WO2017138338A1 - 表面処理銅箔及びこれを用いて製造される銅張積層板 - Google Patents
表面処理銅箔及びこれを用いて製造される銅張積層板 Download PDFInfo
- Publication number
- WO2017138338A1 WO2017138338A1 PCT/JP2017/002145 JP2017002145W WO2017138338A1 WO 2017138338 A1 WO2017138338 A1 WO 2017138338A1 JP 2017002145 W JP2017002145 W JP 2017002145W WO 2017138338 A1 WO2017138338 A1 WO 2017138338A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper foil
- layer
- silane
- insulating substrate
- roughened
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 239000011889 copper foil Substances 0.000 title claims abstract description 178
- 239000000758 substrate Substances 0.000 claims abstract description 140
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 41
- 229910000077 silane Inorganic materials 0.000 claims abstract description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000011282 treatment Methods 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 12
- -1 styryl silane Chemical compound 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 230000002265 prevention Effects 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 claims description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 45
- 238000007788 roughening Methods 0.000 abstract description 45
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 188
- 238000000034 method Methods 0.000 description 35
- 238000007747 plating Methods 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 25
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 230000008569 process Effects 0.000 description 16
- 239000002738 chelating agent Substances 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- 239000012792 core layer Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000032798 delamination Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- FFDNCLQDXZUPCF-UHFFFAOYSA-N [V].[Zn] Chemical compound [V].[Zn] FFDNCLQDXZUPCF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-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
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006855 networking Effects 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—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
- 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
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Definitions
- the present invention relates to a surface-treated copper foil that achieves a high level of both reflow heat resistance and transmission characteristics while ensuring sufficient adhesion to an insulating substrate, and a copper-clad laminate manufactured using the same. is there.
- Copper clad laminates are used for such information communication devices.
- the copper clad laminate is produced by heating and pressing an insulating substrate (resin substrate) and a copper foil.
- a resin with excellent dielectric properties must be used for an insulating substrate that constitutes a copper clad laminate for high frequencies, but a resin with a low relative dielectric constant or dielectric loss tangent has a polarity that contributes to adhesion to copper foil.
- the surface roughness of the copper foil serving as the conductive layer for the high-frequency copper-clad laminate be as small as possible.
- the reason why low profile of such a copper foil is required is that current becomes concentrated and flows on the surface portion of the copper foil as the frequency becomes high, so that the surface roughness of the copper foil increases, This is because the transmission loss tends to increase.
- a fine uneven surface (hereinafter simply referred to as an uneven surface) formed on the copper foil substrate by electrodeposition of roughened particles.
- an uneven surface formed on the copper foil substrate by electrodeposition of roughened particles.
- a roughened layer is formed and adhesion is improved by a physical effect (anchor effect).
- a surface-treated copper foil in which the level difference (surface roughness) of the surface roughness of the roughened layer is reduced, or a non-roughened smooth copper foil that is not subjected to a roughening treatment it is desirable to use Further, in order to ensure the adhesion of the copper foil having such a small surface roughness, it is desirable to form a silane coupling agent layer that forms a chemical bond between the copper foil and the insulating substrate.
- reflow heat resistance refers to heat resistance in a solder reflow process performed when a high-frequency circuit board is manufactured.
- the solder reflow process is a method of heating and soldering through a reflow furnace in a state where paste-like solder is adhered to the wiring of the circuit board and the contact of the electronic component.
- lead (Pb) -free solder used for electrical joints of circuit boards has been advanced.
- Pb-free solder has a higher melting point than conventional solder, and when applied to a solder reflow process, the circuit board is exposed to a high temperature of about 260 ° C., for example, compared to the case where conventional solder is used. It is necessary to have a high level of reflow heat resistance. Therefore, especially for copper foils used in such applications, it is a new challenge to achieve both high levels of reflow heat resistance and transmission characteristics while ensuring sufficient adhesion to the insulating substrate. It has become.
- the present applicant also relates to a surface-treated copper foil having a roughened surface on which at least one surface of the electrolytic copper foil has a projection of 1 to 5 ⁇ m formed from roughened particles. Proposed.
- the surface-treated copper foil described in Patent Document 2 has a relatively high height of protrusions, is not intended to improve reflow heat resistance, and is free to form a silane coupling layer. Although it has excellent adhesion to the film, it has a tendency to increase transmission loss due to increased surface roughness by attaching roughened particles. When applied to an insulating substrate, it is not possible to sufficiently cope with it, and there is a case where sufficient reflow heat resistance cannot be obtained, and there is room for improvement.
- Patent Document 3 discloses a surface-treated copper foil for copper-clad laminate in which roughened particles are formed by a roughening process using copper-cobalt-nickel alloy plating.
- a copper foil is applied to a high-frequency circuit board, the contact area between the copper foil and the resin increases, so that good adhesion can be ensured, but the surface area of the copper foil becomes too large, so the transmission characteristics are Inferior, and in addition, no consideration is given to reflow heat resistance.
- Patent Document 4 discloses a copper foil whose transmission characteristics, adhesion, and heat resistance are improved by a copper roughening treatment. When such a copper foil is used, an improvement in transmission characteristics can be expected, but delamination occurs between the copper foil and the insulating substrate (resin substrate) under heating conditions around 260 ° C in the reflow test. It is not possible to demonstrate satisfactory characteristics.
- the surface-treated copper foil with an ultrathin primer resin layer is subjected to silane treatment in order to improve the adhesion between the resin and the copper foil, and the normal adhesion is improved.
- silane treatment when such a silane treatment is performed, the uniform treatment of silane generally tends to be insufficient, which adversely affects the heat resistance reflow property.
- Patent Document 6 discloses a copper foil for electromagnetic wave shielding in which a black or brown treatment layer made of fine roughened particles is provided on one surface of a copper foil.
- a black or brown treatment layer made of fine roughened particles is provided on one surface of a copper foil.
- electrolysis is performed in a bath to which a chelating agent such as trisodium citrate is added.
- a chelating agent such as trisodium citrate
- Patent Document 7 discloses a copper foil in which a copper fine-roughened particle treatment layer is applied to at least one surface of the copper foil.
- the roughening particles are refined by adding the chelating agent diethylenetriaminepentaacetic acid pentasodium to the roughening plating bath.
- the transmission loss characteristic is lowered due to the influence of fine irregularities on the surface, and the characteristic becomes insufficient.
- JP 2013-158935 A Japanese Patent No. 4833556 JP 2013-147688 A International Publication 2011/090175 Pamphlet International Publication No. 2006/134868 Pamphlet JP 2006-278881 A JP 2007-332418 A
- the present invention is compatible with high performance and high functionality of information communication equipment that increases the frequency in order to process high-capacity information at high speed, and provides an insulating substrate with excellent dielectric properties with low dielectric constant and dielectric loss tangent.
- An object of the present invention is to provide a surface-treated copper foil that achieves a high level of both reflow heat resistance and transmission characteristics while ensuring sufficient adhesion, and a copper-clad laminate produced using the surface-treated copper foil.
- the present inventors have measured along the uneven surface of the roughened layer with respect to the creeping length Db measured along the copper foil substrate surface in a cross section orthogonal to the copper foil substrate surface. It was found that the ratio Da / Db (hereinafter also referred to as “wire length ratio”) of the creepage length Da greatly affects the reflow heat resistance.
