CN108696987B - Surface-treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device - Google Patents
Surface-treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device Download PDFInfo
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- CN108696987B CN108696987B CN201810290908.9A CN201810290908A CN108696987B CN 108696987 B CN108696987 B CN 108696987B CN 201810290908 A CN201810290908 A CN 201810290908A CN 108696987 B CN108696987 B CN 108696987B
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- copper foil
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- resin
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- 238000000034 method Methods 0.000 title claims abstract description 130
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- 230000008569 process Effects 0.000 claims abstract description 5
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 20
- 239000011888 foil Substances 0.000 claims description 19
- 238000010168 coupling process Methods 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
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- 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 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- ORALBXGQQPETFY-UHFFFAOYSA-N 2-[(4-propylphenyl)methyl]oxirane Chemical compound C1=CC(CCC)=CC=C1CC1OC1 ORALBXGQQPETFY-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WBHAUHHMPXBZCQ-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound COC1=CC=CC(C)=C1O WBHAUHHMPXBZCQ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- DUYKOAQJUCADEC-UHFFFAOYSA-N [SiH4].N1=NN=CC=C1 Chemical compound [SiH4].N1=NN=CC=C1 DUYKOAQJUCADEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition 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
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-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
- 238000002788 crimping Methods 0.000 description 1
- 150000001916 cyano esters Chemical class 0.000 description 1
- 230000007547 defect Effects 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-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
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate 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
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 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
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 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
- 239000002966 varnish Substances 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
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及表面处理铜箔、附有载体的铜箔、积层体、印刷布线板的制造方法及电子机器的制造方法。表面处理铜箔具有铜箔和位于铜箔的至少一个表面的粗化处理层。粗化处理层的粗化粒子的纵横比(粗化粒子的高度/粗化粒子的粗度)满足以下(1)、(2)中的任一项以上。(1)粗化粒子的纵横比为3以下，(2)满足以下(2‑1)或(2‑2)中的任一项，(2‑1)在粗化粒子的高度大于500nm且为1000nm以下的情况下，粗化粒子的纵横比为10以下，(2‑2)在粗化粒子的高度为500nm以下的情况下，粗化粒子的纵横比为15以下。表面处理铜箔的粗化处理层侧表面的TD的光泽度为70％以下。
The present invention relates to a surface-treated copper foil, a copper foil with a carrier, a laminate, a method for producing a printed wiring board, and a method for producing an electronic device. The surface-treated copper foil has a copper foil and a roughening treatment layer on at least one surface of the copper foil. The aspect ratio of the roughened particles in the roughening treatment layer (the height of the roughened particles/the thickness of the roughened particles) satisfies any one or more of the following (1) and (2). (1) The aspect ratio of the roughened particles is 3 or less, (2) Either one of the following (2-1) or (2-2) is satisfied, (2-1) The height of the roughened particles is greater than 500 nm and is When the height of the roughened particles is 1000 nm or less, the aspect ratio of the roughened particles is 10 or less, and (2-2) When the height of the roughened particles is 500 nm or less, the aspect ratio of the roughened particles is 15 or less. The glossiness of TD of the roughening process layer side surface of the surface-treated copper foil is 70 % or less.
Description
Technical Field
The present invention relates to a surface-treated copper foil, a surface-treated copper foil with a resin layer, a copper foil with a carrier, a laminate, a method for manufacturing a printed wiring board, and a method for manufacturing an electronic device.
Background
Printed wiring boards have made great progress over the last half century and are now used in almost all electronic machines. In recent years, with the increasing demand for smaller and higher performance electronic devices, high-density mounting of mounted components has been advanced, and miniaturization (fine pitch) of conductor patterns has been demanded for printed wiring boards.
A printed wiring board is a copper-clad laminate obtained by laminating a copper foil and an insulating substrate mainly composed of a glass epoxy substrate, a BT resin, a polyimide film, or the like. The bonding may be performed by a method (a lamination method) in which the insulating substrate and the copper foil are stacked and then heated and pressed, or a method (a casting method) in which a varnish as a precursor of the insulating substrate material is applied to the surface of the copper foil having the coating layer and then heated and cured.
In order to solve the problem of fine pitch, for example, patent document 1 discloses a method for processing a copper foil for a printed circuit, the method comprising: the surface of the copper foil is plated with copper-cobalt-nickel alloy to be coarsened, so that a cobalt-nickel alloy plating layer is formed, and further a zinc-nickel alloy plating layer is formed. It is also described that fine pitches of the conductor patterns can be achieved by this configuration.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent No. 2849059 publication
Disclosure of Invention
[ problems to be solved by the invention ]
In the above-described method for manufacturing a printed wiring board, it is sometimes necessary to remove foreign matter on the surface of the copper foil or the surface of the printed wiring board using a special device or the like. The roughened layer provided on the surface of the copper foil to improve adhesion to the insulating resin is made fine to cope with the miniaturization of the wiring as described above. Therefore, when the foreign matter is removed, the roughened particles constituting the roughened layer are detached from the surface of the copper foil (also referred to as dust falling) and transferred as conductive foreign matter to the copper foil or a carrier device for a printed wiring board. The conductive foreign matter thus attached to the surface of the copper foil or the printed wiring board carrier may be transferred again to the surface of the copper foil or the printed wiring board. This case may cause a short circuit in a circuit formed using the copper foil or in the printed wiring board.
However, the studies on a technique for satisfactorily suppressing the falling off (dusting) of the roughening particles in the surface-treated copper foil having the roughening-treated layer have not been sufficient, and there is still room for improvement. In addition, in the case of manufacturing a printed wiring board or the like using a surface-treated copper foil, a laminate may be produced by laminating the surface-treated copper foil and a resin, but when the surface-treated copper foil is laminated with an insulating substrate such as a resin, there is a problem that wrinkles or stripes may be generated. In addition, when the roughened layer is fine, the above-described wrinkles or streaks tend to be easily generated. The problem of bonding to an insulating substrate is also to be improved. Accordingly, an object of the present invention is to provide a surface-treated copper foil in which separation of the roughened particles from the roughened particle layer provided on the surface of the copper foil is favorably suppressed, and generation of wrinkles and streaks at the time of bonding to an insulating substrate is favorably suppressed.
[ means for solving problems ]
As a result of extensive and intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by controlling the gloss of TD on the surface of the roughened layer of the surface-treated copper foil on the side of the roughened layer to a predetermined value or less while setting the aspect ratio of the roughened particles in the roughened layer to a predetermined value from the surface of the copper foil.
The present invention has been accomplished on the basis of the above findings, and one aspect is a surface-treated copper foil having a copper foil and a roughened layer on at least one surface of the copper foil,
the aspect ratio of the coarsening particles of the coarsening treatment layer (height of the coarsening particles/thickness of the coarsening particles) satisfies one of the following (1) and (2) or more,
(1) the aspect ratio of the coarsening particles is less than 3,
(2) satisfies any one of the following (2-1) and (2-2),
(2-1) in the case where the height of the coarsening particles is more than 500nm and 1000nm or less, the aspect ratio of the coarsening particles is 10 or less,
(2-2) in the case where the height of the coarse particles is 500nm or less, the aspect ratio of the coarse particles is 15 or less,
the surface of the surface-treated copper foil on the side of the roughened layer has a TD gloss of 70% or less.
In one embodiment, the surface-treated copper foil of the present invention has a color difference Δ E according to JIS Z8730 on the surface of the roughened layer side of the surface-treated copper foil*ab is 65 or less.
In another embodiment of the surface-treated copper foil of the present invention, the height of the roughened particles is 1000nm or more, and the aspect ratio of the roughened particles is 3.0 or less.
In still another embodiment of the surface-treated copper foil according to the present invention, the height of the roughened particles is 500nm or more, and the aspect ratio of the roughened particles is 10.0 or less.
In still another embodiment of the surface-treated copper foil according to the present invention, the height of the roughened particles is 500nm or less, and the aspect ratio of the roughened particles is 1.9 or less.
In still another embodiment of the surface-treated copper foil according to the present invention, the aspect ratio of the roughened particles satisfies at least one of the above (1) and (2-2), and the height of the roughened particles is 400nm or less.
In another embodiment of the surface-treated copper foil of the present invention, the height of the roughening particles is 1200nm or less.
In still another embodiment of the surface-treated copper foil of the present invention, the color difference Δ E of the roughened layer side surface according to JIS Z8730 is*ab is 45 to 65 inclusive.
In still another embodiment of the surface-treated copper foil of the present invention, the color difference Δ E of the roughened layer side surface according to JIS Z8730 is*ab is 50.0 or less.
In still another embodiment of the surface-treated copper foil according to the present invention, the surface-treated copper foil has a TD glossiness of 21% or more on the roughened layer side surface.
In another embodiment of the surface-treated copper foil of the present invention, the roughened layer has 1 or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer, and a silane coupling treatment layer on the surface thereof.
In another embodiment, the surface-treated copper foil of the present invention is used for heat dissipation.
Another aspect of the present invention is a surface-treated copper foil with a resin layer, which is provided with a resin layer on the surface of the surface-treated copper foil according to the present invention on the roughened layer side.
In one embodiment, the resin layer is an adhesive resin and/or a semi-cured resin.
The present invention also provides a copper foil with a carrier, which comprises a carrier, an intermediate layer, and an extremely thin copper layer, wherein the extremely thin copper layer is the surface-treated copper foil of the present invention or the surface-treated copper foil with a resin layer of the present invention.
The present invention also provides a laminate comprising the surface-treated copper foil of the present invention or the surface-treated copper foil with a resin layer of the present invention.
Still another aspect of the present invention is a laminate having the copper foil with a carrier of the present invention.
Still another aspect of the present invention is a laminate comprising the carrier-attached copper foil of the present invention and a resin, wherein part or all of an end face of the carrier-attached copper foil is covered with the resin.
The present invention also provides a laminate having two copper foils with a carrier of the present invention.
Still another aspect of the present invention is a method for manufacturing a printed wiring board using the surface-treated copper foil of the present invention or the surface-treated copper foil with a resin layer of the present invention or the copper foil with a carrier of the present invention.
Another aspect of the present invention is a method of manufacturing a printed wiring board, including the steps of:
a step of forming a copper-clad laminate comprising any one of the following (21-1) to (21-3),
(21-1) laminating the surface-treated copper foil of the present invention and an insulating substrate,
(21-2) laminating the surface-treated copper foil with a resin layer of the present invention and an insulating substrate,
(21-3) a carrier obtained by laminating the copper foil with a carrier of the present invention and an insulating substrate and then peeling the copper foil with a carrier; and
and a step of forming a circuit using the copper-clad laminate by any one of a semi-additive method (セミアディティブ method), a subtractive method (サブトラクティブ method), a partial additive method (パートリーアディティブ method), or a modified semi-additive method (モ デ ィ フ ァ イ ド セミアディティブ method).
Another aspect of the present invention is a method of manufacturing a printed wiring board, including the steps of: forming a circuit on the surface of the surface-treated copper foil of the present invention, or forming a circuit on the surface of the copper foil with a carrier of the present invention; forming a resin layer on a surface of the surface-treated copper foil or a surface of the copper foil with a carrier so as to bury the circuit; forming a circuit on the resin layer; and exposing the circuit buried in the resin layer by removing the surface-treated copper foil after forming the circuit on the resin layer, or by removing the extra thin copper layer or the carrier after peeling the carrier or the extra thin copper layer.
Another aspect of the present invention is a method of manufacturing a printed wiring board, including the steps of: laminating the surface-treated copper foil of the present invention on a resin substrate, or laminating the copper foil with a carrier of the present invention on a resin substrate; forming a circuit on a surface of the surface-treated copper foil on a side opposite to a side on which the copper foil with a carrier is laminated on the resin substrate or on a surface of the copper foil with a carrier on a side opposite to the side on which the copper foil with a carrier is laminated on the resin substrate; forming a resin layer on a surface of the surface-treated copper foil on a side opposite to the side on which the copper foil with a carrier is laminated or on a surface of the surface-treated copper foil on a side opposite to the side on which the copper foil with a carrier is laminated so as to bury the circuit; forming a circuit on the resin layer; and exposing the circuit buried in the resin layer by removing the surface-treated copper foil after forming the circuit on the resin layer, or by removing the extra thin copper layer or the carrier after peeling the carrier or the extra thin copper layer.
Another aspect of the present invention is a method of manufacturing a printed wiring board, including the steps of: laminating the surface-treated copper foil of the present invention or the copper foil with a carrier of the present invention and a resin substrate; providing at least one resin layer and a circuit on the surface of the surface-treated copper foil or the copper foil with a carrier opposite to the side on which the resin substrates are laminated; and removing the surface-treated copper foil of the present invention after the resin layer and the circuit are formed, or peeling the carrier or the extra thin copper layer from the copper foil with carrier.
Another aspect of the present invention is a method of manufacturing a printed wiring board, including the steps of: at least one primary resin layer and a circuit are provided on at least one surface of the laminate of the present invention; and peeling the carrier or the extra thin copper layer from the copper foil with a carrier constituting the laminate after the resin layer and the circuit are formed.
Still another aspect of the present invention is a method of manufacturing an electronic machine using a printed wiring board manufactured by the method of the present invention.
[ Effect of the invention ]
According to the present invention, it is possible to provide a surface-treated copper foil in which separation of the roughened particles in the roughened particle layer provided on the surface of the copper foil is favorably suppressed, and occurrence of wrinkles and streaks at the time of bonding to an insulating substrate is favorably suppressed.
Drawings
Fig. 1A to C are schematic diagrams of a cross section of a wiring board in a step up to plating of a circuit and removal of a resist (レジスト) in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier of the present invention.
Fig. 2D to F are schematic diagrams of the cross section of the wiring board in the steps from the step of laminating the resin and the 2 nd layer of the copper foil with a carrier to the step of laser drilling in a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.
Fig. 3G to I are schematic diagrams of the cross section of the wiring board in the steps from the formation of the via hole (ビアフィル) to the peeling of the layer 1 carrier in a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.
Fig. 4J to K are schematic diagrams of the cross section of the wiring board in the steps from the rapid etching (フラッシュエッチング) to the formation of the bumps and copper pillars in a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.
