JPS6214233B2 - - Google Patents
Info
- Publication number
- JPS6214233B2 JPS6214233B2 JP1446682A JP1446682A JPS6214233B2 JP S6214233 B2 JPS6214233 B2 JP S6214233B2 JP 1446682 A JP1446682 A JP 1446682A JP 1446682 A JP1446682 A JP 1446682A JP S6214233 B2 JPS6214233 B2 JP S6214233B2
- Authority
- JP
- Japan
- Prior art keywords
- acids
- acid
- copper
- nickel
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 26
- -1 aliphatic sulfonic acids Chemical group 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 15
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000011180 diphosphates Nutrition 0.000 claims description 7
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- 229920001542 oligosaccharide Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Chemical class 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000002826 nitrites Chemical class 0.000 claims description 3
- 150000002482 oligosaccharides Chemical class 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 1
- 150000004676 glycans Chemical class 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000004804 polysaccharides Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- RGHNJXZEOKUKBD-TXICZTDVSA-N (2r,3r,4r,5r)-2,3,4,5,6-pentahydroxyhexanoic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-TXICZTDVSA-N 0.000 description 1
- RGHNJXZEOKUKBD-STGXQOJASA-N (2s,3s,4s,5r)-2,3,4,5,6-pentahydroxyhexanoic acid Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-STGXQOJASA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- VGVLFMIJNWWPBR-UHFFFAOYSA-N 2,2,3-trihydroxypentanedioic acid Chemical compound OC(=O)CC(O)C(O)(O)C(O)=O VGVLFMIJNWWPBR-UHFFFAOYSA-N 0.000 description 1
- PLYZRRVRRKNGRW-UHFFFAOYSA-N 2-(2-oxohydrazinyl)benzoic acid Chemical compound ON=NC1=CC=CC=C1C(O)=O PLYZRRVRRKNGRW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- JFPJVTNYCURRAB-UHFFFAOYSA-N 2-nitro-n-phenylacetamide Chemical compound [O-][N+](=O)CC(=O)NC1=CC=CC=C1 JFPJVTNYCURRAB-UHFFFAOYSA-N 0.000 description 1
- GZJIQNJINXQYTG-UHFFFAOYSA-N 2-nitrooxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O[N+]([O-])=O GZJIQNJINXQYTG-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ZGKDNJHGCZXEGY-UHFFFAOYSA-N 2-nitrosobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1N=O ZGKDNJHGCZXEGY-UHFFFAOYSA-N 0.000 description 1
- RROUDFJBEBRUGL-UHFFFAOYSA-N 2-nitrosooxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1ON=O RROUDFJBEBRUGL-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- DBTMGCOVALSLOR-UHFFFAOYSA-N 32-alpha-galactosyl-3-alpha-galactosyl-galactose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(OC2C(C(CO)OC(O)C2O)O)OC(CO)C1O DBTMGCOVALSLOR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- LKDRXBCSQODPBY-JDJSBBGDSA-N D-allulose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@H]1O LKDRXBCSQODPBY-JDJSBBGDSA-N 0.000 description 1
- RGHNJXZEOKUKBD-AIHAYLRMSA-N D-altronic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-AIHAYLRMSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- FZWBNHMXJMCXLU-YRBKNLIBSA-N manninotriose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-YRBKNLIBSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- KOOMFXGDLMRWSN-UHFFFAOYSA-N n-phenylnitrous amide Chemical compound O=NNC1=CC=CC=C1 KOOMFXGDLMRWSN-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 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
