JP5666384B2 - Ultrathin copper foil with support and method for producing the same - Google Patents
Ultrathin copper foil with support and method for producing the same Download PDFInfo
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- JP5666384B2 JP5666384B2 JP2011121780A JP2011121780A JP5666384B2 JP 5666384 B2 JP5666384 B2 JP 5666384B2 JP 2011121780 A JP2011121780 A JP 2011121780A JP 2011121780 A JP2011121780 A JP 2011121780A JP 5666384 B2 JP5666384 B2 JP 5666384B2
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- thin copper
- plating bath
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 156
- 239000011889 copper foil Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 114
- 239000010949 copper Substances 0.000 claims description 114
- 238000007747 plating Methods 0.000 claims description 107
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 29
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 26
- 108010010803 Gelatin Proteins 0.000 claims description 25
- 239000008273 gelatin Substances 0.000 claims description 25
- 229920000159 gelatin Polymers 0.000 claims description 25
- 235000019322 gelatine Nutrition 0.000 claims description 25
- 235000011852 gelatine desserts Nutrition 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000010410 layer Substances 0.000 description 162
- 238000005530 etching Methods 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 30
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 15
- -1 triazole compound Chemical class 0.000 description 14
- 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 13
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 11
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000007788 roughening Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YCEZCVWJUDFQKH-UHFFFAOYSA-K [Ni+2].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Cu+2] Chemical compound [Ni+2].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Cu+2] YCEZCVWJUDFQKH-UHFFFAOYSA-K 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000013459 approach 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は、微細回路の形成に適する支持体付極薄銅箔とその製造方法に関する。 The present invention relates to an ultrathin copper foil with a support suitable for forming a fine circuit and a method for producing the same.
プリント配線板の製造技術に基づく種々の半導体パッケージが提案、実用化されている。これらの半導体パッケージでは多端子化と高密度化に対応するため、微細回路を形成することが要求される。なお、微細回路とは、回路の幅ならびに回路の間隔が狭小なことを意味する。微細回路の形成にはセミアディティブ工法が用いられる傾向がある。セミアディティブ工法は次の工程からなる。すなわち、（１）樹脂基材上に極薄銅層を形成する工程、（２）回路部以外の極薄銅層上にレジストを形成する工程、（３）レジストで被覆された以外の部分の極薄銅層上に電気めっきにより回路の導体厚さを増加する工程、（４）レジストを除去する工程、（５）回路間の薄銅層をエッチング除去する工程、である。極薄銅層を樹脂基材上に形成するには、一般的な厚さの電解銅箔を樹脂基材と積層形成後に全面エッチングする方法もあるが、均一な厚さを確保することが難しい。一方、支持体上に剥離可能な極薄銅層を形成した支持体付極薄銅箔を樹脂基材と積層形成後に支持体を除去する方法は、極薄銅層の厚さが均一で、微細回路の形成に適している（特許文献１）。支持体付極薄銅箔は、支持体上に剥離層を形成後、硫酸浴等を用いた銅めっきにより極薄銅層を剥離層上に形成して製造する。極薄銅層の厚さは２〜５μｍが一般的である。なぜなら極薄銅層は上記（３）の電気めっきにおける給電層として必須であるが、厚いと上記（５）のエッチング工程において、回路が過剰なエッチングを受け、断面が不整形となるからである。また、極薄銅層のエッチング速度が上記（３）の電気めっきで形成された回路の銅層に比べて遅いと同様に断面が不整形となり、好ましくない。更に微細回路間の絶縁性を確保するため、回路の直線性が良好であることが要求される。 Various semiconductor packages based on printed wiring board manufacturing technology have been proposed and put to practical use. In these semiconductor packages, it is required to form a fine circuit in order to cope with the increase in the number of terminals and the increase in density. The fine circuit means that the circuit width and the circuit interval are narrow. There is a tendency that a semi-additive method is used for forming a fine circuit. The semi-additive construction method consists of the following steps. That is, (1) a step of forming an ultrathin copper layer on a resin substrate, (2) a step of forming a resist on an ultrathin copper layer other than the circuit portion, and (3) a portion other than the portion covered with the resist A step of increasing the conductor thickness of the circuit by electroplating on the ultrathin copper layer, (4) a step of removing the resist, and (5) a step of etching away the thin copper layer between the circuits. In order to form an ultra-thin copper layer on a resin substrate, there is a method of etching the entire surface of an electrolytic copper foil having a general thickness after being laminated with the resin substrate, but it is difficult to ensure a uniform thickness. . On the other hand, the method of removing the support after forming the ultrathin copper foil with support on which the peelable ultrathin copper layer is laminated with the resin base material, the thickness of the ultrathin copper layer is uniform, It is suitable for forming fine circuits (Patent Document 1). The ultrathin copper foil with a support is produced by forming an exfoliation layer on the support and then forming an ultrathin copper layer on the exfoliation layer by copper plating using a sulfuric acid bath or the like. The thickness of the ultrathin copper layer is generally 2 to 5 μm. This is because the ultrathin copper layer is indispensable as a power feeding layer in the electroplating of (3) above, but if it is thick, the circuit is excessively etched in the etching process of (5) above, and the cross section becomes irregular. . Further, if the etching rate of the ultra-thin copper layer is slower than the copper layer of the circuit formed by the electroplating of (3) above, the cross-section becomes irregular, which is not preferable. Furthermore, in order to ensure the insulation between the fine circuits, it is required that the circuit has good linearity.
エッチング性（速度、直線性）を決定する要因は３つある。第１は防錆処理金属に起因する要因で、防錆金属の種類、量によって調整することができる。なお、防錆処理金属は極薄銅層の露出された表面に形成されたニッケルやコバルト等を含有する金属の薄膜で、表面の好ましくない劣化を防止するために必須である。第２は樹脂基材との密着性を確保するために接着面に施される粗化処理に起因する要因で、粗化粒子の状態（高さ、密度等）によって調整することができる。第３は薄銅層の結晶状態に起因する要因である。 There are three factors that determine the etching properties (speed, linearity). The first is a factor resulting from the rust-proof metal, and can be adjusted by the type and amount of the rust-proof metal. The rust-proof metal is a metal thin film containing nickel, cobalt or the like formed on the exposed surface of the ultrathin copper layer, and is essential for preventing undesired deterioration of the surface. The second is a factor resulting from the roughening treatment applied to the adhesive surface in order to ensure adhesion with the resin substrate, and can be adjusted according to the state (height, density, etc.) of the roughened particles. The third is a factor resulting from the crystalline state of the thin copper layer.
銅層のエッチング速度を改善する手段として、有機物を意図的に高濃度に分散させた高炭素含有銅にすることが特許文献２に示されている。しかし、炭素含有量が増加すると導電性が低下し、高速信号への対応が必要な半導体パッケージに使用するのは問題がある。また、円柱状結晶及び双晶境界がなく平均粒子サイズが１０μｍ以下であること、６００Ｎ／ｍｍ２を超える常態引張強さとすることが特許文献３に示されている。しかし、製造工程において結晶状態の観察が必要であるが、これは工業的な量産では困難であり、また、支持体付極薄銅箔では極薄銅層の引張強さが６００Ｎ／ｍｍ２を超えると内部応力により極薄銅側にカールが大きく発生し、取扱い性が著しく困難で実際の製造ラインで使用することができない。 As a means for improving the etching rate of the copper layer, Patent Document 2 discloses that a high carbon content copper in which an organic substance is intentionally dispersed at a high concentration is used. However, when the carbon content increases, the conductivity decreases, and there is a problem in using it for a semiconductor package that needs to cope with high-speed signals. Patent Document 3 discloses that there is no columnar crystal and twin boundary, the average particle size is 10 μm or less, and the normal tensile strength exceeds 600 N / mm 2 . However, although it is necessary to observe the crystalline state in the manufacturing process, this is difficult in industrial mass production, and in the ultrathin copper foil with a support, the tensile strength of the ultrathin copper layer is 600 N / mm 2 . If it exceeds, curling will occur greatly on the ultrathin copper side due to internal stress, handling will be extremely difficult and it will not be possible to use it in an actual production line.
このようなことから、本発明では支持体付極薄銅箔の薄銅層の結晶状態を定量的に評価可能とし、エッチング性が良好で微細回路の加工に適すると共に、ハンドリング時の耐傷性を改善した支持体付極薄銅箔を提供することを目的とする。 Therefore, in the present invention, the crystalline state of the thin copper layer of the ultrathin copper foil with a support can be quantitatively evaluated, the etching property is good and suitable for processing a fine circuit, and the scratch resistance at the time of handling is improved. An object is to provide an ultrathin copper foil with an improved support.