Fig. 5 is an explanatory view of a method for measuring the height (stacking height) of the roughened particles of the roughened layer from the surface of the copper foil.
Detailed Description
< surface-treated copper foil >
The surface-treated copper foil of the present invention has a roughened layer on one surface and/or both surfaces of the copper foil. In the present invention, the term "one surface" and/or both "surfaces" of the copper foil means a surface (outermost surface) after surface treatment when the surface of the copper foil is subjected to surface treatment (e.g., bottom plating such as copper plating on the surface of the copper foil) (e.g., a surface-treated copper foil treated in the order of copper foil/surface treatment/roughening treatment). After the surface-treated copper foil of the present invention is laminated on an insulating substrate to produce a laminate (copper-clad laminate), the surface-treated copper foil is etched into a target conductor pattern, and finally a printed wiring board can be produced. The surface-treated copper foil of the present invention can also be used as a surface-treated copper foil for heat dissipation, which can receive and release heat from a heat-generating component with good efficiency, for example.
< copper foil >
The form of the copper foil that can be used in the present invention is not particularly limited, and typically, the copper foil used in the present invention may be any of an electrolytic copper foil and a rolled copper foil. In general, an electrolytic copper foil is produced by depositing copper electrolytically precipitated from a copper sulfate plating bath onto a titanium or stainless steel drum, and a rolled copper foil is produced by repeating plastic working with a rolling roll and heat treatment. Among the uses requiring bendability, rolled copper foil is most often used.
As the copper foil material, in addition to high purity copper such as pure copper (JIS H3100, alloy No. C1100) or oxygen-free copper (JIS H3100, alloy No. C1020; or JIS H3510, alloy No. C1011) which is generally used for a conductor pattern of a printed wiring board, for example, tin (Sn) -containing copper, silver (Ag) -containing copper, copper alloys to which chromium (Cr), zirconium (Zr), magnesium (Mg), or the like is added, and copper alloys such as casson (コルソン) -based copper alloys to which nickel (Ni) and silicon (Si) are added may be used. In the present specification, the term "copper foil" includes a copper alloy foil when used alone.
The thickness of the copper foil is not particularly limited, and is, for example, 1 μm or more and 1000 μm or less, or 1 μm or more and 500 μm or less, or 1 μm or more and 300 μm or less, or 3 μm or more and 100 μm or less, or 5 μm or more and 70 μm or less, or 6 μm or more and 35 μm or less, or 9 μm or more and 18 μm or less.
In addition, another aspect of the present invention is a copper foil with a carrier, which has a carrier, an intermediate layer, and an extra thin copper layer in this order, the extra thin copper layer being the surface-treated copper foil of the present invention. In the present invention, when a copper foil with a carrier is used, a surface treatment layer such as a roughening treatment layer described below is provided on the surface of the extra thin copper layer. Another embodiment of the copper foil with a carrier will be described below.
< roughening layer >
In general, a roughened surface of the copper foil to be bonded to the resin base material is roughened by "nodular" plating on the surface of the degreased copper foil in order to increase the peel strength of the laminated copper foil. The electrolytic copper foil has irregularities during production, and the protrusions of the electrolytic copper foil are reinforced by roughening treatment to make the irregularities larger. In some cases, ordinary copper plating or the like is performed as a pretreatment before roughening, and in some cases, ordinary copper plating or the like is performed as a finishing treatment after roughening to prevent plating from falling off. In the present invention, the above preprocessing and finishing are collectively referred to as "roughening processing".
The roughened particles in the roughened layer of the surface-treated copper foil of the present invention have an aspect ratio (height of the roughened particles/roughness of the roughened particles) that is a ratio of the height of the roughened particles from the surface of the copper foil to the roughness of the roughened particles, and that satisfies one or more of the following (1) and (2).
(1) The aspect ratio of the coarsened particles is 3 or less,
(2) satisfies any one of the following (2-1) and (2-2),
(2-1) when the height of the coarse particles is more than 500nm and 1000nm or less, the aspect ratio of the coarse particles is 10 or less,
(2-2) when the height of the coarse particles is 500nm or less, the aspect ratio of the coarse particles is 15 or less.
With this configuration, the adhesion between the surface of the copper foil and the insulating resin can be ensured, and the powder falling can be controlled well.
In the above (1), the aspect ratio of the coarsened particles is preferably 2.9 or less, more preferably 2.8 or less, even more preferably 2.7 or less, even more preferably 2.6 or less, even more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, even more preferably 2.2 or less, even more preferably 2.1 or less, even more preferably 2.0 or less. In addition, regarding the above (1), the aspect ratio of the coarsened particles is preferably 0.1 or more, preferably 0.2 or more, preferably 0.3 or more, preferably 0.4 or more, preferably 0.5 or more, preferably 0.6 or more, preferably 0.7 or more, preferably 0.8 or more, preferably 0.9 or more, preferably 1.0 or more, preferably 1.1 or more, preferably 1.2 or more, preferably 1.3 or more, preferably 1.4 or more, preferably 1.5 or more, preferably 1.6 or more.
In the case where the height of the coarse particles is greater than 500nm and not more than 1000nm, the aspect ratio of the coarse particles is preferably 9.5 or less, more preferably 9.0 or less, more preferably 8.5 or less, more preferably 8.0 or less, more preferably 7.5 or less, more preferably 7.0 or less, more preferably 6.5 or less, more preferably 6.4 or less, more preferably 6.3 or less, more preferably 6.2 or less, more preferably 6.1 or less, more preferably 6.0 or less, more preferably 5.9 or less, more preferably 5.5 or less, more preferably 5.0 or less, and even more preferably 4.5 or less.
In the case where the height of the coarse particles is greater than 500nm and not more than 1000nm, the aspect ratio of the coarse particles is preferably 0.1 or more, preferably 0.5 or more, preferably 1.0 or more, preferably 1.5 or more, preferably 1.7 or more, preferably 1.9 or more, preferably 2.1 or more, preferably 2.3 or more, preferably 2.6 or more, preferably 2.9 or more, preferably 3.2 or more, preferably 3.5 or more, preferably 3.8 or more as described above in relation to (2-1).
With respect to the above-mentioned (2-2), in the case where the height of the coarsened particles is 500nm or less, the aspect ratio of the coarsened particles is preferably 14.5 or less, preferably 14.0 or less, preferably 13.9 or less, preferably 13.8 or less, preferably 13.5 or less, preferably 13.0 or less, preferably 12.5 or less, preferably 12.0 or less, preferably 11.5 or less, preferably 11.0 or less, preferably 10.5 or less, preferably 10.0 or less, preferably 9.5 or less, more preferably 9.0 or less, more preferably 8.5 or less, more preferably 8.0 or less, more preferably 7.5 or less, more preferably 7.0 or less, more preferably 6.6 or less, more preferably 6.5 or less, more preferably 6.4 or less, more preferably 6.3 or less, more preferably 6.2 or less, more preferably 6.1 or less, more preferably 6.0 or less, more preferably 5.9 or less, more preferably 5.8 or less, more preferably 5.7 or less, more preferably 5.6 or less, more preferably 5.5.5.5 or less, more preferably 5.5.5 or less, more preferably 5.5 or less, more preferably 1 or less, more preferably 5.0 or less, more preferably 4.9 or less, more preferably 4.8 or less, more preferably 4.7 or less, more preferably 4.6 or less, more preferably 4.5 or less, more preferably 4.2 or less, more preferably 3.9 or less, more preferably 3.6 or less, more preferably 3.4 or less, more preferably 3.3 or less, more preferably 3.0 or less, more preferably 2.7 or less, more preferably 2.5 or less, more preferably 2.4 or less, further more preferably 2.3 or less, and further more preferably 1.9 or less.
Regarding (2-2), when the height of the coarse particles is 500nm or less, the aspect ratio of the coarse particles is preferably 0.1 or more, preferably 0.5 or more, preferably 1.0 or more, preferably 1.5 or more, preferably 1.7 or more, preferably 1.9 or more, preferably 2.1 or more, preferably 2.3 or more, preferably 2.6 or more, preferably 2.9 or more, preferably 3.2 or more, preferably 3.5 or more, preferably 3.8 or more.
If the upper limit of the aspect ratio of the coarse particles is controlled as described above, the coarse particles may be less likely to be broken when the coarsened particles have the same thickness, and the powder drop may be further reduced. Further, if the lower limit of the aspect ratio of the roughened particles is controlled as described above, the adhesion between the surface-treated copper foil and the resin base material may be improved.
The roughness of the roughened particles in the roughened layer of the surface-treated copper foil of the present invention is not particularly limited, and typically, the roughness is, for example, 5nm or more, for example, 10nm or more, for example, 13nm or more. The roughness of the roughened particles in the roughened layer of the surface-treated copper foil of the present invention is not particularly limited, but typically, it is 1200nm or less, for example, 1100nm or less, for example, 1000nm or less, for example, 900nm or less, for example, 800nm or less, for example, 700nm or less, for example, 600nm or less, for example, 500nm or less, for example, 400nm or less.
Furthermore, the coarsened particles may be deposited.
Further, since the roughened particles of the roughened layer are likely to break and cause powder falling if the height of the roughened particles is 1000nm or more, the aspect ratio of the roughened particles (height of the roughened particles/thickness of the roughened particles) is preferably 3.0 or less, preferably 2.9 or less, preferably 2.8 or less, preferably 2.7 or less, preferably 2.6 or less, preferably 2.5 or less, preferably 2.4 or less, preferably 2.3 or less, preferably 2.2 or less, preferably 2.1 or less, and more preferably 2.0 or less. By controlling the aspect ratio of the coarsening particles within the above range, the coarsening particles are less likely to break and less likely to generate powder falling.
Further, if the roughened particles of the roughened layer are particles having a height of 500nm or more, the roughened particles may be easily broken and powder falling may easily occur, and therefore the aspect ratio of the roughened particles (height of the roughened particles/thickness of the roughened particles) is preferably 10.0 or less, preferably 9.5 or less, preferably 9.0 or less, preferably 8.5 or less, more preferably 8.0 or less, more preferably 7.5 or less, more preferably 7.0 or less, more preferably 6.5 or less, more preferably 6.0 or less, and more preferably 5.5 or less. By controlling the aspect ratio of the coarsening particles within the above range, the coarsening particles are less likely to break and less likely to generate powder falling.
In addition, from the viewpoint of further optimizing productivity, the height of the coarsened particles is preferably 400nm or less.
In addition, from the viewpoint of further optimizing the etching property, the height of the coarsening particles is preferably 1200nm or less.
The height of the coarse particles of the coarse treatment layer and/or the thickness of the coarse particles of the coarse treatment layer according to the present invention can be controlled by the current density and/or the plating time and/or the plating solution temperature at the time of plating. By increasing the current density, the height of the coarsened particles can be increased and/or the coarseness of the coarsened particles can be increased. By reducing the current density, the height of the coarsened particles can be reduced and/or the coarseness of the coarsened particles can be reduced. By extending the plating time, the height of the coarsened particles can be increased and/or the coarseness of the coarsened particles can be increased. By shortening the plating time, the height of the coarsened particles can be reduced and/or the coarseness of the coarsened particles can be reduced. By lowering the plating solution temperature, the height of the coarsened particles can be increased and/or the coarseness of the coarsened particles can be increased. By increasing the plating solution temperature, the height of the coarsened particles can be reduced and/or the coarseness of the coarsened particles can be reduced. In addition, the coarseness of the coarsened particles can be increased by increasing the copper concentration in the plating solution. Conversely, the coarseness of the coarsened particles can be reduced by reducing the copper concentration in the plating solution.
As described above, the aspect ratio of the coarsened particles can be increased by increasing the height of the coarsened particles and/or decreasing the coarseness of the coarsened particles. In addition, as described above, the aspect ratio of the coarsened particles can be reduced by reducing the height of the coarsened particles and/or increasing the coarseness of the coarsened particles.
The surface-treated copper foil of the present invention is preferably prepared by roughening the surface of the treated layer side with a white plate (X of the white plate in a 10-degree field of view using a D65 light source)10Y10Z10The tristimulus value of the color System (JIS Z87011999) is X10＝80.7、Y10＝85.6、Z10＝91.5，L*a*b*The object color of the white plate under the color system is L*＝94.14、a*＝-0.90、b*0.24) as a reference color, that is, a color difference Δ E according to JIS Z8730*ab control is 65 or less. With this configuration, it is possible to further reduce the possibility of causing the color difference Δ E*ab the frequency of existence of the coarse and large layered product of coarse particles, which increases, can control the powder falling more favorably. The roughened layer side of the surface-treated copper foil of the present inventionColor difference Δ E of surface based on JIS Z8730*ab is preferably 62 or less, more preferably 60 or less, more preferably 57 or less, and more preferably 50.0 or less.
In addition, regarding the color difference Δ E*If the lower limit value ab is controlled to 42 or more, for example, the following conditions are satisfied: in the process of manufacturing a printed wiring board, when a circuit is formed on the surface of a copper foil, the contrast between the copper foil and the circuit becomes clear, so that the circuit is visually recognized well and the circuit can be positioned with high accuracy. In addition, in order to increase the density of the integrated circuit of the printed wiring board, a method of forming laser holes and connecting the inner layer and the outer layer through the holes is generally adopted, and in this case, if the color difference Δ E of the roughened layer side surface of the surface-treated copper foil is set to be larger than the color difference Δ E of the inner layer*ab control is 42 or more, the following are the cases: when performing lamination positioning of a multilayer FPC using a CCD camera, it is necessary to confirm the position of a copper foil circuit on a white stage through PI (polyimide), and therefore the positioning accuracy is improved. In addition, since copper has extremely low absorptivity to laser light in a wavelength region of far infrared to infrared rays such as carbon dioxide gas laser light, Δ E is used*ab is 42 or more, and the absorption rate may be improved. Said color difference Δ E*ab is preferably 45 or more, more preferably 47 or more, more preferably 49 or more, more preferably 50 or more, more preferably 51 or more, more preferably 52 or more. In some cases, the adhesion between the surface of the copper foil and the insulating resin can be further optimized, and therefore, the color difference Δ E ab is preferably 49.1 or more.
In the present invention, the "surface on the side of the roughened layer" means the surface (outermost surface) of the surface-treated layer when various surface-treated layers such as a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a silane-coupling-treated layer are provided on the surface of the roughened layer.
