JP6214355B2 - Electrolytic gold plating solution and gold film obtained using the same - Google Patents
Electrolytic gold plating solution and gold film obtained using the same Download PDFInfo
- Publication number
- JP6214355B2 JP6214355B2 JP2013242513A JP2013242513A JP6214355B2 JP 6214355 B2 JP6214355 B2 JP 6214355B2 JP 2013242513 A JP2013242513 A JP 2013242513A JP 2013242513 A JP2013242513 A JP 2013242513A JP 6214355 B2 JP6214355 B2 JP 6214355B2
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- JP
- Japan
- Prior art keywords
- gold
- methyl
- ethyl
- butyl
- propyl
- 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.)
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 339
- 239000010931 gold Substances 0.000 title claims description 336
- 229910052737 gold Inorganic materials 0.000 title claims description 336
- 238000007747 plating Methods 0.000 title claims description 244
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- -1 pyridinium compound Chemical group 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 230000008021 deposition Effects 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 125000001424 substituent group Chemical group 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 150000001868 cobalt Chemical class 0.000 claims description 20
- 150000002505 iron Chemical class 0.000 claims description 19
- 150000002815 nickel Chemical class 0.000 claims description 19
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 claims description 17
- 229910001020 Au alloy Inorganic materials 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 7
- 125000005138 alkoxysulfonyl group Chemical group 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 230000000704 physical effect Effects 0.000 claims description 7
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 7
- 230000002159 abnormal effect Effects 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 claims description 5
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000000007 visual effect Effects 0.000 claims description 5
- LJJNEPKMBSUEND-UHFFFAOYSA-O azanium;gold;cyanide Chemical compound [NH4+].[Au].N#[C-] LJJNEPKMBSUEND-UHFFFAOYSA-O 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KLNYRFBLEYSXHW-UHFFFAOYSA-N 1,2-diethylpyridin-1-ium Chemical compound CCC1=CC=CC=[N+]1CC KLNYRFBLEYSXHW-UHFFFAOYSA-N 0.000 claims description 3
- UMZDENILBZKMFY-UHFFFAOYSA-N 1,2-dimethylpyridin-1-ium Chemical compound CC1=CC=CC=[N+]1C UMZDENILBZKMFY-UHFFFAOYSA-N 0.000 claims description 3
- FCVKBWXKTRJXTQ-UHFFFAOYSA-N 1,3-diethylpyridin-1-ium Chemical compound CCC1=CC=C[N+](CC)=C1 FCVKBWXKTRJXTQ-UHFFFAOYSA-N 0.000 claims description 3
- MPUIJCPHOVBPOB-UHFFFAOYSA-N 1,3-dimethylpyridin-1-ium Chemical compound CC1=CC=C[N+](C)=C1 MPUIJCPHOVBPOB-UHFFFAOYSA-N 0.000 claims description 3
- ZCDUZNFTZFGENR-UHFFFAOYSA-N 1,4-diethylpyridin-1-ium Chemical compound CCC1=CC=[N+](CC)C=C1 ZCDUZNFTZFGENR-UHFFFAOYSA-N 0.000 claims description 3
- IZPNVUYQWBZYEA-UHFFFAOYSA-N 1,4-dimethylpyridin-1-ium Chemical compound CC1=CC=[N+](C)C=C1 IZPNVUYQWBZYEA-UHFFFAOYSA-N 0.000 claims description 3
- FUZQTBHDJAOMJB-UHFFFAOYSA-N 1-ethyl-2-methylpyridin-1-ium Chemical compound CC[N+]1=CC=CC=C1C FUZQTBHDJAOMJB-UHFFFAOYSA-N 0.000 claims description 3
- REITYCXGQIGALX-UHFFFAOYSA-N 1-ethyl-3-methylpyridin-1-ium Chemical compound CC[N+]1=CC=CC(C)=C1 REITYCXGQIGALX-UHFFFAOYSA-N 0.000 claims description 3
- WMHWQEPQRZIOCT-UHFFFAOYSA-N 1-ethyl-4-methylpyridin-1-ium Chemical compound CC[N+]1=CC=C(C)C=C1 WMHWQEPQRZIOCT-UHFFFAOYSA-N 0.000 claims description 3
- NRLXPVZIUXKQNM-UHFFFAOYSA-O 1-ethylpyridin-1-ium-2-amine Chemical compound CC[N+]1=CC=CC=C1N NRLXPVZIUXKQNM-UHFFFAOYSA-O 0.000 claims description 3
- RMQQNPSAFWUCHF-UHFFFAOYSA-N 1-ethylpyridin-1-ium-3-amine Chemical compound CC[N+]1=CC=CC(N)=C1 RMQQNPSAFWUCHF-UHFFFAOYSA-N 0.000 claims description 3
- HCRYCWTVXHOOJP-UHFFFAOYSA-N 1-ethylpyridin-1-ium-3-carboxylate Chemical compound CC[N+]1=CC(=CC=C1)C([O-])=O HCRYCWTVXHOOJP-UHFFFAOYSA-N 0.000 claims description 3
- SSKSEXZATXLXLL-UHFFFAOYSA-O 1-ethylpyridin-1-ium-4-amine Chemical compound CC[N+]1=CC=C(N)C=C1 SSKSEXZATXLXLL-UHFFFAOYSA-O 0.000 claims description 3
- VSYHVKJFHDVGMY-UHFFFAOYSA-N 1-ethylpyridin-1-ium-4-carboxylate Chemical compound C(C)[N+]1=CC=C(C=C1)C(=O)[O-] VSYHVKJFHDVGMY-UHFFFAOYSA-N 0.000 claims description 3
- SSDQZFNBHWFLIZ-UHFFFAOYSA-O 1-methylpyridin-1-ium-2-amine Chemical compound C[N+]1=CC=CC=C1N SSDQZFNBHWFLIZ-UHFFFAOYSA-O 0.000 claims description 3
- YBNCNAMRNBKKMS-UHFFFAOYSA-N 1-methylpyridin-1-ium-2-sulfonate Chemical compound C[N+]1=CC=CC=C1S([O-])(=O)=O YBNCNAMRNBKKMS-UHFFFAOYSA-N 0.000 claims description 3
- MVZHRMOZEJOWBB-UHFFFAOYSA-N 1-methylpyridin-1-ium-3-amine Chemical compound C[N+]1=CC=CC(N)=C1 MVZHRMOZEJOWBB-UHFFFAOYSA-N 0.000 claims description 3
- AVYIOHJNFRTXIT-UHFFFAOYSA-N 1-methylpyridin-1-ium-3-sulfonate Chemical compound C[N+]1=CC=CC(S([O-])(=O)=O)=C1 AVYIOHJNFRTXIT-UHFFFAOYSA-N 0.000 claims description 3
- JWTVWQUUKNZIHH-UHFFFAOYSA-O 1-methylpyridin-1-ium-4-amine Chemical compound C[N+]1=CC=C(N)C=C1 JWTVWQUUKNZIHH-UHFFFAOYSA-O 0.000 claims description 3
- LIAGOUMUFAHYLR-UHFFFAOYSA-N 2-butyl-1-ethylpyridin-1-ium Chemical compound C(CCC)C1=[N+](C=CC=C1)CC LIAGOUMUFAHYLR-UHFFFAOYSA-N 0.000 claims description 3
- OQCPVKQCFOATGG-UHFFFAOYSA-N 2-butyl-1-methylpyridin-1-ium Chemical compound CCCCC1=CC=CC=[N+]1C OQCPVKQCFOATGG-UHFFFAOYSA-N 0.000 claims description 3
- BJMBCVIFMXOIIH-UHFFFAOYSA-N 2-ethyl-1-methylpyridin-1-ium Chemical compound CCC1=CC=CC=[N+]1C BJMBCVIFMXOIIH-UHFFFAOYSA-N 0.000 claims description 3
- AASZMVCEXMIZFY-UHFFFAOYSA-N 3-butyl-1-ethylpyridin-1-ium Chemical compound CCCCC1=CC=C[N+](CC)=C1 AASZMVCEXMIZFY-UHFFFAOYSA-N 0.000 claims description 3
- JMOGTQWBRQHFMX-UHFFFAOYSA-N 3-butyl-1-methylpyridin-1-ium Chemical compound CCCCC1=CC=C[N+](C)=C1 JMOGTQWBRQHFMX-UHFFFAOYSA-N 0.000 claims description 3
- OLOJVDZXVFIAFJ-UHFFFAOYSA-N 3-ethyl-1-methylpyridin-1-ium Chemical compound CCC1=CC=C[N+](C)=C1 OLOJVDZXVFIAFJ-UHFFFAOYSA-N 0.000 claims description 3
- IXZBPXNIGKHOTB-UHFFFAOYSA-N 4-butyl-1-ethylpyridin-1-ium Chemical compound CCCCC1=CC=[N+](CC)C=C1 IXZBPXNIGKHOTB-UHFFFAOYSA-N 0.000 claims description 3
- HWNIGXALAYSLON-UHFFFAOYSA-N 4-butyl-1-methylpyridin-1-ium Chemical compound CCCCC1=CC=[N+](C)C=C1 HWNIGXALAYSLON-UHFFFAOYSA-N 0.000 claims description 3
- JMWUAFSVHRBNNW-UHFFFAOYSA-N 4-ethyl-1-methylpyridin-1-ium Chemical compound CCC1=CC=[N+](C)C=C1 JMWUAFSVHRBNNW-UHFFFAOYSA-N 0.000 claims description 3
- BRTLKRNVNFIOPJ-UHFFFAOYSA-N Betaine homarine Chemical compound C[N+]1=CC=CC=C1C([O-])=O BRTLKRNVNFIOPJ-UHFFFAOYSA-N 0.000 claims description 3
- FZGRFJYOJAEPMN-UHFFFAOYSA-N C(C)[N+]1=C(C=CC=C1)S(=O)(=O)OC Chemical compound C(C)[N+]1=C(C=CC=C1)S(=O)(=O)OC FZGRFJYOJAEPMN-UHFFFAOYSA-N 0.000 claims description 3
- AEIKRLSJXPCTLV-UHFFFAOYSA-N C(C)[N+]1=CC(=CC=C1)S(=O)(=O)OC Chemical compound C(C)[N+]1=CC(=CC=C1)S(=O)(=O)OC AEIKRLSJXPCTLV-UHFFFAOYSA-N 0.000 claims description 3
- VAXJWTMNMYKWPU-UHFFFAOYSA-N C(C)[N+]1=CC=C(C=C1)S(=O)(=O)OC Chemical compound C(C)[N+]1=CC=C(C=C1)S(=O)(=O)OC VAXJWTMNMYKWPU-UHFFFAOYSA-N 0.000 claims description 3
- AEKOIAOHLALWSX-UHFFFAOYSA-N CC[N+](C=C1)=CC=C1S([O-])(=O)=O Chemical compound CC[N+](C=C1)=CC=C1S([O-])(=O)=O AEKOIAOHLALWSX-UHFFFAOYSA-N 0.000 claims description 3
- SNTUATBRHTWZDS-UHFFFAOYSA-N CC[N+](C=CC=C1)=C1S([O-])(=O)=O Chemical compound CC[N+](C=CC=C1)=C1S([O-])(=O)=O SNTUATBRHTWZDS-UHFFFAOYSA-N 0.000 claims description 3
- IHSFPUCWLKJYMA-UHFFFAOYSA-N CC[N+]1=CC(S([O-])(=O)=O)=CC=C1 Chemical compound CC[N+]1=CC(S([O-])(=O)=O)=CC=C1 IHSFPUCWLKJYMA-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- WWNNZCOKKKDOPX-UHFFFAOYSA-N N-methylnicotinate Chemical compound C[N+]1=CC=CC(C([O-])=O)=C1 WWNNZCOKKKDOPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- SEAHFJOGYJDIHO-UHFFFAOYSA-N methyl 1-methylpyridin-1-ium-2-sulfonate Chemical compound COS(=O)(=O)c1cccc[n+]1C SEAHFJOGYJDIHO-UHFFFAOYSA-N 0.000 claims description 3
- WESNPQJBCVYCGE-UHFFFAOYSA-N methyl 1-methylpyridin-1-ium-3-sulfonate Chemical compound COS(=O)(=O)C1=CC=C[N+](C)=C1 WESNPQJBCVYCGE-UHFFFAOYSA-N 0.000 claims description 3
- 125000005609 naphthenate group Chemical group 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- OHZCFWMJMWFNFP-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;iron(2+) Chemical compound [Fe+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O OHZCFWMJMWFNFP-ZVGUSBNCSA-L 0.000 claims description 2
- LLEGABMHJIWVBB-UHFFFAOYSA-N 1,2-dibutylpyridin-1-ium Chemical compound CCCCC1=CC=CC=[N+]1CCCC LLEGABMHJIWVBB-UHFFFAOYSA-N 0.000 claims description 2
- FIPPSZYNXPCLEN-UHFFFAOYSA-N 1,3-dibutylpyridin-1-ium Chemical compound CCCCC1=CC=C[N+](CCCC)=C1 FIPPSZYNXPCLEN-UHFFFAOYSA-N 0.000 claims description 2
- VVEZNACXGXKZAB-UHFFFAOYSA-N 1,4-dibutylpyridin-1-ium Chemical compound CCCCC1=CC=[N+](CCCC)C=C1 VVEZNACXGXKZAB-UHFFFAOYSA-N 0.000 claims description 2
- GYZXRPOUUZKBAT-UHFFFAOYSA-N 1-butyl-2-ethylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1CC GYZXRPOUUZKBAT-UHFFFAOYSA-N 0.000 claims description 2
- BHIGPVGNEXDQBL-UHFFFAOYSA-N 1-butyl-2-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1C BHIGPVGNEXDQBL-UHFFFAOYSA-N 0.000 claims description 2
- OCNKMULWDVKODZ-UHFFFAOYSA-N 1-butyl-2-phenylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1C1=CC=CC=C1 OCNKMULWDVKODZ-UHFFFAOYSA-N 0.000 claims description 2
- CMLKRBXRFRWXTB-UHFFFAOYSA-N 1-butyl-3-ethylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC(CC)=C1 CMLKRBXRFRWXTB-UHFFFAOYSA-N 0.000 claims description 2
- DADKKHHMGSWSPH-UHFFFAOYSA-N 1-butyl-3-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC(C)=C1 DADKKHHMGSWSPH-UHFFFAOYSA-N 0.000 claims description 2
- GOXLZJUESUTSNC-UHFFFAOYSA-N 1-butyl-3-phenylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC(C=2C=CC=CC=2)=C1 GOXLZJUESUTSNC-UHFFFAOYSA-N 0.000 claims description 2
- ILGRYUSDDHFIPM-UHFFFAOYSA-N 1-butyl-4-ethylpyridin-1-ium Chemical compound CCCC[N+]1=CC=C(CC)C=C1 ILGRYUSDDHFIPM-UHFFFAOYSA-N 0.000 claims description 2
- NNLHWTTWXYBJBQ-UHFFFAOYSA-N 1-butyl-4-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=C(C)C=C1 NNLHWTTWXYBJBQ-UHFFFAOYSA-N 0.000 claims description 2
- MAXUKZQLDUBMIK-UHFFFAOYSA-N 1-butyl-4-phenylpyridin-1-ium Chemical compound C1=C[N+](CCCC)=CC=C1C1=CC=CC=C1 MAXUKZQLDUBMIK-UHFFFAOYSA-N 0.000 claims description 2
- OFRXKYMHDBRLDO-UHFFFAOYSA-O 1-butylpyridin-1-ium-2-amine Chemical compound C(CCC)[N+]1=C(C=CC=C1)N OFRXKYMHDBRLDO-UHFFFAOYSA-O 0.000 claims description 2
- BXXIUBGYUOLRGB-UHFFFAOYSA-N 1-butylpyridin-1-ium-2-carbonitrile Chemical compound C(CCC)[N+]1=C(C=CC=C1)C#N BXXIUBGYUOLRGB-UHFFFAOYSA-N 0.000 claims description 2
- BNBJXURATVCNFF-UHFFFAOYSA-N 1-butylpyridin-1-ium-3-amine Chemical compound CCCC[N+]1=CC=CC(N)=C1 BNBJXURATVCNFF-UHFFFAOYSA-N 0.000 claims description 2
- ZUEBXEMPERSGRG-UHFFFAOYSA-N 1-butylpyridin-1-ium-3-carbonitrile Chemical compound CCCC[N+]1=CC=CC(C#N)=C1 ZUEBXEMPERSGRG-UHFFFAOYSA-N 0.000 claims description 2
- RBECHKIPAAAWPP-UHFFFAOYSA-N 1-butylpyridin-1-ium-3-carboxylate Chemical compound C(CCC)[N+]1=CC(=CC=C1)C(=O)[O-] RBECHKIPAAAWPP-UHFFFAOYSA-N 0.000 claims description 2
- UFFOZCFPZLLUHQ-UHFFFAOYSA-N 1-ethyl-2-phenylpyridin-1-ium Chemical compound CC[N+]1=CC=CC=C1C1=CC=CC=C1 UFFOZCFPZLLUHQ-UHFFFAOYSA-N 0.000 claims description 2
- TUMQPMKVYZEMTE-UHFFFAOYSA-N 1-ethyl-3-phenylpyridin-1-ium Chemical compound CC[N+]1=CC=CC(C=2C=CC=CC=2)=C1 TUMQPMKVYZEMTE-UHFFFAOYSA-N 0.000 claims description 2
- RKXWFNKMYXFZTK-UHFFFAOYSA-N 1-ethyl-4-phenylpyridin-1-ium Chemical compound C1=C[N+](CC)=CC=C1C1=CC=CC=C1 RKXWFNKMYXFZTK-UHFFFAOYSA-N 0.000 claims description 2
- AKCOIKJYWRMBRJ-UHFFFAOYSA-N 1-ethylpyridin-1-ium-2-carbonitrile Chemical compound CC[N+]1=CC=CC=C1C#N AKCOIKJYWRMBRJ-UHFFFAOYSA-N 0.000 claims description 2
- SYNMYUXNPWDHQX-UHFFFAOYSA-N 1-ethylpyridin-1-ium-3-carbonitrile Chemical compound CC[N+]1=CC=CC(C#N)=C1 SYNMYUXNPWDHQX-UHFFFAOYSA-N 0.000 claims description 2
- PQYVXRUPWMDYRR-UHFFFAOYSA-N 1-ethylpyridin-1-ium-4-carbonitrile Chemical compound CC[N+]1=CC=C(C#N)C=C1 PQYVXRUPWMDYRR-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAOQQGJXUMPS-UHFFFAOYSA-N 1-methyl-2-phenylpyridin-1-ium Chemical compound C[N+]1=CC=CC=C1C1=CC=CC=C1 ZLNAOQQGJXUMPS-UHFFFAOYSA-N 0.000 claims description 2