- the present inventors when performing a roughening treatment such as forming a roughened layer having a rough surface by electrodeposition of roughened particles on a copper foil substrate, the present inventors have found that the average height of the unevenness on the rough surface is low.
- the gist configuration of the present invention is as follows.
- a surface-treated copper foil in which a roughened layer is provided on a copper foil substrate, wherein the roughened layer has an uneven surface formed by roughened particles, and the copper foil base The ratio (Da / Db) of the creeping length (Da) measured along the rough surface of the roughened layer to the creeping length (Db) measured along the copper foil substrate surface in a cross section orthogonal to the body surface ) Is in the range of 1.05 to 4.00, the average height difference (H) of the unevenness on the uneven surface is in the range of 0.2 to 1.3 ⁇ m, and further directly on the roughened layer.
- the said surface-treated copper foil characterized by the said uneven
- the creepage length ratio (Da / Db) is in the range of 1.05 to 3.20, the average height difference (H) of the unevenness is in the range of 0.2 to 0.8 ⁇ m, and
- the manufacturing direction of copper foil means the longitudinal direction of a roll in the case of electrolytic copper foil, and means the rolling direction in the case of rolled copper foil.
- the creeping length ratio (Da / Db) is in the range of 1.05 to 1.60, the average height difference (H) of the irregularities is in the range of 0.2 to 0.3 ⁇ m,
- the surface-treated copper foil wherein the number of bubbles at the interface between the roughened layer and the insulating substrate is 1 or less on a 2.54 ⁇ m line in the width direction of the copper foil substrate.
- the surface-treated copper foil wherein a silane adhesion amount of the silane coupling agent layer is 0.0005 to 0.0120 mg / dm 2 .
- middle layer is comprised by at least 1 layer selected from the base layer containing Ni, the heat-resistant process layer containing Zn, and the antirust process layer containing Cr.
- the silane coupling agent layer is composed of epoxy silane, amino silane, vinyl silane, methacryl silane, acrylic silane, styryl silane, ureido silane, mercapto silane, sulfide silane and isocyanate silane.
- the said surface-treated copper foil which consists of at least 1 sort (s) selected from inside.
- a copper clad laminate produced using the surface-treated copper foil and having an insulating substrate on the surface of the surface-treated copper foil on the roughened layer side.
- the ratio of the interface length (Da ′) measured along the interface between the roughened layer and the insulating substrate to the creepage length (Db) measured along the copper foil substrate surface (Da ′ / Db) is in the range of 1.05 to 4.00, the average height difference (H ′) of the irregularities at the interface is in the range of 0.2 to 1.3 ⁇ m, and the roughened layer and the insulation
- a copper-clad laminate comprising a silane coupling agent layer having a silane adhesion amount of 0.0003 to 0.0300 mg / dm 2 directly or via an intermediate layer between the substrate and the substrate.
- the copper clad laminate described above, wherein the number of bubbles at the interface between the roughened layer and the insulating substrate is 2 or less on the 2.54 ⁇ m
- the present invention it is possible to cope with high-performance and high-performance information communication equipment that transmits high-capacity information at high speed, and it is sufficient to have an insulating substrate excellent in dielectric characteristics with low relative permittivity and dielectric loss tangent. It is possible to provide a surface-treated copper foil that ensures both reflow heat resistance and transmission characteristics at a high level while ensuring adhesion. Moreover, the copper clad laminated board manufactured using this surface treatment copper foil can be provided.
- FIG. 1 is sectional drawing which shows the state of the roughening layer which has a neck shape of this invention.
- the neck shape is a shape in which the root width of the roughened particles is narrower than the maximum width of the roughened particles, and the root of the roughened particles has a dent.
- FIG. 2B is a cross-sectional view showing a state of a conventional roughened layer.
- FIG. 2 is a cross-sectional view schematically showing the average height difference H of the unevenness constituting the uneven surface constituting the roughened layer. It is sectional drawing which shows typically the creeping length Da in the uneven
- FIG. 4A is a cross-sectional view showing the base line BL1 for measuring the average height difference H of the unevenness constituting the uneven surface constituting the roughened layer.
- FIG. 4B is a cross-sectional view similarly showing the base line BL2.
- FIG. 5 is a cross-sectional view schematically showing bubbles present at the interface between the roughened layer and the insulating substrate.
- FIG. 1A shows a cross-sectional structure when a roughened layer is formed on the surface of a copper foil constituting a typical surface-treated copper foil according to the present invention.
- the surface-treated copper foil of the present invention is mainly composed of a copper foil 110, a roughened layer 120, and a silane coupling agent layer (not shown). That is, in the present invention, a surface-treated copper foil is formed by forming a roughened layer 120 as a surface treatment on a copper foil 110 and further forming a silane coupling agent layer (not shown) as a surface treatment.
- the copper foil 110 can be appropriately selected from an electrolytic copper foil, an electrolytic copper alloy foil, a rolled copper foil, or a rolled same alloy foil according to the application.
- the roughened layer 120 is provided by performing a roughening process on the copper foil substrate 110, and the surface has fine irregularities with a substantially granular shape.
- copper electrodeposition is performed while generating hydrogen at a current density exceeding the limit current density, so that a so-called burnt plating state is formed, and granular electrodeposits are formed. Make a rough surface. In the present invention, such a fine uneven surface is simply referred to as an uneven surface.
- grains in this invention shall point out this granular electrodeposit.
- creeping length Da measured along the uneven
- the (line length) ratio Da / Db is in the range of 1.05 to 4.00.
- the line length ratio Da / Db may be in the range of 1.05 to 3.20, and the line length ratio Da / Db may be in the range of 1.05 to 1.60.
- the wire length ratio Da / Db is less than 1.05, the reflow heat resistance is lowered and satisfactory performance cannot be obtained.
- the line length ratio Da / Db is more than 4.00, the surface unevenness is excessively increased, so that the transmission loss is increased due to the skin effect and the transmission characteristics are deteriorated. Therefore, the line length ratio Da / Db is 1 The range was from .05 to 4.00. A method for measuring the line length ratio Da / Db will be described later.
- a method for producing a reflow heat test specimen will be described.
- An insulating substrate (base material) in which copper foil is laminated on both surfaces is used as a core layer.
- the core layer is etched with a copper (II) chloride solution or the like, and all the copper foil is dissolved and removed.
- a reflow test piece is prepared by laminating a prepreg layer made of an insulating material and a copper foil on both surfaces of an insulating substrate (base material) remaining after etching the core layer.
- the line length ratio Da / Db is less than 1.05, the area that is replicated by etching decreases, and as a result, the area where the insulating substrate (base material) and the prepreg layer are in contact with each other decreases. It is considered that a region with low adhesion is generated, and when heated, gas volatilized from the base material accumulates in the region between layers, and peeling is likely to occur.
- Patent Document 4 As a parameter for quantifying the roughened shape, a surface area ratio measured by a laser microscope is known as shown in Patent Document 4 (WO2011-090175).
- WO2011-090175 As a problem, for example, as shown in FIG. 1, when (a) roughening with a constricted shape 11 and (b) roughening without a constricted shape exist, in principle, the surface area of the laser microscope is perpendicular to the copper foil. Therefore, it is difficult to measure the difference in the presence or absence of the neck shape in FIGS. 1 (a) and 1 (b).
- Patent Document 4 when the surface area ratio is measured with a laser microscope as in Patent Document 4, the presence or absence of a wedge shape cannot be reflected in the measured value. Controlling the surface shape of the foil is inappropriate for this case.
