JP4719822B2 - 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
- JP4719822B2 JP4719822B2 JP2010516799A JP2010516799A JP4719822B2 JP 4719822 B2 JP4719822 B2 JP 4719822B2 JP 2010516799 A JP2010516799 A JP 2010516799A JP 2010516799 A JP2010516799 A JP 2010516799A JP 4719822 B2 JP4719822 B2 JP 4719822B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- nickel
- plating solution
- cobalt
- gold plating
- 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 359
- 239000010931 gold Substances 0.000 title claims description 356
- 229910052737 gold Inorganic materials 0.000 title claims description 356
- 238000007747 plating Methods 0.000 title claims description 275
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 125
- 229910052759 nickel Inorganic materials 0.000 claims description 63
- 230000008021 deposition Effects 0.000 claims description 36
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 27
- 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 21
- 150000001868 cobalt Chemical class 0.000 claims description 18
- 150000002815 nickel Chemical class 0.000 claims description 18
- 150000002505 iron Chemical class 0.000 claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 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
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 4
- LJJNEPKMBSUEND-UHFFFAOYSA-O azanium;gold;cyanide Chemical compound [NH4+].[Au].N#[C-] LJJNEPKMBSUEND-UHFFFAOYSA-O 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims description 4
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 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
- PCKYORHAGTXIMY-UHFFFAOYSA-N 1,3-dinitroisoquinoline Chemical compound C1=CC=C2C([N+]([O-])=O)=NC([N+](=O)[O-])=CC2=C1 PCKYORHAGTXIMY-UHFFFAOYSA-N 0.000 claims description 2
- VDTUSEIYUROSGJ-UHFFFAOYSA-N 1-nitroisoquinoline Chemical compound C1=CC=C2C([N+](=O)[O-])=NC=CC2=C1 VDTUSEIYUROSGJ-UHFFFAOYSA-N 0.000 claims description 2
- ZTGWXXOUUKHQLW-UHFFFAOYSA-N 1-nitropyrimidine-2,4-dione Chemical compound [O-][N+](=O)N1C=CC(=O)NC1=O ZTGWXXOUUKHQLW-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- MWHSQZUWOVLZPV-UHFFFAOYSA-N 2,3-dinitro-1h-pyrrole Chemical compound [O-][N+](=O)C=1C=CNC=1[N+]([O-])=O MWHSQZUWOVLZPV-UHFFFAOYSA-N 0.000 claims description 2
- AJZPTZYGBZCEKQ-UHFFFAOYSA-N 2,3-dinitropyrazine Chemical compound [O-][N+](=O)C1=NC=CN=C1[N+]([O-])=O AJZPTZYGBZCEKQ-UHFFFAOYSA-N 0.000 claims description 2
- RUPDGJAVWKTTJW-UHFFFAOYSA-N 2,3-dinitropyridine Chemical compound [O-][N+](=O)C1=CC=CN=C1[N+]([O-])=O RUPDGJAVWKTTJW-UHFFFAOYSA-N 0.000 claims description 2
- RRBUKOWICXHUHD-UHFFFAOYSA-N 2,3-dinitroquinoline Chemical compound C1=CC=C2N=C([N+]([O-])=O)C([N+](=O)[O-])=CC2=C1 RRBUKOWICXHUHD-UHFFFAOYSA-N 0.000 claims description 2
- PEZBUBWBOBZQEK-UHFFFAOYSA-N 2,4-dinitro-1,3-oxazole Chemical compound [N+](=O)([O-])C=1N=C(OC=1)[N+](=O)[O-] PEZBUBWBOBZQEK-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
- HUNDJKXYCIAYJT-UHFFFAOYSA-N 2-nitro-1,3-oxazole Chemical compound [O-][N+](=O)C1=NC=CO1 HUNDJKXYCIAYJT-UHFFFAOYSA-N 0.000 claims description 2
- HCGYMSSYSAKGPK-UHFFFAOYSA-N 2-nitro-1h-indole Chemical compound C1=CC=C2NC([N+](=O)[O-])=CC2=C1 HCGYMSSYSAKGPK-UHFFFAOYSA-N 0.000 claims description 2
- FTBBGQKRYUTLMP-UHFFFAOYSA-N 2-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C1=CC=CN1 FTBBGQKRYUTLMP-UHFFFAOYSA-N 0.000 claims description 2
- NVIATZSDAYSNSB-UHFFFAOYSA-N 2-nitro-7h-purin-6-amine Chemical compound NC1=NC([N+]([O-])=O)=NC2=C1NC=N2 NVIATZSDAYSNSB-UHFFFAOYSA-N 0.000 claims description 2
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims description 2
- MNURQUMUZCBVPI-UHFFFAOYSA-N 2-nitropyrazine Chemical compound [O-][N+](=O)C1=CN=CC=N1 MNURQUMUZCBVPI-UHFFFAOYSA-N 0.000 claims description 2
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 claims description 2
- UQOKRDJILZMZKU-UHFFFAOYSA-N 2-nitropyrimidine Chemical compound [O-][N+](=O)C1=NC=CC=N1 UQOKRDJILZMZKU-UHFFFAOYSA-N 0.000 claims description 2
- UDAIGHZFMLGNDQ-UHFFFAOYSA-N 2-nitroquinoline Chemical compound C1=CC=CC2=NC([N+](=O)[O-])=CC=C21 UDAIGHZFMLGNDQ-UHFFFAOYSA-N 0.000 claims description 2
- SEZWIQPRALTVDE-UHFFFAOYSA-N 3,4-dinitro-1,2-oxazole Chemical compound [N+](=O)([O-])C=1C(=NOC1)[N+](=O)[O-] SEZWIQPRALTVDE-UHFFFAOYSA-N 0.000 claims description 2
- QMELUUBWGOOEAR-UHFFFAOYSA-N 3,4-dinitropyridazine Chemical compound [O-][N+](=O)C1=CC=NN=C1[N+]([O-])=O QMELUUBWGOOEAR-UHFFFAOYSA-N 0.000 claims description 2
- UKZXCZWGGXVKNN-UHFFFAOYSA-N 3,5-dinitro-1h-pyrazole Chemical compound [O-][N+](=O)C=1C=C([N+]([O-])=O)NN=1 UKZXCZWGGXVKNN-UHFFFAOYSA-N 0.000 claims description 2
- AOIHSSHDSKUPRK-UHFFFAOYSA-N 3-nitro-1,2-oxazole Chemical compound [O-][N+](=O)C=1C=CON=1 AOIHSSHDSKUPRK-UHFFFAOYSA-N 0.000 claims description 2
- BHZYGVOPDOCROF-UHFFFAOYSA-N 3-nitropyridazine Chemical compound [O-][N+](=O)C1=CC=CN=N1 BHZYGVOPDOCROF-UHFFFAOYSA-N 0.000 claims description 2