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 1
- ZKIHLVYBGPFUAD-UHFFFAOYSA-N quinoline-2-sulfonic acid Chemical compound C1=CC=CC2=NC(S(=O)(=O)O)=CC=C21 ZKIHLVYBGPFUAD-UHFFFAOYSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 235000008521 threonine Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 235000014393 valine Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は光沢銅―ニツケル合金電気めつき浴、
特に、ピロリン酸浴に関するものである。
一般に銅―ニツケル合金は耐食性に優れてお
り、展延性もよく、加工性が高く、強度もある優
れた合金である。また、金率固溶系であり、鋳造
容易であるので種々の組成のもとで広範囲に利用
されている。そのため合金電気めつきとしてもシ
アン化浴、クエン酸浴、酢酸浴、酒石酸浴、チオ
硫酸浴、アンモニア浴、ピロリン酸浴など数多く
の浴が研究され報告されている。しかしながらい
ずれも実用化に至るほどには充分なものではな
く、現在のところ、銅―ニツケル合金めつきは工
業化されていない。この銅―ニツケル合金めつき
の実用化が今までになされ得なかつた原因として
次のようなことが考えられる。すなわち、銅―ニ
ツケル合金電気めつきにおいては銅の析出電位が
ニツケルに比べて非常に貴であり、単純塩浴では
もちろんのこと、錯塩浴によつても銅の優先析出
を抑制するのが難しいこと。そのため電流密度、
電解条件のわずかな変化に対して色むらが発生す
ること。またさらに問題となるのは良好な外観の
皮膜が得られにくいことである。すなわち無光沢
皮膜の析出、粉状析出、不溶性化合物の析出等が
起こる。本発明と同じピロリン酸浴を用いている
報告についても例えばラマチヤー(Rama
Char)の報告(AES Tech.Proc.、46 76
(1959)、Electroplating Met.Fin.、10 391
(1957)、電気化学25 573(1957)があるが皮膜
の外観は良好ではない。またスリバスタバ
(Srivastava)らによる報告(Surface Tech.、9
171(1979)やコロビン(Korovin)による報
告(Zhur.Fisiche.Khimi.、34 1351(1960))等
は電気化学的な考察を主にした学術論文であり、
用いた浴はコロビンの場合はまつたく無添加浴で
あり、またスリバスタバの浴は塩化アンモニウム
が加えられているのみで、得られる皮膜の外観は
非常に悪く、いずれも実用浴としては不適当であ
る。
本発明者は、銅―ニツケル合金めつきが工業化
されていないという上記の現状に鑑み、特に銅―
ニツケル合金めつきのピロリン酸浴について鋭意
研究を行つた。上記のとおり、ニツケル塩、銅塩
およびピロリン酸塩のみからなるいわゆる無添加
めつき浴からの電析皮膜は、低電流密度域では極
端に赤銅色であり、一方高電流密度域では緑色の
不溶性化合物が析出する。また0.5〜3A/dm2付
近の常用の電流密度域においても無光沢であつた
り半光沢であつたりして皮膜の外観は非常に悪
い。しかしながらこの主めつき浴に第1次添加剤
として単糖類とその誘導体である糖アルコール
類、アルドン酸類、アルダン酸類及びオリゴ糖
類、多糖類、モノカルボン酸、ジカルボン酸、オ
キシカルボン酸、アミノ酸、アミノポリカルボン
酸、メルカプトカルボン酸等の有機カルボン酸
類、脂肪族スルホン酸類、芳香族スルホン酸類等
のスルホン酸基を有する化合物、及びそれらの塩
等の少なくとも1種を添加することによつて、広
い電流密度範囲にわたつて緻密な皮膜を得ること
ができること、さらに第2次添加剤として硝酸
塩、亜硝酸塩、水溶性芳香族ニトロ化合物および
水溶性芳香族ニトロソ化合物等の少なくとも1種
を添加することによつて優れた鏡面皮膜を得るこ
とができることを見出した。本発明は上記知見に
基いて完成されたものであり、本発明のピロリン
酸浴からの銅ニツケル合金めつきはこの第1次添
加剤及び第2次添加剤をめつき浴に添加したこと
を特徴とする。すなわち本発明は、ニツケル塩、
銅塩およびピロリン酸塩よりなる主めつき浴に、
少なくとも1種の第1次添加剤と、少なくとも1
種の第2次添加剤を添加したことを特徴とする光
沢銅―ニツケル合金電気めつき浴である。上記第
1次添加剤は、単糖類とその誘導体である糖アル
コール類、アルドン酸類、アルダン酸類及びオリ
ゴ糖類、多糖類;モノカルボン酸、ジカルボン
酸、オキシカルボン酸、アミノ酸、アミノポリカ
ルボン酸、メルカプトカルボン酸等の有機カルボ
ン酸類;脂肪族スルホン酸類、芳香族スルホン酸
類等のスルホン酸基を有する化合物、およびそれ
らの塩から選ばれる。また、上記第2次添加剤
は、硝酸塩及び亜硝酸塩;水溶性芳香族ニトロ化
合物及び水溶性芳香族ニトロソ化合物から選ばれ
る。
本発明において使用するニツケル塩としては硫
酸ニツケル、塩化ニツケル、硝酸ニツケル、ピロ
リン酸ニツケル、スルフアミン酸ニツケル、ギ酸
ニツケル、酢酸ニツケル、シユウ酸ニツケル等が
例示できる。また銅塩としてはピロリン酸銅、硫
酸銅、塩化第二銅、硝酸銅、スルフアミン酸銅、
シユウ酸第二銅、酢酸第二銅、塩基性炭酸銅等が
例示できる。ピロリン酸塩としては溶解度の高い
ピロリン酸カリウムが適当である。また上記第1
次及び第2次添加剤の具体例としては下記の化合
物、ないしはその塩を例示できる。なお塩として
はカリウム塩や、ナトリウム塩等のアルカリ金属
塩あるいはアンモニウム塩等が適当である。
第1次添加剤の例
単糖類〜アルドース グリコールアルデヒド、グ
リセリンアルデヒド、トレオ
ース、エリトロース、アラビ
ノース、リキソース、キシロ
ース、リボース、グルコース
(ブドウ糖)、グロース、マン
ノース、イドース、ガラクト
ース、タロース、アルトロー
ス、アロース等
〜ケトース ジヒドロキシアセトン、エリトル
ロース、リブロース、キシル
ロース、プシコース、フルク
トース(果糖)、ソルボー
ス、タガトース等
糖アルコール類 エチレングリコール、グリセリ
ン、エリトリツト、メソエリ
トリツト、アラビツト、キシ
リツト、アドニツト、ソルビ
ツト、マンニツト、イジツ
ト、ズルシツト、ノヌリツ
ト、アリツト等
アルダン酸類 グリコール類、グリセリン酸、ト
レオン酸、エリトロン酸、ア
ラボン酸、リキノン酸、キシ
ロン酸、リボン酸、グルコン
酸、グロン酸、マンノン酸、
イドン酸、ガラクトン酸、タ
ロン酸、アルトロン酸、アロ
ン酸等及びそれらの塩
アルドン酸類 シユウ酸、タルトロン酸、酒石
酸、メソ酒石酸、トリヒドロ
キシグルタル酸、キシロトリ
ヒドロキシグルタル酸、リボ
トリヒドロキシグルタル酸、
グルコ糖酸、マンノ糖酸、イ
ド糖酸、粘液酸、タロ粘液
酸、アロ粘液酸、等及びそれ
らの塩
オリゴ糖類 トレハロース、サツカロース(シヨ
糖)、マルトース(麦芽糖)、
セロビオース、ゲンチオビオ
ース、ラクトース(乳糖)、
ラフイノース、ゲンチアノー
ス、メレチトース、マルトト
リオース、セロトリオース、
マンニノトリオース、スタキ
オース等
多糖類 スターチ(澱粉)、イヌリン、アルギン
酸及びその塩等
モノカルボン酸類 ギ酸、酢酸、ピロピオン酸、
安息香酸、フエニル酢酸、等
及びそれらの塩
ジカルボン酸類 マロン酸、コハク酸、グルタン
酸、フマル酸、マレイン酸、