本発明者らは結晶粒の大きさに着目し、エッチング性との関係を検討することとして本発明を完成した。極薄銅層の結晶状態はめっき条件によって変化させることができる。一般的にはめっき時の電流密度がめっき浴の限界電流密度に近くなるほど結晶は微細化する。めっき電流密度を上げる以外には浴温度の低下、めっき液中銅濃度の低下、撹拌量の低下等はいずれも同様な効果がある。また、ゼラチン、膠等の有機添加剤を添加することによっても結晶は微細化できる。 The present inventors have completed the present invention by paying attention to the size of the crystal grains and examining the relationship with the etching property. The crystal state of the ultrathin copper layer can be changed depending on the plating conditions. Generally, the crystal becomes finer as the current density during plating approaches the limit current density of the plating bath. In addition to increasing the plating current density, a decrease in bath temperature, a decrease in copper concentration in the plating solution, a decrease in the amount of stirring, etc. all have similar effects. Crystals can be refined by adding organic additives such as gelatin and glue.
一方、プリント配線板を製造する場合には樹脂基材を硬化させるため加熱・加圧処理が行われる。一般的なＦＲ−４基材で１８０℃、１時間程度、高耐熱性基材の場合には２３０℃の加熱が行われる。この時、微細化した結晶は加熱条件及び薄銅層製造条件により程度の差はあるものの再結晶が進み結晶が大きくなる。 On the other hand, when manufacturing a printed wiring board, a heating / pressurizing process is performed to cure the resin base material. A general FR-4 base material is heated at 180 ° C. for about 1 hour, and a high heat resistant base material is heated at 230 ° C. At this time, although the refined crystal has a degree of difference depending on the heating condition and the thin copper layer manufacturing condition, recrystallization proceeds and the crystal becomes large.
結晶が大きいとエッチング速度が遅いとともに細線の形成が難しくなる問題点がある。これは結晶界面が結晶内部よりもエッチングされやすいことによる。すなわち、結晶粒が小さいと結晶界面が多数存在し、エッチングが容易に行われること、さらに、結晶粒内部のエッチングではエッチングの不均一さが生じやすく、結局、エッチングにより形成される断面が不整形となりやすいことによる。結果としてエッチングにより形成された回路の直線性が十分でないこととなり、これは特に回路間隔が狭い場合には深刻な問題となる。 When the crystal is large, there are problems that the etching rate is slow and it is difficult to form fine lines. This is because the crystal interface is more easily etched than inside the crystal. That is, if the crystal grains are small, there are many crystal interfaces, and etching is easily performed. Further, etching inside the crystal grains tends to cause non-uniform etching, and the cross section formed by etching is irregularly formed. Because it tends to be. As a result, the linearity of the circuit formed by etching is not sufficient, which is a serious problem especially when the circuit interval is narrow.
特にセミアディティブ工法で用いられる硫酸−過酸化水素系のエッチング液ではその影響が顕著となる。回路間隔が１０μｍ以下の微細配線になると直線性の低い回路では回路間の絶縁性が確保できず、ショートする可能性が高まる。 In particular, the influence becomes remarkable in the sulfuric acid-hydrogen peroxide etching solution used in the semi-additive method. If the circuit spacing is fine wiring of 10 μm or less, a circuit with low linearity cannot secure insulation between circuits, and the possibility of short-circuiting increases.
また、再結晶した銅層は一般に機械的強度（引張強さ）が小さい。機械的強度が小さいと、ハンドリング時に傷つきやすく、薄銅層では貫通した穴となりやすく、形成された微細回路に欠陥が生じる恐れがある。 Further, the recrystallized copper layer generally has a low mechanical strength (tensile strength). If the mechanical strength is low, it is easy to be damaged during handling, and a thin copper layer tends to be a through-hole, which may cause a defect in the formed fine circuit.
従って、銅張積層板の製造時における薄銅層のエッチング性、耐傷性、ハンドリング性を評価するためには、積層工程時と同様の加熱履歴後の薄銅層の特性を管理することが必要となる。 Therefore, in order to evaluate the etching properties, scratch resistance, and handling properties of thin copper layers during the manufacture of copper-clad laminates, it is necessary to manage the characteristics of the thin copper layers after the heating history as in the lamination process. It becomes.
本発明者らが検討した結果、平均分子量が５０００以下のゼラチンを添加剤として１５〜３５ｐｐｍ添加した硫酸銅めっき浴を用いて支持体上や、支持体上の剥離層上に陰極電解処理することにより、高温加熱後も適度な機械的強度を有し、エッチング性に優れ、かつハンドリング性にも優れる薄銅層を形成できることを見出した。 As a result of the study by the present inventors, cathodic electrolysis treatment is performed on a support or a release layer on a support using a copper sulfate plating bath in which 15 to 35 ppm of gelatin having an average molecular weight of 5000 or less is added as an additive. Thus, it has been found that a thin copper layer having an appropriate mechanical strength even after high-temperature heating, excellent etching properties and excellent handling properties can be formed.
即ち、本発明は、（１）支持体上に薄銅層が剥離可能に形成されている支持体付極薄銅箔であって、薄銅層の２３０℃１時間加熱処理後（以下、単に加熱後ということがある。）のビッカース硬度が１８０〜２４０Ｈｖであることを特徴とする支持体付極薄銅箔に関する。 That is, the present invention is (1) an ultrathin copper foil with a support in which a thin copper layer is formed on a support so that the thin copper layer can be peeled off. It may be after heating.) Vickers hardness of 180 to 240 Hv.
また、本発明は、（２）薄銅層の２３０℃１時間加熱処理後の引張強さが５００〜６００Ｎ／ｍｍ２であることを特徴とする（１）に記載の支持体付極薄銅箔に関する。 In addition, the present invention provides: (2) Ultrathin copper with support according to (1), wherein the thin copper layer has a tensile strength of 500 to 600 N / mm 2 after heat treatment at 230 ° C. for 1 hour. Regarding foil.
また、本発明は、（３）薄銅層の２３０℃１時間加熱処理後の断面の結晶粒度が０．０００５ｍｍ以下であることを特徴とする（１）又は（２）に支持体付極薄銅箔に関する。 The present invention is also characterized in that (3) the crystal grain size of the cross section after heat treatment at 230 ° C. for 1 hour of the thin copper layer is 0.0005 mm or less, (1) or (2) Related to copper foil.
また、本発明は、（４）支持体が金属からなる支持体金属層であり、支持体金属層と薄銅層との間に、薄銅層を剥離可能とする剥離層を有する（１）〜（３）いずれかに記載の支持体付極薄銅箔に関する。 Moreover, this invention is (4) a support body metal layer which a support body consists of a metal, and has a peeling layer which can peel a thin copper layer between a support body metal layer and a thin copper layer (1). -(3) It is related with the ultra-thin copper foil with a support in any one.
また、本発明は、（５）平均分子量が５０００以下のゼラチンを１５〜３５ｐｐｍ含有する硫酸銅めっき浴を用いて電解処理することにより形成される薄銅層を、支持体上に剥離可能に形成することを特徴とする（１）〜（４）いずれかに記載の支持体付極薄銅箔の製造方法に関する。なお、本明細書中、ゼラチンの平均分子量とは、写真用ゼラチン試験方法第１０版（２００６年版）の平均分子量測定法に規定される重量平均分子量を意味する。 Further, the present invention provides (5) a thin copper layer formed by electrolytic treatment using a copper sulfate plating bath containing 15 to 35 ppm of gelatin having an average molecular weight of 5000 or less so as to be peelable on the support. The invention relates to a method for producing an ultrathin copper foil with a support according to any one of (1) to (4). In the present specification, the average molecular weight of gelatin means the weight average molecular weight defined in the average molecular weight measurement method of Photographic Gelatin Test Method 10th Edition (2006 version).
また、本発明は、（６）（１）〜（４）いずれかに記載の支持体付極薄銅箔を用いて得られる銅張積層板に関する。 Moreover, this invention relates to the copper clad laminated board obtained using the ultra-thin copper foil with a support body in any one of (6) (1)-(4).
本発明による薄銅層を有する支持体付極薄銅箔は、エッチング性が良好で微細回路形成に適すると共に、ハンドリング時の耐傷性を改善できるので、半導体パッケージ等の製造に用いるセミアディティブ工法に適する。 The ultrathin copper foil with a support having a thin copper layer according to the present invention has good etching properties and is suitable for fine circuit formation, and can improve scratch resistance during handling, so that it is a semi-additive method for manufacturing semiconductor packages and the like. Suitable.
