JP6090693B2 - Surface-treated copper foil and printed wiring board using the surface-treated copper foil - Google Patents
Surface-treated copper foil and printed wiring board using the surface-treated copper foil Download PDFInfo
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- JP6090693B2 JP6090693B2 JP2012287322A JP2012287322A JP6090693B2 JP 6090693 B2 JP6090693 B2 JP 6090693B2 JP 2012287322 A JP2012287322 A JP 2012287322A JP 2012287322 A JP2012287322 A JP 2012287322A JP 6090693 B2 JP6090693 B2 JP 6090693B2
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- copper foil
- nickel
- layer
- copper
- silane coupling
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 90
- 239000011889 copper foil Substances 0.000 title claims description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000010419 fine particle Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 25
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 4
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 241000605059 Bacteroidetes Species 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000007788 roughening Methods 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 18
- 238000005530 etching Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000006866 deterioration Effects 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 230000002265 prevention Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 chlorine ions Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 230000000694 effects Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 3
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001361 White metal Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000010969 white metal Substances 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 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
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Description
本発明は、銅箔表面にクロム成分を含有する層を形成しなくても引き剥がし強さ及び長期防錆性を備え、粉落ちしない表面処理銅箔及び当該表面処理銅箔を使用したプリント配線板に関する。 The present invention provides a surface-treated copper foil having a peeling strength and a long-term antirust property without forming a layer containing a chromium component on the surface of the copper foil, and a printed wiring using the surface-treated copper foil. Regarding the board.
プリント配線板に使用する銅箔には通常の環境（常態）において樹脂基材と容易に引き剥がれない引き剥がし強さが要求されることに加えて、高温環境や吸湿後であっても、或いは、プリント配線板の製造工程で使用される様々な薬品に浸漬しても劣化せずに引き剥がし強さを維持すること、及び、粉落ちやエッチング残渣が発生しないこと、更には、長期に亘る防錆性も要求される。
前記要求を満たすため、通常プリント配線板用の銅箔の表面にはクロム成分を含有する層が形成されており、多くはクロメート皮膜が形成されている。
The copper foil used for the printed wiring board is required to have a peeling strength that does not easily peel off from the resin base material in a normal environment (normal state). , Maintain the peel strength without deterioration even when immersed in various chemicals used in the manufacturing process of printed wiring boards, and do not generate powder or etching residue. Rust prevention is also required.
In order to satisfy the above requirements, a layer containing a chromium component is usually formed on the surface of a copper foil for a printed wiring board, and in many cases a chromate film is formed.
クロメート皮膜のクロム成分は、Ｘ線光電子分光法やジフェニルカルバジド吸光光度法による測定で、毒性がなく環境負荷も少ない三価クロムであることが確認されている。しかしながら、クロメート皮膜処理の処理液中には六価クロムが含まれており、また、クロメート皮膜が形成された表面処理銅箔の廃棄処理方法を誤った場合や、廃棄時の外的環境要因によって、三価クロムが酸化されて六価クロムになることがある。 The chromium component of the chromate film has been confirmed to be trivalent chromium which is not toxic and has a low environmental impact, as measured by X-ray photoelectron spectroscopy or diphenylcarbazide absorptiometry. However, the chromate film treatment solution contains hexavalent chromium, and if the disposal method of the surface-treated copper foil with the chromate film formed is wrong or due to external environmental factors at the time of disposal, Trivalent chromium may be oxidized to hexavalent chromium.
六価クロムは毒性が非常に強く、環境負荷が高い物質であり、欧州では、使用済み自動車の環境に与える負荷を低減するためのELV指令（End-of Life Vehicles Directive）により、自動車部品やその材料に鉛、水銀、カドミウムと同様に六価クロムの使用が原則禁止され、また、同じく欧州の電気・電子機器における特定有害物質の使用を制限するRoHS指令（Restriction of the use of certainHazardous Substances in electrical and electronic equipment）においても六価クロムの使用は禁止されており、クロム成分を含有する表面処理銅箔を使用しているプリント配線板もその対象物となっている。 Hexavalent chromium is a highly toxic substance with a high environmental impact. In Europe, in accordance with the ELV Directive (End-of Life Vehicles Directive) for reducing the environmental impact of used vehicles, automotive parts and their The use of hexavalent chromium is prohibited in principle, as is the case with lead, mercury and cadmium, and the RoHS Directive (Restriction of the use of certain Hazardous Substances in electrical) and electronic equipment) are also prohibited from using hexavalent chromium, and printed wiring boards using surface-treated copper foil containing a chromium component are also the object.
このような、環境負荷に対する意識が高まるにつれて、無毒であるクロム成分であっても有毒である六価クロムへ変化する虞があるので、クロム成分を全く含有せず、かつ、プリント配線板に使用できる特性を備えた表面処理銅箔の開発が望まれていた。 As the awareness of environmental load increases, even non-toxic chromium components may change to toxic hexavalent chromium, so they do not contain any chromium components and are used for printed wiring boards. The development of a surface-treated copper foil having such characteristics has been desired.
特許文献１には、銅箔の表面にニッケル又はニッケル合金層及び熱風乾燥により酸化ニッケル層を形成し、酸化ニッケル層の表面にシランカップリング層を形成したプリント配線板用銅箔で、粗化メッキ層を備えるプリント配線板用銅箔が開示されている。
In
特許文献２には、粗化処理を施した銅箔の表面にバリヤー層としてニッケル又はニッケル合金層、耐熱層として亜鉛層又は亜鉛合金層、防錆処理層としてモリブデン化合物皮膜、及び、シランカップリング剤層を順に形成したプリント配線板用銅箔が開示されている。
特許文献１及び特許文献２は、表面に粗化処理を施し表面粗さを上昇させて、投錨効果による接着強度を得ながらクロメート皮膜に代わる引き剥がし強さを確保しようとしている。
粗化処理によって表面粗さが上がれば、投錨効果により樹脂基材とより強固に接着して引き剥がし強さが上昇することはよく知られており、クロメート皮膜に代わる引き剥がし強さを得るには表面粗さは上げた方が良い。 It is well known that if the surface roughness is increased by the roughening treatment, the anchoring effect will result in a stronger adhesion to the resin base material and an increase in the peel strength, so that a peel strength can be obtained instead of the chromate film. It is better to increase the surface roughness.
しかしながら、最近のプリント配線板は、電子機器の小型化に伴って回路が極端に狭ピッチ化しており、表面粗さが上がると狭ピッチの回路を正確に形成できないという問題がある。 However, recent printed wiring boards have a problem in that circuits are extremely narrowed with downsizing of electronic devices, and when the surface roughness is increased, narrow pitch circuits cannot be formed accurately.
また、表面粗さが上がるとエッチングファクターが低下したり、基板上にエッチング残渣や粉落ちが生じるという問題がある。 Further, when the surface roughness increases, there are problems that the etching factor is reduced and etching residues and powder fall off on the substrate.