フタル酸、等及びそれらの塩
オキシカルボン酸類 乳酸、ヒドロアクリル酸、
リンゴ酸、クエン酸、サリチ
ル酸、等及びそれらの塩
アミノ酸類 グリシン、アラニン、バリン、セリ
ン、トレオニン、アスパラギ
ン酸、グルタミン酸、システ
イン、メチオニン、等、及び
それらの塩
アミノポリカルボン酸 ニトリロ三酢酸
(NTA)、エチレンジアミン
四酢酸(EDTA)、ジエチレ
ントリアミン五酢酸
(DTPA)等及びそれらの塩
メルカプトカルボン酸 チオグリコール酸、チオ
乳酸、チオリンゴ酸、チオサ
リチル酸、等、及びそれらの
塩
脂肪族スルホン酸類 メタンスルホン酸、アリル
スルホン酸、等及びそれらの
塩
芳香族スルホン酸類 ベンゼンスルホン酸、ナフ
タレンスルホン酸、スルホサ
リチル酸、フエノールスルホ
ン酸、トルエンスルホン酸等
及びそれらの塩
その他のスルホン酸類 ピリジンスルホン酸、キ
ノリンスルホン酸等、及びそ
れらの塩
第2次添加剤の例
硝酸塩 硝酸ナトリウム、硝酸カリウム、硝酸ア
ンモニウム等
亜硝酸塩 亜硝酸ナトリウム、亜硝酸カリウム、
亜硝酸アンモニウム等
水溶性芳香族ニトロ化合物 ニトロ安息香酸、ニ
トロサリチル酸、ニトロフエ
ノール、ニトロフエノールス
ルホン酸、ニトロベンゼンス
ルホン酸、ニトロアセトアニ
リド等及びそれらの塩
水溶性芳香族ニトロソ化合物 ニトロソ安息香
酸、ニトロソサリチル酸、ニ
トロソフエノール、ニトロソ
アニリン、ニトロソアントラ
ニル酸、ニトロソR塩等及び
それらの塩
なお主めつき浴成分の金属塩として上記の添加
剤の塩、例えば硝酸ニツケル、ギ酸ニツケル、酢
酸ニツケル、シユウ酸ニツケル、硝酸銅、シユウ
酸銅、酢酸銅、等を用いた場合は相当する添加剤
の添加量を軽減ないしは省略することができる。
本発明の電気めつき浴の各成分はそれぞれ次の
ような濃度範囲で使用することができる。
ニツケル塩(金属ニツケル分として):2〜30
g/(0.03〜0.5mol/)
銅塩(金属銅分として):0.3〜10g/(0.005
〜0.16mol/)
ピロリン酸塩(ピロリン酸分として):金属ニツ
ケル分の1.5倍モル、金属銅分の2.5倍モルを合
わせたモル量
添加剤(第1次、第2次それぞれ):0.01〜100
g/あるいは溶解限
上記の浴組成において金属分の添加量としてニ
ツケルで30g/までに限るのは、それ以上の添
加ではたとえピロリン酸分を大過剰に加えても時
間が経過すると沈澱が生成するためである。また
銅分を10g/までに限るのはそれ以上では皮膜
の外観を著しく損なうためである。なお、いずれ
の金属分もあまりに低濃度では浴組成の変化が大
きすぎるので好ましくない。また銅分の比率もニ
ツケルに対してあまり高めない方が皮膜の外観の
点からも好ましい。さらに添加剤は0.01〜100g/
という広い範囲を例示したが、一般的には0.5
〜70g/の範囲で添加すればよい。ただメルカ
プトカルボン酸類は微量の添加でよく、その範囲
は0.01〜5g/が好ましい。また多糖類、芳香
族ニトロ化合物、芳香族ニトロソ化合物等は一般
的には溶解度が低いので、その溶解限が、添加量
の限度となる。
本発明によつて銅―ニツケル合金めつき皮膜を
得るには、従来のめつき法と何ら異なる工程また
は技法を必要としない。めつき条件も浴温20〜80
℃、浴のPH7.0〜11.0そして陰極電流密度0.1〜10
A/dm2の範囲で使用することができる。またかく
はんについては無かくはんでも機械的あるいは空
気かくはんでもどちらでもよいが、高電流密度部
で、無かくはんの場合ガスあとが生ずる場合があ
るのでその際にはかくはんをするとよい。陽極は
カーボン、白金、白金めつきチタン板等の不溶解
性陽極を用いればよい。銅―ニツケル合金陽極も
使用できるが陰極電流効率と陽極電流効率を調
べ、浴管理に留意する必要がある。
本発明による銅―ニツケル合金めつき浴によれ
ば広い電流密度範囲にわたつてムラのない良好な
外観の光沢のある皮膜を得ることができる。
また本発明による合金めつき浴においては金属
濃度、添加剤の種類、濃度等、浴組成を変えるこ
とによつて銀白色、淡紅色、赤銅色とその色調を
変化させることも出来る。
以下実施例、比較例等をあげて本発明の特徴を
より一層明らかにする。
実施例 1
塩化ニツケル(NiCl2・6H2O)20g/(金属
ニツケル分4.94g/)、ピロリン酸銅
(Cu2P2O7)2g/(金属銅分0.84g/)、およ
びピロリン酸カリウム(K4P2O7)100g/から
なる主めつき浴に、第1次添加剤としてグルコー
ス20g/、第2次添加剤として硝酸アンモニウ
ム(NH4NO3)20g/を加えてめつき浴を調製
した。このめつき浴からの銅ニツケル合金めつき
皮膜の外観と、第2次添加剤を含まない浴(比較
例1)および第1次、第2次添加剤をともに含ま
ない浴(比較例2)からのめつき皮膜の外観とを
ハルセル試験により比較した。その結果を第1図
に示す。
めつき条件:総電流2A、浴温50℃、PH9.0、無か
くはん及び空気かくはん、陽極:白
金板、陰極:光沢ニツケルめつきし
た黄銅板。
実施例 2〜11
本発明による銅―ニツケル合金電気めつき浴を
第1表に示す種々の浴組成で調製し、第2表に示
すめつき条件で合金めつき皮膜を電析させた。そ
の結果を第2表に合せて示す。
【表】
【表】
【表】
比較例 3〜12
公知のピロリン酸浴を用いてハルセル試験を行
つた。いずれの場合にも本発明のような広い電流
密度域にわたつてすぐれた外観のめつき皮膜は得
られなかつた。めつき浴組成およびめつき条件を
第3表に、結果を第2図にそれぞれ示す。
【表】
【表】
試験例
本発明による電気めつき浴からの銅―ニツケル
合金めつき皮膜の耐食性及び耐変色性を公知の銅
めつき皮膜、ニツケルめつき皮膜、黄銅めつき皮
膜、クロムめつき皮膜と比較した。その結果を第
4表に示す。
【表】
浸漬試験
試験溶液:濃塩酸、1+1硫酸、1+3硝酸、10
規定水酸化ナトリウム水溶液
試験溶液の温度:約30℃
浸漬時間:約5分間
キヤス試験
JIS H8617附属書2に準じた。
アンモニア蒸気試験
試験溶液:1+9アンモニア水
試験条件:密閉容器中に試料が試験溶液に浸漬し
ないように保持し、50℃に加温して
10分間放置
なお、いずれの試験においても試験後各試料を
水洗した後、皮膜の腐食の具合ないしは変色度を
観察した。評価はまつたく変化ないものを〇と
し、わずかに変化のあつたものを△とし、大きく
変化したものを×とした。
【表】
〓 無かくはん
【表】
〓 無かくはん
[Detailed Description of the Invention] The present invention provides a bright copper-nickel alloy electroplating bath,