- the aspect ratio shown in Patent Document 4 simply represents the ratio between the “height” and “width” of the roughened particles, and no constriction shape is taken into consideration.
- the interface between the roughened layer and the insulating substrate is formed.
- the interface length (Da ′) measured along the line tends to be slightly reduced due to pressure contact with the insulating substrate. For this reason, it is necessary that the line length ratio is maintained in the above range even after the insulating substrate is in close contact, and the cross section perpendicular to the copper foil base surface after the insulating substrate is in close contact with the copper foil base surface.
- the ratio (Da '/ Db) of the interface length (Da') measured along the interface between the roughened layer and the insulating substrate to the measured creepage length (Db) is 1.05-4. By making it be in the range of 00, the same effect as in the case of (Da / Db) can be obtained.
- the average height difference (corresponding to the average height of the roughened particles) H on the uneven surface of the copper foil is set in the range of 0.2 to 1.3 ⁇ m.
- the average height difference H of the unevenness on the uneven surface is less than 0.2 ⁇ m, the anchor effect is weak, so that sufficient adhesion between the copper foil and the insulating substrate cannot be obtained.
- the average height difference H of the unevenness on the uneven surface exceeds 1.3 ⁇ m, the unevenness on the surface becomes too large, and the transmission loss increases due to the skin effect.
- the average height difference H of the unevenness on the uneven surface may be in the range of 0.2 to 0.8 ⁇ m, and the average height difference H of the unevenness on the uneven surface may be in the range of 0.2 to 0.3 ⁇ m. Good.
- the unevenness difference H of the roughened layer is the insulating substrate.
- H ′ in the range of 0.2 to 1.3 ⁇ m, the same effect as in the case of H can be obtained.
- the concentration of the chelating agent in the roughening methods such as Reference 6 and Reference 7 Therefore, it has been found that Da / Db increases excessively when a large number of fine roughened particles are formed on the surface of the copper foil, resulting in a deterioration in transmission loss.
- the concentration of the chelating agent added to the plating bath is preferably in the range of 0.1 to 5 g / L.
- the reaction mechanism is that the chelating agent has a low concentration, and the overvoltage at the time of electrolysis lowers than the high concentration condition, so that the frequency of nucleation is reduced, the effect of miniaturization is moderately suppressed, and the size is moderate. It is inferred that roughened particles were formed.
- the chelating agent when the chelating agent is at a low concentration, the number of chelating molecules in the bath is small, so that metal ions with a lot of chelate coordination (such as Cu) and metal ions with no chelate coordination in the bath It becomes a mixed state, and particles with different precipitation modes are formed at the same time due to the difference in the coordination state of the chelate, resulting in a complicated particle shape having a constricted shape, and heat resistance and adhesion even in an appropriate Da / Db range However, it is thought that both have been achieved at a high level.
- the chelating agent when the chelating agent is at a low concentration, the growth in the height direction of the roughened particles is moderately suppressed, and the average height difference H of the unevenness falls within an appropriate range.
- Precipitation mode in the state where metal ions (such as Cu) with a lot of chelates coordinated and metal ions without chelates are mixed in the bath the orientation of the precipitation becomes random, and the growth in the height direction Is considered to be suppressed.
- the method of adding two types of chelating agents to a roughening bath was also effective as a method for appropriately controlling Da / Db.
- metals with different coordination states of the chelate are electrolyzed at the same time, and particles with different shapes are precipitated at the same time, so that the roughened particle shape becomes complicated and the anchor effect is easily exhibited. Inferred.
- the treatment time needs to be shortened.
- the current density is high, the amount of hydrogen gas generated on the cathode increases. It is presumed that the surface shape with moderately large irregularities can be obtained because the roughening deposition timing becomes discontinuous because the spots are not plated until the hydrogen is released from the cathode into the liquid.
- the present invention has a silane coupling agent layer formed on the roughened layer 120 with a silane adhesion amount of 0.0003 to 0.0300 mg / dm 2 directly or via an intermediate layer.
- a silane adhesion amount of the silane coupling agent constituting the silane coupling agent layer is less than 0.0003 mg / dm 2 , the reflow heat resistance is lowered.
- it exceeds 0.0300 mg / dm 2 the silane coupling agent layer becomes too thick, and the adhesion strength decreases on the contrary.
- the silane adhesion amount of the silane coupling agent constituting the silane coupling agent layer may be 0.0005 to 0.0120 mg / dm 2 .
- a silane coupling agent layer after apply
- the applied coupling agent layer is dried, the effect of the present invention can be fully exerted if water evaporates.
- the coating layer is heated and dried at 50 to 180 ° C., the reaction between the silane coupling agent and the copper foil is promoted. It is suitable.
- the silane coupling agent layer is preferably an epoxy silane, amino silane, vinyl silane, methacrylic silane, acrylic silane, styryl silane, ureido silane, mercapto silane, sulfide silane, or isocyanate silane. Contains any one or more.
- the concavo-convex surface of the present invention preferably has a number of constricted shapes. By having a large number of constricted shapes, a strong anchor effect is exhibited despite the fact that the roughening is fine, and the adhesiveness between the copper foil and the insulating substrate is increased and the heat resistance can be improved.
- the average height difference H of the concavo-convex is in the range of 0.2 to 1.3 ⁇ m and Da / Db is in the range of 1.4 to 4.0 as described above.
- the number of bubbles at the interface between the roughened layer and the insulating substrate is preferably 2 or less on the width of the substrate, for example, 2.54 ⁇ m.
- the roughening layer of the copper foil in the reflow test piece and the interface of the insulating substrate It was found that the influence of the number of bubbles was large.
- the bubble in this case refers to the area
- size is 1.0 micrometer or less with a major axis.
- the alcohol is added to the aqueous silane coupling agent solution.
- the alcohol include methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. It is considered that the addition of alcohol improves the dispersibility of silane molecules in the solution and improves the wettability to the resin by uniformly treating the roughened layer of the copper foil with the silane coupling agent.
- the molten resin gets wet well with the roughened layer, so that the filling property is improved, and the number of bubbles at the interface between the roughened layer and the substrate is reduced. Inferred. It is also effective to increase the time from treating the copper foil with an aqueous silane solution to drying it with warm air. By increasing the time from treatment with a silane aqueous solution to drying with warm air, the silane molecules are regularly oriented on the surface of the roughened layer of copper foil, improving the wettability to the resin, and as a result It is assumed that the number of bubbles at the interface between the roughened layer and the insulating substrate decreases. For example, in the case of silane treatment as introduced in Patent Document 4, the wettability of the resin with respect to the roughened layer is not considered, and the number of bubbles at the interface between the roughened layer and the insulating substrate tends to increase.
- the number of bubbles at the interface between the roughened layer of copper foil and the insulating substrate may be 2 or less on a 2.54 ⁇ m line in the width direction of the substrate.
- the number of bubbles may be 1 or less or 0 on the same line.
- the gas generated from the insulating substrate during the reflow test concentrates on the bubbles and reflow is likely to occur. Heat resistance (between the copper foil and the prepreg layer) tends to decrease.
- a base layer containing Ni As other embodiments, it is selected from a base layer containing Ni, a heat-resistant treatment layer containing Zn, and a rust prevention treatment layer containing Cr between the roughening layer 120 and the silane coupling agent layer. It may further have at least one intermediate layer.