本発明で用いる支持体としては、アルミニウム箔、アルミニウム合金箔、ステンレス箔、チタン箔、チタン合金箔、圧延銅箔及び電解銅箔等の金属からなる支持体金属層が挙げられ、その厚さも、特に規定するものではない。コストや製造工程、機械特性及び化学特性から、銅からなる支持体金属層を用いることが好ましく、例えば、厚さ８μｍ〜３５μｍの電解銅箔が好ましい。表面粗さについては、薄銅層と樹脂基材との接着強度が必要な場合は、支持体金属層の表面粗さは、回路直線性に影響しない範囲で大きいことが好ましく、一方、微細回路の形成が必要な場合は、表面粗さが小さいことが望ましい。また、薄銅層が薄い場合も表面粗さの小さいことが好ましい。 Examples of the support used in the present invention include a support metal layer made of a metal such as an aluminum foil, an aluminum alloy foil, a stainless steel foil, a titanium foil, a titanium alloy foil, a rolled copper foil and an electrolytic copper foil. It is not specified. From the viewpoint of cost, manufacturing process, mechanical properties, and chemical properties, it is preferable to use a support metal layer made of copper. For example, an electrolytic copper foil having a thickness of 8 μm to 35 μm is preferable. As for the surface roughness, when the adhesive strength between the thin copper layer and the resin base material is required, the surface roughness of the support metal layer is preferably large as long as it does not affect the circuit linearity. When it is necessary to form the film, it is desirable that the surface roughness be small. Also, when the thin copper layer is thin, it is preferable that the surface roughness is small.
支持体金属層が、アルミニウム、アルミニウム合金、ステンレス、チタン、チタン合金等の材質からなる場合には、支持体金属層の上にめっき処理によって直接薄銅層を形成することにより、薄銅層を剥離可能に形成することができる。 When the support metal layer is made of a material such as aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, etc., the thin copper layer is formed directly on the support metal layer by plating. It can form so that peeling is possible.
支持体金属層の材質が銅である場合には、支持体金属層と薄銅層との間に、剥離を可能とする剥離層を設けることが好ましい。剥離層は有機系剥離層、無機系剥離層のいずれであってもよく、また、それらの組合せでも用いることができる。 When the material of the support metal layer is copper, it is preferable to provide a release layer capable of peeling between the support metal layer and the thin copper layer. The release layer may be either an organic release layer or an inorganic release layer, or a combination thereof.
有機系剥離層としては、例えば、ベンゾトリアゾール等のトリアゾール化合物、オレイン酸等のカルボン酸化合物、チオール化合物等からなる剥離層が挙げられる。無機系剥離層としては、例えば、鉄、ニッケル、コバルト等から選ばれる１種以上の金属及びその金属酸化物、並びに、クロム、モリブデン、タングステンから選ばれる１種以上の金属及びその金属酸化物を含有する剥離層が挙げられる。また、上記有機系剥離層と無機系剥離層とを組み合わせた剥離層としてもよい。耐熱性の点から無機系剥離層が好ましい。 Examples of the organic release layer include a release layer made of a triazole compound such as benzotriazole, a carboxylic acid compound such as oleic acid, a thiol compound, and the like. Examples of the inorganic release layer include one or more metals selected from iron, nickel, cobalt, and the like, and metal oxides thereof, and one or more metals selected from chromium, molybdenum, tungsten, and the metal oxides thereof. An exfoliation layer to contain is mentioned. Moreover, it is good also as a peeling layer which combined the said organic type peeling layer and the inorganic type peeling layer. In view of heat resistance, an inorganic release layer is preferred.
剥離層の形成前に、支持体金属層の表面を適切な前処理によって清浄化することが好ましい。通常の酸洗処理のほか、アルカリ脱脂や電解洗浄を行ってもよい。 Prior to the formation of the release layer, the surface of the support metal layer is preferably cleaned by an appropriate pretreatment. In addition to the usual pickling treatment, alkaline degreasing or electrolytic cleaning may be performed.
無機系剥離層の具体例としては、例えば特許文献１に示される方法で形成される剥離層が挙げられる。この剥離層は、タングステンの合金及びタングステンを含有する金属酸化物を含有する層、又はモリブデンの合金及びモリブデンを含有する金属酸化物を含有する層である。この剥離層は、めっき浴として、タングステン酸化合物若しくはモリブデン酸化合物と、鉄族元素を含有する化合物と、クエン酸とを含有するめっき浴を用いて電解めっきすることにより形成され、一方の表面がタングステン又はモリブデンの合金から主としてなり、他方の表面がタングステン又はモリブデンを含有する金属酸化物から主としてなる剥離層が形成される。支持体金属層を陰極として電解めっきを行うと、支持体金属層に接する剥離層の表面は、合金を主として含有する表面となる。剥離層の他方の表面は、金属酸化物を主として含有する表面となり、薄銅層の剥離を可能とする。めっき浴に用いられる鉄族元素としては、ニッケルが好ましく用いられる。めっき浴には、液抵抗値調整の目的で、硫酸ナトリウムなどの無機塩を添加してもよい。めっき浴中のタングステン酸化合物又はモリブデン酸化合物の濃度は、各々金属換算で、通常、０．１〜１０ｇ／ｌ、好ましくは０．５〜２ｇ／ｌである。また、鉄族元素を含有する化合物の濃度は、金属換算で、通常、０．６〜６０ｇ／ｌ、好ましくは３〜１２ｇ／ｌである。クエン酸の濃度は、ナトリウムイオン等の析出しない金属を除く金属種に対してモル換算で、すなわち、タングステン酸化合物又はモリブデン酸化合物と鉄族元素を含有する化合物との合計モル数に対して、通常、０．２〜５倍、好ましくは０．５〜２倍である。タングステン酸化合物としては、例えば、タングステン酸ナトリウム２水和物等のタングステン酸塩又はその水和物を用いることができる。モリブデン酸化合物としては、例えば、モリブデン酸ナトリウム２水和物等のモリブデン酸塩又はその水和物を用いることができる。鉄族元素を含有する化合物としては、例えば、硫酸ニッケル６水和物等のニッケル塩又はその水和物を用いることができる。クエン酸源としては、例えば、クエン酸３ナトリウム２水和物等のクエン酸塩又はその水和物を用いることができる。めっき浴の溶媒は通常水である。めっき浴温度は、通常、５〜７０℃、好ましくは１０〜５０℃である。電流密度は、通常、０．２〜１０Ａ／ｄｍ２、好ましくは０．５〜５Ａ／ｄｍ２である。また、めっき浴のｐＨは、通常、２〜８、好ましくは４〜７の範囲である。上記の条件で電気めっきを行うと、まず、主として金属が析出し、電解めっきの進行とともに酸化物が主として析出される。酸化物から主としてなる表面が剥離機能を発現し、一方、金属を主体とする表面は、銅原子の熱拡散による層構造の一体化を抑制する。剥離層の厚さと組成は、めっき浴の組成と電解条件によって制御される。通常、このようにして形成する剥離層の厚さは、０．００５〜０．５μｍとなる。剥離層は、一段で形成してもよいが、電気めっきを複数回繰り返して形成してもよい。 As a specific example of the inorganic release layer, for example, a release layer formed by the method disclosed in Patent Document 1 can be given. This release layer is a layer containing a tungsten alloy and a metal oxide containing tungsten, or a layer containing a molybdenum alloy and molybdenum containing metal oxide. This release layer is formed by electrolytic plating using a plating bath containing a tungstic acid compound or molybdic acid compound, a compound containing an iron group element, and citric acid as a plating bath, and one surface thereof is formed. A release layer mainly formed of an alloy of tungsten or molybdenum and the other surface mainly formed of a metal oxide containing tungsten or molybdenum is formed. When electrolytic plating is performed using the support metal layer as a cathode, the surface of the release layer in contact with the support metal layer becomes a surface mainly containing an alloy. The other surface of the release layer is a surface mainly containing a metal oxide, and enables the thin copper layer to be peeled off. Nickel is preferably used as the iron group element used in the plating bath. An inorganic salt such as sodium sulfate may be added to the plating bath for the purpose of adjusting the liquid resistance value. The concentration of the tungstic acid compound or molybdate compound in the plating bath is usually 0.1 to 10 g / l, preferably 0.5 to 2 g / l, in terms of metal. Moreover, the density | concentration of the compound containing an iron group element is 0.6-60 g / l normally in metal conversion, Preferably it is 3-12 g / l. The concentration of citric acid is in terms of mole with respect to the metal species excluding the metal that does not precipitate such as sodium ions, that is, with respect to the total number of moles of the tungstate compound or molybdate compound and the compound containing the iron group element, Usually, it is 0.2 to 5 times, preferably 0.5 to 2 times. As the tungstic acid compound, for example, tungstate such as sodium tungstate dihydrate or a hydrate thereof can be used. As the molybdate compound, for example, a molybdate such as sodium molybdate dihydrate or a hydrate thereof can be used. As the compound containing an iron group element, for example, a nickel salt such as nickel sulfate hexahydrate or a hydrate thereof can be used. As the citric acid source, for example, a citrate such as trisodium citrate dihydrate or a hydrate thereof can be used. The solvent for the plating bath is usually water. The plating bath temperature is usually 5 to 70 ° C, preferably 10 to 50 ° C. The current density is usually 0.2 to 10 A / dm 2 , preferably 0.5 to 5 A / dm 2 . Moreover, pH of a plating bath is 2-8 normally, Preferably it is the range of 4-7. When electroplating is performed under the above conditions, first, metal is mainly precipitated, and oxide is mainly precipitated as the electrolytic plating proceeds. The surface mainly composed of oxide exhibits a peeling function, while the surface mainly composed of metal suppresses the integration of the layer structure due to thermal diffusion of copper atoms. The thickness and composition of the release layer are controlled by the composition of the plating bath and the electrolysis conditions. Usually, the thickness of the release layer thus formed is 0.005 to 0.5 μm. The release layer may be formed in one step, but may be formed by repeating electroplating a plurality of times.
