JP6895936B2 - 表面処理銅箔、並びにこれを用いた銅張積層板及び回路基板 - Google Patents
表面処理銅箔、並びにこれを用いた銅張積層板及び回路基板 Download PDFInfo
- Publication number
- JP6895936B2 JP6895936B2 JP2018184302A JP2018184302A JP6895936B2 JP 6895936 B2 JP6895936 B2 JP 6895936B2 JP 2018184302 A JP2018184302 A JP 2018184302A JP 2018184302 A JP2018184302 A JP 2018184302A JP 6895936 B2 JP6895936 B2 JP 6895936B2
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- Prior art keywords
- copper foil
- copper
- treated copper
- roughened
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 110
- 239000011889 copper foil Substances 0.000 title claims description 81
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 43
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 16
- 238000007747 plating Methods 0.000 description 33
- 239000010949 copper Substances 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 28
- 238000011282 treatment Methods 0.000 description 25
- 239000002245 particle Substances 0.000 description 24
- 238000007788 roughening Methods 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 229910052706 scandium Inorganic materials 0.000 description 9
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- 239000005078 molybdenum compound Substances 0.000 description 7
- 150000002752 molybdenum compounds Chemical class 0.000 description 7
- 150000003326 scandium compounds Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- -1 polyethylene naphthalate Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
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- 229920001955 polyphenylene ether Polymers 0.000 description 2
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- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 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
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Images
Classifications
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
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Description
本発明は、優れたレーザー加工性を備える表面処理銅箔を提供することを課題とする。また、本発明は、製造が容易な銅張積層板及び回路基板を提供することを併せて課題とする。
また、本発明の他の態様に係る銅張積層板及び回路基板は、上記一態様に係る表面処理銅箔を備えることを要旨とする。
ここで、表面歪度Sskは、平均面を中心とした表面の高さの対称性の度合いを表すものであり、ISO25178−2に規定されている(下記式を参照)。また、頂点曲率算術平均Sscは、様々な山構造の平均サミット曲率である(下記式を参照)。
このような本実施形態の表面処理銅箔は、優れた樹脂密着性及びレーザー加工性を備えている。よって、本実施形態の表面処理銅箔は、例えば、高周波伝送用銅張積層板等の銅張積層板や高周波伝送用回路基板等の回路基板を製造する際に使用する表面処理銅箔として好適である。
表面処理銅箔の粗化面の表面歪度Sskは、例えば粗化面に対して垂直をなす位置から、例えば白色光干渉式三次元粗さ測定器等の三次元粗さ測定器を用いて測定することができる。
本実施形態の表面処理銅箔は、銅張積層板の製造に好適に用いられる。また、このような銅張積層板は、回路基板の製造に好適に用いられる。
液晶ポリマーには、溶融状態で液晶性を示すサーモトロピック液晶ポリマーと、溶液状態で液晶性を示すレオトロピック液晶ポリマーとがある。本実施形態では、何れの液晶ポリマーも用い得るが、熱可塑性であること、誘電特性がより優れる観点から、サーモトロピック液晶ポリマーが好適に用いられる。
本実施形態で使用する液晶ポリマーフィルムは、誘電特性などのため、実質的に液晶ポリマーのみから構成することが好ましい。一方、液晶ポリマーは、剪断応力をかけると強い異方性を示すため、必要に応じて、液晶ポリマーを溶融加工する際に生じる分子配向の異方性を緩和するためのフィラーを配合してもよい。かかる配向緩和用のフィラーを導入することにより、例えば、押し出された後の液晶ポリマーフィルムの表面が平滑になり、また均配向性・等方性が得られやすくなる。その他、液晶ポリマーフィルムの色調を制御するために、着色のフィラーを配合してもよい。
液晶ポリマーフィルムの誘電特性は、一般的に優れている。具体的には、3GHzの周波数で測定した場合、誘電正接が0.0035以下であることが好ましく、0.003以下であることがより好ましく、比誘電率が3.5以下であることがさらに好ましい。なお、誘電体である樹脂基材上に形成した回路に交流電気信号が伝播する際には、その信号の電力の一部が誘電体に吸収されてしまい、信号が減衰・損失する傾向にある。この時に吸収された電力と通過(伝播)した電力との比が誘電正接であり、誘電正接の小さい誘電体を用いた回路では、伝送損失を小さくすることができる。
また、上記銅張積層板の表面処理銅箔の一部を、常法により化学的にエッチングすることにより所望の回路パターンを形成し、回路基板を作製することができる。また、回路パターン上には、勿論、電子回路部品を実装することができる。電子回路部品としては、電子回路基板に実装されるものであれば特に制限されず、半導体素子単体以外にも、例えば、チップ抵抗、チップコンデンサー、半導体パッケージ(PKG)などを挙げることができる。