- CMJZRLIOGSSFJB-UHFFFAOYSA-N 1-methyl-3-phenylpyridin-1-ium Chemical compound C[N+]1=CC=CC(C=2C=CC=CC=2)=C1 CMJZRLIOGSSFJB-UHFFFAOYSA-N 0.000 claims description 2
- QCKQICVQNDDMCF-UHFFFAOYSA-N 1-methylpyridin-1-ium-2-carbonitrile Chemical compound C[N+]1=CC=CC=C1C#N QCKQICVQNDDMCF-UHFFFAOYSA-N 0.000 claims description 2
- YPQVJNCIBVIPOK-UHFFFAOYSA-N 1-methylpyridin-1-ium-3-carbonitrile Chemical compound C[N+]1=CC=CC(C#N)=C1 YPQVJNCIBVIPOK-UHFFFAOYSA-N 0.000 claims description 2
- NQQUGKKTJLAUHC-UHFFFAOYSA-N 1-methylpyridin-1-ium-4-carbonitrile Chemical compound C[N+]1=CC=C(C#N)C=C1 NQQUGKKTJLAUHC-UHFFFAOYSA-N 0.000 claims description 2
- QITIEADGFBVLCV-UHFFFAOYSA-O 1-methylpyridin-1-ium-4-carboxylic acid Chemical compound C[N+]1=CC=C(C(O)=O)C=C1 QITIEADGFBVLCV-UHFFFAOYSA-O 0.000 claims description 2
- FUJJZJMBKRTCBU-UHFFFAOYSA-O 1-propylpyridin-1-ium-2-amine Chemical compound NC1=[N+](C=CC=C1)CCC FUJJZJMBKRTCBU-UHFFFAOYSA-O 0.000 claims description 2
- NXEZPRFUUKFFBH-UHFFFAOYSA-N 1-propylpyridin-1-ium-2-carbonitrile Chemical compound CCC[N+]1=CC=CC=C1C#N NXEZPRFUUKFFBH-UHFFFAOYSA-N 0.000 claims description 2
- PWUZITCCFVUYDD-UHFFFAOYSA-N 1-propylpyridin-1-ium-2-carboxylate Chemical compound CCC[N+]1=CC=CC=C1C([O-])=O PWUZITCCFVUYDD-UHFFFAOYSA-N 0.000 claims description 2
- JIMQMQJPBVZXOW-UHFFFAOYSA-N 1-propylpyridin-1-ium-3-amine Chemical compound CCC[N+]1=CC=CC(N)=C1 JIMQMQJPBVZXOW-UHFFFAOYSA-N 0.000 claims description 2
- IEXLXUWMLFLGCD-UHFFFAOYSA-N 1-propylpyridin-1-ium-3-carbonitrile Chemical compound CCC[N+]1=CC=CC(C#N)=C1 IEXLXUWMLFLGCD-UHFFFAOYSA-N 0.000 claims description 2
- GTCDMBKNJFDSLO-UHFFFAOYSA-O 1-propylpyridin-1-ium-4-amine Chemical compound CCC[N+]1=CC=C(N)C=C1 GTCDMBKNJFDSLO-UHFFFAOYSA-O 0.000 claims description 2
- XVHKWYMHOZMYPO-UHFFFAOYSA-N 1-propylpyridin-1-ium-4-carbonitrile Chemical compound CCC[N+]1=CC=C(C#N)C=C1 XVHKWYMHOZMYPO-UHFFFAOYSA-N 0.000 claims description 2
- MADJIGKWMAVAHR-UHFFFAOYSA-N 2-butyl-1-propylpyridin-1-ium Chemical compound C(CC)[N+]1=C(C=CC=C1)CCCC MADJIGKWMAVAHR-UHFFFAOYSA-N 0.000 claims description 2
- FGECIVXGNAJTTP-UHFFFAOYSA-N 2-ethyl-1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1CC FGECIVXGNAJTTP-UHFFFAOYSA-N 0.000 claims description 2
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 claims description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 2
- ZLDXKKLJACLTIN-UHFFFAOYSA-N 2-methyl-1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1C ZLDXKKLJACLTIN-UHFFFAOYSA-N 0.000 claims description 2
- PDGGHTVUPNUFKJ-UHFFFAOYSA-N 2-phenyl-1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1C1=CC=CC=C1 PDGGHTVUPNUFKJ-UHFFFAOYSA-N 0.000 claims description 2
- GOAMZHSXPISVHU-UHFFFAOYSA-N 3-butyl-1-propylpyridin-1-ium Chemical compound CCCCC1=CC=C[N+](CCC)=C1 GOAMZHSXPISVHU-UHFFFAOYSA-N 0.000 claims description 2
- PDWXNKQWHXSDOZ-UHFFFAOYSA-N 3-phenyl-1-propylpyridin-1-ium Chemical compound C(CC)[N+]1=CC(=CC=C1)C1=CC=CC=C1 PDWXNKQWHXSDOZ-UHFFFAOYSA-N 0.000 claims description 2
- FZFKWBCVFYZXJE-UHFFFAOYSA-N 4-ethyl-1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=C(CC)C=C1 FZFKWBCVFYZXJE-UHFFFAOYSA-N 0.000 claims description 2
- CBCJWJVPFPANIA-UHFFFAOYSA-N 4-methyl-1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=C(C)C=C1 CBCJWJVPFPANIA-UHFFFAOYSA-N 0.000 claims description 2
- BYZXAJYUFWGUJG-UHFFFAOYSA-N 4-phenyl-1-propylpyridin-1-ium Chemical compound C1=C[N+](CCC)=CC=C1C1=CC=CC=C1 BYZXAJYUFWGUJG-UHFFFAOYSA-N 0.000 claims description 2
- STAQLRZVCQCDSZ-UHFFFAOYSA-N C(CC)[N+]1=C(C=CC=C1)S(=O)(=O)OC Chemical compound C(CC)[N+]1=C(C=CC=C1)S(=O)(=O)OC STAQLRZVCQCDSZ-UHFFFAOYSA-N 0.000 claims description 2
- RDNOBSHVZKYPMX-UHFFFAOYSA-N C(CC)[N+]1=CC(=CC=C1)S(=O)(=O)OC Chemical compound C(CC)[N+]1=CC(=CC=C1)S(=O)(=O)OC RDNOBSHVZKYPMX-UHFFFAOYSA-N 0.000 claims description 2
- CUILMOIMRYDSEW-UHFFFAOYSA-N C(CCC)[N+]1=C(C=CC=C1)S(=O)(=O)OC Chemical compound C(CCC)[N+]1=C(C=CC=C1)S(=O)(=O)OC CUILMOIMRYDSEW-UHFFFAOYSA-N 0.000 claims description 2
- NMQHAMAEQKDTLK-UHFFFAOYSA-N C(CCC)[N+]1=CC(=CC=C1)S(=O)(=O)OC Chemical compound C(CCC)[N+]1=CC(=CC=C1)S(=O)(=O)OC NMQHAMAEQKDTLK-UHFFFAOYSA-N 0.000 claims description 2
- NZXAAVINQRJTSR-UHFFFAOYSA-N C(CCC)[N+]1=CC=C(C=C1)S(=O)(=O)OC Chemical compound C(CCC)[N+]1=CC=C(C=C1)S(=O)(=O)OC NZXAAVINQRJTSR-UHFFFAOYSA-N 0.000 claims description 2
- JHOURDIGBUZNCF-UHFFFAOYSA-N CCCC[N+](C=C1)=CC=C1C([O-])=O Chemical compound CCCC[N+](C=C1)=CC=C1C([O-])=O JHOURDIGBUZNCF-UHFFFAOYSA-N 0.000 claims description 2
- CDYZOQAXDBYOLK-UHFFFAOYSA-N CCCC[N+](C=C1)=CC=C1S([O-])(=O)=O Chemical compound CCCC[N+](C=C1)=CC=C1S([O-])(=O)=O CDYZOQAXDBYOLK-UHFFFAOYSA-N 0.000 claims description 2
- OZATWQBCBVFRDV-UHFFFAOYSA-N CCCC[N+]1=CC(S([O-])(=O)=O)=CC=C1 Chemical compound CCCC[N+]1=CC(S([O-])(=O)=O)=CC=C1 OZATWQBCBVFRDV-UHFFFAOYSA-N 0.000 claims description 2
- VFRLASJDDPZWFI-UHFFFAOYSA-N CCCC[N+]1=CC=CC=C1C([O-])=O Chemical compound CCCC[N+]1=CC=CC=C1C([O-])=O VFRLASJDDPZWFI-UHFFFAOYSA-N 0.000 claims description 2
- MLTVUAZOJLRCFH-UHFFFAOYSA-N CCC[N+](C=C1)=CC=C1C([O-])=O Chemical compound CCC[N+](C=C1)=CC=C1C([O-])=O MLTVUAZOJLRCFH-UHFFFAOYSA-N 0.000 claims description 2
- WIIBNNLIGNURDU-UHFFFAOYSA-N CCC[N+](C=CC=C1)=C1S([O-])(=O)=O Chemical compound CCC[N+](C=CC=C1)=C1S([O-])(=O)=O WIIBNNLIGNURDU-UHFFFAOYSA-N 0.000 claims description 2
- NHVBLTFGJWYQRE-UHFFFAOYSA-N CCC[N+]1=CC(S([O-])(=O)=O)=CC=C1 Chemical compound CCC[N+]1=CC(S([O-])(=O)=O)=CC=C1 NHVBLTFGJWYQRE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- FMGYKKMPNATWHP-UHFFFAOYSA-N Cyperquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=CC=C1 FMGYKKMPNATWHP-UHFFFAOYSA-N 0.000 claims description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 2
- 239000011706 ferric diphosphate Substances 0.000 claims description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- 235000002332 ferrous fumarate Nutrition 0.000 claims description 2
- 239000011773 ferrous fumarate Substances 0.000 claims description 2
- 229960000225 ferrous fumarate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 229940057006 ferrous tartrate Drugs 0.000 claims description 2
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 claims description 2
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 2
- SUBFIBLJQMMKBK-UHFFFAOYSA-K iron(3+);trithiocyanate Chemical compound [Fe+3].[S-]C#N.[S-]C#N.[S-]C#N SUBFIBLJQMMKBK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- JTWGMQNVHMVHID-UHFFFAOYSA-N methyl 1-butylpyridin-1-ium-2-carboxylate Chemical compound C(CCC)[N+]1=C(C=CC=C1)C(=O)OC JTWGMQNVHMVHID-UHFFFAOYSA-N 0.000 claims description 2
- WPXPFGWZWWKMRC-UHFFFAOYSA-N methyl 1-butylpyridin-1-ium-3-carboxylate Chemical compound CCCC[N+]1=CC=CC(C(=O)OC)=C1 WPXPFGWZWWKMRC-UHFFFAOYSA-N 0.000 claims description 2
- HSUHZNFQBWDCGZ-UHFFFAOYSA-N methyl 1-butylpyridin-1-ium-4-carboxylate Chemical compound CCCC[N+]1=CC=C(C(=O)OC)C=C1 HSUHZNFQBWDCGZ-UHFFFAOYSA-N 0.000 claims description 2
- NHLODYYBTPQSIA-UHFFFAOYSA-N methyl 1-ethylpyridin-1-ium-2-carboxylate Chemical compound CC[N+]1=CC=CC=C1C(=O)OC NHLODYYBTPQSIA-UHFFFAOYSA-N 0.000 claims description 2
- CVSCOWLLIFGJFS-UHFFFAOYSA-N methyl 1-ethylpyridin-1-ium-3-carboxylate Chemical compound CC[N+]1=CC=CC(C(=O)OC)=C1 CVSCOWLLIFGJFS-UHFFFAOYSA-N 0.000 claims description 2
- NFZJPEAJXDDBBW-UHFFFAOYSA-N methyl 1-methylpyridin-1-ium-2-carboxylate Chemical compound COC(=O)C1=CC=CC=[N+]1C NFZJPEAJXDDBBW-UHFFFAOYSA-N 0.000 claims description 2
- PUCDEIAKSXKMSO-UHFFFAOYSA-N methyl 1-methylpyridin-1-ium-3-carboxylate Chemical compound COC(=O)C1=CC=C[N+](C)=C1 PUCDEIAKSXKMSO-UHFFFAOYSA-N 0.000 claims description 2
- QSTZQJMQOOWRNP-UHFFFAOYSA-N methyl 1-methylpyridin-1-ium-4-carboxylate Chemical compound COC(=O)C1=CC=[N+](C)C=C1 QSTZQJMQOOWRNP-UHFFFAOYSA-N 0.000 claims description 2
- DVLXLCPXUWOJGV-UHFFFAOYSA-N methyl 1-propylpyridin-1-ium-2-carboxylate Chemical compound C(CC)[N+]1=C(C=CC=C1)C(=O)OC DVLXLCPXUWOJGV-UHFFFAOYSA-N 0.000 claims description 2
- IEZPTMJVDKALMQ-UHFFFAOYSA-N methyl 1-propylpyridin-1-ium-3-carboxylate Chemical compound CCC[N+]1=CC=CC(C(=O)OC)=C1 IEZPTMJVDKALMQ-UHFFFAOYSA-N 0.000 claims description 2
- LIQDUWFSTIUBGW-UHFFFAOYSA-N methyl 1-propylpyridin-1-ium-4-carboxylate Chemical compound CCC[N+]1=CC=C(C(=O)OC)C=C1 LIQDUWFSTIUBGW-UHFFFAOYSA-N 0.000 claims description 2
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 claims description 2
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- ALYMILAYQDOMFU-UHFFFAOYSA-L nickel(2+);dithiocyanate Chemical compound [Ni+2].[S-]C#N.[S-]C#N ALYMILAYQDOMFU-UHFFFAOYSA-L 0.000 claims description 2
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- XRLUJVFOGKUSMQ-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O XRLUJVFOGKUSMQ-ZVGUSBNCSA-L 0.000 claims 1
- DXVOEFOMGMELCV-UHFFFAOYSA-O 1-butylpyridin-1-ium-4-amine Chemical compound CCCC[N+]1=CC=C(N)C=C1 DXVOEFOMGMELCV-UHFFFAOYSA-O 0.000 claims 1
- SFOKDWPZOYRZFF-UHFFFAOYSA-H 2,3-dihydroxybutanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SFOKDWPZOYRZFF-UHFFFAOYSA-H 0.000 claims 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- HMOAXHZPTTWIFB-UHFFFAOYSA-N C(CC)[N+]1=CC(=CC=C1)CC.C(CC)[N+]1=CC(=CC=C1)C Chemical compound C(CC)[N+]1=CC(=CC=C1)CC.C(CC)[N+]1=CC(=CC=C1)C HMOAXHZPTTWIFB-UHFFFAOYSA-N 0.000 claims 1
- BPNAUVQOLHYMJC-UHFFFAOYSA-N C[N+](C=C1)=CC=C1S([O-])(=O)=O.C[N+](C=C1)=CC=C1S(OC)(=O)=O Chemical compound C[N+](C=C1)=CC=C1S([O-])(=O)=O.C[N+](C=C1)=CC=C1S(OC)(=O)=O BPNAUVQOLHYMJC-UHFFFAOYSA-N 0.000 claims 1
- 229910000531 Co alloy Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- CAACQKBQSPQWGE-UHFFFAOYSA-N [Co].[Na].[Na].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O Chemical compound [Co].[Na].[Na].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O CAACQKBQSPQWGE-UHFFFAOYSA-N 0.000 claims 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 claims 1
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims 1
- 235000013924 ferrous gluconate Nutrition 0.000 claims 1
- 239000004222 ferrous gluconate Substances 0.000 claims 1
- 229960001645 ferrous gluconate Drugs 0.000 claims 1
- DXTCFKRAUYBHRC-UHFFFAOYSA-L iron(2+);dithiocyanate Chemical compound [Fe+2].[S-]C#N.[S-]C#N DXTCFKRAUYBHRC-UHFFFAOYSA-L 0.000 claims 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 138
- 230000000694 effects Effects 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000003353 gold alloy Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical group 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 244000248349 Citrus limon Species 0.000 description 7
- 235000005979 Citrus limon Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
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- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003352 sequestering agent Substances 0.000 description 5
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 4
- 230000005856 abnormality Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
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- ZGAZPDWSRYNUSZ-UHFFFAOYSA-N nonane-1-sulfonic acid Chemical compound CCCCCCCCCS(O)(=O)=O ZGAZPDWSRYNUSZ-UHFFFAOYSA-N 0.000 description 1
- KETHQOOVMIVLCH-UHFFFAOYSA-M nonyl sulfate(1-) Chemical compound CCCCCCCCCOS([O-])(=O)=O KETHQOOVMIVLCH-UHFFFAOYSA-M 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HSHPOTHYMFBSDH-UHFFFAOYSA-N pentane-1-sulfinic acid Chemical compound CCCCCS(O)=O HSHPOTHYMFBSDH-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-N pentane-1-sulfonic acid Chemical compound CCCCCS(O)(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CSMFSDCPJHNZRY-UHFFFAOYSA-N sulfuric acid monodecyl ester Natural products CCCCCCCCCCOS(O)(=O)=O CSMFSDCPJHNZRY-UHFFFAOYSA-N 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
Landscapes
- 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)
- Electroplating Methods And Accessories (AREA)
Description
本発明は、特定の組成を有する電解金めっき液、その電解金めっき液を用いて得られた金皮膜、及び、特にニッケル皮膜上の金皮膜に関するものである。 The present invention relates to an electrolytic gold plating solution having a specific composition, a gold film obtained by using the electrolytic gold plating solution, and particularly a gold film on a nickel film.