In particular, it concerns pyrophosphate baths. In general, copper-nickel alloys are excellent alloys that have excellent corrosion resistance, good malleability, high workability, and strength. Furthermore, since it is a solid solution type with a gold content and is easy to cast, it is widely used in various compositions. Therefore, many baths have been studied and reported for alloy electroplating, including cyanide bath, citric acid bath, acetic acid bath, tartaric acid bath, thiosulfuric acid bath, ammonia bath, and pyrophosphoric acid bath. However, none of these methods are sufficient for practical use, and copper-nickel alloy plating has not been industrialized at present. The following may be the reason why this copper-nickel alloy plating has not been put into practical use until now. In other words, in copper-nickel alloy electroplating, the deposition potential of copper is much nobler than that of nickel, and it is difficult to suppress the preferential deposition of copper not only in a simple salt bath but also in a complex salt bath. thing. Therefore, the current density,
Color unevenness occurs due to slight changes in electrolytic conditions. Another problem is that it is difficult to obtain a film with a good appearance. That is, precipitation of a matte film, powdery precipitation, precipitation of insoluble compounds, etc. occur. Regarding reports using the same pyrophosphate bath as the present invention, for example, Rama
Char) report (AES Tech.Proc., 46 76
(1959), Electroplating Met.Fin., 10 391
(1957) and Electrochemistry 25 573 (1957), but the appearance of the film is not good. Also, a report by Srivastava et al. (Surface Tech., 9
171 (1979) and the report by Korovin (Zhur.Fisiche.Khimi., 34 1351 (1960)) are academic papers that mainly focus on electrochemical considerations.
In the case of Corobin, the baths used were additive-free, and in the case of Srivastava, only ammonium chloride was added, and the appearance of the resulting film was very poor, making both of them unsuitable as practical baths. be. In view of the above-mentioned current situation that copper-nickel alloy plating has not been industrialized, the present inventor specifically
We conducted extensive research on pyrophosphoric acid baths for nickel alloy plating. As mentioned above, the deposited film from a so-called additive-free plating bath consisting only of nickel salts, copper salts, and pyrophosphates is extremely coppery in the low current density range, while it is green and insoluble in the high current density range. The compound precipitates. Further, even in the commonly used current density range of around 0.5 to 3 A/dm 2 , the appearance of the film is very poor, being matte or semi-glossy. However, the primary additives used in this glazing bath are monosaccharides and their derivatives, sugar alcohols, aldonic acids, aldanic acids, oligosaccharides, polysaccharides, monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids, amino acids, amino acids, etc. By adding at least one of organic carboxylic acids such as polycarboxylic acids and mercaptocarboxylic acids, compounds having sulfonic acid groups such as aliphatic sulfonic acids and aromatic sulfonic acids, and salts thereof, a wide current can be achieved. It is possible to obtain a dense film over a range of densities, and by adding at least one of nitrates, nitrites, water-soluble aromatic nitro compounds, and water-soluble aromatic nitroso compounds as secondary additives. It has been found that it is possible to obtain an excellent mirror-like coating. The present invention has been completed based on the above findings, and the copper-nickel alloy plating from the pyrophosphoric acid bath of the present invention is based on the addition of the primary additive and the secondary additive to the plating bath. Features. That is, the present invention provides nickel salt,
