JP7409760B2 - Method for manufacturing surface-treated copper foil, copper foil with carrier, laminate, printed wiring board, and manufacturing method for electronic equipment - Google Patents
Method for manufacturing surface-treated copper foil, copper foil with carrier, laminate, printed wiring board, and manufacturing method for electronic equipment Download PDFInfo
- Publication number
- JP7409760B2 JP7409760B2 JP2017205410A JP2017205410A JP7409760B2 JP 7409760 B2 JP7409760 B2 JP 7409760B2 JP 2017205410 A JP2017205410 A JP 2017205410A JP 2017205410 A JP2017205410 A JP 2017205410A JP 7409760 B2 JP7409760 B2 JP 7409760B2
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- Prior art keywords
- layer
- copper foil
- carrier
- resin
- treated
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 562
- 239000011889 copper foil Substances 0.000 title claims description 361
- 238000000034 method Methods 0.000 title claims description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 57
- 239000010410 layer Substances 0.000 claims description 665
- 229920005989 resin Polymers 0.000 claims description 226
- 239000011347 resin Substances 0.000 claims description 226
- 229910052802 copper Inorganic materials 0.000 claims description 207
- 239000010949 copper Substances 0.000 claims description 207
- 239000000758 substrate Substances 0.000 claims description 93
- 239000002335 surface treatment layer Substances 0.000 claims description 93
- 239000011164 primary particle Substances 0.000 claims description 65
- 239000011163 secondary particle Substances 0.000 claims description 51
- 238000011282 treatment Methods 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 229910052725 zinc Inorganic materials 0.000 claims description 42
- 238000005530 etching Methods 0.000 claims description 40
- 238000010030 laminating Methods 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000956 alloy Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 238000007788 roughening Methods 0.000 claims description 20
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 19
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
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- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 238000003475 lamination Methods 0.000 claims description 17
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- 229910052718 tin Inorganic materials 0.000 claims description 14
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910018605 Ni—Zn Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 description 114
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 91
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- 229920000647 polyepoxide Polymers 0.000 description 40
- 239000000243 solution Substances 0.000 description 33
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- 239000007788 liquid Substances 0.000 description 29
- 230000005540 biological transmission Effects 0.000 description 26
- 239000011888 foil Substances 0.000 description 26
- 238000007772 electroless plating Methods 0.000 description 24
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- 239000002184 metal Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
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- 238000009713 electroplating Methods 0.000 description 18
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- 239000000126 substance Substances 0.000 description 11
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000005304 joining Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229920006393 polyether sulfone Polymers 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910003296 Ni-Mo Inorganic materials 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000004962 Polyamide-imide Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
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- 229910000679 solder Inorganic materials 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 2
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Description
本発明は、表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法に関する。 The present invention relates to a method for manufacturing a surface-treated copper foil, a copper foil with a carrier, a laminate, a printed wiring board, and a method for manufacturing an electronic device.
プリント配線板はここ半世紀に亘って大きな進展を遂げ、今日ではほぼすべての電子機器に使用されるまでに至っている。近年の電子機器の小型化、高性能化ニーズの増大に伴い搭載部品の高密度実装化や信号の高周波化が進展し、プリント配線板に対して優れた高周波対応が求められている。 Printed wiring boards have made great progress over the past half century and are now used in almost all electronic devices. In recent years, as electronic devices have become smaller and the need for higher performance has increased, components have become more densely packaged and signals have higher frequencies, and printed wiring boards are required to have excellent high frequency support.
高周波用基板には、出力信号の品質を確保するため、伝送損失の低減が求められている。伝送損失は、主に、樹脂（基板側）に起因する誘電体損失と、導体（銅箔側）に起因する導体損失からなっている。誘電体損失は、樹脂の誘電率及び誘電正接が小さくなるほど減少する。高周波信号において、導体損失は、周波数が高くなるほど電流は導体の表面しか流れなくなるという表皮効果によって電流が流れる断面積が減少し、抵抗が高くなることが主な原因となっている。 High frequency substrates are required to reduce transmission loss in order to ensure the quality of output signals. Transmission loss mainly consists of dielectric loss caused by the resin (board side) and conductor loss caused by the conductor (copper foil side). Dielectric loss decreases as the dielectric constant and dielectric loss tangent of the resin decrease. In high-frequency signals, the main cause of conductor loss is that as the frequency increases, the cross-sectional area through which current flows decreases due to the skin effect, in which current flows only on the surface of the conductor, and the resistance increases.
高周波用銅箔の伝送損失を低減させることを目的とした技術としては、例えば、特許文献１に、金属箔表面の片面又は両面に、銀又は銀合金属を被覆し、該銀又は銀合金被覆層の上に、銀又は銀合金以外の被覆層が前記銀又は銀合金被覆層の厚さより薄く施されている高周波回路用金属箔が開示されている。そして、これによれば、衛星通信で使用されるような超高周波領域においても表皮効果による損失を小さくした金属箔を提供することができると記載されている。 As a technique aimed at reducing the transmission loss of high-frequency copper foil, for example, Patent Document 1 discloses that one or both sides of the surface of the metal foil is coated with silver or silver alloy, and the silver or silver alloy coating is applied. A metal foil for high frequency circuits is disclosed, in which a coating layer made of a material other than silver or silver alloy is formed on the layer to be thinner than the silver or silver alloy coating layer. According to this document, it is stated that it is possible to provide a metal foil with reduced loss due to the skin effect even in an ultra-high frequency region such as that used in satellite communications.
また、特許文献２には、圧延銅箔の再結晶焼鈍後の圧延面でのＸ線回折で求めた（２００）面の積分強度（Ｉ（２００））が、微粉末銅のＸ線回折で求めた（２００）面の積分強度（Ｉ０（２００））に対し、Ｉ（２００）／Ｉ０（２００）＞４０であり、該圧延面に電解メッキによる粗化処理を行った後の粗化処理面の算術平均粗さ（以下、Ｒａとする）が０．０２μｍ～０．２μｍ、十点平均粗さ（以下、Ｒｚとする）が０．１μｍ～１．５μｍであって、プリント回路基板用素材であることを特徴とする高周波回路用粗化処理圧延銅箔が開示されている。そして、これによれば、１ＧＨｚを超える高周波数下での使用が可能なプリント回路板を提供することができると記載されている。 Furthermore, Patent Document 2 describes that the integrated intensity (I(200)) of the (200) plane determined by X-ray diffraction on the rolled surface after recrystallization annealing of rolled copper foil is determined by X-ray diffraction of fine powder copper. Roughening treatment after performing roughening treatment by electrolytic plating on the rolled surface where I(200)/I0(200)>40 with respect to the calculated integral strength (I0(200)) of the (200) plane The surface has an arithmetic mean roughness (hereinafter referred to as Ra) of 0.02 μm to 0.2 μm, a ten point average roughness (hereinafter referred to as Rz) of 0.1 μm to 1.5 μm, and is suitable for printed circuit boards. A roughened rolled copper foil for high frequency circuits is disclosed. According to this document, it is stated that a printed circuit board that can be used at high frequencies exceeding 1 GHz can be provided.
さらに、特許文献３には、銅箔の表面の一部がコブ状突起からなる表面粗度が２μｍ～４μｍの凹凸面であることを特徴とする電解銅箔が開示されている。そして、これによれば、高周波伝送特性に優れた電解銅箔を提供することができると記載されている。 Furthermore, Patent Document 3 discloses an electrolytic copper foil characterized in that a portion of the surface of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm, which is made up of knob-like protrusions. And, according to this, it is described that an electrolytic copper foil having excellent high frequency transmission characteristics can be provided.
高周波回路基板に用いたときの銅箔の伝送損失の制御については上記のように種々の研究がなされているが、未だ開発の余地が大きく残されている。また、表面処理銅箔は表面処理層側から樹脂と積層し、所定の温度および所定の時間（１８０℃で１０日間）加熱した後に、表面処理銅箔と樹脂との剥離強度（ピール強度）が良好であることが必要である。 As mentioned above, various studies have been conducted on controlling the transmission loss of copper foil when used in high-frequency circuit boards, but there is still much room for further development. In addition, the surface-treated copper foil is laminated with a resin from the surface-treated layer side, and after heating at a predetermined temperature and for a predetermined time (180°C for 10 days), the peel strength between the surface-treated copper foil and the resin is determined. Must be in good condition.
本発明者らは、銅箔に一次粒子層を形成して得られる表面処理層、または一次粒子層及び二次粒子層を形成して得られる表面処理層における所定の金属の付着量及び表面処理層の最表面の十点平均粗さＲｚを制御することで、高周波回路基板に用いても伝送損失を良好に減少させることが可能となり、且つ、樹脂と積層し、所定の温度および所定の時間（１８０℃で１０日間）加熱した後に、表面処理銅箔と樹脂との剥離強度（ピール強度）が良好となることを見出した。 The present inventors have determined the amount of adhesion of a predetermined metal and the surface treatment in a surface treatment layer obtained by forming a primary particle layer on a copper foil, or a surface treatment layer obtained by forming a primary particle layer and a secondary particle layer. By controlling the ten-point average roughness Rz of the outermost surface of the layer, it is possible to reduce transmission loss well even when used in high-frequency circuit boards, and when laminated with resin, it can be heated at a predetermined temperature and for a predetermined time. It has been found that after heating (at 180° C. for 10 days), the peel strength between the surface-treated copper foil and the resin becomes good.
本発明は上記知見を基礎として完成したものであり、一側面において、銅箔と、前記銅箔の一方または両方の面に表面処理層とを有する表面処理銅箔であって、前記表面処理層は一次粒子層を有するか、または、一次粒子層と二次粒子層とを前記銅箔側からこの順に有し、前記表面処理層はＺｎを含み、前記表面処理層におけるＺｎの付着量が１５０μｇ／ｄｍ2以上であり、前記表面処理層はＮｉを含まないか、または、前記表面処理層がＮｉを含む場合には、前記表面処理層におけるＮｉの付着量は８００μｇ／ｄｍ2以下であり、前記表面処理層はＣｏを含まないか、または、前記表面処理層がＣｏを含む場合には、前記表面処理層におけるＣｏの付着量は３０００μｇ／ｄｍ2以下であり、前記表面処理層の最表面の十点平均粗さＲｚが１．５μｍ以下である表面処理銅箔である。 The present invention has been completed based on the above findings, and one aspect of the present invention is a surface-treated copper foil comprising a copper foil and a surface-treated layer on one or both surfaces of the copper foil, the surface-treated copper foil comprising: has a primary particle layer, or has a primary particle layer and a secondary particle layer in this order from the copper foil side, the surface treatment layer contains Zn, and the amount of Zn attached in the surface treatment layer is 150 μg /dm 2 or more, and the surface treatment layer does not contain Ni, or if the surface treatment layer contains Ni, the amount of Ni deposited in the surface treatment layer is 800 μg/dm 2 or less, The surface treatment layer does not contain Co, or when the surface treatment layer contains Co, the amount of Co attached in the surface treatment layer is 3000 μg/dm 2 or less, and the outermost surface of the surface treatment layer The surface-treated copper foil has a ten-point average roughness Rz of 1.5 μm or less.
本発明は別の一側面において、銅箔と、前記銅箔の一方または両方の面に表面処理層とを有する表面処理銅箔であって、前記表面処理層は一次粒子層を有するか、または、一次粒子層と、二次粒子層とを前記銅箔側からこの順に有し、前記表面処理層はＺｎ及びＭｏを含み、前記表面処理層におけるＺｎ及びＭｏの合計付着量が２００μｇ／ｄｍ2以上であり、前記表面処理層はＮｉを含まないか、または、前記表面処理層がＮｉを含む場合には、前記表面処理層におけるＮｉの付着量は８００μｇ／ｄｍ2以下であり、前記表面処理層はＣｏを含まないか、または、前記表面処理層がＣｏを含む場合には、前記表面処理層におけるＣｏの付着量は３０００μｇ／ｄｍ2以下であり、前記表面処理層の最表面の十点平均粗さＲｚが１．５μｍ以下である表面処理銅箔である。 In another aspect, the present invention is a surface-treated copper foil comprising a copper foil and a surface treatment layer on one or both surfaces of the copper foil, the surface treatment layer having a primary particle layer, or , having a primary particle layer and a secondary particle layer in this order from the copper foil side, the surface treatment layer containing Zn and Mo, and the total adhesion amount of Zn and Mo in the surface treatment layer being 200 μg/dm 2 The above, the surface treatment layer does not contain Ni, or when the surface treatment layer contains Ni, the amount of Ni deposited in the surface treatment layer is 800 μg/dm 2 or less, and the surface treatment layer The layer does not contain Co, or if the surface treatment layer contains Co, the amount of Co deposited in the surface treatment layer is 3000 μg/dm 2 or less, and the top ten points of the surface treatment layer This is a surface-treated copper foil having an average roughness Rz of 1.5 μm or less.
本発明の表面処理銅箔は別の一実施形態において、前記表面処理層はＣｏを含む。 In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Co.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層はＮｉを含む。 In yet another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Ni.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層はＣｏ及びＮｉを含み、前記表面処理層におけるＣｏ及びＮｉの合計付着量が３５００μｇ／ｄｍ2以下である。 In yet another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer contains Co and Ni, and the total amount of Co and Ni deposited in the surface-treated layer is 3500 μg/dm 2 or less.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理銅箔と樹脂とを準備し、前記表面処理銅箔を前記表面処理層側から前記樹脂と積層した後に、前記樹脂から前記表面処理銅箔を剥離する際のピール強度が０．５ｋｇ／ｃｍ以上である。 In yet another embodiment of the surface-treated copper foil of the present invention, the surface-treated copper foil and a resin are prepared, and the surface-treated copper foil is laminated with the resin from the surface-treated layer side, and then the surface-treated copper foil is laminated with the resin from the surface-treated layer side. The peel strength when peeling off the surface-treated copper foil is 0.5 kg/cm or more.
本発明の表面処理銅箔は更に別の一実施形態において、前記ピール強度が０．７ｋｇ／ｃｍ以上である。 In yet another embodiment of the surface-treated copper foil of the present invention, the peel strength is 0.7 kg/cm or more.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層は前記一次粒子層または前記二次粒子層の上に、
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、及び、
（Ｂ）クロメート処理層
のいずれか一方、又は、両方を前記銅箔側からこの順で有する。
In yet another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer is on the primary particle layer or the secondary particle layer,
(A) an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and
(B) One or both of the chromate treatment layers are provided in this order from the copper foil side.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層は前記一次粒子層または前記二次粒子層の上に、
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、及び、
（Ｂ）クロメート処理層
のいずれか一方、又は、両方と、シランカップリング処理層とを前記銅箔側からこの順で有する。
In yet another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer is on the primary particle layer or the secondary particle layer,
(A) an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and
(B) One or both of the chromate treated layers and the silane coupling treated layer are provided in this order from the copper foil side.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層は前記一次粒子層または前記二次粒子層の上に、Ｎｉ－Ｚｎ合金層、及び、クロメート処理層のいずれか一方、又は、両方を前記銅箔側からこの順で有する。 In yet another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer is formed by forming one of a Ni--Zn alloy layer and a chromate treatment layer on the primary particle layer or the secondary particle layer. , or both in this order from the copper foil side.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層は前記一次粒子層または前記二次粒子層の上に、Ｎｉ－Ｚｎ合金層、及び、クロメート処理層のいずれか一方、又は、両方と、シランカップリング処理層とを前記銅箔側からこの順で有する。 In yet another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer is formed by forming one of a Ni--Zn alloy layer and a chromate treatment layer on the primary particle layer or the secondary particle layer. , or both and a silane coupling treated layer in this order from the copper foil side.
本発明の表面処理銅箔は更に別の一実施形態において、前記表面処理層の表面に樹脂層を備える。 In yet another embodiment, the surface-treated copper foil of the present invention includes a resin layer on the surface of the surface-treated layer.
本発明の表面処理銅箔は更に別の一実施形態において、高周波回路基板に用いられる。 In yet another embodiment, the surface-treated copper foil of the present invention is used for a high-frequency circuit board.
本発明は更に別の一側面において、キャリアの一方の面、又は、両方の面に、中間層、極薄銅層をこの順に有するキャリア付銅箔であって、前記極薄銅層が本発明の表面処理銅箔であるキャリア付銅箔である。 In still another aspect, the present invention provides a carrier-attached copper foil having an intermediate layer and an ultra-thin copper layer in this order on one surface or both surfaces of the carrier, wherein the ultra-thin copper layer is the one according to the present invention. This is a copper foil with a carrier, which is a surface-treated copper foil.
本発明は更に別の一側面において、本発明の表面処理銅箔または本発明のキャリア付銅箔を有する積層体である。 In yet another aspect, the present invention is a laminate having the surface-treated copper foil of the present invention or the carrier-attached copper foil of the present invention.
本発明は更に別の一側面において、本発明のキャリア付銅箔と樹脂とを含む積層体であって、前記キャリア付銅箔の端面の一部または全部が前記樹脂により覆われた積層体である。 In still another aspect, the present invention provides a laminate comprising the carrier-attached copper foil of the present invention and a resin, wherein a part or all of an end surface of the carrier-attached copper foil is covered with the resin. be.
本発明は更に別の一側面において、一つの本発明のキャリア付銅箔が、前記キャリア側又は前記極薄銅層側から、もう一つの本発明のキャリア付銅箔の前記キャリア側又は前記極薄銅層側に積層された積層体である。 In still another aspect of the present invention, one copper foil with a carrier of the present invention is transferred from the carrier side or the ultra-thin copper layer side to the carrier side or the pole of another copper foil with a carrier of the present invention. This is a laminate stacked on the thin copper layer side.
本発明は更に別の一側面において、本発明の表面処理銅箔または本発明のキャリア付銅箔を用いたプリント配線板の製造方法である。 In yet another aspect, the present invention is a method for manufacturing a printed wiring board using the surface-treated copper foil of the present invention or the carrier-attached copper foil of the present invention.
本発明は更に別の一側面において、本発明の表面処理銅箔または本発明のキャリア付銅箔と、絶縁基板とを準備する工程、
前記表面処理銅箔と前記絶縁基板とを積層する工程を経て銅張積層板を形成する工程、または、前記キャリア付銅箔と前記絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成する工程、及び、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程を含むプリント配線板の製造方法である。
In yet another aspect, the present invention provides a step of preparing a surface-treated copper foil of the present invention or a carrier-attached copper foil of the present invention and an insulating substrate;
A step of laminating the surface-treated copper foil and the insulating substrate to form a copper-clad laminate, or a step of laminating the carrier-attached copper foil and the insulating substrate, and then laminating the carrier-attached copper foil with a carrier. forming a copper-clad laminate through a peeling process, and
The method for manufacturing a printed wiring board includes the step of thereafter forming a circuit by any one of a semi-additive method, a subtractive method, a part-additive method, or a modified semi-additive method.
本発明は更に別の一側面において、本発明の表面処理銅箔の前記表面処理層側表面に回路を形成する工程、または、本発明のキャリア付銅箔の前記極薄銅層側表面或いは前記キャリア側表面に回路を形成する工程、
前記回路が埋没するように前記表面処理銅箔の前記表面処理層側表面、または、前記キャリア付銅箔の前記極薄銅層側表面或いは前記キャリア側表面に樹脂層を形成する工程、及び、
前記樹脂層を形成した後に、前記表面処理銅箔を除去することで、または、前記キャリアまたは前記極薄銅層を剥離させた後に、前記極薄銅層または前記キャリアを除去することで、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法である。
In still another aspect, the present invention provides a step of forming a circuit on the surface of the surface-treated copper foil of the present invention on the surface-treated layer side, or on the surface of the carrier-attached copper foil of the present invention on the ultra-thin copper layer side, or A process of forming a circuit on the carrier side surface,
forming a resin layer on the surface of the surface-treated copper foil on the surface treatment layer side, the surface of the carrier-attached copper foil on the ultra-thin copper layer side, or the surface of the carrier side so that the circuit is buried;
By removing the surface-treated copper foil after forming the resin layer, or by removing the ultra-thin copper layer or the carrier after peeling off the carrier or the ultra-thin copper layer, This method of manufacturing a printed wiring board includes a step of exposing a circuit buried in a resin layer.
本発明は更に別の一側面において、本発明のキャリア付銅箔の前記キャリア側表面または前記極薄銅層側表面と、樹脂基板とを積層する工程、
前記キャリア付銅箔の樹脂基板と積層した側とは反対側表面に、樹脂層と回路との２層を、少なくとも１回設ける工程、及び、
前記樹脂層及び回路の２層を形成した後に、前記キャリア付銅箔から前記キャリアまたは前記極薄銅層を剥離させる工程
を含むプリント配線板の製造方法である。
In still another aspect of the present invention, a step of laminating the carrier-side surface or the ultra-thin copper layer-side surface of the carrier-attached copper foil of the present invention and a resin substrate;
a step of providing two layers, a resin layer and a circuit, at least once on the surface of the carrier-attached copper foil opposite to the side laminated with the resin substrate;
The method for manufacturing a printed wiring board includes the step of peeling off the carrier or the ultra-thin copper layer from the carrier-attached copper foil after forming two layers, the resin layer and the circuit.
本発明は更に別の一側面において、本発明の積層体のいずれか一方または両方の面に樹脂層と回路との２層を、少なくとも１回設ける工程、及び、
前記樹脂層及び回路の２層を形成した後に、前記積層体を構成しているキャリア付銅箔から前記キャリアまたは前記極薄銅層を剥離させる工程
を含むプリント配線板の製造方法である。
In still another aspect, the present invention provides a step of providing two layers, a resin layer and a circuit, at least once on either or both surfaces of the laminate of the present invention, and
The method for manufacturing a printed wiring board includes the step of peeling off the carrier or the ultra-thin copper layer from the carrier-attached copper foil constituting the laminate after forming the two layers of the resin layer and the circuit.
本発明は更に別の一側面において、本発明の方法で製造されたプリント配線板を用いた電子機器の製造方法である。 In yet another aspect, the present invention is a method of manufacturing an electronic device using a printed wiring board manufactured by the method of the present invention.
本発明によれば、高周波回路基板に用いても伝送損失を良好に減少させることが可能となり、且つ、樹脂と積層し、所定の温度および所定の時間（１８０℃で１０日間）加熱した後に、表面処理銅箔と樹脂との剥離強度（ピール強度）が良好となる表面処理銅箔を提供することができる。 According to the present invention, it is possible to satisfactorily reduce transmission loss even when used in a high frequency circuit board, and after laminating with resin and heating at a predetermined temperature and a predetermined time (180° C. for 10 days), It is possible to provide a surface-treated copper foil with good peel strength between the surface-treated copper foil and the resin.