したがって、基板上に残渣等を発生させず、狭ピッチの回路を正確に形成するには表面粗さは上げない方が好ましく、粗化処理を施さない場合も増えている。しかしながら、粗化処理を施さない場合には、十分な投錨効果が得られず接着強度が下がるため引き剥がし強さも低下するという問題が生じる。 Therefore, it is preferable not to increase the surface roughness in order to accurately form a narrow-pitch circuit without generating a residue or the like on the substrate, and the number of cases where the roughening treatment is not performed is increasing. However, when the roughening treatment is not performed, a sufficient anchoring effect cannot be obtained, and the adhesive strength is lowered, resulting in a problem that the peeling strength is also lowered.
本発明者らは、前記諸問題点を解決することを技術的課題とし、試行錯誤的な数多くの試作・実験を重ねた結果、銅箔の一方の面に粗化処理層と０．３μｍ以下の銅粒子、銅-ニッケル粒子、銅-コバルト粒子若しくは銅-ニッケル-コバルト粒子からなる微細粒子層とニッケル又はニッケル-リンからなる層とアルカリ金属ケイ酸塩及びシランカップリング剤からなる層とをこの順に形成すれば、常態引き剥がし強さだけではなく、高温環境や吸湿後、或いは、プリント配線板の製造工程で使用される様々な薬品に浸漬しても引き剥がし強さが維持されると共に長期に亘る防錆性が得られ、かつ、狭ピッチの回路も正確に形成でき、加えて、前記微細粒子層を形成することによって増加する表面積を１７７μｍ２ の領域当り６０μｍ２〜９００μｍ２の範囲にすれば粉落ちしない表面処理銅箔になるという刮目すべき知見を得て前記技術的課題を達成したものである。
The present inventors made it a technical subject to solve the above-mentioned problems, and as a result of many trial and error trial manufactures and experiments, a roughened layer and 0.3 μm or less were formed on one surface of the copper foil. A fine particle layer composed of copper particles, copper-nickel particles, copper-cobalt particles or copper-nickel-cobalt particles, a layer composed of nickel or nickel-phosphorus, and a layer composed of an alkali metal silicate and a silane coupling agent. If formed in this order, not only the normal peel strength, but also the peel strength is maintained even after being immersed in various chemicals used in high temperature environment, moisture absorption, or printed circuit board manufacturing process. rust resistance can be obtained over a long term, and narrow circuit pitch can be accurately formed, in addition, the area per 60 [mu] m 2 of 177 .mu.m 2 a surface area increased by forming fine particle layer ~900μm The above technical problem has been achieved by obtaining a remarkable knowledge that a surface-treated copper foil that does not fall off is obtained in the range of 2 .
前記技術的課題は本発明によって解決できる。 The technical problem can be solved by the present invention.
本発明は、銅箔の一方の面に粗化処理層と銅粒子、銅-ニッケル粒子、銅-コバルト粒子、銅-ニッケル-コバルト粒子から選択される１種の微細粒子からなる微細粒子層とニッケル又はニッケル-リンからなる層とアルカリ金属ケイ酸塩及びシランカップリング剤からなる層とがこの順に形成されており前記微細粒子の粒子径が０．３μｍ以下（但し０μｍは含まない）であり前記微細粒子層の表面積が前記微細粒子層形成前の前記粗化処理層の表面積より１７７μｍ２ の領域当り６０μｍ２〜９００μｍ２上昇していることを特徴とする表面処理銅箔に関する（請求項１）。
The present invention provides a roughening layer on one surface of a copper foil and a fine particle layer comprising one kind of fine particles selected from copper particles, copper-nickel particles, copper-cobalt particles, and copper-nickel-cobalt particles. A layer made of nickel or nickel-phosphorus and a layer made of an alkali metal silicate and a silane coupling agent are formed in this order, and the particle diameter of the fine particles is 0.3 μm or less (excluding 0 μm). the surface treated copper foil related (claim 1 the surface area of the fine particle layer, characterized in that the are area per 60μm 2 ~900μm 2 increase of 177 .mu.m 2 than the surface area of the fine particle layer formed prior to the roughening treatment layer ).
また本発明は、前記アルカリ金属ケイ酸塩がM2O・xSiO2・nH2O（M=Na又はK, x=2〜4）で表される水ガラスであることを特徴とする請求項１記載の表面処理銅箔に関する（請求項２）。 The present invention is also characterized in that the alkali metal silicate is water glass represented by M 2 O · xSiO 2 · nH 2 O (M = Na or K, x = 2 to 4). The surface-treated copper foil according to claim 1 (claim 2).
また本発明は、前記シランカップリング剤がアミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤、ビニル基含有シランカップリング剤から選択される１種以上であることを特徴とする請求項１又は２記載の表面処理銅箔に関する（請求項３）。 In the present invention, the silane coupling agent is at least one selected from an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, and a vinyl group-containing silane coupling agent. It is related with the surface-treated copper foil of 1 or 2.
また本発明は、樹脂基材上に請求項１乃至３いずれかに記載の表面処理銅箔を使用した
プリント配線板に関する（請求項４）。
Moreover, this invention relates to the printed wiring board which uses the surface-treated copper foil in any one of
本発明によれば、クロム成分を含む層を形成しなくても、エッチング性を損なわずに常態の引き剥がし強さが得られ、また、高温環境や吸湿後においても、或いは、プリント配線板の製造工程で使用される様々な薬品に浸漬しても引き剥がし強さを維持できることに加えて、粉落ちせず、長期防錆性があるので、プリント配線板に使用する銅箔に求められる特性を備えた表面処理銅箔になる。 According to the present invention, even if a layer containing a chromium component is not formed, a normal peeling strength can be obtained without impairing the etching property, and even after a high temperature environment or after moisture absorption, In addition to being able to maintain the peel strength even when immersed in various chemicals used in the manufacturing process, it does not fall off and has long-term rust prevention properties, so the characteristics required for copper foil used for printed wiring boards It becomes the surface treatment copper foil provided with.
本発明の表面処理銅箔に形成される微細粒子層を構成する微細粒子の粒子径は０．３μｍ以下（但し０μｍは含まない）なので、表面粗さの上昇を抑制して表面積を上昇させることができるため、樹脂基材と強固に固着させることができ、クロム成分を含む層を形成しなくても十分な引き剥がし強さを得ることができる。 Since the particle diameter of the fine particles constituting the fine particle layer formed on the surface-treated copper foil of the present invention is 0.3 μm or less (however, 0 μm is not included), the increase in surface roughness is suppressed and the surface area is increased. Therefore, it can be firmly fixed to the resin base material, and sufficient peel strength can be obtained without forming a layer containing a chromium component.
また、表面粗さの上昇が少ないので、エッチング残渣や粉落ちの発生頻度が低下し、かつ、狭ピッチの回路も正確に形成することができるため、小型化した電子機器のプリント配線板にも好適に用いることができる表面処理銅箔になる。 In addition, since the increase in surface roughness is small, the frequency of occurrence of etching residue and powder fall is reduced, and a narrow-pitch circuit can be accurately formed. It becomes the surface treatment copper foil which can be used suitably.