金めっきは、優れた耐食性、機械的特性、電機特性等を有するため、広く用いられている。特に、ニッケル皮膜上に施す金めっきは、金が優れた耐食性、機械的特性、電機特性等を有し、ニッケルが下地金属として優れた耐熱性等を有するため、電子電気部品等の分野で広く用いられている。更に、その中でも、コバルト、ニッケル、鉄等の金属と合金化された金めっき皮膜は、その高い硬度と優れた耐摩耗性を生かして、コネクター等の差し込み部材；スイッチ等の接点部材等のコンタクト接合部のめっき皮膜として広く使用されている。コバルト塩、ニッケル塩及び／又は鉄塩を含有する電解金めっき液を用いためっきは、硬質電解金めっきとも言われている。 Gold plating is widely used because it has excellent corrosion resistance, mechanical properties, electrical properties, and the like. In particular, the gold plating applied on the nickel coating is widely used in the field of electronic and electrical parts because gold has excellent corrosion resistance, mechanical characteristics, electrical characteristics, etc., and nickel has excellent heat resistance as a base metal. It is used. Furthermore, among them, gold plating films alloyed with metals such as cobalt, nickel, iron, etc. make use of their high hardness and excellent wear resistance, so that they are plug-ins such as connectors; contacts such as contacts such as switches Widely used as a plating film for joints. Plating using an electrolytic gold plating solution containing a cobalt salt, nickel salt and / or iron salt is also referred to as hard electrolytic gold plating.
近年、生産コストの低減のために、コネクター等に使用される硬質金めっきには、金の析出効率を上げて、めっき時間の短縮やめっき液中の金含有量を節約することが強く望まれているが、硬質金めっきは、金の析出効率を上げると、光沢剤等として金めっき液に含有されているコバルト、ニッケル等の析出量が金の析出量に比べて非常に少なくなり、光沢剤としての効果を充分に得ることができずに外観不良を発生するという問題があった。 In recent years, in order to reduce production costs, hard gold plating used for connectors, etc., is strongly desired to increase gold deposition efficiency, shorten plating time and save gold content in plating solution. However, with hard gold plating, if the gold deposition efficiency is increased, the amount of deposits of cobalt, nickel, etc. contained in the gold plating solution as a brightening agent becomes very small compared to the amount of gold deposited. There is a problem in that the appearance as an agent is not achieved because the effect as an agent cannot be sufficiently obtained.
この問題を解決するために、特許文献１では、ペンチルスルホネート、ペンチルスルフェネート、ヘキシルスルフェネート、ヘプチルスルホネート、ヘプチルスルフェネート、オクチルスルフェート、ノニルスルホネート、ノニルスルフェート、デシルスルフェート、ドデシルスルホネート、ドデシルスルフェート、シクロヘキシルスルホネート若しくはシクロヘキシルスルフェート、又は、これらの異性体を酸性浴に配合することにより、光沢のある金皮膜を析出させ得る範囲で、適用可能な電流密度を高い電流密度の方向へと推移させるか、又はその範囲を拡大させる技術が開示されている。 In order to solve this problem, Patent Document 1 discloses pentyl sulfonate, pentyl sulfinate, hexyl sulfonate, heptyl sulfonate, heptyl sulfonate, octyl sulfate, nonyl sulfonate, nonyl sulfate, decyl sulfate, dodecyl. By adding sulfonate, dodecyl sulfate, cyclohexyl sulfonate or cyclohexyl sulfate, or isomers thereof to an acidic bath, the applicable current density can be increased within a range where a shiny gold film can be deposited. A technique for shifting in the direction or expanding the range is disclosed.
また、特許文献１中には、通例として、特許文献４に記載されている、ピリジン−３−スルホン酸や、ニコチン酸、ニコチン酸アミド、３−（３−ピリジル）−アクリル酸、３−（４−イミダゾリル）−アクリル酸、３−ピリジルヒドロキシメタンスルホン酸、ピリジン、ピコリン、キノリンスルホン酸、３−アミノピリジン、２，３−ジアミノピリジン、２，３−ジー（２−ピリジル）−ピラジン、２−（ピリジル）−４−エタンスルホン酸、１−（３−スルホプロピル）−ピリジニウムベタイン、１−（３−スルホプロピル）−イソキノリニウムベタインを用いる旨の記載がある。 Further, in Patent Document 1, pyridine-3-sulfonic acid, nicotinic acid, nicotinic acid amide, 3- (3-pyridyl) -acrylic acid, 3- ( 4-imidazolyl) -acrylic acid, 3-pyridylhydroxymethanesulfonic acid, pyridine, picoline, quinolinesulfonic acid, 3-aminopyridine, 2,3-diaminopyridine, 2,3-di (2-pyridyl) -pyrazine, 2 There is a description that-(pyridyl) -4-ethanesulfonic acid, 1- (3-sulfopropyl) -pyridinium betaine, 1- (3-sulfopropyl) -isoquinolinium betaine is used.
また、特許文献２には、脂肪族アルコールを添加すると、金めっき可能な電流密度範囲の最大値が高くなり、金めっき皮膜の析出速度が向上すると開示されている。 Patent Document 2 discloses that when an aliphatic alcohol is added, the maximum value of the current density range in which gold plating can be performed is increased, and the deposition rate of the gold plating film is improved.
また、特許文献３には、アルカノールアミン、ジアルカノールアミン、トリアルカノールアミン、アミノ酸、ピリジンカルボン酸、チオカルボン酸からなる群から選ばれる１以上の化合物を添加することにより、広い電流密度において用いることが可能となり、特に高電流密度域においても良好な光沢を有する金合金めっき皮膜を得ることができる旨が開示されている。 Further, Patent Document 3 can be used in a wide current density by adding one or more compounds selected from the group consisting of alkanolamine, dialkanolamine, trialkanolamine, amino acid, pyridinecarboxylic acid, and thiocarboxylic acid. It is disclosed that it is possible to obtain a gold alloy plating film having a good gloss even in a high current density region.
しかしながら、これら従来技術では、更に生産量を増加するために必要な析出速度を得ようとすると外観不良が発生し、一方、金めっき液中の金含有量を減量すると生産に充分な金の析出速度が得られず、生産効率を充分に上げることができない等という問題点があった。
近年、生産コスト低減のため、特に硬質金めっき液には、金の析出効率を上げることによる電解金めっき時間の短縮、金めっき液中の金含有量の節約等が強く望まれているが、そのためには、更なる改良が必要であった。
However, with these conventional technologies, appearance defects occur when trying to obtain the deposition rate necessary to further increase the production volume, while sufficient gold deposition for production occurs when the gold content in the gold plating solution is reduced. There was a problem that the speed could not be obtained and the production efficiency could not be sufficiently increased.
In recent years, in order to reduce production costs, especially for hard gold plating solutions, it is strongly desired to shorten the electrolytic gold plating time by increasing gold deposition efficiency, and to save the gold content in the gold plating solution. For that purpose, further improvement was necessary.
本発明は、上記背景技術に鑑みてなされたものであり、その課題は、金めっき皮膜の物性については従来の電解金めっき液を用いて得られたものと同等の機械特性、耐摩耗性、電気特性等を維持しつつ、金めっき皮膜の外観不良が発生することなく析出効率を従来の金めっき液よりも高くでき、金めっき析出時間の短縮化、金めっき液に含有する高価な金を低濃度化し生産コストを大幅に低減することが可能な電解金めっき液を提供することにある。 The present invention has been made in view of the above-mentioned background art, and the problem is that the physical properties of the gold plating film are equivalent to those obtained using a conventional electrolytic gold plating solution, wear resistance, While maintaining the electrical characteristics, etc., the deposition efficiency can be higher than that of conventional gold plating solutions without causing defects in the appearance of the gold plating film, shortening the gold plating deposition time, and the expensive gold contained in the gold plating solution. An object of the present invention is to provide an electrolytic gold plating solution capable of reducing the concentration and greatly reducing the production cost.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、特定のピリジニウム化合物を必須成分として含有する電解金めっき液を用いて金皮膜を形成すれば、前期問題点を解消し、上記課題を解決し、金皮膜の外観不良の発生を防止したまま金の析出効率の上昇を可能として、生産コストを大幅に低減することが可能となることを見出し、本発明の完成に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor solved the previous problem by forming a gold film using an electrolytic gold plating solution containing a specific pyridinium compound as an essential component. The present inventors have found that the problem can be solved, the gold deposition efficiency can be increased while preventing the appearance defect of the gold film from occurring, and the production cost can be greatly reduced, and the present invention has been completed.
すなわち、本発明は、金源としてのシアン化金塩、並びに、１位の窒素原子にアルキル基が結合され、２位ないし６位の１個ないし５個が、アルキル基、アリール基、カルボキシ基、アルコキシカルボニル基、スルホ基、アルコキシスルホニル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基及びシアノ基からなる群より選ばれた１種又は２種以上の特定置換基で置換された特定ピリジニウム化合物を含有することを特徴とする電解金めっき液を提供するものである。 That is, the present invention relates to a gold cyanide salt as a gold source, and an alkyl group bonded to the nitrogen atom at the 1st position, and 1 to 5 positions at the 2nd to 6th positions are alkyl groups, aryl groups, carboxy groups. A specific pyridinium compound substituted with one or more specific substituents selected from the group consisting of an alkoxycarbonyl group, a sulfo group, an alkoxysulfonyl group, an amino group, an alkylamino group, a dialkylamino group and a cyano group. It is intended to provide an electrolytic gold plating solution characterized by containing.
また、本発明は、更に、コバルト塩、ニッケル塩及び／又は鉄塩を含有する上記の電解金めっき液を提供するものである。 The present invention further provides the above electrolytic gold plating solution containing a cobalt salt, a nickel salt and / or an iron salt.
また、本発明は、上記の電解金めっき液を用いて、ニッケル皮膜上に電解金めっきを行うことによって得られたものであることを特徴とする金皮膜を提供するものである。 The present invention also provides a gold film characterized by being obtained by performing electrolytic gold plating on a nickel film using the above electrolytic gold plating solution.
本発明の電解金めっき液によれば、従来からの電解金めっき液を用いて得られる金皮膜の、優れた耐摩耗性等の機械特性、耐食性、電気特性等を維持したまま、金めっき液中の金含有量が同じであれば、従来のものよりも非常に速い析出速度が得られ、析出効率を高くでき、金めっき時間を短くでき生産性の大幅な向上が実現できる。
更に、その析出速度が速いという特性を利用すれば、逆に従来と同等の生産性を維持したままで、電解金めっき液中において高価な金の含有量を減量することが可能となり、大幅なコストダウンを実現することができる。
According to the electrolytic gold plating solution of the present invention, the gold plating solution obtained by using the conventional electrolytic gold plating solution maintains the excellent mechanical properties such as wear resistance, corrosion resistance, and electrical properties while maintaining the gold plating solution. If the gold content is the same, it is possible to obtain a deposition rate much faster than the conventional one, increase the deposition efficiency, shorten the gold plating time, and realize a significant improvement in productivity.
Furthermore, if the property that the deposition rate is fast is used, it is possible to reduce the amount of expensive gold in the electrolytic gold plating solution while maintaining the same productivity as the conventional one. Cost reduction can be realized.
また、電解金めっき液中の金の含有量を同一にして従来品と比べた場合であっても、従来の電解金めっき液と比較して、電流密度を上げても「ヤケ」等の外観不良が起こり難く、すなわち、金皮膜表面に、「目視での外観」で判定できる「金の析出異常」が認められ難い電解金めっき液が実現でき、その点からも、金の析出速度を上げて電解金めっきを行なうことが可能で、金めっき時間を著しく短くでき、その結果、生産性の大幅な向上が実現できる。 In addition, even if the gold content in the electrolytic gold plating solution is the same and compared with the conventional product, even if the current density is increased compared to the conventional electrolytic gold plating solution, the appearance such as “discoloration” It is possible to realize an electrolytic gold plating solution in which it is difficult for defects to occur, that is, it is difficult to recognize “gold deposition anomaly” that can be judged by “visual appearance” on the surface of the gold film. Electrolytic gold plating can be carried out, and the gold plating time can be remarkably shortened. As a result, productivity can be greatly improved.
以下、本発明について説明するが、本発明は以下の実施の具体的形態に限定されるものではなく、技術的思想の範囲で任意に変形して実施することができる。 Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.
＜特定ピリジニウム化合物＞
本発明の電解金めっき液は、少なくとも、シアン化金塩を金源として含有し、更に、以下に示す「特定ピリジニウム化合物」を含有することが必須である。
「特定ピリジニウム化合物」とは、１位の窒素原子にアルキル基が結合され、２位ないし６位の１個ないし５個が、アルキル基、アリール基、カルボキシ基、アルコキシカルボニル基、スルホ基、アルコキシスルホニル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基及びシアノ基からなる群より選ばれた１種又は２種以上の特定置換基で置換されたピリジニウム化合物をいう。
<Specific pyridinium compounds>
The electrolytic gold plating solution of the present invention contains at least a gold cyanide salt as a gold source, and further contains the “specific pyridinium compound” shown below.