For example, in the present invention, the "color difference Δ E based on JIS Z8730 of the surface on the roughened layer side" is*ab', when various surface treatment layers such as a heat-resistant layer, a rust-preventive layer, a chromate treatment layer, and a silane coupling treatment layer are provided on the surface of the roughened layer, it means that the color difference Δ E according to JIS Z8730 of the surface (outermost surface) of the surface treatment layer is*ab. Watch of the inventionColor difference Δ E in accordance with JIS Z8730 on the surface of roughened layer side of surface-treated copper foil*ab is more preferably 52 or more, more preferably 54 or more.
Here, the color difference Δ E*ab is represented by the following formula. The color differences Δ L, Δ a, Δ b in the following formulae were measured using a color difference meter, and black/white/red/green/yellow/blue was added thereto, and L was used in accordance with JIS Z8730(2009)*a*b*And the comprehensive index represented by a color system, namely delta L represents black and white, delta a represents red and green, and delta b represents yellow and blue. The color differences (Δ L, Δ a, Δ b) can be measured using a color difference meter MiniScan XE Plus manufactured by HunterLab. The color differences Δ L, Δ a, and Δ b are color differences in accordance with JIS Z8730(2009) when the object color of the white plate is set as a reference color, and Δ L is L defined in JIS Z8729(2004)*a*b*CIE luminance L of two object colors in color system*Δ a, Δ b are L defined in JIS Z8729(2004)*a*b*Color coordinates a of two object colors in color system*Or b*The difference of (a).
The color difference may be controlled by the formation condition of the roughened layer. Specifically, when the roughened layer is formed, the color difference can be controlled by using an electrolytic solution containing a plurality of elements, for example, one or more elements selected from the group consisting of copper, nickel, cobalt, tungsten, molybdenum, phosphorus, zinc, tin, chromium, and iron, and controlling the current density, the treatment time, and the temperature of the treatment liquid. In order that the height and/or color difference of the roughening particles can be easily controlled, the roughening-treated layer is preferably an alloy containing copper. By increasing the current density, the chromatic aberration can be increased. By reducing the current density, the chromatic aberration can be reduced. By extending the plating time, the color difference can be increased. By shortening the plating time, color difference can be reduced. By lowering the plating solution temperature, the color difference can be increased. By increasing the plating solution temperature, the color difference can be reduced.
In addition, the color difference can be increased by decreasing the copper concentration and increasing the concentration of a metal other than copper as the metal composition of the roughening treatment liquid.
The surface-treated copper foil of the present invention has a TD gloss of 70% or less on the surface of the roughened layer side of the surface-treated copper foil. If the TD gloss on the surface of the roughened layer side of the surface-treated copper foil exceeds 70%, wrinkles or streaks may occur when the surface-treated copper foil is bonded to a resin. The surface treated copper foil preferably has a TD gloss of 69% or less, more preferably 68% or less, more preferably 67% or less, more preferably 66% or less, even more preferably 65% or less, even more preferably 60% or less, even more preferably 55% or less, even more preferably 50% or less, even more preferably 45% or less, even more preferably 25% or less, even more preferably 20% or less, even more preferably 10% or less, even more preferably 5% or less on the roughened layer side surface. The lower limit of the TD gloss on the roughened layer side surface of the surface-treated copper foil is not particularly limited, but is typically, for example, 0.01% or more, for example, 0.1% or more, for example, 0.3% or more, for example, 0.5% or more. In addition, the surface treated copper foil preferably has a TD gloss of 21% or more on the surface on the roughened layer side because the powder falling can be controlled more favorably.
The gloss of the TD on the roughened layer side surface of the surface-treated copper foil can be controlled by the gloss of the TD of the copper foil or carrier before surface treatment, and/or the current density and/or plating time and/or plating solution temperature at the time of plating the copper foil. By reducing the TD glossiness of the copper foil or carrier before the surface treatment, the TD glossiness of the surface on the roughened layer side of the surface-treated copper foil can be reduced. By increasing the TD gloss of the copper foil or carrier before surface treatment, the TD gloss of the surface on the roughened layer side of the surface-treated copper foil can be increased. By increasing the current density, the TD gloss of the surface-treated copper foil on the roughened layer side can be reduced. By reducing the current density, the TD gloss of the surface-treated copper foil on the roughened layer side can be improved. By extending the plating time, the TD gloss of the surface-treated copper foil on the roughened layer side can be reduced. By shortening the plating time, the TD gloss of the surface-treated copper foil on the roughened layer side can be improved. By lowering the plating solution temperature, the TD gloss of the surface on the roughened layer side of the surface-treated copper foil can be lowered. By increasing the temperature of the plating solution, the TD gloss of the surface-treated copper foil on the roughened layer side can be increased.
In the present invention, the "TD gloss on the surface on the roughened layer side" means the TD gloss on the surface (outermost surface) of the surface treated layer when various surface treated layers such as a heat-resistant layer, a rust-preventive layer, a chromate treated layer, and a silane coupling treated layer are provided on the surface of the roughened layer.
In the surface-treated copper foil of the present invention, the coarsening particles of the coarsened layer preferably have a coarseness of 5nm or more. If the coarsening particles of the coarsened layer have a coarseness of 5nm or more, the following conditions apply: the peel strength can be further optimized when the resin is peeled from the surface-treated copper foil after the surface-treated copper foil is laminated on the resin from the roughened layer side. From the viewpoint of further optimizing the peel strength, the coarsened particles of the coarsened layer have a coarseness of more preferably 7nm or more, more preferably 10nm or more, more preferably 15nm or more, more preferably 20nm or more, more preferably 21nm or more, more preferably 25nm or more, more preferably 27nm or more, more preferably 30nm or more, even more preferably 35nm or more, and even more preferably 40nm or more.
In the surface-treated copper foil of the present invention, the coarsening particles of the coarsened layer preferably have a coarseness of 500nm or less. If the coarsening particles of the coarsened layer have a coarseness of 500nm or less, the following effects may be obtained: when a circuit is formed by laminating a surface-treated copper foil on a resin from the side of a roughened layer and then removing unnecessary portions of the surface-treated copper foil by etching, residues of the surface-treated copper foil are less likely to remain on the surface of the resin from which the surface-treated copper foil has been removed. From the viewpoint of making it less likely that residues of the surface-treated copper foil remain, the coarsened particles of the coarsened layer have a coarseness of more preferably 480nm or less, more preferably 460nm or less, more preferably 440nm or less, more preferably 420nm or less, more preferably 400nm or less, more preferably 380nm or less, more preferably 360nm or less, more preferably 340nm or less, more preferably 320nm or less, more preferably 300nm or less, more preferably 280nm or less, more preferably 260nm or less, more preferably 250nm or less, even more preferably 240nm or less, and even more preferably 220nm or less. In addition, from the viewpoint of further improving the following productivity, 79nm or less is preferable.
The roughened layer in the surface-treated copper foil of the present invention can be produced under the following conditions.
(roughening treatment layer plating conditions)
An example of the plating conditions for forming the roughened layer is as follows.
The liquid composition is as follows: copper is 10g/L to 25g/L inclusive, cobalt is 7g/L to 10g/L inclusive, nickel is 7g/L to 10g/L inclusive
pH value: 2.0 to 3.0 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 10A/dm2Above 60A/dm2The following
Plating time: 0.2 to 1.6 seconds inclusive
Coulomb quantity: 0.6As/dm2Above and 100As/dm2The following
In the case where the current density is high, it is necessary to set the plating solution temperature to the range and/or shorten the plating time. In the case where the current density is low, it is necessary to set the plating solution temperature to a higher value within the range and/or to extend the plating time to some extent.
The liquid composition for forming the roughened layer may be any of the following (a) to (E). Other conditions may employ the conditions.
(A) 10-20 g/L of copper, 3-10 g/L of nickel and 0.1-2.0 g/L of phosphorus
(B) 3-10 g/L of copper, 10-20 g/L of cobalt and 10-20 g/L of nickel
(C) 3-10 g/L of copper, 10-20 g/L of cobalt, 10-20 g/L of nickel, and 0.001-5 g/L of tungsten
(D) 5-15 g/L of copper, 5-15 g/L of nickel and 0.1-10 g/L of molybdenum
(E) 5-15 g/L of copper, 5-15 g/L of nickel, 0.1-10 g/L of molybdenum, 0.1-2.0 g/L of phosphorus
The treatment liquid for forming the roughened layer may contain one or more elements selected from nickel, cobalt, tungsten, molybdenum, phosphorus, zinc, tin, chromium, and iron.
As described above, the roughened layer may be formed on one surface of the surface-treated copper foil of the present invention, or on both surfaces.
< copper foil with Carrier >
The copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an extremely thin copper layer on one or both surfaces of the carrier in this order. The extra thin copper layer is the surface-treated copper foil according to the embodiment of the present invention.
< vector >
The carrier that can be used in the present invention is typically a metal foil or a resin film, and is provided in the form of, for example, a copper foil, a copper alloy foil, a nickel alloy foil, an iron alloy foil, a stainless steel foil, an aluminum alloy foil, an insulating resin film, a polyimide film, an LCP (liquid crystal polymer) film, a fluororesin film, a PET (polyethylene terephthalate) film, a PP (polypropylene) film, a polyamide film, or a polyamideimide film.
The carrier usable in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. In general, an electrolytic copper foil is produced by depositing copper electrolytically precipitated from a copper sulfate plating bath onto a titanium or stainless steel drum, and a rolled copper foil is produced by repeating plastic working with a rolling roll and heat treatment. As the material of the copper foil, in addition to high purity copper such as fine copper (JIS H3100, alloy No. C1100) or oxygen-free copper (JIS H3100, alloy No. C1020; or JIS H3510, alloy No. C1011), for example, copper alloys such as tin (Sn) -containing copper, silver (Ag) -containing copper, copper alloys to which chromium (Cr), zirconium (Zr), magnesium (Mg) or the like is added, and Carson-based copper alloys to which nickel (Ni) and silicon (Si) or the like are added may be used. In the present specification, the term "copper foil" includes a copper alloy foil when used alone.
The thickness of the carrier that can be used in the present invention is not particularly limited, and may be appropriately adjusted to an appropriate thickness so as to function as a carrier, and may be, for example, 5 μm or more. However, since the production cost increases if the thickness is too large, it is generally preferable to be 35 μm or less. Therefore, the thickness of the support is typically 8 μm or more and 70 μm or less, more typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less. In addition, the thickness of the carrier is preferably small from the viewpoint of reducing the cost of raw materials. Accordingly, 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, preferably 5 μm or more and 10 μm or less. In addition, if the thickness of the carrier is small, folding and wrinkling are likely to occur when the carrier is passed through the foil. In order to prevent the occurrence of folding and wrinkling, it is effective to, for example, keep the conveying rollers of the copper foil manufacturing apparatus with a carrier smooth or shorten the distance between one conveying roller and the next conveying roller. In addition, when the copper foil with a carrier is used in an embedding method (embedded Process) which is one of the methods for manufacturing a printed wiring board, 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 more preferably 35 μm or more and 70 μm or less.
Further, a roughened layer may be provided on the surface of the carrier opposite to the surface on the side where the extremely thin copper layer is provided. The roughened layer may be provided by a known method, or may be provided by roughening as described below. The roughening treatment layer is provided on the surface of the carrier opposite to the surface on the side where the extremely thin copper layer is provided, and has the following advantages: when the carrier is laminated on a support such as a resin substrate from the surface side having the roughened layer, the carrier and the resin substrate are less likely to peel off.
Hereinafter, an example of manufacturing conditions in the case of using an electrolytic copper foil as a carrier will be described.
< composition of electrolyte >
Copper: 90g/L to 110g/L inclusive
Sulfuric acid: 90g/L to 110g/L inclusive
Chlorine: 50ppm or more and 100ppm or less
Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10ppm or more and 30ppm or less
Leveling agent 2 (amine compound): 10ppm or more and 30ppm or less
As the amine compound, an amine compound of the following chemical formula can be used.
The remaining part of the treatment liquid used in the electrolysis, surface treatment, plating, or the like used in the present invention is water unless otherwise specified.
[ solution 1]
(in the formula, R1And R2Selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups. )
< manufacturing Condition >
Current density: 70A/dm2Above and 100A/dm2The following
Temperature of the electrolyte: 50 ℃ or higher and 60 ℃ or lower
Linear velocity of electrolyte: 3m/sec or more and 5m/sec or less
And (3) electrolysis time: 0.5 to 10 minutes inclusive
< intermediate layer >
An intermediate layer is disposed on the support. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is configured such that the extra thin copper layer is not easily peeled off from the carrier before the step of laminating the copper foil with a carrier onto the insulating substrate, and the extra thin copper layer can be peeled off from the carrier after the step of laminating the copper foil with a carrier onto the insulating substrate. For example, the intermediate layer of the copper foil with a carrier of the present invention may contain one or more selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys of these metals, hydrates of these metals, oxides of these metals, and organic substances. In addition, the intermediate layer may be a multilayer.
The intermediate layer may be formed by, for example, forming a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the support side, or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, and forming a layer composed of a hydrate or an oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance thereon, or forming a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or forming a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and Zn, or forming a single metal layer composed of Cr, Ni, Co, Fe, Mo, Ti, W, and Zn, An alloy layer composed of one or more elements selected from the group consisting of P, Cu, Al and Zn.
When the intermediate layer is provided only on one side, it is preferable to provide a rust-preventive layer such as a nickel (Ni) plated layer on the opposite side of the support. Further, when an intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of metals to which chromium, zinc, or the like are attached may be hydrates or oxides.
The intermediate layer may be formed by, for example, sequentially laminating nickel, a nickel-phosphorus alloy, or a nickel-cobalt alloy and chromium on the support. Since the adhesion between nickel and copper is higher than that between chromium and copper, when the extremely thin copper layer is peeled, peeling occurs at the interface between the extremely thin copper layer and chromium. In addition, nickel in the intermediate layer is expected to have a barrier effect of preventing diffusion of copper components from the carrier to the extremely thin copper layer. The amount of nickel adhered to the intermediate layer is preferably 100. mu.g/dm2Above and 40000. mu.g/dm2Hereinafter, more preferably 100. mu.g/dm2Above and 4000 mug/dm2Hereinafter, more preferably 100. mu.g/dm2Above 2500 [ mu ] g/dm2Hereinafter, more preferably 100. mu.g/dm2Above and less than 1000 [ mu ] g/dm2The amount of chromium adhered to the intermediate layer is preferably 5. mu.g/dm2Above and 100. mu.g/dm2The following.