以下に実施例及び比較例を示して、本発明をさらに具体的に説明する。まず、硫酸−硫酸銅水溶液を電解液とし、以下のような操作により厚さ12μmの電解銅箔を製造した。すなわち、アノードと、アノードに対向して設けられたカソードドラムとの間に電解液を供給し、カソードドラムを一定速度で回転させながらアノードとカソードドラムとの間に直流電流を通電することにより、カソードドラムの表面上に銅を析出させた。そして、析出した銅をカソードドラムの表面から引き剥がし、連続的に巻き取ることにより、電解銅箔を製造した。
得られた電解銅箔の十点平均粗さRzは1.3μmであった。電解銅箔の十点平均粗さRzは、株式会社小坂研究所製の接触式表面粗さ測定機「サーフコーダーSE1700」を用いて測定した。
実施例1〜6の表面処理銅箔には、以下に示す条件の粗化処理1を施した。また、実施例7〜12の表面処理銅箔には以下に示す条件の粗化処理2を施し、実施例13〜21の表面処理銅箔には以下に示す条件の粗化処理3を施し、実施例22〜30の表面処理銅箔には以下に示す条件の粗化処理4を施した。電気メッキに用いるメッキ液は、銅、硫酸、モリブデン、スカンジウムを含有しており、各濃度を以下に示す。
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として2.0〜3.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.001〜0.002ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として3.0〜4.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.001〜0.002ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として2.0〜3.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.002〜0.003ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として3.0〜4.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.002〜0.003ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として2.0〜4.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0〜0.001ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として0〜2.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.001〜0.004ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として60g/L
硫酸濃度:150g/L
モリブデン化合物の濃度:モリブデン濃度として2.0〜4.0g/L
スカンジウム化合物の濃度:スカンジウム濃度として0.004〜0.005ppm
液温:15〜30℃
電流密度:30〜40A/dm2
メッキ処理時間:5〜60秒
硫酸銅の濃度:銅濃度として80g/L
硫酸濃度:120g/L
液温:20〜30℃
電流密度:1.5〜4A/dm2
メッキ処理時間:5〜60秒
クロムメッキに用いるメッキ液は、クロムを含有しており、クロム濃度は5g/Lである。また、メッキ液の温度は30℃、pHは2.2であり、電流密度は5A/dm2、メッキ処理時間は5秒間である。
ブルカー株式会社製白色光干渉式表面形状測定装置Contour GT-X(Model:831-567-1)を使用して、表面処理銅箔の粗化面の表面歪度Ssk及び頂点曲率算術平均Sscを測定した。
具体的には、内部レンズの倍率が1倍、対物レンズの倍率が50倍でVSI/VXIモードを選択し、Terms Removal(F-Operator、Cylinder and Tilt)、Data Restore(Method: Legacy、Interations:5、Restore Edge選択無し)、Fourier Filter(Fourier Filter Window: Gaussian、High Freq Pass、Frequency Cutoff: 62.5[1/mm])、Statistic Filterの順に、測定値のフィルター処理を行う設定を行った。その上で、3D Analysisに列挙されるパラメータ群のうち、「S Parameters-Hybrid」を選択して頂点曲率算術平均Sscを測定し、「S Parameters-Height」を選択して表面歪度Sskを測定した。1回の測定において走査回数は3回とし、3回の走査において得られた数値の平均値を、測定値として採用した。
次に、得られた実施例1〜30及び比較例1〜22の表面処理銅箔の評価を行った。評価項目は樹脂密着性、レーザー加工性、及び粉落ちの有無である。各評価項目の評価方法について以下に説明する。
厚さ50μmの液晶ポリマーフィルム(株式会社伊勢村田製作所製、厚さ精度:0.7μm、比誘電率:3.4、誘電正接:0.0020、熱線膨張係数の最小値に対する最大値の比:1.4)の一方の面に、上記の実施例又は比較例の表面処理銅箔を積層し、他方の面に離形材としてポリイミドフィルム(宇部興業株式会社製の「ユーピレックス20S」)を積層した。
作製した片面銅張積層板を株式会社島津製作所製の引張試験機「AGS−H」に装着し、JIS C6471−1995に規定の方法に準拠して、液晶ポリマーフィルムから表面処理銅箔を引き剥がし、ピール強度を測定した。
厚さ50μmの液晶ポリマーフィルム(株式会社伊勢村田製作所製、比誘電率:3.4、誘電正接:0.0020、熱線膨張係数の最小値に対する最大値の比:1.4)の一方の面に、上記の実施例又は比較例の表面処理銅箔を、「樹脂密着性の評価方法について」において前記した方法と同様の方法で貼り合せて、片面銅張積層板を作製した。このとき、表面処理銅箔の粗化面に液晶ポリマーフィルムを貼り合せた。
上記の実施例又は比較例の表面処理銅箔の粗化面上に、幅30mm、長さ100mmの試験紙(濾紙Grade2)を置き、さらにその上に質量200g、底面の直径30mmの分銅を置いた。そして、試験紙を水平方向に引っ張り120mm引き摺った後に、試験紙への銅粒子粉の付着の有無を目視にて確認した。銅粒子粉の付着が確認されなかった場合は、粉落ちがなかったと評価し、表1、2においては「OK」印で示し、銅粒子粉の付着が確認された場合は、粉落ちがあったと評価し、表1、2においては「NG」印で示した。
これに対して、比較例1〜6の表面処理銅箔は、粗化面の表面歪度Sskが0を上回って正の値であるため、レーザー加工性が不良であった。また、比較例17〜22の表面処理銅箔は、粗化面の表面歪度Sskが−0.300を下回っているため、レーザー加工性が不良であった。
Claims (5)
- 表面を粗化処理して粗化面とした表面処理銅箔であって、三次元粗さ測定器を用いて測定される前記粗化面の表面歪度Sskが−0.300以上0未満の範囲内であり、且つ、頂点曲率算術平均Sscが0.0220nm-1以上0.0300nm-1未満の範囲内である表面処理銅箔。
- 前記粗化面の表面歪度Sskが−0.300以上−0.100未満の範囲内であり、且つ、頂点曲率算術平均Sscが0.0250nm-1以上0.0300nm-1未満の範囲内である請求項1に記載の表面処理銅箔。
- 請求項1又は請求項2に記載の表面処理銅箔を備える銅張積層板。
- 前記表面処理銅箔と、前記表面処理銅箔の粗化面に積層された樹脂基材と、を備え、前記樹脂基材は液晶ポリマーを含有する請求項3に記載の銅張積層板。
- 請求項3又は請求項4に記載の銅張積層板を備える回路基板。
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