- CCRNCEKMSVYFLU-UHFFFAOYSA-N 4,5-dinitro-1h-imidazole Chemical compound [O-][N+](=O)C=1N=CNC=1[N+]([O-])=O CCRNCEKMSVYFLU-UHFFFAOYSA-N 0.000 claims description 2
- AAQNBUSGUPVHBJ-UHFFFAOYSA-N 4,5-dinitro-2h-triazole Chemical compound [O-][N+](=O)C=1N=NNC=1[N+]([O-])=O AAQNBUSGUPVHBJ-UHFFFAOYSA-N 0.000 claims description 2
- XMZLUFJPQXVRCM-UHFFFAOYSA-N 4,6-dinitropyrimidine Chemical compound [N+](=O)([O-])C1=CC(=NC=N1)[N+](=O)[O-] XMZLUFJPQXVRCM-UHFFFAOYSA-N 0.000 claims description 2
- YXFWFUSVDJIVIV-UHFFFAOYSA-N 4-nitro-2h-triazole Chemical compound [O-][N+](=O)C=1C=NNN=1 YXFWFUSVDJIVIV-UHFFFAOYSA-N 0.000 claims description 2
- YZXKWVREBLYPID-UHFFFAOYSA-N 4-nitromorpholine Chemical compound [O-][N+](=O)N1CCOCC1 YZXKWVREBLYPID-UHFFFAOYSA-N 0.000 claims description 2
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 claims description 2
- ZGZLYKUHYXFIIO-UHFFFAOYSA-N 5-nitro-2h-tetrazole Chemical compound [O-][N+](=O)C=1N=NNN=1 ZGZLYKUHYXFIIO-UHFFFAOYSA-N 0.000 claims description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 2
- 229930024421 Adenine Natural products 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- YRVBTDHHEFABGU-UHFFFAOYSA-N [Co].[Na].[Na].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O Chemical compound [Co].[Na].[Na].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O YRVBTDHHEFABGU-UHFFFAOYSA-N 0.000 claims description 2
- KHPVNEHMLTYJMC-UHFFFAOYSA-N [O-][N+](=O)Cc1c[nH]c(=O)[nH]c1=O Chemical compound [O-][N+](=O)Cc1c[nH]c(=O)[nH]c1=O KHPVNEHMLTYJMC-UHFFFAOYSA-N 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
- 229960000643 adenine Drugs 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
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 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
- 229940104302 cytosine Drugs 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
- 239000004222 ferrous gluconate Substances 0.000 claims description 2
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 2
- 229960001645 ferrous gluconate 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
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-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
- DXTCFKRAUYBHRC-UHFFFAOYSA-L iron(2+);dithiocyanate Chemical compound [Fe+2].[S-]C#N.[S-]C#N DXTCFKRAUYBHRC-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
- 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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 2
- 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 description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- HNENOFQWYYKDAP-UHFFFAOYSA-N n-(2-oxo-1h-pyrimidin-6-yl)nitramide Chemical compound [O-][N+](=O)NC=1C=CNC(=O)N=1 HNENOFQWYYKDAP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000009499 grossing Methods 0.000 description 1
- NHEPKQDGPJQVOO-UHFFFAOYSA-N hex-1-yn-1-amine Chemical compound CCCCC#CN NHEPKQDGPJQVOO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 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
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000001384 succinic acid Substances 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- 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及びその電解金めっき液を用いて得られた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 and a gold coating on a nickel coating obtained using the electrolytic gold plating solution.
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。そのなかでも、コバルト、ニッケル等の金属と合金化された硬質金めっきは、その高い硬度と優れた耐摩耗性を生かして、コネクター等の差込部材、スイッチ等の接点部材等のコンタクト接合部の金めっきとして広く使用されている。 Gold plating on the nickel coating is widely used in the field of electronic and electrical parts because gold has excellent corrosion resistance, mechanical properties, electrical properties, etc., and nickel has excellent heat resistance as a base metal. ing. Among them, hard gold plating alloyed with metals such as cobalt and nickel makes use of its high hardness and excellent wear resistance to make contact joints such as connectors such as connectors and contact members such as switches. Widely used as gold plating.
近年、電子機器の小型化により、コネクター等の差込部材やスイッチ等の接点部材も小型化され、形状も複雑化され、半田接合が必要な箇所と接点として機能しなければならない箇所の間隔が著しく狭くなり、半田接合が必要でない部分にまで半田がヌレ広がってしまう現象が問題となっている。そこで、接点部分と半田接合部分の間に金めっきを施さない部分を設けて、半田が必要な部分にしかヌレ広がらないようにすることにより、この問題を解決しようとしている。 In recent years, due to miniaturization of electronic devices, plug members such as connectors and contact members such as switches have also been miniaturized, the shape has become complicated, and there is a gap between locations where solder bonding is required and locations that must function as contacts. There is a problem that the solder becomes so narrow that the solder spreads to a portion where solder bonding is not necessary. Therefore, an attempt is made to solve this problem by providing a portion that is not subjected to gold plating between the contact portion and the solder joint portion so as to spread only on the portion that requires solder.