本発明における薄銅層は、２３０℃、１時間加熱処理後のビッカース硬度が１８０〜２４０Ｈｖであり、１８５〜２３５Ｈｖであることが好ましい。加熱後のビッカース硬度が１８０Ｈｖ未満であると、加熱によって薄銅層の再結晶が進んで結晶粒度が大きくなっており、エッチング後の回路直線性が低下する。一方、加熱後のビッカース硬度が２４０Ｈｖより大きい場合には、薄銅層が硬くなり過ぎて脆くなる傾向があり、ハンドリング時に割れが発生する恐れがある。 The thin copper layer in the present invention has a Vickers hardness of 180 to 240 Hv after heat treatment at 230 ° C. for 1 hour, preferably 185 to 235 Hv. If the Vickers hardness after heating is less than 180 Hv, recrystallization of the thin copper layer proceeds by heating, the crystal grain size is increased, and circuit linearity after etching is deteriorated. On the other hand, when the Vickers hardness after heating is greater than 240 Hv, the thin copper layer tends to be too hard and brittle, and cracking may occur during handling.
また、薄銅層は、２３０℃、１時間加熱処理後の引張強さが５００〜６００Ｎ／ｍｍ２であることが好ましく、５０５〜５８０Ｎ／ｍｍ２であることがより好ましい。加熱後の引張強さが５００Ｎ／ｍｍ２未満の場合には、薄銅層の再結晶が進んで結晶粒度が大きくなってしまっており、エッチング後の回路直線性が低下する。一方、加熱後の引張強さが６００Ｎ／ｍｍ２より大きい場合には、薄銅層めっき後加熱前の薄銅層の内部応力（引張応力）が高くなりすぎ、支持体付極薄銅箔全体がカールして搬送時に不具合が発生することがある。 The thin copper layer preferably has a tensile strength of 500 to 600 N / mm 2 at 230 ° C. for 1 hour, and more preferably 505 to 580 N / mm 2 . When the tensile strength after heating is less than 500 N / mm 2 , the recrystallization of the thin copper layer proceeds and the crystal grain size becomes large, and the circuit linearity after etching decreases. On the other hand, when the tensile strength after heating is greater than 600 N / mm 2 , the internal stress (tensile stress) of the thin copper layer after the thin copper layer plating and before heating becomes too high, and the entire ultrathin copper foil with support May curl and cause problems during transportation.
さらに、薄銅層は、２３０℃、１時間加熱処理後の断面の結晶粒度が０．０００５ｍｍ以下であることが好ましく、０．０００２５〜０．０００５ｍｍであることがより好ましい。結晶粒度が０．０００５ｍｍより大きい場合にはエッチング後の回路直線性が低下する傾向がある。結晶粒度が０．０００２ｍｍ以下である場合には、薄銅層めっき後加熱前の内部応力（引張応力）が高くなりすぎ、支持体付極薄銅箔全体がカールして搬送時に不具合が発生する傾向がある。 Furthermore, the thin copper layer preferably has a crystal grain size of 0.0005 mm or less, more preferably 0.00025 to 0.0005 mm, after heat treatment at 230 ° C. for 1 hour. When the crystal grain size is larger than 0.0005 mm, circuit linearity after etching tends to be lowered. When the crystal grain size is 0.0002 mm or less, the internal stress (tensile stress) before heating after the thin copper layer plating becomes too high, and the entire ultrathin copper foil with a support curls, causing problems during transportation. Tend.
薄銅層の厚さは用途に応じて任意に設定することができる。微細回路を形成するためには、通常、０．１〜１０μｍが好ましく、２〜５μｍとするとより好ましい。 The thickness of the thin copper layer can be arbitrarily set according to the application. In order to form a fine circuit, 0.1 to 10 μm is usually preferable, and 2 to 5 μm is more preferable.
薄銅層は、平均分子量が５０００以下のゼラチンを添加剤として１５〜３５ｐｐｍ（ｍｇ／ｌ、以下同様）含有する硫酸銅めっき浴を用いて陰極電解処理して形成することが好ましい。薄銅層の形成は、支持体金属層又は剥離層を形成した支持体金属層を陰極とし、上記の硫酸銅めっき浴を用いて電解処理して支持体金属層又は剥離層上に銅めっきすることにより行うことが好ましい。 The thin copper layer is preferably formed by cathodic electrolysis using a copper sulfate plating bath containing 15 to 35 ppm (mg / l, the same shall apply hereinafter) with gelatin having an average molecular weight of 5000 or less as an additive. The thin copper layer is formed by using the support metal layer on which the support metal layer or the release layer is formed as a cathode, and subjecting the support metal layer or the release layer to copper plating by electrolytic treatment using the copper sulfate plating bath. It is preferable to do so.
ゼラチンの平均分子量が５０００よりも大きい場合、加熱による薄銅層の再結晶が著しくなり、加熱後の結晶が大きくなってしまう。この理由については十分に解明されていないが、ゼラチンの分子量が大きくなるとめっき時に結晶粒界に取り込まれ難くなり、結果として再結晶が進みやすくなるためと考えられる。ゼラチンの平均分子量は、５００〜５０００であることが好ましく、１０００〜５０００であることがより好ましい。ゼラチンの平均分子量が５００未満であると、硫酸銅めっき浴に添加したゼラチンが酸性溶液中で分解されて更に低分子量のアミノ酸等の有機化合物に分解され、めっき時に結晶粒界に取り込まれても再結晶を防止する効果が小さくなる傾向がある。 When the average molecular weight of gelatin is larger than 5000, recrystallization of the thin copper layer by heating becomes remarkable, and the crystal after heating becomes large. Although the reason for this has not been fully elucidated, it is considered that when the molecular weight of gelatin increases, it becomes difficult to be taken into the crystal grain boundary during plating, and as a result, recrystallization easily proceeds. The average molecular weight of gelatin is preferably 500 to 5000, and more preferably 1000 to 5000. If the average molecular weight of the gelatin is less than 500, the gelatin added to the copper sulfate plating bath is decomposed in an acidic solution and further decomposed into an organic compound such as a low molecular weight amino acid and taken into the grain boundary during plating. The effect of preventing recrystallization tends to be small.
硫酸銅めっき浴中のゼラチンの濃度は１５〜３５ｐｐｍであることが好ましい。ゼラチンの濃度が１５ｐｐｍ未満の場合、加熱による再結晶の抑制効果が低く、加熱後に微細な結晶状態が維持できない。ゼラチンの濃度が３５ｐｐｍを超えると、加熱による再結晶は抑制されるが、めっきにより形成される薄銅層の内部応力が高くなりすぎ、支持体付極薄銅箔がカールして、搬送時に不具合が発生する。 The gelatin concentration in the copper sulfate plating bath is preferably 15 to 35 ppm. When the gelatin concentration is less than 15 ppm, the effect of suppressing recrystallization by heating is low, and a fine crystal state cannot be maintained after heating. When the gelatin concentration exceeds 35 ppm, recrystallization due to heating is suppressed, but the internal stress of the thin copper layer formed by plating becomes too high, and the ultrathin copper foil with support curls, causing problems during transportation. Will occur.
硫酸銅めっき浴としては、例えば、硫酸銅５水和物、硫酸、ゼラチン及び塩素を含有する硫酸酸性硫酸銅メッキ浴が好適に用いられる。硫酸銅めっき浴中の硫酸銅５水和物の濃度は、好ましくは５０ｇ／ｌ〜３００ｇ／ｌ、より好ましくは１００ｇ／ｌ〜２００ｇ／ｌである。硫酸の濃度は、好ましくは４０ｇ／ｌ〜１６０ｇ／ｌ、より好ましくは８０ｇ／ｌ〜１２０ｇ／ｌである。ゼラチンの濃度は、上記のとおりである。塩素の濃度は、好ましくは１〜２０ｐｐｍ、より好ましくは３〜１０ｐｐｍである。めっき浴の溶媒は、通常、水である。めっき浴の温度は、好ましくは２０〜６０℃、より好ましくは３０〜５０℃である。電解処理時の電流密度は、好ましくは１〜１５Ａ／ｄｍ２であり、より好ましくは２〜１０Ａ／ｄｍ２である。 As the copper sulfate plating bath, for example, a sulfuric acid copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid, gelatin and chlorine is preferably used. The concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50 g / l to 300 g / l, more preferably 100 g / l to 200 g / l. The concentration of sulfuric acid is preferably 40 g / l to 160 g / l, more preferably 80 g / l to 120 g / l. The concentration of gelatin is as described above. The concentration of chlorine is preferably 1 to 20 ppm, more preferably 3 to 10 ppm. The solvent for the plating bath is usually water. The temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 1 to 15 A / dm 2 , more preferably 2 to 10 A / dm 2 .