The “specific pyridinium compound” means that an alkyl group is bonded to the 1st nitrogen atom, and 1 to 5 of the 2nd to 6th positions are an alkyl group, aryl group, carboxy group, alkoxycarbonyl group, sulfo group, alkoxy group. A pyridinium compound substituted with one or more specific substituents selected from the group consisting of a sulfonyl group, an amino group, an alkylamino group, a dialkylamino group and a cyano group.
「特定ピリジニウム化合物」においては、窒素原子にアルキル基（−Ｒ１）が結合されていることによって、該窒素原子はプラス電荷を有し、ピリジニウム化合物となっている。本発明においては、「窒素原子に結合してピリジニウム化合物となる結合原子」から水素原子は除かれる。窒素原子に結合している結合原子が水素原子の場合には、前記した本発明の効果が得られ難い。 In the “specific pyridinium compound”, an alkyl group (—R 1 ) is bonded to a nitrogen atom, so that the nitrogen atom has a positive charge and is a pyridinium compound. In the present invention, hydrogen atoms are excluded from “bonding atoms that are bonded to nitrogen atoms to form pyridinium compounds”. When the bonding atom bonded to the nitrogen atom is a hydrogen atom, it is difficult to obtain the effect of the present invention described above.
窒素原子に結合したアルキル基（−Ｒ１）は、直鎖アルキル基又は分岐アルキル基の何れでもよく、炭素数も特に限定はないが、前記した本発明の効果を発揮し易く、良好なめっき性能、入手の容易さ等の点から、炭素数１〜５個のアルキル基が好ましく、炭素数１〜４個のアルキル基がより好ましく、炭素数１〜３個が特に好ましく、炭素数１個又は２個が更に好ましい。
また、窒素原子に結合している基がアルキル基（−Ｒ１）ではなく、水素原子である場合には、前記した本発明の効果が発揮されず、特に、高電流密度でめっき処理した場合に外観不良を発生する場合がある。
The alkyl group (—R 1 ) bonded to the nitrogen atom may be either a linear alkyl group or a branched alkyl group, and the number of carbon atoms is not particularly limited. From the viewpoints of performance and availability, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, 1 to 3 carbon atoms is particularly preferable, and 1 carbon atom is included. Or two is more preferable.
Further, when the group bonded to the nitrogen atom is not an alkyl group (—R 1 ) but a hydrogen atom, the above-described effect of the present invention is not exhibited, and in particular, when plating is performed at a high current density. May cause poor appearance.
本発明における「特定ピリジニウム化合物」は、電解金めっき液中で上記化学構造を有していることが必須であり、電解金めっき液中で上記化学構造を有するものに変化したものでもよく、電解金めっき液の調液の際に添加する物質の化学構造については特に限定はない。ただ、上記化学構造を有しているものを添加する（用いて調液する）ことが好ましい。 The “specific pyridinium compound” in the present invention must have the above chemical structure in the electrolytic gold plating solution, and may be changed to one having the above chemical structure in the electrolytic gold plating solution. There is no particular limitation on the chemical structure of the substance added during preparation of the gold plating solution. However, it is preferable to add (prepare using) one having the above chemical structure.
本発明の電解金めっき液中に含有される「特定ピリジニウム化合物」の陰イオンについては特に限定はないが、具体的には、例えば、硫酸イオン、硝酸イオン、塩素イオン、臭素イオン、ヨウ素イオンが挙げられる。陰イオンの交換（塩交換）が、電解金めっき液中で起こってもよく、電解液の組成としてのものが本発明に含まれる。
陰イオンの交換（塩交換）が起こったとしても、上記陰イオンを有しているものを添加する（用いて調液する）ことが好ましい。
The anion of the “specific pyridinium compound” contained in the electrolytic gold plating solution of the present invention is not particularly limited, and specifically, for example, sulfate ion, nitrate ion, chlorine ion, bromine ion, iodine ion Can be mentioned. Anion exchange (salt exchange) may occur in the electrolytic gold plating solution, and the composition of the electrolytic solution is included in the present invention.
Even if anion exchange (salt exchange) occurs, it is preferable to add (prepare using) the above-mentioned anion-containing substances.
本発明における「特定ピリジニウム化合物」は、２位ないし６位の１個ないし５個が、アルキル基、アリール基、カルボキシ基、アルコキシカルボニル基、スルホ基、アルコキシスルホニル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基及びシアノ基からなる群より選ばれた１種又は２種以上の置換基で置換されているものであることが必須である。本発明においては、かかる置換基を「特定置換基」という。
すなわち、本発明における「特定ピリジニウム化合物」は、６員環であるピリジン環（ピリジニウム環）において、窒素原子は１位であるので、窒素原子以外の環を構成する炭素原子５個に結合した５個の水素のうち、１個ないし５個が、異なっていてもよい上記の特定置換基で置換されているものである。
The “specific pyridinium compound” in the present invention is an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group, a sulfo group, an alkoxysulfonyl group, an amino group, an alkylamino group, wherein 1 to 5 at the 2nd to 6th positions are It is essential that it is substituted with one or more substituents selected from the group consisting of a dialkylamino group and a cyano group. In the present invention, such a substituent is referred to as a “specific substituent”.
That is, the “specific pyridinium compound” in the present invention is a 6-membered pyridine ring (pyridinium ring), and since the nitrogen atom is at position 1, it is bonded to 5 carbon atoms constituting the ring other than the nitrogen atom. 1 to 5 hydrogen atoms are substituted with the above-mentioned specific substituents which may be different.
特定置換基としてのアルキル基は、直鎖アルキル基又は分岐アルキル基の何れでもよく、置換基を有していてもよく、炭素数も特に限定はないが、本発明の前記効果をより発揮するために、炭素数１〜６個のアルキル基が好ましく、炭素数１〜５個のアルキル基がより好ましく、炭素数１〜４個のアルキル基、すなわち、メチル基、エチル基、プロピル基又はブチル基が特に好ましい。
炭素数の多過ぎるアルキル基が結合していると、金析出速度の低下や、金外観不良を発生する場合がある。
The alkyl group as the specific substituent may be either a linear alkyl group or a branched alkyl group, and may have a substituent, and the number of carbon atoms is not particularly limited, but the effect of the present invention is more exhibited. Therefore, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms, that is, a methyl group, an ethyl group, a propyl group, or butyl. The group is particularly preferred.
If an alkyl group having too many carbon atoms is bonded, the gold deposition rate may be lowered or the gold appearance may be poor.
特定置換基としてのアリール基は、アルキル基等の置換基を有していてもよく、特に限定はないが、具体的には、例えば、フェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。 The aryl group as the specific substituent may have a substituent such as an alkyl group and is not particularly limited. Specific examples thereof include a phenyl group, a naphthyl group, a tolyl group, and a xylyl group. It is done.
特定置換基としてのカルボキシ基は、「−ＣＯＯＨ」で表される基であり、「アルコキシカルボニル基」は、「−ＣＯＯＲ１１」で表される基であり、カルボン酸エステルの残基である。上記式中で、Ｒ１１は、アルキル基又はアリール基を示し、好ましいものは、前記特定置換基としてのアルキル基やアリール基と同様であり、特に好ましくはメチル基である。 The carboxy group as a specific substituent is a group represented by “—COOH”, the “alkoxycarbonyl group” is a group represented by “—COOR 11 ”, and is a residue of a carboxylic acid ester. In the above formula, R 11 represents an alkyl group or an aryl group, and preferable one is the same as the alkyl group or aryl group as the specific substituent, and particularly preferably a methyl group.
特定置換基としてのスルホ基は、「−ＳＯ３Ｈ」で表される基であり、スルホン酸基とも言われる。
特定置換基としてのアルコキシスルホニル基は、以下の一般式（ａ）で表される基であり、スルホン酸エステル残基である。
The sulfo group as the specific substituent is a group represented by “—SO 3 H” and is also referred to as a sulfonic acid group.
The alkoxysulfonyl group as the specific substituent is a group represented by the following general formula (a) and is a sulfonate residue.
一般式（ａ）中、Ｒ１２は、アルキル基又はアリール基を示すが、好ましいもの等は、前記特定置換基としてのアルキル基やアリール基と同様であり、更に好ましくはメチル基である。 In general formula (a), R 12 represents an alkyl group or an aryl group, but preferred ones are the same as the alkyl group and aryl group as the specific substituent, and more preferably a methyl group.
特定置換基としてのアミノ基は、「−ＮＨ２」で表される基であり、アルキルアミノ基は、「−ＮＨＲ１３」で表される基であり、ジアルキルアミノ基は、「−ＮＲ１４Ｒ１５」で表される基である。
上記式中で、Ｒ１３、Ｒ１４、Ｒ１５は、それぞれ異なっていてもよいアルキル基又はアリール基を示し、好ましいものは、前記特定置換基としてのアルキル基やアリール基と同様であり、特に好ましくはメチル基である。
The amino group as the specific substituent is a group represented by “—NH 2 ”, the alkylamino group is a group represented by “—NHR 13 ”, and the dialkylamino group is represented by “—NR 14 R”. 15 ".
In the above formula, R 13 , R 14 , and R 15 each represent an alkyl group or an aryl group that may be different from each other, and preferable ones are the same as the alkyl group and aryl group as the specific substituent, A methyl group is preferred.
特定置換基としてのシアノ基は、「−ＣＮ」で表される基である。 The cyano group as the specific substituent is a group represented by “—CN”.
中でも、アルキル基、カルボキシ基、アルコキシスルホニル基及びアミノ基からなる群より選ばれた１種又は２種以上の置換基が置換しているものが、前記した本発明の効果を発揮し易く、良好なめっき性能、入手の容易さ等のから特に好ましい。 Among them, those substituted with one or more substituents selected from the group consisting of an alkyl group, a carboxy group, an alkoxysulfonyl group, and an amino group are easy to exert the effect of the present invention as described above. It is particularly preferable because of its excellent plating performance and availability.
本発明の電解金めっき液は、ピリジニウム環の２位ないし４位の１個ないし３個が、１種又は２種以上の上記特定置換基で置換されたピリジニウム化合物を含有することが、前記効果を更に好適に発揮する点で好ましい。
かかるピリジニウム化合物は、下記一般式（１）で表される。
The electrolytic gold plating solution of the present invention contains the pyridinium compound in which one to three of the 2nd to 4th positions of the pyridinium ring are substituted with one or more of the specific substituents described above. Is preferable in that it is more suitably exhibited.
Such a pyridinium compound is represented by the following general formula (1).
窒素原子に結合したアルキル基（Ｒ１）は、直鎖アルキル基又は分岐アルキル基の何れでもよく、炭素数も特に限定はないが、炭素数１〜６個のアルキル基が好ましく、炭素数１〜５個のアルキル基がより好ましく、炭素数１〜４個のアルキル基、すなわち、メチル基、エチル基、プロピル基又はブチル基が特に好ましい。炭素数の多過ぎるアルキル基が結合していると、入手が困難であったり、金の析出速度が低下したり、金の外観不良が発生する場合がある。 The alkyl group (R 1 ) bonded to the nitrogen atom may be either a linear alkyl group or a branched alkyl group, and the number of carbon atoms is not particularly limited, but an alkyl group having 1 to 6 carbon atoms is preferable, and the number of carbon atoms is 1 ˜5 alkyl groups are more preferred, and alkyl groups having 1 to 4 carbon atoms, ie, methyl group, ethyl group, propyl group or butyl group are particularly preferred. If an alkyl group having too many carbon atoms is bonded, it may be difficult to obtain, the deposition rate of gold may be reduced, or the appearance of gold may be poor.
Ｒ２、Ｒ３及びＲ４は、互いに異なっていてもよい水素原子、アルキル基、アリール基、カルボキシ基、アルコキシカルボニル基、スルホ基、アルコキシスルホニル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基又はシアノ基を示し、ただし、Ｒ２、Ｒ３及びＲ４の全てが水素原子である場合を除く。
すなわち、本発明における「特定ピリジニウム化合物」は、ピリジニウム環の２位ないし４位の１個ないし３個が、１種又は２種以上の上記した「特定置換基」で置換されたものであることが好ましい。
Ｒ２、Ｒ３及びＲ４は、前記したものが、前記効果を更に好適に発揮する点でより（特に）好ましい。
R 2 , R 3 and R 4 may be different from each other as a hydrogen atom, alkyl group, aryl group, carboxy group, alkoxycarbonyl group, sulfo group, alkoxysulfonyl group, amino group, alkylamino group, dialkylamino group or A cyano group is shown except that R 2 , R 3 and R 4 are all hydrogen atoms.
That is, the “specific pyridinium compound” in the present invention is one in which one to three of the 2-position to 4-position of the pyridinium ring are substituted with one or more of the above-mentioned “specific substituents”. Is preferred.
R 2 , R 3, and R 4 are more preferably (particularly) from the viewpoint of more suitably exhibiting the above-described effects.
一般式（１）の陰イオン（対イオン）については特に限定はないが、具体的には、例えば、硫酸イオン、硝酸イオン、塩素イオン、臭素イオン、ヨウ素イオン等、前記したものが挙げられる。 Although there is no limitation in particular about the anion (counter ion) of General formula (1), Specifically, what was mentioned above, such as a sulfate ion, a nitrate ion, a chlorine ion, a bromine ion, an iodine ion, is mentioned, for example.
特定ピリジニウム化合物を含有することにより、従来の電解金めっき皮膜の優れた高耐食性、機械特性、電気特性を維持したままで、金含有量が同じであれば、従来よりも非常に速い析出速度が得られ、すなわち、金の析出効率を上げられ、めっき処理時間を短くでき生産性の大幅な向上が実現できる優れた電解金めっき液を得ることができる。更に、その析出速度が速いという特性を利用すれば、従来と同等の生産性を維持した上で高価な金含有量を減量することが可能となり、大幅なコストダウンが実現される。 By containing the specific pyridinium compound, if the gold content is the same while maintaining the excellent high corrosion resistance, mechanical properties, and electrical properties of the conventional electrolytic gold plating film, the deposition rate is much faster than before. In other words, it is possible to obtain an excellent electrolytic gold plating solution capable of increasing the gold deposition efficiency, shortening the plating treatment time, and realizing a significant improvement in productivity. Furthermore, if the property that the deposition rate is high is used, it is possible to reduce the expensive gold content while maintaining the same productivity as the conventional one, and a significant cost reduction is realized.