この方法は、一般にニッケルバリアめっきと呼ばれる電解金めっき技術であり、１つの部品の中で金めっきが必要な部分と不必要な部分を作るために、金めっきが不必要な部分（ニッケルバリア部分）にシリコンゴム等の部材を機械的に押さえつけて金めっき液と被めっき部品が接触できないようにして、１つの部品の中に金めっきが施されている部分と、金めっきが施されていない部分（ニッケルバリア部分）を設ける方法である。 This method is an electrolytic gold plating technique generally referred to as nickel barrier plating. In order to create a part that requires gold plating and an unnecessary part in one part, a part that does not require gold plating (nickel barrier part). ) The parts such as silicon rubber are mechanically pressed down so that the gold plating solution and the part to be plated cannot be in contact with each other. This is a method of providing a portion (nickel barrier portion).
しかしながら、１つの部品の中で金めっきを施す部分と施さない部分を作らなければならないため、たとえ機械的に金めっきが不必要な部分をシリコンゴム等の部材で押さえつけたとしても、その部分に金めっき液が漏れ出ることを完全に防止することは、めっき装置的に非常に難しいという問題があった。 However, since it is necessary to make a part that does not perform gold plating in one part, even if a part that does not require gold plating mechanically is pressed with a member such as silicon rubber, There has been a problem that it is very difficult for the plating apparatus to completely prevent the gold plating solution from leaking out.
この問題を解決するために、金コバルトめっき液を弱酸性に保持し、かつヘキサメチレンテトラミンを添加して、不要な部分への金めっき皮膜の析出が抑制される金めっき浴が特許文献１に開示されている。しかしながら、この技術は、金析出の選択性において充分な性能を有しているとは言えず、また、還元性のヘキサメチレンテトラミンを金めっき浴に添加していることから、金が金めっき浴中で異常析出し、めっき液を循環するためのポンプの軸部分に金が付着して、ポンプが停止してしまったり、金がめっき反応以外にも消費されたりして、非常に不経済であり実用的ではなかった。 In order to solve this problem, Patent Document 1 discloses a gold plating bath that keeps a gold cobalt plating solution weakly acidic and adds hexamethylenetetramine to suppress deposition of a gold plating film on unnecessary portions. It is disclosed. However, this technique cannot be said to have sufficient performance in the selectivity of gold deposition, and since reducing hexamethylenetetramine is added to the gold plating bath, the gold is a gold plating bath. It is very uneconomical that gold deposits on the shaft part of the pump for circulating the plating solution and stops the pump, or gold is consumed in addition to the plating reaction. It was not practical.
近年、電子機器の小型化により、金めっきが施されている部分と施されていない部分を明確に区別して作らなければならなくなったが、従来の技術ではそれは達成されておらず、更なる改良が必要であった。 In recent years, due to the downsizing of electronic equipment, it has become necessary to make a distinction between the parts that have been plated with gold and the parts that have not been plated, but this has not been achieved with conventional technology, and further improvements have been made. 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、ニッケルバリアめっきに適した電解金めっき液を提供することにある。すなわち、部材を機械的に押さえつけた「金めっきが不必要な部分（ニッケルバリア部分）」での金析出を抑制し、金めっきが必要な部分では良好な金析出が起こり、また、金の異常析出がなく安定した製品製造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, An object of the present invention is to provide an electrolytic gold plating solution suitable for nickel barrier plating while maintaining electrical characteristics and the like. In other words, it suppresses gold deposition at “parts that do not require gold plating (nickel barrier part)” that mechanically pressed the member, and good gold deposition occurs at parts that require gold plating, and abnormal gold An object of the present invention is to provide an electrolytic gold plating solution capable of producing a stable product without precipitation.
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、金めっき液が被めっき部分に触れる部分は高電流密度（設定電流密度）でめっき反応が進行し、金めっき液が被めっき部分に触れない部分は低電流密度でめっき反応が進行することに着目し、その差を利用して電解金めっき液を開発すればよいことを見出した。 As a result of intensive studies to solve the above-mentioned problems, the inventor proceeds the plating reaction at a high current density (set current density) at the portion where the gold plating solution touches the portion to be plated, and the gold plating solution is plated. Focusing on the fact that the plating reaction proceeds at a low current density in the part that does not touch the part, it was found that an electrolytic gold plating solution should be developed using the difference.
図１は、汎用の電解金めっき液と本発明の実施例１記載の組成の電解金めっき液を用いて測定したもので、横軸に電流密度（Ａ／ｄｍ２）、縦軸に１０秒間金めっき処理をした後の金皮膜の膜厚（μｍ）をとったグラフである。すなわち、汎用の電解金めっき液の金濃度を実施例１の電解金めっき液の金換算の濃度（９ｇ／Ｌ）に調整し、浴温を５０℃に昇温して、後述する表２記載の工程で、１０ｍｍ×１０ｍｍの銅板上の１次光沢ニッケルめっき皮膜２．０μｍ上に金めっきを施した。金めっきは、口径８ｍｍの円状の噴流口から毎分１８Ｌの流量で金めっき液をポンプにより噴流攪拌しながら、電流密度を１Ａ／ｄｍ２、５Ａ／ｄｍ２、１０Ａ／ｄｍ２、２０Ａ／ｄｍ２、３０Ａ／ｄｍ２、４０Ａ／ｄｍ２、５０Ａ／ｄｍ２、６０Ａ／ｄｍ２と変化させて１０秒間ずつ金めっき処理をし、円状に金めっき処理された中心付近を蛍光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、測定結果をプロットしたグラフである。FIG. 1 shows measurement using a general-purpose electrolytic gold plating solution and an electrolytic gold plating solution having the composition described in Example 1 of the present invention. The horizontal axis represents current density (A / dm 2 ), and the vertical axis represents 10 seconds. It is the graph which took the film thickness (micrometer) of the gold film after performing a gold plating process. That is, the gold concentration of a general-purpose electrolytic gold plating solution is adjusted to the gold equivalent concentration (9 g / L) of the electrolytic gold plating solution of Example 1, and the bath temperature is raised to 50 ° C. In this step, 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 gold plating, the current density is 1 A / dm 2 , 5 A / dm 2 , 10 A / dm 2 , 20 A / h while stirring the gold plating solution with a pump at a flow rate of 18 L / min from a circular jet port having a diameter of 8 mm. dm 2 , 30 A / dm 2 , 40 A / dm 2 , 50 A / dm 2 , 60 A / dm 2 , gold plating treatment was performed for 10 seconds each time, and fluorescent X-ray analysis was performed around the center that was gold-plated in a circular shape It is the graph which measured the film thickness of the gold film using the apparatus (the Seiko Instruments Inc. make, SFT9255) according to the conventional method, and plotted the measurement result.