- the base layer containing nickel (Ni) for example, copper (Cu) in the copper foil base 110 or the roughened layer 120 may diffuse to the insulating substrate side, causing copper damage and lowering adhesion. In this case, it is preferable to form between the roughening layer 120 and the silane coupling agent layer.
- the underlayer containing Ni contains at least one of nickel (Ni), nickel (Ni) -phosphorus (P), and nickel (Ni) -zinc (Zn). Of these, nickel-phosphorus is preferable from the viewpoint of suppressing the remaining nickel during etching of the copper foil when forming the circuit wiring.
- the heat-resistant treatment layer is made of, for example, zinc or an alloy containing zinc, that is, zinc (Zn) -tin (Sn), zinc (Zn) -nickel (Ni), zinc (Zn) -cobalt (Co), zinc (Zn ) -Copper (Cu), zinc (Zn) -chromium (Cr), and zinc (Zn) -vanadium (V), preferably an alloy containing at least one kind of zinc.
- zinc-vanadium is particularly preferable from the viewpoint of suppressing undercut during etching when forming circuit wiring.
- Heat resistance refers to the property that the adhesion strength between the surface-treated copper foil and the insulating substrate is less likely to decrease after the insulating substrate is laminated on the surface-treated copper foil and the resin is cured by heating. This is a characteristic different from reflow heat resistance.
- the antirust treatment layer containing Cr may be formed when it is necessary to further improve the corrosion resistance.
- the antirust treatment layer include a chromium layer formed by chromium plating and a chromate layer formed by chromate treatment.
- the base layer, the heat-resistant treatment layer, and the rust-proofing treatment layer may be formed in this order on the roughened layer. Any one layer or only two layers may be formed depending on the characteristics to be performed.
- the surface-treated copper foil of this invention for manufacture of a copper clad laminated board.
- the copper clad laminate has an insulating substrate on the surface of the surface-treated copper foil on the roughened layer side.
- Insulating substrates used for copper-clad laminates are thermosetting polyphenylene ether resins, thermosetting polyphenylene ether resins including polystyrene-based polymers, resin compositions containing triallyl cyanurate polymers and copolymers, methacrylic or acrylic Modified epoxy resin composition, phenol addition butadiene polymer, diallyl phthalate resin, divinylbenzene resin, polyfunctional methacryloyl resin, unsaturated polyester resin, polybutadiene resin, styrene-butadiene, styrene-butadiene / styrene-butadiene cross-linked polymer An insulating resin selected from the above is used.
- the surface-treated copper foil having a silane coupling agent layer and an insulating substrate may be produced by heat-pressing and adhering.
- coating a silane coupling agent on an insulated substrate, and making it adhere with a copper foil which has a rust prevention process layer on the outermost surface with a heat press also has an effect equivalent to this invention. .
- Roughening layer forming step A roughening layer having an uneven surface is formed on a copper foil by electrodeposition of roughening particles.
- a technique of reducing the overvoltage during electrolysis in order to reduce the nucleation frequency can be taken, and a specific example thereof is a low concentration of the chelating agent.
- a method can be employed in which the current density during the roughening treatment is increased to 70 to 90 A / dm 2 and the processing time is shortened.
- the concentration of the chelating agent added to the plating bath for the roughening treatment is suitably 0.1 to 5 g / L.
- chelating agents include DL-malic acid, sodium EDTA solution, sodium gluconate, and diethylenetriaminepentaacetic acid pentasodium (DTPA).
- DTPA diethylenetriaminepentaacetic acid pentasodium
- a technique in which metals having different coordination states of chelates can be electrolyzed at the same time can be taken.
- Specific examples thereof include two types of chelates in a roughening treatment bath. Adding an agent.
- An example is a combination of DL-malic acid and DTPA.
- the wettability of the roughened layer to the insulating substrate surface so that the number of bubbles at the interface between the roughened layer and the insulating substrate is 2 or less on the 2.54 ⁇ m line in the width direction of the copper foil substrate. It is possible to adopt a method for improving the above. For this purpose, for example, (i) silane coupling treatment is performed so that the silane coupling agent layer is uniformly formed on the roughened layer, and (ii) silane molecules in the silane coupling agent layer are regularly formed. There are means such as performing a silane coupling treatment so as to be oriented.
- a method of adding alcohol to a silane coupling agent aqueous solution and as a specific example of (ii), a roughened copper foil is treated with a silane aqueous solution and then dried with warm air. For example, a method of extending the time.
- the copper clad laminate of this embodiment is manufactured by the following process.
- (1) Production of surface-treated copper foil A surface-treated copper foil is produced according to the above (1) to (5).
- (2) Manufacturing (laminating) step of copper clad laminate The surface-treated copper foil and insulating substrate produced above are the surfaces of the silane coupling agent layer constituting the surface-treated copper foil facing the bonding surface of the insulating substrate. After being superposed, a copper clad laminate is produced by heating and pressurizing to bring them into close contact.
- the place mentioned above only showed the example of embodiment of this invention, and can make a various change in the range which does not deviate from the meaning of this invention.
- Example 1 A surface-treated copper foil was prepared under the following conditions on a copper foil substrate having a thickness of 18 ⁇ m and no roughening (surface roughness Rz was about 0.8 ⁇ m).
- substrate performs the roughening plating process 1 on the conditions of Table 1, and then follows the procedure of the roughening plating process 2 shown below. And a roughened layer was formed.
- Ni-containing foundation layer After the formation of the roughened layer on the surface of the copper foil substrate, the underlying layer (Ni) is formed on the roughened layer by electrolytic plating under the Ni plating conditions shown below. A deposit amount of 0.06 mg / dm 2 ) was formed.
- Ni plating conditions Nickel sulfate: 5.0 g / L as nickel metal Ammonium persulfate 40.0 g / L Boric acid 28.5g / L Current density 1.5 A / dm 2 pH 3.8 Temperature 28.5 ° C Time 1 second-2 minutes
- the rust-proofing layer (Cr adhesion amount: 0) is formed on the heat-resistant layer under the following chromium plating conditions. 0.02 mg / dm 2 ).
- chromium plating conditions (Chromium plating bath) Chromic anhydride CrO 3 2.5 g / L pH 2.5 Current density 0.5 A / dm 2 Temperature 15 ⁇ 45 °C Time 1 second-2 minutes
- Examples 2 to 18 The roughening plating treatment 1 was carried out in accordance with the contents of Table 1, the silane coupling agent treatment was carried out in accordance with the contents of Table 2, and the other treatments were carried out in the same manner as in Example 1.
- Comparative Examples 1-7 and 9-14 The roughening plating treatment 1 was carried out in accordance with the contents of Table 1, the silane coupling agent treatment was carried out in accordance with the contents of Table 2, and the other treatments were carried out in the same manner as in Example 1.
- the line length ratio Da / Db as described above is obtained by observing the cross section of each test piece processed by an ion milling device (manufactured by Hitachi, Ltd .: IM4000) using a scanning electron microscope (SEM: manufactured by Hitachi, Ltd .: SU8020). The measurement was performed according to the following procedure. The magnification was calculated from an observed image enlarged to 10000 times (the actual width of the visual field in the present image is 12.7 ⁇ m). The creeping length Da on the uneven surface of the roughened layer was measured by image analysis software Winroof (Mitani Corporation) as shown by the thick line in FIG. Note that the same measurement is possible using other image analysis software.
- the SEM magnification is preferably such that the width of the SEM image is in the range of 5 to 15 ⁇ m.