＜表面処理銅箔＞
本発明の表面処理銅箔は銅箔と、銅箔の一方または両方の面に表面処理層とを有する。本発明の表面処理銅箔を絶縁基板に貼り合わせた後、表面処理銅箔を目的とする導体パターンにエッチングし、最終的にプリント配線板を製造することができる。本発明の表面処理銅箔は、高周波回路基板用の表面処理銅箔として用いてもよい。ここで、高周波回路基板とは、当該回路基板の回路を用いて伝送される信号の周波数が１ＧＨｚ以上である回路基板のことを言う。また、好ましくは前記信号の周波数が３ＧＨｚ以上、より好ましくは５ＧＨｚ以上、より好ましくは８ＧＨｚ以上、より好ましくは１０ＧＨｚ以上、より好ましくは１５ＧＨｚ以上、より好ましくは１８ＧＨｚ以上、より好ましくは２０ＧＨｚ以上、より好ましくは３０ＧＨｚ以上、より好ましくは３８ＧＨｚ以上、より好ましくは４０ＧＨｚ以上である。
<Surface treated copper foil>
The surface-treated copper foil of the present invention has a copper foil and a surface-treated layer on one or both surfaces of the copper foil. After the surface-treated copper foil of the present invention is bonded to an insulating substrate, the surface-treated copper foil can be etched into a desired conductor pattern to finally produce a printed wiring board. The surface-treated copper foil of the present invention may be used as a surface-treated copper foil for high-frequency circuit boards. Here, the high-frequency circuit board refers to a circuit board in which the frequency of a signal transmitted using the circuit of the circuit board is 1 GHz or more. Preferably, the frequency of the signal is 3 GHz or more, more preferably 5 GHz or more, more preferably 8 GHz or more, more preferably 10 GHz or more, more preferably 15 GHz or more, more preferably 18 GHz or more, more preferably 20 GHz or more, and more preferably is 30 GHz or more, more preferably 38 GHz or more, and even more preferably 40 GHz or more.
＜銅箔＞
本発明に用いることのできる銅箔の形態に特に制限はなく、典型的には本発明において使用する銅箔は、電解銅箔或いは圧延銅箔いずれでも良い。一般的には、電解銅箔は硫酸銅メッキ浴からチタンやステンレスのドラム上に銅を電解析出して製造され、圧延銅箔は圧延ロールによる塑性加工と熱処理を繰り返して製造される。屈曲性が要求される用途には圧延銅箔を適用することが多い。
銅箔材料としてはプリント配線板の導体パターンとして通常使用されるタフピッチ銅（ＪＩＳ Ｈ３１００ 合金番号Ｃ１１００）や無酸素銅（ＪＩＳ Ｈ３１００ 合金番号Ｃ１０２０またはＪＩＳ Ｈ３５１０ 合金番号Ｃ１０１１）やりん脱酸銅（ＪＩＳ Ｈ３１００ 合金番号Ｃ１２０１、Ｃ１２２０またはＣ１２２１）や電気銅といった高純度の銅の他、例えばＳｎ入り銅、Ａｇ入り銅、Ｃｒ、Ｆｅ、Ｐ、Ｔｉ、Ｓｎ、Ｚｎ、Ｍｎ、Ｍｏ、Ｃｏ、Ｎｉ、Ｓｉ、Ｚｒ、及び／又はＭｇ等を添加した銅合金、Ｎｉ及びＳｉ等を添加したコルソン系銅合金のような銅合金も使用可能である。また、公知の組成を有する銅箔および銅合金箔も使用可能である。なお、本明細書において用語「銅箔」を単独で用いたときには銅合金箔も含むものとする。
なお、銅箔の板厚は特に限定する必要は無いが、例えば１～１０００μｍ、あるいは１～５００μｍ、あるいは１～３００μｍ、あるいは３～１００μｍ、あるいは５～７０μｍ、あるいは６～３５μｍ、あるいは９～１８μｍである。
また、本発明は別の側面において、キャリアの一方の面、又は、両方の面に、中間層、極薄銅層をこの順に有するキャリア付銅箔であって、極薄銅層が本発明の表面処理銅箔である。本発明においてキャリア付銅箔を使用する場合、極薄銅層表面に以下の粗化処理層等の表面処理層を設ける。なお、キャリア付銅箔の別の実施の形態については後述する。
<Copper foil>
There is no particular restriction on the form of the copper foil that can be used in the present invention, and typically the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Generally, electrolytic copper foil is manufactured by electrolytically depositing copper onto a titanium or stainless steel drum from a copper sulfate plating bath, and rolled copper foil is manufactured by repeatedly undergoing plastic working with rolling rolls and heat treatment. Rolled copper foil is often used in applications that require flexibility.
Copper foil materials include tough pitch copper (JIS H3100 alloy number C1100), oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), and phosphor deoxidized copper (JIS H3100 alloy number C1011), which are commonly used as conductor patterns for printed wiring boards. In addition to high-purity copper such as alloy number C1201, C1220 or C1221) and electrolytic copper, for example, Sn-containing copper, Ag-containing copper, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, Copper alloys such as copper alloys to which Zr and/or Mg, etc. are added, and Corson-based copper alloys to which Ni, Si, etc. are added, can also be used. Further, copper foils and copper alloy foils having known compositions can also be used. Note that in this specification, when the term "copper foil" is used alone, it also includes copper alloy foil.
Note that the thickness of the copper foil does not need to be particularly limited, but may be, for example, 1 to 1000 μm, 1 to 500 μm, 1 to 300 μm, 3 to 100 μm, 5 to 70 μm, 6 to 35 μm, or 9 to 18 μm. It is.
Further, in another aspect, the present invention provides a carrier-attached copper foil having an intermediate layer and an ultra-thin copper layer in this order on one surface or both surfaces of the carrier, the ultra-thin copper layer according to the present invention. It is surface treated copper foil. When using a copper foil with a carrier in the present invention, a surface treatment layer such as the following roughening treatment layer is provided on the surface of the ultra-thin copper layer. Note that another embodiment of the carrier-attached copper foil will be described later.
＜表面処理層＞
表面処理層は一次粒子層を有するか、または、一次粒子層と二次粒子層とを銅箔側からこの順に有する。一次粒子層及び二次粒子層は、電気メッキ層により形成する。この二次粒子の特徴は、前記一次粒子の上に成長した１又は複数個の粒子である。または二次粒子層は前記一次粒子の上に成長した正常メッキである。二次粒子は樹枝状の形状を有してもよい。すなわち、本明細書において用語「二次粒子層」を用いた場合には、被せメッキ等の正常メッキ層も含まれるものとする。また、二次粒子層は粗化粒子により形成される層を一層以上有する層であってもよく、正常メッキ層を一層以上有する層であってもよく、粗化粒子により形成される層と正常メッキ層とをそれぞれ一層以上有する層であってもよい。なお、表面処理層は一次粒子層や二次粒子層以外の一つまたは複数の他の層を有しても良い。
なお、一次粒子層とは、銅箔の上に直接形成されている粗化粒子と、当該粗化粒子の上に積み重なっている粗化粒子であって、銅箔の上に直接形成されている粗化粒子と組成が同様であるか、銅箔の上に直接形成されている粗化粒子が含有する元素と同じ元素を有する粗化粒子を含む層とする。二次粒子層とは、一次粒子層に含まれる粗化粒子の上に形成されている粗化粒子であって、一次粒子層を形成する粗化粒子とは組成が異なるか、または、一次粒子層を形成する粗化粒子が含まない元素を含む粗化粒子を含む層とする。
また、上述の一次粒子および／または二次粒子を構成する元素の有無、および／または、当該元素の濃度若しくは付着量を測定することができない場合には、一次粒子及び二次粒子は、例えば走査型電子顕微鏡写真で観察した際に、重なって見える粒子であって銅箔側（下方）に存在する粒子、および、重なっていない粒子を一次粒子とし、重なって見える粒子であって他の粒子の上に存在する粒子を二次粒子と判定することができる。
<Surface treatment layer>
The surface treatment layer has a primary particle layer, or a primary particle layer and a secondary particle layer in this order from the copper foil side. The primary particle layer and the secondary particle layer are formed by electroplating layers. This secondary particle is characterized by one or more particles grown on the primary particle. Alternatively, the secondary particle layer is a normal plating grown on the primary particles. The secondary particles may have a dendritic shape. That is, when the term "secondary particle layer" is used in this specification, a normal plating layer such as cover plating is also included. Further, the secondary particle layer may be a layer having one or more layers formed by roughening particles, or may be a layer having one or more normal plating layers, and a layer formed by roughening particles and a normal plating layer may be a layer having one or more layers formed by roughening particles. Each layer may have one or more plating layers. Note that the surface treatment layer may include one or more layers other than the primary particle layer and the secondary particle layer.
Note that the primary particle layer refers to roughening particles that are formed directly on the copper foil and roughening particles that are piled up on the roughening particles, and is formed directly on the copper foil. The layer contains roughening particles having the same composition as the roughening particles or having the same element as that contained in the roughening particles directly formed on the copper foil. The secondary particle layer is roughened particles formed on the roughened particles included in the primary particle layer, and has a different composition from the roughened particles forming the primary particle layer, or The layer contains roughening particles containing an element that is not included in the roughening particles forming the layer.
In addition, if it is not possible to measure the presence or absence of an element constituting the above-mentioned primary particles and/or secondary particles, and/or the concentration or adhesion amount of the element, the primary particles and secondary particles can be measured by scanning, for example. When observed in an electron micrograph, particles that appear to overlap and exist on the copper foil side (lower side) and particles that do not overlap are considered primary particles, and particles that appear to overlap and are present on the copper foil side (lower side) are considered primary particles. Particles present above can be determined to be secondary particles.
本発明の表面処理銅箔は、一側面において、表面処理層はＺｎを含み、表面処理層におけるＺｎの付着量が１５０μｇ／ｄｍ2以上である。Ｚｎの付着量が１５０μｇ／ｄｍ2未満であると高周波回路基板用の表面処理銅箔として用いたときに耐熱性が不良となるおそれがある。当該Ｚｎの付着量は、好ましくは１５５μｇ／ｄｍ2以上、好ましくは１６５μｇ／ｄｍ2以上、好ましくは１８０μｇ／ｄｍ2以上、好ましくは２００μｇ／ｄｍ2以上、好ましくは２５０μｇ／ｄｍ2以上、好ましくは２７０μｇ／ｄｍ2以上、好ましくは２８０μｇ／ｄｍ2以上、更により好ましくは２９０μｇ／ｄｍ2以上である。当該Ｚｎの付着量の上限は特に設ける必要は無いが、典型的には例えば５００００μｇ／ｄｍ2以下、例えば３００００μｇ／ｄｍ2以下、例えば１００００μｇ／ｄｍ2以下、例えば５０００μｇ／ｄｍ2以下、例えば３０００μｇ／ｄｍ2以下、例えば２０００μｇ／ｄｍ2以下、例えば１０００μｇ／ｄｍ2以下である。 In one aspect of the surface-treated copper foil of the present invention, the surface-treated layer contains Zn, and the amount of Zn deposited in the surface-treated layer is 150 μg/dm 2 or more. If the amount of Zn deposited is less than 150 μg/dm 2 , the heat resistance may be poor when used as a surface-treated copper foil for high frequency circuit boards. The amount of Zn deposited is preferably 155 μg/dm 2 or more, preferably 165 μg/dm 2 or more, preferably 180 μg/dm 2 or more, preferably 200 μg/dm 2 or more, preferably 250 μg/dm 2 or more, preferably 270 μg. /dm 2 or more, preferably 280 μg/dm 2 or more, even more preferably 290 μg/dm 2 or more. There is no need to set an upper limit for the amount of Zn deposited, but typically, for example, 50,000 μg/dm 2 or less, for example, 30,000 μg/dm 2 or less, for example, 10,000 μg/dm 2 or less, for example, 5,000 μg/dm 2 or less, for example, 3,000 μg/dm 2 or less. dm 2 or less, for example 2000 μg/dm 2 or less, for example 1000 μg/dm 2 or less.
なお、本発明において、表面処理層におけるＺｎ、Ｎｉ、Ｃｏ、Ｍｏ等の元素の付着量を規定しているが、これらは表面処理層が銅箔の両方の面に存在する場合には、一方の面の表面処理層における規定であり、両方の面に形成された表面処理層に含有される元素（例えばＺｎ等）の合計値ではない。 In addition, in the present invention, the adhesion amount of elements such as Zn, Ni, Co, Mo, etc. in the surface treatment layer is specified, but when the surface treatment layer is present on both sides of the copper foil, the adhesion amount of elements such as Zn, Ni, Co, Mo, etc. This is the regulation for the surface treatment layer of the surface, and is not the total value of elements (for example, Zn, etc.) contained in the surface treatment layers formed on both surfaces.
本発明の表面処理銅箔は、別の一側面において、表面処理層はＺｎ及びＭｏを含み、表面処理層におけるＺｎ及びＭｏの合計付着量が２００μｇ／ｄｍ2以上である。Ｚｎ及びＭｏの合計付着量が２００μｇ／ｄｍ2未満であると高周波回路基板用の表面処理銅箔として用いたときに耐熱性が不良となるおそれがある。当該Ｚｎ及びＭｏの合計付着量は、好ましくは２５０μｇ／ｄｍ2以上、より好ましくは３００μｇ／ｄｍ2以上、より好ましくは３４０μｇ／ｄｍ2以上、より好ましくは３６０μｇ／ｄｍ2以上、より好ましくは４００μｇ／ｄｍ2以上、より好ましくは４２０μｇ／ｄｍ2以上、より好ましくは４５０μｇ／ｄｍ2以上、より好ましくは４６０μｇ／ｄｍ2以上、より好ましくは５００μｇ／ｄｍ2以上である。当該Ｚｎ及びＭｏの合計付着量の上限は特に設ける必要は無いが、典型的には例えば１０００００μｇ／ｄｍ2以下、例えば５００００μｇ／ｄｍ2以下、例えば３００００μｇ／ｄｍ2以下、例えば１００００μｇ／ｄｍ2以下、例えば８０００μｇ／ｄｍ2以下、例えば５０００μｇ／ｄｍ2以下、例えば３０００μｇ／ｄｍ2以下、例えば１０００μｇ／ｄｍ2以下である。 In another aspect of the surface-treated copper foil of the present invention, the surface-treated layer contains Zn and Mo, and the total adhesion amount of Zn and Mo in the surface-treated layer is 200 μg/dm 2 or more. If the total adhesion amount of Zn and Mo is less than 200 μg/dm 2 , the heat resistance may be poor when used as a surface-treated copper foil for high frequency circuit boards. The total adhesion amount of Zn and Mo is preferably 250 μg/dm 2 or more, more preferably 300 μg/dm 2 or more, more preferably 340 μg/dm 2 or more, more preferably 360 μg/dm 2 or more, and even more preferably 400 μg/dm 2 or more. dm 2 or more, more preferably 420 μg/dm 2 or more, more preferably 450 μg/dm 2 or more, more preferably 460 μg/dm 2 or more, and even more preferably 500 μg/dm 2 or more. There is no need to set an upper limit for the total adhesion amount of Zn and Mo, but typically, for example, 100,000 μg/dm 2 or less, for example, 50,000 μg/dm 2 or less, for example, 30,000 μg/dm 2 or less, for example, 10,000 μg/dm 2 or less, For example, it is 8000 μg/dm 2 or less, for example 5000 μg/dm 2 or less, for example 3000 μg/dm 2 or less, for example 1000 μg/dm 2 or less.
本発明の表面処理銅箔の表面処理層はＣｏを含まないか、または、表面処理層がＣｏを含む場合には、表面処理層におけるＣｏの付着量は３０００μｇ／ｄｍ2以下である。当該Ｃｏの付着量が３０００μｇ／ｄｍ2を超えると、高周波伝送特性が悪化するという問題が生じるおそれがある。当該Ｃｏの付着量は、より好ましくは２９００μｇ／ｄｍ2以下、より好ましくは２８００μｇ／ｄｍ2以下、より好ましくは２７９０μｇ／ｄｍ2以下、より好ましくは２７００μｇ／ｄｍ2以下、より好ましくは２５００μｇ／ｄｍ2以下、更により好ましくは１５００μｇ／ｄｍ2以下、更により好ましくは１０００μｇ／ｄｍ2以下である。なお、表面処理層がＣｏを含む場合の、表面処理層におけるＣｏの付着量の下限は特に限定する必要はないが、典型的には、例えばＣｏの付着量は０μｇ／ｄｍ2より大きい、例えば０．１０μｇ／ｄｍ2以上、例えば１μｇ／ｄｍ2以上、例えば２μｇ／ｄｍ2以上、例えば３μｇ／ｄｍ2以上、例えば４μｇ／ｄｍ2以上、例えば５μｇ／ｄｍ2以上、例えば１０μｇ／ｄｍ2以上、例えば１５μｇ／ｄｍ2以上、例えば２０μｇ／ｄｍ2以上である。なお、表面処理層がＣｏを含む場合、Ｃｏを含まない場合と比較して表面処理銅箔の耐候性が向上するという効果を奏する場合がある。 The surface treatment layer of the surface treatment copper foil of the present invention does not contain Co, or when the surface treatment layer contains Co, the amount of Co deposited in the surface treatment layer is 3000 μg/dm 2 or less. If the amount of Co attached exceeds 3000 μg/dm 2 , there is a risk that the high frequency transmission characteristics will deteriorate. The amount of Co attached is more preferably 2900 μg/dm 2 or less, more preferably 2800 μg/dm 2 or less, more preferably 2790 μg/dm 2 or less, more preferably 2700 μg/dm 2 or less, more preferably 2500 μg/dm 2 Below, it is still more preferably 1500 μg/dm 2 or less, even more preferably 1000 μg/dm 2 or less. Note that when the surface treatment layer contains Co, there is no need to particularly limit the lower limit of the amount of Co attached in the surface treatment layer, but typically, for example, the amount of Co attached is greater than 0 μg/dm 2 , for example. 0.10 μg/dm 2 or more, e.g. 1 μg/dm 2 or more, e.g. 2 μg/dm 2 or more, e.g. 3 μg/dm 2 or more, e.g. 4 μg/dm 2 or more, e.g. 5 μg/dm 2 or more, e.g. 10 μg/dm 2 or more, For example, it is 15 μg/dm 2 or more, for example, 20 μg/dm 2 or more. In addition, when the surface treatment layer contains Co, there may be an effect that the weather resistance of the surface treated copper foil is improved compared to a case where the surface treatment layer does not contain Co.
本発明の表面処理銅箔の表面処理層はＮｉを含まないか、または、表面処理層がＮｉを含む場合には、表面処理層におけるＮｉの付着量は８００μｇ／ｄｍ2以下である。当該Ｎｉの付着量が８００μｇ／ｄｍ2を超えると、高周波伝送特性が悪化するという問題が生じるおそれがある。当該Ｎｉの付着量は、より好ましくは７５０μｇ／ｄｍ2以下、更により好ましくは６００μｇ／ｄｍ2以下、更により好ましくは４００μｇ／ｄｍ2以下、更により好ましくは２５０μｍ／ｄｍ2以下である。なお、表面処理層がＮｉを含む場合の、表面処理層におけるＮｉの付着量の下限は特に限定する必要はないが、典型的には、例えばＮｉの付着量は０μｇ／ｄｍ2より大きい、例えば０．１０μｇ／ｄｍ2以上、例えば１μｇ／ｄｍ2以上、例えば２μｇ／ｄｍ2以上、例えば３μｇ／ｄｍ2以上、例えば４μｇ／ｄｍ2以上、例えば５μｇ／ｄｍ2以上、例えば１０μｇ／ｄｍ2以上、例えば１５μｇ／ｄｍ2以上、例えば２０μｇ／ｄｍ2以上である。なお、表面処理層がＮｉを含む場合、Ｎｉを含まない場合と比較して表面処理銅箔の耐薬品性が向上するという効果を奏する場合がある。 The surface treatment layer of the surface treatment copper foil of the present invention does not contain Ni, or when the surface treatment layer contains Ni, the amount of Ni deposited in the surface treatment layer is 800 μg/dm 2 or less. If the amount of Ni deposited exceeds 800 μg/dm 2 , there is a possibility that the problem of deterioration of high frequency transmission characteristics may occur. The amount of Ni deposited is more preferably 750 μg/dm 2 or less, even more preferably 600 μg/dm 2 or less, even more preferably 400 μg/dm 2 or less, and even more preferably 250 μm/dm 2 or less. Note that when the surface treatment layer contains Ni, there is no need to particularly limit the lower limit of the amount of Ni deposited in the surface treatment layer, but typically, for example, the amount of Ni deposited is greater than 0 μg/dm 2 , e.g. 0.10 μg/dm 2 or more, e.g. 1 μg/dm 2 or more, e.g. 2 μg/dm 2 or more, e.g. 3 μg/dm 2 or more, e.g. 4 μg/dm 2 or more, e.g. 5 μg/dm 2 or more, e.g. 10 μg/dm 2 or more, For example, it is 15 μg/dm 2 or more, for example, 20 μg/dm 2 or more. In addition, when the surface treatment layer contains Ni, there may be an effect that the chemical resistance of the surface treated copper foil is improved compared to a case where the surface treatment layer does not contain Ni.
本発明の表面処理銅箔は、表面処理層はさらにＣｏ及びＮｉを含み、表面処理層におけるＣｏ及びＮｉの合計付着量が３５００μｇ／ｄｍ2以下であるのが好ましい。当該Ｃｏ及びＮｉの合計付着量が３５００μｇ／ｄｍ2を超えると、高周波伝送特性が悪化するという問題が生じるおそれがある。当該Ｃｏ及びＮｉの合計付着量は、より好ましくは３１００μｇ／ｄｍ2以下、更により好ましくは１９００μｇ／ｄｍ2以下、更により好ましくは１４００μｇ／ｄｍ2以下である。なお、表面処理層がＣｏ及びＮｉを含む場合の、表面処理層におけるＣｏ及びＮｉの合計付着量の下限は特に限定する必要はないが、典型的には、例えばＣｏ及びＮｉの合計付着量は０μｇ／ｄｍ2より大きい、例えば０．１０μｇ／ｄｍ2以上、例えば１μｇ／ｄｍ2以上、例えば２μｇ／ｄｍ2以上、例えば３μｇ／ｄｍ2以上、例えば４μｇ／ｄｍ2以上、例えば５μｇ／ｄｍ2以上、例えば１０μｇ／ｄｍ2以上、例えば１５μｇ／ｄｍ2以上、例えば２０μｇ／ｄｍ2以上、例えば３０μｇ／ｄｍ2以上、例えば４０μｇ／ｄｍ2以上、例えば５０μｇ／ｄｍ2以上、例えば６０μｇ／ｄｍ2以上、例えば７０μｇ／ｄｍ2以上である。なお、表面処理層がＣｏ及びＮｉを含む場合、Ｃｏ及びＮｉを含まない場合と比較して表面処理銅箔の耐薬品性および耐候性が向上するという効果を奏する場合がある。 In the surface-treated copper foil of the present invention, the surface-treated layer further contains Co and Ni, and the total amount of Co and Ni deposited in the surface-treated layer is preferably 3500 μg/dm 2 or less. If the total amount of Co and Ni deposited exceeds 3500 μg/dm 2 , there is a risk that the high frequency transmission characteristics will deteriorate. The total amount of Co and Ni deposited is more preferably 3100 μg/dm 2 or less, even more preferably 1900 μg/dm 2 or less, even more preferably 1400 μg/dm 2 or less. Note that when the surface treatment layer contains Co and Ni, there is no need to particularly limit the lower limit of the total amount of Co and Ni deposited in the surface treatment layer, but typically, for example, the total amount of Co and Ni deposited is Greater than 0 μg/dm 2 , such as 0.10 μg/dm 2 or more, such as 1 μg/dm 2 or more, such as 2 μg/dm 2 or more, such as 3 μg/dm 2 or more, such as 4 μg/dm 2 or more, such as 5 μg/dm 2 or more. , for example, 10 μg/dm 2 or more, such as 15 μg/dm 2 or more, such as 20 μg/dm 2 or more, such as 30 μg/dm 2 or more, such as 40 μg/dm 2 or more, such as 50 μg/dm 2 or more, such as 60 μg/dm 2 or more, For example, it is 70 μg/dm 2 or more. Note that when the surface treatment layer contains Co and Ni, there may be an effect that the chemical resistance and weather resistance of the surface treated copper foil are improved compared to a case where the surface treatment layer does not contain Co and Ni.