図１における０Ａ／ｄｍ２から５Ａ／ｄｍ２（以下、「低電流密度域」と略記する）は、ニッケルバリアめっき技術における金めっきを施さない部分に相当し、低電流密度域での金皮膜の膜厚は薄ければ薄いほどニッケルバリア特性が良好になると判断した。また、図１における２０Ａ／ｄｍ２から６０Ａ／ｄｍ２（以下、「高電流密度域」と略記する）は、ニッケルバリアめっき技術における金めっきを施す部分に相当し、高電流密度域での金皮膜の膜厚は厚ければ厚いほどニッケルバリア特性が良好になると判断した。実施例１記載の組成の電解金めっき液のプロットグラフ参照。In FIG. 1, 0 A / dm 2 to 5 A / dm 2 (hereinafter abbreviated as “low current density region”) corresponds to a portion not subjected to gold plating in the nickel barrier plating technology, and a gold film in the low current density region. It was judged that the thinner the film thickness, the better the nickel barrier properties. Further, 20 A / dm 2 to 60 A / dm 2 (hereinafter, abbreviated as “high current density region”) in FIG. 1 corresponds to a portion to be subjected to gold plating in the nickel barrier plating technology, and gold in the high current density region It was judged that the thicker the film, the better the nickel barrier properties. See the plot graph of the electrolytic gold plating solution having the composition described in Example 1.
ニッケルバリアめっき技術において、前記したように、金めっきが不必要な部分をシリコンゴム等の部材で機械的に押さえつけたとしても、その部分に金めっき液が漏れ出ることを完全に防止することは装置的に非常に難しいという現状にあっては、ニッケルバリアめっき技術に要求される電解金めっき液の特性は、低電流密度域での金析出膜厚が非常に薄く、かつ低電流密度域での金析出量と高電流密度域での金析出量の差が大きく、製品に金めっき皮膜を形成させる高電流密度域での金析出量は最大限確保できる特性であることを見出した。そして、そのような特性を有する電解金めっき液が、金析出に関して選択性があり、ニッケルバリアめっき技術に適した電解金めっき液であると考えた。 In the nickel barrier plating technology, as described above, even if a part that does not require gold plating is mechanically pressed with a member such as silicon rubber, it is possible to completely prevent the gold plating solution from leaking into that part. In the current situation where the equipment is very difficult, the characteristics of the electrolytic gold plating solution required for the nickel barrier plating technology are that the gold deposition film thickness in the low current density region is very thin, and in the low current density region. It was found that the difference between the amount of deposited gold and the amount of deposited gold in the high current density region was large, and that the amount of deposited gold in the high current density region where the gold plating film was formed on the product could be secured to the maximum. Then, it was considered that an electrolytic gold plating solution having such characteristics has selectivity for gold deposition and is an electrolytic gold plating solution suitable for nickel barrier plating technology.
そこで、本発明者は、上記課題を電解金めっき液の組成の点から解決すべく鋭意検討を重ねた結果、シアン化金塩、及び、「環中に窒素原子を１個以上有する複素環式化合物で、該環中の炭素原子にニトロ基が１個以上置換している複素環式化合物」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、前記問題点を解消し、上記課題を解決し、金めっき皮膜の低電流密度域での金析出が抑制され、金の異常析出もなく安定した製品の製造ができることを見出し、本発明の完成に至った。 Therefore, as a result of intensive studies to solve the above problems in terms of the composition of the electrolytic gold plating solution, the present inventor has obtained a gold cyanide salt and “a heterocyclic ring having one or more nitrogen atoms in the ring. If the gold film is formed using an electrolytic gold plating solution containing a compound, a heterocyclic compound in which one or more nitro groups are substituted on the carbon atom in the ring as an essential component, the above-mentioned problems are solved. Then, the present inventors have solved the above problems, found that gold deposition in the low current density region of the gold plating film is suppressed, and that stable products can be produced without abnormal gold deposition, 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と、環中に窒素原子を１個以上有し、該環中の炭素原子にニトロ基が１個以上置換している複素環式化合物と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, a heterocyclic compound having one or more nitrogen atoms in the ring, and one or more nitro groups substituted on the carbon atoms in the ring; 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、ジェット噴流式めっき装置を用いて、電流密度を５Ａ／ｄｍ２と４０Ａ／ｄｍ２に設定してそれぞれ１０秒間めっき処理をした場合、電流密度５Ａ／ｄｍ２での金皮膜の膜厚が０．１μｍ以下であり、かつ４０Ａ／ｄｍ２での金皮膜の膜厚が、５Ａ／ｄｍ２での金皮膜の膜厚の５倍以上である上記の電解金めっき液を提供するものである。Further, the present invention provides a gold film at a current density of 5 A / dm 2 when the current density is set to 5 A / dm 2 and 40 A / dm 2 using a jet jet plating apparatus and plating is performed for 10 seconds. Provided is the above electrolytic gold plating solution in which the thickness of the gold film is 0.1 μm or less and the thickness of the gold film at 40 A / dm 2 is at least 5 times the thickness of the gold film at 5 A / dm 2 To do.