- the average height difference of the uneven surface was measured as follows. First, the observation magnification is increased to 200 times (the actual width of the visual field in the image is 63.5 ⁇ m), and the extending direction of the uneven surface and the horizontal direction of the screen are ⁇ 1 ° at an arbitrary position. Adjust to be in the range of. Next, the observation magnification is increased to 10,000 times (the actual width of the visual field in the present image is 12.7 ⁇ m), and the unevenness forming the uneven surface projected in the SEM image at an arbitrary position. Among these, the bottom position of the first recess having the bottom position serving as the lowest point position is defined as A point.
- the bottom position of the second recess having the bottom position serving as the lowest point position is defined as B point.
- a straight line connecting points A and B is defined as a base line BL1 (FIG. 4A).
- the bottom position that is the lowest point position among the unevenness forming the uneven surface at an arbitrary position The base line BL2 is drawn in parallel with the base line BL1 so as to pass through the bottom position of the third concave part having a height, and the distance from the base line BL2 to the apex of the convex part farthest in the vertical direction is measured as the height difference H. (FIG. 4B).
- the height difference was measured in each of the five visual fields, and the average value thereof was defined as the average height difference H.
- the number of bubbles at the interface between the roughened layer and the insulating substrate 42 was measured by the following procedure. First, using a press machine, press the insulating substrate 42 (prepreg layer) and the copper foil 43 under the standard pressing conditions recommended by the insulating substrate manufacturer to produce a laminate (in this case, the MEGTRON6 of Panasonic Corporation as the insulating substrate 42: Using R-5670, lamination was performed under a press temperature of 200 ° C., a press pressure of 35 kgf / cm 2, a press time of 160 minutes, and the cross section of the laminate processed by the ion milling apparatus was scanned.
- a press machine press the insulating substrate 42 (preg layer) and the copper foil 43 under the standard pressing conditions recommended by the insulating substrate manufacturer to produce a laminate (in this case, the MEGTRON6 of Panasonic Corporation as the insulating substrate 42: Using R-5670, lamination was performed under a press temperature of 200 ° C., a press pressure of 35 kgf / cm 2, a
- the actual width of the visual field in this image is 2.54 ⁇ m
- the interface between the roughened layer 43 and the insulating substrate 42 of the laminate was observed, as shown in FIG.
- the number of bubbles 41 existing at the interface between the roughened layer 43 and the insulating substrate 42 on the line having a width of 2.54 ⁇ m is measured at 10 locations, and the average value of the number of bubbles at 10 locations is roughened.
- the bubble in this case refers to a region where the insulating substrate is not filled at the interface between the roughened layer and the insulating substrate, and the size is 1.0 ⁇ m or less in the major axis. Is.
- Transmission characteristics (measurement of transmission loss at high frequency) After bonding each copper foil to the insulating substrate, a sample for measuring transmission characteristics was prepared, and the transmission loss in the high frequency band was measured.
- a commercially available polyphenylene ether-based insulating material (Megtron 6 manufactured by Panasonic Corporation) was used.
- the substrate for transmission loss measurement was adjusted to have a stripline structure, a conductor length of 400 mm, a conductor thickness of 18 ⁇ m, a conductor width of 0.14 mm, an overall thickness of 0.31 mm, and a characteristic impedance of 50 ⁇ .
- transmission loss at 10 GHz and 40 GHz was measured using a vector network analyzer E8363B (KEYSIGHT TECHNOLOGIES).
- the transmission loss measured when the conductor length was 400 mm and the value converted when the conductor length was 1000 mm was taken as the transmission loss measurement result, and the unit was dB / m.
- a value obtained by multiplying the value of the transmission loss measured at the conductor length of 400 mm by 2.5 was set as the measured value of the transmission loss.
- Table 3 As for the transmission characteristics, the transmission loss was less than 19.5 dB / m at 10 GHz, and the transmission loss was less than 66.0 dB / m at 40 GHz.
- Adhesion strength The adhesion strength between the surface-treated copper foil and the insulating substrate was measured.
- a commercially available polyphenylene ether substrate was used as the insulating substrate.
- the curing conditions for the insulating (resin) substrate were 210 ° C. and 1 hour.
- For adhesion strength use a universal material testing machine (Tensilon, manufactured by A & D Co., Ltd.) to bond the copper foil and the insulating substrate, and then etch the test piece into a 10 mm wide circuit wiring.
- the initial adhesion was determined to be acceptable when the peel strength was 0.4 kN / m or higher, and rejected when the peel strength was less than 0.4 kN / m.
- Reflow heat resistance between core layer and prepreg layer
- An insulating substrate having copper foil laminated on both sides is used as a core layer.
- the core layer is etched with a copper (II) chloride solution or the like to dissolve all the copper foil.
- a reflow test piece was prepared by laminating a prepreg layer, which is an insulating substrate, and a copper foil on both surfaces of the etched core layer. In this case, the size of the reflow test piece (between the core layer and the prepreg layer) was 100 mm ⁇ 100 mm.
- the prepared test piece is passed through a reflow furnace and passed 10 times at a top temperature of 260 ° C. for 10 seconds.
- “ ⁇ (pass)” indicates that no delamination occurred between the core layer and the prepreg layer
- the content of the reflow test conformed to JIS C-60068-2-58.
- Comparative Example 3 the reflow heat resistance was inferior because the line length ratios Da / Db and Da / Db 'were small and the amount of silane adhered was small.
- Comparative Example 4 the line length ratios Da / Db and Da ′ / Db were small, the average height differences H and H ′ of the unevenness on the uneven surface were low, and the adhesion amount was low because of the large amount of silane adhesion.
- Comparative Examples 5 to 7 the line length ratios Da / Db and Da / Db ′ are large, the average height differences H and H ′ are large, and in addition, the number of bubbles at the interface between the roughened layer and the insulating substrate is large. The reflow heat resistance was poor.
- Comparative Example 8 the line length ratios Da / Db and Da '/ Db were small, and the average height difference H of the unevenness on the uneven surface was low, so the adhesion strength was low.
- Comparative Examples 9 to 14 have large line length ratios Da / Db and Da ′ / Db. In particular, Comparative Examples 9 to 11 have high transmission loss due to high average height differences H and H ′ of the unevenness on the uneven surface, and thus transmission characteristics. Was inferior.
- the present invention it is possible to cope with high-performance and high-performance information communication equipment that transmits high-capacity information at high speed, and it is sufficient to have an insulating substrate excellent in dielectric characteristics with low relative permittivity and dielectric loss tangent. It is possible to provide a surface-treated copper foil that achieves a high level of both reflow heat resistance and transmission characteristics while ensuring adhesion, and to provide a copper-clad laminate manufactured using the surface-treated copper foil. It was.