加えて、微細粒子層を形成することによる表面積の増加が、１７７μｍ２ の領域当り６０μｍ２〜９００μｍ２なので、引き剥がし強さを確保できるが粉落ちやエッチング残渣は発生しないというプリント配線板に使用する上で好ましい性質を兼ね備えた表面処理銅箔になる。
In addition, an increase in surface area due to the formation of the fine particle layer, 1 77 m 2 of So areas per 60μm 2 ~900μm 2, peel strength can be secured although dusting or etching residue on a printed wiring board that do not occur It becomes the surface-treated copper foil which has a preferable property when using it.
本発明における表面処理銅箔にはニッケル又はニッケル-リン層が形成されているので、高温環境でも、或いは、プリント配線板の製造工程に使用される様々な薬品に浸漬したとしても引き剥がし強さを維持できる。 Since the nickel or nickel-phosphorus layer is formed on the surface-treated copper foil in the present invention, the peel strength even in a high temperature environment or even when immersed in various chemicals used in the printed wiring board manufacturing process Can be maintained.
また、ニッケル-リン層は選択エッチング性のあるアルカリエッチング液にも可溶であるため、汎用性が高い。 In addition, the nickel-phosphorus layer is highly versatile because it is soluble in an alkaline etching solution having selective etching properties.
本発明における表面処理銅箔にはアルカリ金属ケイ酸塩及びシランカップリング剤からなる層が形成されているので、樹脂基材と強固に固着して常態引き剥がし強さが向上し、また、吸湿後であっても劣化が抑制されて引き剥がし強さが維持されると共に防錆性も向上する。 Since the surface-treated copper foil in the present invention is formed with a layer comprising an alkali metal silicate and a silane coupling agent, the surface-treated copper foil is firmly fixed to the resin base material to improve the normal peel strength, and also absorbs moisture. Even after, deterioration is suppressed, the peel strength is maintained, and rust prevention is improved.
特に、M2O・xSiO2・nH2O（M=Na又はK, x=2〜4）で表される水ガラスとアミノ基含有、エポキシ基含有若しくはビニル基含有のシランカップリング剤とを使用すれば吸湿後の劣化がより抑制され、防錆性もより向上する。 In particular, water glass represented by M 2 O.xSiO 2 .nH 2 O (M = Na or K, x = 2 to 4) and an amino group-containing, epoxy group-containing or vinyl group-containing silane coupling agent If used, deterioration after moisture absorption is further suppressed, and rust prevention is further improved.
（銅箔）
本発明に使用する各処理前の銅箔（以下未処理銅箔という）は特に限定されるものではなく、表裏の区別のない銅箔、表裏の区別のある銅箔いずれも使用することができる。
(Copper foil)
The copper foil before each treatment (hereinafter referred to as untreated copper foil) used in the present invention is not particularly limited, and any copper foil having no distinction between the front and back and a copper foil having a distinction between the front and back can be used. .
表面処理を施す一方の面（以下処理面という）は特に限定されるものではなく、圧延銅箔はいずれの面でも良いことはもちろんのこと、電解銅箔においても析出面又は光沢面のいずれの面でも良い。 One surface to be surface-treated (hereinafter referred to as the treated surface) is not particularly limited, and the rolled copper foil may be any surface, and any electrolytic copper foil may be either a precipitation surface or a glossy surface. The surface is good.
未処理銅箔の厚さは表面処理後にプリント配線板に使用できる厚さであれば特に限定されるものではないが、６μｍ〜３００μｍが好ましく、より好ましくは９μｍ〜１５０μｍである。 Although the thickness of untreated copper foil will not be specifically limited if it is the thickness which can be used for a printed wiring board after surface treatment, 6 micrometers-300 micrometers are preferable, More preferably, they are 9 micrometers-150 micrometers.
本発明において、未処理銅箔の処理面には予め粗化処理を施すことが好ましい。微細粒子層が形成しやすくなると共に、常態の引き剥がし強さの向上も望めるからである。
しかしながら、粗化処理による表面粗さの上昇が好ましくない場合には、未処理銅箔の処理面に直接微細粒子層を形成させることもできる。本発明における微細粒子層は表面粗さは上昇させないが、表面積を上昇させるので、樹脂基材と固着して引き剥がし強さが得られるからである。
In the present invention, it is preferable to subject the treated surface of the untreated copper foil to a roughening treatment in advance. This is because a fine particle layer can be easily formed and an improvement in the normal peeling strength can be expected.
However, when an increase in surface roughness due to the roughening treatment is not preferable, a fine particle layer can be directly formed on the treated surface of the untreated copper foil. This is because the fine particle layer in the present invention does not increase the surface roughness, but increases the surface area, so that the fine particle layer adheres to the resin substrate and provides a peel strength.
粗化処理を施す場合としては、処理面に銅又は銅合金の樹枝状粉を付着させた後に被覆めっきを施す方法を例示することができる。 An example of the case where the roughening treatment is performed is a method in which coating plating is performed after the dendritic powder of copper or copper alloy is attached to the treated surface.
前記粗化処理は、限界電流密度以上の電流で銅又は銅合金の樹枝状粉を付着させる工程（工程１）と付着した樹枝状粉の脱落を防ぐために、限界電流密度未満の電流で被覆めっきする工程（工程２）とから構成される。 In the roughening treatment, in order to prevent the step of attaching the dendritic powder of copper or copper alloy with a current equal to or higher than the limit current density (step 1) and the dropping of the attached dendritic powder, the coating is performed with a current less than the limit current density. (Step 2).
例えば、工程１は、硫酸銅五水和物１２g/L〜７０g/L、硫酸３０g/L〜２００g/Lの混合液に塩素イオン、コバルトイオン、ニッケルイオン、鉄イオン、チタンイオン、モリブデンイオン、バナジウムイオン、亜鉛イオン、タングステンイオン、アルミニウムイオン、1−10−フェナントロリン、4,7−ジフェニル−1,10−フェナントロリン、3−メルカプト−1−プロパンスルホン酸から選択される１又は２種以上を添加し、液温２５℃〜５０℃に調整した後、電極に白金属酸化物被覆チタン板等の不溶性電極を使用して、電流密度５A/dm2〜１００A/dm2の条件で樹枝状銅粉を付着させればよい。
For example, in
例えば、工程２は、硫酸銅五水和物１５０g/L〜３００g/L、硫酸５０g/L〜２００g/Lの混合液を液温２５℃〜５０℃に調整した後、電極に白金属酸化物被覆チタン板等の不溶性電極を使用して電流密度２A/dm2〜６０A/dm2の条件で被覆めっきすればよい。なお、必要に応じて公知技術であるゼラチンを適量添加してもよい。
For example, in
（微細粒子層）
微細粒子層を形成する粒子は粒子径が０．３μｍ以下の銅粒子、銅-ニッケル粒子、銅-コバルト粒子又は銅-ニッケル-コバルト粒子であり、より好ましくは０．２５μｍ以下の前記微細粒子である。
(Fine particle layer)
The particles forming the fine particle layer are copper particles having a particle size of 0.3 μm or less, copper-nickel particles, copper-cobalt particles or copper-nickel-cobalt particles, and more preferably the fine particles having a particle size of 0.25 μm or less. is there.
