JP6501280B2 - クロムめっき液、電気めっき方法及びクロムめっき液の製造方法 - Google Patents
クロムめっき液、電気めっき方法及びクロムめっき液の製造方法 Download PDFInfo
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- JP6501280B2 JP6501280B2 JP2017516525A JP2017516525A JP6501280B2 JP 6501280 B2 JP6501280 B2 JP 6501280B2 JP 2017516525 A JP2017516525 A JP 2017516525A JP 2017516525 A JP2017516525 A JP 2017516525A JP 6501280 B2 JP6501280 B2 JP 6501280B2
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- Prior art keywords
- chromium
- palladium
- plating solution
- gold
- ions
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- 238000007747 plating Methods 0.000 title claims description 199
- 239000011651 chromium Substances 0.000 title claims description 148
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 144
- 229910052804 chromium Inorganic materials 0.000 title claims description 144
- 238000000034 method Methods 0.000 title claims description 42
- 238000009713 electroplating Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 108
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 87
- -1 palladium ions Chemical class 0.000 claims description 83
- 239000010931 gold Substances 0.000 claims description 74
- 229910052737 gold Inorganic materials 0.000 claims description 71
- 229910052763 palladium Inorganic materials 0.000 claims description 64
- 229910001430 chromium ion Inorganic materials 0.000 claims description 59
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 18
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 11
- 150000002941 palladium compounds Chemical class 0.000 claims description 11
- 229910001020 Au alloy Inorganic materials 0.000 claims description 10
- 239000003353 gold alloy Substances 0.000 claims description 10
- 150000002344 gold compounds Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 239000000243 solution Substances 0.000 description 125
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 235000006408 oxalic acid Nutrition 0.000 description 11
- 238000007654 immersion Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 6
- 229910000457 iridium oxide Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000001845 chromium compounds Chemical class 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000006174 pH buffer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- DGOHFTDNMSZWDQ-UHFFFAOYSA-N N#C[Au]C#N Chemical class N#C[Au]C#N DGOHFTDNMSZWDQ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- XFJRTXJMYXFAEE-UHFFFAOYSA-K [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O XFJRTXJMYXFAEE-UHFFFAOYSA-K 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZEMWIYASLJTEHQ-UHFFFAOYSA-J aluminum;sodium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZEMWIYASLJTEHQ-UHFFFAOYSA-J 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process 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
- 229910052796 boron Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- OGXRULUQTHSMSF-UHFFFAOYSA-H butanedioate chromium(3+) Chemical compound [Cr+3].[Cr+3].[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O OGXRULUQTHSMSF-UHFFFAOYSA-H 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229940064958 chromium citrate Drugs 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- SWXXYWDHQDTFSU-UHFFFAOYSA-K chromium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cr+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SWXXYWDHQDTFSU-UHFFFAOYSA-K 0.000 description 1