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Abstract
Description
銅張積層板を構成する銅箔の絶縁基板に対する密着性を改善するために、銅箔基体上に、粗化粒子の電析により形成した微細な凹凸表面(以下、単に凹凸表面という。)をもつ粗面化層を形成し、物理的な効果(アンカー効果)により密着力を向上させるのが一般的である。凹凸表面の高低差(表面粗さ)を大きくすれば、密着力は向上するが、伝送損失は、前記の理由により増加してしまうにもかかわらず、現状では、銅箔基体上に形成した粗面化層の表面を、凹凸表面にして、密着力を確保することを優先し、凹凸表面にすることによるある程度の伝送損失の低下については容認されてきた。しかし、最近では、対応周波数が20GHz以上である次世代の高周波回路基板の開発が進んでおり、かかる基板では、従来以上に伝送損失の低減を図ることが望まれている。
特許文献5においては、極薄プライマ樹脂層付表面処理銅箔について樹脂と銅箔の密着性を向上させるためにシラン処理を実施しており、常態の密着性の改善が成されている。しかし、この様なシラン処理を実施した場合、一般にシランの均一処理が不十分になる傾向にあり耐熱リフロー性に対して悪影響を及ぼしてしまう。
(1)銅箔基体上に粗面化層が設けられてなる表面処理銅箔であって、該粗面化層は、粗化粒子により凹凸表面が形成されたものであり、該銅箔基体面と直交する断面において、前記銅箔基体面に沿って測定した沿面長さ(Db)に対する、前記粗面化層の凹凸表面に沿って測定した沿面長さ(Da)の比(Da/Db)が、1.05~4.00の範囲であり、前記凹凸表面における凹凸の平均高低差(H)が0.2~1.3μmの範囲であり、さらに前記粗面化層上に、直接、または中間層を介して0.0003~0.0300mg/dm2のシラン付着量で形成されたシランカップリング剤層を有していることを特徴とする表面処理銅箔。
(3)前記沿面長さの比(Da/Db)が1.05~3.20の範囲であり、前記凹凸の平均高低差(H)が0.2~0.8μmの範囲であり、且つ銅箔と絶縁基板を積層した際に前記銅箔基体上の前記銅箔の製造方向に垂直な方向である幅方向の2.54μmの線上において前記粗面化層と絶縁基板の界面の気泡数が2個以下上記表面処理銅箔。なお、銅箔の製造方向とは、電解銅箔の場合はロールの長手方向を意味し、圧延銅箔の場合は圧延方向を意味する。
(5)前記シランカップリング剤層のシラン付着量が、0.0005~0.0120mg/dm2である上記表面処理銅箔。
(7)前記シランカップリング剤層は、エポキシ系シラン、アミノ系シラン、ビニル系シラン、メタクリル系シラン、アクリル系シラン、スチリル系シラン、ウレイド系シラン、メルカプト系シラン、スルフィド系シランおよびイソシアネート系シランの中から選択される少なくとも1種からなる上記表面処理銅箔。
(8)上記の表面処理銅箔を用いて製造され、該表面処理銅箔の粗面化層側の面に、絶縁基板を有する銅張積層板。
(10)前記銅箔基体の幅方向の2.54μm線上において、粗面化層と絶縁基板との界面の気泡数が2個以下である上記の銅張積層板。
本発明の表面処理銅箔は、銅箔110、粗面化層120およびシランカップリング剤層(図示せず)で主に構成されている。すなわち、本発明においては、銅箔110上に、表面処理として粗面化層120を形成し、さらに表面処理としてシランカップリング剤層(図示せず)を形成したものを表面処理銅箔という。
粗面化層120は、銅箔基体110上に粗面化処理を施すことによって設けられ、表面が略粒状の微細な凹凸をなしている。当該粗面化処理においては、限界電流密度を上回る電流密度で水素発生を伴いながら銅電析を行うことにより、いわゆるヤケめっきの状態となり、粒状の電析物が形成されて、ミクロンオーダの微細な凹凸表面をなす。本発明において、このような微細な凹凸表面を単に凹凸表面という。また、本発明における粗化粒子とは、この粒状の電析物を指すものとする。
他にDa/Dbを適切に管理する方法として、従来は粉落ち等の不具合により用いられていない70~90A/dm2の電流密度で粗化粒子を形成することも有効である。但し処理時間が長いと粒子が鉛直方向に成長し過ぎて粉落ちしやすくなる為、処理時間は短くする必要がある。高電流密度とすると、カソード上における水素ガスの発生量が増加する。水素がカソードから液中へ離脱するまでの間はめっきできないスポットとなるために、粗化の析出のタイミングが不連続となり、結果凹凸が適度に多い表面形状が得られるものと推察される。
本発明の凹凸表面は多数のクビレ形状を有していることが好ましい。クビレ形状を多数有することにより、粗化が微細であるにもかかわらず、強力なアンカー効果が発現し、銅箔と絶縁基板の密着性が高まり耐熱性を向上させることができる。多数のクビレ形状を有する凹凸表面を形成するには、上述したように凹凸の平均高低差Hを0.2~1.3μmの範囲内とし、Da/Dbを1.4~4.0の範囲内に制御することにより、粗化層の輪郭長さが長くなり、結果としてクビレ形状を多く有する粗化形状を得ることができる。
ニッケル(Ni)を含有する下地層は、例えば銅箔基体110や粗面化層120中の銅(Cu)が、絶縁基板側に拡散し銅害が発生して密着性が低下することがある場合に、粗面化層120とシランカップリング剤層との間に形成することが好ましい。Niを含有する下地層は、ニッケル(Ni)、ニッケル(Ni)-りん(P)、ニッケル(Ni)-亜鉛(Zn)のうち少なくとも1種以上を含有する。このうち、回路配線形成時における銅箔エッチング時のニッケル残りを抑制できるという観点で好ましいのはニッケル-りんである。
上記の下地層、耐熱処理層及び防錆処理層は、これらの三層の全てを形成する場合には、粗面化層上に、この順序で形成してもよく、また、用途や目的とする特性に応じて、いずれか一層または二層のみを形成してもよい。
銅張積層板に用いる絶縁基板は、熱硬化性ポリフェニレンエーテル樹脂、ポリスチレン系重合体を含む熱硬化性ポリフェニレンエーテル樹脂、トリアリルシアヌレートの重合体や共重合体を含む樹脂組成物、メタクリル又はアクリル変性したエポキシ樹脂組成物、フェノール類付加ブタジエン重合体、ジアリルフタレート樹脂、ジビニルベンゼン樹脂、多官能性メタクリロイル樹脂、不飽和ポリエステル樹脂、ポリブタジエン樹脂、スチレン-ブタジエン、スチレン-ブタジエン・スチレン-ブタジエンの架橋ポリマーなどから選ばれる絶縁樹脂が用いられる。
銅張積層板を製造する場合には、シランカップリング剤層を有する表面処理銅箔と、絶縁基板を加熱プレスして密着させることによって製造すればよい。なお、絶縁基板上にシランカップリング剤を塗布し、最表面に防錆処理層を有する銅箔と加熱プレスによって密着させることにより作製された銅張積層板も、本発明と同等の効果を有する。
(1)粗面化層の形成工程
銅箔上に、粗化粒子の電析により、凹凸表面をもつ粗面化層を形成する。
線長比Da/Dbを制御するうえでは、(i)粗化粒子の大きさを適切に制御すること、(ii)形状の異なる粗化粒子が同時に析出し易くすること、が好ましい。
(i)の観点からは、例えば、核生成頻度を小さくするために電解時の過電圧を小さくする手法を採ることができ、その具体例としては、キレート剤を低濃度とすることが挙げられる。あるいは、粗化処理を行う際の電流密度を70~90A/dm2と高くし、処理時間を短くする手法を採ることもできる。