The main plating bath consists of copper salts and pyrophosphates,
at least one primary additive; and at least one
This is a bright copper-nickel alloy electroplating bath characterized by the addition of secondary additives. The above primary additives include monosaccharides and their derivatives, sugar alcohols, aldonic acids, aldanic acids and oligosaccharides, polysaccharides; monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids, amino acids, aminopolycarboxylic acids, mercapto It is selected from organic carboxylic acids such as carboxylic acids; compounds having sulfonic acid groups such as aliphatic sulfonic acids and aromatic sulfonic acids, and salts thereof. Further, the secondary additive is selected from nitrates and nitrites; water-soluble aromatic nitro compounds and water-soluble aromatic nitroso compounds. Examples of the nickel salts used in the present invention include nickel sulfate, nickel chloride, nickel nitrate, nickel pyrophosphate, nickel sulfamate, nickel formate, nickel acetate, and nickel oxalate. Copper salts include copper pyrophosphate, copper sulfate, cupric chloride, copper nitrate, copper sulfamate,
Examples include cupric oxalate, cupric acetate, and basic copper carbonate. Potassium pyrophosphate, which has high solubility, is suitable as the pyrophosphate. Also, the first
Specific examples of the secondary and secondary additives include the following compounds and salts thereof. Suitable salts include potassium salts, alkali metal salts such as sodium salts, and ammonium salts. Examples of primary additives Monosaccharides - Aldose Glycolaldehyde, glyceraldehyde, threose, erythrose, arabinose, lyxose, xylose, ribose, glucose, gulose, mannose, idose, galactose, talose, altrose, allose, etc. Ketose Dihydroxyacetone, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, tagatose, etc. Sugar alcohols Ethylene glycol, glycerin, erythritol, mesoerythritol, arabitol, xylitol, adonitol, sorbitol, mannitol, ilzitol, zulcitol, nonuritol, arizitol Aldanic acids such as glycols, glyceric acid, threonic acid, erythronic acid, arabonic acid, liquinonic acid, xylonic acid, ribbon acid, gluconic acid, gulonic acid, mannonic acid,
Idonic acid, galactonic acid, talonic acid, altronic acid, allonic acid, etc. and their salts aldonic acids, oxalic acid, tartronic acid, tartaric acid, mesotartaric acid, trihydroxyglutaric acid, xylotrihydroxyglutaric acid, ribotrihydroxyglutaric acid,
Glucosaccharide, mannosugar acid, idosugaracid, mucinic acid, talomucucacid, allomucucacid, etc. and their salt oligosaccharides, trehalose, sutucarose, maltose,
Cellobiose, gentiobiose, lactose (milk sugar),
raffinose, gentianose, meletitose, maltotriose, cellotriose,
Polysaccharides such as manninotriose and stachyose Monocarboxylic acids such as starch, inulin, alginic acid and its salts Formic acid, acetic acid, pyropionic acid,
Benzoic acid, phenylacetic acid, etc. and their salts dicarboxylic acids Malonic acid, succinic acid, glutanic acid, fumaric acid, maleic acid,
Phthalic acid, etc. and their salts oxycarboxylic acids, lactic acid, hydroacrylic acid,