- QWWLTGUEZNQHMO-UHFFFAOYSA-H chromium(3+);propanedioate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)CC([O-])=O.[O-]C(=O)CC([O-])=O.[O-]C(=O)CC([O-])=O QWWLTGUEZNQHMO-UHFFFAOYSA-H 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
項1.3価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含む、クロムめっき液。
項2.3価クロムイオンと、6価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含む、クロムめっき液。
項3.前記6価クロムイオンの濃度(g/L)が全てのクロムイオンの濃度(g/L)に対して5〜50%の割合である、上記項2に記載のクロムめっき液。
項4.パラジウムイオンもしくは金イオンの濃度が0.1mg/L以上、1000mg/L以下である、上記項1〜3のいずれか1項に記載のクロムめっき液。
項5.請求項1〜4のいずれか1項に記載のクロムめっき液によって、めっき対象物を10質量%以上のクロムを含む金属でめっきをする、電気めっき方法。
項6.パラジウム及び/又は金を含む陽極を使用する、上記項5に記載の電気めっき方法。
項7.上記項1〜4のいずれか1項に記載のクロムめっき液の製造方法であって、
金属パラジウム、パラジウム合金、パラジウム化合物、金属金、金合金及び金化合物からなる群より選ばれる少なくとも1種を溶解させる工程、及び、金属パラジウム、パラジウム合金、パラジウム化合物、金属金、金合金及び金化合物からなる群より選ばれる少なくとも1種を浸漬させる工程の少なくともいずれかの工程によって、パラジウムイオンを導入する、クロムめっき液の製造方法。
本実施形態のクロムめっき液は、3価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含む。また、本実施形態の他の形態として、クロムめっき液は、3価クロムイオンと、6価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含む。以下、3価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含むクロムめっき液を「第1クロムめっき液」、3価クロムイオンと、6価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含むクロムめっき液を「第2クロムめっき液」と略記する。また、「第1クロムめっき液」及び「第2クロムめっき液」をまとめて「クロムめっき液」と表記する。
上述のクロムめっき液を用いてめっき対象物のめっきを行う方法は特に制限されず、例えば、公知の電気めっき方法を採用することができる。
硫酸クロムを26g/L(3価クロムとして7g/L含有)、伝導塩として硫酸ナトリウムを160g/L、pH緩衝剤としてホウ酸を75g/Lおよび錯化剤としてリンゴ酸10g/Lを蒸留水に溶解させ、これにアンモニア水および硫酸パラジウムをパラジウム濃度が50mg/Lとなるように添加した。
3価クロムめっき液の調製において、硫酸パラジウムを使用しなかったこと以外は、実施例1と同様の条件で3価クロムめっき液を調製して、クロムめっきを行った。3価クロムめっき液中のパラジウムイオンの濃度は0mg/Lであった。
3価クロム濃度88g/L、6価クロム濃度16g/L、シュウ酸濃度230g/Lとなるように6価クロムイオン源としての無水クロム酸200g/Lと還元剤および錯化剤としてのシュウ酸二水和物640g/Lを蒸留水中で反応させ、これに伝導塩及びpH緩衝剤として硫酸アンモニウム75g/L、硫酸パラジウム約200mg/Lを加えることで、3価クロムと6価クロムとの折衷液(第2クロムめっき液)の調製を行った。得られためっき液中のパラジウムイオンの濃度は100mg/Lであった。なお、3価クロムは6価クロムとシュウ酸との反応により導入されたものであり、めっき液の初期の全クロムイオン濃度は104g/Lである。
折衷液の調製において硫酸パラジウムの量を約20mg/Lに変更したこと以外は実施例2と同様の条件でクロムめっきを行った。得られためっき液中のパラジウムイオンの濃度は10mg/Lであった。
折衷液の調製において硫酸パラジウムの量を約2mg/Lに変更したこと以外は実施例2と同様の条件でクロムめっきを行った。得られためっき液中のパラジウムイオンの濃度は1mg/Lであった。
折衷液の調製において硫酸パラジウムを使用せず、かつ、めっき前にパラジウム被覆白金陽極を5h通電することで陽極のパラジウムをめっき液にパラジウムイオンとして導入し、そのままパラジウム被覆白金陽極にてめっきを行ったこと以外は実施例2と同様の条件でクロムめっきを行った。めっき時のめっき液中のパラジウムイオンの濃度は8mg/Lであった。
折衷液の調製において硫酸パラジウムを使用せず、めっき前に金陽極を使用して5h通電することでめっき液に金イオンを導入し、めっき時は酸化イリジウム被覆チタン陽極を使用したこと以外は実施例2と同様の条件でクロムめっきを行った。めっき時のめっき液中の金イオン濃度は200mg/Lであった。
折衷液の調製において、硫酸パラジウムを使用しなかったこと以外は、実施例1と同様の条件で3価クロムと6価クロムの折衷液を調製して、クロムめっきを行った。めっき液中のパラジウムイオンの濃度は0mg/Lであった。
折衷液の調製において硫酸パラジウムを使用せず、また、陽極を鉛陽極に変更したこと以外は実施例2と同様の条件でクロムめっきを行った。めっき液中のパラジウムイオンの濃度は0mg/Lであった。
折衷液の調製において硫酸パラジウムを使用せず、また、陽極を白金陽極に変更したこと以外は実施例2と同様の条件でクロムめっきを行った。めっき液中のパラジウムイオンの濃度は0mg/Lであった。
Claims (7)
- 3価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含み、ハロゲンイオンは含まない、クロムめっき液。
- 3価クロムイオンと、6価クロムイオンと、パラジウムイオン及び金イオンからなる群より選ばれる少なくとも1種とを含み、ハロゲンイオンは含まない、クロムめっき液。
- 前記6価クロムイオンの濃度(g/L)が全てのクロムイオンの濃度(g/L)に対して5〜50%の割合である、請求項2に記載のクロムめっき液。
- パラジウムイオンもしくは金イオンの濃度が0.1mg/L以上、1000mg/L以下である、請求項1〜3のいずれか1項に記載のクロムめっき液。
- 請求項1〜4のいずれか1項に記載のクロムめっき液によって、めっき対象物を10質量%以上のクロムを含む金属でめっきをする、電気めっき方法。
- パラジウム及び金イオンからなる群より選ばれる少なくとも1種を含む陽極を使用する、請求項5に記載の電気めっき方法。
- 請求項1〜4のいずれか1項に記載のクロムめっき液の製造方法であって、
金属パラジウム、パラジウム合金、パラジウム化合物、金属金、金合金及び金化合物からなる群より選ばれる少なくとも1種を溶解させる工程、及び、金属パラジウム、パラジウム合金、パラジウム化合物、金属金、金合金及び金化合物からなる群より選ばれる少なくとも1種を浸漬させる工程の少なくともいずれかの工程によって、パラジウムイオンもしくは金イオンを導入する、クロムめっき液の製造方法。
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