また、(ii)の観点からは、例えばキレートの配位状態が異なる金属が同時に電解されるようにする手法を採ることができ、その具体例としては、粗面化処理浴に2種類のキレート剤を添加することが挙げられる。例として、DL-りんご酸とDTPAとの組合せがある。
粗面化層上に、必要によりNiを含有する下地層を形成する。
(3)耐熱処理層の形成工程
粗面化層上または下地層上に、必要によりZnを含有する耐熱処理層を形成する。
(4)防錆処理層の形成工程
上記層を形成した銅箔を、必要により、pHが3.5未満のCr化合物を含有する水溶液に浸し、0.3A/dm2以上の電流密度でクロムめっき処理することによって、粗面化層上、下地層上または耐熱処理層上に防錆処理層を形成する。
(5)シランカップリング剤層の形成工程
粗面化層上、下地層上、耐熱処理層上または防錆処理層上に、シランカップリング剤層を形成する。
本実施形態の銅張積層板は、次のような工程で製造する。
(1)表面処理銅箔の作製
上記(1)~(5)に従い、表面処理銅箔を作製する。
(2)銅張積層板の製造(積層)工程
上記で作製した表面処理銅箔と絶縁基板とを、表面処理銅箔を構成するシランカップリング剤層の表面が絶縁基板の貼合せ面と向かい合うように重ね合わせた後、加熱・加圧処理して両者を密着させることによって、銅張積層板を製造する。
なお、上述したところは、本発明の実施形態の例を示したにすぎず、本発明の趣旨を逸脱しない範囲において種々の変更を加えることができる。
厚さ18μmの無粗化(表面粗さRzは約0.8μm)の銅箔基体に下記条件で表面処理銅箔を作製した。
(1)粗面化層の形成
銅箔基体の表面への粗面化処理は、表1の条件で粗面化めっき処理1を行い、次に下記に示す粗面化めっき処理2の手順で行い、粗面化層を形成した。
硫酸銅:銅濃度として13~72g/L
硫酸濃度:26~133g/L
液温:18~67℃
電流密度:3~67A/dm2
処理時間:1秒~1分55秒
銅箔基体の表面への粗面化層の形成後、粗面化層上に、下記に示すNiめっき条件で電解めっきすることにより下地層(Niの付着量0.06mg/dm2)を形成した。
<Niめっき条件>
硫酸ニッケル: ニッケル金属として5.0g/L
過硫酸アンモニウム40.0g/L
ほう酸28.5g/L
電流密度1.5A/dm2
pH 3.8
温度28.5℃
時間1秒~2分
下地層の形成後、この下地層上に、下記に示すZnめっき条件で電解めっきすることにより耐熱処理層(Znの付着量:0.05mg/dm2)を形成した。
<Znめっき条件>
硫酸亜鉛7水和物1~30g/L
水酸化ナトリウム10~300g/L
電流密度0.1~10A/dm2
温度5~60℃
時間1秒~2分
<クロムめっき条件>
(クロムめっき浴)
無水クロム酸CrO3 2.5g/L
pH 2.5
電流密度0.5A/dm2
温度15~45℃
時間1秒~2分
防錆処理層の形成後、この防錆処理層上に、表2に示す条件で、シランカップリング剤水溶液にメタノールまたはエタノールを添加し、所定のpHに調整した処理液を塗布した。その後、所定の時間保持してから温風で乾燥させることにより、表3に示すシラン付着量のシランカップリング剤層を形成した。なお、表3中の下線部の数値は、本発明の適正範囲外の数値であることを示す。
粗面化めっき処理1は表1の内容で、シランカップリング剤処理は表2の内容で其々行い、それ以外は実施例1と同じ処理を実施した。
(比較例1~7及び9~14)
粗面化めっき処理1は表1の内容で、シランカップリング剤処理は表2の内容で其々行い、それ以外は実施例1と同じ処理を実施した。
ロール状液晶ポリマーフィルム(クラレ(株)製のVecster(登録商標)CT-Z)を用いて、水酸化カリウム溶液(液温80℃)に処理時間10分間浸してエッチングし粗面化処理を行った。続いて、粗面化処理した熱可塑性樹脂フィルムに下記の無電解銅めっき浴により無電解銅めっきを形成した。
硫酸銅・5水和物(銅成分として) 19g/L
HEEDTA(キレート剤) 50g/L
ホスフィン酸ナトリウム(還元剤) 30g/L
塩化ナトリウム20g/L
リン酸水素二ナトリウム15g/L
その後、硫酸銅浴を用いて、熱可塑性樹脂フィルム上に形成される無電解銅めっき層を含めた銅めっき層全体の厚さが20μmになるように電解銅めっき層を形成した。なお、比較例8は、特許文献1に記載された発明の範囲を満足する条件で作製したものである。
各試験片につき各種測定、評価を行い、その結果を表3に示した。
(1)線長比Da/Db及び凹凸表面における凹凸の平均高低差Hの測定
図3中に両矢印で示す銅箔基体面(面方向P)と直交する断面において、前記銅箔基体110の面に沿って測定した沿面長さDbに対する、前記粗面化層の凹凸表面120に沿って測定した沿面長さDaの比Da/Dbを線長比とする。当該断面における粗面化層の凹凸表面が、より多くの、あるいは、より大きな凹凸を有する形状をなす場合に線長比は大きくなる。
図5に示したように、粗面化層43と絶縁基板42の界面の気泡数は以下に示す手順によって測定した。始めにプレス機を用い絶縁基板メーカーが推奨する標準のプレス条件で絶縁基板42(プリプレグ層)と銅箔43をプレスし積層体を作製する(本件では、絶縁基板42としてパナソニック株式会社のMEGTRON6:R-5670を使用し、プレス温度:200℃、プレス圧力:35kgf/cm2、プレス時間:160分のプレス条件で積層した。次に前記イオンミリング装置にて処理した前記積層体の断面を前記走査型電子顕微鏡で、50000倍(本件の画像内視野の実際の幅が2.54μmである。)に拡大し、積層体の粗面化層43と絶縁基板42の界面を観察した。図5の様に、幅が2.54μmの線上における粗面化層43と絶縁基板42の界面に存在する気泡41の数を10箇所でそれぞれ測定し、10箇所の気泡の数の平均値を粗面化層43と絶縁基板42の界面の気泡数Viとした。本件における気泡とは、粗面化層と絶縁基板の界面において絶縁基板が充填されていない領域を指しており、その大きさは長径で1.0μm以下のものである。
蛍光X線分析装置((株)リガク製ZSXPrimus、分析径:Φ35mmにて分析した。
(4)絶縁基板密着後の線長比Da’/Db及び凹凸表面における凹凸の平均高低差H’の測定
各銅箔を絶縁基板と接着後に、線長比Da’/Db及び凹凸表面における凹凸の平均高低差H’は、上記Da/DbおよびHの測定と同様の方法によって行った。
各銅箔を絶縁基板と接着後に、伝送特性測定用のサンプルを作製し高周波帯域における伝送損失を測定した。絶縁基板としては市販のポリフェニレンエーテル系絶縁(パナソニック(株)製メグトロン6)を使用した。伝送損失測定用の基板は、構造をストリップライン構造とし導体長さ400mm、導体厚さ18μm、導体幅を0.14mm、全体の厚さを0.31mm、特性インピーダンスが50Ωになる様に調整した。評価は、ベクトルネットワークアナライザE8363B(KEYSIGHT TECHNOLOGIES)を用いて、10GHzおよび40GHzにおける伝送損失を測定した。導体長さが400mm場合に測定した伝送損失を、導体長さが1000mmの場合に換算した値を伝送損失の測定結果とし、単位はdB/mとした。具体的には導体長さ400mmで測定した伝送損失の値に2.5を掛けた値を伝送損失の測定値とした。結果を表3に示したが、伝送特性は、10GHzで伝送損失が19.5dB/m未満を合格、40GHzで伝送損失が66.0dB/m未満を合格とした。