粒子径が０．３μｍより大きければ表面粗さが著しく上がり、エッチング性が悪くなると共に固着性も弱くなり、粉落ちが発生して生産ラインの汚染が生じたり、基板面にエッチング残渣が発生する虞があるため好ましくない。 If the particle size is larger than 0.3 μm, the surface roughness is remarkably increased, the etching property is deteriorated and the sticking property is also weakened, powder falling occurs and the production line is contaminated, or an etching residue is generated on the substrate surface. Since there is a possibility, it is not preferable.
未処理銅箔の処理面に微細粒子層を形成することにより上昇する表面積は１７７μｍ２ の領域当り６０μｍ２〜９００μｍ２であることが好ましく、より好ましくは７０μｍ２〜８００μｍ２、さらに好ましくは１００μｍ２〜７００μｍ２である。
６０μｍ２未満であると十分な引き剥がし強さを得ることができず、また、吸湿後の劣化率が大きくなるので好ましくなく、また、９００μｍ２より多ければ、引き剥がし強さは得られるものの、表面粗さが上がり、粉落ちも発生するので生産ラインの汚染が生じたり、基板面にエッチング残渣が発生する虞があり、プリント配線板に使用する表面処理銅箔としては好ましくない。
Preferably the surface area increases by forming a fine particle layer on the treated surface of the untreated copper foil is an area per 60μm 2 ~900μm 2 of 177 .mu.m 2, more preferably 70μm 2 ~800μm 2, more preferably 100 [mu] m 2 ˜700 μm 2 .
Can not be is less than 60 [mu] m 2 to obtain a sufficient peel strength, also not preferable because the deterioration rate after moisture absorption is large, if the amount exceeds 900 .mu.m 2, although the peel strength is obtained, Since the surface roughness increases and powder falling occurs, the production line may be contaminated, and etching residue may be generated on the substrate surface, which is not preferable as a surface-treated copper foil used for a printed wiring board.
表面積は、例えば、可視光限界波長４０８nmのバイオレットレーザーを使用したレーザー顕微鏡等で測定することができる。 The surface area can be measured by, for example, a laser microscope using a violet laser having a visible light limit wavelength of 408 nm.
本発明における微細粒子層は電気めっき法によって形成することができる。 The fine particle layer in the present invention can be formed by electroplating.
本発明の微細粒子層は、例えば、銅含有化合物１０g/L〜１００g/L又は銅含有化合物１０g/L〜１００g/Lとコバルト含有化合物１g/L〜６０g/L、及び/又は、ニッケル含有化合物１g/L〜６０g/Lを含有する液に、ジエチレントリアミン塩を５g/L〜３００g/Lとなるように添加した混合液をｐHが２．５〜１３．０、液温が２０℃〜７０℃になるよう調整し、陽極に銅を用いて電流密度０．５A/dm2〜１０．０A/dm2、電気量１０A・sec/dm2〜４００A・sec/dm2の条件で形成することができる。 The fine particle layer of the present invention is, for example, a copper-containing compound 10 g / L to 100 g / L or a copper-containing compound 10 g / L to 100 g / L and a cobalt-containing compound 1 g / L to 60 g / L and / or a nickel-containing compound. A liquid mixture containing 1 g / L to 60 g / L and a diethylenetriamine salt added so as to be 5 g / L to 300 g / L has a pH of 2.5 to 13.0 and a liquid temperature of 20 ° C. to 70 ° C. And using copper as the anode, the current density is 0.5 A / dm 2 to 10.0 A / dm 2 and the amount of electricity is 10 A · sec / dm 2 to 400 A · sec / dm 2. it can.
銅含有化合物としては硫酸銅五水和物、コバルト含有化合物として硫酸コバルト七水和物、塩化コバルト、ニッケル含有化合物としては硫酸ニッケル六水和物、塩化ニッケルが好適である。 The copper-containing compound is preferably copper sulfate pentahydrate, the cobalt-containing compound is cobalt sulfate heptahydrate, cobalt chloride, and the nickel-containing compound is nickel sulfate hexahydrate or nickel chloride.
ジエチレントリアミン塩としてはジエチレントリアミン五酢酸五ナトリウムが好適である。 Diethylenetriaminepentaacetic acid pentasodium is preferred as the diethylenetriamine salt.
（ニッケル又はニッケル-リン層）
本発明におけるニッケル又はニッケル-リン層の付着量は５mg/m2〜３００mg/m2が好ましく、より好ましくは１０mg/m2〜２００mg/m2である。５mg/m2未満であると微細粒子層が形成されている銅箔表面を完全に被覆できずに、樹脂基材と銅が反応して脆弱層を形成して高温環境や薬品浸漬後の引き剥がし強さの劣化率が上昇する虞があるため好ましくない。また、付着量が３００mg/m2より多ければ、エッチング残渣の発生や、エッチングの速度が遅くなる虞があるため好ましくなく、また、３００mg/m2より多くても耐熱・耐薬品特性の向上は望めないためである。
(Nickel or nickel-phosphorus layer)
Nickel or nickel in the present invention - the adhesion amount of the phosphorus layer is preferably 5mg / m 2 ~300mg / m 2 , more preferably from 10mg / m 2 ~200mg / m 2 . If it is less than 5 mg / m 2 , the copper foil surface on which the fine particle layer is formed cannot be completely coated, and the resin base material reacts with copper to form a brittle layer, which is pulled after high temperature environment or chemical immersion. This is not preferable because the deterioration rate of the peel strength may increase. Further, if the amount exceeds the amount of adhered 300 mg / m 2, generation of etching residue is not preferable because there is a risk that the rate of etching is slow, also be greater than 300 mg / m 2 increase in heat and chemical characteristics It is because it cannot be expected.
本発明におけるニッケル又はニッケル-リン層は電気めっき法により形成することができる。 The nickel or nickel-phosphorus layer in the present invention can be formed by electroplating.
本発明におけるニッケル又はニッケル-リン層は、例えば、ニッケル含有化合物１０g/L〜１００g/L又はニッケル含有化合物１０g/L〜１００g/Lにリン酸塩０．１g/L〜１０g/Lを含有する液に酢酸ナトリウム三水和物を２g/L〜２０g/Lとなるように添加した混合液を、ｐHが３．０〜５．５、液温が２０℃〜５０℃になるよう調整し、陽極に白金を用いて電流密度０．１A/dm2〜１０．０A/dm2、電気量１．０A・sec/dm2〜３０．０A・sec/dm2の条件で形成することができる。 The nickel or nickel-phosphorus layer in the present invention contains, for example, a nickel-containing compound of 10 g / L to 100 g / L or a nickel-containing compound of 10 g / L to 100 g / L and a phosphate of 0.1 g / L to 10 g / L. The liquid mixture in which sodium acetate trihydrate was added to the liquid so as to be 2 g / L to 20 g / L was adjusted so that the pH was 3.0 to 5.5 and the liquid temperature was 20 ° C. to 50 ° C., It can be formed using platinum as the anode under the conditions of a current density of 0.1 A / dm 2 to 10.0 A / dm 2 and an electric quantity of 1.0 A · sec / dm 2 to 30.0 A · sec / dm 2 .