なお、表面処理層が含有する元素の付着量は、表面処理層を形成する際に使用する表面処理液中の当該元素の濃度を高くするか、および／または、表面処理がめっきの場合には、電流密度を高くするか、および／または、表面処理時間（めっきをする際の通電時間）を長くする、こと等により、多くすることが出来る。また、表面処理層が含有する元素の付着量は、表面処理層を形成する際に使用する表面処理液中の当該元素の濃度を低くするか、および／または、表面処理がめっきの場合には、電流密度を低くするか、および／または、表面処理時間（めっきをする際の通電時間）を短くする、こと等により、少なくすることが出来る。 The amount of the element contained in the surface treatment layer can be determined by increasing the concentration of the element in the surface treatment liquid used when forming the surface treatment layer, and/or if the surface treatment is plating. This can be increased by increasing the current density and/or lengthening the surface treatment time (current application time during plating). In addition, the adhesion amount of the element contained in the surface treatment layer can be determined by lowering the concentration of the element in the surface treatment liquid used when forming the surface treatment layer, and/or when the surface treatment is plating. This can be reduced by lowering the current density and/or shortening the surface treatment time (current application time during plating).
本発明の表面処理銅箔は、表面処理層の最表面の十点平均粗さＲｚが１．５μｍ以下である。表面処理層の最表面の十点平均粗さＲｚが１．５μｍを超えると、高周波伝送特性が悪化するという問題が生じるおそれがある。表面処理層の最表面の十点平均粗さＲｚは、より好ましくは１．３μｍ以下、更により好ましくは１．１μｍ以下、更により好ましくは１．０μｍ以下、更により好ましくは０．９μｍ以下である。「表面処理層の最表面」とは、表面処理により形成された複数の層により表面処理層が形成されている場合には、当該複数の層の一番外側（最表面）の層の表面を意味する。そして、当該複数の層の一番外側（最表面）の層の表面について十点平均粗さＲｚを測定する。表面処理層の最表面の十点平均粗さＲｚの下限は特に限定をする必要はないが、典型的には例えば０．０１μｍ以上、例えば０．０５μｍ以上、例えば０．１μｍ以上である。 In the surface-treated copper foil of the present invention, the ten-point average roughness Rz of the outermost surface of the surface-treated layer is 1.5 μm or less. If the ten-point average roughness Rz of the outermost surface of the surface treatment layer exceeds 1.5 μm, there is a risk that the high frequency transmission characteristics will deteriorate. The ten-point average roughness Rz of the outermost surface of the surface treatment layer is more preferably 1.3 μm or less, even more preferably 1.1 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.9 μm or less. be. "The outermost surface of the surface treatment layer" means, when the surface treatment layer is formed by multiple layers formed by surface treatment, the surface of the outermost (outermost) layer of the multiple layers. means. Then, the ten-point average roughness Rz of the surface of the outermost (outermost) layer of the plurality of layers is measured. The lower limit of the ten-point average roughness Rz of the outermost surface of the surface treatment layer is not particularly limited, but is typically, for example, 0.01 μm or more, for example, 0.05 μm or more, for example, 0.1 μm or more.
本発明の表面処理銅箔の表面処理層は一次粒子層または二次粒子層の上に、
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、及び、
（Ｂ）クロメート処理層
のいずれか一方、又は、両方を前記銅箔側からこの順で有してもよい。
The surface treatment layer of the surface treated copper foil of the present invention is on the primary particle layer or the secondary particle layer,
(A) an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and
(B) Either one or both of the chromate treatment layers may be provided in this order from the copper foil side.
また、本発明の表面処理銅箔の表面処理層は一次粒子層または二次粒子層の上に、
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、及び、
（Ｂ）クロメート処理層
のいずれか一方、又は、両方と、シランカップリング処理層とを銅箔側からこの順で有してもよい。
Moreover, the surface treatment layer of the surface treated copper foil of the present invention is on the primary particle layer or the secondary particle layer,
(A) an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and
(B) Either or both of the chromate treatment layers and the silane coupling treatment layer may be included in this order from the copper foil side.
また、本発明の表面処理銅箔の表面処理層は一次粒子層または二次粒子層の上に、Ｎｉ－Ｚｎ合金層、及び、クロメート処理層のいずれか一方、又は、両方を銅箔側からこの順で有してもよい。 In addition, the surface treatment layer of the surface treated copper foil of the present invention includes a Ni-Zn alloy layer and/or a chromate treatment layer on the primary particle layer or the secondary particle layer from the copper foil side. They may be included in this order.
また、本発明の表面処理銅箔の表面処理層は一次粒子層または二次粒子層の上に、Ｎｉ－Ｚｎ合金層、及び、クロメート処理層のいずれか一方、又は、両方と、シランカップリング処理層とを銅箔側からこの順で有してもよい。
なお、前述のＮｉ－Ｚｎ合金層はＮｉとＺｎとを含む合金の層を意味する。Ｎｉ－Ｚｎ合金層はＮｉとＺｎの合計濃度が８０原子％以上の層であってもよい。ＮｉとＺｎの合計濃度はＸＰＳ等を用いた深さ方向のＮｉとＺｎの原子濃度分析をし、得られたＮｉ原子濃度とＺｎ原子濃度を合計することによって測定することができる。Ｎｉ－Ｚｎ合金層はＮｉとＺｎのみからなる層であってもよい。
Further, the surface treatment layer of the surface treated copper foil of the present invention is formed by silane coupling with either or both of the Ni-Zn alloy layer and the chromate treatment layer on the primary particle layer or the secondary particle layer. The treated layer may be included in this order from the copper foil side.
Note that the above-mentioned Ni--Zn alloy layer means a layer of an alloy containing Ni and Zn. The Ni--Zn alloy layer may have a total concentration of Ni and Zn of 80 atomic % or more. The total concentration of Ni and Zn can be measured by analyzing the atomic concentrations of Ni and Zn in the depth direction using XPS or the like and summing the obtained Ni atomic concentration and Zn atomic concentration. The Ni--Zn alloy layer may be a layer consisting only of Ni and Zn.
本発明の表面処理銅箔は、当該表面処理銅箔と樹脂とを準備し、表面処理銅箔を表面処理層側から当該樹脂と積層し、当該表面処理銅箔をエッチングして１０ｍｍ幅の回路を作成した後に、当該樹脂から当該回路を９０°方向に剥離する際のピール強度０．５ｋｇ／ｃｍ以上、さらにはピール強度０．７ｋｇ／ｃｍ以上を達成することができる。
また、本発明の表面処理銅箔は、当該表面処理銅箔と樹脂とを準備し、表面処理銅箔を表面処理層側から当該樹脂と積層し、当該表面処理銅箔をエッチングして１０ｍｍ幅の回路を作成し、当該回路を大気下で１８０℃で１０日間加熱後に、当該樹脂から当該回路を９０°方向に剥離する際のピール強度０．４ｋｇ／ｃｍ以上、さらにはピール強度０．５ｋｇ／ｃｍ以上を達成することができる。
なお、前述の樹脂および前記積層の条件は以下の（１）～（３）のいずれか一つまたは二つまたは三つである。すなわち、以下の（１）～（３）の条件のいずれかに基づいて得られたピール強度が上記範囲内であることが好ましい。
（１）樹脂：ヒドロキシ安息香酸とヒドロキシナフトエ酸との共重合体である液晶ポリマー樹脂、厚み５０μｍ
積層の条件：圧力３．５ＭＰａ、加熱温度３００℃、加熱時間１０分間
（２）樹脂：低誘電ポリイミド樹脂、厚み５０μｍ
積層の条件：圧力４ＭＰａ、加熱温度３６０℃、加熱時間５分間
（３）樹脂：ポリテトラフルオロエチレン、厚み５０μｍ
積層の条件：圧力５ＭＰａ、加熱温度３５０℃、加熱時間３０分間
The surface-treated copper foil of the present invention prepares the surface-treated copper foil and a resin, laminates the surface-treated copper foil with the resin from the surface-treated layer side, and etches the surface-treated copper foil to form a 10 mm wide circuit. After creating the circuit, it is possible to achieve a peel strength of 0.5 kg/cm or more when peeling the circuit from the resin in a 90° direction, and further a peel strength of 0.7 kg/cm or more.
In addition, the surface-treated copper foil of the present invention can be obtained by preparing the surface-treated copper foil and a resin, laminating the surface-treated copper foil with the resin from the surface-treated layer side, and etching the surface-treated copper foil to a width of 10 mm. After creating a circuit and heating the circuit at 180°C in the atmosphere for 10 days, the peel strength when peeling the circuit from the resin in the 90° direction is 0.4 kg/cm or more, furthermore, the peel strength is 0.5 kg. /cm or more can be achieved.
Note that the conditions for the resin and the lamination are any one, two, or three of the following (1) to (3). That is, it is preferable that the peel strength obtained based on any of the following conditions (1) to (3) is within the above range.
(1) Resin: Liquid crystal polymer resin that is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 μm
Lamination conditions: pressure 3.5 MPa, heating temperature 300°C, heating time 10 minutes (2) Resin: low dielectric polyimide resin, thickness 50 μm
Lamination conditions: pressure 4 MPa, heating temperature 360°C, heating time 5 minutes (3) Resin: polytetrafluoroethylene, thickness 50 μm
Lamination conditions: pressure 5 MPa, heating temperature 350°C, heating time 30 minutes
＜伝送損失＞
伝送損失が小さい場合、高周波で信号伝送を行う際の、信号の減衰が抑制されるため、高周波で信号の伝送を行う回路において、安定した信号の伝送を行うことができる。そのため、伝送損失の値が小さい方が、高周波で信号の伝送を行う回路用途に用いることに適するため好ましい。表面処理銅箔を、市販の液晶ポリマー樹脂（株式会社クラレ製Ｖｅｃｓｔａｒ ＣＴＺ－厚み５０μｍ、ヒドロキシ安息香酸（エステル）とヒドロキシナフトエ酸（エステル）との共重合体である樹脂）と貼り合わせた後、エッチングで特性インピーダンスが５０Ωのとなるようマイクロストリップ線路を形成し、ＨＰ社製のネットワークアナライザーＨＰ８７２０Ｃを用いて透過係数を測定し、周波数２０ＧＨｚおよび周波数４０ＧＨｚでの伝送損失を求めた場合に、周波数２０ＧＨｚにおける伝送損失が、５．０ｄＢ／１０ｃｍ未満が好ましく、４．１ｄＢ／１０ｃｍ未満がより好ましく、３．７ｄＢ／１０ｃｍ未満が更により好ましい。
<Transmission loss>
When the transmission loss is small, signal attenuation is suppressed when transmitting signals at high frequencies, so that stable signal transmission can be performed in a circuit that transmits signals at high frequencies. Therefore, it is preferable that the transmission loss value is smaller because it is suitable for use in circuit applications that transmit signals at high frequencies. After bonding the surface-treated copper foil with a commercially available liquid crystal polymer resin (Vecstar CTZ manufactured by Kuraray Co., Ltd. - thickness 50 μm, resin that is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), A microstrip line is formed by etching so that the characteristic impedance is 50Ω, and the transmission coefficient is measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is determined. The transmission loss is preferably less than 5.0 dB/10 cm, more preferably less than 4.1 dB/10 cm, and even more preferably less than 3.7 dB/10 cm.
＜キャリア付銅箔＞
本発明の別の実施の形態であるキャリア付銅箔は、キャリアの一方の面、又は、両方の面に、中間層、極薄銅層をこの順に有する。そして、前記極薄銅層が前述の本発明の一つの実施の形態である表面処理銅箔である。
<Copper foil with carrier>
A copper foil with a carrier, which is another embodiment of the present invention, has an intermediate layer and an ultra-thin copper layer on one or both surfaces of the carrier in this order. The ultra-thin copper layer is the surface-treated copper foil according to one embodiment of the present invention.
＜キャリア＞
本発明に用いることのできるキャリアは典型的には金属箔または樹脂フィルムであり、例えば銅箔、銅合金箔、ニッケル箔、ニッケル合金箔、鉄箔、鉄合金箔、ステンレス箔、アルミニウム箔、アルミニウム合金箔、絶縁樹脂フィルム、ポリイミドフィルム、ＬＣＰ（液晶ポリマー）フィルム、フッ素樹脂フィルム、ポリエチレンテレフタラート（ＰＥＴ）フィルム、ポリプロピレン（ＰＰ）フィルム、ポリアミドフィルム、ポリアミドイミドフィルムの形態で提供される。
本発明に用いることのできるキャリアは典型的には圧延銅箔や電解銅箔の形態で提供される。一般的には、電解銅箔は硫酸銅めっき浴からチタンやステンレスのドラム上に銅を電解析出して製造され、圧延銅箔は圧延ロールによる塑性加工と熱処理を繰り返して製造される。銅箔の材料としてはタフピッチ銅（ＪＩＳ Ｈ３１００ 合金番号Ｃ１１００）や無酸素銅（ＪＩＳ Ｈ３１００ 合金番号Ｃ１０２０またはＪＩＳ Ｈ３５１０ 合金番号Ｃ１０１１）やりん脱酸銅や電気銅といった高純度の銅の他、例えばＳｎ入り銅、Ａｇ入り銅、Ｃｒ、Ｚｒ又はＭｇ等を添加した銅合金、Ｎｉ及びＳｉ等を添加したコルソン系銅合金のような銅合金も使用可能である。また、公知の銅合金も使用可能である。なお、本明細書において用語「銅箔」を単独で用いたときには銅合金箔も含むものとする。
<Career>
The carrier that can be used in the present invention is typically a metal foil or a resin film, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum It is provided in the form of alloy foil, insulating resin film, polyimide film, LCP (liquid crystal polymer) film, fluororesin film, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyamide film, and polyamideimide film.
The carrier that can be used in the present invention is typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, electrolytic copper foil is manufactured by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, and rolled copper foil is manufactured by repeatedly undergoing plastic working with rolling rolls and heat treatment. Materials for copper foil include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100), oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), phosphor-deoxidized copper, and electrolytic copper. Copper alloys such as alloyed copper, copper containing Ag, copper alloys to which Cr, Zr, or Mg, etc. are added, and Corson-based copper alloys to which Ni, Si, and the like are added can also be used. Additionally, known copper alloys can also be used. Note that in this specification, when the term "copper foil" is used alone, it also includes copper alloy foil.
本発明に用いることのできるキャリアの厚さについても特に制限はないが、キャリアとしての役目を果たす上で適した厚さに適宜調節すればよく、例えば５μｍ以上とすることができる。但し、厚すぎると生産コストが高くなるので一般には３５μｍ以下とするのが好ましい。従って、キャリアの厚みは典型的には８～７０μｍであり、より典型的には１２～７０μｍであり、より典型的には１８～３５μｍである。また、原料コストを低減する観点からはキャリアの厚みは小さいことが好ましい。そのため、キャリアの厚みは、典型的には５μｍ以上３５μｍ以下であり、好ましくは５μｍ以上１８μｍ以下であり、好ましくは５μｍ以上１２μｍ以下であり、好ましくは５μｍ以上１１μｍ以下であり、好ましくは５μｍ以上１０μｍ以下である。なお、キャリアの厚みが小さい場合には、キャリアの通箔の際に折れシワが発生しやすい。折れシワの発生を防止するため、例えばキャリア付銅箔製造装置の搬送ロールを平滑にすることや、搬送ロールと、その次の搬送ロールとの距離を短くすることが有効である。なお、プリント配線板の製造方法の一つである埋め込み工法（エンベッティド法(Ｅｎｂｅｄｄｅｄ Ｐｒｏｃｅｓｓ)）にキャリア付銅箔が用いられる場合には、キャリアの剛性が高いことが必要である。そのため、埋め込み工法に用いる場合には、キャリアの厚みは１８μｍ以上３００μｍ以下であることが好ましく、２５μｍ以上１５０μｍ以下であることが好ましく、３５μｍ以上１００μｍ以下であることが好ましく、３５μｍ以上７０μｍ以下であることが更により好ましい。
なお、キャリアの極薄銅層を設ける側の表面とは反対側の表面に一次粒子層及び二次粒子層を設けてもよい。キャリアの極薄銅層を設ける側の表面とは反対側の表面に一次粒子層及び二次粒子層を設けることは、キャリアを当該一次粒子層及び二次粒子層を有する表面側から樹脂基板などの支持体に積層する際、キャリアと樹脂基板が剥離し難くなるという利点を有する。
There are no particular limitations on the thickness of the carrier that can be used in the present invention, but it may be appropriately adjusted to a thickness suitable for fulfilling its role as a carrier, and can be, for example, 5 μm or more. However, if it is too thick, the production cost will increase, so it is generally preferable that the thickness is 35 μm or less. Thus, the carrier thickness is typically 8-70 μm, more typically 12-70 μm, and more typically 18-35 μm. Further, from the viewpoint of reducing raw material costs, it is preferable that the thickness of the carrier is small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, and preferably 5 μm or more and 10 μm or less. It is as follows. Note that if the thickness of the carrier is small, folds and wrinkles are likely to occur when the carrier is threaded. In order to prevent the occurrence of folds and wrinkles, it is effective to, for example, smooth the conveyance roll of the carrier-attached copper foil manufacturing apparatus or to shorten the distance between one conveyance roll and the next conveyance roll. Note that when a carrier-attached copper foil is used in an embedded process, which is one of the methods for manufacturing printed wiring boards, the carrier needs to have high rigidity. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.
Note that the primary particle layer and the secondary particle layer may be provided on the surface of the carrier opposite to the surface on which the ultra-thin copper layer is provided. Providing a primary particle layer and a secondary particle layer on the surface of the carrier opposite to the surface on which the ultra-thin copper layer is provided means that the carrier is attached to a resin substrate, etc. from the surface side having the primary particle layer and secondary particle layer. It has the advantage that the carrier and resin substrate are difficult to separate when laminated on a support.
以下に、キャリアとして電解銅箔を使用する場合の製造条件の一例を示す。
＜電解液組成＞
銅：９０～１１０ｇ／Ｌ
硫酸：９０～１１０ｇ／Ｌ
塩素：５０～１００ｐｐｍ
レべリング剤１（ビス（３スルホプロピル）ジスルフィド）：１０～３０ｐｐｍ
レべリング剤２（アミン化合物）：１０～３０ｐｐｍ
上記のアミン化合物には以下の化学式のアミン化合物を用いることができる。
An example of manufacturing conditions when using electrolytic copper foil as a carrier is shown below.
<Electrolyte composition>
Copper: 90-110g/L
Sulfuric acid: 90-110g/L
Chlorine: 50-100ppm
Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
An amine compound having the following chemical formula can be used as the above amine compound.
なお、本発明に用いられる電解、表面処理又はめっき等に用いられる処理液の残部は特に明記しない限り水である。 Note that the remainder of the treatment liquid used in electrolysis, surface treatment, plating, etc. used in the present invention is water unless otherwise specified.
＜製造条件＞
電流密度：７０～１００Ａ／ｄｍ2
電解液温度：５０～６０℃
電解液線速：３～５ｍ／ｓｅｃ
電解時間：０．５～１０分間
<Manufacturing conditions>
Current density: 70-100A/dm 2
Electrolyte temperature: 50-60℃
Electrolyte linear velocity: 3 to 5 m/sec
Electrolysis time: 0.5-10 minutes
＜中間層＞
キャリア上には中間層を設ける。キャリアと中間層との間に他の層を設けてもよい。本発明で用いる中間層は、キャリア付銅箔が絶縁基板への積層工程前にはキャリアから極薄銅層が剥離し難い一方で、絶縁基板への積層工程後にはキャリアから極薄銅層が剥離可能となるような構成であれば特に限定されない。例えば、本発明のキャリア付銅箔の中間層はＣｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎ、これらの合金、これらの水和物、これらの酸化物、有機物からなる群から選択される一種又は二種以上を含んでも良い。また、中間層は複数の層であっても良い。
また、例えば、中間層はキャリア側からＣｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎで構成された元素群から選択された一種の元素からなる単一金属層、或いは、Ｃｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎで構成された元素群から選択された一種又は二種以上の元素からなる合金層を形成し、その上にＣｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎで構成された元素群から選択された一種又は二種以上の元素の水和物または酸化物、あるいは有機物からなる層、あるいはＣｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎで構成された元素群から選択された一種の元素からなる単一金属層、或いは、Ｃｒ、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｏ、Ｔｉ、Ｗ、Ｐ、Ｃｕ、Ａｌ、Ｚｎで構成された元素群から選択された一種又は二種以上の元素からなる合金層を形成することで構成することができる。
<Middle layer>
An intermediate layer is provided on the carrier. Other layers may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultra-thin copper layer is difficult to peel off from the carrier before the carrier-coated copper foil is laminated to the insulating substrate, but the ultra-thin copper layer is difficult to peel off from the carrier after the laminating process to the insulating substrate. There is no particular limitation as long as the structure is such that it can be peeled off. For example, the intermediate layer of the carrier-attached copper foil of the present invention may include Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, It may contain one or more selected from the group consisting of organic substances. Further, the intermediate layer may include a plurality of layers.
For example, the intermediate layer is a single metal layer made of a type of element selected from the group of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. , or forming an alloy layer consisting of one or more elements selected from the element group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn; A hydrate or oxide of one or more elements selected from the element group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance. or a single metal layer consisting of an element selected from the element group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or Cr, It can be constructed by forming an alloy layer consisting of one or more elements selected from the element group consisting of Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. .
中間層を片面にのみ設ける場合、キャリアの反対面にはＮｉメッキ層などの防錆層を設けることが好ましい。なお、中間層をクロメート処理や亜鉛クロメート処理やメッキ処理で設けた場合には、クロムや亜鉛など、付着した金属の一部は水和物や酸化物となっている場合があると考えられる。
また、例えば、中間層は、キャリア上に、ニッケル、ニッケル－リン合金又はニッケル－コバルト合金と、クロムとがこの順で積層されて構成することができる。ニッケルと銅との接着力はクロムと銅の接着力よりも高いので、極薄銅層を剥離する際に、極薄銅層とクロムとの界面で剥離するようになる。また、中間層のニッケルにはキャリアから銅成分が極薄銅層へと拡散していくのを防ぐバリア効果が期待される。中間層におけるニッケルの付着量は好ましくは１００μｇ／ｄｍ2以上４００００μｇ／ｄｍ2以下、より好ましくは１００μｇ／ｄｍ2以上４０００μｇ／ｄｍ2以下、より好ましくは１００μｇ／ｄｍ2以上２５００μｇ／ｄｍ2以下、より好ましくは１００μｇ／ｄｍ2以上１０００μｇ／ｄｍ2未満であり、中間層におけるクロムの付着量は５μｇ／ｄｍ2以上１００μｇ／ｄｍ2以下であることが好ましい。
When the intermediate layer is provided on only one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. Note that when the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metals such as chromium and zinc may become hydrates or oxides.
Further, for example, the intermediate layer can be formed by laminating nickel, a nickel-phosphorus alloy, or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultra-thin copper layer is peeled off, the peeling occurs at the interface between the ultra-thin copper layer and chromium. Furthermore, the nickel in the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultra-thin copper layer. The amount of nickel deposited in the intermediate layer is preferably 100 μg/dm 2 or more and 40000 μg/dm 2 or less, more preferably 100 μg/dm 2 or more and 4000 μg/dm 2 or less, more preferably 100 μg/dm 2 or more and 2500 μg/dm 2 or less, and more. It is preferably 100 μg/dm 2 or more and less than 1000 μg/dm 2 , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm 2 or more and 100 μg/dm 2 or less.