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 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、低電流密度域での金析出速度を非常に遅く、高電流密度域での金析出速度を非常に速くでき（以下、この性能を「金選択析出性能」という）、それによって低電流密度域の金析出膜厚と高電流密度域の金析出膜厚の差を大きくできる。 According to the electrolytic gold plating solution of the present invention, a gold film obtained by using a conventional electrolytic gold plating solution has low current density while maintaining excellent mechanical properties such as wear resistance, corrosion resistance, and electrical properties. The gold deposition rate in the region is very slow, and the gold deposition rate in the high current density region can be very fast (this performance is hereinafter referred to as “gold selective deposition performance”). The difference between the thickness and the gold deposition film thickness in the high current density region can be increased.
その結果として、シリコンゴム等の部材によって機械的に押さえつけられた「金めっきが不必要な部分（ニッケルバリア部分）」での金析出を抑制し、押さえつけられていない部分（金めっきが必要な部分）では良好な金析出を実現でき、また、金の異常析出がなく安定した製品製造が可能な電解金めっき液を提供でき、近年の電子機器のコネクター等の接点部材等に要求されるニッケルバリアめっき技術に好適に適応できる。 As a result, it is possible to suppress gold deposition at “parts that do not require gold plating (nickel barrier parts)” that are mechanically pressed by a member such as silicon rubber, and parts that are not pressed down (parts that require gold plating). ) Can provide good gold deposition, and can provide an electrolytic gold plating solution that does not cause abnormal gold deposition and enables stable product production. Nickel barriers required for contact members such as connectors of electronic devices in recent years It can be suitably applied to plating technology.
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、技術的思想の範囲内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 carried out by being arbitrarily modified within the scope of the technical idea.
本発明は、少なくとも、シアン化金塩を金源として含有し、更に「環中に窒素原子を１個以上有する複素環式化合物で、該環中の炭素原子にニトロ基が１個以上置換している複素環式化合物」を必須成分として含有することを特徴とする電解金めっき液である。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、金以外の金属を含有していてもよい。 The present invention contains at least a gold cyanide salt as a gold source, and further “a heterocyclic compound having one or more nitrogen atoms in the ring, wherein one or more nitro groups are substituted on the carbon atoms in the ring. It is an electrolytic gold plating solution characterized by containing “a heterocyclic compound” as an essential component. The “electrolytic gold plating solution” of the present invention also includes “electrolytic gold alloy plating solution”. In addition, the “gold film” of the present invention includes “gold alloy film”. That is, a metal other than gold may be contained.
硬質金めっきをするために本発明の電解金めっき液を使用する場合には、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。 When the electrolytic gold plating solution of the present invention is used for hard gold plating, it 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.
＜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. Secondary gold ammonium and the like can be mentioned. 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。電解金めっき液中のシアン化金塩の含有量が少なすぎると、黄金色の金めっきが困難になる場合がある。一方、電解金めっき液中の金属金の含有量が多すぎる場合は、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な金属であり、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。 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. If the content of the gold cyanide salt in the electrolytic gold plating solution is too small, golden gold plating may be difficult. On the other hand, when the content of metal gold in the electrolytic gold plating solution is too large, there is no particular problem with the performance of the electrolytic gold plating solution, but gold cyanide salt is a very expensive metal. 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.
＜複素環式化合物＞
本発明の電解金めっき液には、「環中に窒素原子を１個以上有し、該環中の炭素原子にニトロ基が１個以上置換している複素環式化合物」（以下、括弧内を「特定複素環式化合物」と略記することがある）を必須成分として含有する。特定複素環式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、電気特性等を維持したままで、低電流密度域での金析出膜厚を小さくでき、低電流密度域での金析出膜厚と高電流密度域での金析出膜厚の差を非常に大きくできる。すなわち、特定複素環式化合物を含有することにより、金選択析出性能に優れた電解金めっき液を得ることができ、ニッケルバリアめっきに最適な電解金めっき液が実現される。<Heterocyclic compound>
The electrolytic gold plating solution of the present invention includes a “heterocyclic compound having at least one nitrogen atom in the ring and having at least one nitro group substituted on the carbon atom in the ring” (hereinafter, in parentheses). Is abbreviated as “specific heterocyclic compound”) as an essential component. By containing a specific heterocyclic compound, it is possible to reduce the thickness of the gold deposit in the low current density region while maintaining the excellent high corrosion resistance, mechanical properties, electrical properties, etc. of the conventional electrolytic gold plating film. The difference between the gold deposited film thickness in the current density region and the gold deposited film thickness in the high current density region can be greatly increased. That is, by containing a specific heterocyclic compound, an electrolytic gold plating solution excellent in gold selective deposition performance can be obtained, and an electrolytic gold plating solution optimal for nickel barrier plating is realized.
上記特定複素環式化合物中の複素環は特に限定はなく、芳香族性を有しているものでも有していないものでもよいが、芳香族性を有しているものの方が、良好なめっき性能、入手の容易さ等の点、上記効果を特に奏する点で好ましい。複素環を構成する炭素原子以外の異原子は特に限定はなく、窒素、酸素、イオウ等が挙げられるが、異原子の少なくとも１つは窒素原子であることが必須である。また、複素環を構成する異原子が窒素原子のみであることが、良好なめっき性能、入手の容易さ等の点で好ましい。 The heterocyclic ring in the specific heterocyclic compound is not particularly limited, and may be aromatic or non-aromatic. However, the aromatic ring has better plating. It is preferable in terms of performance, availability, etc., and in particular that the above-described effects are exhibited. There are no particular limitations on the heteroatoms other than the carbon atoms constituting the heterocycle, and examples include nitrogen, oxygen, sulfur, etc., but at least one of the heteroatoms must be a nitrogen atom. Moreover, it is preferable from the point of favorable plating performance, availability, etc. that the hetero atom which comprises a heterocyclic ring is only a nitrogen atom.