ニッケル含有化合物としては、硫酸ニッケル六水和物、塩化ニッケル、リン酸塩としては次亜リン酸ナトリウム一水和物、亜リン酸ナトリウムが好適である。 As the nickel-containing compound, nickel sulfate hexahydrate, nickel chloride, and as the phosphate, sodium hypophosphite monohydrate and sodium phosphite are suitable.
（アルカリ金属ケイ酸塩及びシランカップリング剤層）
本発明におけるアルカリ金属ケイ酸塩は特に限定されるものではないが、M2O・xSiO2・nH2O（M=Na又はK，x=2〜4）で表される水ガラスが好適に用いられる。水ガラスは、ナトリウム塩、カリウム塩いずれも使用することができるが、カリウム塩がより好ましい。
(Alkali metal silicate and silane coupling agent layer)
The alkali metal silicate in the present invention is not particularly limited, but water glass represented by M 2 O · xSiO 2 · nH 2 O (M = Na or K, x = 2 to 4) is preferable. Used. As the water glass, either a sodium salt or a potassium salt can be used, but a potassium salt is more preferable.
本発明におけるシランカップリング剤は特に限定されるものではなく、ビニル基、エポキシ基、スチリル基、メタクリル基、アクリル基、アミノ基、ウレイド基及びメルカプト基を含有するシランカップリング剤を使用することができるが、アミノ基、エポキシ基又はビニル基含有のシランカップリング剤は耐吸湿性と防錆性の効果が非常に高く、より好適である。 The silane coupling agent in the present invention is not particularly limited, and a silane coupling agent containing a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, a ureido group, and a mercapto group should be used. However, amino group, epoxy group or vinyl group-containing silane coupling agents are more suitable because they have very high effects of moisture absorption resistance and rust prevention.
シランカップリング剤は１種でも、２種以上を組み合わせて使用しても良い。 A silane coupling agent may be used alone or in combination of two or more.
本発明におけるアルカリ金属ケイ酸塩及びシランカップリング剤層は、アルカリ金属ケ
イ酸塩とシランカップリング剤とを溶解して、２０℃〜６０℃に調整した混合水溶液に浸漬した後、または、スプレー等の方法で散布した後、水洗することで形成することができる。
In the present invention, the alkali metal silicate and silane coupling agent layer is prepared by dissolving an alkali metal silicate and a silane coupling agent and immersing them in a mixed aqueous solution adjusted to 20 ° C. to 60 ° C. or spraying. It can form by spraying by the method etc., and washing with water.
混合水溶液中のアルカリ金属ケイ酸塩の濃度は０．５mL/L〜１００mL/Lが好ましく、更に好ましくは１mL/L〜８０mL/Lである。０．５mL/L未満では吸湿処理後の引き剥がし強さの劣化率が高くなるので好ましくなく、１００mL/Lを超えて添加しても、それ以上の吸湿後の劣化率の低下は望めないためである。 The concentration of the alkali metal silicate in the mixed aqueous solution is preferably 0.5 mL / L to 100 mL / L, more preferably 1 mL / L to 80 mL / L. If it is less than 0.5 mL / L, the deterioration rate of the peel strength after the moisture absorption treatment is increased, which is not preferable. Even if it is added in excess of 100 mL / L, no further decrease in the deterioration rate after moisture absorption can be expected. It is.
混合水溶液中のシランカップリング剤の濃度は０．３mL/L〜１００mL/Lが好ましく、より好ましくは０．５mL/L〜８０mL/Lである。０．３mL/L未満だと吸湿後の劣化率の低下及び防錆性の効果が十分ではなく、また、１００mL/Lを超えて添加してもそれ以上の効果の向上は望めないためである。 The concentration of the silane coupling agent in the mixed aqueous solution is preferably 0.3 mL / L to 100 mL / L, more preferably 0.5 mL / L to 80 mL / L. If it is less than 0.3 mL / L, the deterioration rate after moisture absorption and the effect of rust prevention are not sufficient, and even if added over 100 mL / L, no further improvement in effect can be expected. .
以下に本発明の実施例を示すが、本発明はこれに限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
（粗化処理）
表面粗さRzJIS １．１μm、厚さ１８μmの圧延銅箔を硫酸銅五水和物４５g/L、硫酸１００g/L、塩素イオン２０ppm、液温３０℃に調整した混合液に浸漬した後、白金を陽極として電流密度１０A/dm2、電解時間１２秒の条件で、圧延銅箔表面に樹枝状銅粉を付着させた。
(Roughening treatment)
After immersing a rolled copper foil having a surface roughness of RzJIS 1.1 μm and a thickness of 18 μm in a mixed liquid adjusted to 45 g / L of copper sulfate pentahydrate, 100 g / L of sulfuric acid, 20 ppm of chloride ions, and a liquid temperature of 30 ° C., platinum As an anode, dendritic copper powder was adhered to the surface of the rolled copper foil under the conditions of a current density of 10 A / dm 2 and an electrolysis time of 12 seconds.
付着した樹枝状銅粉の脱落を防止するため硫酸銅五水和物２５０g/L、硫酸１００g/L、液温３０℃に調整した混合液に浸漬した後、白金を陽極として電流密度５A/dm2、電解時間７０秒で電解して、付着した樹枝状銅粉を銅めっきで完全に被覆し、粗化処理を施した圧延銅箔を得た。 In order to prevent the adhering dendritic copper powder from falling off, it was immersed in a mixed solution adjusted to 250 g / L of copper sulfate pentahydrate, 100 g / L of sulfuric acid, and a liquid temperature of 30 ° C., and then current density of 5 A / dm using platinum as an anode. 2. Electrolysis was performed in an electrolysis time of 70 seconds, and the attached dendritic copper powder was completely covered with copper plating to obtain a rolled copper foil subjected to roughening treatment.
本発明の実施例及び比較例は全て粗化処理を施した圧延銅箔を使用した。 All the examples and comparative examples of the present invention used rolled copper foil subjected to roughening treatment.
（微細粒子層）
粗化処理を施した圧延銅箔を１０秒間水洗後、硫酸銅五水和物、硫酸ニッケル六水和物、硫酸コバルト七水和物、ジエチレントリアミン五酢酸五ナトリウム（商品名:クレワットDP８０ (含有率３５〜４５%)・ナガセケムテックス株式会社製）を表１記載の割合で混合し、銅を陽極として、同じく表１記載のpH、液温、電流密度及び電解時間の条件で電気めっきを行って、実施例１〜１２及び比較例１〜５の表面処理銅箔の微細粒子層を形成した。
(Fine particle layer)
Roughened rolled copper foil was washed with water for 10 seconds, copper sulfate pentahydrate, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, diethylenetriaminepentaacetic acid pentasodium (trade name: Clewat DP80 (content rate 35 to 45%) ・ Nagase ChemteX Co., Ltd.) is mixed at the ratio shown in Table 1, and copper is used as the anode, and electroplating is performed under the same conditions of pH, liquid temperature, current density and electrolysis time as shown in Table 1. And the fine particle layer of the surface treatment copper foil of Examples 1-12 and Comparative Examples 1-5 was formed.