薄銅層を形成する際、上記の硫酸銅めっき浴を用いる電解処理前に、ピンホールの発生を防止するため、いわゆる付きまわりの良いめっき浴を用いたストライクめっきを用いることができる。ストライクめっきに用いられるめっき浴としては、例えば、ピロリン酸銅めっき浴、クエン酸銅めっき浴、クエン酸銅ニッケルめっき浴などが挙げられる。 When the thin copper layer is formed, strike plating using a so-called good plating bath can be used before the electrolytic treatment using the copper sulfate plating bath to prevent the generation of pinholes. Examples of the plating bath used for strike plating include a copper pyrophosphate plating bath, a copper citrate plating bath, and a copper nickel citrate plating bath.
ピロリン酸銅めっき浴としては、例えば、ピロリン酸銅及びピロリン酸カリウムを含有するめっき浴が好適である。ピロリン酸銅めっき浴中のピロリン酸銅の濃度は、好ましくは６０ｇ／ｌ〜１１０ｇ／ｌ、より好ましくは７０ｇ／ｌ〜９０ｇ／ｌである。ピロリン酸カリウムの濃度は、好ましくは２４０ｇ／ｌ〜４７０ｇ／ｌ、より好ましくは３００ｇ／ｌ〜４００ｇ／ｌである。めっき浴の溶媒は、通常、水である。めっき浴のｐＨは、好ましくは８．０〜９．０、より好ましくは８．２〜８．８である。ｐＨ値調整のために、アンモニア水等を添加してもよい（以下同様）。めっき浴の温度は、好ましくは２０〜６０℃、より好ましくは３０〜５０℃である。電解処理時の電流密度は、好ましくは０．５〜１０Ａ／ｄｍ２であり、より好ましくは１〜７Ａ／ｄｍ２である。電解処理時間は、好ましくは５〜４０秒、より好ましくは１０〜３０秒である。 As the copper pyrophosphate plating bath, for example, a plating bath containing copper pyrophosphate and potassium pyrophosphate is suitable. The concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably 60 g / l to 110 g / l, more preferably 70 g / l to 90 g / l. The concentration of potassium pyrophosphate is preferably 240 g / l to 470 g / l, more preferably 300 g / l to 400 g / l. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 8.0 to 9.0, more preferably 8.2 to 8.8. In order to adjust the pH value, ammonia water or the like may be added (hereinafter the same). The temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 10 A / dm 2 , more preferably 1 to 7 A / dm 2 . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
クエン酸銅めっき浴としては、例えば、硫酸銅５水和物及びクエン酸３ナトリウム２水和物を含有するめっき浴が好適である。クエン酸銅めっき浴中の硫酸銅５水和物の濃度は、好ましくは１０ｇ／ｌ〜５０ｇ／ｌ、より好ましくは２０ｇ／ｌ〜４０ｇ／ｌである。クエン酸３ナトリウム２水和物の濃度は、好ましくは２０ｇ／ｌ〜６０ｇ／ｌ、より好ましくは３０ｇ／ｌ〜５０ｇ／ｌである。めっき浴の溶媒は、通常、水である。めっき浴のｐＨは、好ましくは５．５〜７．５、より好ましくは６．０〜７．０である。めっき浴の温度は、好ましくは２０〜６０℃、より好ましくは３０〜５０℃である。電解処理時の電流密度は、好ましくは０．５〜８Ａ／ｄｍ２であり、より好ましくは１〜４Ａ／ｄｍ２である。電解処理時間は、好ましくは５〜４０秒、より好ましくは１０〜３０秒である。 As the copper citrate plating bath, for example, a plating bath containing copper sulfate pentahydrate and trisodium citrate dihydrate is suitable. The concentration of copper sulfate pentahydrate in the copper citrate plating bath is preferably 10 g / l to 50 g / l, more preferably 20 g / l to 40 g / l. The concentration of trisodium citrate dihydrate is preferably 20 g / l to 60 g / l, more preferably 30 g / l to 50 g / l. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 8 A / dm 2 , more preferably 1 to 4 A / dm 2 . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
クエン酸銅ニッケルめっき浴としては、例えば、硫酸銅５水和物、硫酸ニッケル６水和物及びクエン酸３ナトリウム２水和物を含有するめっき浴が好適である。クエン酸銅ニッケルめっき浴中の硫酸銅５水和物の濃度は、好ましくは１０ｇ／ｌ〜５０ｇ／ｌ、より好ましくは２０ｇ／ｌ〜４０ｇ／ｌである。硫酸ニッケル６水和物の濃度は、好ましくは１ｇ／ｌ〜１０ｇ／ｌ、より好ましくは３ｇ／ｌ〜８ｇ／ｌである。クエン酸３ナトリウム２水和物の濃度は、好ましくは２０ｇ／ｌ〜６０ｇ／ｌ、より好ましくは３０ｇ／ｌ〜５０ｇ／ｌである。めっき浴の溶媒は、通常、水である。めっき浴のｐＨは、好ましくは５．５〜７．５、より好ましくは６．０〜７．０である。めっき浴の温度は、好ましくは２０〜６０℃、より好ましくは３０〜５０℃である。電解処理時の電流密度は、好ましくは０．５〜８Ａ／ｄｍ２であり、より好ましくは１〜４Ａ／ｄｍ２である。電解処理時間は、好ましくは５〜４０秒、より好ましくは１０〜３０秒である。 As the copper nickel citrate plating bath, for example, a plating bath containing copper sulfate pentahydrate, nickel sulfate hexahydrate and trisodium citrate dihydrate is suitable. The concentration of copper sulfate pentahydrate in the copper nickel citrate plating bath is preferably 10 g / l to 50 g / l, more preferably 20 g / l to 40 g / l. The concentration of nickel sulfate hexahydrate is preferably 1 g / l to 10 g / l, more preferably 3 g / l to 8 g / l. The concentration of trisodium citrate dihydrate is preferably 20 g / l to 60 g / l, more preferably 30 g / l to 50 g / l. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 8 A / dm 2 , more preferably 1 to 4 A / dm 2 . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
薄銅層の表面には、公知の方法で、樹脂基材との接着性を向上させる目的で粗化処理を行なってもよく、また、クロメート処理などの公知の方法により防錆処理を行ってもよい。また、必要に応じて、樹脂基材との接着性を向上させる目的で、シランカップリング剤等による接着強化処理を行ってもよい。また、コバルトやニッケルなどの薄膜を形成することにより、基材樹脂と薄銅層の相互作用による劣化を防止することができる。 The surface of the thin copper layer may be subjected to a roughening treatment for the purpose of improving the adhesion to the resin base material by a known method, and a rust prevention treatment is performed by a known method such as chromate treatment. Also good. Moreover, you may perform the adhesion strengthening process by a silane coupling agent etc. for the purpose of improving the adhesiveness with a resin base material as needed. Further, by forming a thin film such as cobalt or nickel, it is possible to prevent deterioration due to the interaction between the base resin and the thin copper layer.