複素環中の炭素原子には、本発明の効果を損なわない範囲において任意の置換基が置換していてもよい。複素環中の炭素原子に対する置換基の少なくとも１つはニトロ基であることが必須である。ニトロ基以外の置換基としては、アルキル基、ヒドロキシ基、フェニル基等が挙げられる。複素環中の炭素原子に置換しているニトロ基の数は１個以上であれば特に限定はないが、１〜３個が好ましく、１〜２個が特に好ましい。 Arbitrary substituents may be substituted on the carbon atom in the heterocyclic ring as long as the effects of the present invention are not impaired. It is essential that at least one of the substituents for the carbon atom in the heterocycle is a nitro group. Examples of the substituent other than the nitro group include an alkyl group, a hydroxy group, and a phenyl group. The number of nitro groups substituted on the carbon atom in the heterocyclic ring is not particularly limited as long as it is 1 or more, but 1 to 3 is preferable and 1 to 2 is particularly preferable.
上記の特定複素環式化合物の具体例としては、例えば、ピロール、イミダゾール、ピラゾール、トリアゾール、テトラゾール、オキサゾール、イソオキサゾール、インドール、ピリジン、ピリダジン、ピリミジン、ピラジン、ウラシル、シトシン、チミン、アデニン、グアニン、キノリン、イソキノリン、キサリン、イソキサリン、アクリジン、シンノソリン又はモルホリンの環を構成する炭素原子にニトロ基が１個以上置換しているものが好ましいものとして挙げられる。 Specific examples of the specific heterocyclic compound include, for example, pyrrole, imidazole, pyrazole, triazole, tetrazole, oxazole, isoxazole, indole, pyridine, pyridazine, pyrimidine, pyrazine, uracil, cytosine, thymine, adenine, guanine, Preferred examples include those in which one or more nitro groups are substituted on the carbon atoms constituting the ring of quinoline, isoquinoline, oxaline, isoxaline, acridine, cinnosoline or morpholine.
更に具体的には、ニトロピロール、ジニトロピロール、ニトロイミダゾール、ジニトロイミダゾール、ニトロピラゾール、ジニトロピラゾール、ニトロトリアゾール、ジニトロトリアゾール、ニトロテトラゾール、ニトロオキサゾール、ジニトロオキサゾール、ニトロイソオキサゾール、ジニトロイソオキサゾール、ニトロインドール、ニトロピリジン、ジニトロピリジン、ニトロピリダジン、ジニトロピリダジン、ニトロピリミジン、ジニトロピリミジン、ニトロピラジン、ジニトロピラジン、ニトロウラシル、ニトロシトシン、ニトロチミン、ニトロアデニン、ニトログアニン、ニトロキノリン、ジニトロキノリン、ニトロイソキノリン、ジニトロイソキノリン、ニトロキサリン、ジニトロイソキサリン、ニトロアクリジン、ニトロシンノソリン、ジニトロシンノソリン、ニトロモルホリン、ジニトロモルホリン等が、良好なめっき性能、水への溶解の容易さ、低電流密度域でめっきした場合の金析出の抑制性能、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。 More specifically, nitropyrrole, dinitropyrrole, nitroimidazole, dinitroimidazole, nitropyrazole, dinitropyrazole, nitrotriazole, dinitrotriazole, nitrotetrazole, nitrooxazole, dinitrooxazole, nitroisoxazole, dinitroisoxazole, nitroindole, Nitropyridine, dinitropyridine, nitropyridazine, dinitropyridazine, nitropyrimidine, dinitropyrimidine, nitropyrazine, dinitropyrazine, nitrouracil, nitrocytosine, nitrothymine, nitroadenine, nitroguanine, nitroquinoline, dinitroquinoline, nitroisoquinoline, dinitroisoquinoline, Nitroxaline, dinitroisoxaline, nitroacridine, nitrocin Sorin, dinitrocinnosoline, nitromorpholine, dinitromorpholine, etc. have good plating performance, ease of dissolution in water, ability to suppress gold deposition when plated in a low current density range, availability, low cost From the viewpoint of the above, it is particularly preferable.
本発明において、特定複素環式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、好ましくは１０ｐｐｍ〜５００００ｐｐｍ、より好ましくは５０ｐｐｍ〜３００００ｐｐｍ、特に好ましくは１００ｐｐｍ〜１００００ｐｐｍである。なお、上記の特定複素環式化合物を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複素環式化合物の含有量が少なすぎると、低電流密度域でめっきした場合の金析出が抑制されなかったり、金皮膜の外観不良を起こしたりする場合がある。一方、含有量が多すぎると、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 heterocyclic compound is not particularly limited, but is preferably 10 ppm to 50000 ppm, more preferably 50 ppm to 30000 ppm, and particularly preferably 100 ppm to 10000 ppm with respect to the entire electrolytic gold plating solution. . In addition, when 2 or more types of said specific heterocyclic compounds are contained, the said numerical value shows those total content. If the content of the specific heterocyclic compound in the electrolytic gold plating solution is too small, gold deposition may not be suppressed when the plating is performed in a low current density region, or 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 expected, and it may become uneconomical.
上記の特定複素環式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、本発明の電解金合金めっき液の調液の際に、溶解させる原料として、上記の特定複素環式化合物を用いることが好ましい。 The above description about the specific heterocyclic compound specifies the form present in the electrolytic gold plating solution of the present invention, but is a raw material to be dissolved in the preparation of the electrolytic gold alloy plating solution of the present invention. As above, it is preferable to use the above-mentioned specific heterocyclic compound.