表面処理銅箔と絶縁基板との密着強度を測定した。絶縁基板としては市販のポリフェニレンエーテル基板を使用した。絶縁(樹脂)基板の硬化条件は、210℃、1時間とした。密着強度は、万能材料試験機(テンシロン、株式会社エー・アンド・デイ製)を使用して、銅箔と絶縁基板とを接着後、試験片を10mm幅の回路配線にエッチング加工し、絶縁側を両面テープによりステンレス板に固定し、回路配線を90度方向に50mm/分の速度で剥離して求めた。初期密着性は、剥離強度が0.4kN/m以上である場合を合格とし、剥離強度が0.4kN/m未満である場合を不合格と判定した。
先ず、リフロー耐熱試験(銅箔とプリプレグ層との間)の試験片の作製方法を説明する。両面に銅箔を積層しリフロー試験片(銅箔とプリプレグ層との間)を作製した。本件ではリフロー試験片(銅箔とプリプレグ層との間)のサイズは100mm×100mmであった。次に作製した試験片をリフロー炉に通し、トップ温度260℃で10秒間の加熱条件で10回通した。前記条件で加熱した後に、フクレが生じたものはフクレの領域の断面をマイクロスコープで観察し銅箔とプリプレグ層との間に層間剥離があるか確認した。銅箔とプリプレグ層との間で層間剥離が生じなかったものを「○(合格)」、銅箔とプリプレグ層の間で層間剥離が1箇所のものを「△(合格)」、銅箔とプリプレグ層との間の層間剥離が2箇所以上のものを「×(不合格)」と判定した。尚、リフロー試験の内容はJIS C 60068-2-58に準拠した。
リフロー耐熱試験(コア層とプリプレグ層との間)の試験片の作製方法を説明する。両面に銅箔を積層した絶縁基板をコア層とする。コア層は塩化銅(II)溶液等によりエッチングされ全ての銅箔が溶解される。エッチングしたコア層の両面に絶縁基板であるプリプレグ層と銅箔を積層することにより、リフロー試験片を作製した。本件ではリフロー試験片(コア層とプリプレグ層との間)のサイズは100mm×100mmであった。
110 銅箔基体
120 粗面化層
Da 粗面化層の凹凸表面に沿って測定した沿面長さ
Db 前記銅箔基体面に沿って測定した沿面長さ
P 基板の幅
41 気泡
42 絶縁基板
43 粗面化層
Claims (10)
- 銅箔基体上に粗面化層が設けられてなる表面処理銅箔であって、前記粗面化層は、複数の粗化粒子を有し、前記粗面化層の表面は凹凸表面として構成され、前記銅箔基体面と直交する断面において、前記銅箔基体面に沿って測定した沿面長さ(Db)に対する、前記粗面化層の凹凸表面に沿って測定した沿面長さ(Da)の比(Da/Db)が、1.05~4.00の範囲であり、前記凹凸表面における凹凸の平均高低差(H)が0.2~1.3μmの範囲であり、さらに前記粗面化層上に、直接、または中間層を介して0.0003~0.0300mg/dm2のシラン付着量で形成されたシランカップリング剤層を有することを特徴とする、表面処理銅箔。
- 前記凹凸表面はクビレ形状を有することを特徴とする、請求項1に記載の表面処理銅箔。
- 前記沿面長さの比(Da/Db)が1.05~3.20倍の範囲であり、前記凹凸の平均高低差(H)が0.2~0.8μmの範囲であり、且つ銅箔と絶縁基板を積層した際に前記銅箔基体上の前記銅箔の製造方向に垂直な方向である幅方向の2.54μmの線上において前記粗面化層と絶縁基板の界面の気泡数が2個以下である請求項1または2に記載の表面処理銅箔。
- 前記沿面長さの比(Da/Db)が1.05~1.60倍の範囲であり、前記凹凸の平均高低差(H)が0.2~0.3μmの範囲であり、且つ銅箔と絶縁基板を積層した際に前記銅箔基体の幅方向の2.54μmの線上において前記粗面化層と絶縁基板の界面の気泡数が1個以下である請求項1~3のいずれか1項に記載の表面処理銅箔。
- 前記シランカップリング剤層のシラン付着量が、0.0005~0.0120mg/dm2である請求項1~4のいずれか1項に記載の表面処理銅箔。
- 前記中間層が、Niを含有する下地層、Znを含有する耐熱処理層およびCrを含有する防錆処理層の中から選択される少なくとも1層で構成される請求項1~5のいずれか1項に記載の表面処理銅箔。
- 前記シランカップリング剤層は、エポキシ系シラン、アミノ系シラン、ビニル系シラン、メタクリル系シラン、アクリル系シラン、スチリル系シラン、ウレイド系シラン、メルカプト系シラン、スルフィド系シランおよびイソシアネート系シランの中から選択される少なくとも1種からなる請求項1~6のいずれか1項に記載の表面処理銅箔。
- 請求項1~7のいずれか1項に記載の表面処理銅箔の粗面化層側の面に、絶縁基板を有する銅張積層板。
- 銅箔基体上に粗面化層が設けられてなる表面処理銅箔の前記粗面化層側に絶縁基板を有する銅張積層板であって、該銅箔基体面と直交する断面において、前記銅箔基体面に沿って測定した沿面長さ(Db)に対する、前記粗面化層と前記絶縁基板との界面に沿って測定した界面長さ(Da’)の比(Da’/Db)が、1.05~4.00倍の範囲であり、前記界面における凹凸の平均高低差(H’)が0.2~1.3μmの範囲であり、さらに前記粗面化層と前記絶縁基板との間に、直接、または中間層を介して0.0003~0.0300mg/dm2のシラン付着量のシランカップリング剤層を有していることを特徴とする銅張積層板。
- 前記銅箔基体の幅方向の2.54μmの線上において、前記粗面化層と前記絶縁基板との界面の気泡数が2個以下である請求項9に記載の銅張積層板。
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CN112118672A (zh) * | 2019-06-19 | 2020-12-22 | 金居开发股份有限公司 | 具有长岛状微结构的进阶反转电解铜箔及应用其的铜箔基板 |
WO2022215330A1 (ja) * | 2021-04-09 | 2022-10-13 | 福田金属箔粉工業株式会社 | 表面処理銅箔及び該表面処理銅箔を用いた銅張積層板並びにプリント配線板 |
JP2022161636A (ja) * | 2021-04-09 | 2022-10-21 | 福田金属箔粉工業株式会社 | 表面処理銅箔及び該表面処理銅箔を用いた銅張積層板並びにプリント配線板 |
JP7273883B2 (ja) | 2021-04-09 | 2023-05-15 | 福田金属箔粉工業株式会社 | 表面処理銅箔及び該表面処理銅箔を用いた銅張積層板並びにプリント配線板 |
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TW201800242A (zh) | 2018-01-01 |
TWI704048B (zh) | 2020-09-11 |
JPWO2017138338A1 (ja) | 2018-02-22 |
KR102230999B1 (ko) | 2021-03-22 |
CN108603303A (zh) | 2018-09-28 |
JP6248231B1 (ja) | 2017-12-13 |
KR20180112769A (ko) | 2018-10-12 |
CN108603303B (zh) | 2020-11-13 |
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