上記の特定ピリジニウム化合物の好ましい具体例としては、例えば、
１−メチル−２−メチルピリジニウム、１−メチル−２−エチルピリジニウム、１−メチル−２−ブチルピリジニウム、１−メチル−２−スルホピリジニウム、１−メチル−２−メトキシスルホニルピリジニウム、１−メチル−２−アミノピリジニウム、１−メチル−２−カルボキシピリジニウム、１−メチル−２−メトキシカルボニルピリジニウム、１−メチル−２−フェニルピリジニウム、１−メチル−２−シアノピリジニウム、
１−エチル−２−メチルピリジニウム、１−エチル−２−エチルピリジニウム、１−エチル−２−ブチルピリジニウム、１−エチル−２−スルホピリジニウム、１−エチル−２−メトキシスルホニルピリジニウム、１−エチル−２−アミノピリジニウム、１−エチル−２−カルボキシピリジニウム、１−エチル−２−メトキシカルボニルピリジニウム、１−エチル−２−フェニルピリジニウム、１−エチル−２−シアノピリジニウム、
１−プロピル−２−メチルピリジニウム、１−プロピル−２−エチルピリジニウム、１−プロピル−２−ブチルピリジニウム、１−プロピル−２−スルホピリジニウム、１−プロピル−２−メトキシスルホニルピリジニウム、１−プロピル−２−アミノピリジニウム、１−プロピル−２−カルボキシピリジニウム、１−プロピル−２−メトキシカルボニルピリジニウム、１−プロピル−２−フェニルピリジニウム、１−プロピル−２−シアノピリジニウム、
１−ブチル−２−メチルピリジニウム、１−ブチル−２−エチルピリジニウム、１−ブチル−２−ブチルピリジニウム、１−ブチル−２−スルホピリジニウム、１−ブチル−２−メトキシスルホニルピリジニウム、１−ブチル−２−アミノピリジニウム、１−ブチル−２−カルボキシピリジニウム、１−ブチル−２−メトキシカルボニルピリジニウム、１−ブチル−２−フェニルピリジニウム、１−ブチル−２−シアノピリジニウム、
１−メチル−３−メチルピリジニウム、１−メチル−３−エチルピリジニウム、１−メチル−３−ブチルピリジニウム、１−メチル−３−スルホピリジニウム、１−メチル−３−メトキシスルホニルピリジニウム、１−メチル−３−アミノピリジニウム、１−メチル−３−カルボキシピリジニウム、１−メチル−３−メトキシカルボニルピリジニウム、１−メチル−３−フェニルピリジニウム、１−メチル−３−シアノピリジニウム、
１−エチル−３−メチルピリジニウム、１−エチル−３−エチルピリジニウム、１−エチル−３−ブチルピリジニウム、１−エチル−３−スルホピリジニウム、１−エチル−３−メトキシスルホニルピリジニウム、１−エチル−３−アミノピリジニウム、１−エチル−３−カルボキシピリジニウム、１−エチル−３−メトキシカルボニルピリジニウム、１−エチル−３−フェニルピリジニウム、１−エチル−３−シアノピリジニウム、
１−プロピル−３−メチルピリジニウム、１−プロピル−３−エチルピリジニウム、１−プロピル−３−ブチルピリジニウム、１−プロピル−３−スルホピリジニウム、１−プロピル−３−メトキシスルホニルピリジニウム、１−プロピル−３−アミノピリジニウム、１−プロピル−３−カルボキシピリジニウム、１−プロピル−３−メトキシカルボニルピリジニウム、１−プロピル−３−フェニルピリジニウム、１−プロピル−３−シアノピリジニウム、
１−ブチル−３−メチルピリジニウム、１−ブチル−３−エチルピリジニウム、１−ブチル−３−ブチルピリジニウム、１−ブチル−３−スルホピリジニウム、１−ブチル−３−メトキシスルホニルピリジニウム、１−ブチル−３−アミノピリジニウム、１−ブチル−３−カルボキシピリジニウム、１−ブチル−３−メトキシカルボニルピリジニウム、１−ブチル−３−フェニルピリジニウム、１−ブチル−３−シアノピリジニウム、
１−メチル−４−メチルピリジニウム、１−メチル−４−エチルピリジニウム、１−メチル−４−ブチルピリジニウム、１−メチル−４−スルホピリジニウム、１−メチル−４−メトキシスルホニルピリジニウム、１−メチル−４−アミノピリジニウム、１−メチル−４−カルボキシピリジニウム、１−メチル−４−メトキシカルボニルピリジニウム、１−メチル−４−フェニルピリジニウム、１−メチル−４−シアノピリジニウム、
１−エチル−４−メチルピリジニウム、１−エチル−４−エチルピリジニウム、１−エチル−４−ブチルピリジニウム、１−エチル−４−スルホピリジニウム、１−エチル−４−メトキシスルホニルピリジニウム、１−エチル−４−アミノピリジニウム、１−エチル−４−カルボキシピリジニウム、１−エチル−４−フェニルピリジニウム、１−エチル−４−シアノピリジニウム、
１−プロピル−４−メチルピリジニウム、１−プロピル−４−エチルピリジニウム、１−プロピル−４−ブチルピリジニウム、１−プロピル−４−スルホピリジニウム、１−プロピル−４−アミノピリジニウム、１−プロピル−４−カルボキシピリジニウム、１−プロピル−４−メトキシカルボニルピリジニウム、１−プロピル−４−フェニルピリジニウム、１−プロピル−４−シアノピリジニウム、
１−ブチル−４−メチルピリジニウム、１−ブチル−４−エチルピリジニウム、１−ブチル−４−ブチルピリジニウム、１−ブチル−４−スルホピリジニウム、１−ブチル−４−メトキシスルホニルピリジニウム、１−ブチル−４−アミノピリジニウム、１−ブチル−４−カルボキシピリジニウム、１−ブチル−４−メトキシカルボニルピリジニウム、１−ブチル−４−フェニルピリジニウム、１−ブチル−４−シアノピリジニウム
等が挙げられる。
As preferable specific examples of the specific pyridinium compound, for example,
1-methyl-2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1-methyl-2-butylpyridinium, 1-methyl-2-sulfopyridinium, 1-methyl-2-methoxysulfonylpyridinium, 1-methyl- 2-aminopyridinium, 1-methyl-2-carboxypyridinium, 1-methyl-2-methoxycarbonylpyridinium, 1-methyl-2-phenylpyridinium, 1-methyl-2-cyanopyridinium,
1-ethyl-2-methylpyridinium, 1-ethyl-2-ethylpyridinium, 1-ethyl-2-butylpyridinium, 1-ethyl-2-sulfopyridinium, 1-ethyl-2-methoxysulfonylpyridinium, 1-ethyl- 2-aminopyridinium, 1-ethyl-2-carboxypyridinium, 1-ethyl-2-methoxycarbonylpyridinium, 1-ethyl-2-phenylpyridinium, 1-ethyl-2-cyanopyridinium,
1-propyl-2-methylpyridinium, 1-propyl-2-ethylpyridinium, 1-propyl-2-butylpyridinium, 1-propyl-2-sulfopyridinium, 1-propyl-2-methoxysulfonylpyridinium, 1-propyl- 2-aminopyridinium, 1-propyl-2-carboxypyridinium, 1-propyl-2-methoxycarbonylpyridinium, 1-propyl-2-phenylpyridinium, 1-propyl-2-cyanopyridinium,
1-butyl-2-methylpyridinium, 1-butyl-2-ethylpyridinium, 1-butyl-2-butylpyridinium, 1-butyl-2-sulfopyridinium, 1-butyl-2-methoxysulfonylpyridinium, 1-butyl- 2-aminopyridinium, 1-butyl-2-carboxypyridinium, 1-butyl-2-methoxycarbonylpyridinium, 1-butyl-2-phenylpyridinium, 1-butyl-2-cyanopyridinium,
1-methyl-3-methylpyridinium, 1-methyl-3-ethylpyridinium, 1-methyl-3-butylpyridinium, 1-methyl-3-sulfopyridinium, 1-methyl-3-methoxysulfonylpyridinium, 1-methyl- 3-aminopyridinium, 1-methyl-3-carboxypyridinium, 1-methyl-3-methoxycarbonylpyridinium, 1-methyl-3-phenylpyridinium, 1-methyl-3-cyanopyridinium,
1-ethyl-3-methylpyridinium, 1-ethyl-3-ethylpyridinium, 1-ethyl-3-butylpyridinium, 1-ethyl-3-sulfopyridinium, 1-ethyl-3-methoxysulfonylpyridinium, 1-ethyl- 3-aminopyridinium, 1-ethyl-3-carboxypyridinium, 1-ethyl-3-methoxycarbonylpyridinium, 1-ethyl-3-phenylpyridinium, 1-ethyl-3-cyanopyridinium,
1-propyl-3-methylpyridinium, 1-propyl-3-ethylpyridinium, 1-propyl-3-butylpyridinium, 1-propyl-3-sulfopyridinium, 1-propyl-3-methoxysulfonylpyridinium, 1-propyl- 3-aminopyridinium, 1-propyl-3-carboxypyridinium, 1-propyl-3-methoxycarbonylpyridinium, 1-propyl-3-phenylpyridinium, 1-propyl-3-cyanopyridinium,
1-butyl-3-methylpyridinium, 1-butyl-3-ethylpyridinium, 1-butyl-3-butylpyridinium, 1-butyl-3-sulfopyridinium, 1-butyl-3-methoxysulfonylpyridinium, 1-butyl- 3-aminopyridinium, 1-butyl-3-carboxypyridinium, 1-butyl-3-methoxycarbonylpyridinium, 1-butyl-3-phenylpyridinium, 1-butyl-3-cyanopyridinium,
1-methyl-4-methylpyridinium, 1-methyl-4-ethylpyridinium, 1-methyl-4-butylpyridinium, 1-methyl-4-sulfopyridinium, 1-methyl-4-methoxysulfonylpyridinium, 1-methyl- 4-aminopyridinium, 1-methyl-4-carboxypyridinium, 1-methyl-4-methoxycarbonylpyridinium, 1-methyl-4-phenylpyridinium, 1-methyl-4-cyanopyridinium,
1-ethyl-4-methylpyridinium, 1-ethyl-4-ethylpyridinium, 1-ethyl-4-butylpyridinium, 1-ethyl-4-sulfopyridinium, 1-ethyl-4-methoxysulfonylpyridinium, 1-ethyl- 4-aminopyridinium, 1-ethyl-4-carboxypyridinium , 1 -ethyl-4-phenylpyridinium, 1-ethyl-4-cyanopyridinium,
1-propyl-4-methylpyridinium, 1-propyl-4-ethylpyridinium, 1-propyl-4-butylpyridinium, 1-propyl-4-sulfopyridinium , 1 -propyl-4-aminopyridinium, 1-propyl-4 -Carboxypyridinium, 1-propyl-4-methoxycarbonylpyridinium, 1-propyl-4-phenylpyridinium, 1-propyl-4-cyanopyridinium,
1-butyl-4-methylpyridinium, 1-butyl-4-ethylpyridinium, 1-butyl-4-butylpyridinium, 1-butyl-4-sulfopyridinium, 1-butyl-4-methoxysulfonylpyridinium, 1-butyl- Examples include 4-aminopyridinium, 1-butyl-4-carboxypyridinium, 1-butyl-4-methoxycarbonylpyridinium, 1-butyl-4-phenylpyridinium, 1-butyl-4-cyanopyridinium, and the like.
これらの特定ピリジニウム化合物は、前記した本発明の効果を発揮し易く、更に、良好な電解金めっき性能、水への溶解のし易さ、入手のし易さ、低コスト等の観点からも好ましい。 These specific pyridinium compounds are easy to exhibit the effects of the present invention described above, and are also preferable from the viewpoints of good electrolytic gold plating performance, ease of dissolution in water, availability, low cost, etc. .
それらの中でも、特に好ましい具体例としては、例えば、
１−メチル−２−メチルピリジニウム、１−メチル−２−エチルピリジニウム、１−メチル−２−ブチルピリジニウム、１−メチル−２−スルホピリジニウム、１−メチル−２−メトキシスルホニルピリジニウム、１−メチル−２−アミノピリジニウム、１−メチル−２−カルボキシピリジニウム、
１−エチル−２−メチルピリジニウム、１−エチル−２−エチルピリジニウム、１−エチル−２−ブチルピリジニウム、１−エチル−２−スルホピリジニウム、１−エチル−２−メトキシスルホニルピリジニウム、１−エチル−２−アミノピリジニウム、１−エチル−２−カルボキシルピリジニウム、
１−メチル−３−メチルピリジニウム、１−メチル−３−エチルピリジニウム、１−メチル−３−ブチルピリジニウム、１−メチル−３−スルホピリジニウム、１−メチル−３−メトキシスルホニルピリジニウム、１−メチル−３−アミノピリジニウム、１−メチル−３−カルボキシルピリジニウム、
１−エチル−３−メチルピリジニウム、１−エチル−３−エチルピリジニウム、１−エチル−３−ブチルピリジニウム、１−エチル−３−スルホピリジニウム、１−エチル−３−メトキシスルホニルピリジニウム、１−エチル−３−アミノピリジニウム、１−エチル−３−カルボキシルピリジニウム、
１−メチル−４−メチルピリジニウム、１−メチル−４−エチルピリジニウム、１−メチル−４−ブチルピリジニウム、１−メチル−４−スルホピリジニウム、１−メチル−４−メトキシスルホニルピリジニウム、１−メチル−４−アミノピリジニウム、１−メチル−４−カルボキシルピリジニウム、
１−エチル−４−メチルピリジニウム、１−エチル−４−エチルピリジニウム、１−エチル−４−ブチルピリジニウム、１−エチル−４−スルホピリジニウム、１−エチル−４−メトキシスルホニルピリジニウム、１−エチル−４−アミノピリジニウム、１−エチル−４−カルボキシルピリジニウム
等が挙げられる。
Among them, as a particularly preferable specific example, for example,
1-methyl-2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1-methyl-2-butylpyridinium, 1-methyl-2-sulfopyridinium, 1-methyl-2-methoxysulfonylpyridinium, 1-methyl- 2-aminopyridinium, 1-methyl-2-carboxypyridinium,
1-ethyl-2-methylpyridinium, 1-ethyl-2-ethylpyridinium, 1-ethyl-2-butylpyridinium, 1-ethyl-2-sulfopyridinium, 1-ethyl-2-methoxysulfonylpyridinium, 1-ethyl- 2-aminopyridinium, 1-ethyl-2-carboxylpyridinium,
1-methyl-3-methylpyridinium, 1-methyl-3-ethylpyridinium, 1-methyl-3-butylpyridinium, 1-methyl-3-sulfopyridinium, 1-methyl-3-methoxysulfonylpyridinium, 1-methyl- 3-aminopyridinium, 1-methyl-3-carboxylpyridinium,
1-ethyl-3-methylpyridinium, 1-ethyl-3-ethylpyridinium, 1-ethyl-3-butylpyridinium, 1-ethyl-3-sulfopyridinium, 1-ethyl-3-methoxysulfonylpyridinium, 1-ethyl- 3-aminopyridinium, 1-ethyl-3-carboxylpyridinium,
1-methyl-4-methylpyridinium, 1-methyl-4-ethylpyridinium, 1-methyl-4-butylpyridinium, 1-methyl-4-sulfopyridinium, 1-methyl-4-methoxysulfonylpyridinium, 1-methyl- 4-aminopyridinium, 1-methyl-4-carboxylpyridinium,
1-ethyl-4-methylpyridinium, 1-ethyl-4-ethylpyridinium, 1-ethyl-4-butylpyridinium, 1-ethyl-4-sulfopyridinium, 1-ethyl-4-methoxysulfonylpyridinium, 1-ethyl- 4-aminopyridinium, 1-ethyl-4-carboxylpyridinium, etc. are mentioned.
これらの特定ピリジニウム化合物は、前記した本発明の効果をより発揮し易く、更に、良好な電解金めっき性能、水への溶解のし易さ、入手のし易さ、低コスト等の観点から特に好ましいものとして挙げられる。 These specific pyridinium compounds are particularly easy to exhibit the effects of the present invention described above, and more particularly from the viewpoint of good electrolytic gold plating performance, ease of dissolution in water, availability, low cost, etc. It is mentioned as preferable.
本発明において、特定ピリジニウム化合物の含有量については特に限定はないが、電解金めっき液全体に対して、質量で、好ましくは１０ｐｐｍ〜５００００ｐｐｍ、より好ましくは３０ｐｐｍ〜３００００ｐｐｍ、特に好ましくは５０ｐｐｍ〜１００００ｐｐｍである。なお、上記の特定ピリジニウム化合物を２種以上含有するときは、上記数値はそれらの合計含有量を示す。
電解金めっき液中の特定ピリジニウム化合物の含有量が少な過ぎると、前記した本発明の効果を発揮し難くなり、金皮膜の外観不良を起こしたりする場合がある。一方、含有量が多過ぎると本発明の上記効果の更なる増加は期待できず不経済となる場合がある。
In the present invention, the content of the specific pyridinium compound is not particularly limited, but is preferably from 10 ppm to 50000 ppm, more preferably from 30 ppm to 30000 ppm, and particularly preferably from 50 ppm to 10000 ppm by mass with respect to the entire electrolytic gold plating solution. is there. In addition, when 2 or more types of said specific pyridinium compounds are contained, the said numerical value shows those total content.
If the content of the specific pyridinium compound in the electrolytic gold plating solution is too small, the effect of the present invention described above becomes difficult to be exhibited, and the appearance of the gold film may be deteriorated. On the other hand, when there is too much content, the further increase of the said effect of this invention cannot be anticipated, and it may become uneconomical.
上記の特定ピリジニウム化合物についての記載は、本発明の電解金めっき液中に存在する形態を特定するものであるが、本発明の電解金めっき液の調液の際に、溶解させる原料として、上記の特定ピリジニウム化合物を用いることが好ましい。 The above description about the specific pyridinium compound specifies the form present in the electrolytic gold plating solution of the present invention, but as a raw material to be dissolved in the preparation of the electrolytic gold plating solution of the present invention, It is preferable to use the specific pyridinium compound.