＜コバルト塩、ニッケル塩、鉄塩＞
本発明の電解金合金めっき液は、シアン化金塩、上記の特定複素環式化合物に加えて、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、ニッケルバリアめっきに最適な硬質金皮膜を形成できる電解金めっき液が得られるために好ましい。<Cobalt salt, nickel salt, iron salt>
In the electrolytic gold alloy plating solution of the present invention, in addition to the gold cyanide salt and the above-mentioned specific heterocyclic compound, a cobalt salt, a nickel salt and / or an iron salt are further used in combination for the nickel barrier plating. It is preferable because an electrolytic gold plating solution capable of forming a hard gold film is obtained.
上記のコバルト塩、ニッケル塩又は鉄塩は、ニッケルめっき皮膜上の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 above cobalt salt, nickel salt or iron salt precipitates (eutectoid) with gold in the gold plating film on the nickel plating film, forms a hard gold film, and is necessary for contact members such as connectors of electronic components. High hardness and high wear resistance can be realized.
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、異なる金属の金属塩を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, the metal salt of a different metal 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。 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, ethylenediaminetetraacetic 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 plating performance, ease of dissolution in water, ease of eutectoid deposition on gold film, From the viewpoint of easy 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 plating performance, easy dissolution in water, From the viewpoints of eutectoid deposition on the gold film, availability, low cost, etc., 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、酒石酸第２鉄、チオシアン酸第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、エチレンジアミン四酢酸鉄、硝酸第１鉄、硝酸第２鉄等が、良好なめっき性能、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 iron salt is not particularly limited. For example, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous citrate, ferric citrate, ferric formate, Ferric hypophosphite, ferric naphthenate, ferric stearate, ferric pyrophosphate, ferrous tartrate, ferric tartrate, ferrous thiocyanate, ferric thiocyanate, fumaric acid Ferrous iron, ferrous gluconate, ferric ethylenediaminetetraacetate, ferrous nitrate, ferric nitrate, etc. have good plating performance, ease of dissolution in water, and ease of eutectoid deposition on gold film From the viewpoint of availability, low cost, etc., 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。含有量が少なすぎると、金皮膜への共析量が少なすぎて充分な硬度が得られない場合がある。一方、含有量が多すぎると、金皮膜への共析量が多くなりすぎて、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 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, which may cause poor color tone of the gold film, increase in contact resistance, and further increase in hardness may not be expected. is there.
＜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を、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 influence when impurity metals are mixed in the electrolytic gold plating solution, surfactant to improve the pinhole removal of the gold coating or electrolytic gold plating solution, gold coating A brightening agent or the like for smoothing the surface can be appropriately used.
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 buffer contained in the electrolytic gold plating solution of the present invention as needed is not particularly limited as long as it is a known buffer, but is not limited to inorganic acids such as boric acid and phosphoric acid; citric acid, tartaric acid, malic acid And oxycarboxylic acids such as 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すぎると、緩衝効果が発揮され難い場合があり、一方、多す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 the content is too large, 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, 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すぎると、電導効果が発揮され難い場合があり、一方、多す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。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 buffering effect may not be increased and it 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. Acid-based chelating agents; phosphonic acid-based chelating agents such as hydroxyethylidene diphosphonic acid, nitrilomethylene phosphonic acid, and ethylenediaminetetramethylene 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すぎると、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、多す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 exert. On the other hand, if the content is too large, 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−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。 Nonionic surfactants include ether type nonionic surfactants such as noniphenol polyalkoxylate, α-naphthol polyalkoxylate, dibutyl-β-naphthol polyalkoxylate, styrenated phenol polyalkoxylate; octylamine polyalkoxy Examples thereof include amine-type nonionic surfactants such as rate, hexynylamine polyalkoxylate, and linoleylamine polyalkoxylate.
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。 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; 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ベタイン、Ｎ−ステアリル−Ｎ、Ｎ−ジメチル−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 betaine, N-stearyl-N, N-dimethyl-N-carboxymethylbetaine, lauryldimethylamine oxide, and the like.
カチオン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。 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.
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。 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、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。 The brightener contained in the electrolytic gold plating solution of the present invention as needed is not particularly limited as long as it is a known brightener, and examples thereof include amine compounds having a pyridine skeleton. These may be used alone or in combination of two or more.
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。 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よく、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.
＜電解金めっき液の物性＞
本発明の電解金めっき液を用いれば、ジェット噴流式めっき装置を用いて、電流密度を５Ａ／ｄｍ２と４０Ａ／ｄｍ２に設定してそれぞれ１０秒間めっき処理をした場合、電流密度５Ａ／ｄｍ２での金皮膜の膜厚を０．１μｍ以下にでき、かつ４０Ａ／ｄｍ２での金皮膜の膜厚を、５Ａ／ｄｍ２での金皮膜の膜厚の５倍以上にできる。更には、電流密度５Ａ／ｄｍ２での金皮膜の膜厚を０．０８μｍ以下にもでき、４０Ａ／ｄｍ２での金皮膜の膜厚を、５Ａ／ｄｍ２での金皮膜の膜厚の７倍以上にもできる。<Physical properties of electrolytic gold plating solution>
When the electrolytic gold plating solution of the present invention is used, when a current density is set to 5 A / dm 2 and 40 A / dm 2 using a jet-jet plating apparatus and plating is performed for 10 seconds, the current density is 5 A / dm. The film thickness of the gold film at 2 can be 0.1 μm or less, and the film thickness of the gold film at 40 A / dm 2 can be 5 times or more the film thickness of the gold film at 5 A / dm 2 . Furthermore, the film thickness of the gold film at a current density of 5 A / dm 2 can be 0.08 μm or less, and the film thickness of the gold film at 40 A / dm 2 can be reduced to the film thickness of the gold film at 5 A / dm 2 . Can be more than 7 times.