本発明の支持体付極薄銅箔と樹脂基材とを、薄銅層側を樹脂基材に面して積層成形して銅張積層板とし、プリント配線板の製造に用いることができる。樹脂基材としては、例えば、ポリイミド系樹脂、エポキシ系樹脂、マレイミド系樹脂、トリアジン系樹脂、ポリフェニレンエーテル系樹脂、ポリブタジエン系樹脂のいずれか一種を少なくとも含有するものを用いることができる。ポリイミド系樹脂としては、例えばポリイミド、ポリアミドイミドや、それらの前駆体、例えばポリアミド酸などが挙げられる。銅張積層板の製造には、通常、これら樹脂の少なくとも１種をガラス布等に含浸させたプリプレグが樹脂基材として用いられ、支持体付極薄銅箔と樹脂基材とを、薄銅層側を樹脂基材に面して加熱加圧することにより銅張積層板を製造する。また、本発明において、銅張積層板は、銅張樹脂フィルムも含むものであり、銅張樹脂フィルムの製造には、通常、上記の樹脂の少なくとも１種を含有する樹脂基材溶液が用いられる。即ち、本発明の支持体付極薄銅箔の薄銅層上に樹脂基材溶液を塗布し、加熱することによって銅張樹脂フィルムとし、プリント配線板の製造に用いることもできる。プリント配線板の製造に当たっては、銅張積層板又は銅張樹脂フィルムから支持体（支持体金属層の材質が銅であって、支持体金属層と薄銅層との間に剥離層が形成されている場合には、支持体金属層及び剥離層）を剥離した後、薄銅層をエッチング加工して回路を形成することにより、プリント配線板を得ることができる。また、回路形成は、前述のセミアディティブ法で行うこともでき、特に制限はない。 The ultra-thin copper foil with a support of the present invention and a resin base material can be laminated and formed with the thin copper layer side facing the resin base material to form a copper-clad laminate, which can be used in the production of a printed wiring board. As the resin base material, for example, one containing at least one of polyimide resin, epoxy resin, maleimide resin, triazine resin, polyphenylene ether resin, and polybutadiene resin can be used. Examples of the polyimide resin include polyimide, polyamideimide, and precursors thereof such as polyamic acid. In the production of a copper clad laminate, a prepreg obtained by impregnating at least one of these resins into a glass cloth or the like is usually used as a resin base material, and an ultrathin copper foil with a support and a resin base material are made of thin copper. A copper clad laminate is produced by heating and pressing the layer side facing the resin substrate. In the present invention, the copper-clad laminate also includes a copper-clad resin film, and a resin base solution containing at least one of the above resins is usually used for the production of a copper-clad resin film. . That is, a resin base solution is applied on the thin copper layer of the ultrathin copper foil with a support of the present invention and heated to form a copper-clad resin film, which can also be used for the production of a printed wiring board. In the production of a printed wiring board, a copper-clad laminate or a copper-clad resin film is used as a support (the support metal layer is made of copper, and a release layer is formed between the support metal layer and the thin copper layer. In this case, the printed wiring board can be obtained by peeling the support metal layer and the peeling layer) and then etching the thin copper layer to form a circuit. In addition, the circuit formation can be performed by the above-described semi-additive method, and there is no particular limitation.
以下、本発明を実施例及び比較例によって具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.
［実施例１］
１．支持体付極薄銅箔の製造
（１）支持体金属層となる金属箔として厚さ１８μｍの電解銅箔を用い、硫酸３０ｇ／ｌの水溶液で４秒間陰極電解処理を行い表面清浄化後に流水で３０秒間水洗を行った。
（２）洗浄した電解銅箔を陰極とし、酸化イリジウムコーテイングを施したＴｉ極板を陽極（以下の陽極は全て同様）として、硫酸ニッケル６水和物３０ｇ／ｌ、モリブデン酸ナトリウム２水和物３．０ｇ／ｌ、クエン酸３ナトリウム２水和物３０ｇ／ｌ、ｐＨ６．０、液温度３０℃の浴にて電解銅箔の光沢面に電流密度２０Ａ／ｄｍ２で５秒間電解処理し、ニッケルとモリブデンからなる金属及び金属酸化物を含有する剥離層を形成した。
（３）剥離層の形成後、ピロリン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）ピロリン酸銅めっき
電解液組成：ピロリン酸銅８０ｇ／ｌ、ピロリン酸カリウム３２０ｇ／ｌ、アンモニア水２ｍｌ／ｌ
ｐＨ：８．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量５０００のゼラチン（ニッピ社製、商品名ＰＢＨ）１５ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
（４）薄銅層を形成後の表面に、硫酸銅５水和物１５０ｇ／ｌ、硫酸１００ｇ／ｌ、液温度３０℃に調整しためっき浴（限界電流密度１５Ａ／ｄｍ２）を用いて１．電流密度３０Ａ／ｄｍ２で３秒間陰極電解処理し、２．電流密度５Ａ／ｄｍ２で８０秒間陰極電解処理してコブ状の銅粒子からなる粗化層を形成した。
（５）次に粗化層を形成後の表面に、重クロム酸ナトリウム２水和物３．５ｇ／ｌ、ｐＨ４．０、液温度２８℃に調整した水溶液を用いて電流密度０．５ Ａ／ｄｍ２で２．５秒間陰極電解処理し、粗化層上にクロメート層を形成した。
（６）クロメート層を形成した表面に、３−グリシドキシプロピルトリメトキシシラン０．１ｗｔ％の水溶液に浸漬後、直ちに８０℃で乾燥して、クロメート層上にシランカップリング剤処理層を形成した。
[Example 1]
1. Production of ultrathin copper foil with support (1) An electrolytic copper foil having a thickness of 18 μm was used as a metal foil as a support metal layer. Cathodic electrolytic treatment was performed for 4 seconds with an aqueous solution of 30 g / l of sulfuric acid, and water was washed after surface cleaning. And washed with water for 30 seconds.
(2) Nickel sulfate hexahydrate 30 g / l, sodium molybdate dihydrate, using the washed electrolytic copper foil as a cathode and a Ti electrode plate coated with iridium oxide as an anode (the following anodes are all the same) 3.0 g / l, trisodium citrate dihydrate 30 g / l, pH 6.0, electrolysis treatment for 5 seconds at a current density of 20 A / dm 2 on the glossy surface of the electrolytic copper foil in a bath at a liquid temperature of 30 ° C. A release layer containing a metal composed of nickel and molybdenum and a metal oxide was formed.
(3) After forming the release layer, a thin copper layer having a thickness of 3 μm was formed using a copper pyrophosphate plating bath and a copper sulfate plating bath in this order. The plating conditions for forming the thin copper layer are as follows.
i) Copper pyrophosphate plating electrolyte composition: copper pyrophosphate 80 g / l, potassium pyrophosphate 320 g / l, ammonia water 2 ml / l
pH: 8.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 5000 (product name PBH manufactured by Nippi) 15 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
(4) The surface after forming the thin copper layer is 1 using a plating bath (limit current density 15 A / dm 2 ) adjusted to copper sulfate pentahydrate 150 g / l, sulfuric acid 100 g / l, and liquid temperature 30 ° C. . 1. Cathodic electrolytic treatment at a current density of 30 A / dm 2 for 3 seconds; Cathodic electrolysis was performed at a current density of 5 A / dm 2 for 80 seconds to form a roughened layer made of bump-shaped copper particles.
(5) Next, a current density of 0.5 A was used on the surface after forming the roughened layer using an aqueous solution adjusted to sodium dichromate dihydrate 3.5 g / l, pH 4.0, and liquid temperature 28 ° C. Cathodic electrolytic treatment was performed at / dm 2 for 2.5 seconds to form a chromate layer on the roughened layer.
(6) The surface on which the chromate layer is formed is immersed in a 0.1 wt% 3-glycidoxypropyltrimethoxysilane aqueous solution and then immediately dried at 80 ° C. to form a silane coupling agent treatment layer on the chromate layer. did.
２．ビッカース硬度の測定
ビッカース硬度の測定は、ＪＩＳ Ｚ ２２４４に準拠し、以下の手順で、アカシ社製、微小硬度計（型番ＭＶＫ−２Ｈ）を用いて２３℃で行った。
（１）薄銅層まで形成した支持体付極薄銅箔を２３０℃に加熱したオーブン（窒素雰囲気）中に１時間放置した後、１０×１０ｍｍ角にカットした。
（２）カット試料に負荷速度３μｍ／秒、試験荷重５ｇｆ、保持時間１５秒の条件で圧痕をつけ、圧痕の測定結果からビッカース硬度を算出した。
（３）任意の５点のビッカース硬度を測定した平均値をその条件の値とした。
測定結果をまとめて表１に示す。
2. Measurement of Vickers Hardness Vickers hardness was measured at 23 ° C. using a micro hardness meter (model number MVK-2H) manufactured by Akashi Corporation according to JIS Z 2244 according to the following procedure.
(1) The ultrathin copper foil with support formed up to a thin copper layer was left in an oven (nitrogen atmosphere) heated to 230 ° C. for 1 hour, and then cut into 10 × 10 mm squares.
(2) An indentation was made on the cut sample under conditions of a load speed of 3 μm / second, a test load of 5 gf, and a holding time of 15 seconds, and Vickers hardness was calculated from the measurement result of the indentation.
(3) An average value obtained by measuring Vickers hardness at any five points was taken as the value of the condition.
The measurement results are summarized in Table 1.