< ultra thin copper layer >
An extremely thin copper layer is provided on the intermediate layer. Other layers may also be provided between the intermediate layer and the extremely thin copper layer. The extra thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, or the like, and a copper sulfate bath that can form a copper foil at a high current density and is used for a general electrolytic copper foil is preferable. The thickness of the extremely thin copper layer is not particularly limited, but is generally thinner than the carrier, and is, for example, 12 μm or less. Typically 0.5 μm or more and 12 μm or less, more typically 1 μm or more and 5 μm or less, further typically 1.5 μm or more and 5 μm or less, further typically 2 μm or more and 5 μm or less. In addition, very thin copper layers may also be provided on both sides of the carrier.
Thus, a copper foil with a carrier is produced, which comprises a carrier, an intermediate layer laminated on the carrier, and an extremely thin copper layer laminated on the intermediate layer. The copper foil with a carrier itself is known to be used in a method of laminating the surface of an extremely thin copper layer on an insulating substrate such as a paper base phenolic resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth/paper composite base epoxy resin, a glass cloth/glass nonwoven fabric composite base epoxy resin, a glass cloth base epoxy resin, a polyester film, or a polyimide film, followed by thermocompression bonding, and then peeling off the carrier to form a copper-clad laminate, and etching the extremely thin copper layer bonded to the insulating substrate into a desired conductor pattern to finally obtain a printed wiring board.
< other surface treatment >
After the roughening treatment, a heat-resistant layer or a rust-proof layer may be formed of a simple metal of Ni, Co, Cu, Zn, a Ni alloy, a Co alloy, a Cu alloy, a Zn alloy, an alloy containing one or more elements selected from Ni, Co, Cu, and Zn, or the like, and the surface thereof may be further subjected to chromate treatment, silane coupling treatment, or the like. That is, 1 or more kinds of layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughened layer. The heat-resistant layer, the rust-preventive layer, the chromate treatment layer, and the silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 or more layers, 3 or more layers, etc.).
In the present specification, the chromate treatment layer refers to a layer treated with a solution containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer may further contain elements (in the form of metal, alloy, oxide, nitride, sulfide, etc.) such As Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti. Specific examples of the chromate treatment layer include: a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treatment layer treated with a treatment liquid containing chromic anhydride, potassium dichromate, and zinc.
As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and/or the rust-preventive layer may be a layer containing 1 or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, mercury, platinum group elements, iron, and tantalum, or may be a metal layer or an alloy layer containing 1 or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, mercury, platinum group elements, iron, and tantalum. In addition, the heat-resistant layer and/or the rust-preventive layer may also contain an oxide, a nitride, a silicide containing the element. In addition, the heat-resistant layer and/or the rust preventive layer may also be a layer containing a nickel-zinc alloy. In addition, the heat-resistant layer and/or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% or more and 99 wt% or less of nickel, and 50 wt% or more and 1 wt% or less of zinc, in addition to unavoidable impurities. The total amount of zinc and nickel deposited in the nickel-zinc alloy layer may be 5mg/m2Above and 1000mg/m2Below, preferably 10mg/m2Above and 500mg/m2Below, preferably 20mg/m2Above and 100mg/m2The following. In the layer containing a nickel-zinc alloy or the nickel-zinc alloy layer, the ratio of the amount of nickel deposited to the amount of zinc deposited (nickel deposited/zinc deposited) is preferably 1.5 or more and 10 or less. In addition, the nickel attachment amount in the layer comprising a nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5mg/m2Above and 500mg/m2Below, more preferably 1mg/m2Above and 50mg/m2The following. In the case where the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, when the through-hole is formedWhen the inner wall of the (スルーホール) or the via (ビアホール) comes into contact with the desmear (デスミア) solution, the interface between the copper foil and the resin substrate is not easily corroded by the desmear solution, and the adhesion between the copper foil and the resin substrate is improved.
The silane coupling treatment layer may be formed using a known silane coupling agent, or may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, or triazine silane. Further, 2 or more of these silane coupling agents may be used in combination. Among them, a silane coupling treatment layer formed using an amino silane coupling agent or an epoxy silane coupling agent is preferable.
Further, the surface of the copper foil, the extremely thin copper layer, the roughening-treated layer, the heat-resistant layer, the rust-preventive layer, the silane-coupling-treated layer or the chromate-treated layer may be subjected to surface treatment as described in International publication No. WO2008/053878, Japanese patent laid-open No. 2008-111169, Japanese patent No. 5024930, International publication No. WO2006/028207, Japanese patent No. 4828427, International publication No. WO2006/134868, Japanese patent No. 5046927, International publication No. WO2007/105635, Japanese patent No. 5180815, Japanese patent laid-open No. 2013-19056. Alternatively, the surface of the copper foil, the extra thin copper layer, the roughening-treated layer, the heat-resistant layer, the rust-preventive layer, the silane-coupling-treated layer or the chromate-treated layer may be subjected to a known surface treatment.
< resin layer >
The surface-treated copper foil may be a resin-layer-attached surface-treated copper foil having a resin layer on the surface on the roughened layer side. The resin layer may be an adhesive or an insulating resin layer in a semi-cured state (B stage) for adhesion. The semi-cured state (B-stage) includes a state in which the insulating resin layers can be stored in a stacked state without having a sticky feeling even when the surfaces thereof are touched with a finger, and a curing reaction occurs when the insulating resin layers are subjected to a heat treatment.
The resin layer may contain a thermosetting resin or a thermoplastic resin. In addition, the resin layer may also contain a thermoplastic resin. The kind of resin is not particularly limited, and examples thereof include resins selected from the group consisting of epoxy resins, polyimide resins, polyfunctional cyanate ester compounds, maleimide compounds, polymaleimide compounds, maleimide resins, aromatic maleimide resins, polyvinyl acetal resins, urethane resins, polyethersulfone resins, aromatic polyamide resin polymers, rubbery resins, polyamines, aromatic polyamines, polyamideimide resins, rubber-modified epoxy resins, phenoxy resins, carboxyl-modified acrylonitrile-butadiene resins, polyphenylene ethers, bismaleimide triazine resins, thermosetting polyphenylene ether resins, cyanate ester resins, carboxylic acid anhydrides, polycarboxylic acid anhydrides, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2-bis (4-cyanatophenyl) propane, and mixtures thereof, Phosphorus-containing phenolic compounds, manganese naphthenate, 2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate ester resins, siloxane-modified polyamideimide resins, cyano ester resins, phosphazene (フォスファゼン) resins, rubber-modified polyamideimide resins, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy groups, high-molecular epoxy resins, aromatic polyamides, fluorine resins, bisphenols, and block copolymerized polyimide resins.
The epoxy resin can be used without any particular problem as long as it has 2 or more epoxy groups in the molecule and can be used for electrical and electronic material applications. The epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having 2 or more glycidyl groups in the molecule. Further, 1 or 2 or more selected from the group consisting of 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 epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, triglycidyl isocyanurate, glycidyl amine compound such as N, N-diglycidylaniline, glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenol aldehyde type epoxy resin, trihydroxyphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin may be used in combination, or a hydride or halide of the epoxy resin may be used.
As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. The phosphorus-containing epoxy resin is preferably an epoxy resin obtained, for example, as a derivative derived from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having 2 or more epoxy groups in the molecule.
The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric substance (any dielectric substance such as a dielectric substance containing an inorganic compound and/or an organic compound, a dielectric substance containing a metal oxide, or the like may be used), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, or the like. Further, as the resin layer, for example, International publication No. WO2008/004399, International publication No. WO2008/053878, International publication No. WO2009/084533, Japanese patent laid-open No. 11-5828, Japanese patent laid-open No. 11-140281, Japanese patent No. 3184485, International publication No. WO97/02728, Japanese patent No. 3676375, Japanese patent laid-open No. 2000-43188, Japanese patent No. 3612594, Japanese patent laid-open No. 2002-179772, Japanese patent laid-open No. 2002-9444, Japanese patent laid-open No. 2003-304068, Japanese patent No. 3992225, Japanese patent laid-open No. 2003-249739, Japanese patent No. 4136509, Japanese patent laid-open No. 2004-82687, Japanese patent No. 4025177, Japanese patent laid-open No. 2004-349654, Japanese patent No. 4286060, Japanese patent laid-open No. 262506, Japanese patent laid-open No. 4570070, Japanese patent laid-open No. 53218-open No. 3559218-open No. 359444-open, Japanese patent No. 3949676, Japanese patent No. 4178415, International publication No. WO2004/005588, Japanese patent application laid-open No. 2006-257153, Japanese patent application laid-open No. 2007-326923, Japanese patent application laid-open No. 2008-111169, Japanese patent No. 5024930, International publication No. WO2006/028207, Japanese patent No. 4828427, Japanese patent application laid-open No. 2009-67029, International publication No. WO2006/134868, Japanese patent No. 5046927, Japanese patent application laid-open No. 2009-173017, International publication No. WO2007/105635, Japanese patent No. 5180815, International publication No. WO2008/114858, International publication No. WO2009/008471, Japanese patent application laid-open No. 2011-14727, International publication No. WO2009/001850, International publication No. WO2009/145179, International publication No. WO2011/068157, Japanese patent laid-open No. 19056 (resin hardener, resin, compound), Japanese patent application laid-open No. WO 2011-1903), Curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) and/or a resin layer. The resin layer may be formed by using a known method and apparatus for forming a resin layer.
These resins are dissolved in a solvent such as MEK (methyl ethyl ketone), toluene, or the like to prepare a resin solution, and the prepared resin solution is applied onto the extremely thin copper layer, or the heat-resistant layer, the rust-preventive layer, or the chromate coating layer, or the silane coupling agent layer by, for example, a roll coating method, followed by heating and drying as necessary to remove the solvent, thereby bringing the resultant into a B-stage state. For example, the drying may be performed by using a hot air drying oven, and the drying temperature may be 100 ℃ or higher and 250 ℃ or lower, preferably 130 ℃ or higher and 200 ℃ or lower.
The carrier-attached copper foil (resin-attached carrier-attached copper foil) provided with the resin layer is used in the following form: after the resin layer is stacked on a substrate, the entire body is thermally press-bonded to thermally cure the resin layer, and then the carrier is peeled off to expose the extremely thin copper layer (of course, the surface on the intermediate layer side of the extremely thin copper layer is exposed), and a predetermined wiring pattern is formed on the exposed surface.
The use of the copper foil with the resin-attached carrier can reduce the number of prepreg materials used in the production of a multilayer printed wiring board. Further, the resin layer can be made thick enough to ensure interlayer insulation, and the copper-clad laminate can be manufactured without using any prepreg material. In this case, the surface of the substrate may be coated with an insulating resin to further improve the surface smoothness.
In addition, without using the prepreg material, there are the following advantages: the method is economically advantageous in that the material cost of the prepreg is saved and the lamination step is simplified, and furthermore, the thickness of the multilayer printed wiring board to be manufactured is reduced by not including the thickness of the prepreg, thereby enabling the manufacture of an extremely thin multilayer printed wiring board having a single-layer thickness of 100 μm or less.
The thickness of the resin layer is preferably 0.1 μm or more and 80 μm or less. If the thickness of the resin layer is less than 0.1 μm, the adhesion is lowered, and when the copper foil with the resin-attached carrier is laminated on a base material provided with an inner layer material without interposing a prepreg material, it may be difficult to secure interlayer insulation with a circuit of the inner layer material.
On the other hand, if the thickness of the resin layer is more than 80 μm, it is difficult to form a resin layer of a target thickness by 1 coating step, which consumes excessive material cost and man-hours, and is thus economically disadvantageous. Further, the formed resin layer is poor in flexibility, and therefore cracks and the like are likely to occur during handling, and when thermocompression bonding is performed with the inner layer material, excess resin flows and smooth lamination is difficult in some cases.
Further, as another product form of the copper foil with the resin-attached carrier, a copper foil with a resin in which no carrier is present can be produced by coating the extra thin copper layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer with a resin layer to be in a semi-cured state and then peeling off the carrier.
The printed wiring board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" includes the printed wiring board, and the printed circuit board on which the electronic components are mounted.
Further, an electronic device may be manufactured using the printed wiring board on which electronic components are mounted, or an electronic device may be manufactured using the printed circuit board on which electronic components are mounted. Hereinafter, some examples of the steps of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described. In addition, a printed wiring board can be produced similarly when the surface-treated copper foil of the present invention is used as an extremely thin copper layer of a copper foil with a carrier.
In one embodiment of the method for manufacturing a printed wiring board of the present invention, the method includes the steps of: preparing the copper foil with a carrier and the insulating substrate of the present invention; laminating the copper foil with carrier and an insulating substrate; the copper foil with carrier and the insulating substrate are laminated so that the extremely thin copper layer side faces the insulating substrate, the carrier of the copper foil with carrier is peeled off to form a copper-clad laminate, and then a circuit is formed by any one of a semi-additive method, a modified semi-additive method, a partial additive method, and a subtractive method. The insulating substrate may be provided with an inner layer circuit.
In the present invention, the semi-addition method refers to the following method: a thin electroless plating is performed on an insulating substrate or a copper foil seed layer to form a pattern, and then a conductor pattern is formed by electroplating and etching.
Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
removing the entire extremely thin copper layer exposed by peeling the carrier by etching using an etching solution such as an acid or by a plasma method;
providing a through hole or/and a blind hole (ブラインドビア) in the resin exposed by removing the extremely thin copper layer by etching;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
arranging an electroless plating layer on the resin and the area containing the through hole or/and the blind hole;
disposing a plating inhibitor on the electroless plating layer;
exposing the plating resist, and then removing the plating resist in a circuit area to be formed;
arranging an electrolytic plating layer on the circuit area to be formed from which the plating inhibitor is removed;
removing the plating inhibitor;
the electroless plated layer present in the region other than the circuit region to be formed is removed by rapid etching or the like.