＜極薄銅層＞
中間層の上には極薄銅層を設ける。中間層と極薄銅層との間には他の層を設けてもよい。極薄銅層は、硫酸銅、ピロリン酸銅、スルファミン酸銅、シアン化銅等の電解浴を利用した電気メッキにより形成することができ、一般的な電解銅箔で使用され、高電流密度での銅箔形成が可能であることから硫酸銅浴が好ましい。極薄銅層の厚みは特に制限はないが、一般的にはキャリアよりも薄く、例えば１２μｍ以下である。典型的には０．５～１２μｍであり、より典型的には１～５μｍ、更に典型的には１．５～５μｍ、更に典型的には２～５μｍである。なお、キャリアの両面に極薄銅層を設けてもよい。
<Ultra-thin copper layer>
An ultra-thin copper layer is provided on top of the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. Ultra-thin copper layers can be formed by electroplating using electrolytic baths such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and are used in common electrolytic copper foils and can be applied at high current densities. A copper sulfate bath is preferred because it allows the formation of a copper foil. The thickness of the ultra-thin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically from 0.5 to 12 μm, more typically from 1 to 5 μm, even more typically from 1.5 to 5 μm, even more typically from 2 to 5 μm. Note that ultrathin copper layers may be provided on both sides of the carrier.
＜一次粒子層、二次粒子層の形成条件＞
表面処理銅箔の場合は銅箔の上に、また、キャリア付銅箔の場合は極薄銅層の上に、一次粒子層を形成、または一次粒子層及び二次粒子層をこの順で形成する。一次粒子層、二次粒子層の形成条件を以下に示すが、これはあくまで好適な例を示すものであり、使用される樹脂との密着強度が十分、例えば初期ピールで０．５ｋｇ／ｃｍ以上である範囲であれば、下記に表示する以外のメッキ条件であることは何ら妨げるものではない。本発明はこれらを包含するものである。
<Formation conditions of primary particle layer and secondary particle layer>
Form a primary particle layer, or form a primary particle layer and a secondary particle layer in this order, on the copper foil in the case of surface-treated copper foil, or on the ultra-thin copper layer in the case of carrier-coated copper foil. do. The conditions for forming the primary particle layer and secondary particle layer are shown below, but these are just preferred examples, and the adhesion strength with the resin used is sufficient, for example, 0.5 kg/cm or more at initial peeling. There is no hindrance to plating conditions other than those shown below as long as the conditions are within a certain range. The present invention includes these.
・一次粒子層
一次粒子めっき液（Ｉ）で処理した後、一次粒子めっき液（ＩＩ）で処理する場合は以下の条件で一次粒子層を形成することが可能である。
（一次粒子めっき液（Ｉ）による処理）
＜電解液組成＞
銅：５～１０ｇ／Ｌ
硫酸：７０～８０ｇ／Ｌ
＜製造条件＞
電流密度：５０～５５Ａ／ｄｍ2
電解液温度：３５℃
電解時間：０．５～１．６秒
（一次粒子めっき液（ＩＩ）による処理）
＜電解液組成＞
銅：２０～５０ｇ／Ｌ
硫酸：６０～１００ｇ／Ｌ
＜製造条件＞
電流密度：４～１０Ａ／ｄｍ2
電解液温度：３５～４５℃
電解時間：１．４～２．５秒
- Primary particle layer When processing with the primary particle plating solution (II) after processing with the primary particle plating solution (I), it is possible to form the primary particle layer under the following conditions.
(Processing with primary particle plating solution (I))
<Electrolyte composition>
Copper: 5-10g/L
Sulfuric acid: 70-80g/L
<Manufacturing conditions>
Current density: 50-55A/dm 2
Electrolyte temperature: 35℃
Electrolysis time: 0.5 to 1.6 seconds (processing with primary particle plating solution (II))
<Electrolyte composition>
Copper: 20-50g/L
Sulfuric acid: 60-100g/L
<Manufacturing conditions>
Current density: 4-10A/dm 2
Electrolyte temperature: 35-45℃
Electrolysis time: 1.4-2.5 seconds
一次粒子めっき液（Ｉ）による処理のみで一次粒子層を形成する場合は以下の一次粒子めっき液（Ｉ）による処理１または、一次粒子めっき液（Ｉ）による処理２に記載の条件で実施することが可能である。
（一次粒子めっき液（Ｉ）による処理１）
＜電解液組成＞
銅：１０～４５ｇ／Ｌ
コバルト：５～３０ｇ／Ｌ
ニッケル：５～３０ｇ／Ｌ
ｐＨ：２．８～３．２
＜製造条件＞
電流密度：３０～４５Ａ／ｄｍ2
電解液温度：３０～４０℃
電解時間：０．３～０．８秒
When forming a primary particle layer only by treatment with primary particle plating solution (I), carry out under the conditions described in Treatment 1 with primary particle plating solution (I) or Treatment 2 with primary particle plating solution (I) below. Is possible.
(Treatment 1 with primary particle plating solution (I))
<Electrolyte composition>
Copper: 10-45g/L
Cobalt: 5-30g/L
Nickel: 5-30g/L
pH: 2.8-3.2
<Manufacturing conditions>
Current density: 30-45A/dm 2
Electrolyte temperature: 30-40℃
Electrolysis time: 0.3-0.8 seconds
（一次粒子めっき液（Ｉ）による処理２）
＜電解液組成＞
銅：５～１５ｇ／Ｌ
ニッケル：３～３０ｇ／Ｌ
ｐＨ：２．６～３．０
＜製造条件＞
電流密度：５０～７０Ａ／ｄｍ2
電解液温度：３０～４０℃
電解時間：０．３～０．９秒
(Processing with primary particle plating solution (I) 2)
<Electrolyte composition>
Copper: 5-15g/L
Nickel: 3-30g/L
pH: 2.6-3.0
<Manufacturing conditions>
Current density: 50-70A/dm 2
Electrolyte temperature: 30-40℃
Electrolysis time: 0.3-0.9 seconds
・二次粒子層
二次粒子層を形成する場合は、以下の二次粒子めっき液（Ｉ）、または、二次粒子めっき液（ＩＩ）による処理で実施することが可能である。
（二次粒子めっき液（Ｉ）による処理）
＜電解液組成＞
銅：１０～１５ｇ／Ｌ
コバルト：５～１５ｇ／Ｌ
ニッケル：５～１５ｇ／Ｌ
ｐＨ：２．８～３．２
＜製造条件＞
電流密度：３０～３５Ａ／ｄｍ2
電解液温度：３３～３７℃
電解時間：０．５～１．０秒
- Secondary particle layer When forming a secondary particle layer, it is possible to carry out the treatment with the following secondary particle plating solution (I) or secondary particle plating solution (II).
(Processing with secondary particle plating solution (I))
<Electrolyte composition>
Copper: 10-15g/L
Cobalt: 5-15g/L
Nickel: 5-15g/L
pH: 2.8-3.2
<Manufacturing conditions>
Current density: 30-35A/dm 2
Electrolyte temperature: 33-37℃
Electrolysis time: 0.5-1.0 seconds
（二次粒子めっき液（ＩＩ）による処理）
＜電解液組成＞
銅：５～１２ｇ／Ｌ
ニッケル：２～１１ｇ／Ｌ
ｐＨ：２．８
＜製造条件＞
電流密度：５５～６５Ａ／ｄｍ2
電解液温度：３５～４０℃
電解時間：０．３～０．９秒
(Processing with secondary particle plating solution (II))
<Electrolyte composition>
Copper: 5-12g/L
Nickel: 2-11g/L
pH: 2.8
<Manufacturing conditions>
Current density: 55-65A/dm 2
Electrolyte temperature: 35-40℃
Electrolysis time: 0.3-0.9 seconds
＜かぶせめっき＞
一次粒子層の上に、または、二次粒子層が形成されている場合は二次粒子層の上に、かぶせめっきを行う。かぶせめっきによって形成する層は、例えば、Ｚｎ－Ｃｒ合金層、Ｎｉ－Ｍｏ合金層、Ｚｎ層、Ｃｏ－Ｍｏ合金層、Ｃｏ－Ｎｉ合金層、Ｎｉ－Ｗ合金層、Ｎｉ－Ｐ合金層、Ｎｉ－Ｆｅ合金層、Ｎｉ－Ａｌ合金層、Ｃｏ－Ｚｎ合金層、Ｃｏ－Ｐ合金層Ｚｎ－Ｃｏ合金層、Ｎｉ層、Ｃｏ層、Ｃｒ層、Ａｌ層、Ｓｎ層、Ｓｎ－Ｎｉ層、Ｎｉ－Ｓｎ層またはＺｎ－Ｎｉ合金層等のような、Ｚｎ、Ｃｒ、Ｎｉ、Ｆｅ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、Ａｓ、Ｔｉ、Ｍｏ及びＣｏ等からなる群から選択される一種の元素からなる金属層、または、Ｚｎ、Ｃｒ、Ｎｉ、Ｆｅ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、Ａｓ、Ｔｉ、Ｍｏ及びＣｏからなる群から選択される２種または３種以上を含む合金層または前述の元素群から選択される２種または３種以上の元素からなる合金層が挙げられる。
かぶせめっきは、以下のかぶせめっき液等による処理を行うことで、または、これらを組み合わせることで実施することができる。また、湿式めっきで設けることができない金属層、および／または、合金層はスパッタリング、物理蒸着（ＰＶＤ）、化学蒸着（ＣＶＤ）等の乾式めっき法により設けることができる。
<Cover plating>
Cover plating is performed on the primary particle layer or, if a secondary particle layer is formed, on the secondary particle layer. Examples of the layers formed by cover plating include Zn-Cr alloy layer, Ni-Mo alloy layer, Zn layer, Co-Mo alloy layer, Co-Ni alloy layer, Ni-W alloy layer, Ni-P alloy layer, Ni -Fe alloy layer, Ni-Al alloy layer, Co-Zn alloy layer, Co-P alloy layer Zn-Co alloy layer, Ni layer, Co layer, Cr layer, Al layer, Sn layer, Sn-Ni layer, Ni- selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo and Co, such as a Sn layer or a Zn-Ni alloy layer, etc. A metal layer consisting of one kind of element, or two or three selected from the group consisting of Zn, Cr, Ni, Fe, Ta, Cu, Al, P, W, Mn, Sn, As, Ti, Mo, and Co. Examples include an alloy layer containing at least one element, or an alloy layer consisting of two or more elements selected from the above-mentioned element group.
Cover plating can be carried out by performing a treatment using the following cover plating solution, etc., or by combining these. Furthermore, metal layers and/or alloy layers that cannot be provided by wet plating can be provided by dry plating methods such as sputtering, physical vapor deposition (PVD), and chemical vapor deposition (CVD).
・かぶせめっき液による処理（１）Ｚｎ－Ｃｒ
液組成：重クロム酸カリウム１～１ｇ／Ｌ、Ｚｎ０．１～５ｇ／Ｌ
液温：４０～６０℃
ｐＨ：０．５～１０
電流密度：０．０１～２．６Ａ／ｄｍ2
通電時間：０．０５～３０秒
・Processing with cover plating solution (1) Zn-Cr
Liquid composition: Potassium dichromate 1-1 g/L, Zn 0.1-5 g/L
Liquid temperature: 40-60℃
pH: 0.5-10
Current density: 0.01-2.6A/dm 2
Energizing time: 0.05-30 seconds
・かぶせめっき液による処理（２）Ｎｉ－Ｍｏ
液組成：硫酸ニッケル２７０～２８０ｇ／Ｌ、塩化ニッケル３５～４５ｇ／Ｌ、酢酸ニッケル１０～２０ｇ／Ｌ、モリブデン酸ナトリウム１～６０ｇ／Ｌ、クエン酸三ナトリウム１０～５０ｇ／Ｌ、ドデシル硫酸ナトリウム５０～９０ｐｐｍ
液温：２０～６５℃
ｐＨ：４～１２
電流密度：０．５～５Ａ／ｄｍ2
通電時間：０．１～５秒
・Processing with cover plating solution (2) Ni-Mo
Liquid composition: nickel sulfate 270-280g/L, nickel chloride 35-45g/L, nickel acetate 10-20g/L, sodium molybdate 1-60g/L, trisodium citrate 10-50g/L, sodium dodecyl sulfate 50 ～90ppm
Liquid temperature: 20-65℃
pH: 4-12
Current density: 0.5-5A/dm 2
Energization time: 0.1 to 5 seconds
・かぶせめっき液による処理（３）Ｚｎ
液組成：Ｚｎ１～１５ｇ／Ｌ
液温：２５～５０℃
ｐＨ：２～６
電流密度：０．５～５Ａ／ｄｍ2
通電時間：０．０１～０．３秒
・Processing with cover plating solution (3) Zn
Liquid composition: Zn1-15g/L
Liquid temperature: 25-50℃
pH: 2-6
Current density: 0.5-5A/dm 2
Energization time: 0.01 to 0.3 seconds
・かぶせめっき液による処理（４）Ｃｏ－Ｍｏ
液組成：Ｃｏ１～２０ｇ／Ｌ、モリブデン酸ナトリウム１～６０ｇ／Ｌ、クエン酸ナトリウム１０～１１０ｇ／Ｌ
液温：２５～５０℃
ｐＨ：５～７
電流密度：１～４Ａ／ｄｍ2
通電時間：０．１～５秒
・Processing with cover plating solution (4) Co-Mo
Liquid composition: Co1-20g/L, sodium molybdate 1-60g/L, sodium citrate 10-110g/L
Liquid temperature: 25-50℃
pH: 5-7
Current density: 1-4A/dm 2
Energization time: 0.1 to 5 seconds
・かぶせめっき液による処理（５）Ｃｏ－Ｎｉ
液組成：Ｃｏ１～２０ｇ／Ｌ、Ｎ１～２０ｇ／Ｌ
液温：３０～８０℃
ｐＨ：１．５～３．５
電流密度：１～２０Ａ／ｄｍ2
通電時間：０．１～４秒
・Processing with cover plating solution (5) Co-Ni
Liquid composition: Co1-20g/L, N1-20g/L
Liquid temperature: 30-80℃
pH: 1.5-3.5
Current density: 1-20A/dm 2
Energization time: 0.1 to 4 seconds
・かぶせめっき液による処理（６）Ｚｎ－Ｎｉ
液組成：Ｚｎ１～３０ｇ／Ｌ、Ｎ１～３０ｇ／Ｌ
液温：４０～５０℃
ｐＨ：２～５
電流密度：０．５～５Ａ／ｄｍ2
通電時間：０．０１～０．３秒
・Processing with cover plating solution (6) Zn-Ni
Liquid composition: Zn1-30g/L, N1-30g/L
Liquid temperature: 40-50℃
pH: 2-5
Current density: 0.5-5A/dm 2
Energization time: 0.01 to 0.3 seconds
・かぶせめっき液による処理（７）Ｎｉ－Ｗ
液組成：Ｎｉ１～３０ｇ／Ｌ、Ｗ１～３００ｍｇ／Ｌ
液温：３０～５０℃
ｐＨ：２～５
電流密度：０．１～５Ａ／ｄｍ2
通電時間：０．０１～０．３秒
・Processing with cover plating solution (7) Ni-W
Liquid composition: Ni 1-30g/L, W1-300mg/L
Liquid temperature: 30-50℃
pH: 2-5
Current density: 0.1-5A/dm 2
Energization time: 0.01 to 0.3 seconds
・かぶせめっき液による処理（８）Ｎｉ－Ｐ
液組成：Ｎｉ１～３０ｇ／Ｌ、Ｐ１～１０ｇ／Ｌ
液温：３０～５０℃
ｐＨ：２～５
電流密度：０．１～５Ａ／ｄｍ2
通電時間：０．０１～０．３秒
・Processing with cover plating solution (8) Ni-P
Liquid composition: Ni1-30g/L, P1-10g/L
Liquid temperature: 30-50℃
pH: 2-5
Current density: 0.1-5A/dm 2
Energization time: 0.01 to 0.3 seconds
＜その他の表面処理＞
かぶせめっき後、更にその表面にクロメート処理、シランカップリング処理などの処理を施してもよい。すなわち、一次粒子層または二次粒子層の表面に、耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された１種以上の層を形成してもよい。なお、上述の耐熱層、防錆層、クロメート処理層、シランカップリング処理層はそれぞれ複数の層で形成されてもよい（例えば２層以上、３層以上など）。
<Other surface treatments>
After cover plating, the surface may be further subjected to treatments such as chromate treatment and silane coupling treatment. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-proofing layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface of the primary particle layer or the secondary particle layer. Note that each of the above-mentioned heat-resistant layer, anti-rust layer, chromate-treated layer, and silane coupling-treated layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.).
本明細書において、クロメート処理層とは無水クロム酸、クロム酸、二クロム酸、クロム酸塩または二クロム酸塩を含む液で処理された層のことをいう。クロメート処理層はＣｏ、Ｆｅ、Ｎｉ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｓｎ、ＡｓおよびＴｉ等の元素（金属、合金、酸化物、窒化物、硫化物等どのような形態でもよい）を含んでもよい。クロメート処理層の具体例としては、無水クロム酸または二クロム酸カリウム水溶液で処理したクロメート処理層や、無水クロム酸または二クロム酸カリウムおよび亜鉛を含む処理液で処理したクロメート処理層等が挙げられる。 In this specification, a chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer is made of elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti (in any form such as metal, alloy, oxide, nitride, sulfide, etc.). ) may also be included. Specific examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic acid anhydride or potassium dichromate, and a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc. .
耐熱層、防錆層としては公知の耐熱層、防錆層を用いることができる。例えば、耐熱層および／または防錆層はニッケル、亜鉛、錫、コバルト、モリブデン、銅、タングステン、リン、ヒ素、クロム、バナジウム、チタン、アルミニウム、金、銀、白金族元素、鉄、タンタルの群から選ばれる１種以上の元素を含む層であってもよく、ニッケル、亜鉛、錫、コバルト、モリブデン、銅、タングステン、リン、ヒ素、クロム、バナジウム、チタン、アルミニウム、金、銀、白金族元素、鉄、タンタルの群から選ばれる１種以上の元素からなる金属層または合金層であってもよい。また、耐熱層および／または防錆層は前述の元素を含む酸化物、窒化物、珪化物を含んでもよい。また、耐熱層および／または防錆層はニッケル－亜鉛合金を含む層であってもよい。また、耐熱層および／または防錆層はニッケル－亜鉛合金層であってもよい。前記ニッケル－亜鉛合金層は、不可避不純物を除き、ニッケルを５０ｗｔ％～９９ｗｔ％、亜鉛を５０ｗｔ％～１ｗｔ％含有するものであってもよい。前記ニッケル－亜鉛合金層の亜鉛及びニッケルの合計付着量が５～１０００ｍｇ／ｍ2、好ましくは１０～５００ｍｇ／ｍ2、好ましくは２０～１００ｍｇ／ｍ2であってもよい。また、前記ニッケル－亜鉛合金を含む層または前記ニッケル－亜鉛合金層のニッケルの付着量と亜鉛の付着量との比（＝ニッケルの付着量／亜鉛の付着量）が１．５～１０であることが好ましい。また、前記ニッケル－亜鉛合金を含む層または前記ニッケル－亜鉛合金層のニッケルの付着量は０．５ｍｇ／ｍ2～５００ｍｇ／ｍ2であることが好ましく、１ｍｇ／ｍ2～５０ｍｇ／ｍ2であることがより好ましい。耐熱層および／または防錆層がニッケル－亜鉛合金を含む層である場合、スルーホールやビアホール等の内壁部がデスミア液と接触したときに銅箔と樹脂基板との界面がデスミア液に浸食されにくく、銅箔と樹脂基板との密着性が向上する。 As the heat-resistant layer and rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and/or the anti-corrosion layer may include nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum. The layer may contain one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. The layer may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of , iron, and tantalum. Further, the heat-resistant layer and/or the rust-preventive layer may contain an oxide, nitride, or silicide containing the above-mentioned elements. Furthermore, the heat-resistant layer and/or the anti-rust layer may be a layer containing a nickel-zinc alloy. Furthermore, the heat-resistant layer and/or the anti-rust layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, excluding unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m 2 , preferably 10 to 500 mg/m 2 , and preferably 20 to 100 mg/m 2 . Further, the ratio of the amount of nickel deposited to the amount of zinc deposited in the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (=deposition amount of nickel/deposition amount of zinc) is 1.5 to 10. It is preferable. Further, the amount of nickel deposited in the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg/m 2 to 500 mg/m 2 , and preferably 1 mg/m 2 to 50 mg/m 2 . It is more preferable that there be. If the heat-resistant layer and/or anti-corrosion layer is a layer containing a nickel-zinc alloy, when the inner wall of a through hole or via hole comes into contact with the desmear liquid, the interface between the copper foil and the resin substrate may be eroded by the desmear liquid. This improves the adhesion between the copper foil and the resin substrate.
例えば耐熱層および／または防錆層は、付着量が１ｍｇ／ｍ2～１００ｍｇ／ｍ2、好ましくは５ｍｇ／ｍ2～５０ｍｇ／ｍ2のニッケルまたはニッケル合金層と、付着量が１ｍｇ／ｍ2～８０ｍｇ／ｍ2、好ましくは５ｍｇ／ｍ2～４０ｍｇ／ｍ2のスズ層とを順次積層したものであってもよく、前記ニッケル合金層はニッケル－モリブデン合金、ニッケル－亜鉛合金、ニッケル－モリブデン－コバルト合金、ニッケル－スズ合金のいずれか一種により構成されてもよい。 For example, the heat-resistant layer and/or the anti-rust layer may include a nickel or nickel alloy layer with an adhesion amount of 1 mg/m 2 to 100 mg/m 2 , preferably 5 mg/m 2 to 50 mg/m 2 , and a nickel or nickel alloy layer with an adhesion amount of 1 mg/m 2 ~80mg/m 2 , preferably 5mg/m 2 ~40mg/m 2 tin layers may be sequentially laminated, and the nickel alloy layer may be a nickel-molybdenum alloy, a nickel-zinc alloy, a nickel-molybdenum - May be composed of either a cobalt alloy or a nickel-tin alloy.
シランカップリング処理層は、公知のシランカップリング剤を使用して形成してもよく、エポキシ系シラン、アミノ系シラン、メタクリロキシ系シラン、メルカプト系シラン、ビニル系シラン、イミダゾール系シラン、トリアジン系シランなどのシランカップリング剤などを使用して形成してもよい。なお、このようなシランカップリング剤は、２種以上混合して使用してもよい。中でも、アミノ系シランカップリング剤又はエポキシ系シランカップリング剤を用いて形成したものであることが好ましい。 The silane coupling treatment layer may be formed using a known silane coupling agent, such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, or triazine silane. It may be formed using a silane coupling agent such as. Note that two or more kinds of such silane coupling agents may be used in combination. Among these, those formed using an amino-based silane coupling agent or an epoxy-based silane coupling agent are preferable.
また、銅箔、極薄銅層、粗化処理層、耐熱層、防錆層、シランカップリング処理層またはクロメート処理層の表面に、公知の表面処理を行うことができる。 Further, a known surface treatment can be performed on the surface of the copper foil, ultra-thin copper layer, roughening layer, heat-resistant layer, anticorrosion layer, silane coupling layer, or chromate layer.