（ニッケル又はニッケル-リン層）
微細粒子層が形成された圧延銅箔を１０秒間水洗後、硫酸ニッケル六水和物、次亜リン酸ナトリウム一水和物、酢酸ナトリウム三水和物を表２記載の割合で混合し、白金を陽極として、同じく表２記載のpH、液温、電流密度及び電解時間の条件で電気めっきを行って、実施例１〜１２のニッケル又はニッケル−リン層を形成した。また、比較例１〜５は実施例１と同一の条件で形成した。
(Nickel or nickel-phosphorus layer)
The rolled copper foil on which the fine particle layer was formed was washed with water for 10 seconds, and then nickel sulfate hexahydrate, sodium hypophosphite monohydrate, and sodium acetate trihydrate were mixed at the ratio shown in Table 2 to obtain platinum. Was used as an anode, and electroplating was carried out under the conditions of pH, liquid temperature, current density and electrolysis time shown in Table 2 to form nickel or nickel-phosphorous layers of Examples 1-12. Further, Comparative Examples 1 to 5 were formed under the same conditions as in Example 1.
（アルカリ金属ケイ酸塩及びシランカップリング剤層）
微細粒子層とニッケル又はニッケル−リン層とが形成された圧延銅箔を１０秒間水洗後、ケイ酸カリウム（２Ｋ珪酸カリ：日本化学工業株式会社製）、ケイ酸ナトリウム、ケイ酸リチウムと、Ｎ−２（アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、ビ
ニルトリメトキシシランとを表３記載のとおり混合し、同じく表３記載の液温及び浸漬時間で浸漬した後、１０秒間水洗し、その後、自然乾燥を行って実施例１〜１２にアルカリ金属ケイ酸塩及びシランカップリング剤層を形成した。比較例１〜５は実施例１と同一の条件で形成した。
(Alkali metal silicate and silane coupling agent layer)
After the rolled copper foil on which the fine particle layer and the nickel or nickel-phosphorous layer are formed is washed with water for 10 seconds, potassium silicate (2K potassium silicate: manufactured by Nippon Chemical Industry Co., Ltd.), sodium silicate, lithium silicate, N -2 (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane were mixed as shown in Table 3, and Table 3 After dipping at the described liquid temperature and dipping time, it was washed with water for 10 seconds and then naturally dried to form alkali metal silicate and silane coupling agent layers in Examples 1-12. Comparative Examples 1 to 5 were formed under the same conditions as in Example 1.
（比較例６）
微細粒子層を形成させない以外は実施例１と同一条件で作成した。
(Comparative Example 6)
It was created under the same conditions as in Example 1 except that the fine particle layer was not formed.
（比較例７)
ニッケル又はニッケル−リン層を形成させない以外は実施例１と同一条件で作成した。
(Comparative Example 7)
It was created under the same conditions as in Example 1 except that no nickel or nickel-phosphorus layer was formed.
(比較例８)
アルカリ金属ケイ酸塩及びシランカップリング剤層を形成させない以外は実施例１と同一条件で作成した。
(Comparative Example 8)
It was created under the same conditions as in Example 1 except that the alkali metal silicate and silane coupling agent layers were not formed.
（比較例９）
粗化処理を施した圧延銅箔を使用し、硫酸ニッケル六水和物１７６g/L、クエン酸一水和物２０g/Lの混合液を液温４０℃に調整し、陽極に白金を使用して、電流密度２．０A/dm2、電解時間４秒間の条件でニッケルめっき層を形成した。
(Comparative Example 9)
Using a rolled copper foil that has been roughened, a mixed solution of nickel sulfate hexahydrate 176 g / L and citric acid monohydrate 20 g / L is adjusted to a liquid temperature of 40 ° C., and platinum is used for the anode. Then, a nickel plating layer was formed under the conditions of a current density of 2.0 A / dm 2 and an electrolysis time of 4 seconds.
その後、２００℃の大気中で熱風乾燥を行うことでニッケルめっき表面に酸化ニッケル層を形成した後、５mL/Lの３-アミノプロピルトリメトキシシラン水溶液に１０秒間浸漬し、水洗することなく大気中にて２００℃、１分間の乾燥を行って作成した。 Then, after forming a nickel oxide layer on the nickel plating surface by performing hot air drying in the atmosphere at 200 ° C., it is immersed in a 5 mL / L 3-aminopropyltrimethoxysilane aqueous solution for 10 seconds and washed in the air without being washed with water. And was dried at 200 ° C. for 1 minute.
(比較例１０)
粗化処理を施した圧延銅箔を使用し、硫酸ニッケル六水和物３００g/L、塩化ニッケル４５g/L、ホウ酸５０g/Lの混合液を、液温５０℃に調整し、陽極に白金を使用して、電流密度２A/dm2、電解時間４秒間の条件でニッケルめっき層を形成した。
(Comparative Example 10)
Using a roughed rolled copper foil, a mixed solution of nickel sulfate hexahydrate 300 g / L, nickel chloride 45 g / L, boric acid 50 g / L was adjusted to a liquid temperature of 50 ° C., and platinum was used as the anode. Was used to form a nickel plating layer under the conditions of a current density of 2 A / dm 2 and an electrolysis time of 4 seconds.
ニッケルメッキ層を形成させた圧延銅箔を１０秒間水洗後、硫酸亜鉛３００g/L、硫酸ナトリウム７０g/Lの混合液を、液温４０℃に調整し、陽極に白金を使用して、電流密度２A/dm2、電解時間４秒間の条件で、亜鉛めっき層を形成した。 The rolled copper foil on which the nickel plating layer is formed is washed with water for 10 seconds, and then a mixed solution of zinc sulfate 300 g / L and sodium sulfate 70 g / L is adjusted to a liquid temperature of 40 ° C. A galvanized layer was formed under the conditions of 2 A / dm 2 and electrolysis time of 4 seconds.
１０秒間水洗後、モリブデン酸ナトリウム二水和物２５g/L、クエン酸ナトリウム二水和物３０g/Lの混合液を液温２５℃、pH５に調整し、陽極に白金を使用して、電流密度０．２A/dm2、陰極電解時間３０秒間の条件でモリブデン酸皮膜を形成した。
After washing with water for 10 seconds, the mixture of sodium molybdate dihydrate 25 g / L and sodium citrate dihydrate 30 g / L was adjusted to a liquid temperature of 25 ° C. and
その後１０秒間水洗し、１０%の３-アミノプロピルトリメトキシシラン液に室温で１０秒間浸漬し、直ちに８０℃で乾燥を行って作成した。 Thereafter, it was washed with water for 10 seconds, immersed in a 10% 3-aminopropyltrimethoxysilane solution at room temperature for 10 seconds, and immediately dried at 80 ° C. to prepare.
（比較例１１）
粗化処理を施した圧延銅箔を使用し、硫酸ニッケル六水和物３０g/L、次亜リン酸ナトリウム一水和物０．２g/L、酢酸ナトリウム三水和物１０g/Lの混合液を液温３０℃、pH４．５に調整し、陽極に白金を使用して、電流密度２．０A/dm2、電解時間２秒の条件でニッケル-リンめっき層を形成した。
(Comparative Example 11)
Using a rolled copper foil that has been roughened, a mixture of nickel sulfate hexahydrate 30 g / L, sodium hypophosphite monohydrate 0.2 g / L, and sodium acetate trihydrate 10 g / L The solution was adjusted to a liquid temperature of 30 ° C. and a pH of 4.5, and platinum was used for the anode to form a nickel-phosphorous plating layer under the conditions of a current density of 2.0 A / dm 2 and an electrolysis time of 2 seconds.