In another embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
providing a through hole or/and a blind hole in the ultra-thin copper layer exposed by peeling the carrier and the insulating resin substrate;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
removing the entire extremely thin copper layer exposed by peeling the carrier by etching using an etching solution such as an acid or by a plasma method;
providing an electroless plating layer on the resin exposed by removing the extremely thin copper layer by etching or the like and a region including the through hole or/and the blind via;
disposing a plating inhibitor on the electroless plating layer;
exposing the plating resist, and then removing the plating resist in a circuit area to be formed;
arranging an electrolytic plating layer on the circuit area to be formed from which the plating inhibitor is removed;
removing the plating inhibitor;
the electroless plated layer present in the region other than the circuit region to be formed is removed by rapid etching or the like.
In another embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
providing a through hole or/and a blind hole in the ultra-thin copper layer exposed by peeling the carrier and the insulating resin substrate;
removing the entire extremely thin copper layer exposed by peeling the carrier by etching using an etching solution such as an acid or by a plasma method;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
providing an electroless plating layer on the resin exposed by removing the extremely thin copper layer by etching or the like and a region including the through hole or/and the blind via;
disposing a plating inhibitor on the electroless plating layer;
exposing the plating resist, and then removing the plating resist in a circuit area to be formed;
arranging an electrolytic plating layer on the circuit area to be formed from which the plating inhibitor is removed;
removing the plating inhibitor;
the electroless plated layer present in the region other than the circuit region to be formed is removed by rapid etching or the like.
In another embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
removing the entire extremely thin copper layer exposed by peeling the carrier by etching using an etching solution such as an acid or by a plasma method;
providing an electroless plating layer on the surface of the resin exposed by removing the extremely thin copper layer by etching;
disposing a plating inhibitor on the electroless plating layer;
exposing the plating resist, and then removing the plating resist in a circuit area to be formed;
arranging an electrolytic plating layer on the circuit area to be formed from which the plating inhibitor is removed;
removing the plating inhibitor;
the electroless plated layer and the extremely thin copper layer present in the region other than the circuit region to be formed are removed by rapid etching or the like.
In the invention, the improved semi-addition method refers to the following method: a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, copper in the circuit forming portion is thickened by electrolytic plating, the resist is removed, and the metal foil other than the circuit forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.
Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using the modified semi-additive method, the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
arranging a through hole or/and a blind hole on the ultra-thin copper layer and the insulation substrate which are exposed by stripping the carrier;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
providing an electroless plating layer in the region containing the through hole or/and the blind hole;
disposing a plating inhibitor on the surface of the extremely thin copper layer exposed by peeling the carrier;
forming a circuit by electrolytic plating after the plating inhibitor is provided,
removing the plating inhibitor;
the extremely thin copper layer exposed by removing the plating resist is removed by rapid etching.
In another embodiment of the method for manufacturing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
providing a plating inhibitor on the extremely thin copper layer exposed by peeling the carrier;
exposing the plating resist, and then removing the plating resist in a circuit area to be formed;
arranging an electrolytic plating layer on the circuit area to be formed from which the plating inhibitor is removed;
removing the plating inhibitor;
the electroless plated layer and the extremely thin copper layer present in the region other than the circuit region to be formed are removed by rapid etching or the like.
In the present invention, the partial addition method refers to the following method: a printed wiring board is manufactured by applying a catalytic nucleus to a substrate having a conductor layer or a substrate having a through hole or a via hole as needed, etching the substrate to form a conductor circuit, providing a solder resist or a plating resist as needed, and then thickening the conductor circuit, the through hole or the via hole, etc. by electroless plating.
Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using a partial addition method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
arranging a through hole or/and a blind hole on the ultra-thin copper layer and the insulation substrate which are exposed by stripping the carrier;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
imparting a catalytic core to a region containing the through-holes or/and blind-holes;
providing a resist on the surface of the extremely thin copper layer exposed by peeling off the carrier;
exposing the resist to form a circuit pattern;
removing the extremely thin copper layer and the catalytic nuclei by etching using an etching solution such as an acid or a plasma method to form a circuit;
removing the resist;
providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the extra thin copper layer and the catalytic nuclei by etching using an etching solution such as an acid or by a plasma method;
and providing an electroless plating layer in a region where the solder resist or the plating resist is not provided.
In the present invention, the subtractive method means the following method: unnecessary portions of the copper foil on the copper-clad laminate are selectively removed by etching or the like to form a conductor pattern.
Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using a subtractive method, the method includes the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
arranging a through hole or/and a blind hole on the ultra-thin copper layer and the insulation substrate which are exposed by stripping the carrier;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
providing an electroless plating layer in the region containing the through hole or/and the blind hole;
an electrolytic plating layer is arranged on the surface of the electroless plating layer;
providing a corrosion inhibitor on the surface of the electrolytic plating layer or/and the extremely thin copper layer;
exposing the resist to form a circuit pattern;
removing the extremely thin copper layer, the electroless plating layer, and the electrolytic plating layer by etching using an etching solution such as an acid or by a plasma method, thereby forming a circuit;
and removing the resist.
In another embodiment of the method for manufacturing a printed wiring board of the present invention using a subtractive method, the method comprises the steps of:
preparing the copper foil with a carrier and the insulating substrate of the present invention;
laminating the copper foil with carrier and an insulating substrate;
laminating the copper foil with carrier and an insulating substrate, and peeling off the carrier of the copper foil with carrier;
arranging a through hole or/and a blind hole on the ultra-thin copper layer and the insulation substrate which are exposed by stripping the carrier;
carrying out glue residue removal treatment on the area containing the through hole or/and the blind hole;
providing an electroless plating layer in the region containing the through hole or/and the blind hole;
forming a mask on the surface of the electroless plating layer;
providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed;
providing a corrosion inhibitor on the surface of the electrolytic plating layer or/and the extremely thin copper layer;
exposing the resist to form a circuit pattern;
removing the extremely thin copper layer and the electroless plating layer by etching using an etching solution such as an acid or by a plasma method to form a circuit;
and removing the resist.
The step of arranging the through holes or/and the blind holes and the subsequent step of removing the glue residues are not required.
Here, a specific example of a 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.
First, as shown in fig. 1-a, a copper foil with a carrier (first layer) having an extra thin copper layer with a roughened layer formed on the surface thereof is prepared.
Then, as shown in fig. 1-B, a resist is applied to the roughened layer of the extremely thin copper layer, exposed, and developed, and the resist is etched into a predetermined shape.
Then, as shown in fig. 1-C, after the circuit plating layer is formed, the resist is removed, thereby forming a circuit plating layer of a prescribed shape.
Then, as shown in fig. 2-D, a resin layer is laminated by providing an embedded resin on the extra thin copper layer so as to cover the circuit plating layer (so as to bury the embedded circuit plating layer), and then another copper foil with a carrier (second layer) is bonded to the resin layer from the extra thin copper layer side.
Then, as shown in fig. 2-E, the carrier is peeled from the carrier-attached copper foil of the second layer.
Then, as shown in fig. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating layer to form a blind via.
Then, as shown in fig. 3G, copper is embedded in the blind via to form a via-fill.
Then, as shown in FIG. 3-H, a circuit plating layer is formed on the filled hole as shown in FIGS. 1-B and 1-C.
Then, as shown in fig. 3-I, the carrier is peeled from the carrier-attached copper foil of the first layer.
Then, as shown in fig. 4-J, the surfaces of the circuit plating layers within the resin layer are exposed by removing the extremely thin copper layers of both surfaces by rapid etching.
Then, as shown in fig. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. The printed wiring board using the carrier-attached copper foil of the present invention is produced through the above steps.
In the method for manufacturing a printed wiring board, the "extra thin copper layer" may be replaced with a carrier, the "carrier" may be replaced with an extra thin copper layer, a circuit may be formed on the surface of the carrier side of the copper foil with the carrier, and the circuit may be buried with a resin to manufacture a printed wiring board.
The other copper foil with carrier (second layer) may be the copper foil with carrier of the present invention, a conventional copper foil with carrier, or a general copper foil. Further, a 1-layer or multi-layer circuit may be formed on the circuit of the second layer shown in fig. 3-H, and these circuits may be formed by any of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method.
Since the printed wiring board is configured such that the circuit plating layer is embedded in the resin layer by the above-described method for manufacturing a printed wiring board, when an extremely thin copper layer is removed by rapid etching as shown in fig. 4-J, for example, the circuit plating layer is protected by the resin layer and retains its shape, and thus a fine circuit can be easily formed. Further, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the conduction of the circuit wiring is favorably suppressed. Therefore, a fine circuit is easily formed. In addition, as shown in fig. 4-J and 4-K, when the extremely thin copper layer is removed by rapid etching, the exposed surface of the circuit plating layer is recessed from the resin layer, so that bumps are easily formed on the circuit plating layer, and copper pillars are easily formed thereon, thereby improving the manufacturing efficiency.
The embedding resin may be a known resin or a prepreg. For example, BT (bismaleimide triazine) resin, a prepreg made of a glass cloth impregnated with BT resin, an ABF film or ABF manufactured by kaomokoku corporation, wozhisu fine chemicals (kaomosu ファインテクノ) can be used. The resin layer and/or the resin and/or the prepreg described in the present specification may be used as the embedding resin.
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. The copper foil with a carrier used for the first layer is supported by the substrate or the resin layer, and hence wrinkles are less likely to occur, which is advantageous in that productivity is improved. In addition, various substrates or resin layers can be used as long as they exhibit the effect of supporting the copper foil with carrier used for the first layer. For example, the substrate or the resin layer may be a carrier, a prepreg, or a resin layer described in the specification of the present application, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, or a foil of an organic compound.
The method for manufacturing a printed wiring board of the present invention may be a method for manufacturing a printed wiring board (coreless method) including the steps of: laminating the surface of the copper foil with a carrier of the present invention on the surface of the extra thin copper layer or the surface of the carrier and a resin substrate; providing at least one resin layer and a circuit on a surface of the copper foil with a carrier on a side of the surface of the extra thin copper layer laminated on the resin substrate or on a side opposite to the surface of the carrier; and peeling the carrier or the extra thin copper layer from the copper foil with carrier after the resin layer and the circuit are formed. As a specific example of the coreless method, a laminate (also referred to as a copper-clad laminate or a copper-clad laminate) is first produced by laminating the surface on the side of the extra thin copper layer or the surface on the side of the carrier of the copper foil with a carrier of the present invention and a resin substrate. Then, a resin layer is formed on the surface of the copper foil with a carrier on the surface of the ultra-thin copper layer to be laminated with the resin substrate or on the opposite side of the surface of the carrier. Further, another copper foil with carrier may be laminated on the resin layer formed on the side of the carrier or the side of the extra thin copper layer, the another copper foil with carrier being laminated from the side of the carrier or the side of the extra thin copper layer. Alternatively, a laminate having a structure in which copper foils with carriers are laminated in the order of carrier/intermediate layer/extra thin copper layer or in the order of extra thin copper layer/intermediate layer/carrier on both surface sides of a resin substrate or resin or prepreg as a center, a laminate having a structure in which copper foils with carriers are laminated in the order of carrier/intermediate layer/extra thin copper layer/resin substrate or prepreg/carrier/intermediate layer/extra thin copper layer, a laminate having a structure in which carriers/intermediate layer/extra thin copper layer/resin substrate/carrier/intermediate layer/extra thin copper layer are laminated in the order of carrier/intermediate layer/extra thin copper layer, or a laminate having a structure in which extra thin copper layer/intermediate layer/carrier/resin substrate/carrier/intermediate layer/extra thin copper layer are laminated in the order of extra thin copper layer/intermediate layer/resin substrate/carrier/intermediate layer/extra thin copper layer A method for manufacturing the printed wiring board (coreless method). Then, another resin layer is provided on the surfaces of the extremely thin copper layers or carriers at both ends of the laminate exposed, and a copper layer or a metal layer is further provided, and then the copper layer or the metal layer is processed to form a circuit. Further, another resin layer may be provided on the circuit so as to embed the circuit therein. Further, the formation of such a circuit and a resin layer may be performed at least once (build-up method). Then, the extra thin copper layer of the copper foil with a carrier or the carrier is separated from the carrier or the extra thin copper layer of the thus formed laminate (hereinafter also referred to as a laminate B) to produce a coreless substrate. Further, the coreless substrate may be produced by using 2 sheets of the carrier-attached copper foil, and a laminate having a structure of extremely thin copper layer/intermediate layer/carrier/intermediate layer/extremely thin copper layer, a laminate having a structure of carrier/intermediate layer/extremely thin copper layer/intermediate layer/carrier, or a laminate having a structure of carrier/intermediate layer/extremely thin copper layer/carrier/intermediate layer/extremely thin copper layer may be produced, and the laminate may be used in the center. The coreless substrate can be produced by providing the resin layer and the circuit at one or more times on the surfaces of the extra thin copper layers or the carrier on both sides of the laminate (hereinafter also referred to as laminate a), and then separating the extra thin copper layers or the carrier of the copper foil with the carrier from the carrier or the extra thin copper layers after providing the resin layer and the circuit at one or more times. The laminate may also have other layers on the surface of the extremely thin copper layer, on the surface of the carrier, between the carrier and the carrier, between the extremely thin copper layer and the extremely thin copper layer, and between the extremely thin copper layer and the carrier. The other layer may be a resin substrate or a resin layer. In the present specification, "surface of extremely thin copper layer", "surface of carrier", "surface of laminate" is a concept including a surface (outermost surface) of the extremely thin copper layer, carrier, and laminate when the extremely thin copper layer, carrier, and laminate have another layer on the surface of the extremely thin copper layer, the surface of the carrier, and the surface of the laminate. In addition, the laminate preferably has a structure of extremely thin copper layer/intermediate layer/carrier/intermediate layer/extremely thin copper layer. This is because, when a coreless substrate is manufactured using the laminate, the extremely thin copper layer is disposed on the coreless substrate side, and thus a circuit is easily formed on the coreless substrate by using a modified semi-additive method. In addition, the extra thin copper layer is easily removed because of its thin thickness, and a circuit is easily formed on the coreless substrate by using a semi-additive method after the extra thin copper layer is removed.