本発明の表面処理層は前述した表面処理により形成される層を含んでもよい。例えば本発明の表面処理層は前述のかぶせめっき層、および／または、金属層、および／または、合金層、および／または、耐熱層、および／または、防錆層、および／または、クロメート処理層、および／または、シランカップリング処理層、および／または、粗化処理層を一つまたは複数含んでもよい。 The surface treatment layer of the present invention may include a layer formed by the surface treatment described above. For example, the surface treatment layer of the present invention is the above-mentioned cover plating layer, and/or metal layer, and/or alloy layer, and/or heat resistant layer, and/or rust prevention layer, and/or chromate treatment layer. , and/or a silane coupling treatment layer, and/or a roughening treatment layer or one or more layers.
このようにして、表面処理銅箔、および／または、キャリアと、キャリア上に積層された中間層と、中間層の上に積層された極薄銅層とを備えたキャリア付銅箔が製造される。表面処理銅箔、および／または、キャリア付銅箔自体の使用方法は当業者に周知であるが、例えば表面処理銅箔、および／または、極薄銅層の表面を紙基材フェノール樹脂、紙基材エポキシ樹脂、合成繊維布基材エポキシ樹脂、ガラス布・紙複合基材エポキシ樹脂、ガラス布・ガラス不織布複合基材エポキシ樹脂及びガラス布基材エポキシ樹脂、ポリエステルフィルム、ポリイミドフィルム、液晶ポリマー、フッ素樹脂、ポリアミド樹脂、低誘電ポリイミドフィルム等の絶縁基板に貼り合わせて、（キャリア付銅箔の場合は熱圧着後にキャリアを剥がして）銅張積層板とし、絶縁基板に接着した表面処理銅箔、および、または、極薄銅層を目的とする導体パターンにエッチングし、最終的にプリント配線板を製造することができる。 In this way, a surface-treated copper foil and/or a carrier-attached copper foil comprising a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer is manufactured. Ru. The method of using the surface-treated copper foil and/or the copper foil with a carrier itself is well known to those skilled in the art. For example, the surface of the surface-treated copper foil and/or the ultra-thin copper layer can be Base material epoxy resin, synthetic fiber cloth base material epoxy resin, glass cloth/paper composite base material epoxy resin, glass cloth/glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystal polymer, Surface-treated copper foil that is bonded to an insulating substrate such as fluororesin, polyamide resin, or low dielectric polyimide film (in the case of copper foil with a carrier, the carrier is removed after thermocompression bonding) to form a copper-clad laminate, and then bonded to the insulating substrate. , and/or the ultra-thin copper layer can be etched into the desired conductor pattern and ultimately produce a printed wiring board.
＜樹脂層＞
本発明の表面処理銅箔は、表面処理層の表面に樹脂層を備えてもよい。また、Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、または、クロメート処理層、または、シランカップリング処理層、または、Ｎｉ－Ｚｎ合金層の表面に樹脂層を備えてもよい。樹脂層は、表面処理銅箔の最表面に形成されているのがより好ましい。
本発明のキャリア付銅箔は一次粒子層または二次粒子層上に、耐熱層、防錆層、クロメート処理層、または、シランカップリング処理層の上に樹脂層を備えても良い。
<Resin layer>
The surface-treated copper foil of the present invention may include a resin layer on the surface of the surface-treated layer. Further, an alloy layer consisting of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, or a chromate A resin layer may be provided on the surface of the treated layer, the silane coupling treated layer, or the Ni--Zn alloy layer. More preferably, the resin layer is formed on the outermost surface of the surface-treated copper foil.
The carrier-attached copper foil of the present invention may include a resin layer on the primary particle layer or the secondary particle layer, a heat-resistant layer, a rust-proofing layer, a chromate treatment layer, or a silane coupling treatment layer.
前記樹脂層は接着剤であってもよく、接着用の半硬化状態（Ｂステージ）の絶縁樹脂層であってもよい。半硬化状態（Ｂステージ）とは、その表面に指で触れても粘着感はなく、該絶縁樹脂層を重ね合わせて保管することができ、更に加熱処理を受けると硬化反応が起こる状態のことを含む。 The resin layer may be an adhesive, or may be an insulating resin layer in a semi-cured state (B stage) for adhesion. The semi-cured state (B stage) is a state in which there is no sticky feeling when the surface is touched with a finger, the insulating resin layers can be stacked and stored, and a curing reaction occurs when further heat treatment is performed. including.
また前記樹脂層は熱硬化性樹脂を含んでもよく、熱可塑性樹脂であってもよい。また、前記樹脂層は熱可塑性樹脂を含んでもよい。その種類は格別限定されるものではないが、例えば、エポキシ樹脂、ポリイミド樹脂、多官能性シアン酸エステル化合物、マレイミド化合物、ポリマレイミド化合物、マレイミド系樹脂、芳香族マレイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂、ポリエーテルスルホン（ポリエーテルサルホン、ポリエーテルサルフォンともいう）、ポリエーテルスルホン（ポリエーテルサルホン、ポリエーテルサルフォンともいう）樹脂、芳香族ポリアミド樹脂、芳香族ポリアミド樹脂ポリマー、ゴム性樹脂、ポリアミン、芳香族ポリアミン、ポリアミドイミド樹脂、ゴム変成エポキシ樹脂、フェノキシ樹脂、カルボキシル基変性アクリロニトリル－ブタジエン樹脂、ポリフェニレンオキサイド、ビスマレイミドトリアジン樹脂、熱硬化性ポリフェニレンオキサイド樹脂、シアネートエステル系樹脂、カルボン酸の無水物、多価カルボン酸の無水物、架橋可能な官能基を有する線状ポリマー、ポリフェニレンエーテル樹脂、２，２－ビス（４－シアナトフェニル）プロパン、リン含有フェノール化合物、ナフテン酸マンガン、２，２－ビス（４－グリシジルフェニル）プロパン、ポリフェニレンエーテル－シアネート系樹脂、シロキサン変性ポリアミドイミド樹脂、シアノエステル樹脂、フォスファゼン系樹脂、ゴム変成ポリアミドイミド樹脂、イソプレン、水素添加型ポリブタジエン、ポリビニルブチラール、フェノキシ、高分子エポキシ、芳香族ポリアミド、フッ素樹脂、ビスフェノール、ブロック共重合ポリイミド樹脂およびシアノエステル樹脂の群から選択される一種以上を含む樹脂を好適なものとして挙げることができる。 Moreover, the resin layer may contain a thermosetting resin or may be a thermoplastic resin. Further, the resin layer may include a thermoplastic resin. The types are not particularly limited, but examples include epoxy resins, polyimide resins, polyfunctional cyanate ester compounds, maleimide compounds, polymaleimide compounds, maleimide resins, aromatic maleimide resins, polyvinyl acetal resins, and urethane resins. , polyethersulfone (also called polyethersulfone, polyethersulfone), polyethersulfone (also called polyethersulfone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin , polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid Anhydride, polyhydric carboxylic acid anhydride, linear polymer with crosslinkable functional groups, polyphenylene ether resin, 2,2-bis(4-cyanatophenyl)propane, phosphorus-containing phenolic compound, manganese naphthenate, 2 , 2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy Suitable resins include one or more selected from the group consisting of , polymeric epoxy, aromatic polyamide, fluororesin, bisphenol, block copolyimide resin, and cyanoester resin.
また前記エポキシ樹脂は、分子内に２個以上のエポキシ基を有するものであって、電気・電子材料用途に用いることのできるものであれば、特に問題なく使用できる。また、前記エポキシ樹脂は分子内に２個以上のグリシジル基を有する化合物を用いてエポキシ化したエポキシ樹脂が好ましい。また、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ブロム化（臭素化）エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ゴム変性ビスフェノールＡ型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、トリグリシジルイソシアヌレート、Ｎ，Ｎ－ジグリシジルアニリン等のグリシジルアミン化合物、テトラヒドロフタル酸ジグリシジルエステル等のグリシジルエステル化合物、リン含有エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、の群から選ばれる１種又は２種以上を混合して用いることができ、又は前記エポキシ樹脂の水素添加体やハロゲン化体を用いることができる。
前記リン含有エポキシ樹脂として公知のリンを含有するエポキシ樹脂を用いることができる。また、前記リン含有エポキシ樹脂は例えば、分子内に２以上のエポキシ基を備える９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイドからの誘導体として得られるエポキシ樹脂であることが好ましい。
Further, the epoxy resin can be used without any particular problem as long as it has two or more epoxy groups in the molecule and can be used for electrical/electronic materials. Further, the epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy resin Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N,N - Glycidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl-type epoxy resins, biphenyl novolac-type epoxy resins, trishydroxyphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins One kind or a mixture of two or more kinds selected from the group of epoxy resins can be used, or a hydrogenated product or a halogenated product of the above-mentioned epoxy resin can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. Further, the phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. is preferred.
前記樹脂層は公知の樹脂、樹脂硬化剤、化合物、硬化促進剤、誘電体（無機化合物及び／または有機化合物を含む誘電体、金属酸化物を含む誘電体等どのような誘電体を用いてもよい）、反応触媒、架橋剤、ポリマー、プリプレグ、骨格材等を含んでよい。また、前記樹脂層は公知の形成方法、形成装置を用いて形成してもよい。 The resin layer may be made of any known resin, resin curing agent, compound, curing accelerator, dielectric material (dielectric material containing an inorganic compound and/or organic compound, dielectric material containing a metal oxide, etc.). may include reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, etc. Further, the resin layer may be formed using a known forming method and forming apparatus.
上述したこれらの樹脂を例えばメチルエチルケトン（ＭＥＫ）、トルエンなどの溶剤に溶解して樹脂液とし、これを前記表面処理銅箔上、および／または、前記極薄銅層上、あるいは前記耐熱層、防錆層、あるいは前記クロメート皮膜層、あるいは前記シランカップリング剤層等を含む表面処理層の上に、例えばロールコータ法などによって塗布し、ついで必要に応じて加熱乾燥して溶剤を除去しＢステージ状態にする。乾燥には例えば熱風乾燥炉を用いればよく、乾燥温度は１００～２５０℃、好ましくは１３０～２００℃であればよい。 These resins mentioned above are dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to form a resin liquid, and this is applied on the surface-treated copper foil and/or on the ultra-thin copper layer, or on the heat-resistant layer or barrier layer. It is coated on the surface treatment layer including the rust layer, the chromate film layer, the silane coupling agent layer, etc. by, for example, a roll coater method, and then, if necessary, heat-dried to remove the solvent and perform the B stage. state. For example, a hot air drying oven may be used for drying, and the drying temperature may be 100 to 250°C, preferably 130 to 200°C.
樹脂層付表面処理銅箔、および／または、キャリア付銅箔（樹脂付キャリア付銅箔）は、その樹脂層を基材に重ね合わせたのち全体を熱圧着して該樹脂層を熱硬化せしめ、ついでキャリア付銅箔である場合にはキャリアを剥離して極薄銅層を表出せしめ（当然に表出するのは該極薄銅層の中間層側の表面である）、表面処理銅箔または極薄銅層に所定の配線パターンを形成するという態様で使用される。 Surface-treated copper foil with a resin layer and/or copper foil with a carrier (copper foil with a carrier and resin) is produced by overlapping the resin layer on a base material and then thermocompression-bonding the entire resin layer to thermoset the resin layer. Then, in the case of copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (naturally, the surface of the ultra-thin copper layer on the intermediate layer side is exposed), and the surface-treated copper is removed. It is used to form a predetermined wiring pattern on a foil or ultra-thin copper layer.
この樹脂層付表面処理銅箔、および／または、キャリア付銅箔を使用すると、多層プリント配線基板の製造時におけるプリプレグ材の使用枚数を減らすことができる。しかも、樹脂層の厚みを層間絶縁が確保できるような厚みにしたり、プリプレグ材を全く使用していなくても銅張積層板を製造することができる。またこのとき、基材の表面に絶縁樹脂をアンダーコートして表面の平滑性を更に改善することもできる。 By using this surface-treated copper foil with a resin layer and/or the copper foil with a carrier, it is possible to reduce the number of sheets of prepreg material used when manufacturing a multilayer printed wiring board. Moreover, the copper-clad laminate can be manufactured even if the thickness of the resin layer is set to a thickness that ensures interlayer insulation, or even if no prepreg material is used at all. Further, at this time, the surface of the base material can be undercoated with an insulating resin to further improve the surface smoothness.
なお、プリプレグ材を使用しない場合には、プリプレグ材の材料コストが節約され、また積層工程も簡略になるので経済的に有利となり、しかも、プリプレグ材の厚み分だけ製造される多層プリント配線基板の厚みは薄くなり、１層の厚みが１００μｍ以下である極薄の多層プリント配線基板を製造することができるという利点がある。 In addition, when prepreg material is not used, the material cost of prepreg material is saved and the lamination process is simplified, which is economically advantageous. There is an advantage that the thickness becomes thinner, and an ultra-thin multilayer printed wiring board in which each layer has a thickness of 100 μm or less can be manufactured.
この樹脂層の厚みは０．１～８０μｍであることが好ましい。樹脂層の厚みが０．１μｍより薄くなると、接着力が低下し、プリプレグ材を介在させることなくこの樹脂付きキャリア付銅箔を内層材を備えた基材に積層したときに、内層材の回路との間の層間絶縁を確保することが困難になる場合がある。 The thickness of this resin layer is preferably 0.1 to 80 μm. When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength decreases, and when this resin-coated copper foil with a carrier is laminated on a base material provided with an inner layer material without intervening prepreg material, the circuit of the inner layer material is It may be difficult to ensure interlayer insulation between the
一方、樹脂層の厚みを８０μｍより厚くすると、１回の塗布工程で目的厚みの樹脂層を形成することが困難となり、余分な材料費と工数がかかるため経済的に不利となる。更には、形成された樹脂層はその可撓性が劣るので、ハンドリング時にクラックなどが発生しやすくなり、また内層材との熱圧着時に過剰な樹脂流れが起こって円滑な積層が困難になる場合がある。 On the other hand, if the thickness of the resin layer is made thicker than 80 μm, it becomes difficult to form a resin layer of the desired thickness in a single coating process, which is economically disadvantageous since extra material costs and man-hours are required. Furthermore, since the formed resin layer has poor flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.
更に、樹脂付きキャリア付銅箔のもう一つの製品形態としては、前記極薄銅層が有する表面処理層上、あるいは前記耐熱層、防錆層、あるいは前記クロメート処理層、あるいは前記シランカップリング処理層の上に樹脂層で被覆し、半硬化状態とした後、ついでキャリアを剥離して、キャリアが存在しない樹脂付き銅箔の形で製造することも可能である。 Furthermore, as another product form of the resin-coated carrier-attached copper foil, the surface treatment layer of the ultra-thin copper layer, the heat-resistant layer, the rust-proofing layer, the chromate treatment layer, or the silane coupling treatment can be used. It is also possible to coat the layer with a resin layer, bring it into a semi-cured state, and then peel off the carrier to produce a resin-coated copper foil without a carrier.
プリント配線板に電子部品類を搭載することで、プリント回路板が完成する。本発明において、「プリント配線板」にはこのように電子部品類が搭載されたプリント配線板およびプリント回路板およびプリント基板も含まれることとする。
また、当該プリント配線板を用いて電子機器を作製してもよく、当該電子部品類が搭載されたプリント回路板を用いて電子機器を作製してもよく、当該電子部品類が搭載されたプリント基板を用いて電子機器を作製してもよい。以下に、本発明に係るキャリア付銅箔を用いたプリント配線板の製造工程の例を幾つか示す。なお、キャリア付銅箔の極薄銅層として本発明の表面処理銅箔を用いても同様にプリント配線板を製造することができる。
A printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the term "printed wiring board" includes printed wiring boards, printed circuit boards, and printed circuit boards on which electronic components are mounted in this manner.
Furthermore, electronic devices may be manufactured using the printed wiring board, electronic devices may be manufactured using the printed circuit board on which the electronic components are mounted, and electronic devices may be manufactured using the printed circuit board on which the electronic components are mounted. An electronic device may be manufactured using the substrate. Below, some examples of the manufacturing process of a printed wiring board using the carrier-attached copper foil according to the present invention will be shown. Note that a printed wiring board can be similarly manufactured using the surface-treated copper foil of the present invention as the ultra-thin copper layer of the carrier-attached copper foil.
本発明に係るプリント配線板の製造方法の一実施形態においては、本発明に係るキャリア付銅箔（以下、「キャリア付銅箔」および「極薄銅層」を「表面処理銅箔」または「樹脂層付表面処理銅箔」と読み替え、また「極薄銅層側」を「表面処理層側」または「樹脂層付表面処理銅箔側」と読み替えて、プリント配線板を製造しても良い。前述のように読み替えた場合、キャリアについての記載はないものとして、プリント配線板を製造してもよい。）と絶縁基板とを準備する工程、前記キャリア付銅箔と絶縁基板を積層する工程、前記キャリア付銅箔と絶縁基板を極薄銅層側が絶縁基板と対向するように積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、その後、セミアディティブ法、モディファイドセミアディティブ法、パートリーアディティブ法及びサブトラクティブ法の何れかの方法によって、回路を形成する工程を含む。絶縁基板は内層回路入りのものとすることも可能である。 In one embodiment of the method for manufacturing a printed wiring board according to the present invention, the copper foil with a carrier according to the present invention (hereinafter, "copper foil with carrier" and "ultra-thin copper layer") is replaced with "surface-treated copper foil" or " Printed wiring boards may also be manufactured by reading "surface-treated copper foil with resin layer" and replacing "ultra-thin copper layer side" with "surface-treated layer side" or "surface-treated copper foil side with resin layer". (If read as above, a printed wiring board may be manufactured even if there is no description of the carrier.) and an insulating substrate, and a step of laminating the carrier-attached copper foil and the insulating substrate. After laminating the carrier-attached copper foil and the insulating substrate so that the ultra-thin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling off the carrier of the carrier-attached copper foil, and then semi-additive The method includes a step of forming a circuit by any one of a method, a modified semi-additive method, a part-additive method, and a subtractive method. The insulating substrate may also include an inner layer circuit.
本発明において、セミアディティブ法とは、絶縁基板又は銅箔シード層上に薄い無電解めっきを行い、パターンを形成後、電気めっき及びエッチングを用いて導体パターンを形成する方法を指す。 In the present invention, the semi-additive method refers to a method in which thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductor pattern is formed using electroplating and etching.
従って、セミアディティブ法を用いた本発明に係るプリント配線板の製造方法の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した前記樹脂にスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記樹脂および前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。
Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using a semi-additive method, the step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and removing all the exposed ultra-thin copper layer by a method such as etching using a corrosive solution such as acid or plasma;
a step of providing through holes and/or blind vias in the resin exposed by removing the ultra-thin copper layer by etching;
performing a desmear process on a region including the through hole or/and blind via;
providing an electroless plating layer on a region including the resin and the through hole or/and blind via;
providing a plating resist on the electroless plating layer;
exposing the plating resist to light, and then removing the plating resist in a region where a circuit is to be formed;
providing an electrolytic plating layer in the region where the circuit is formed from which the plating resist has been removed;
a step of removing the plating resist;
a step of removing the electroless plating layer in an area other than the area where the circuit is formed by flash etching or the like;
including.
セミアディティブ法を用いた本発明に係るプリント配線板の製造方法の別の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と、前記絶縁樹脂基板とにスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチング等により除去することにより露出した前記樹脂および前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。
In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a carrier-attached copper foil and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of providing through holes and/or blind vias in the ultra-thin copper layer exposed by peeling off the carrier and the insulating resin substrate;
performing a desmear process on a region including the through hole or/and blind via;
a step of peeling off the carrier and removing all the exposed ultra-thin copper layer by a method such as etching using a corrosive solution such as acid or plasma;
providing an electroless plating layer on the region including the resin and the through hole or/and blind via exposed by removing the ultra-thin copper layer by etching or the like;
providing a plating resist on the electroless plating layer;
exposing the plating resist to light, and then removing the plating resist in a region where a circuit is to be formed;
providing an electrolytic plating layer in the region where the circuit is formed from which the plating resist has been removed;
a step of removing the plating resist;
a step of removing the electroless plating layer in an area other than the area where the circuit is formed by flash etching or the like;
including.
セミアディティブ法を用いた本発明に係るプリント配線板の製造方法の別の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と、前記絶縁樹脂基板とにスルーホールまたは／およびブラインドビアを設ける工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記極薄銅層をエッチング等により除去することにより露出した前記樹脂および前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。
In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a carrier-attached copper foil and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of providing through holes and/or blind vias in the ultra-thin copper layer exposed by peeling off the carrier and the insulating resin substrate;
a step of peeling off the carrier and removing all the exposed ultra-thin copper layer by a method such as etching using a corrosive solution such as acid or plasma;
performing a desmear process on a region including the through hole or/and blind via;
providing an electroless plating layer on the region including the resin and the through hole or/and blind via exposed by removing the ultra-thin copper layer by etching or the like;
providing a plating resist on the electroless plating layer;
exposing the plating resist to light, and then removing the plating resist in a region where a circuit is to be formed;
providing an electrolytic plating layer in the region where the circuit is formed from which the plating resist has been removed;
a step of removing the plating resist;
a step of removing the electroless plating layer in an area other than the area where the circuit is formed by flash etching or the like;
including.
セミアディティブ法を用いた本発明に係るプリント配線板の製造方法の別の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した前記樹脂の表面について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。
In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a carrier-attached copper foil and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and removing all the exposed ultra-thin copper layer by a method such as etching using a corrosive solution such as acid or plasma;
providing an electroless plating layer on the surface of the resin exposed by removing the ultra-thin copper layer by etching;
providing a plating resist on the electroless plating layer;
exposing the plating resist to light, and then removing the plating resist in a region where a circuit is to be formed;
providing an electrolytic plating layer in the region where the circuit is formed from which the plating resist has been removed;
a step of removing the plating resist;
a step of removing the electroless plating layer and the ultra-thin copper layer in areas other than the area where the circuit is formed by flash etching or the like;
including.
本発明において、モディファイドセミアディティブ法とは、絶縁層上に金属箔を積層し、めっきレジストにより非回路形成部を保護し、電解めっきにより回路形成部の銅厚付けを行った後、レジストを除去し、前記回路形成部以外の金属箔を（フラッシュ）エッチングで除去することにより、絶縁層上に回路を形成する方法を指す。 In the present invention, the modified semi-additive method refers to laminating metal foil on an insulating layer, protecting non-circuit forming areas with a plating resist, applying thick copper to the circuit forming area using electrolytic plating, and then removing the resist. However, it refers to a method of forming a circuit on an insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching.
従って、モディファイドセミアディティブ法を用いた本発明に係るプリント配線板の製造方法の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記キャリアを剥がして露出した極薄銅層表面にめっきレジストを設ける工程、
前記めっきレジストを設けた後に、電解めっきにより回路を形成する工程、
前記めっきレジストを除去する工程、
前記めっきレジストを除去することにより露出した極薄銅層をフラッシュエッチングにより除去する工程、
を含む。
Therefore, in an embodiment of the method for manufacturing a printed wiring board according to the present invention using a modified semi-additive method, the steps of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and providing through holes and/or blind vias in the exposed ultra-thin copper layer and the insulating substrate;
performing a desmear process on a region including the through hole or/and blind via;
providing an electroless plating layer on the region including the through hole or/and blind via;
a step of peeling off the carrier and providing a plating resist on the exposed ultra-thin copper layer surface;
forming a circuit by electrolytic plating after providing the plating resist;
a step of removing the plating resist;
a step of removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.
モディファイドセミアディティブ法を用いた本発明に係るプリント配線板の製造方法の別の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。
In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a modified semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and providing a plating resist on the exposed ultra-thin copper layer;
exposing the plating resist to light, and then removing the plating resist in a region where a circuit is to be formed;
providing an electrolytic plating layer in the region where the circuit is formed from which the plating resist has been removed;
a step of removing the plating resist;
a step of removing the electroless plating layer and the ultra-thin copper layer in areas other than the area where the circuit is formed by flash etching or the like;
including.
