접착하여 동박적층판으로 제조된 경우, 휨 변형이 0.5 mm 이하인 것을 특징으로 하는 표면처리동박.
- 제1항에 있어서,상기 표면 처리 동박의 적어도 한 면의 10점 평균 조도는 0.5 μm이하이고, 광택도는 200이상인 것을 특징으로 하는 표면처리동박.
- 제1항에 있어서,상기 구리 원박은 전해 동박인 것을 특징으로 하는 표면처리동박.
- 제1항에 있어서,상기 표면처리동박은 저유전 수지, 폴리이미드, 하이드로카본 또는 폴리테트라플루오로에틸렌 필름과의 접착강도가 0.5 kgf/cm 이상인 것을 특징으로 하는 표면처리동박.
- 제1항에 있어서,상기 표면처리동박은 20 GHz에서의 전송손실(S21)이 3.0 dB/100㎜ 이하인 것을 특징으로 하는 표면처리동박.
- 제1항에 있어서,상기 산화방지층은 니켈, 코발트, 아연, 니켈, 주석 및 인으로 이루어진 그룹 중에서 선택된 최소한 1종의 원소를 함유한 것을 특징으로 하는 표면 처리 동박.
- 제7항에 있어서,상기 산화방지층은 니켈 및 인을 포함하는 것을 특징으로 하는 표면처리동박.
- 수지 기판상에 제1항 내지 제8항에 중 어느 한 항에 기재된 표면처리동박이 적층된 동박적층판.
- 제9항 기재의 동박적층판을 사용하여 형성된 프린트 배선판.
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JP2023546150A JP2024505241A (ja) | 2021-03-11 | 2022-01-11 | 低い曲げ変形を有する低粗度表面処理銅箔、これを含む銅箔積層板及びプリント配線板 |
US18/275,329 US20240121902A1 (en) | 2021-03-11 | 2022-01-11 | Low-roughness surface-treated copper foil with low bending deformation, copper clad laminate comprising same, and printed wiring board |
EP22767299.5A EP4307846A1 (en) | 2021-03-11 | 2022-01-11 | Low-roughness surface-treated copper foil with low bending deformation, copper clad laminate comprising same, and printed wiring board |
CN202280011278.1A CN116762482A (zh) | 2021-03-11 | 2022-01-11 | 具有低表面粗糙度及低翘曲的表面处理铜箔、包括该铜箔的铜箔基板及包括该铜箔的印刷配线板 |
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US20090136725A1 (en) * | 2006-03-24 | 2009-05-28 | Hiroto Shimokawa | Process for producing copper wiring polyimide film, and copper wiring polyimide film |
WO2010110092A1 (ja) * | 2009-03-27 | 2010-09-30 | 日鉱金属株式会社 | プリント配線板用銅箔及びその製造方法 |
KR20130132111A (ko) * | 2012-05-25 | 2013-12-04 | 일진머티리얼즈 주식회사 | 표면처리동박, 상기 동박을 포함하는 프린트배선판용 동부착적층판, 상기 프린트배선판의 제조방법, 및 상기 표면처리동박의 제조방법 |
JP2016149438A (ja) * | 2015-02-12 | 2016-08-18 | 福田金属箔粉工業株式会社 | 処理銅箔及び該処理銅箔を用いた銅張積層板並びにプリント配線板 |
KR20190135878A (ko) * | 2018-05-29 | 2019-12-09 | 케이씨에프테크놀로지스 주식회사 | 고강도 동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조 방법 |
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JP2003268567A (ja) | 2002-03-19 | 2003-09-25 | Hitachi Cable Ltd | 導電材被覆耐食性金属材料 |
JP6083619B2 (ja) * | 2015-07-29 | 2017-02-22 | 福田金属箔粉工業株式会社 | 低誘電性樹脂基材用処理銅箔及び該処理銅箔を用いた銅張積層板並びにプリント配線板 |
KR101944783B1 (ko) * | 2017-01-16 | 2019-04-18 | 일진머티리얼즈 주식회사 | 캐리어박 부착 극박동박 |
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2021
- 2021-03-11 KR KR1020210032133A patent/KR102495997B1/ko active IP Right Grant
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2022
- 2022-01-11 WO PCT/KR2022/000439 patent/WO2022191402A1/ko active Application Filing
- 2022-01-11 JP JP2023546150A patent/JP2024505241A/ja active Pending
- 2022-01-11 EP EP22767299.5A patent/EP4307846A1/en active Pending
- 2022-01-11 CN CN202280011278.1A patent/CN116762482A/zh active Pending
- 2022-01-11 US US18/275,329 patent/US20240121902A1/en active Pending
- 2022-02-16 TW TW111105622A patent/TW202246581A/zh unknown
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US6194056B1 (en) | 1996-05-13 | 2001-02-27 | Mitsui Mining & Smelting Co., Ltd. | High tensile strength electrodeposited copper foil |
US20090136725A1 (en) * | 2006-03-24 | 2009-05-28 | Hiroto Shimokawa | Process for producing copper wiring polyimide film, and copper wiring polyimide film |
WO2010110092A1 (ja) * | 2009-03-27 | 2010-09-30 | 日鉱金属株式会社 | プリント配線板用銅箔及びその製造方法 |
KR20130132111A (ko) * | 2012-05-25 | 2013-12-04 | 일진머티리얼즈 주식회사 | 표면처리동박, 상기 동박을 포함하는 프린트배선판용 동부착적층판, 상기 프린트배선판의 제조방법, 및 상기 표면처리동박의 제조방법 |
JP2016149438A (ja) * | 2015-02-12 | 2016-08-18 | 福田金属箔粉工業株式会社 | 処理銅箔及び該処理銅箔を用いた銅張積層板並びにプリント配線板 |
KR20190135878A (ko) * | 2018-05-29 | 2019-12-09 | 케이씨에프테크놀로지스 주식회사 | 고강도 동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조 방법 |
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EP4307846A1 (en) | 2024-01-17 |
US20240121902A1 (en) | 2024-04-11 |
CN116762482A (zh) | 2023-09-15 |
KR20220127618A (ko) | 2022-09-20 |
JP2024505241A (ja) | 2024-02-05 |
KR102495997B1 (ko) | 2023-02-06 |
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