Malic acid, citric acid, salicylic acid, etc. and their salts Amino acids Glycine, alanine, valine, serine, threonine, aspartic acid, glutamic acid, cysteine, methionine, etc. and their salts Aminopolycarboxylic acid Nitrilotriacetic acid (NTA) , ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), etc. and their salts, mercaptocarboxylic acid, thioglycolic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, etc., and their salts, aliphatic sulfonic acids, methanesulfonic acid, allyl Sulfonic acids, etc. and their salts Aromatic sulfonic acids Benzene sulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, phenolsulfonic acid, toluenesulfonic acid, etc. and their salts and other sulfonic acids Pyridine sulfonic acid, quinolinesulfonic acid, etc. Examples of salt secondary additivesNitrates Sodium nitrate, potassium nitrate, ammonium nitrate, etc.Nitrites Sodium nitrite, potassium nitrite,
Water-soluble aromatic nitro compounds such as ammonium nitrite Nitrobenzoic acid, nitrosalicylic acid, nitrophenol, nitrophenolsulfonic acid, nitrobenzenesulfonic acid, nitroacetanilide, etc. and their saltsWater-soluble aromatic nitroso compounds Nitrosobenzoic acid, nitrososalicylic acid, nitrosophenol, Nitrosoaniline, nitrosoanthranilic acid, nitroso R salt, etc. and salts thereof. Salts of the above-mentioned additives such as nickel nitrate, nickel formate, nickel acetate, nickel oxalate, copper nitrate, nickel nitrate, etc. as metal salts of the main glare bath components. When copper acid, copper acetate, etc. are used, the amount of the corresponding additive can be reduced or omitted. Each component of the electroplating bath of the present invention can be used in the following concentration ranges. Nickel salt (as nickel metal): 2-30
g/(0.03-0.5mol/) Copper salt (as metallic copper): 0.3-10g/(0.005
~0.16 mol/) Pyrophosphate (as pyrophosphoric acid): molar amount of 1.5 times the mole of nickel metal and 2.5 times the mole of copper metal Additive (primary and secondary, respectively): 0.01 ~ 100
g/or solubility limit In the above bath composition, the amount of metal added is limited to 30g/ of nickel because if it is added more than that, a precipitate will form over time even if pyrophosphoric acid is added in large excess. It's for a reason. Further, the reason why the copper content is limited to 10 g/m is because the appearance of the film will be seriously impaired if it exceeds this amount. It should be noted that if the concentration of any of the metals is too low, the change in the bath composition will be too large, which is not preferable. Also, from the viewpoint of the appearance of the film, it is preferable that the copper content ratio is not too high compared to nickel. Furthermore, additives are 0.01~100g/
Although the example shows a wide range of 0.5
It may be added in a range of ~70g/. However, a trace amount of mercaptocarboxylic acids may be added, and the preferable range is 0.01 to 5 g. Further, since polysaccharides, aromatic nitro compounds, aromatic nitroso compounds, etc. generally have low solubility, their solubility limit becomes the limit of the amount to be added. Obtaining a copper-nickel alloy plating film according to the present invention does not require any different process or technique from conventional plating methods. Plating conditions are bath temperature 20-80
℃, bath PH7.0~11.0 and cathode current density 0.1~10