本発明において、パートリーアディティブ法とは、導体層を設けてなる基板、必要に応じてスルーホールやバイアホール用の孔を穿けてなる基板上に触媒核を付与し、エッチングして導体回路を形成し、必要に応じてソルダレジストまたはメッキレジストを設けた後に、前記導体回路上、スルーホールやバイアホールなどに無電解めっき処理によって厚付けを行うことにより、プリント配線板を製造する方法を指す。 In the present invention, the part-additive method refers to adding catalyst nuclei to a substrate provided with a conductor layer, or a substrate having holes for through holes or via holes formed as necessary, and etching it to form a conductor circuit. However, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by applying thickening to the through holes, via holes, etc. on the conductor circuit by electroless plating.
従って、パートリーアディティブ法を用いた本発明に係るプリント配線板の製造方法の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは／およびブラインドビアを含む領域について触媒核を付与する工程、
前記キャリアを剥がして露出した極薄銅層表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して露出した前記絶縁基板表面に、ソルダレジストまたはメッキレジストを設ける工程、
前記ソルダレジストまたはメッキレジストが設けられていない領域に無電解めっき層を設ける工程、
を含む。
Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the part-additive method, the steps of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and providing through holes and/or blind vias in the exposed ultra-thin copper layer and the insulating substrate;
performing a desmear process on a region including the through hole or/and blind via;
a step of providing a catalyst core in a region including the through hole or/and blind via;
a step of peeling off the carrier and providing an etching resist on the exposed ultra-thin copper layer surface;
a step of exposing the etching resist to form a circuit pattern;
forming a circuit by removing the ultra-thin copper layer and the catalyst core by etching using a corrosive solution such as an acid, plasma, or the like;
removing the etching resist;
a step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalyst nucleus by etching using a corrosive solution such as an acid or using a method such as plasma;
providing an electroless plating layer in an area where the solder resist or plating resist is not provided;
including.
本発明において、サブトラクティブ法とは、銅張積層板上の銅箔の不要部分を、エッチングなどによって、選択的に除去して、導体パターンを形成する方法を指す。 In the present invention, the subtractive method refers to a method in which unnecessary portions of copper foil on a copper-clad laminate are selectively removed by etching or the like to form a conductor pattern.
従って、サブトラクティブ法を用いた本発明に係るプリント配線板の製造方法の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面に、電解めっき層を設ける工程、
前記電解めっき層または／および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層および前記電解めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。
Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using a subtractive method, the steps of preparing a carrier-attached copper foil and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and providing through holes and/or blind vias in the exposed ultra-thin copper layer and the insulating substrate;
performing a desmear process on a region including the through hole or/and blind via;
providing an electroless plating layer on the region including the through hole or/and blind via;
a step of providing an electrolytic plating layer on the surface of the electroless plating layer;
providing an etching resist on the surface of the electrolytic plating layer and/or the ultra-thin copper layer;
a step of exposing the etching resist to form a circuit pattern;
forming a circuit by removing the ultra-thin copper layer, the electroless plating layer, and the electrolytic plating layer by a method such as etching using a corrosive solution such as acid or plasma;
removing the etching resist;
including.
サブトラクティブ法を用いた本発明に係るプリント配線板の製造方法の別の一実施形態においては、本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは／およびブラインドビアを設ける工程、
前記スルーホールまたは／およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは／およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面にマスクを形成する工程、
マスクが形成されいない前記無電解めっき層の表面に電解めっき層を設ける工程、
前記電解めっき層または／および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。
In another embodiment of the method for manufacturing a printed wiring board according to the present invention using a subtractive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
a step of laminating the carrier-attached copper foil and the insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil;
a step of peeling off the carrier and providing through holes and/or blind vias in the exposed ultra-thin copper layer and the insulating substrate;
performing a desmear process on a region including the through hole or/and blind via;
providing an electroless plating layer on the region including the through hole or/and blind via;
forming a mask on the surface of the electroless plating layer;
a step of providing an electrolytic plating layer on the surface of the electroless plating layer on which a mask is not formed;
providing an etching resist on the surface of the electrolytic plating layer and/or the ultra-thin copper layer;
a step of exposing the etching resist to form a circuit pattern;
forming a circuit by removing the ultra-thin copper layer and the electroless plating layer by etching using a corrosive solution such as acid, plasma or the like;
removing the etching resist;
including.
スルーホールまたは／およびブラインドビアを設ける工程、及びその後のデスミア工程は行わなくてもよい。 The process of providing through holes and/or blind vias and the subsequent desmear process may not be performed.
ここで、本発明のキャリア付銅箔を用いたプリント配線板の製造方法の具体例を図面を用いて詳細に説明する。なお、ここでは一次粒子層及び二次粒子層を粗化処理層として設けた場合について説明している。
まず、図１－Ａに示すように、表面に粗化処理層が形成された極薄銅層を有するキャリア付銅箔（１層目）を準備する。
次に、図１－Ｂに示すように、極薄銅層の粗化処理層上にレジストを塗布し、露光・現像を行い、レジストを所定の形状にエッチングする。
次に、図１－Ｃに示すように、回路用のめっきを形成した後、レジストを除去することで、所定の形状の回路めっきを形成する。
次に、図２－Ｄに示すように、回路めっきを覆うように（回路めっきが埋没するように）極薄銅層上に埋め込み樹脂を設けて樹脂層を積層し、続いて別のキャリア付銅箔（２層目）を極薄銅層側から接着させる。
次に、図２－Ｅに示すように、２層目のキャリア付銅箔からキャリアを剥がす。
次に、図２－Ｆに示すように、樹脂層の所定位置にレーザー穴あけを行い、回路めっきを露出させてブラインドビアを形成する。
次に、図３－Ｇに示すように、ブラインドビアに銅を埋め込みビアフィルを形成する。
次に、図３－Ｈに示すように、ビアフィル上に、上記図１－Ｂ及び図１－Ｃのようにして回路めっきを形成する。
次に、図３－Ｉに示すように、１層目のキャリア付銅箔からキャリアを剥がす。
次に、図４－Ｊに示すように、フラッシュエッチングにより両表面の極薄銅層を除去し、樹脂層内の回路めっきの表面を露出させる。
次に、図４－Ｋに示すように、樹脂層内の回路めっき上にバンプを形成し、当該はんだ上に銅ピラーを形成する。このようにして本発明のキャリア付銅箔を用いたプリント配線板を作製する。
なお、上述のプリント配線板の製造方法で、「極薄銅層」をキャリアに、「キャリア」を極薄銅層に読み替えて、キャリア付銅箔のキャリア側の表面に回路を形成して、樹脂で回路を埋め込み、プリント配線板を製造することも可能である。
Here, a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention will be described in detail with reference to the drawings. In addition, here, the case where the primary particle layer and the secondary particle layer are provided as a roughening treatment layer is explained.
First, as shown in FIG. 1-A, a carrier-attached copper foil (first layer) having an ultra-thin copper layer with a roughened layer formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied on the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 1C, after forming circuit plating, the resist is removed to form circuit plating in a predetermined shape.
Next, as shown in Figure 2-D, an embedded resin is provided on the ultra-thin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and the resin layer is laminated, followed by another layer with a carrier. Adhere the copper foil (second layer) from the ultra-thin copper layer side.
Next, as shown in FIG. 2-E, the carrier is peeled off from the second layer of carrier-attached copper foil.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position in the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is buried in the blind via to form a via fill.
Next, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C above.
Next, as shown in FIG. 3-I, the carrier is peeled off from the first layer of carrier-attached copper foil.
Next, as shown in FIG. 4-J, the ultra-thin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating within the resin layer.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating within the resin layer, and copper pillars are formed on the solder. In this way, a printed wiring board using the carrier-attached copper foil of the present invention is produced.
In addition, in the above-mentioned method for manufacturing a printed wiring board, the "ultra-thin copper layer" is replaced with the carrier, and the "carrier" is replaced with the ultra-thin copper layer, and a circuit is formed on the carrier-side surface of the carrier-attached copper foil. It is also possible to manufacture printed wiring boards by embedding circuits in resin.
上記別のキャリア付銅箔（２層目）は、本発明のキャリア付銅箔を用いてもよく、従来のキャリア付銅箔を用いてもよく、さらに通常の銅箔を用いてもよい。また、図３－Ｈに示される２層目の回路上に、さらに回路を１層或いは複数層形成してもよく、それらの回路形成をセミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって行ってもよい。 For the above-mentioned another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, the conventional copper foil with a carrier may be used, or furthermore, a normal copper foil may be used. Moreover, one or more circuit layers may be further formed on the second layer circuit shown in FIG. It may be performed by any additive method.
上述のようなプリント配線板の製造方法によれば、回路めっきが樹脂層に埋め込まれた構成となっているため、例えば図４－Ｊに示すようなフラッシュエッチングによる極薄銅層の除去の際に、回路めっきが樹脂層によって保護され、その形状が保たれ、これにより微細回路の形成が容易となる。また、回路めっきが樹脂層によって保護されるため、耐マイグレーション性が向上し、回路の配線の導通が良好に抑制される。このため、微細回路の形成が容易となる。また、図４－Ｊ及び図４－Ｋに示すようにフラッシュエッチングによって極薄銅層を除去したとき、回路めっきの露出面が樹脂層から凹んだ形状となるため、当該回路めっき上にバンプが、さらにその上に銅ピラーがそれぞれ形成しやすくなり、製造効率が向上する。 According to the method of manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, it is difficult to remove the ultra-thin copper layer by flash etching as shown in Figure 4-J, for example. Second, the circuit plating is protected by the resin layer and its shape is maintained, which facilitates the formation of fine circuits. Moreover, since the circuit plating is protected by the resin layer, migration resistance is improved and conduction of the circuit wiring is suppressed well. Therefore, it becomes easy to form a fine circuit. Furthermore, as shown in Figures 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating becomes recessed from the resin layer, resulting in bumps on the circuit plating. , furthermore, it becomes easier to form copper pillars thereon, improving manufacturing efficiency.
なお、埋め込み樹脂には公知の樹脂、プリプレグを用いることができる。例えば、ＢＴ（ビスマレイミドトリアジン）樹脂やＢＴ樹脂を含浸させたガラス布であるプリプレグ、味の素ファインテクノ株式会社製ＡＢＦフィルムやＡＢＦを用いることができる。また、前記埋め込み樹脂には本明細書に記載の樹脂層および／または樹脂および／またはプリプレグを使用することができる。 Note that a known resin or prepreg can be used as the embedding resin. For example, prepreg, which is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd., or ABF can be used. Moreover, the resin layer and/or resin and/or prepreg described in this specification can be used for the embedding resin.
また、前記一層目に用いられるキャリア付銅箔は、当該キャリア付銅箔の表面に基板または樹脂層を有してもよい。当該基板または樹脂層を有することで一層目に用いられるキャリア付銅箔は支持され、しわが入りにくくなるため、生産性が向上するという利点がある。なお、前記基板または樹脂層には、前記一層目に用いられるキャリア付銅箔を支持する効果するものであれば、全ての基板または樹脂層を用いることが出来る。例えば前記基板または樹脂層として本願明細書に記載のキャリア、プリプレグ、樹脂層や公知のキャリア、プリプレグ、樹脂層、金属板、金属箔、無機化合物の板、無機化合物の箔、有機化合物の板、有機化合物の箔を用いることができる。 Further, the carrier-attached copper foil used for the first layer may have a substrate or a resin layer on the surface of the carrier-attached copper foil. By having the substrate or the resin layer, the carrier-attached copper foil used as the first layer is supported and wrinkles are less likely to occur, which has the advantage of improving productivity. Note that any substrate or resin layer can be used as the substrate or resin layer as long as it has the effect of supporting the carrier-attached copper foil used in the first layer. For example, as the substrate or resin layer, the carrier described in this specification, prepreg, resin layer, known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, Foils of organic compounds can be used.
また、本発明のプリント配線板の製造方法は、本発明のキャリア付銅箔の前記極薄銅層側表面または前記キャリア側表面と樹脂基板とを積層する工程、前記樹脂基板と積層した極薄銅層側表面または前記キャリア側表面とは反対側のキャリア付銅箔の表面に、樹脂層と回路との２層を、少なくとも１回設ける工程、及び、前記樹脂層及び回路の２層を形成した後に、前記キャリア付銅箔から前記キャリアまたは前記極薄銅層を剥離させる工程を含むプリント配線板の製造方法（コアレス工法）であってもよい。当該コアレス工法について、具体的な例としては、まず、本発明のキャリア付銅箔の極薄銅層側表面またはキャリア側表面と樹脂基板とを積層して積層体（銅張積層板、銅張積層体ともいう）を製造する。その後、樹脂基板と積層した極薄銅層側表面または前記キャリア側表面とは反対側のキャリア付銅箔の表面に樹脂層を形成する。キャリア側表面又は極薄銅層側表面に形成した樹脂層には、さらに別のキャリア付銅箔をキャリア側又は極薄銅層側から積層してもよい。また、樹脂基板又は樹脂又はプリプレグを中心として、当該樹脂基板又は樹脂又はプリプレグの両方の表面側に、キャリア／中間層／極薄銅層の順あるいは極薄銅層／中間層／キャリアの順でキャリア付銅箔が積層された構成を有する積層体あるいは「キャリア／中間層／極薄銅層／樹脂基板又は樹脂又はプリプレグ／キャリア／中間層／極薄銅層」の順に積層された構成を有する積層体あるいは「キャリア／中間層／極薄銅層／樹脂基板／キャリア／中間層／極薄銅層」の順に積層された構成を有する積層体あるいは「極薄銅層／中間層／キャリア／樹脂基板／キャリア／中間層／極薄銅層」の順に積層された構成を有する積層体を上述のプリント配線板の製造方法（コアレス工法）に用いてもよい。そして、当該積層体の両端の極薄銅層あるいはキャリアの露出した表面には、別の樹脂層を設け、さらに銅層又は金属層を設けた後、当該銅層又は金属層を加工することで回路を形成してもよい。さらに、別の樹脂層を当該回路上に、当該回路を埋め込むように設けても良い。また、このような回路及び樹脂層の形成を１回以上行ってもよい（ビルドアップ工法）。そして、このようにして形成した積層体（以下、積層体Ｂとも言う）について、それぞれのキャリア付銅箔の極薄銅層またはキャリアをキャリアまたは極薄銅層から剥離させてコアレス基板を作製することができる。なお、前述のコアレス基板の作製には、２つのキャリア付銅箔を用いて、後述する極薄銅層／中間層／キャリア／キャリア／中間層／極薄銅層の構成を有する積層体や、キャリア／中間層／極薄銅層／極薄銅層／中間層／キャリアの構成を有する積層体や、キャリア／中間層／極薄銅層／キャリア／中間層／極薄銅層の構成を有する積層体を作製し、当該積層体を中心に用いることもできる。これら積層体（以下、積層体Ａとも言う）の両側の極薄銅層またはキャリアの表面に樹脂層及び回路の２層を１回以上設け、樹脂層及び回路の２層を１回以上設けた後に、それぞれのキャリア付銅箔の極薄銅層またはキャリアをキャリアまたは極薄銅層から剥離させてコアレス基板を作製することができる。前述の積層体は、極薄銅層の表面、キャリアの表面、キャリアとキャリアとの間、極薄銅層と極薄銅層との間、極薄銅層とキャリアとの間には他の層を有してもよい。他の層は樹脂基板または樹脂層であってもよい。なお、本明細書において「極薄銅層の表面」、「極薄銅層側表面」、「極薄銅層表面」、「キャリアの表面」、「キャリア側表面」、「キャリア表面」、「積層体の表面」、「積層体表面」は、極薄銅層、キャリア、積層体が、極薄銅層表面、キャリア表面、積層体表面に他の層を有する場合には、当該他の層の表面（最表面）を含む概念とする。また、積層体は極薄銅層／中間層／キャリア／キャリア／中間層／極薄銅層の構成を有することが好ましい。当該積層体を用いてコアレス基板を作製した際、コアレス基板側に極薄銅層が配置されるため、モディファイドセミアディティブ法を用いてコアレス基板上に回路を形成しやすくなるためである。また、極薄銅層の厚みは薄いため、当該極薄銅層の除去がしやすく、極薄銅層の除去後にセミアディティブ法を用いて、コアレス基板上に回路を形成しやすくなるためである。
なお、本明細書において、「積層体Ａ」または「積層体Ｂ」と特に記載していない「積層体」は、少なくとも積層体Ａ及び積層体Ｂを含む積層体を示す。
Further, the method for manufacturing a printed wiring board of the present invention includes a step of laminating the ultra-thin copper layer side surface or the carrier-side surface of the carrier-attached copper foil of the present invention and a resin substrate, A step of providing two layers, a resin layer and a circuit, at least once on the copper layer side surface or the surface of the carrier-attached copper foil on the opposite side to the carrier side surface, and forming the two layers of the resin layer and the circuit. The method for manufacturing a printed wiring board (coreless method) may include a step of peeling off the carrier or the ultra-thin copper layer from the carrier-attached copper foil after doing so. As a specific example of the coreless construction method, first, a laminate (copper-clad laminate, copper-clad laminate, copper-clad laminate, copper-clad laminate, (also referred to as a laminate). Thereafter, a resin layer is formed on the surface of the ultra-thin copper layer laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier-side surface. On the resin layer formed on the carrier side surface or the ultra-thin copper layer side surface, another carrier-attached copper foil may be laminated from the carrier side or the ultra-thin copper layer side. In addition, with the resin substrate, resin, or prepreg at the center, a carrier/intermediate layer/ultra-thin copper layer or an ultra-thin copper layer/intermediate layer/carrier may be placed on the surface side of both of the resin substrate, resin, or prepreg. A laminate having a structure in which copper foil with a carrier is laminated or a structure in which "carrier/intermediate layer/ultra-thin copper layer/resin substrate or resin or prepreg/carrier/intermediate layer/ultra-thin copper layer" is laminated in the order A laminate or a laminate having a laminated structure in the order of "carrier/intermediate layer/ultra-thin copper layer/resin substrate/carrier/intermediate layer/ultra-thin copper layer" or "ultra-thin copper layer/intermediate layer/carrier/resin" A laminate having a structure in which "substrate/carrier/intermediate layer/ultra-thin copper layer" is laminated in this order may be used in the above-mentioned printed wiring board manufacturing method (coreless method). Then, after providing another resin layer on the ultra-thin copper layer at both ends of the laminate or the exposed surface of the carrier, and further providing a copper layer or metal layer, the copper layer or metal layer is processed. A circuit may also be formed. Furthermore, another resin layer may be provided on the circuit so as to embed the circuit. Moreover, the formation of such a circuit and resin layer may be performed one or more times (build-up method). Then, for the laminate thus formed (hereinafter also referred to as laminate B), the ultra-thin copper layer or carrier of each carrier-attached copper foil is peeled off from the carrier or the ultra-thin copper layer to produce a coreless board. be able to. In addition, in the production of the above-mentioned coreless board, two copper foils with carriers are used to produce a laminate having a configuration of ultra-thin copper layer/intermediate layer/carrier/carrier/intermediate layer/ultra-thin copper layer, which will be described later. A laminate having the configuration of carrier/intermediate layer/ultra-thin copper layer/ultra-thin copper layer/intermediate layer/carrier, or a laminate having the configuration of carrier/intermediate layer/ultra-thin copper layer/carrier/intermediate layer/ultra-thin copper layer. It is also possible to produce a laminate and use the laminate as the center. Two layers of a resin layer and a circuit were provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as laminate A), and two layers of a resin layer and a circuit were provided at least once. Later, the ultra-thin copper layer or carrier of each carrier-attached copper foil can be peeled off from the carrier or the ultra-thin copper layer to produce a coreless substrate. The above-mentioned laminate has other surfaces on the surface of the ultra-thin copper layer, on the surface of the carrier, between the carriers, between the ultra-thin copper layers, and between the ultra-thin copper layer and the carrier. It may have layers. The other layer may be a resin substrate or a resin layer. In addition, in this specification, "surface of ultra-thin copper layer", "surface on ultra-thin copper layer side", "surface on ultra-thin copper layer", "surface of carrier", "surface on carrier side", "carrier surface", ""Surface of the laminate" and "Surface of the laminate" refer to the ultra-thin copper layer, the carrier, and when the laminate has other layers on the ultra-thin copper layer surface, the carrier surface, and the laminate surface, the other layers. The concept includes the surface (the outermost surface) of Further, it is preferable that the laminate has a configuration of ultra-thin copper layer/intermediate layer/carrier/carrier/intermediate layer/ultra-thin copper layer. This is because when a coreless substrate is produced using the laminate, an ultra-thin copper layer is placed on the coreless substrate side, making it easier to form a circuit on the coreless substrate using a modified semi-additive method. In addition, since the ultra-thin copper layer is thin, it is easy to remove the ultra-thin copper layer, and after removing the ultra-thin copper layer, it is easier to form a circuit on the coreless board using a semi-additive method. .
In addition, in this specification, "laminate", which is not specifically described as "laminate A" or "laminate B", refers to a laminate that includes at least laminate A and laminate B.