In the present specification, the "laminate" not particularly described as "laminate a" or "laminate B" means a laminate including at least laminate a and laminate B.
In the method for manufacturing a coreless substrate, the carrier-attached copper foil or a part or all of the end faces of the laminate (including the laminate a) are covered with a resin, whereby, in the case of manufacturing a printed wiring board by a build-up method, it is possible to prevent a chemical solution from penetrating between the intermediate layer or one carrier-attached copper foil and the other carrier-attached copper foil constituting the laminate, and it is possible to prevent the separation of the extra thin copper layer and the carrier or the corrosion of the carrier-attached copper foil due to the penetration of the chemical solution, and it is possible to improve the yield. As the "resin covering a part or all of the end face of the copper foil with a carrier" or "resin covering a part or all of the end face of the laminate" used herein, a resin usable for the resin layer or a known resin can be used. In the method for manufacturing a coreless substrate, at least a part of the outer periphery of the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the extra thin copper layer, or the laminated portion of one copper foil with carrier and another copper foil with carrier) may be covered with a resin or a prepreg when the copper foil with carrier or the laminated body is viewed in a plan view. The laminated body (laminated body a) formed by the method for manufacturing a coreless substrate may be formed by bringing a pair of copper foils with carriers into contact with each other so as to be separable. In addition, when the copper foil with carrier is viewed in a plan view, the entire outer periphery or the entire surface of the laminated portion of the copper foil with carrier or the laminated body (the laminated portion of the carrier and the extra thin copper layer, or the laminated portion of one copper foil with carrier and another copper foil with carrier) may be covered with a resin or a prepreg. In addition, the resin or prepreg is preferably larger than the copper foil with a carrier or the laminate or the laminated part of the laminate in a plan view, and the laminate having the following structure is preferably produced: the resin or prepreg is laminated on both surfaces of the copper foil with carrier or the laminate, and the copper foil with carrier or the laminate is sealed (wrapped) with the resin or prepreg. With this configuration, when the copper foil with carrier or the laminate is viewed in plan view, the laminated portion of the copper foil with carrier or the laminate is covered with the resin or the prepreg, and collision with another member in the lateral direction of the portion, that is, in the lateral direction with respect to the laminating direction can be prevented, and as a result, peeling between the carrier and the extra thin copper layer or the copper foil with carrier can be reduced during handling. Further, by covering the outer periphery of the copper foil with carrier or the laminated portion of the laminate with resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from penetrating into the interface of the laminated portion in the chemical solution treatment step, and it is possible to prevent the copper foil with carrier from being corroded or eroded. Further, when one copper foil with a carrier is separated from a pair of copper foils with a carrier of a laminate or when a carrier of a copper foil with a carrier and a copper foil (an extra thin copper layer) are separated, if a laminated portion of the copper foil with a carrier or the laminate (a laminated portion of the carrier and the extra thin copper layer, or a laminated portion of one copper foil with a carrier and another copper foil with a carrier) covered with a resin or a prepreg is firmly adhered by the resin or the prepreg, the laminated portion or the like may need to be removed by cutting or the like.
The laminate of the present invention may have 2 copper foils with a carrier of the present invention. Specifically, the copper foil with a carrier of the present invention may be laminated on the carrier side or the extra thin copper layer side of another copper foil with a carrier of the present invention or the extra thin copper layer side to form a laminate. Further, the laminate may be one obtained by directly laminating the carrier-side surface or the extra thin copper layer-side surface of the one carrier-attached copper foil and the carrier-side surface or the extra thin copper layer-side surface of the other carrier-attached copper foil via an adhesive, if necessary. Further, the carrier or the extra thin copper layer of one copper foil with a carrier and the carrier or the extra thin copper layer of the other copper foil with a carrier may be joined. Here, the term "joined" also includes a form in which the carrier or the extremely thin copper layer is joined to each other through the surface treatment layer when the carrier or the extremely thin copper layer has the surface treatment layer. In addition, a part or all of the end faces of the laminate may be covered with a resin.
The stacking of the carriers, the extra thin copper layers, and the copper foils with the carriers can be performed by, for example, the following method, in addition to the simple stacking.
(a) The metallurgical bonding method comprises the following steps: fusion welding (arc welding, TIG (tungsten-inert gas) welding, MIG (metal-inert gas) welding, resistance welding, seam welding, spot welding), crimping (ultrasonic welding, friction stir welding), brazing;
(b) the mechanical jointing method comprises the following steps: caulking, rivet joining (self-piercing rivet (セルフピアッシングリベット) joining, rivet joining), stapling (ステッチャー);
(c) the physical bonding method comprises the following steps: adhesive agent, (double-sided) adhesive tape
By laminating one carrier and the other carrier or the extremely thin copper layer by bonding a part or the whole of one carrier and a part or the whole of one carrier or a part or the whole of the extremely thin copper layer by using the above bonding method, a laminated body can be manufactured in which carriers are detachably brought into contact with each other or a carrier and an extremely thin copper layer. In the case where one carrier and the other carrier or the extremely thin copper layer are laminated by weakly bonding the one carrier and the other carrier or the extremely thin copper layer, the one carrier and the other carrier or the extremely thin copper layer can be separated without removing a bonding portion of the one carrier and the other carrier or the extremely thin copper layer. In addition, in the case where one carrier and the other carrier or the extremely thin copper layer are bonded relatively firmly, the bonded portion of the one carrier and the other carrier or the extremely thin copper layer is removed by cutting, chemical polishing (etching or the like), mechanical polishing or the like, whereby the one carrier and the other carrier or the extremely thin copper layer can be separated.
Further, the coreless printed wiring board can be produced by providing the laminate with the resin layer and the circuit at least once, and after forming the resin layer and the circuit at least once, peeling the extra thin copper layer or the carrier from the copper foil with a carrier of the laminate, and performing the above steps. Further, a resin layer and a circuit may be provided on one surface or both surfaces of the laminate.
The resin substrate, resin layer, resin, and prepreg used in the laminate may be the resin layer described in the present specification, or may include a resin, a resin curing agent, a compound, a curing accelerator, a dielectric substance, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like used in the resin layer described in the present specification. The carrier-attached copper foil or laminate may be smaller than the resin or prepreg or resin substrate or resin layer in a plan view. Further, the resin substrate, the resin layer, the resin, the prepreg, and the surface-treated copper foil of the present invention described above or below may be laminated to produce a copper-clad laminate. Further, the surface-treated copper foil of the copper-clad laminate is processed into copper wiring by etching or the like, whereby a printed wiring board can be manufactured.
The resin substrate is not particularly limited as long as it has properties applicable to a printed wiring board and the like, and for example, in the case of rigid PWBs, paper-based phenolic resins, paper-based epoxy resins, synthetic fiber cloth-based epoxy resins, glass cloth-paper composite-based epoxy resins, glass cloth-glass nonwoven fabric composite-based epoxy resins, glass cloth-based epoxy resins, and the like can be used, and in the case of FPCs, polyester films, polyimide films, LCP (liquid crystal polymer) films, fluororesin films, low dielectric constant polyimide films, COP (cycloolefin polymer) films, and the like can be used. In addition, 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 an LCP (liquid crystal polymer) film or a fluororesin film is used, the copper circuit is covered with the cover layer after the copper circuit is formed, whereby the film and the copper circuit are less likely to be peeled off, and peeling of the film and the copper circuit due to a decrease in peel strength can be prevented.
Further, since an LCP (liquid crystal polymer) film or a fluororesin film or a low dielectric constant polyimide resin film or a COP (cycloolefin polymer) resin film has a small dielectric loss tangent, a copper-clad laminate, a printed wiring board, and a printed wiring board using an LCP (liquid crystal polymer) film or a fluororesin film or a low dielectric constant polyimide resin film or a COP (cycloolefin polymer) resin film and the surface-treated copper foil of the present invention are suitable for use in high-frequency circuits (circuits using high-frequency transmission signals). The surface-treated copper foil of the present invention is also suitable for high-frequency circuit applications because the aspect ratio of the roughened particles is controlled to a predetermined shape. In the present specification, a polyimide resin having a dielectric loss tangent of 0.01 or less is referred to as a low-dielectric-constant polyimide resin. The dielectric loss tangent can be measured by the three-plate resonator method described in "copper-clad laminate for printed wiring board test method relative dielectric constant and dielectric loss tangent" JPCA-TM001-2007, Japan electronic Circuit Industrial Association, general Community. Further, a copper-clad laminate may be formed by laminating a copper foil and an insulating base material with an adhesive. The adhesive may be a known adhesive. In addition, a low dielectric constant adhesive is preferably used as the adhesive. In the present specification, an adhesive having a dielectric constant of 3.5 or less is referred to as a low dielectric constant adhesive. In the present specification, the values of the dielectric constant (base dielectric constant, substrate dielectric constant, dielectric constant of resin) and the dielectric loss tangent (base dielectric loss tangent, substrate dielectric loss tangent, dielectric loss tangent of resin) mean the values of the dielectric constant and the dielectric loss tangent at a signal frequency of 1 GHz.
The surface-treated copper foil or the copper foil with a carrier of the present invention is also suitable for a battery material such as a negative electrode collector of a secondary battery such as a lithium ion secondary battery. The surface-treated copper foil or the copper foil with a carrier of the present invention has the following advantages compared to the surface-treated copper foil or the copper foil with a carrier which is not controlled as described above, because the aspect ratio and the glossiness of the roughened particles are controlled to be within the predetermined ranges. The surface-treated copper foil or the copper foil with a carrier of the present invention has excellent adhesion to an active material. Further, since the roughening particles are less likely to fall off, contamination of manufacturing equipment by the roughening particles in a step of providing an active material on the surface of the surface-treated copper foil or the copper foil with a carrier can be reduced. In addition, for example, the surface-treated copper foil or the copper foil with a carrier of the present invention can be used as a current collector of a battery or a secondary battery, and an active material thin film is formed on the surface-treated copper foil or the copper foil with a carrier to produce an electrode. Finally, a battery or a secondary battery having the electrode as an electrode (either a positive electrode or a negative electrode) can be manufactured. The method for forming the active material thin film on the current collector is not particularly limited, and examples thereof include: CVD, sputtering, vapor deposition, sputtering, a method of coating a liquid containing an active material on a current collector and then drying the coated current collector, a plating method, or the like. Among these thin film forming methods, CVD method, sputtering method and vapor deposition method are particularly preferably used. Alternatively, an intermediate layer may be formed on the current collector, and an active material thin film may be formed on the intermediate layer. The surface-treated copper foil or the copper foil with a carrier of the present invention can be used for a known electrode, a known collector, and a known battery. Examples of known batteries include: lithium ion secondary batteries, all-solid-state secondary batteries, air batteries (lithium-air batteries, zinc-air batteries, and the like), sodium ion batteries, magnesium ion batteries, multivalent ion batteries, secondary batteries using a sulfur-based material for the positive electrode, secondary batteries using an organic material exhibiting redox activity for the positive electrode, nickel-cadmium batteries, manganese batteries (dry batteries), alkaline batteries (dry batteries), lithium batteries (dry batteries), and the like. Examples of the known electrode and the known collector include those used in the known battery.
[ examples ]
The following description will be made based on examples and comparative examples. The present embodiment is only an example, and the present invention is not limited to this example. That is, the present invention includes other forms and modifications.
Examples 1 to 34, comparative examples 1 to 13 and 15, and reference example 14
Various copper foils prepared under the conditions described in table 1 were prepared, and one surface was subjected to plating treatment as roughening treatment under the conditions described in tables 2 and 3. In reference example 14, as shown in table 3, treatment 1 and treatment 2 were performed in this order. The treatment 1 is a treatment in which the current density and plating time of the treatment 1-1 are performed, and then the current density and plating time of the treatment 1-2 are performed.
In examples 19 to 23, the metal foils described in table 1 were prepared as various carriers, and 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 under the following conditions. Then, the surface of the extremely thin copper layer was plated as a roughening treatment under the conditions described in tables 2 and 3.
EXAMPLE 19
< intermediate layer >
(1) Ni layer (Ni plating)
As for the carrier, 1000. mu.g/dm was formed by electroplating on a continuous plating line of a roll-to-roll type under the following conditions2The deposited amount of Ni layer. The plating conditions are specifically as follows.
Nickel sulfate: 270g/L to 280g/L inclusive
Nickel chloride: 35g/L or more and 45g/L or less
Nickel acetate: 10g/L to 20g/L inclusive
Boric acid: 30g/L to 40g/L inclusive
Gloss agent: saccharin, butynediol, and the like
Sodium lauryl sulfate: 55ppm or more and 75ppm or less
pH value: 4 to 6 inclusive
Bath temperature: 55 ℃ or higher and 65 ℃ or lower
Current density: 10A/dm2The following
(2) Cr layer (electrolytic chromate treatment)
Then, the Ni layer formed in (1) was washed with water and acid, and then, on a continuous plating line of roll-to-roll type, electrolytic chromate treatment was carried out under the following conditions to deposit an Ni layerIs at 11 mu g/dm2The amount of Cr layer deposited.
Potassium dichromate 1g/L to 10g/L, zinc 0g/L
pH value: 7 to 10 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 2A/dm2The following
< ultra thin copper layer >
Then, the surface of the Cr layer formed in (2) was washed with water and acid, and then, an extra thin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating under the following conditions on a continuous roll-to-roll plating line, thereby producing an extra thin copper foil with a carrier.
Copper concentration: 90g/L to 110g/L inclusive
Concentration of sulfuric acid: 90g/L to 110g/L inclusive
Chloride ion concentration: 50ppm or more and 90ppm or less
Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10ppm or more and 30ppm or less
Leveling agent 2 (amine compound): 10ppm or more and 30ppm or less
Further, the following amine compound was used as the leveling agent 2.
[ solution 2]
(in the formula, R1And R2Selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups. )
Temperature of the electrolyte: 50 ℃ or higher and 80 ℃ or lower
Current density: 100A/dm2The following
Linear velocity of electrolyte: 1.5m/sec or more and 5m/sec or less
EXAMPLE 20
< intermediate layer >
(1) Ni-Mo layer (Nickel-molybdenum alloy)
As for the carrier, 3000. mu.g/dm was formed by electroplating on a continuous plating line of a roll-to-roll type under the following conditions2The attached amount of Ni-Mo layer. The plating conditions are specifically as follows.