Can be used in the A/ DM2 range. Regarding stirring, either non-stirring, mechanical or air stirring may be used, but it is recommended to stir in high current density areas, as gas marks may be produced if there is no stirring. As the anode, an insoluble anode such as carbon, platinum, or platinum-plated titanium plate may be used. A copper-nickel alloy anode can also be used, but it is necessary to check the cathode current efficiency and anode current efficiency, and pay attention to bath management. According to the copper-nickel alloy plating bath according to the present invention, it is possible to obtain a glossy film with a uniform and good appearance over a wide current density range. Furthermore, in the alloy plating bath according to the present invention, the color tone can be changed from silvery white to pale pink to coppery red by changing the bath composition such as the metal concentration, the type and concentration of additives, etc. Examples, comparative examples, etc. will be given below to further clarify the characteristics of the present invention. Example 1 Nickel chloride (NiCl 2 6H 2 O) 20g/(metallic nickel content 4.94g/), copper pyrophosphate (Cu 2 P 2 O 7 ) 2g/(metallic copper content 0.84g/), and potassium pyrophosphate To a main plating bath consisting of 100g/(K 4 P 2 O 7 ), 20g/glucose as a primary additive and 20g/ammonium nitrate (NH 4 NO 3 ) as a secondary additive were added. Prepared. The appearance of the copper-nickel alloy plating film from this plating bath, a bath containing no secondary additives (Comparative Example 1), and a bath containing neither primary nor secondary additives (Comparative Example 2) The appearance of the plated film was compared using the Hull cell test. The results are shown in FIG. Plating conditions: total current 2A, bath temperature 50℃, PH9.0, no stirring or air stirring, anode: platinum plate, cathode: brass plate with bright nickel plating. Examples 2 to 11 Copper-nickel alloy electroplating baths according to the present invention were prepared with various bath compositions shown in Table 1, and alloy plating films were electrodeposited under the plating conditions shown in Table 2. The results are also shown in Table 2. [Table] [Table] [Table] Comparative Examples 3 to 12 A Hull cell test was conducted using a known pyrophosphoric acid bath. In either case, a plated film with excellent appearance over a wide current density range as in the present invention could not be obtained. The plating bath composition and plating conditions are shown in Table 3, and the results are shown in FIG. 2. [Table] [Table] Test Example The corrosion resistance and discoloration resistance of the copper-nickel alloy plating film produced from the electroplating bath according to the present invention were evaluated using known copper plating films, nickel plating films, brass plating films, and chrome plating films. Comparison was made with a coated film. The results are shown in Table 4. [Table] Immersion test test solution: concentrated hydrochloric acid, 1+1 sulfuric acid, 1+3 nitric acid, 10
Temperature of normal sodium hydroxide aqueous test solution: Approximately 30°C Immersion time: Approximately 5 minutes Cast test According to JIS H8617 Annex 2. Ammonia vapor test Test solution: 1+9 Ammonia water test conditions: Hold the sample in a closed container so that it is not immersed in the test solution, and heat it to 50℃.