なお、上述のコアレス基板の製造方法において、キャリア付銅箔または上述の積層体（積層体Ａを含む）の端面の一部または全部を樹脂で覆うことにより、ビルドアップ工法でプリント配線板を製造する際に、中間層または積層体を構成する１つのキャリア付銅箔ともう１つのキャリア付銅箔の間のへの薬液の染み込みを防止することができ、薬液の染み込みによる極薄銅層とキャリアの分離やキャリア付銅箔の腐食を防止することができ、歩留りを向上させることができる。ここで用いる「キャリア付銅箔の端面の一部または全部を覆う樹脂」または「積層体の端面の一部または全部を覆う樹脂」としては、樹脂層に用いることができる樹脂または公知の樹脂を使用することができる。また、上述のコアレス基板の製造方法において、キャリア付銅箔または積層体において平面視したときにキャリア付銅箔または積層体の積層部分（キャリアと極薄銅層との積層部分、または、１つのキャリア付銅箔ともう１つのキャリア付銅箔との積層部分）の外周の少なくとも一部が樹脂又はプリプレグで覆ってもよい。また、上述のコアレス基板の製造方法で形成する積層体（積層体Ａ）は、一対のキャリア付銅箔を互いに分離可能に接触させて構成されていてもよい。また、当該キャリア付銅箔において平面視したときにキャリア付銅箔または積層体の積層部分（キャリアと極薄銅層との積層部分、または、１つのキャリア付銅箔ともう１つのキャリア付銅箔との積層部分）の外周の全体又は積層部分の全面にわたって樹脂又はプリプレグで覆われてなるものであってもよい。また、平面視した場合に樹脂又はプリプレグはキャリア付銅箔または積層体または積層体の積層部分よりも大きい方が好ましく、当該樹脂又はプリプレグをキャリア付銅箔または積層体の両面に積層し、キャリア付銅箔または積層体が樹脂又はプリプレグにより袋とじ（包まれている）されている構成を有する積層体とすることが好ましい。このような構成とすることにより、キャリア付銅箔または積層体を平面視したときに、キャリア付銅箔または積層体の積層部分が樹脂又はプリプレグにより覆われ、他の部材がこの部分の側方向、すなわち積層方向に対して横からの方向から当たることを防ぐことができるようになり、結果としてハンドリング中のキャリアと極薄銅層またはキャリア付銅箔同士の剥がれを少なくすることができる。また、キャリア付銅箔または積層体の積層部分の外周を露出しないように樹脂又はプリプレグで覆うことにより、前述したような薬液処理工程におけるこの積層部分の界面への薬液の浸入を防ぐことができ、キャリア付銅箔の腐食や侵食を防ぐことができる。なお、積層体の一対のキャリア付銅箔から一つのキャリア付銅箔を分離する際、またはキャリア付銅箔のキャリアと銅箔（極薄銅層）を分離する際には、樹脂又はプリプレグで覆われているキャリア付銅箔又は積層体の積層部分（キャリアと極薄銅層との積層部分、または、１つのキャリア付銅箔ともう１つのキャリア付銅箔との積層部分）が樹脂又はプリプレグ等により強固に密着している場合には、当該積層部分等を切断等により除去する必要が生じる場合がある。 In addition, in the above-mentioned method for manufacturing a coreless board, a printed wiring board is manufactured by a build-up method by covering part or all of the end face of the carrier-attached copper foil or the above-mentioned laminate (including laminate A) with resin. When doing so, it is possible to prevent the chemical liquid from seeping into the space between one carrier-coated copper foil and another carrier-coated copper foil constituting the intermediate layer or laminate, and to prevent the chemical liquid from seeping into the ultra-thin copper layer. Separation of the carrier and corrosion of the carrier-attached copper foil can be prevented, and the yield can be improved. The "resin that covers part or all of the end face of the carrier-attached copper foil" or the "resin that covers part or all of the end face of the laminate" used here is a resin that can be used for the resin layer or a known resin. can be used. In addition, in the method for manufacturing a coreless board described above, when the copper foil with a carrier or the laminate is viewed in plan, the laminated portion of the copper foil with the carrier or the laminate (the laminated portion of the carrier and the ultra-thin copper layer, or the laminated portion of the carrier and the ultra-thin copper layer, or At least a portion of the outer periphery of the laminated portion of the carrier-attached copper foil and another carrier-attached copper foil may be covered with resin or prepreg. Moreover, the laminate (laminated body A) formed by the above-described coreless substrate manufacturing method may be configured by making a pair of carrier-attached copper foils contact each other so as to be separable. In addition, when the copper foil with a carrier is viewed from above, the laminated part of the copper foil with a carrier or the laminate (the laminated part of the carrier and the ultra-thin copper layer, or the copper foil with the carrier and the copper foil with the other carrier) The entire outer periphery of the laminated portion with foil or the entire surface of the laminated portion may be covered with resin or prepreg. In addition, when viewed from above, the resin or prepreg is preferably larger than the copper foil with carrier or the laminate or the laminated part of the laminate. It is preferable to use a laminate having a structure in which the copper foil or the laminate is bound (wrapped) with resin or prepreg. With such a configuration, when the carrier-attached copper foil or the laminate is viewed from above, the laminated part of the carrier-attached copper foil or the laminate is covered with the resin or prepreg, and the other members are covered in the lateral direction of this part. In other words, it is possible to prevent the carrier from being hit from the side in the direction of lamination, and as a result, it is possible to reduce peeling between the carrier and the ultra-thin copper layer or carrier-attached copper foil during handling. In addition, by covering the outer periphery of the carrier-coated copper foil or the laminated portion of the laminate with resin or prepreg so as not to expose it, it is possible to prevent the chemical from entering the interface of the laminated portion in the chemical treatment process as described above. , it is possible to prevent corrosion and erosion of the carrier-coated copper foil. In addition, when separating one copper foil with a carrier from a pair of copper foils with carriers in a laminate, or when separating the carrier and copper foil (ultra-thin copper layer) of copper foils with carriers, use resin or prepreg. The covered copper foil with a carrier or the laminated part of the laminate (the laminated part of a carrier and an ultra-thin copper layer, or the laminated part of one copper foil with a carrier and another copper foil with a carrier) is made of resin or If there is strong adhesion due to prepreg or the like, it may be necessary to remove the laminated portion by cutting or the like.
本発明のキャリア付銅箔をキャリア側又は極薄銅層側から、もう一つの本発明のキャリア付銅箔のキャリア側または極薄銅層側に積層して積層体を構成してもよい。また、前記一つのキャリア付銅箔の前記キャリア側表面又は前記極薄銅層側表面と前記もう一つのキャリア付銅箔の前記キャリア側表面又は前記極薄銅層側表面とが、必要に応じて接着剤を介して、直接積層させて得られた積層体であってもよい。また、前記一つのキャリア付銅箔のキャリア又は極薄銅層と、前記もう一つのキャリア付銅箔のキャリア又は極薄銅層とが接合されていてもよい。ここで、当該「接合」は、キャリア又は極薄銅層が表面処理層を有する場合は、当該表面処理層を介して互いに接合されている態様も含む。また、当該積層体の端面の一部または全部が樹脂により覆われていてもよい。 A laminate may be constructed by laminating the carrier-attached copper foil of the present invention from the carrier side or ultra-thin copper layer side to the carrier-attached copper foil of the present invention on the carrier side or ultra-thin copper layer side. Further, the carrier-side surface or the ultra-thin copper layer-side surface of the one carrier-attached copper foil and the carrier-side surface or the ultra-thin copper layer-side surface of the another carrier-attached copper foil may be adjusted as necessary. It may also be a laminate obtained by directly laminating them with an adhesive between them. Moreover, the carrier or ultra-thin copper layer of the one carrier-attached copper foil and the carrier or ultra-thin copper layer of the another carrier-attached copper foil may be joined. Here, when the carrier or the ultra-thin copper layer has a surface treatment layer, the term "joining" also includes a mode in which they are joined to each other via the surface treatment layer. Further, part or all of the end faces of the laminate may be covered with resin.
キャリア同士、極薄銅層同士、キャリアと極薄銅層、キャリア付銅箔同士の積層は、単に重ね合わせる他、例えば以下の方法で行うことができる。
（ａ）冶金的接合方法：融接（アーク溶接、ＴＩＧ（タングステン・イナート・ガス）溶接、ＭＩＧ（メタル・イナート・ガス）溶接、抵抗溶接、シーム溶接、スポット溶接）、圧接（超音波溶接、摩擦撹拌溶接）、ろう接；
（ｂ）機械的接合方法：かしめ、リベットによる接合（セルフピアッシングリベットによる接合、リベットによる接合）、ステッチャー；
（ｃ）物理的接合方法：接着剤、（両面）粘着テープ
Lamination of carriers, ultra-thin copper layers, carriers and ultra-thin copper layers, and carrier-attached copper foils can be carried out, for example, by the following method, in addition to simply stacking them on each other.
(a) Metallurgical joining methods: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, friction stir welding), brazing;
(b) Mechanical joining methods: caulking, joining by rivets (joining by self-piercing rivets, joining by rivets), stitcher;
(c) Physical joining method: adhesive, (double-sided) adhesive tape
一方のキャリアの一部若しくは全部と他方のキャリアの一部若しくは全部若しくは極薄銅層の一部若しくは全部とを、上記接合方法を用いて接合することにより、一方のキャリアと他方のキャリアまたは極薄銅層を積層し、キャリア同士またはキャリアと極薄銅層を分離可能に接触させて構成される積層体を製造することができる。一方のキャリアと他方のキャリアまたは極薄銅層とが弱く接合されて、一方のキャリアと他方のキャリアまたは極薄銅層とが積層されている場合には、一方のキャリアと他方のキャリアまたは極薄銅層との接合部を除去しないでも、一方のキャリアと他方のキャリアまたは極薄銅層とは分離可能である。また、一方のキャリアと他方のキャリアまたは極薄銅層とが強く接合されている場合には、一方のキャリアと他方のキャリアまたは極薄銅層とが接合されている箇所を切断や化学研磨（エッチング等）、機械研磨等により除去することにより、一方のキャリアと他方のキャリアまたは極薄銅層を分離することができる。 By joining part or all of one carrier to part or all of the other carrier or part or all of the ultra-thin copper layer using the above joining method, one carrier and the other carrier or A laminate can be manufactured by laminating thin copper layers and making the carriers contact each other or the carriers and the ultra-thin copper layers in a separable manner. When one carrier and the other carrier or ultra-thin copper layer are laminated with weak bonding between one carrier and the other carrier or ultra-thin copper layer, one carrier and the other carrier or ultra-thin copper layer are One carrier can be separated from the other carrier or the ultra-thin copper layer without removing the joint with the thin copper layer. In addition, if one carrier and the other carrier or ultra-thin copper layer are strongly bonded, cut or chemically polish the bonded portion of one carrier and the other carrier or ultra-thin copper layer. One carrier and the other carrier or the ultra-thin copper layer can be separated by removing them by etching, etc.), mechanical polishing, etc.
また、このように構成した積層体に樹脂層と回路との２層を、少なくとも１回設ける工程、及び、前記樹脂層及び回路の２層を少なくとも１回形成した後に、前記積層体のキャリア付銅箔から前記極薄銅層又はキャリアを剥離させる工程を実施することでコアを有さないプリント配線板を作製することができる。なお、当該積層体の一方または両方の表面に、樹脂層と回路との２層を設けてもよい。
前述した積層体に用いる樹脂基板、樹脂層、樹脂、プリプレグは、本明細書に記載した樹脂層であってもよく、本明細書に記載した樹脂層に用いる樹脂、樹脂硬化剤、化合物、硬化促進剤、誘電体、反応触媒、架橋剤、ポリマー、プリプレグ、骨格材等を含んでもよい。なお、前述のキャリア付銅箔または積層体は平面視したときに樹脂又はプリプレグ又は樹脂基板又は樹脂層よりも小さくてもよい。
Further, the step of providing two layers of a resin layer and a circuit at least once on the laminate configured in this way, and after forming the two layers of the resin layer and the circuit at least once, attaching a carrier to the laminate. A printed wiring board without a core can be produced by carrying out the step of peeling off the ultra-thin copper layer or carrier from the copper foil. Note that two layers, a resin layer and a circuit, may be provided on one or both surfaces of the laminate.
The resin substrate, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification It may also contain accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, and the like. Note that the carrier-attached copper foil or laminate described above may be smaller than the resin, prepreg, resin substrate, or resin layer when viewed in plan.
また、樹脂基板はプリント配線板等に適用可能な特性を有するものであれば特に制限を受けないが、例えば、リジッドＰＷＢ用に紙基材フェノール樹脂、紙基材エポキシ樹脂、合成繊維布基材エポキシ樹脂、ガラス布・紙複合基材エポキシ樹脂、ガラス布・ガラス不織布複合基材エポキシ樹脂及びガラス布基材エポキシ樹脂等を使用し、ＦＰＣ用にポリエステルフィルムやポリイミドフィルム、ＬＣＰ（液晶ポリマー）フィルム、フッ素樹脂等を使用する事ができる。なお、ＬＣＰ（液晶ポリマー）フィルムやフッ素樹脂フィルムを用いた場合、ポリイミドフィルムを用いた場合よりも、当該フィルムと表面処理銅箔とのピール強度が小さくなる傾向にある。よって、ＬＣＰ（液晶ポリマー）フィルムやフッ素樹脂フィルムを用いた場合には、銅回路を形成後、銅回路をカバーレイで覆うことによって、当該フィルムと銅回路とが剥がれにくくし、ピール強度の低下による当該フィルムと銅回路との剥離を防止することができる。 In addition, the resin substrate is not particularly limited as long as it has characteristics applicable to printed wiring boards, etc., but for example, for rigid PWB, paper-based phenol resin, paper-based epoxy resin, synthetic fiber cloth base Epoxy resin, glass cloth/paper composite base epoxy resin, glass cloth/glass nonwoven composite base epoxy resin, glass cloth base epoxy resin, etc. are used for FPC, such as polyester film, polyimide film, LCP (liquid crystal polymer) film. , fluororesin, etc. can be used. Note that when an LCP (liquid crystal polymer) film or a fluororesin film is used, the peel strength between the film and the surface-treated copper foil tends to be smaller than when a polyimide film is used. Therefore, when using an LCP (liquid crystal polymer) film or a fluororesin film, covering the copper circuit with a coverlay after forming the copper circuit makes it difficult for the film and the copper circuit to peel off, reducing peel strength. It is possible to prevent the film from peeling off from the copper circuit due to
以下、実施例及び比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例のみに制限されるものではない。すなわち、本発明に含まれる他の態様または変形を包含するものである。
実施例１～２、４～６、９～１６及び比較例１～２、４、６～７の原箔には、厚さ１２μｍの標準圧延銅箔ＴＰＣ（ＪＩＳ Ｈ３１００ Ｃ１１００に規格されているタフピッチ銅、ＪＸ金属製、表面の十点平均粗さＲｚ＝０．７μｍ）を使用した。実施例３、８及び比較例３、５の原箔には、厚さ１２μｍの電解銅箔（ＪＸ金属製 ＨＬＰ箔、析出面（Ｍ面）の表面の十点平均粗さＲｚ＝０．７μｍ）を使用し、析出面（Ｍ面）に表面処理層を設けた。
また、実施例７及び比較例８の原箔には以下の方法により製造したキャリア付銅箔を用いた。
実施例７は、厚さ１８μｍの電解銅箔（ＪＸ金属製 ＪＴＣ箔）をキャリアとして準備し、比較例８については上述の厚さ１８μｍの標準圧延銅箔ＴＰＣをキャリアとして準備した。そして下記条件で、キャリアの表面に中間層を形成し、中間層の表面に極薄銅層を形成した。なお、キャリアが電解銅箔の場合には光沢面（Ｓ面）に中間層を形成した。
The following will explain based on Examples and Comparative Examples. Note that this embodiment is just an example, and the present invention is not limited to this example. That is, other aspects or modifications included in the present invention are included.
The raw foils of Examples 1-2, 4-6, 9-16 and Comparative Examples 1-2, 4, 6-7 were made of standard rolled copper foil TPC with a thickness of 12 μm (tough pitch specified in JIS H3100 C1100). Copper, made by JX Metals, and surface roughness Rz = 0.7 μm) was used. The raw foils of Examples 3 and 8 and Comparative Examples 3 and 5 were electrolytic copper foils with a thickness of 12 μm (HLP foil manufactured by JX Metals, with a ten-point average roughness of the surface of the deposition surface (M side) Rz = 0.7 μm. ), and a surface treatment layer was provided on the precipitation surface (M-plane).
Moreover, carrier-attached copper foil manufactured by the following method was used as the raw foil in Example 7 and Comparative Example 8.
In Example 7, an electrolytic copper foil (JTC foil manufactured by JX Metals) with a thickness of 18 μm was prepared as a carrier, and in Comparative Example 8, the above-mentioned standard rolled copper foil TPC with a thickness of 18 μm was prepared as a carrier. Then, under the following conditions, an intermediate layer was formed on the surface of the carrier, and an extremely thin copper layer was formed on the surface of the intermediate layer. In addition, when the carrier was an electrolytic copper foil, an intermediate layer was formed on the glossy surface (S surface).
・実施例７、比較例８
＜中間層＞
（１）Ｎｉ層（Ｎｉメッキ）
キャリアに対して、以下の条件でロール・トウ・ロール型の連続メッキラインで電気メッキすることにより１０００μｇ／ｄｍ2の付着量のＮｉ層を形成した。具体的なメッキ条件を以下に記す。
硫酸ニッケル：２７０～２８０ｇ／Ｌ
塩化ニッケル：３５～４５ｇ／Ｌ
酢酸ニッケル：１０～２０ｇ／Ｌ
ホウ酸：３０～４０ｇ／Ｌ
光沢剤：サッカリン、ブチンジオール等
ドデシル硫酸ナトリウム：５５～７５ｐｐｍ
ｐＨ：４～６
液温：５５～６５℃
電流密度：１０Ａ／ｄｍ2
（２）Ｃｒ層（電解クロメート処理）
次に、（１）にて形成したＮｉ層表面を水洗及び酸洗後、引き続き、ロール・トウ・ロール型の連続メッキライン上でＮｉ層の上に１１μｇ／ｄｍ2の付着量のＣｒ層を以下の条件で電解クロメート処理することにより付着させた。
重クロム酸カリウム１～１０ｇ／Ｌ、亜鉛０ｇ／Ｌ
ｐＨ：７～１０
液温：４０～６０℃
電流密度：２Ａ／ｄｍ2
＜極薄銅層＞
次に、（２）にて形成したＣｒ層表面を水洗及び酸洗後、引き続き、ロール・トウ・ロール型の連続メッキライン上で、Ｃｒ層の上に厚み１．５μｍの極薄銅層を以下の条件で電気メッキすることにより形成し、キャリア付銅箔を作製した。
銅濃度：９０～１１０ｇ／Ｌ
硫酸濃度：９０～１１０ｇ／Ｌ
塩化物イオン濃度：５０～９０ｐｐｍ
レベリング剤１（ビス（３スルホプロピル）ジスルフィド）：１０～３０ｐｐｍ
レベリング剤２（アミン化合物）：１０～３０ｐｐｍ
なお、レベリング剤２として下記のアミン化合物を用いた。
電解液温度：５０～８０℃
電流密度：１００Ａ／ｄｍ2
電解液線速：１．５～５ｍ／ｓｅｃ
・Example 7, Comparative Example 8
<Middle layer>
(1) Ni layer (Ni plating)
A Ni layer with a deposition amount of 1000 μg/dm 2 was formed on the carrier by electroplating on a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280g/L
Nickel chloride: 35-45g/L
Nickel acetate: 10-20g/L
Boric acid: 30-40g/L
Brighteners: saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75ppm
pH: 4-6
Liquid temperature: 55-65℃
Current density: 10A/dm 2
(2) Cr layer (electrolytic chromate treatment)
Next, after washing the surface of the Ni layer formed in (1) with water and pickling, a Cr layer with a coating weight of 11 μg/dm 2 was applied on the Ni layer on a roll-to-roll continuous plating line. It was attached by electrolytic chromate treatment under the following conditions.
Potassium dichromate 1-10g/L, zinc 0g/L
pH: 7-10
Liquid temperature: 40-60℃
Current density: 2A/dm 2
<Ultra-thin copper layer>
Next, after washing the surface of the Cr layer formed in (2) with water and pickling, an ultra-thin copper layer with a thickness of 1.5 μm was applied on the Cr layer on a roll-to-roll continuous plating line. A copper foil with a carrier was produced by electroplating under the following conditions.
Copper concentration: 90-110g/L
Sulfuric acid concentration: 90-110g/L
Chloride ion concentration: 50-90ppm
Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
Note that the following amine compound was used as the leveling agent 2.
Electrolyte temperature: 50-80℃
Current density: 100A/dm 2
Electrolyte linear velocity: 1.5-5m/sec
続いて、圧延銅箔、電解銅箔またはキャリア付銅箔の極薄銅層表面に、表１～３に示す条件範囲で一次粒子層または、一次粒子層及び二次粒子層を形成した。表１の一次粒子電流条件欄に電流条件、クーロン量が２つ記載されている例は、左に記載されている条件でメッキを行った後に、右に記載されている条件で更にメッキを行ったことを意味する。例えば、実施例１の一次粒子電流条件欄には「（５０Ａ／ｄｍ2、６５Ａｓ／ｄｍ2）＋（８Ａ／ｄｍ2、１６Ａｓ／ｄｍ2）」と記載されているが、これは一次粒子を形成する電流密度を５０Ａ／ｄｍ2、クーロン量を６５Ａｓ／ｄｍ2でメッキを行った後に、更に一次粒子を形成する電流密度を８Ａ／ｄｍ2、クーロン量を１６Ａｓ／ｄｍ2としてメッキを行ったことを示す。 Subsequently, a primary particle layer or a primary particle layer and a secondary particle layer were formed on the surface of the ultrathin copper layer of the rolled copper foil, electrolytic copper foil, or carrier-attached copper foil under the conditions shown in Tables 1 to 3. In the example where two current conditions and coulomb amounts are listed in the primary particle current condition column of Table 1, plating is performed under the conditions listed on the left, and then further plating is performed under the conditions listed on the right. It means something. For example, in the primary particle current condition column of Example 1, "(50A/dm 2 , 65As/dm 2 )+(8A/dm 2 , 16As/dm 2 )" is written, but this does not mean that the primary particle After plating was performed at a current density of 50 A/dm 2 and a coulomb amount of 65 As/dm 2 , plating was further performed with a current density of 8 A/dm 2 and a coulomb amount of 16 As/dm 2 to form primary particles. Show that.
続いて、一次粒子層の上に、または二次粒子層が形成されているものは二次粒子層の上に、表１、４に示す条件範囲でかぶせめっきを形成した。なお、かぶせめっきの欄に複数の処理を行ったことが記載されている場合には、左側の処理から順に行ったことを意味する。例えば、実施例２において表１に「かぶせめっき条件（表４のかぶせめっき液）」の欄に「（２）Ｎｉ―Ｍｏ＋（１）Ｚｎ―Ｃｒ」と記載されており、「かぶせめっき通電時間（秒）」の欄に「（２）０．１７,（１）１．０」と記載されている。これは実施例２において、かぶせめっきを表４の（２）Ｎｉ－Ｍｏめっき、（１）Ｚｎ－Ｃｒめっきの順に行い、その通電時間をそれぞれ、（２）Ｎｉ－Ｍｏめっきは０．１７秒、（１）Ｚｎ－Ｃｒめっきは１．０秒としたことを意味する。 Subsequently, cover plating was formed on the primary particle layer or, if a secondary particle layer was formed, on the secondary particle layer under the conditions shown in Tables 1 and 4. In addition, when it is written in the column of cover plating that a plurality of treatments were performed, it means that the treatments were performed in order from the left side. For example, in Example 2, "(2) Ni-Mo+(1) Zn-Cr" is written in the column of "Overlap plating conditions (Overlap plating solution in Table 4)" in Table 1, and "Overlap plating energization time (Seconds)" column states "(2) 0.17, (1) 1.0". This is because in Example 2, cover plating was performed in the order of (2) Ni-Mo plating and (1) Zn-Cr plating in Table 4, and the energization time was 0.17 seconds for (2) Ni-Mo plating, respectively. , (1) Zn--Cr plating means that the time was 1.0 seconds.
＜一次粒子層及び二次粒子層及びかぶせめっき以外の表面処理層＞
かぶせめっき形成後、実施例３、５、比較例６については以下の電解クロメート処理を行った。それ以外の実施例、比較例については以下の電解クロメート処理を行わなかった。
・電解クロメート処理
液組成：重クロム酸カリウム１～１ｇ／Ｌ
液温：４０～６０℃
ｐＨ：０．５～１０
電流密度：０．０１～２．６Ａ／ｄｍ2
通電時間：０．０５～３０秒
その後、実施例３～５、１０について以下のジアミノシランを用いたシランカップリング処理を行った。
・シランカップリング処理
シランカップリング剤：Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン
シランカップリング剤濃度：０．５～１．５ｖｏｌ％
処理温度：２０～７０℃
処理時間：０．５～５秒
<Primary particle layer, secondary particle layer, and surface treatment layer other than cover plating>
After the cover plating was formed, Examples 3 and 5 and Comparative Example 6 were subjected to the following electrolytic chromate treatment. For other Examples and Comparative Examples, the following electrolytic chromate treatment was not performed.
・Electrolytic chromate treatment Liquid composition: Potassium dichromate 1 to 1 g/L
Liquid temperature: 40-60℃
pH: 0.5-10
Current density: 0.01-2.6A/dm 2
Current application time: 0.05 to 30 seconds Thereafter, Examples 3 to 5 and 10 were subjected to silane coupling treatment using the following diaminosilane.