(liquid composition) nickel sulfate hexahydrate: 50g/dm3Sodium molybdate dihydrate: 60g/dm3And sodium citrate: 90g/dm3
(liquid temperature) 30 DEG C
(Current Density) 1A/dm2Above and 4A/dm2The following
(energization time) 3 to 25 seconds inclusive
< ultra thin copper layer >
Forming an extremely thin copper layer on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in example 19, except that the thickness of the extremely thin copper layer was 1.5 μm.
EXAMPLE 21
< intermediate layer >
(1) Ni layer (Ni plating)
An Ni layer was formed under the same conditions as in example 19.
(2) Organic layer (organic layer formation treatment)
Then, after the surface of the Ni layer formed in (1) is washed with water and acid, an aqueous solution containing CBTA (carboxybenzotriazole) at a liquid temperature of 40 ℃ and a pH of 5 at a concentration of 1g/L to 30g/L is sprayed on the surface of the Ni layer under the following conditions, and an organic material layer is formed by spraying for 20 seconds to 120 seconds.
< ultra thin copper layer >
Forming an extremely thin copper layer on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in example 19, except that the thickness of the extremely thin copper layer was set to 5 μm.
Examples 22 and 23
< intermediate layer >
(1) Co-Mo layer (cobalt molybdenum alloy)
As for the carrier, 4000. mu.g/dm was formed by electroplating on a continuous plating line of a roll-to-roll type under the following conditions2The amount of Co-Mo deposited. Plating ofThe coating conditions are specifically as follows.
(liquid composition) cobalt sulfate: 50g/dm3Sodium molybdate dihydrate: 60g/dm3And sodium citrate: 90g/dm3
(liquid temperature) 30 DEG C
(Current Density) 1A/dm2Above and 4A/dm2The following
(energization time) 3 to 25 seconds inclusive
< ultra thin copper layer >
Forming an extremely thin copper layer on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in example 19 except that the thickness of the extremely thin copper layer in example 22 was set to 3 μm and the thickness of the extremely thin copper layer in example 23 was set to 1 μm.
After the plating treatment (described in tables 2 and 3) as the roughening treatment, as described in table 5, the plating treatment and/or the silane coupling treatment for forming the heat-resistant layer and/or the rust-proof layer described below were performed for examples 1 to 18 and 24 to 34 and comparative examples 9 to 12 and 15. In addition, "Ni-Co", "Ni-Co (2)", "Ni-Co (3)", "Ni-P", "Ni-Zn (2)", "Ni-Zn (3)", "Ni-W", "chromate", and "silane coupling treatment" described in Table 5 refer to the following surface treatments.
The formation conditions of the heat-resistant layer 1 are as follows.
Heat-resistant layer 1
[ Ni-Co ]: nickel-cobalt alloy plating
The liquid composition is as follows: nickel 5g/L to 20g/L inclusive, cobalt 1g/L to 8g/L inclusive
pH value: 2 to 3 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 5A/dm2Above 20A/dm2The following
Coulomb quantity: 10As/dm2Above 20As/dm2The following
[ Ni-Co (2) ]: nickel-cobalt alloy plating
The liquid composition is as follows: nickel 5g/L to 20g/L inclusive, cobalt 1g/L to 8g/L inclusive
pH value: 2 to 3 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 5A/dm2Above 20A/dm2The following
Coulomb quantity: 35As/dm2Above and 50As/dm2The following
[ Ni-Co (3) ]: nickel-cobalt alloy plating
The liquid composition is as follows: nickel 5g/L to 20g/L inclusive, cobalt 1g/L to 8g/L inclusive
pH value: 2 to 3 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 5A/dm2Above 20A/dm2The following
Coulomb quantity: 25As/dm2Above 35As/dm2The following
[ Ni-P ]: nickel-phosphorus alloy plating
The liquid composition is as follows: nickel 5g/L to 20g/L inclusive, phosphorus 2g/L to 8g/L inclusive
pH value: 2 to 3 inclusive
Liquid temperature: 40 ℃ or higher and 60 ℃ or lower
Current density: 5A/dm2Above 20A/dm2The following
Coulomb quantity: 10As/dm2Above 20As/dm2The following
Heat-resistant layer 2
[ Ni-Zn ]: nickel-zinc alloy plating
In examples and comparative examples described in the column of heat-resistant layer 2 in table 5, heat-resistant layer 2 was formed on a copper foil on which heat-resistant layer 1 was provided. In comparative examples 9 to 12, the heat-resistant layer 2 was formed without providing the heat-resistant layer 1. The formation conditions of the heat-resistant layer 2 are as follows.
The liquid composition is as follows: nickel 2g/L to 30g/L inclusive, zinc 2g/L to 30g/L inclusive
pH value: 3 to 4 inclusive
Liquid temperature: 30 ℃ or higher and 50 ℃ or lower
Current density: 1A/dm2Above and 2A/dm2The following
Coulomb quantity: 1As/dm2Above and 2As/dm2The following
[ Ni-Zn (2) ]: nickel-zinc alloy plating
The liquid composition is as follows: nickel 2g/L to 30g/L inclusive, zinc 2g/L to 30g/L inclusive
pH value: 3 to 4 inclusive
Liquid temperature: 30 ℃ or higher and 50 ℃ or lower
Current density: 1A/dm2Above and 2A/dm2The following
Coulomb quantity: 3As/dm2Above and 4As/dm2The following
[ Ni-Zn (3) ]: nickel-zinc alloy plating
The liquid composition is as follows: nickel 2g/L to 30g/L inclusive, zinc 2g/L to 30g/L inclusive
pH value: 3 to 4 inclusive
Liquid temperature: 30 ℃ or higher and 50 ℃ or lower
Current density: 1A/dm2Above and 2A/dm2The following
Coulomb quantity: 2As/dm2Above and 3As/dm2The following
[ Ni-W ]: nickel-tungsten alloy plating
The liquid composition is as follows: nickel 2g/L to 30g/L inclusive, tungsten 0.5g/L to 20g/L inclusive
pH value: 3 to 4 inclusive
Liquid temperature: 30 ℃ or higher and 50 ℃ or lower
Current density: 1A/dm2Above and 2A/dm2The following
Coulomb quantity: 1As/dm2Above and 2As/dm2The following
Anti-rust layer
[ chromate ]: chromate treatment
A copper foil other than that of example 23 was further provided with a rust-preventive layer on the copper foil provided with the heat-resistant layer 1 and/or 2 or the copper foil not provided with the heat-resistant layer. The formation conditions of the rust preventive layer were as follows.
The liquid composition is as follows: potassium dichromate is 1g/L to 10g/L inclusive, zinc is 0g/L to 5g/L inclusive
pH value: 3 to 4 inclusive
Liquid temperature: 50 ℃ or higher and 60 ℃ or lower
Current density: 0A/dm2Above and 2A/dm2The following (for immersion chromate treatment)
Coulomb quantity: 0As/dm2Above and 2As/dm2The following (for immersion chromate treatment)
Weather resistant layer
A weather-resistant layer is further formed on the copper foil on which the heat-resistant layers 1, 2 and the rust-preventive layer have been provided. The formation conditions were as follows.
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (examples 1 to 5, 12 to 17, 19 to 21, 23 to 26, comparative examples 1 to 13, and reference example 14), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (examples 6 to 10), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (example 11), and 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine (example 18) were applied as silane coupling agents having an amino group and dried to form a weather resistant layer. 2 or more of these silane coupling agents may be used in combination. Similarly, in comparative examples 1 to 12, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was applied and dried to form a weather-resistant layer.
The rolled copper foil is produced as follows. Copper ingots having the compositions shown in Table 1 were produced, hot rolled, and then subjected to annealing and cold rolling in a continuous annealing line of 300 ℃ to 800 ℃ repeatedly to obtain rolled sheets having a thickness of 1mm to 2 mm. The rolled sheet was annealed and recrystallized in a continuous annealing line at 300 ℃ to 800 ℃, and finally cold-rolled under the conditions shown in table 1 to the thickness shown in table 1 to obtain a copper foil. In the column of "type" in table 1, "fine copper" means fine copper defined in JIS H3100C 1100, and "oxygen-free copper" means oxygen-free copper defined in JIS H3100C 1020. In addition, "fine copper + Ag: 100ppm "means that 100ppm by mass of Ag is added to the refined copper.
As the electrolytic copper foil, an electrolytic copper foil HLP foil manufactured by JX metal corporation was used. In examples 19 to 23, a predetermined surface treatment, an intermediate layer, and an extremely thin copper layer were formed on the deposition surface (the surface opposite to the surface in contact with the electrolytic drum during the production of the electrolytic copper foil). Table 1 also shows the surface roughness Rz and the glossiness of the deposition surface side of the electrolytic copper foil.
Table 1 also shows the key points of the copper foil production steps before the surface treatment. The "high-gloss rolling" refers to a final cold rolling (cold rolling after final recrystallization annealing) performed according to the value of the oil film equivalent described. The term "usual rolling" means that the final cold rolling (cold rolling after the final recrystallization annealing) is performed according to the value of the oil film equivalent described.
The samples of the examples and comparative examples prepared in the above manner were subjected to various evaluations as follows.
Measurement of surface roughness (Rz):
the surface of the copper foil before the surface treatment including the roughening treatment was measured for ten-point average roughness using a contact roughness meter Surfcorder SE-3C manufactured by Osaka research corporation, Inc. in accordance with JIS B0601-1982. Under the conditions of a measurement reference length of 0.8mm, an evaluation length of 4mm, a critical value of 0.25mm, and a transfer speed of 0.1 mm/sec, the measurement position was changed in the direction perpendicular to the rolling direction (TD direction, width direction perpendicular to the foil passing direction in the case of electrolytic copper foil), 10 measurements were performed, and the average of the 10 measurements was taken as the value of the surface roughness (Rz).
Gloss degree:
according to JIS Z8741, the glossiness in the direction perpendicular to the rolling direction (TD, the direction perpendicular to the foil passing direction in the case of electrolytic copper foil) was measured at an incident angle of 60 degrees for each of the copper foil surface before the surface treatment including the roughening treatment and the copper foil surface after the surface treatment including the roughening treatment using a handheld gloss meter (ハンディーグロスメーター) PG-1 manufactured by japan electro-chromic industrial co. The measurement position was changed, the measurement of the gloss was performed 10 times, and the average value of 10 times was taken as the value of the gloss.
Visual recognizability:
the surface-treated side of the surface-treated copper foil was bonded to both sides of a polyimide film (manufactured by カネカ, thickness 25 μm (PIXEO (polyimide type: FRS)), a polyimide film with an adhesive layer for a copper-clad laminate, a PMDA (pyromellitic anhydride) polyimide film (PMDA-ODA (4,4' -diaminodiphenyl ether) polyimide film)), and the surface-treated copper foil was removed by etching (ferric trichloride aqueous solution) to prepare a sample film, and the roughened side of the copper foil was bonded to the polyimide film to prepare the sample film, and a printed matter (black circle having a diameter of 6 cm) was bonded to one side of the obtained resin layer, and the visual recognition of the printed matter was judged by allowing the resin layer to permeate from the opposite side, and the outline of the black circle of the printed matter was clear within a length range of 60% or more of the length, then rated "excellent"; the outline of the black circle is clear in a length range of 50% or more and less than 60% of the circumference, and evaluated as "o" (acceptable above); the black circle was evaluated as "Δ" (failed) in the range of 0% to less than 50% of the circumference in terms of sharp contour and deformed contour. In addition, in the case where the surface treatment is performed for providing a heat-resistant layer, a rust-preventive layer, a weather-resistant layer, and the like after or without roughening the surface of the copper foil, the surface of the surface-treated copper foil subjected to the surface treatment such as the heat-resistant layer, the rust-preventive layer, the weather-resistant layer, and the like is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer of a copper foil with a carrier, the above measurement is performed on the roughened surface of the extremely thin copper layer.
Color difference:
using a color difference meter MiniScan XE Plus manufactured by HunterLab corporation, according to JIS Z8730, the surface of the copper heat dissipating material was measured for a white plate (X of the white plate when a light source D65 was used and a field of view of 10 degrees was observed)10Y10Z10The tristimulus value of the color System (JIS Z87011999) is X10＝80.7、Y10＝85.6、Z10＝91.5，L*a*b*The object color of the white plate under the color system is L*＝94.14、a*＝-0.90、b*0.24) as a reference color. This is achieved byIn the color difference meter, the measured value of the color difference of the white plate is Δ E*ab is 0, and the measured value of the chromatic aberration when the measurement hole was covered with a black pocket (light trap) and measured was Δ E ab 94.14, and the chromatic aberration was corrected. Here, the color difference Δ E*ab is defined with the white plate set to 0 and black set to 94.14. Further, the color difference Δ E in accordance with JIS Z8730 in a minute region such as a copper circuit surface*ab can be measured using a known measurement apparatus such as a micro-spectrocolorimeter (model: VSS400, etc.) manufactured by nippon electro-chromatic industries, ltd, or a micro-spectrocolorimeter (model: SC-50 μ, etc.) manufactured by syzygium aromaticum, ltd, スガ, test.
Powder falling:
the powder falling was evaluated by sticking a transparent invisible tape to the surface of the surface-treated side of the surface-treated copper foil and by the discoloration of the tape due to the falling particles adhering to the adhesive surface of the tape when the tape was peeled off. The case where the adhesive tape was not discolored was-.
Peel strength (adhesive strength):
the surface of the surface-treated side of the surface-treated copper foil was laminated on a polyimide film (thickness 25 μm, ユーピレックス manufactured by yu ken corporation) { ユーピレックス (registered trademark) -VT, BPDA (biphenyltetracarboxylic dianhydride) -based (BPDA-PDA (p-phenylenediamine) -based) polyimide resin substrate }, and then the normal peel strength was measured by using a tensile tester オートグラフ 100 according to IPC-TM-650. Further, the surface-treated copper foil having a normal peel strength of 0.5N/mm or more is a surface-treated copper foil that can be used for a build-up substrate.