１０秒間水洗後、重クロム酸ナトリウム１０g/L、水酸化ナトリウム４０g/Lの混合液を、液温３０℃に調整し、陽極に白金を使用して、電流密度２．０A/dm2、電解時間５秒の条件でクロメート層を形成した後、１０秒間水洗し、自然乾燥を行った。 After washing with water for 10 seconds, a mixed solution of sodium dichromate 10 g / L and sodium hydroxide 40 g / L is adjusted to a liquid temperature of 30 ° C., platinum is used for the anode, current density is 2.0 A / dm 2 , electrolysis A chromate layer was formed under conditions of 5 seconds, then washed with water for 10 seconds and air dried.
本発明の実施例及び比較例の測定方法について記載する。 The measuring method of the Example of this invention and a comparative example is described.
（十点平均粗さRzJIS）
JISB0651-2001に規定される触針式表面粗さ計を用いた。
触針は先端の半径２μmのものを使用し、粗さ曲線用カットオフ値０．８mm、測定距離４．０mmとしてJISB０６０１-１９９４に定義される十点平均粗さRzJISを測定した。
(10-point average roughness RzJIS)
A stylus type surface roughness meter defined in JISB0651-2001 was used.
A stylus having a tip radius of 2 μm was used, and a 10-point average roughness RzJIS defined in JISB0601-1994 was measured with a cut-off value for a roughness curve of 0.8 mm and a measurement distance of 4.0 mm.
（表面積の測定)
カラー3Dレーザー顕微鏡、可視光限界波長４０８nmのバイオレットレーザー（株式会社キーエンス製VK-9710）を使用し、表面積１７７μm2の領域を対物レンズ１５０倍、高精細、光学６倍ズーム条件で測定した。
(Surface area measurement)
Using a color 3D laser microscope and a violet laser with a visible light limit wavelength of 408 nm (VK-9710 manufactured by Keyence Corporation), an area with a surface area of 177 μm 2 was measured under the objective lens 150 times, high definition, and optical 6 times zoom conditions.
なお、前記測定方法にて測定した粗化処理後の表面粗さはRzJIS２.９μmであった。
したがって、粗化処理によって上昇した表面粗さはRzJIS１．８μmである。
The surface roughness after the roughening treatment measured by the measurement method was RzJIS2.9 μm.
Therefore, the surface roughness increased by the roughening treatment is RzJIS1.8 μm.
また、表面積は１７７μm2 の領域当り８６５μm2であった。
表４記載の「上昇した表面積」の値は微細粒子層形成後の表面積から粗化処理後の表面積である８６５μm2を引いた値である。
Further, the surface area was the region per 865Myuemu 2 of 177 .mu.m 2.
The value of “increased surface area” described in Table 4 is a value obtained by subtracting 865 μm 2 which is the surface area after the roughening treatment from the surface area after the formation of the fine particle layer.
(粒子径)
走査型電子顕微鏡を使用し、倍率10,000倍で微細粒子層を形成する粒子の大きさを測定した。
(Particle size)
Using a scanning electron microscope, the size of particles forming a fine particle layer was measured at a magnification of 10,000.
（常態引き剥がし強さ)
FR-4基材を3枚重ね、圧力４０kgf/cm２、温度１７０℃、時間６０分間でプレス機により加熱・加圧成型を行って銅張積層板を得た。エッチングマシーンを使用し、エッチングにより１mm幅の銅の回路サンプルを作製した。JIS C 6481に準拠し、万能試験機を用いて、引き剥がし強さを測定した。
(Normal peel strength)
Three FR-4 substrates were stacked, and heated and pressure-molded by a press machine at a pressure of 40 kgf / cm 2 , a temperature of 170 ° C., and a time of 60 minutes to obtain a copper-clad laminate. An etching machine was used to produce a 1 mm wide copper circuit sample by etching. In accordance with JIS C 6481, the peel strength was measured using a universal testing machine.
（加熱処理）
１mm幅の銅の回路サンプルを、大気オーブンを使用し、温度１８０℃、４８時間の条件で加熱処理を行い、引き剥がし強さを測定した。
(Heat treatment)
A copper circuit sample having a width of 1 mm was subjected to a heat treatment at a temperature of 180 ° C. for 48 hours using an atmospheric oven, and the peel strength was measured.
（吸湿処理）
１mm幅の銅の回路サンプルを、１２０分間イオン交換水の中で煮沸した。次いで水洗を行い、乾燥した後、引き剥がし強さを測定した。
(Hygroscopic treatment)
A 1 mm wide copper circuit sample was boiled in ion exchange water for 120 minutes. Subsequently, it was washed with water and dried, and then the peel strength was measured.
（塩酸水溶液処理）
１mm幅の銅の回路サンプルを、液温２５±２℃の１８wt%塩酸水溶液に６０分間浸漬した後、水洗し、乾燥後、引き剥がし強さを測定した。
(Hydrochloric acid aqueous solution treatment)
A 1 mm wide copper circuit sample was immersed in an 18 wt% aqueous hydrochloric acid solution having a liquid temperature of 25 ± 2 ° C. for 60 minutes, washed with water, dried, and then peeled off.
（劣化率）
各処理後の劣化率(%)は次式により算出した。
The deterioration rate (%) after each treatment was calculated by the following equation.
（粉落ち試験）
本発明の表面処理銅箔上に、幅３０mm、長さ１００mmの試験紙（濾紙Grade2）を置き、片方に荷重（200g/φ30mm）を掛けて濾紙を水平方向に１２０mm引きずった後、濾紙に付着した銅粉を目視観察し、粉の付着が無い場合は○、粉が付着している場合には×の判定を行った。
(Powder falling test)
Place a test paper (filter paper Grade 2) 30 mm wide and 100 mm long on the surface-treated copper foil of the present invention, apply a load (200 g / φ30 mm) on one side, drag the filter paper 120 mm horizontally, and adhere to the filter paper The obtained copper powder was visually observed, and when there was no powder adhesion, it was judged as “good”, and when powder was adhered, it was judged as “poor”.
(防錆性）
恒温・恒湿器を使用し温度６０℃、湿度８５℃の条件で３日間放置した後、表面処理面を目視によって判定した。
評価は以下の基準で行った。
(Rust prevention)
After leaving for 3 days under conditions of a temperature of 60 ° C. and a humidity of 85 ° C. using a thermo-hygrostat, the surface-treated surface was visually judged.
Evaluation was performed according to the following criteria.
防錆評価基準
○ ： 変色、黒点が認められない
× ： 変色、黒点のいずれか一方が認められる
×× ： 変色、黒点の両方が認められる。
Rust prevention evaluation criteria
○: Discoloration and black spots are not recognized
×: Discoloration or black spot is recognized
XX: Both discoloration and black spots are recognized.