・Silane coupling treatment Silane coupling agent: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane Silane coupling agent concentration: 0.5 to 1.5 vol%
Processing temperature: 20-70℃
Processing time: 0.5-5 seconds
（十点平均粗さＲｚの測定）
粗化処理層側表面の表面粗さＲｚ（十点平均粗さ）をＪＩＳ Ｂ０６０１－１９８２に準拠して株式会社小阪研究所製接触粗さ計Ｓｕｒｆｃｏｒｄｅｒ ＳＥ－３Ｃ触針式粗度計を用いて測定した。Ｒｚを任意に１０箇所測定し、そのＲｚの１０箇所の平均値をＲｚの値とした。
(Measurement of ten-point average roughness Rz)
The surface roughness Rz (ten-point average roughness) of the surface of the roughening treatment layer was measured using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory Co., Ltd. in accordance with JIS B0601-1982. It was measured. Rz was arbitrarily measured at 10 locations, and the average value of the 10 locations was taken as the Rz value.
（伝送損失の測定）
各サンプルについて、液晶ポリマー樹脂基板（株式会社クラレ製Ｖｅｃｓｔａｒ ＣＴＺ－厚み５０μｍ、ヒドロキシ安息香酸（エステル）とヒドロキシナフトエ酸（エステル）との共重合体である樹脂）と貼り合わせた後、エッチングで特性インピーダンスが５０Ωのとなるようマイクロストリップ線路を形成し、ＨＰ社製のネットワークアナライザーＮ５２４７Ａを用いて透過係数を測定し、周波数２０ＧＨｚでの伝送損失を求めた。周波数２０ＧＨｚにおける伝送損失の評価として、４．０ｄＢ／１０ｃｍ以下を○、４．１ｄＢ／１０ｃｍ以上を×とした。
(Measurement of transmission loss)
Each sample was bonded to a liquid crystal polymer resin substrate (Vecstar CTZ manufactured by Kuraray Co., Ltd. - thickness 50 μm, a resin that is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)), and then etched to determine its characteristics. A microstrip line was formed so that the impedance was 50Ω, and the transmission coefficient was measured using a network analyzer N5247A manufactured by HP, to determine the transmission loss at a frequency of 20 GHz. As an evaluation of transmission loss at a frequency of 20 GHz, 4.0 dB/10 cm or less was rated as ○, and 4.1 dB/10 cm or more was rated as ×.
（ピール強度の測定）
銅箔の表面処理面と表２に記載の樹脂基板を熱プレスにて張り合わせて銅張積層板を作製し、一般的な塩化銅回路エッチング液を使用して１０ｍｍ幅の回路を作製し、銅箔を基板から剥いて、９０°方向に引っ張りながら初期ピール強度を測定した。また、作製した回路を１８０℃の大気下オーブンに投入し、１０日後に取り出し、常態ピールと同様に９０°方向に引っ張りながら、加熱後のピール強度を測定した。ピール強度の評価は、初期ピール強度が０．５ｋｇ／ｃｍ以上であり、加熱後ピール強度が０．３ｋｇ／ｃｍ以上である場合を○、初期ピール強度が０．５ｋｇ／ｃｍ未満もしくは加熱後ピール強度が０．３ｋｇ／ｃｍ未満である場合を×とした。
また、表２に記載の積層樹脂について、「ＬＣＰ」は液晶ポリマーであり、「低誘電ＰＩ」は低誘電ポリイミドであり、「ＰＴＦＥ」はポリテトラフルオロエチレンである。
液晶ポリマーにはヒドロキシ安息香酸（エステル）とヒドロキシナフトエ酸（エステル）との共重合体である液晶ポリマー樹脂であるクラレ社製ｖｅｃｓｔｏｒ ＣＴ－Ｚを用いた。
低誘電ポリイミドには、誘電正接の値が０．００２であるポリイミドを用いた。なお本明細書では誘電正接の値が０．０１以下であるポリイミドを、低誘電ポリイミドとする。誘電正接は、一般社団法人 日本電子回路工業会の「プリント配線板用銅張積層板試験方法 比誘電率及び誘電正接」ＪＰＣＡ－ＴＭ００１－２００７に記載されているトリプレート共振器法により測定可能である。
なお、前述の銅箔と樹脂基板の熱プレス条件は以下の通りとした。
液晶ポリマーを樹脂基板とした場合：圧力３．５ＭＰａ、加熱温度３００℃、加熱時間１０分間
低誘電ポリイミドを樹脂基板とした場合：圧力４ＭＰａ、加熱温度３６０℃、加熱時間５分間
ポリテトラフルオロエチレンを樹脂基板とした場合：圧力５ＭＰａ、加熱温度３５０℃、加熱時間３０分間
前述の樹脂基材の厚みは５０μｍである。
上記製造条件及び評価結果を表１～４に示す。
(Measurement of peel strength)
A copper-clad laminate was produced by pasting the surface-treated surface of the copper foil and the resin substrate listed in Table 2 using a hot press, and a 10 mm wide circuit was produced using a common copper chloride circuit etching solution. The foil was peeled off from the substrate and the initial peel strength was measured while being pulled in a 90° direction. Further, the manufactured circuit was placed in an oven at 180° C. in the atmosphere, taken out after 10 days, and the peel strength after heating was measured while being pulled in a 90° direction in the same manner as normal peeling. The evaluation of peel strength is: ○ if the initial peel strength is 0.5 kg/cm or more and the peel strength after heating is 0.3 kg/cm or more, and ○ if the initial peel strength is less than 0.5 kg/cm or peel after heating. A case where the strength was less than 0.3 kg/cm was rated as x.
Regarding the laminated resins listed in Table 2, "LCP" is a liquid crystal polymer, "low dielectric PI" is low dielectric polyimide, and "PTFE" is polytetrafluoroethylene.
As the liquid crystal polymer, VECSTOR CT-Z manufactured by Kuraray Co., Ltd., which is a liquid crystal polymer resin which is a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester), was used.
As the low dielectric polyimide, polyimide having a dielectric loss tangent value of 0.002 was used. Note that in this specification, polyimide having a dielectric loss tangent value of 0.01 or less is referred to as low dielectric polyimide. The dielectric loss tangent can be measured by the triplate resonator method described in "Testing method for copper-clad laminates for printed wiring boards, relative dielectric constant and dielectric loss tangent" JPCA-TM001-2007 of the Japan Electronics Circuits Association. be.
Note that the hot pressing conditions for the copper foil and resin substrate described above were as follows.
When using liquid crystal polymer as a resin substrate: Pressure 3.5 MPa, heating temperature 300°C, heating time 10 minutes When using low dielectric polyimide as a resin substrate: Pressure 4 MPa, heating temperature 360°C, heating time 5 minutes Polytetrafluoroethylene When using a resin substrate: Pressure: 5 MPa, heating temperature: 350° C., heating time: 30 minutes. The thickness of the aforementioned resin substrate is 50 μm.
The above manufacturing conditions and evaluation results are shown in Tables 1 to 4.
（評価結果）
実施例１～１６は、いずれも電送損失が良好に抑制されており、ピール強度も良好であった。
比較例１、６は、表面処理層におけるＺｎの付着量が１５０μｇ／ｄｍ2未満であり、さらに表面処理層におけるＺｎ及びＭｏの合計付着量が２００μｇ／ｄｍ2未満であり、ピール強度が不良であった。
比較例２は、表面処理層におけるＣｏの付着量が３０００μｇ／ｄｍ2超であったため伝送損失が不良であった。
比較例３、８は、表面処理層の最表面の十点平均粗さＲｚが１．５μｍ超であったため、伝送損失が不良であった。
比較例４は、一次粒子層及び二次粒子層を形成しておらず、ピール強度が不良であった。
比較例５は、表面処理層におけるＺｎの付着量が１５０μｇ／ｄｍ2未満であり、またＺｎ及びＭｏの合計付着量が２００μｇ／ｄｍ2未満であり、さらに表面処理層の最表面の十点平均粗さＲｚが１．５μｍ超であったため、電送損失及びピール強度が不良であった。
比較例７は、表面処理層にＮｉを含んでいるが、当該Ｎｉの付着量が８００μｇ／ｄｍ2を超えたため、伝送損失が不良であった。
(Evaluation results)
In Examples 1 to 16, transmission loss was well suppressed and peel strength was also good.
In Comparative Examples 1 and 6, the amount of Zn deposited in the surface treatment layer was less than 150 μg/dm 2 , and the total amount of Zn and Mo deposited in the surface treatment layer was less than 200 μg/dm 2 , and the peel strength was poor. there were.
In Comparative Example 2, the amount of Co adhered to the surface treatment layer was more than 3000 μg/dm 2 , so the transmission loss was poor.
In Comparative Examples 3 and 8, the ten-point average roughness Rz of the outermost surface of the surface treatment layer was more than 1.5 μm, so the transmission loss was poor.
Comparative Example 4 did not form a primary particle layer and a secondary particle layer, and had poor peel strength.
In Comparative Example 5, the amount of Zn deposited on the surface treatment layer was less than 150 μg/dm 2 , the total amount of Zn and Mo deposited was less than 200 μg/dm 2 , and the ten-point average of the outermost surface of the surface treatment layer Since the roughness Rz was more than 1.5 μm, the transmission loss and peel strength were poor.
In Comparative Example 7, the surface treatment layer contained Ni, but the amount of Ni deposited exceeded 800 μg/dm 2 , resulting in poor transmission loss.
Claims (31)
前記表面処理層は一次粒子層と二次粒子層とを有し、
前記一次粒子層は粗化粒子を含み、
前記二次粒子層は粗化粒子を含み、
前記表面処理層におけるＺｎの付着量が１５０μｇ／ｄｍ2以上であり、
前記表面処理層は、Ｎｉの付着量が２０μｇ／ｄｍ2以上８００μｇ／ｄｍ2以下であり、
前記表面処理層は、Ｃｏの付着量が２８４μｇ／ｄｍ2以上３０００μｇ／ｄｍ2以下であり、
さらに、以下の（１）及び（２）のうちの一方又は両方を満たし、
（１）前記表面処理層は、Ｎｉの付着量が４００μｇ／ｄｍ2以下であり、
（２）前記表面処理層は、Ｃｏの付着量が１５００μｇ／ｄｍ2以下であり、
前記表面処理層の最表面の十点平均粗さＲｚが１．５μｍ以下である表面処理銅箔。 A surface-treated copper foil having a surface treatment layer on at least one surface of the copper foil ,
The surface treatment layer has a primary particle layer and a secondary particle layer,
The primary particle layer includes roughening particles,
The secondary particle layer includes roughening particles,
The amount of Zn deposited in the surface treatment layer is 150 μg/dm 2 or more,
The surface treatment layer has a Ni adhesion amount of 20 μg/dm 2 or more and 800 μg/dm 2 or less,
The surface treatment layer has a Co adhesion amount of 284 μg/dm 2 or more and 3000 μg/dm 2 or less,
Furthermore, one or both of the following (1) and (2) are satisfied,
(1) The surface treatment layer has a Ni adhesion amount of 400 μg/dm 2 or less,
(2) The surface treatment layer has a Co adhesion amount of 1500 μg/dm 2 or less,
A surface-treated copper foil in which the outermost surface of the surface-treated layer has a ten-point average roughness Rz of 1.5 μm or less.
前記表面処理層におけるＣｏ及びＮｉの合計付着量が３５００μｇ／ｄｍ2以下である請求項１～８のいずれか一項に記載の表面処理銅箔。 The surface treatment layer contains Co and Ni,
The surface-treated copper foil according to any one of claims 1 to 8, wherein the total amount of Co and Ni deposited in the surface-treated layer is 3500 μg/dm 2 or less.
前記樹脂および前記積層の条件は以下の（１）～（３）のいずれか一つまたは二つまたは三つである、
請求項１～１０のいずれか一項に記載の表面処理銅箔。
（１）樹脂：ヒドロキシ安息香酸とヒドロキシナフトエ酸との共重合体である液晶ポリマー樹脂、厚み５０μｍ
積層の条件：圧力３．５ＭＰａ、加熱温度３００℃、加熱時間１０分間
（２）樹脂：低誘電ポリイミド樹脂、厚み５０μｍ
積層の条件：圧力４ＭＰａ、加熱温度３６０℃、加熱時間５分間
（３）樹脂：ポリテトラフルオロエチレン、厚み５０μｍ
積層の条件：圧力５ＭＰａ、加熱温度３５０℃、加熱時間３０分間 After laminating the surface-treated copper foil with a resin from the surface-treated layer side and etching the surface-treated copper foil to create a circuit with a width of 10 mm, peeling is performed when the circuit is peeled from the resin in a 90° direction. The strength is 0.5 kg/cm or more,
The conditions for the resin and the lamination are any one, two or three of the following (1) to (3):
The surface-treated copper foil according to any one of claims 1 to 10.
(1) Resin: Liquid crystal polymer resin that is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 μm
Lamination conditions: pressure 3.5 MPa, heating temperature 300°C, heating time 10 minutes (2) Resin: low dielectric polyimide resin, thickness 50 μm
Lamination conditions: pressure 4 MPa, heating temperature 360°C, heating time 5 minutes (3) Resin: polytetrafluoroethylene, thickness 50 μm
Lamination conditions: pressure 5 MPa, heating temperature 350°C, heating time 30 minutes
前記樹脂および前記積層の条件は以下の（１）～（３）のいずれか一つまたは二つまたは三つである、
請求項１～１２のいずれか一項に記載の表面処理銅箔。
（１）樹脂：ヒドロキシ安息香酸とヒドロキシナフトエ酸との共重合体である液晶ポリマー樹脂、厚み５０μｍ
積層の条件：圧力３．５ＭＰａ、加熱温度３００℃、加熱時間１０分間
（２）樹脂：低誘電ポリイミド樹脂、厚み５０μｍ
積層の条件：圧力４ＭＰａ、加熱温度３６０℃、加熱時間５分間
（３）樹脂：ポリテトラフルオロエチレン、厚み５０μｍ
積層の条件：圧力５ＭＰａ、加熱温度３５０℃、加熱時間３０分間 The surface-treated copper foil is laminated with a resin from the surface-treated layer side, the surface-treated copper foil is etched to create a 10 mm wide circuit, and after heating the circuit at 180° C. for 10 days in the atmosphere, the resin The peel strength when peeling the circuit in a 90° direction is 0.4 kg/cm or more,
The conditions for the resin and the lamination are any one, two or three of the following (1) to (3):
The surface-treated copper foil according to any one of claims 1 to 12.
(1) Resin: Liquid crystal polymer resin that is a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid, thickness 50 μm
Lamination conditions: pressure 3.5 MPa, heating temperature 300°C, heating time 10 minutes (2) Resin: low dielectric polyimide resin, thickness 50 μm
Lamination conditions: pressure 4 MPa, heating temperature 360°C, heating time 5 minutes (3) Resin: polytetrafluoroethylene, thickness 50 μm
Lamination conditions: pressure 5 MPa, heating temperature 350°C, heating time 30 minutes
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層、及び、
（Ｂ）クロメート処理層
のいずれか一方、又は、両方を有する請求項１～１４のいずれか一項に記載の表面処理銅箔。 The surface treatment layer is on the primary particle layer or the secondary particle layer,
(A) an alloy layer made of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and
(B) The surface-treated copper foil according to any one of claims 1 to 14, which has one or both of the chromate-treated layers.
以下の（Ａ）又は（Ｂ）の少なくとも一方、および（Ｃ）を有する請求項１～１４のいずれか一項に記載の表面処理銅箔。
（Ａ）Ｎｉと、Ｆｅ、Ｃｒ、Ｍｏ、Ｚｎ、Ｔａ、Ｃｕ、Ａｌ、Ｐ、Ｗ、Ｍｎ、Ｓｎ、ＡｓおよびＴｉからなる群から選択された一種以上の元素とからなる合金層
（Ｂ）クロメート処理層
（Ｃ）シランカップリング処理層 The surface treatment layer is on the primary particle layer or the secondary particle layer,
The surface-treated copper foil according to any one of claims 1 to 14, comprising at least one of the following (A) or (B), and (C).
(A) An alloy layer consisting of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti (B) Chromate treatment layer (C) Silane coupling treatment layer
Ｎｉ－Ｚｎ合金層またはクロメート処理層の少なくとも一方を有する請求項１～１４のいずれか一項に記載の表面処理銅箔。 The surface treatment layer is on the primary particle layer or the secondary particle layer,
The surface-treated copper foil according to any one of claims 1 to 14, comprising at least one of a Ni-Zn alloy layer and a chromate treatment layer.
Ｎｉ－Ｚｎ合金層またはクロメート処理層の少なくとも一方、およびシランカップリング処理層と、を有する請求項１～１４のいずれか一項に記載の表面処理銅箔。 The surface treatment layer is on the primary particle layer or the secondary particle layer,
The surface-treated copper foil according to any one of claims 1 to 14, comprising at least one of a Ni-Zn alloy layer or a chromate treatment layer, and a silane coupling treatment layer.
前記キャリア付銅箔の端面の一部または全部が前記樹脂により覆われた積層体。 Including the carrier-attached copper foil and resin according to claim 21,
A laminate in which a part or all of an end surface of the carrier-attached copper foil is covered with the resin.
以下の（１）～（３）のいずれか一つを含む銅張積層板を形成する工程、
（１）前記表面処理銅箔と前記絶縁基板とを積層する工程、
（２）前記樹脂層付表面処理銅箔と前記絶縁基板とを積層する工程、
（３）前記キャリア付銅箔と前記絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
及び、
セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、前記銅張積層板を使用して回路を形成する工程
を含むプリント配線板の製造方法。 Prepare the surface-treated copper foil according to any one of claims 1 to 19, the surface-treated copper foil with a resin layer according to claim 20, or the copper foil with a carrier according to claim 21, and an insulating substrate. process,
A step of forming a copper-clad laminate including any one of the following (1) to (3),
(1) a step of laminating the surface-treated copper foil and the insulating substrate;
(2) a step of laminating the surface-treated copper foil with a resin layer and the insulating substrate;
(3) a step of peeling off the carrier of the carrier-attached copper foil after laminating the carrier-attached copper foil and the insulating substrate;
as well as,
A method for manufacturing a printed wiring board, comprising the step of forming a circuit using the copper-clad laminate by any one of a semi-additive method, a subtractive method, a part-additive method, or a modified semi-additive method.
前記回路が埋没するように前記表面処理銅箔の前記表面処理層側表面、または、前記キャリア付銅箔の前記極薄銅層側表面もしくは前記キャリア側表面に樹脂層を形成する工程、及び、
前記樹脂層を形成した後に前記表面処理銅箔を除去することで、または、前記キャリアもしくは前記極薄銅層を剥離させた後に前記極薄銅層もしくは前記キャリアを除去することで、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法。 The step of forming a circuit on the surface-treated layer side surface of the surface-treated copper foil according to any one of claims 1 to 19, or the ultra-thin copper layer side of the carrier-attached copper foil according to claim 21. forming a circuit on the surface or the carrier side surface;
forming a resin layer on the surface-treated layer-side surface of the surface-treated copper foil, or the ultra-thin copper layer-side surface or the carrier-side surface of the carrier-attached copper foil so that the circuit is buried;
The resin layer can be formed by removing the surface-treated copper foil after forming the resin layer, or by removing the ultra-thin copper layer or the carrier after peeling off the carrier or the ultra-thin copper layer. A method for manufacturing a printed wiring board, which includes a process of exposing circuits buried in the board.
前記キャリア付銅箔の樹脂基板と積層した側とは反対側表面に、樹脂層と回路とを設ける工程、及び、
前記樹脂層及び前記回路を形成した後に、前記キャリア付銅箔から前記キャリアまたは前記極薄銅層を剥離させる工程
を含むプリント配線板の製造方法。 a step of laminating the carrier-side surface or the ultra-thin copper layer-side surface of the carrier-attached copper foil according to claim 21 and a resin substrate;
a step of providing a resin layer and a circuit on the surface of the carrier-attached copper foil opposite to the side laminated with the resin substrate, and
A method for manufacturing a printed wiring board, comprising: after forming the resin layer and the circuit, peeling the carrier or the ultra-thin copper layer from the carrier-attached copper foil.
前記樹脂層及び前記回路を形成した後に、前記積層体を構成しているキャリア付銅箔から前記キャリアまたは前記極薄銅層を剥離させる工程
を含むプリント配線板の製造方法。 Providing a resin layer and a circuit on the laminate according to any one of claims 23 to 25, and
A method for manufacturing a printed wiring board, including the step of peeling off the carrier or the ultra-thin copper layer from the carrier-attached copper foil constituting the laminate after forming the resin layer and the circuit.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW106136727A TWI705738B (en) | 2016-12-05 | 2017-10-25 | Surface-treated copper foil, copper foil with a carrier, laminates, methods for manufacturing printed wiring boards, and methods for manufacturing electronic devices |
| MYPI2017704627A MY196755A (en) | 2016-12-05 | 2017-11-30 | Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| US15/827,056 US10820414B2 (en) | 2016-12-05 | 2017-11-30 | Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| CN201711259755.3A CN108156753A (en) | 2016-12-05 | 2017-12-04 | Surface treatment copper foil, Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine manufacturing method |
| PH12017000346A PH12017000346A1 (en) | 2016-12-05 | 2017-12-05 | Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| KR1020170165727A KR20180064311A (en) | 2016-12-05 | 2017-12-05 | Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
| JP2022188523A JP2023037628A (en) | 2016-12-05 | 2022-11-25 | Surface-treated copper foil, copper foil with carrier, laminate, method for producing printed wiring board, and method for producing electronic device |
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| JP2016236250 | 2016-12-05 | ||
| JP2016236250 | 2016-12-05 |
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| JP2022188523A Division JP2023037628A (en) | 2016-12-05 | 2022-11-25 | Surface-treated copper foil, copper foil with carrier, laminate, method for producing printed wiring board, and method for producing electronic device |
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| JP2022188523A Pending JP2023037628A (en) | 2016-12-05 | 2022-11-25 | Surface-treated copper foil, copper foil with carrier, laminate, method for producing printed wiring board, and method for producing electronic device |
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| KR (1) | KR20180064311A (en) |
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| EP3825121A4 (en) * | 2018-07-18 | 2021-09-08 | Showa Denko Materials Co., Ltd. | Copper-clad laminate, printed wiring board, semiconductor package and method for producing copper-clad laminate |
| WO2020158604A1 (en) * | 2019-01-30 | 2020-08-06 | Ａｇｃ株式会社 | Laminate, method for producing same, method for producing composite laminate, and method for producing polymer film |
| JP7300976B2 (en) * | 2019-12-13 | 2023-06-30 | Ｊｘ金属株式会社 | Surface treated copper foil, copper clad laminate and printed wiring board |
| JP2021095596A (en) * | 2019-12-13 | 2021-06-24 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper-clad laminate, and printed wiring board |
| WO2022014648A1 (en) * | 2020-07-16 | 2022-01-20 | 三井金属鉱業株式会社 | Copper-clad laminate plate and printed wiring board |
| WO2022014647A1 (en) * | 2020-07-16 | 2022-01-20 | 三井金属鉱業株式会社 | Manufacturing methods for copper-clad laminate and printed wiring board |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2018090903A (en) | 2018-06-14 |
| JP2023037628A (en) | 2023-03-15 |
| KR20180064311A (en) | 2018-06-14 |
| MY196755A (en) | 2023-05-03 |
| TW201822597A (en) | 2018-06-16 |
| TWI705738B (en) | 2020-09-21 |
| PH12017000346A1 (en) | 2018-07-30 |
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