＜シアン化金塩＞
本発明の電解金めっき液は、シアン化金塩を含有することが必須である。該シアン化金塩は、本発明の電解金めっき液の金源として用いられる。シアン化金塩は、１種の使用に限定されず２種以上を併用することができる。
<Gold cyanide>
The electrolytic gold plating solution of the present invention must contain a gold cyanide salt. The gold cyanide salt is used as a gold source for the electrolytic gold plating solution of the present invention. The gold cyanide salt is not limited to one type, and two or more types can be used in combination.
該シアン化金塩としては、シアン化金アルカリ金属又はシアン化金アンモニウムが好ましい。また、該シアン化金塩の金の価数（酸化数）としては、１価又は３価のどちらでも使用可能であるが、金の析出効率の観点から１価が好ましい。すなわちシアン化第１金塩が好ましい。 As the gold cyanide salt, alkali metal cyanide or ammonium gold cyanide is preferable. The gold valence (oxidation number) of the gold cyanide salt may be monovalent or trivalent, but monovalent is preferable from the viewpoint of gold deposition efficiency. That is, the first cyanide gold salt is preferable.
該シアン化金塩の具体例としては、例えば、シアン化第１金ナトリウム、シアン化第１金カリウム、シアン化第１金アンモニウム、シアン化第２金ナトリウム、シアン化第２金カリウム、シアン化第２金アンモニウム、等が挙げられる。このうち、金の析出効率等のめっき性能、コスト、入手の容易さ等の観点から、シアン化第１金ナトリウム、シアン化第１金カリウム、シアン化第１金アンモニウムが好ましく、更に同様の観点からシアン化第１金カリウムが特に好ましい。 Specific examples of the gold cyanide salt include, for example, first gold sodium cyanide, first gold potassium cyanide, first gold ammonium cyanide, second gold sodium cyanide, second gold potassium cyanide, cyanide. And secondary gold ammonium. Among these, from the viewpoints of plating performance such as gold deposition efficiency, cost, availability, etc., primary gold sodium cyanide, primary gold potassium cyanide, and primary gold ammonium cyanide are preferable, and further similar viewpoints. To 1st potassium gold cyanide is particularly preferred.
本発明の電解金めっき液中の該シアン化金塩の含有量は特に限定はなく、電解金めっき液全体に対して、金属金として、通常０．０５ｇ／Ｌ〜５０ｇ／Ｌ、好ましくは０．５ｇ／Ｌ〜３０ｇ／Ｌ、特に好ましくは１ｇ／Ｌ〜２０ｇ／Ｌである。 The content of the gold cyanide salt in the electrolytic gold plating solution of the present invention is not particularly limited, and is usually 0.05 g / L to 50 g / L, preferably 0 as metal gold based on the entire electrolytic gold plating solution. 0.5 g / L to 30 g / L, particularly preferably 1 g / L to 20 g / L.
電解金めっき液中のシアン化金塩の含有量が少な過ぎると、正常のレモンイエローの金皮膜の形成が困難になる場合がある。すなわち、金皮膜の色等を目視で観察したときに金の析出異常が認められる場合がある。
一方、電解金めっき液中のシアン化金塩の含有量が多過ぎる場合は、電解金めっき液の性能としては特に問題はないが、シアン化金塩は非常に高価であり、電解金めっき液中に含有した状態で保存するのは不経済となる場合がある。
If the content of the gold cyanide salt in the electrolytic gold plating solution is too small, it may be difficult to form a normal lemon yellow gold film. In other words, abnormal gold deposition may be observed when the color of the gold film is visually observed.
On the other hand, when the content of the gold cyanide salt in the electrolytic gold plating solution is too large, there is no particular problem with the performance of the electrolytic gold plating solution, but the gold cyanide salt is very expensive, and the electrolytic gold plating solution It may be uneconomical to store in the state of being contained.
上記のシアン化金塩についての記載は、本発明の電解金めっき液中に存在する形態を特定するものであるが、本発明の電解金めっき液の調液の際に溶解させる原料として、上記のシアン化金塩を用いることが好ましい。 The above description about the gold cyanide salt specifies the form present in the electrolytic gold plating solution of the present invention, but as a raw material to be dissolved in the preparation of the electrolytic gold plating solution of the present invention, It is preferable to use a gold cyanide salt.
＜コバルト塩、ニッケル塩、鉄塩＞
本発明の「金皮膜」には「金合金皮膜」も含まれる。すなわち、本発明の「金皮膜」には金以外の金属を含有していてもよい。ここで、「金合金皮膜」とは、「金皮膜」中に、０．０１質量％以上「金以外の金属」が含有されている場合（金純度９９．９９質量％未満の場合）をいう。
また、本発明の「電解金めっき液」には「電解金合金めっき液」も含まれる。すなわち、本発明の「電解金めっき液」には、金以外の金属を含有していてもよい。ただし、電解金めっき液中に金以外の金属を含有していても、その電解金めっき液を用いて得られた「金皮膜」が、上記定義による「金合金皮膜」でない場合は、その「電解金めっき液」は「電解金合金めっき液」とはいわない。
<Cobalt salt, nickel salt, iron salt>
The “gold film” of the present invention includes “gold alloy film”. That is, the “gold film” of the present invention may contain a metal other than gold. Here, the “gold alloy film” refers to the case where the “gold film” contains 0.01% by mass or more of “metal other than gold” (the gold purity is less than 99.99% by mass). .
The “electrolytic gold plating solution” of the present invention also includes “electrolytic gold alloy plating solution”. That is, the “electrolytic gold plating solution” of the present invention may contain a metal other than gold. However, even if the electrolytic gold plating solution contains a metal other than gold, if the "gold film" obtained using the electrolytic gold plating solution is not a "gold alloy film" as defined above, “Electrolytic gold plating solution” is not an “electrolytic gold alloy plating solution”.
「金合金皮膜」は「硬質金皮膜」となり得るため、コネクター等の接点部材等、硬度を必要とする部分に用いられる。
硬質金皮膜を形成させるために本発明の電解金めっき液を使用する場合には、本発明の電解金めっき液は、更に、コバルト塩、ニッケル塩及び／又は鉄塩を含有する。すなわち、金源としてのシアン化金塩に加えて、コバルト塩、ニッケル塩、鉄塩の何れか１種又は２種以上を含有する。
Since the “gold alloy film” can be a “hard gold film”, it is used for parts that require hardness, such as contact members such as connectors.
When the electrolytic gold plating solution of the present invention is used to form a hard gold film, the electrolytic gold plating solution of the present invention further contains a cobalt salt, a nickel salt and / or an iron salt. That is, in addition to the gold cyanide salt as a gold source, it contains any one or more of a cobalt salt, a nickel salt, and an iron salt.
本発明の電解金めっき液は、シアン化金塩、特定ピリジニウム化合物に加えて、更に、コバルト塩、ニッケル塩及び／又は鉄塩を併用することが好ましい。
コバルト塩、ニッケル塩及び／又は鉄塩を含有すると、コバルト、ニッケル及び／又は鉄が、金めっき皮膜中に金と共に析出し（共析し）、硬質金皮膜を形成する。
特に、ニッケルめっき皮膜上に、金と共に析出（共析）させると硬質金皮膜を形成し、電子部品のコネクター等の接点部材に必要とされる高硬度や高耐摩耗性等を実現させることができる。
The electrolytic gold plating solution of the present invention preferably further uses a cobalt salt, a nickel salt and / or an iron salt in addition to the gold cyanide salt and the specific pyridinium compound.
When a cobalt salt, nickel salt and / or iron salt is contained, cobalt, nickel and / or iron precipitates (eutectoid) with gold in the gold plating film to form a hard gold film.
In particular, when it is deposited (eutectoid) with gold on a nickel plating film, a hard gold film is formed, and high hardness and high wear resistance required for contact members such as connectors of electronic parts can be realized. it can.
上記のコバルト塩、ニッケル塩及び鉄塩は、水溶性であることが好ましい。
上記のコバルト塩、ニッケル塩及び／又は鉄塩は、それぞれの金属塩の中で１種の使用に限定されず２種以上を併用することができる。また、コバルト塩、ニッケル塩、鉄塩の中で、異なる金属塩を１種に限定されず２種以上を併用することができる。
The cobalt salt, nickel salt and iron salt are preferably water-soluble.
Said cobalt salt, nickel salt, and / or iron salt are not limited to use of 1 type in each metal salt, but 2 or more types can be used together. Moreover, in cobalt salt, nickel salt, and iron salt, a different metal salt is not limited to 1 type, but 2 or more types can be used together.
上記コバルト塩としては特に限定はないが、例えば、硫酸コバルト、塩化コバルト、硝酸コバルト、炭酸コバルト、フタロシアニンコバルト、ステアリン酸コバルト、エチレンジアミン４酢酸二ナトリウムコバルト、ナフテン酸コバルト、ホウ酸コバルト、チオシアン酸コバルト、スルファミン酸コバルト、酢酸コバルト、クエン酸コバルト、水酸化コバルト、シュウ酸コバルト、リン酸コバルト等が、良好な電解金めっき性能、水への溶解のし易さ、金皮膜への共析のし易さ、入手の容易さ、低コスト等の観点から、好ましいものとして挙げられる。 Although there is no limitation in particular as said cobalt salt, For example, cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt phthalocyanine cobalt, stearic acid cobalt, ethylenediamine tetraacetic acid disodium cobalt, naphthenic acid cobalt, boric acid borate, thiocyanic acid cobalt Cobalt sulfamate, cobalt acetate, cobalt citrate, cobalt hydroxide, cobalt oxalate, cobalt phosphate, etc. have good electrolytic gold plating performance, ease of dissolution in water, and eutectoid on the gold film. From the viewpoints of ease, availability, and low cost, it is preferable.
上記ニッケル塩としては特に限定はないが、例えば、硫酸ニッケル、酢酸ニッケル、塩化ニッケル、ホウ酸ニッケル、安息香酸ニッケル、シュウ酸ニッケル、ナフテン酸ニッケル、酸化ニッケル、リン酸ニッケル、ステアリン酸ニッケル、酒石酸ニッケル、チオシアン酸ニッケル、アミド硫酸ニッケル、炭酸ニッケル、クエン酸ニッケル、ギ酸ニッケル、シアン化ニッケル、水酸化ニッケル、硝酸ニッケル、オクタン酸ニッケル等が、良好な電解金めっき性能、水への溶解の容易さ、金皮膜への共析のし易さ、入手の容易さ、低コスト等の観点から、好ましいものとして挙げられる。 The nickel salt is not particularly limited. For example, nickel sulfate, nickel acetate, nickel chloride, nickel borate, nickel benzoate, nickel oxalate, nickel naphthenate, nickel oxide, nickel phosphate, nickel stearate, tartaric acid Nickel, nickel thiocyanate, nickel amidosulfate, nickel carbonate, nickel citrate, nickel formate, nickel cyanide, nickel hydroxide, nickel nitrate, nickel octoate, etc. have good electrolytic gold plating performance, easy dissolution in water In view of easiness of eutectoid deposition on the gold film, availability, low cost and the like, it is preferable.
上記鉄塩としては特に限定はないが、例えば、硫酸第１鉄、硫酸第２鉄、塩化第１鉄、塩化第２鉄、クエン酸第１鉄、クエン酸第２鉄、ギ酸第１鉄、ギ酸第２鉄、次亜リン酸第２鉄、ナフテン酸第２鉄、ステアリン酸第２鉄、ピロリン酸第２鉄、酒石酸第１鉄、チオシアン酸第２鉄、フマル酸第１鉄、グルコン酸第１鉄、エチレンジアミン４酢酸鉄、硝酸第２鉄等が、良好な電解金めっき性能、水への溶解のし易さ、金皮膜への共析のし易さ、入手の容易さ、低コストの観点から、好ましいものとして挙げられる。 The iron salt is not particularly limited. For example, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous citrate, ferric citrate, ferrous formate, Ferric formate, ferric hypophosphite, ferric naphthenate, ferric stearate, ferric pyrophosphate, ferrous tartrate, ferric thiocyanate, ferrous fumarate, gluconic acid Ferrous, ethylenediaminetetraacetic acid iron, ferric nitrate, etc. have good electrolytic gold plating performance, ease of dissolution in water, ease of eutectoid deposition on gold film, easy availability, low cost From the point of view, it is preferable.
本発明の電解金めっき液中の上記コバルト塩、ニッケル塩、鉄塩の含有量については特に限定はないが、電解金めっき液全体に対して、金属として（金属換算で）、好ましくは１ｐｐｍ〜５００００ｐｐｍ、より好ましくは１０ｐｐｍ〜３００００ｐｐｍ、特に好ましくは５０ｐｐｍ〜１００００ｐｐｍである。なお、上記コバルト塩、ニッケル塩、鉄塩を２種以上使用するときは、上記数値はそれらの合計含有量を示す。
含有量が少な過ぎると、金皮膜への共析量が少な過ぎて充分な硬度が得られない場合がある。一方、含有量が多過ぎると、金皮膜への共析量が多くなり過ぎて、金皮膜の色調不良や接触抵抗の増大が発生したり、硬度の更なる増加は期待できなかったりする場合がある。
Although there is no limitation in particular about content of the said cobalt salt, nickel salt, and iron salt in the electrolytic gold plating solution of this invention, as a metal (in metal conversion) with respect to the whole electrolytic gold plating solution, Preferably it is 1 ppm- It is 50000 ppm, more preferably 10 ppm to 30000 ppm, and particularly preferably 50 ppm to 10000 ppm. In addition, when using 2 or more types of the said cobalt salt, nickel salt, and iron salt, the said numerical value shows those total content.
If the content is too small, the amount of eutectoid deposited on the gold film is too small and sufficient hardness may not be obtained. On the other hand, if the content is too high, the amount of eutectoid on the gold film will increase too much, resulting in a poor color tone or increased contact resistance of the gold film, or a further increase in hardness may not be expected. is there.
コバルト塩、ニッケル塩及び／又は鉄塩を含有する電解金めっき液の場合、電流密度を上げて電解金めっきを行なうと、コバルト、ニッケル及び／又は鉄が、金めっき皮膜中に金と共に析出（共析）し難くなる傾向にある。そして、電流密度を上げたときにそれらの金属が共析し難くなる傾向が大きい電解金めっき液だと、電流密度を上げたときに、金の析出異常が起こり易くなり、レモンイエローの金皮膜の形成が困難になる場合がある。
電解金めっき液中に、前記した特定ピリジニウム化合物を含有すると、電流密度を上げて電解金めっきを行なっても、コバルト、ニッケル及び／又は鉄が、金めっき皮膜中に金と共に析出（共析）し易くなる。
従って、本発明の電解金めっき液の効果の一つは、前記した通り、従来の電解金めっき液と比較して、電流密度を上げても「ヤケ」等の「金の析出異常」が認められ難く、電解金めっき時間を短縮できることであるから、該効果を顕著に発揮させるために、本発明の電解金めっき液は、更に、コバルト塩、ニッケル塩及び／又は鉄塩を含有する電解金めっき液、すなわち、電解金合金めっき液であることが好ましい。
In the case of an electrolytic gold plating solution containing a cobalt salt, a nickel salt and / or an iron salt, cobalt, nickel and / or iron precipitates with gold in the gold plating film when the current density is increased and electrolytic gold plating is performed ( Tends to be difficult to eutectoid). And when the current density is increased, an electrolytic gold plating solution that tends to be difficult to co-deposit those metals is likely to cause abnormal gold deposition when the current density is increased. May be difficult to form.
When the above-mentioned specific pyridinium compound is contained in the electrolytic gold plating solution, cobalt, nickel, and / or iron precipitates together with gold in the gold plating film (eutectoid) even when electrolytic gold plating is performed by increasing the current density. It becomes easy to do.
Accordingly, as described above, one of the effects of the electrolytic gold plating solution of the present invention is that “gold precipitation abnormality” such as “burning” is recognized even when the current density is increased as compared with the conventional electrolytic gold plating solution. The electrolytic gold plating solution of the present invention further includes a cobalt salt, a nickel salt and / or an iron salt in order to exert the effect remarkably, because the electrolytic gold plating time can be shortened. A plating solution, that is, an electrolytic gold alloy plating solution is preferable.