Leave for 10 minutes In all tests, after each sample was washed with water, the degree of corrosion or discoloration of the film was observed. The evaluation was rated as ○ if there was no significant change, △ if there was a slight change, and × if there was a large change. [Table] 〓 No stirring [Table] 〓 No stirring
第1図および第2図は、ハルセル試験結果を示
す概略図である。第1図の1a,1bおよび2b
は、実施例1、比較例1および比較例2のめつき
浴をそれぞれ用いて無かくはんでめつきした場合
の結果を示し、1a′,1b′および2b′は、空気か
くはん条件でめつきした場合の結果を示す。第2
図の3b〜12bは、比較例3〜12のめつき浴を
それぞれ用いてめつきした場合の結果を示す。
A…ニツケル色鏡面光沢、A′…淡銅色鏡面光
沢、A″…ニツケル色むらのある光沢、A…ニ
ツケル色半光沢、B…銅色光沢、C…黒つぽい光
沢、C′…黒色無光沢、C″…暗かつ色無光沢、D
…ガスあと、D′…ヤケ、E…不溶性化合物析
出、F…白色無光沢。
FIG. 1 and FIG. 2 are schematic diagrams showing the Hull cell test results. 1a, 1b and 2b in Figure 1
1a′, 1b′, and 2b′ show the results of plating without stirring using the plating baths of Example 1, Comparative Example 1, and Comparative Example 2, respectively, and 1a′, 1b′, and 2b′ show the results of plating with air stirring. The results are shown below. Second
Figures 3b to 12b show the results of plating using the plating baths of Comparative Examples 3 to 12, respectively. A...Nickel-colored specular gloss, A'...Pale copper-colored specular gloss, A''...Nickel-colored uneven gloss, A...Nickel-colored semi-gloss, B...Copper-colored gloss, C...Darkish gloss, C'...Black Matte, C″...Dark and matte color, D
...Gas mark, D'... Discoloration, E... Insoluble compound precipitation, F... White matte.
Claims (1)
る主めつき浴に、下記に示される少なくとも1種
の第1次添加剤と、少なくとも1種の第2次添加
剤を添加したことを特徴とする光沢銅―ニツケル
合金電気めつき浴。 第1次添加剤: 単糖類とその誘導体である糖アルコール類、ア
ルドン酸類、アルダン酸類及びオリゴ糖類、多糖
類;モノカルボン酸、ジカルボン酸、オキシカル
ボン酸、アミノ酸、アミノポリカルボン酸、メル
カプトカルボン酸等の有機カルボン酸類;脂肪族
スルホン酸類、芳香族スルホン酸類等のスルホン
酸基を有する化合物;及びそれらの塩 第2次添加剤: 硝酸塩及び亜硝酸塩;水溶性芳香族ニトロ化合
物及び水溶性芳香族ニトロソ化合物。[Claims] 1. At least one primary additive and at least one secondary additive shown below are added to a main plating bath consisting of a nickel salt, a copper salt, and a pyrophosphate. A bright copper-nickel alloy electroplating bath. Primary additives: Monosaccharides and their derivatives, sugar alcohols, aldonic acids, aldanic acids and oligosaccharides, polysaccharides; monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids, amino acids, aminopolycarboxylic acids, mercaptocarboxylic acids Organic carboxylic acids such as; Compounds with sulfonic acid groups such as aliphatic sulfonic acids and aromatic sulfonic acids; and their salts Secondary additives: Nitrates and nitrites; Water-soluble aromatic nitro compounds and water-soluble aromatic compounds Nitroso compounds.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1446682A JPS58133391A (en) | 1982-02-01 | 1982-02-01 | Electroplating bath for bright copper-nickel alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1446682A JPS58133391A (en) | 1982-02-01 | 1982-02-01 | Electroplating bath for bright copper-nickel alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58133391A JPS58133391A (en) | 1983-08-09 |
JPS6214233B2 true JPS6214233B2 (en) | 1987-04-01 |
Family
ID=11861827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1446682A Granted JPS58133391A (en) | 1982-02-01 | 1982-02-01 | Electroplating bath for bright copper-nickel alloy |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58133391A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4324995C2 (en) * | 1993-07-26 | 1995-12-21 | Demetron Gmbh | Cyanide-alkaline baths for the galvanic deposition of copper-tin alloy coatings |
MY111621A (en) * | 1993-12-16 | 2000-09-27 | Kiyokawa Plating Ind Co Ltd | Method for producing metal film resistor |
JP2009228078A (en) * | 2008-03-24 | 2009-10-08 | Fujitsu Ltd | Electroplating liquid, electroplating method and method of manufacturing semiconductor device |
MX355999B (en) | 2012-04-19 | 2018-05-08 | Dipsol Chem | Copper-nickel alloy electroplating bath and plating method. |
JP6439172B2 (en) * | 2014-08-08 | 2018-12-19 | ディップソール株式会社 | Copper-nickel alloy electroplating bath |
-
1982
- 1982-02-01 JP JP1446682A patent/JPS58133391A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58133391A (en) | 1983-08-09 |
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