Further, the lamination conditions of the surface-treated copper foil and the polyimide film were those recommended by the manufacturer of the polyimide film. In examples 19 to 23, the surface of the surface-treated side of the surface-treated copper foil was laminated on a polyimide film (thickness 25 μm, ユーピレックス manufactured by yu ken corporation) { ユーピレックス (registered trademark) -VT, BPDA (biphenyltetracarboxylic dianhydride) based (BPDA-PDA (p-phenylenediamine) based) polyimide resin substrate }, and then the carrier was peeled off, and copper plating was performed so that the thickness of the carrier and the extra thin copper layer laminated on the polyimide film became 12 μm, and then the peel strength was measured. In addition, in the case where the surface treatment is performed for providing a heat-resistant layer, a rust-preventive layer, a weather-resistant layer, and the like after or without roughening the surface of the copper foil, the surface of the surface-treated copper foil subjected to the surface treatment such as the heat-resistant layer, the rust-preventive layer, the weather-resistant layer, and the like is subjected to the above measurement. In the case where the surface-treated copper foil is an extremely thin copper layer of a copper foil with a carrier, the above measurement is performed on the roughened surface of the extremely thin copper layer.
Height of coarsened particles:
the height of the roughened particles of the roughened layer from the surface of the copper foil (the height of the layer) was measured on a photograph taken with a transmission electron microscope. Specifically, as shown in fig. 5a, a cross section of the copper foil including the surface of the copper foil and the roughened layer, which is parallel to the thickness direction, is photographed using a transmission electron microscope, and a cross-sectional observation photograph is obtained. Next, as shown in fig. 5b, which is an enlarged photograph of the roughened particles in fig. 5a, a straight line 1 is drawn from the tip of the roughened particle to the surface of the copper foil so that the length of the roughened particle in the cross-sectional observation photograph is maximized, and the straight line passes through the roughened particle and intersects the surface of the copper foil at the boundary portion between the roughened particle and the copper foil. In addition, regarding the coarsened particles on which the deposition has occurred, the entirety of the coarsened particles on which the deposition has occurred is regarded as one coarsened particle, and a straight line 1 is drawn for the coarsened particles on which the deposition has occurred (on which the build-up has occurred). Next, the length of a straight line 1 from the tip of the roughened particle to the surface of the copper foil was defined as the height of the roughened particle. When the boundary between the copper foil and the roughening particles is observed on the cross-sectional observation photograph, the boundary between the copper foil and the roughening particles is regarded as the copper foil surface of the boundary portion between the roughening particles and the copper foil.
In addition, when the boundary between the copper foil and the roughening particles is not observed in the cross-sectional observation photograph, as shown in fig. 5c, the starting point of one convex portion of the roughening particles (one point at the bottom of the roughening particles) and the starting point of the other convex portion of the roughening particles (another point at the bottom of the roughening particles) are connected to form a straight line, which is referred to as a straight line 2, and the straight line 2 is regarded as the copper foil surface at the boundary portion between the roughening particles and the copper foil. The height of one coarsening particle (the height of the build-up layer) is, for example, the length of the portion shown in fig. 5b or fig. 5 c.
Arbitrary 10 coarse particles were measured, and the average value was taken as the height of the coarse particles (average value of 10 particles).
Coarseness of coarsened particles:
the coarseness of the coarsened particles forming the coarsened particle layer was measured on a photograph taken by a transmission electron microscope. Specifically, as shown in fig. 5a, a cross section of the copper foil including the surface of the copper foil and the roughened layer, which is parallel to the thickness direction, is photographed using a transmission electron microscope, and a cross-sectional observation photograph is obtained. Next, as shown in fig. 5c, the starting point of one convex portion of the roughened particle (one point at the bottom of the roughened particle) and the starting point of the other convex portion of the roughened particle (another point at the bottom of the roughened particle) are connected to form a straight line, which is denoted as a straight line 2, and the length of the straight line 2 is defined as the thickness of one roughened particle.
Arbitrary 10 coarse particles were measured, and the average value was taken as the coarseness of the coarse particles (average value of 10 particles).
Aspect ratio of coarsened particles:
the ratio of the height of the coarse particles (average of 10 particles) to the thickness of the coarse particles (average of 10 particles) was calculated as the aspect ratio of the coarse particles (height of coarse particles/thickness of coarse particles).
Productivity:
the finer the coarsening particles in the surface-treated coarsening plating layer are, the higher the height thereof is, the more easily the coarsening particles break when subjected to pressure, and the coarsening particles are easily dropped off during roller conveyance when conveyed on a long production line (スリットライン) cutting both ends in the width direction of the copper foil. The coarsened particles that have fallen off and adhered to the roller or the like are fixed as the copper foil is transported, resulting in defects such as indentations or dents in the transported copper foil.
Therefore, in a long line for cutting the edge of the copper foil, the copper foil transfer roller is often cleaned every several kilometers of the copper foil. Therefore, the productivity was evaluated based on the contamination state of the conveying rolls of the long production line. That is, if the degree of contamination is low, the frequency of cleaning the conveying roller can be reduced, and thus productivity is improved. After cleaning the transfer roller, the surface state of the roller after transferring the copper foil 5000m from the start of transferring the copper foil was observed. And the determination is made according to the following criteria.
Very good: the surface of the conveying roller is hardly adhered with coarsening particles, and the conveying roller is basically not polluted
O: the surface of the conveying roller was observed to have a state where a small amount of coarsened particles adhered
X: almost the entire surface of the conveying roller was observed to have coarse particles adhered thereto
Evaluation of copper foil wrinkles and the like due to lamination processing:
the surface-treated copper foils of the examples and comparative examples were each laminated on both surfaces of a polyimide resin (manufactured by カネカ (PIXEO (polyimide type: FRS)), a polyimide film with an adhesive layer for a copper-clad laminate, a PMDA (pyromellitic dianhydride) polyimide film (PMDA-ODA (4,4' -diaminodiphenyl ether) polyimide film)) having a thickness of 25 μm from the surface side having a roughened layer, and a protective film (manufactured by polyimide) having a thickness of 125 μm was further laminated on the surface of each surface-treated copper foil on the side opposite to the side on which the polyimide resin was laminated, in this state, that is, in the state of 5 layers of protective film/surface-treated copper foil/polyimide resin/surface-treated copper foil/protective film, bonding processing (laminating processing) was performed using a laminating roller while applying heat and pressure from the outer sides of the two protective films, and surface-treated copper foils were bonded to both sides of the polyimide resin. Then, after peeling the protective films on both surfaces, the surface of the surface-treated copper foil opposite to the side on which the polyimide resin was laminated was visually observed to confirm the presence or absence of wrinkles or streaks, and evaluated as "excellent" when no wrinkles or streaks were generated at all, and evaluated as "good" when only 1 wrinkle or streak was observed every 5m long on the copper foil, and evaluated as "good" when 2 wrinkles or streaks were observed every 5m long on the copper foil.
Evaluation of etching properties:
the surface-treated copper foil was bonded on both surfaces of a polyimide film (thickness 25 μm, ユーピレックス manufactured by yu ken) with a thermosetting adhesive layer { ユーピレックス (registered trademark) -VT, BPDA (biphenyltetracarboxylic dianhydride) based (BPDA-PDA (p-phenylenediamine) based) polyimide resin substrate } for lamination on the surface-treated surface side. In order to form a fine circuit pattern, the copper foil thickness needs to be uniform, and 12 μm is set as a reference copper foil thickness here. That is, in the case where the thickness is more than 12 μm, the thickness is reduced to 12 μm by electrolytic polishing. On the other hand, in the case where the thickness is less than 12 μm, the thickness is increased to 12 μm by the copper plating treatment. In the case where the surface-treated copper foil is an extra thin copper layer of a copper foil with a carrier, the copper foil with a carrier is bonded to both surfaces of the polyimide film with a thermosetting adhesive layer for lamination from the extra thin copper layer side, and then the carrier is peeled off, followed by copper plating treatment to increase the thickness of the copper foil with a carrier until the total thickness of the extra thin copper layer and the copper plating layer becomes 12 μm. On one surface side of the obtained double-sided laminate, a fine circuit pattern was printed on the copper foil glossy surface side of the laminate by laminating a dry film resist and an exposure step, and the unnecessary portion of the copper foil was subjected to etching treatment under the following conditions to form a fine circuit pattern having an L/S of 30/30 μm. Here, the circuit width is such that the bottom width of the circuit cross section is 30 μm.
(etching conditions)
The device comprises the following steps: spray type small etching device
Spraying pressure: 0.2MPa
Etching solution: ferric chloride aqueous solution (specific gravity 40 baume)
Liquid temperature: 50 deg.C
After the formation of the fine circuit pattern, the photosensitive resist film was peeled off by immersing the substrate in a 45 ℃ NaOH aqueous solution for 1 minute.
For the fine pattern circuit sample obtained above, using a scanning electron microscope S4700 manufactured by hitachi high and new technology corporation (hitachi ハイテクノロジーズ), when the circuit bottom portion was observed at a magnification of 5000 times, each of 10 observed portions was expressed as "excellent" when no etching residue was present at the circuit bottom portion, 10 observed portions were expressed as "o" when 1 etching residue was visible, and 10 observed portions were expressed as "Δ" when 2 or more etching residues were visible.
In addition, in the case where the surface of the copper foil or the surface of the extra thin copper layer of the copper foil with a carrier is subjected to surface treatment for providing a heat-resistant layer, a rust-preventive layer, a weather-resistant layer, or the like after being subjected to roughening treatment or not, the surface of the surface-treated copper foil subjected to surface treatment such as the heat-resistant layer, the rust-preventive layer, the weather-resistant layer, or the like is subjected to the above measurement.
Tables 1 to 5 show the production conditions, evaluation results, and the like of examples and comparative examples.
[ Table 1]
Examples 19 to 23 show carriers of copper foils with carriers.
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
(evaluation results)
In examples 1 to 34, the aspect ratio of the roughening particles (height of the roughening particles/thickness of the roughening particles) in the roughening-treated layer satisfied any one or more of the following (1) and (2).
(1) The aspect ratio of the coarsened particles is 3 or less,
(2) satisfies any one of the following (2-1) and (2-2),
(2-1) when the height of the coarse particles is more than 500nm and 1000nm or less, the aspect ratio of the coarse particles is 10 or less,
(2-2) when the height of the coarse particles is 500nm or less, the aspect ratio of the coarse particles is 15 or less.
In examples 1 to 34, the glossiness was 70% or less.
Therefore, examples 1 to 34 satisfactorily suppress the separation of the roughening particles in the roughening particle layer provided on the surface of the copper foil, and satisfactorily suppress the formation of wrinkles and streaks when the copper foil is bonded to a resin.
Comparative examples 1 to 7 and 15 did not satisfy either of (1) and (2), and therefore had poor powder falling properties.
In comparative examples 8 to 13, the gloss was over 70%, and the occurrence of wrinkles and streaks at the time of bonding with the resin could not be satisfactorily suppressed.
In addition, the present application claims that the entire contents of japanese patent application No. 2017-70418, which was filed on 31/3/2017, is incorporated into the present specification on the basis of its priority.
Claims (29)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-073216 | 2017-03-31 | ||
| JP2017073216 | 2017-03-31 | ||
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| CN201810290908.9A Active CN108696987B (en) | 2017-03-31 | 2018-03-30 | Surface-treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device |
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| CN112969824B (en) * | 2018-11-19 | 2024-10-18 | 三井金属矿业株式会社 | Surface treated copper foil, copper foil with carrier, copper clad laminate and printed circuit board |
| US10581081B1 (en) | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
| CN111799437B (en) * | 2019-04-08 | 2021-07-09 | 宁德时代新能源科技股份有限公司 | Positive pole piece and sodium ion battery |
| TWI719698B (en) | 2019-06-12 | 2021-02-21 | 金居開發股份有限公司 | Advanced reverse treated electrodeposited copper foil and copper clad laminate using the same |
| JP2021088099A (en) * | 2019-12-03 | 2021-06-10 | Ｊｘ金属株式会社 | Molding method of metal resin composite material, metal resin composite component, and manufacturing method of the same |
| CN113416986B (en) * | 2021-07-08 | 2022-10-11 | 江西柔顺科技有限公司 | Method for producing electrolytic copper foil |
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| CN103946425A (en) * | 2012-11-09 | 2014-07-23 | Jx日矿日石金属株式会社 | Surface-treated copper foil and laminate using same |
| JP2014156626A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Copper fine particle dispersion solution, manufacturing method of sintered conductor, and manufacturing method of conductor connection member |
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| JP5475897B1 (en) * | 2012-05-11 | 2014-04-16 | Ｊｘ日鉱日石金属株式会社 | Surface-treated copper foil and laminate using the same, copper foil, printed wiring board, electronic device, and method for manufacturing printed wiring board |
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| JP5885790B2 (en) * | 2013-08-20 | 2016-03-15 | Ｊｘ金属株式会社 | Surface treated copper foil and laminated board using the same, copper foil with carrier, printed wiring board, electronic device, method for manufacturing electronic device, and method for manufacturing printed wiring board |
| JP6083619B2 (en) * | 2015-07-29 | 2017-02-22 | 福田金属箔粉工業株式会社 | Processed copper foil for low dielectric resin substrate, copper-clad laminate and printed wiring board using the treated copper foil |
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| CN105682375A (en) * | 2012-03-26 | 2016-06-15 | Jx日矿日石金属株式会社 | Copper foil with carrier, method of manufacturing the same, copper foil with carrier for printed wiring board, and printed wiring board |
| CN104364426A (en) * | 2012-06-11 | 2015-02-18 | Jx日矿日石金属株式会社 | Surface-treated copper foil and laminated sheet, printed wiring board, and electronic device using same, as well as method for producing printed wiring board |
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| JP2014156626A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Copper fine particle dispersion solution, manufacturing method of sintered conductor, and manufacturing method of conductor connection member |
| CN106455341A (en) * | 2015-08-06 | 2017-02-22 | Ｊｘ金属株式会社 | Carrier-Attached Copper Foil, Laminate, Method For Producing Printed Wiring Board, And Method For Producing Electronic Device |
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| CN108696987A (en) | 2018-10-23 |
| CN108697006A (en) | 2018-10-23 |
| CN108697006B (en) | 2021-07-16 |
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