３．引張強さの測定
引張強さは５μｍ以下の厚さでは正確な測定が困難なため、薄銅層形成時の硫酸銅めっきによる電解処理時間を調整して、１２μｍの厚さまでめっきアップした支持体付極薄銅箔を２３０℃に加熱したオーブン（窒素雰囲気）中に１時間放置してから支持体を剥離し、ＪＩＳ Ｃ ６５１５の付属書Ａに規定された方法に準じて２３℃で測定した。
測定結果をまとめて表１に示す。
3. Measurement of tensile strength Since it is difficult to accurately measure the tensile strength at a thickness of 5 μm or less, the support is plated up to a thickness of 12 μm by adjusting the electrolytic treatment time by copper sulfate plating when forming a thin copper layer. The ultrathin copper foil was left in an oven (nitrogen atmosphere) heated to 230 ° C. for 1 hour, then the support was peeled off, and measured at 23 ° C. according to the method defined in Appendix A of JIS C 6515. .
The measurement results are summarized in Table 1.
４．エッチング速度の測定
［１］エッチング液の調整
（１）蒸留水６５０ｍｌに化学研磨液（三菱瓦斯化学(株)製、商品名：ＣＰＥ−８００）３２０ｍｌと硫酸３０ｍｌを加え、攪拌する。
（２）（１）の液に銅箔５０ｇを少しずつ加えて溶解する。
（３）（２）の液中過酸化水素濃度が１．５±０．１ｗｔ％となるように調整する。
［２］エッチング速度の測定
（１）１．（６）で得られたシランカップリング剤処理まで施した支持体付極薄銅箔の薄銅層側を接着面としてプレス圧力３．８ＭＰａ、プレス温度２３０℃で１時間、高耐熱性ＦＲ−４基材に積層し、銅張積層板を作製する。
（２）銅張積層板を規定サイズ（８０ｍｍ×４０ｍｍ）にカットしてサンプルとし、サンプル寸法をノギスで正確に測定し、面積を算出する。
（３）支持体を剥離層と共に剥離除去した各サンプルの重量を電子天秤で０．１ｍｇの単位まで測定する。
（４）エッチング液の温度を３０℃に保温し、撹拌した状態で試験サンプルをエッチング液に浸漬する。
（５）エッチング時間を変えたサンプルのエッチング後重量を電子天秤で０．１ｍｇの単位まで測定し、エッチング前の重量との差から時間当たりのエッチング量を算出する。
測定結果をまとめて表１に示す。
4). Measurement of etching rate [1] Preparation of etching solution (1) 320 ml of chemical polishing liquid (trade name: CPE-800, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 30 ml of sulfuric acid are added to 650 ml of distilled water and stirred.
(2) Add 50 g of copper foil to the solution of (1) little by little and dissolve.
(3) Adjust the hydrogen peroxide concentration in the liquid of (2) so that it becomes 1.5 ± 0.1 wt%.
[2] Measurement of etching rate (1) Using the thin copper layer side of the ultrathin copper foil with support subjected to the silane coupling agent treatment obtained in (6) as an adhesive surface, press pressure of 3.8 MPa, press temperature of 230 ° C. for 1 hour, high heat resistance FR— 4 Laminated on a base material to produce a copper clad laminate.
(2) Cut the copper-clad laminate to a specified size (80 mm × 40 mm) to obtain a sample, accurately measure the sample dimensions with calipers, and calculate the area.
(3) The weight of each sample from which the support is peeled and removed together with the release layer is measured with an electronic balance to a unit of 0.1 mg.
(4) Keep the temperature of the etching solution at 30 ° C. and immerse the test sample in the etching solution with stirring.
(5) The weight after etching of the sample with different etching time is measured to the unit of 0.1 mg with an electronic balance, and the etching amount per hour is calculated from the difference from the weight before etching.
The measurement results are summarized in Table 1.
５．回路直線性の評価
（１）１．（６）で得られたシランカップリング剤処理まで施した支持体付極薄銅箔の薄銅層側を接着面としてプレス圧力３．８ＭＰａ、プレス温度２３０℃で１時間、高耐熱性ＦＲ-４基材に積層し、銅張積層板を作製する。
（２）支持体を剥離層と共に剥離除去した後、薄銅層表面の酸化銅等を除去するために、表面を化学研磨液（三菱瓦斯化学(株)製、商品名：ＣＰＢ−６０）で５秒間、２３℃でソフトエッチングし、ドライフィルムレジスト（日立化成工業(株)製、商品名：フォテックＨ−Ｎ９２０、厚さ２０μｍ）を用いて、回路幅５０μｍ、回路間隔５０μｍのくし型の回路パターンを露光、現像により作製する。
（３）エッチング速度を測定したエッチング液と同様のエッチング液を用いて回路間の幅が５０μｍとなる条件で薄銅層をエッチングする。
（４）エッチング後の回路を真上から顕微鏡観察し、回路ボトム部の輪郭を目視評価した。
○：顕微鏡観察で、回路ボトム部の輪郭が直線に見える
×：顕微鏡観察で、回路ボトム部の輪郭が曲線状に見える部分がある
測定結果をまとめて表１に示す。
5. Evaluation of circuit linearity (1) Using the thin copper layer side of the ultrathin copper foil with support obtained up to the silane coupling agent treatment obtained in (6) as an adhesive surface, press pressure is 3.8 MPa, press temperature is 230 ° C. for 1 hour, high heat resistance FR − 4 Laminated on a base material to produce a copper clad laminate.
(2) After removing the support together with the release layer, the surface is removed with a chemical polishing liquid (trade name: CPB-60, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in order to remove copper oxide and the like on the surface of the thin copper layer. A comb-shaped circuit with a circuit width of 50 μm and a circuit interval of 50 μm using a dry film resist (manufactured by Hitachi Chemical Co., Ltd., trade name: Photec H-N920, thickness 20 μm) for 5 seconds. A pattern is produced by exposure and development.
(3) The thin copper layer is etched under the condition that the width between the circuits is 50 μm using the same etching solution as the etching solution whose etching rate is measured.
(4) The circuit after etching was observed with a microscope from directly above, and the outline of the circuit bottom portion was visually evaluated.
◯: The outline of the circuit bottom part looks straight in the microscope observation. X: Table 1 summarizes the measurement results including the part in which the outline of the circuit bottom part looks curved in the microscope observation.
６．結晶粒度の評価
ＪＩＳ Ｈ ０５０１に準じて測定した。手順は下記のとおりである。
（１）１．（６）で得られたシランカップリング剤処理まで施した支持体付極薄銅箔の薄銅層側を接着面としてプレス圧力３．８ＭＰａ、プレス温度２３０℃で１時間、高耐熱性ＦＲ-４基材に積層し、銅張積層板を作製する。
（２）支持体を剥離層と共に剥離除去した銅張積層板をＦＩＢ（収束イオンビーム）加工装置で加工し、ＳＩＭ（Scanning Ion Microscope）観察写真を撮影する。
（３）撮影した写真の断面の結晶粒度をＪＩＳ Ｈ ０５０１に規定される比較法の標準写真から算出する。なお、この規格の付図には７５倍で観察した結晶粒度０．０１０ｍｍまでしか示されていないので、最も類似した図と観察時の倍率を勘案して算出した。
測定結果をまとめて表１に示す。また、図１に断面観察写真を示す。図１中、１は薄銅層であり、２は樹脂基材、３はＦＩＢ加工の際に表面を保護する目的で形成されたタングステンの保護膜である。
6). Evaluation of crystal grain size Measured according to JIS H 0501. The procedure is as follows.
(1) 1. Using the thin copper layer side of the ultrathin copper foil with support obtained up to the silane coupling agent treatment obtained in (6) as an adhesive surface, press pressure is 3.8 MPa, press temperature is 230 ° C. for 1 hour, high heat resistance FR − 4 Laminated on a base material to produce a copper clad laminate.
(2) The copper clad laminate from which the support is peeled and removed together with the release layer is processed with a FIB (focused ion beam) processing apparatus, and a SIM (Scanning Ion Microscope) observation photograph is taken.
(3) The crystal grain size of the cross section of the photograph taken is calculated from the standard photograph of the comparative method specified in JIS H 0501. In addition, since the attached drawing of this standard shows only the crystal grain size of 0.010 mm observed at 75 times, it was calculated considering the most similar figure and the magnification at the time of observation.
The measurement results are summarized in Table 1. Moreover, a cross-sectional observation photograph is shown in FIG. In FIG. 1, 1 is a thin copper layer, 2 is a resin base material, 3 is a protective film of tungsten formed for the purpose of protecting the surface during FIB processing.