＜その他の添加剤＞
本発明の電解金めっき液には、上記の成分以外に必要に応じて、電解金めっき液のｐＨを一定に保つための緩衝剤、電解金めっき液の導電性を確保するための電導塩、電解金めっき液中に不純物金属が混入した場合にその影響を除去するための金属イオン封鎖剤、金皮膜のピンホール除去若しくは電解金めっき液の泡切れを良好にするための界面活性剤、金皮膜を平滑にするための光沢剤等、適宣含有させて用いることができる。
<Other additives>
In addition to the above components, the electrolytic gold plating solution of the present invention, if necessary, a buffering agent for keeping the pH of the electrolytic gold plating solution constant, a conductive salt for ensuring the conductivity of the electrolytic gold plating solution, Metal ion sequestering agent to remove the effects of impurities mixed into the electrolytic gold plating solution, surfactant to remove pinholes in the gold film or to eliminate bubbles in the electrolytic gold plating solution, gold A brightening agent for smoothing the film can be contained in an appropriate amount.
本発明の電解金めっき液に必要に応じて含有される緩衝剤としては、周知の緩衝剤であれば特に限定はないが、ホウ酸、リン酸等の無機酸、クエン酸、酒石酸、リンゴ酸等のオキシカルボン酸等が挙げられる。これは、１種又は２種以上を混合して用いることができる。 The buffering agent contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known buffering agent. However, inorganic acids such as boric acid and phosphoric acid, citric acid, tartaric acid, malic acid And oxycarboxylic acids such as This can be used alone or in combination of two or more.
本発明の電解金めっき液中の緩衝剤の含有量は特に限定はないが、電解金めっき液全体に対して、通常１ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは１０ｇ／Ｌ〜１００ｇ／Ｌである。
電解金めっき液中の緩衝剤の含有量が少な過ぎると、緩衝効果が発揮され難い場合があり、一方、多過ぎる場合は緩衝効果の上昇が見られず不経済の場合がある。
The content of the buffering agent in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 1 g / L to 500 g / L, preferably 10 g / L to 100 g / L with respect to the entire electrolytic gold plating solution. .
If the content of the buffering agent in the electrolytic gold plating solution is too small, the buffering effect may be difficult to be exhibited. On the other hand, if it is too much, the buffering effect may not be increased and it may be uneconomical.
本発明の電解金めっき液に必要に応じて含有される電導塩としては、周知の電導塩であれば特に限定はないが、硫酸塩、硝酸塩、リン酸塩等の無機酸、シュウ酸、コハク酸、グルタル酸、マロン酸、クエン酸、酒石酸、リンゴ酸等のカルボン酸等が挙げられる。これらは１種又は２種以上を混合して用いることができる。 The conductive salt contained in the electrolytic gold plating solution of the present invention as needed is not particularly limited as long as it is a known conductive salt, but is not limited to inorganic acids such as sulfates, nitrates, and phosphates, oxalic acid, and succinic acid. Examples thereof include carboxylic acids such as acid, glutaric acid, malonic acid, citric acid, tartaric acid and malic acid. These may be used alone or in combination of two or more.
本発明の電解金めっき液中の電導塩の含有量は特に限定はないが、電解金めっき液全体に対して、通常１ｇ／Ｌ〜５００ｇ／Ｌ、好ましくは１０ｇ／Ｌ〜１００ｇ／Ｌである。
電解金めっき液中の電導塩の含有量が少な過ぎると、電導効果が発揮され難い場合があり、一方、多過ぎる場合は、電導効果の上昇が見られず不経済の場合がある。
また、緩衝剤と同一の成分で共用することも可能である。
The content of the conductive salt in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 1 g / L to 500 g / L, preferably 10 g / L to 100 g / L with respect to the entire electrolytic gold plating solution. .
If the content of the conductive salt in the electrolytic gold plating solution is too small, the conductive effect may be difficult to be exhibited. On the other hand, if the content is too large, the conductive effect may not be increased, which may be uneconomical.
It is also possible to share the same component as the buffer.
本発明の電解金めっき液に必要に応じて含有される金属イオン封鎖剤としては、周知の金属イオン封鎖剤であれば特に限定はないが、イミノジ酢酸、ニトリロトリ酢酸、エチレンジアミンテトラ酢酸等のアミノカルボン酸系キレート剤、ヒドロキシエチリデンジホスホン酸、ニトリロメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸等のホスホン酸系キレート剤等が挙げられる。これらは１種又は２種以上を混合して用いることができる。 The sequestering agent contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known sequestering agent, but aminocarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, etc. Examples include acid-based chelating agents, hydroxyethylidene diphosphonic acid, nitrilomethylene phosphonic acid, and ethylenediamine tetramethylene phosphonic acid. These may be used alone or in combination of two or more.
本発明の電解金めっき液中の金属イオン封鎖剤の含有量は特に限定はないが、電解金めっき液全体に対して、通常０．１ｇ／Ｌ〜１００ｇ／Ｌ、好ましくは０．５ｇ／Ｌ〜５０ｇ／Ｌである。電解金めっき液中の金属イオン封鎖剤の含有量が少な過ぎると、不純物金属の影響を除去する効果が発揮され難い場合があり、一方、多過ぎる場合は不純物金属の影響を除去する効果の上昇が見られず不経済の場合がある。 The content of the sequestering agent in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 0.1 g / L to 100 g / L, preferably 0.5 g / L, based on the entire electrolytic gold plating solution. ~ 50 g / L. If the content of the sequestering agent in the electrolytic gold plating solution is too small, the effect of removing the influence of the impurity metal may be difficult to be exhibited, while if too much, the effect of removing the influence of the impurity metal is increased. May not be seen and may be uneconomical.
本発明の電解金めっき液に必要に応じて含有される界面活性剤としては、周知の界面活性剤であれば特に限定はなく、ノニオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤又はカチオン系界面活性剤が用いられる。これらは１種又は２種以上を混合して用いることができる。 The surfactant contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known surfactant, and is a nonionic surfactant, an anionic surfactant, an amphoteric surfactant. Alternatively, a cationic surfactant is used. These may be used alone or in combination of two or more.
ノニオン系界面活性剤としては、ノニフェノールポリアルコキシレート、α−ナフトールポリアルコキシレート、ジブチルーβ−ナフトールポリアルコキシレート、スチレン化フェノールポリアルコキシレート等のエーテル型ノニオン系界面活性剤、オクチルアミンポリアルコキシレート、ヘキシニルアミンポリアルコキシレート、リノレイルアミンポリアルコキシレート等のアミン型ノニオン系界面活性剤等が挙げられる。
アニオン系界面活性剤としては、ラウリル硫酸ナトリウム等のアルキル硫酸塩、ポリオキシエチレンノニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩等が挙げられる。
Nonionic surfactants include ether type nonionic surfactants such as noniphenol polyalkoxylate, α-naphthol polyalkoxylate, dibutyl β-naphthol polyalkoxylate, and styrenated phenol polyalkoxylate, and octylamine polyalkoxylate. And amine type nonionic surfactants such as hexynylamine polyalkoxylate and linoleylamine polyalkoxylate.
Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene nonyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfates, and alkylbenzene sulfonates. It is done.
両性界面活性剤としては、２−ウンデシル−１−カルボキシメチル−１−ヒドロキシエチルイミダゾリウム、Ｎ−ステアリル−Ｎ，Ｎ−カルボキシメチルベタイン、ラウリルジメチルアミンオキシド等が挙げられる。 Examples of amphoteric surfactants include 2-undecyl-1-carboxymethyl-1-hydroxyethylimidazolium, N-stearyl-N, N-carboxymethylbetaine, lauryldimethylamine oxide, and the like.
カチオン系界面活性剤としては、ラウリルトリメチルアンモニウム塩、ラウリルジメチルアンモニウムベタイン、ラウリルピリジニウム塩、オレイルイミダゾリウム塩又はステアリルアミンアセテート等が挙げられる。
これらは１種又は２種以上を混合して用いることができるが、好ましくはノニオン系界面活性剤又は両性界面活性剤である。
Examples of the cationic surfactant include lauryl trimethyl ammonium salt, lauryl dimethyl ammonium betaine, lauryl pyridinium salt, oleyl imidazolium salt, stearyl amine acetate and the like.
These can be used alone or in combination of two or more, but are preferably nonionic surfactants or amphoteric surfactants.
本発明の電解金めっき液中の界面活性剤の含有量は、電解金めっき液全体に対して、好ましくは０．０１ｇ／Ｌ〜２０ｇ／Ｌであるが、所望の性能を発揮すればよく、特に含有量を限定するものではない。 The content of the surfactant in the electrolytic gold plating solution of the present invention is preferably 0.01 g / L to 20 g / L with respect to the entire electrolytic gold plating solution. The content is not particularly limited.
本発明の電解金めっき液に必要に応じて含有される光沢剤としては、周知の光沢剤であれば特に限定はないが、電解金めっき中で本発明における特定ピリジニウム化合物になり得ない「ピリジン骨格を有するアミン化合物」等が挙げられる。これらは１種又は２種以上を混合して用いることができる。
ピリジン骨格を有するアミン化合物としては、２−アミノピリジン、３−アミノピリジン、４−アミノピリジン等が挙げられる。
The brightener contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a well-known brightener, but “pyridine” cannot be a specific pyridinium compound in the present invention during electrolytic gold plating. And an amine compound having a skeleton ”. These may be used alone or in combination of two or more.
Examples of the amine compound having a pyridine skeleton include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine and the like.
本発明の電解金めっき液中の光沢剤の含有量は、電解金めっき液全体に対して、好ましくは０．０１ｇ／Ｌ〜２０ｇ／Ｌであるが、所望の性能を発揮すれば良く、特に含有量を限定するものではない。 The content of the brightener in the electrolytic gold plating solution of the present invention is preferably 0.01 g / L to 20 g / L with respect to the entire electrolytic gold plating solution. The content is not limited.
本発明の電解金めっき液は、電解金めっき液の物性として、電解金めっき液全体に対して金含有量を９ｇ／Ｌに調合した電解金めっき液を用い、ジェット噴流式めっき装置を用いて、電解金めっき液温度を５０℃、電流密度を６０Ａ／ｄｍ２に設定して１０秒間電解金めっきをした場合、得られた金皮膜の膜厚が１．２μｍ以上であり、かつ、該金皮膜の目視での外観に金の析出異常が認められないような物性を有するものであることが好ましい。
上記「ジェット噴流式めっき装置を用いた電解金めっき」とは、口径８ｍｍの円状の噴流口から毎分１８Ｌの流量で電解金めっき液をポンプにより噴流撹拌しながら行なう電解金めっきのことをいう。
The electrolytic gold plating solution of the present invention uses, as a physical property of the electrolytic gold plating solution, an electrolytic gold plating solution in which the gold content is adjusted to 9 g / L with respect to the entire electrolytic gold plating solution, and uses a jet jet plating apparatus. When the electrolytic gold plating was performed for 10 seconds with the electrolytic gold plating solution temperature set to 50 ° C. and the current density set to 60 A / dm 2 , the resulting gold film had a thickness of 1.2 μm or more, and the gold It is preferable that the film has physical properties such that no abnormal gold deposition is observed in the visual appearance of the film.
The above-mentioned “electrolytic gold plating using a jet-jet type plating apparatus” refers to electrolytic gold plating performed while stirring an electrolytic gold plating solution at a flow rate of 18 L / min from a circular jet port having a diameter of 8 mm. Say.
上記物性の限定は、電解金めっき液の物性を限定するものであって、かかる電解金めっき液の使用方法を限定するものではない。かかる電解金めっき液は、金含有量が９ｇ／Ｌである必要はなく、上位定義のジェット噴流式めっき装置を用いて、電解金めっき液温度を５０℃、電流密度を６０Ａ／ｄｍ２に設定して１０秒間電解金めっきをするためのものには限定されない。また、かかる電解金めっき液を用いて、膜厚１．２μｍ未満の金皮膜を形成してもよい。 The limitation of the above physical properties limits the physical properties of the electrolytic gold plating solution, and does not limit the method of using the electrolytic gold plating solution. Such an electrolytic gold plating solution does not need to have a gold content of 9 g / L. Using an upper-definition jet jet plating apparatus, the electrolytic gold plating solution temperature is set to 50 ° C. and the current density is set to 60 A / dm 2 . And it is not limited to the thing for performing electrolytic gold plating for 10 seconds. Moreover, you may form a gold film with a film thickness of less than 1.2 micrometers using this electrolytic gold plating solution.
本発明における「特定ピリジニウム化合物」を含有成分として用いると、金含有量を９ｇ／Ｌにし、ジェット噴流式めっき装置を用いて、５０℃、電流密度６０Ａ／ｄｍ２で１０秒間電解金めっきをした場合、１．２μｍ以上の金皮膜が得られ、このように高電流密度で電解金めっきをしても金皮膜の外観に析出異常が認められない。かかる物性の電解金めっき液は従来存在しなかった。 When the “specific pyridinium compound” in the present invention is used as a component, the gold content is set to 9 g / L, and electrolytic gold plating is performed for 10 seconds at 50 ° C. and a current density of 60 A / dm 2 using a jet jet plating apparatus. In this case, a gold film having a thickness of 1.2 μm or more can be obtained. Thus, no precipitation abnormality is observed in the appearance of the gold film even when electrolytic gold plating is performed at a high current density. There has been no conventional electrolytic gold plating solution having such physical properties.
＜金皮膜＞
前記した通り、本発明の「電解金めっき液」には、「電解金合金めっき液」も含まれる。また、本発明の「金皮膜」には、「金合金皮膜」も含まれる。すなわち、コバルト、ニッケル、鉄等の「金以外の金属」を含有していてもよい。金以外の金属は、ニッケルめっき皮膜上に金めっき皮膜中に金と共析し、電子部品のコネクター等の接点部材に必要とされる高硬度や高耐摩耗性を実現させることができる。
<Gold film>
As described above, the “electrolytic gold plating solution” of the present invention includes “electrolytic gold alloy plating solution”. In addition, the “gold film” of the present invention includes “gold alloy film”. That is, “metal other than gold” such as cobalt, nickel, and iron may be contained. Metals other than gold are co-deposited with gold in the gold plating film on the nickel plating film, and can realize high hardness and high wear resistance required for contact members such as connectors of electronic components.
本発明の金皮膜中の金の濃度（金純度）は特に限定はないが、「金皮膜」全体に対して、金が９５質量％以上であることが好ましく、９９質量％〜９９．９質量％が特に好ましい。 The gold concentration (gold purity) in the gold film of the present invention is not particularly limited, but the gold content is preferably 95% by mass or more, and 99% by mass to 99.9% by mass with respect to the entire “gold film”. % Is particularly preferred.
＜電解金めっきの条件＞
上記した本発明の電解金めっき液のめっき条件は特に限定されるものではないが、温度条件としては、２０℃〜９０℃であることが好ましく、特に好ましくは３０℃〜７０℃である。また、めっき液のｐＨはｐＨ２．０〜９．０であることが好ましく、特に好ましくは、ｐＨ３．０〜８．０である。
<Conditions for electrolytic gold plating>
The plating conditions for the electrolytic gold plating solution of the present invention described above are not particularly limited, but the temperature conditions are preferably 20 ° C. to 90 ° C., particularly preferably 30 ° C. to 70 ° C. Moreover, it is preferable that pH of a plating solution is pH 2.0-9.0, Most preferably, it is pH 3.0-8.0.
本発明の電解金めっき液を用いて電解金めっきを行うことによって得られる金皮膜の膜厚に特に限定はないが、好ましくは０．０１μｍ〜２０μｍ、特に好ましくは０．０５μｍ〜５μｍである。 The film thickness of the gold film obtained by performing electrolytic gold plating using the electrolytic gold plating solution of the present invention is not particularly limited, but is preferably 0.01 μm to 20 μm, particularly preferably 0.05 μm to 5 μm.
また、電解金めっき液の使用に際しては、金皮膜と下地金属との密着性を良くする目的でフラッシュ金めっきと呼ばれる金皮膜の厚さが０．０１μｍ〜０．０５μｍ程度の薄付け金めっき処理をして、その上に所望の膜厚まで厚金めっき処理をするのが一般的である。本発明の電解金めっきは、このときの厚金めっき処理に好適に使用できるが、本発明の電解金めっき液で厚金めっき処理を施す場合にも、フラッシュ金めっきを施すことは可能であり、フラッシュ金めっきには、市販のフラッシュ金めっき液や、本発明の電解金めっき液を適宣使用することができる。 In addition, when using the electrolytic gold plating solution, the thickness of the gold film called flash gold plating is about 0.01 μm to 0.05 μm for the purpose of improving the adhesion between the gold film and the base metal. In general, a thick gold plating process is generally performed on the film to a desired thickness. The electrolytic gold plating of the present invention can be suitably used for the thick gold plating treatment at this time, but it is possible to perform flash gold plating even when performing the thick gold plating treatment with the electrolytic gold plating solution of the present invention. For flash gold plating, a commercially available flash gold plating solution or the electrolytic gold plating solution of the present invention can be used appropriately.