実施例１〜１２及び比較例１〜１１の常態引き剥がし強さ、各種処理後の引き剥がし強さ及び各引き剥がし強さの劣化率、粉落ち及び防錆性の結果を表４に示す。 Table 4 shows the results of the normal peel strengths of Examples 1 to 12 and Comparative Examples 1 to 11, the peel strength after various treatments, the deterioration rate of each peel strength, the powder falling off, and the rust prevention properties.
前述の粗化処理によって上昇した表面粗さと比較すると、本発明の実施例１〜１２の微細粒子層の形成による表面粗さの上昇は非常に低く、しかしながら、表面積は大幅に増加していることが確認できる（表４）。 Compared with the surface roughness increased by the aforementioned roughening treatment, the increase in surface roughness due to the formation of the fine particle layer of Examples 1 to 12 of the present invention is very low, however, the surface area is greatly increased. Can be confirmed (Table 4).
また、本発明の実施例１〜１２は、クロメート層が形成されている比較例１１よりも常態引き剥がし強さの値が高く、また、各種処理後も引き剥がし強さが維持できると共に粉落ちせず、かつ、変色・黒点が発生しない防錆性に優れたプリント配線板に要求される特性を全て備えたバランスの良い表面処理銅箔であることが確認できる(表４)。 Moreover, Examples 1-12 of this invention have the value of normal state peeling strength higher than the comparative example 11 in which the chromate layer is formed. In addition, it can be confirmed that this is a well-balanced surface-treated copper foil that has all the characteristics required for a printed wiring board excellent in rust prevention property that does not cause discoloration and black spots (Table 4).
加えて、比較例６〜８より、本発明における微細粒子層、ニッケル又はニッケルリン層、アルカリ金属ケイ酸塩及びシランカップリング層のいずれか一つでも欠くと、常態引き剥がし強さが低下し、各処理後の引き剥がし強さの劣化率が上り、また、ニッケル又はニッケルリン層、アルカリ金属ケイ酸塩及びシランカップリング層のいずれかを欠くと防錆性が維持できないので、いずれの層を欠いても本発明の特性を備えた表面処理銅箔にはならないことが確認できる(表４)。 In addition, from Comparative Examples 6 to 8, if any one of the fine particle layer, the nickel or nickel phosphorus layer, the alkali metal silicate layer, and the silane coupling layer in the present invention is lacking, the normal peel strength decreases. , The rate of deterioration of the peel strength after each treatment is increased, and if any of the nickel or nickel phosphorus layer, alkali metal silicate and silane coupling layer is lacking, rust prevention cannot be maintained. It can be confirmed that the surface-treated copper foil having the characteristics of the present invention is not obtained even if lacking (Table 4).
本発明は、クロム成分を含有する層を含まないので環境負荷が低く、クロメート皮膜を形成した表面処理銅箔に代わる常態引き剥がし強さが得られ、また、高温環境や吸湿後に
おいても、或いは、薬品に浸漬後であっても引き剥がし強さが維持できることに加えて、粉落ちせず、長期に亘って防錆性があり、プリント配線板用の銅箔に求められる特性を満たしたバランスの良い表面処理銅箔であって、特別な設備や装置を導入することなく製造できるため産業上の利用可能性が高い。
Since the present invention does not include a layer containing a chromium component, the environmental load is low, a normal peel strength can be obtained in place of the surface-treated copper foil having a chromate film formed, and even in a high temperature environment or after moisture absorption, or In addition to being able to maintain the peel strength even after being immersed in chemicals, it does not fall off, has a long-term rust-proof property, and balance that satisfies the characteristics required for copper foil for printed wiring boards The surface-treated copper foil is highly industrially applicable because it can be manufactured without introducing special equipment or equipment.
１ 銅箔
２ 微細粒子層
３ ニッケル又はニッケル−リン層
４ アルカリ金属ケイ酸塩及びシランカップリング剤層
５ 粗化処理層
1
5 roughening treatment layer
Claims (4)
Ａ群：銅粒子、銅-ニッケル粒子、銅-コバルト粒子、銅-ニッケル-コバルト粒子 A roughened layer on one surface of the copper foil, a fine particle layer made of one kind of fine particles selected from the following group A, a layer made of nickel or nickel-phosphorus, an alkali metal silicate and a silane coupling agent Are formed in this order, and the particle diameter of the fine particles is 0.3 μm or less (however, 0 μm is not included), and the surface area of the fine particle layer is the roughened layer before the formation of the fine particle layer. surface treated copper foil, characterized in that the are area per 60μm 2 ~900μm 2 increase of 177 .mu.m 2 than the surface area.
Group A: copper particles, copper-nickel particles, copper-cobalt particles, copper-nickel-cobalt particles
Ｂ群：アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤、ビニル基含有シランカップリング剤 The surface-treated copper foil according to claim 1 or 2, wherein the silane coupling agent is at least one selected from the following group B.
Group B: amino group-containing silane coupling agent, epoxy group-containing silane coupling agent, vinyl group-containing silane coupling agent
The printed wiring board which uses the surface-treated copper foil in any one of Claims 1 thru | or 3 on a resin base material.
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| JP2012287322A JP6090693B2 (en) | 2012-12-28 | 2012-12-28 | Surface-treated copper foil and printed wiring board using the surface-treated copper foil |
| CN201310079806.XA CN103909696B (en) | 2012-12-28 | 2013-03-13 | Surface treatment copper foil and the printed wiring board of the surface treatment copper foil is used |
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| JP2012287322A JP6090693B2 (en) | 2012-12-28 | 2012-12-28 | Surface-treated copper foil and printed wiring board using the surface-treated copper foil |
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| CN107623990A (en) * | 2017-07-26 | 2018-01-23 | 珠海亚泰电子科技有限公司 | Thicken copper base and preparation technology |
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| JPS6357674A (en) * | 1986-08-28 | 1988-03-12 | Nippon Paint Co Ltd | Treating material and method used in forming hydrophilic coating film |
| JP3769084B2 (en) * | 1996-11-12 | 2006-04-19 | 日本電解株式会社 | Copper foil for printed wiring board and method for producing the same |
| JP3069094B1 (en) * | 1999-07-15 | 2000-07-24 | 株式会社神戸製鋼所 | Surface-coated metal plate and method for producing the same |
| JP5322000B2 (en) * | 2007-12-07 | 2013-10-23 | ディップソール株式会社 | Surface treatment aqueous solution and treatment method for forming a corrosion-resistant film on zinc or zinc alloy plating |
| JP4978456B2 (en) * | 2007-12-19 | 2012-07-18 | 日立電線株式会社 | Copper foil for printed circuit |
| JP5242710B2 (en) * | 2010-01-22 | 2013-07-24 | 古河電気工業株式会社 | Roughening copper foil, copper clad laminate and printed wiring board |
| JP5563849B2 (en) * | 2010-03-02 | 2014-07-30 | 福田金属箔粉工業株式会社 | Treated copper foil |
| JP5634103B2 (en) * | 2010-04-06 | 2014-12-03 | 福田金属箔粉工業株式会社 | A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate. |
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