［実施例２］
剥離層形成までは実施例１と同様に行い、クエン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅めっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量３０００のゼラチン（ニッピ社製、商品名ＰＢＦ）２０ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Example 2]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate plating bath and a copper sulfate plating bath sequentially. The plating conditions for forming the thin copper layer are as follows.
i) Copper citrate plating electrolyte composition: copper sulfate pentahydrate 30 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 3000 (product name: PBF, 20 ppm), chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［実施例３］
剥離層形成までは実施例１と同様に行い、クエン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅めっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量１０００のゼラチン（ニッピ社製、商品名ＰＡ-１０）２５ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Example 3]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate plating bath and a copper sulfate plating bath sequentially. The plating conditions for forming the thin copper layer are as follows.
i) Copper citrate plating electrolyte composition: copper sulfate pentahydrate 30 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 1000 (product name PA-10, manufactured by Nippi) 25 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［実施例４］
剥離層形成までは実施例１と同様に行い、クエン酸銅ニッケルめっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅ニッケルめっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、硫酸ニッケル６水和物５ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量１０００のゼラチン（ニッピ社製、商品名ＰＡ-１０）３５ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Example 4]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate nickel plating bath and a copper sulfate plating bath in this order. The plating conditions for forming the thin copper layer are as follows.
i) Electrolytic solution composition of copper nickel citrate plating: copper sulfate pentahydrate 30 g / l, nickel sulfate hexahydrate 5 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 1000 (product name PA-10, manufactured by Nippi) 35 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［実施例５］
剥離層形成までは実施例１と同様に行い、クエン酸銅ニッケルめっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅ニッケルめっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、硫酸ニッケル６水和物５ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量５０００のゼラチン（ニッピ社製、商品名ＰＢＨ）３０ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Example 5]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate nickel plating bath and a copper sulfate plating bath in this order. The plating conditions for forming the thin copper layer are as follows.
i) Electrolytic solution composition of copper nickel citrate plating: copper sulfate pentahydrate 30 g / l, nickel sulfate hexahydrate 5 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 5000 (Nippi, trade name PBH) 30 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［比較例１］
剥離層形成までは実施例１と同様に行い、ピロリン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）ピロリン酸銅めっき
電解液組成：ピロリン酸銅８０ｇ／ｌ、ピロリン酸カリウム３２０ｇ／ｌ、アンモニア水２ｍｌ／ｌ
ｐＨ：８．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。また、図２に断面観察写真を示す。
[Comparative Example 1]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper pyrophosphate plating bath and a copper sulfate plating bath sequentially. The plating conditions for forming the thin copper layer are as follows.
i) Copper pyrophosphate plating electrolyte composition: copper pyrophosphate 80 g / l, potassium pyrophosphate 320 g / l, ammonia water 2 ml / l
pH: 8.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1. FIG. 2 shows a cross-sectional observation photograph.
［比較例２］
剥離層形成までは実施例１と同様に行い、クエン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅めっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量３０００のゼラチン（ニッピ社製、商品名ＰＢＦ）１０ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Comparative Example 2]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate plating bath and a copper sulfate plating bath sequentially. The plating conditions for forming the thin copper layer are as follows.
i) Copper citrate plating electrolyte composition: copper sulfate pentahydrate 30 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 3000 (manufactured by Nippi, trade name PBF) 10 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［比較例３］
剥離層形成までは実施例１と同様に行い、クエン酸銅めっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅めっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量２０００００のゼラチン（ニッピ社製、商品名ＳＴ１）２０ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Comparative Example 3]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate plating bath and a copper sulfate plating bath sequentially. The plating conditions for forming the thin copper layer are as follows.
i) Copper citrate plating electrolyte composition: copper sulfate pentahydrate 30 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 200,000 (Nippi, trade name ST1) 20 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
［比較例４］
剥離層形成までは実施例１と同様に行い、クエン酸銅ニッケルめっき浴と硫酸銅めっき浴を順次用いて厚さ３μｍの薄銅層を形成した。薄銅層形成のためのめっき条件は、下記のとおりである。
ｉ）クエン酸銅ニッケルめっき
電解液組成：硫酸銅５水和物３０ｇ／ｌ、硫酸ニッケル６水和物５ｇ／ｌ、クエン酸３ナトリウム２水和物４０ｇ／ｌ
ｐＨ：６．５
電流密度：２．０Ａ／ｄｍ２
時間：２０秒
温度：４０℃
ｉｉ）硫酸銅めっき
電解液組成：硫酸銅５水和物１６０ｇ／ｌ、硫酸１００ｇ／ｌ、平均分子量５０００のゼラチン（ニッピ社製、商品名ＰＢＨ）４０ｐｐｍ、塩素５ｐｐｍ、
電流密度：３．５Ａ／ｄｍ２
時間：２２０秒
温度：４０℃
その後の粗化・表面処理及び特性評価も実施例１と同様に行った。全ての測定結果を表１に示す。
[Comparative Example 4]
Until the release layer was formed, a thin copper layer having a thickness of 3 μm was formed using a copper citrate nickel plating bath and a copper sulfate plating bath in this order. The plating conditions for forming the thin copper layer are as follows.
i) Electrolytic solution composition of copper nickel citrate plating: copper sulfate pentahydrate 30 g / l, nickel sulfate hexahydrate 5 g / l, trisodium citrate dihydrate 40 g / l
pH: 6.5
Current density: 2.0 A / dm 2
Time: 20 seconds Temperature: 40 ° C
ii) Copper sulfate plating electrolyte composition: copper sulfate pentahydrate 160 g / l, sulfuric acid 100 g / l, gelatin having an average molecular weight of 5000 (product name PBH manufactured by Nippi) 40 ppm, chlorine 5 ppm,
Current density: 3.5 A / dm 2
Time: 220 seconds Temperature: 40 ° C
Subsequent roughening / surface treatment and property evaluation were performed in the same manner as in Example 1. All the measurement results are shown in Table 1.
本発明による薄銅層を有する支持体付極薄銅箔は、セミアディティブ工法におけるエッチング性が良好で細線加工に適すると共に、ハンドリング時の耐傷性を改善でき、高密プリント配線板の製造に適する。 The ultrathin copper foil with a support having a thin copper layer according to the present invention has good etching properties in a semi-additive method and is suitable for fine wire processing, and can improve scratch resistance during handling, and is suitable for production of a high-density printed wiring board.
１ 薄銅層
２ 樹脂基材
３ タングステン保護層
1 Thin copper layer 2 Resin substrate 3 Tungsten protective layer
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011121780A JP5666384B2 (en) | 2011-05-31 | 2011-05-31 | Ultrathin copper foil with support and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011121780A JP5666384B2 (en) | 2011-05-31 | 2011-05-31 | Ultrathin copper foil with support and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2012246567A JP2012246567A (en) | 2012-12-13 |
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| CN105074058B (en) * | 2013-02-26 | 2016-11-23 | 古河电气工业株式会社 | Band carrier extra thin copper foil, copper clad laminate and coreless substrate |
| JP6247829B2 (en) * | 2013-03-29 | 2017-12-13 | Ｊｘ金属株式会社 | Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate and printed wiring board manufacturing method |
| CN105813839B (en) * | 2013-12-27 | 2017-10-13 | 三井金属矿业株式会社 | Composite metallic material, the composite metallic material with carrier, the metal-coated laminated board and printed substrate obtained with these metal foils |
| JP2015134953A (en) * | 2014-01-17 | 2015-07-27 | Jx日鉱日石金属株式会社 | Surface-treated copper foil, copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board |
| JP6178360B2 (en) * | 2015-05-11 | 2017-08-09 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board |
| KR102413674B1 (en) * | 2015-09-25 | 2022-06-27 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper foil and various products using electrolytic copper foil |
| CN106350836B (en) * | 2016-08-29 | 2019-02-26 | 灵宝华鑫铜箔有限责任公司 | A kind of additive for electrolytic copper foil and the production technology for preparing double photocell electrolytic copper foils |
| CN108977858B (en) * | 2018-09-20 | 2020-09-29 | 惠州联合铜箔电子材料有限公司 | Additive for manufacturing 5-micron high-tensile-strength copper foil and process |
| CN113881980B (en) * | 2021-11-12 | 2023-06-06 | 山东金宝电子有限公司 | Stripping layer treatment liquid and preparation method of strippable carrier-attached ultrathin copper foil |
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| US5431803A (en) * | 1990-05-30 | 1995-07-11 | Gould Electronics Inc. | Electrodeposited copper foil and process for making same |
| JPH0826470B2 (en) * | 1990-07-30 | 1996-03-13 | 日本電解株式会社 | Copper plating solution and method for producing electrolytic copper foil using the same |
| JP3391909B2 (en) * | 1994-08-30 | 2003-03-31 | 株式会社日鉱マテリアルズ | Manufacturing method of high-temperature and high-strength electrolytic copper foil |
| TW200609109A (en) * | 2004-08-02 | 2006-03-16 | Nippon Denkai Ltd | Composite copper foil and method for production thereof |
| JP2007294923A (en) * | 2006-03-31 | 2007-11-08 | Nikko Kinzoku Kk | Manufacturing method of copper strip or copper foil having excellent strength, electric conductivity, and bendability, and electronic component using the same |
| JP2008285727A (en) * | 2007-05-18 | 2008-11-27 | Furukawa Circuit Foil Kk | Electrolytic copper foil with high tensile-strength, and manufacturing method therefor |
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