本発明の電解金めっき液は、前述した電子部品のコネクター等の接点部材に用いられることが好ましい。従って、本発明の電解金めっき液を用いて電解金めっきを行うときは、下地めっき処理としてニッケルめっき皮膜を形成させておくことが好ましい。
このときのニッケルめっき液は特に限定されるものではないが、一般的に実用されているワット浴、スルファミン浴、臭化ニッケル浴等が好適である。また、使用するニッケルめっき液に、ピット防止剤、１次光沢剤、２次光沢剤を必要に応じて添加して用いることができる。ニッケルめっき液の使用方法は、特に限定はなく常法に従って使用する。
The electrolytic gold plating solution of the present invention is preferably used for a contact member such as a connector of the electronic component described above. Therefore, when performing electrolytic gold plating using the electrolytic gold plating solution of the present invention, it is preferable to form a nickel plating film as a base plating treatment.
The nickel plating solution at this time is not particularly limited, but a watt bath, a sulfamine bath, a nickel bromide bath and the like that are generally used are suitable. Moreover, a pit inhibitor, a primary brightener, and a secondary brightener can be added to the nickel plating solution used as needed. The method of using the nickel plating solution is not particularly limited and is used according to a conventional method.
ニッケルめっき皮膜の膜厚は、特に限定されるものではないが、０．１μｍ〜２０μｍであることが好ましく、０．５μｍ〜５μｍが特に好ましい。 The thickness of the nickel plating film is not particularly limited, but is preferably 0.1 μm to 20 μm, and particularly preferably 0.5 μm to 5 μm.
＜作用・原理＞
本発明の電解金めっき液が、電流密度を上げても金の析出異常が認められず（「ヤケ」の発生がなく）、レモンイエローの金皮膜が形成できる作用・原理は明らかではないが、以下のことが考えられる。ただし本発明は、以下の作用・原理が成り立つ範囲に限定されるわけではない。
<Action and principle>
Although the electrolytic gold plating solution of the present invention does not show abnormal gold precipitation even when the current density is increased (no occurrence of “burn”), the action / principle for forming a lemon yellow gold film is not clear, The following can be considered. However, the present invention is not limited to the range where the following actions and principles are established.
また、本発明の電解金めっき液が、コバルト塩、ニッケル塩及び／又は鉄塩を含有する電解金合金めっき液の場合、すなわち、硬質金皮膜を形成できる電解金合金めっき液の場合、前記特定ピリジニウム化合物が含有されると、高電流密度での電解金めっきの場合まで、コバルト、ニッケル及び／又は鉄が金と共析し易くなるため、高電流密度まで、金の析出異常が認められず、レモンイエローの金皮膜が形成できると考えられる。
本発明の電解金めっき液の必須成分である特定ピリジニウム化合物は、電流密度に関わらず光沢剤として浴中に含有されているコバルト、ニッケル、鉄等が金皮膜への共析を一定に保つ効果が高いことにより、高電流密度域でめっき処理した場合の金の外観不良発生を少なくする性能を向上させていると考えられる。
その結果、金めっき速度が上げられ、金の析出効率が高くなり、生産性が上げられる、又は、コストダウンが図れる。
Further, when the electrolytic gold plating solution of the present invention is an electrolytic gold alloy plating solution containing a cobalt salt, a nickel salt and / or an iron salt, that is, an electrolytic gold alloy plating solution capable of forming a hard gold film, the specific When a pyridinium compound is contained, cobalt, nickel, and / or iron are likely to eutect with gold until the case of electrolytic gold plating at high current density, so no gold precipitation abnormality is observed up to high current density. It is considered that a lemon yellow gold film can be formed.
The specific pyridinium compound, which is an essential component of the electrolytic gold plating solution of the present invention, has the effect of keeping cobalt, nickel, iron, etc. contained in the bath as a brightener constant regardless of the current density. This is considered to improve the performance of reducing the appearance defects of gold when plating is performed in a high current density region.
As a result, the gold plating rate is increased, the gold deposition efficiency is increased, the productivity is increased, or the cost can be reduced.
以下に実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。
また、電解金めっき液の組成中の濃度の数値は、その成分が結晶水を含むものである場合は、結晶水を入れない質量から求めた濃度の数値である。
また、「％」は「質量％」を示し、「ｐｐｍ」は「質量ｐｐｍ」を示す。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.
Moreover, the numerical value of the density | concentration in the composition of electrolytic gold plating solution is a numerical value of the density | concentration calculated | required from the mass which does not put crystallization water, when the component contains crystallization water.
“%” Represents “mass%”, and “ppm” represents “mass ppm”.
＜電解金めっき液の調製＞
実施例１〜１０、比較例１〜８
電解金めっき液全体に対して、シアン化金カリウムを、金換算で９ｇ／Ｌ、表１に示す各実施例及び各比較例に記載のコバルト塩、ニッケル塩又は鉄塩を、金属換算で２００ｐｐｍ、特定ピリジニウム化合物の塩若しくはその比較化合物を１０００ｐｐｍ、電導塩と緩衝剤を兼ねた成分としてクエン酸を１００ｇ／Ｌとなるように溶解し、ｐＨを４．３に調整して電解金めっき液とした。
<Preparation of electrolytic gold plating solution>
Examples 1-10, Comparative Examples 1-8
For the entire electrolytic gold plating solution, potassium cyanide is 9 g / L in terms of gold, and the cobalt salt, nickel salt or iron salt described in each Example and each Comparative Example shown in Table 1 is 200 ppm in terms of metal. The salt of a specific pyridinium compound or a comparative compound thereof is dissolved at 1000 ppm, citric acid is dissolved at 100 g / L as a component serving as a conductive salt and a buffer, and the pH is adjusted to 4.3 to adjust the electrolytic gold plating solution. did.
「比較化合物」としては、ピリジン、ピリジン−３−スルホン酸、ピコリン、キノリンスルホン酸、２，３−ジアミノピリジン、３−（３−ピリジル）アクリル酸を用いた。 As “comparative compounds”, pyridine, pyridine-3-sulfonic acid, picoline, quinolinesulfonic acid, 2,3-diaminopyridine, and 3- (3-pyridyl) acrylic acid were used.
なお、ｐＨは２０％水酸化カリウム水溶液とクエン酸にて調整し、電解金めっき液の浴温は、５０℃に設定し、以下に記載の評価を行った。 In addition, pH was adjusted with 20% potassium hydroxide aqueous solution and citric acid, the bath temperature of the electrolytic gold plating solution was set to 50 ° C., and the following evaluation was performed.
実施例１１
コバルト塩、ニッケル塩、鉄塩の何れも含有しない以外は、実施例１と同様に電解金めっき液を調整し、実施例１と同様に電解金めっきをして、同様に以下に記載の評価を行った。
Example 11
An electrolytic gold plating solution was prepared in the same manner as in Example 1 except that neither cobalt salt, nickel salt, or iron salt was contained, and electrolytic gold plating was performed in the same manner as in Example 1. Similarly, the evaluation described below Went.
＜電解金めっきの方法＞
各実施例及び比較例で調製した電解金めっき液を用いて、表２に示す工程にて、１０ｍｍ×１０ｍｍの銅板上の１次光沢ニッケルめっき皮膜２．０μｍ上に、電解金めっきを施した。
電解金めっきは、口径８ｍｍの円状の噴流口から毎分１８Ｌの流量で電解金めっき液をポンプにより噴流撹拌しながら（以下、「ジェット噴流式金めっき法」とする）、電流湯密度を６０Ａ／ｄｍ２で各１０秒間ずつ電解金めっきを施した。
<Method of electrolytic gold plating>
Using the electrolytic gold plating solution prepared in each Example and Comparative Example, electrolytic gold plating was performed on a primary bright nickel plating film of 2.0 μm on a 10 mm × 10 mm copper plate in the steps shown in Table 2. .
Electrolytic gold plating is performed by stirring the electrolytic gold plating solution at a flow rate of 18 L / min from a circular jet port having a diameter of 8 mm with a pump (hereinafter referred to as “jet jet gold plating method”) while adjusting the current hot water density. Electrolytic gold plating was performed at 60 A / dm 2 for 10 seconds each.
なお、１次光沢ニッケルめっき皮膜は、以下の「電解ニッケルめっき液Ａ」を用いて、膜厚２．０μｍに形成した。
すなわち、市販のスルファミン酸ニッケルめっき液（ムラタ株式会社製、「ＳＮコンク」（商品名））５００ｍＬ／Ｌ、市販の塩化ニッケル１０ｇ／Ｌ、市販のホウ酸３０ｇ／Ｌ、及び、ピット防止剤（荏原ユージライト株式会社製、ピット防止剤＃８２（商品名））２ｍＬ／Ｌ、の濃度で調液して、「電解ニッケルめっき液Ａ」を得た。
The primary bright nickel plating film was formed to a thickness of 2.0 μm using the following “electrolytic nickel plating solution A”.
That is, a commercially available nickel sulfamate plating solution (Murata Co., Ltd., “SN Conch” (trade name)) 500 mL / L, commercially available nickel chloride 10 g / L, commercially available boric acid 30 g / L, and a pit inhibitor ( A “electrolytic nickel plating solution A” was obtained by preparing a pit inhibitor # 82 (trade name) 2 mL / L, manufactured by EBARA Eugelite Co., Ltd.
＜金皮膜の膜厚の測定方法＞
上記「電解金めっきの方法」で得られた円状に電解金めっきが施された金皮膜の中心付近を、蛍光Ｘ線分析装置（セイコーインスツルメンツ株式会社製、ＳＦＴ９２５５）を使用して、常法に従って金皮膜の膜厚を測定した。結果を表３に示す。
<Measuring method of gold film thickness>
By using a fluorescent X-ray analyzer (SFT 9255, manufactured by Seiko Instruments Inc.), a conventional method is used in the vicinity of the center of the gold film that has been subjected to electrolytic gold plating in a circular shape obtained by the above “electrolytic gold plating method”. The film thickness of the gold film was measured according to The results are shown in Table 3.
＜金皮膜の色調の測定（観察）方法＞
上記「電解金めっきの方法」で得られた金皮膜を、該金皮膜の真上３０ｃｍのところから目視で観察して、金皮膜の表面の色調を観察した。
<Measurement (observation) method of color tone of gold film>
The gold film obtained by the above “electrolytic gold plating method” was visually observed from a position 30 cm directly above the gold film, and the color tone of the surface of the gold film was observed.
＜析出効率、外観不良（金の析出異常）の判定方法＞
電流密度６０Ａ／ｄｍ２で１０秒間、電解金めっきを施したときの金皮膜の膜厚が１．２μｍ以上で、かつ、目視によりレモンイエローの金色であるものを、金析出効率が高く生産性が高い電解金めっき液と判定した。１．２μｍ以上で、かつ、レモンイエローの金皮膜を「良」とし、１．２μｍ未満、又は、レモンイエロー以外の金皮膜を「不良」とし、結果を表３に示す。
<Deposition efficiency, judgment method of appearance defect (gold deposition abnormality)>
A gold film having a thickness of 1.2 μm or more when electrolytic gold plating is performed for 10 seconds at a current density of 60 A / dm 2 and a gold color of lemon yellow by visual observation has high gold deposition efficiency and productivity. Was determined to be a high electrolytic gold plating solution. The gold film of 1.2 mm or more and lemon yellow was set as “good”, and the gold film of less than 1.2 μm or other than lemon yellow was set as “bad”. The results are shown in Table 3.
＜金皮膜の金純度の測定方法＞
各実施例及び各比較例で調製した電解金めっき液を用いて、表２に示す工程にて、１０ｍｍ×１０ｍｍの銅板上の１次光沢ニッケルめっき皮膜２．０μｍ上に、陰極電流密度４０Ａ／ｄｍ２にて、５０μｍの電解金めっき皮膜をジェット噴流式金めっき法で形成し、硝酸にて銅板及びニッケルめっき皮膜を溶解して金箔を得た。
得られた金箔の重量を測った後、その金箔を王水２０ｍＬに溶解させ、ＩＣＰ発光分光分析装置（セイコーインスツルメンツ株式会社製、ＳＰＳ３０００）にて、不純物元素としてＣｕ、Ｎｉ、Ｃｏ、Ｆｅの定量分析を行い、析出質量と不純物質量とから金純度を算出した。結果を表３に示す。
<Method for measuring gold purity of gold film>
Using the electrolytic gold plating solution prepared in each example and each comparative example, a cathode current density of 40 A / min was applied on a primary bright nickel plating film of 2.0 μm on a 10 mm × 10 mm copper plate in the steps shown in Table 2. At dm 2 , an electrolytic gold plating film of 50 μm was formed by a jet-jet gold plating method, and a copper plate and a nickel plating film were dissolved with nitric acid to obtain a gold foil.
After measuring the weight of the obtained gold foil, the gold foil was dissolved in 20 mL of aqua regia, and quantitative determination of Cu, Ni, Co, and Fe as impurity elements was performed with an ICP emission spectroscopic analyzer (Seiko Instruments Inc., SPS3000). Analysis was performed, and the gold purity was calculated from the precipitation mass and the impurity mass. The results are shown in Table 3.
表３から分かるように、本発明の電解金めっき液を用いると、電解金めっき液中の金含有量を一定にしたときに、同一の電流密度と電解金めっき時間で、厚く金皮膜を形成でき、かつ、金皮膜の色調もレモンイエローで、目視での外観に金の析出異常が認められなかった。
一方、特定ピリジニウム化合物を含有しない電解金めっき液では、金皮膜の膜厚、又は、金皮膜の色調の何れか又は両方が劣っていた。
As can be seen from Table 3, when the electrolytic gold plating solution of the present invention is used, a thick gold film is formed with the same current density and electrolytic gold plating time when the gold content in the electrolytic gold plating solution is constant. In addition, the color of the gold film was lemon yellow, and no abnormal gold deposition was observed in the visual appearance.
On the other hand, in the electrolytic gold plating solution containing no specific pyridinium compound, either the film thickness of the gold film or the color tone of the gold film or both are inferior.
本発明の電解金めっき液を用いて得られた金皮膜（金合金皮膜を含む）は、優れた機械特性、耐食性、電気特性、及び、金合金皮膜の場合には耐摩耗性等を有したまま、金めっき皮膜の外観不良を発生させず析出効率を従来の電解金めっき液よりも高くできるので、電子機器の部材の金めっきに広く利用されるものであり、特にニッケルバリアめっきに最適であり、この分野に特に利用されるものである。 Gold films (including gold alloy films) obtained using the electrolytic gold plating solution of the present invention had excellent mechanical properties, corrosion resistance, electrical characteristics, and wear resistance in the case of gold alloy films. As the deposition efficiency can be made higher than that of conventional electrolytic gold plating solution without causing appearance defects of the gold plating film, it is widely used for gold plating of electronic device parts and is particularly suitable for nickel barrier plating. Yes, especially in this field.
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| KR102354192B1 (en) * | 2016-05-18 | 2022-01-20 | 니혼 고쥰도가가쿠 가부시키가이샤 | Electrolytic nickel (alloy) plating solution |
| CN107059074A (en) * | 2017-05-17 | 2017-08-18 | 江苏金坤科技有限公司 | A kind of efficient gold plating liquid and gold-plated handling process |
| KR20210146520A (en) * | 2020-05-27 | 2021-12-06 | 주식회사 엘지에너지솔루션 | Electrolyte additives for secondary battery, non-aqueous electrolyte for secondary battery comprising the same and secondary battery |
| CN114836795B (en) * | 2021-06-25 | 2023-12-19 | 深圳市铭轩珠宝首饰有限公司 | Electroforming solution for gold cladding and preparation method and application thereof |
| WO2024142789A1 (en) * | 2022-12-27 | 2024-07-04 | 日本高純度化学株式会社 | Gold electroplating solution and method for producing gold-electroplated coating |
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