従って、本発明の電解金めっき液は、前記組成を有し、かつ、ジェット噴流式めっき装置を用いて、電流密度を５Ａ／ｄｍ２と４０Ａ／ｄｍ２に設定してそれぞれ１０秒間めっき処理をした場合、電流密度５Ａ／ｄｍ２での金皮膜の膜厚が０．１μｍ以下であり、かつ４０Ａ／ｄｍ２での金皮膜の膜厚が、５Ａ／ｄｍ２での金皮膜の膜厚の５倍以上である電解金めっき液であることが好ましい。更には、上記条件で、電流密度５Ａ／ｄｍ２での金皮膜の膜厚が０．０８μｍ以下であり、かつ４０Ａ／ｄｍ２での金皮膜の膜厚が、５Ａ／ｄｍ２での金皮膜の膜厚の７倍以上である電解金めっき液であることが特に好ましい。Therefore, the electrolytic gold plating solution of the present invention has the above composition, and the current density is set to 5 A / dm 2 and 40 A / dm 2 using the jet jet plating apparatus, and the plating treatment is performed for 10 seconds respectively. The film thickness of the gold film at a current density of 5 A / dm 2 is 0.1 μm or less, and the film thickness of the gold film at 40 A / dm 2 is equal to the film thickness of the gold film at 5 A / dm 2 . The electrolytic gold plating solution is preferably 5 times or more. Further, under the above conditions, the gold film thickness at a current density of 5 A / dm 2 is 0.08 μm or less, and the gold film thickness at 40 A / dm 2 is 5 A / dm 2. Particularly preferred is an electrolytic gold plating solution having a thickness of 7 times or more.
これにより、本発明の電解金めっき液を、前記したニッケルバリアめっき技術に、特に好適に用いることができる。 Thereby, the electrolytic gold plating solution of the present invention can be particularly suitably used for the above-described nickel barrier plating technique.
＜金皮膜＞
前述した通り、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の金めっき皮膜中に金と共析し、ニッケルバリアめっきに最適な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。<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, you may contain metals other than gold | metal | money, such as cobalt, nickel, and iron. Metals other than gold are co-deposited with gold in the gold plating film on the nickel plating film, forming a hard gold film optimal for nickel barrier plating, and the high hardness required for contact members such as connectors for electronic components And high wear resistance can be realized.
該「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、上記用途のための硬質金皮膜を得るためには、９７質量％〜９９．９９質量％がより好ましく、９９質量％〜９９．９質量％が特に好ましい。 The concentration of gold (gold purity) in the “gold film” is not particularly limited, but the gold content is preferably 95% by mass or more based on the entire “gold film”. In order to obtain the above, it is more preferably 97% by mass to 99.99% by mass, and particularly preferably 99% by mass to 99.9% by mass.
＜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〜ｐＨ９．０であることが好ましく、特に好ましくは、ｐＨ３．０〜ｐＨ８．０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. The pH of the plating solution is preferably pH 2.0 to pH 9.0, and particularly preferably pH 3.0 to pH 8.0.
本発明の電解金めっき液を用いて電解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。 Although there is no limitation in particular in the film thickness of the gold film obtained by performing electroplating using the electrolytic gold plating solution of this invention, Preferably it is 0.01 micrometer-20 micrometers, Most preferably, it is 0.05 micrometer-5 micrometers.
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、その上に更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液は、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, a thin gold plating process called a flash gold plating with a thickness of about 0.01 μm to 0.05 μm is performed for the purpose of improving the adhesion between the gold film and the base metal. Then, it is common to perform a thick gold plating process to a desired film thickness. The electrolytic gold plating solution 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 the thick gold plating treatment is performed with the electrolytic gold plating solution of the present invention. In addition, a commercially available flash gold plating solution or the electrolytic gold plating solution of the present invention can be appropriately used for flash gold plating.
本発明の電解金めっき液は、前記したニッケルバリアめっき技術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 in the above-described nickel barrier plating technique. 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も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、特に好ましくは０．５μｍ〜５μｍである。 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、ニッケルバリアめっき技術に要求される優れた金選択析出性能を示す作用・原理は明らかではなく、本発明は以下の作用・原理の範囲に限定されるものではないが、以下のことが考えられる。すなわち、特に低電流密度域では、シアン化金塩中の金が還元されて金属金になるより、特定複素環式化合物が置換基として有するニトロ基が還元されてニトロソ基になる方が支配的となり、低電流密度域では金の析出が抑えられ、その結果、優れた金選択析出性能を示すようになったと考えられる。<Action and principle>
The action / principle that the electrolytic gold plating solution of the present invention exhibits excellent gold selective deposition performance required for nickel barrier plating technology is not clear, and the present invention is not limited to the scope of the following actions / principles. However, the following can be considered. That is, particularly in the low current density region, the nitro group as a substituent of the specific heterocyclic compound is reduced to become a nitroso group, rather than the gold in the gold cyanide salt being reduced to metal gold. Thus, it is considered that gold deposition was suppressed in the low current density region, and as a result, excellent gold selective deposition performance was exhibited.
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、その要旨を越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。 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.
＜電解金めっき液の調製＞
実施例１〜１０、比較例１〜１２
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、特定複素環式化合物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 1-12
For the entire electrolytic gold plating solution, potassium gold 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 specified to be 200 ppm in terms of metal. A heterocyclic compound or a comparative compound thereof was dissolved at 1000 ppm, citric acid as a component serving both as a conductive salt and a buffering agent was dissolved at 100 g / L, and the pH was adjusted to 4.3 to obtain an electrolytic gold plating solution.
「比較化合物」としては、ヘキサメチレンテトラミン、環中の炭素原子にニトロ基が１個以上置換しているベンゼン環化合物、及びニトロ基が置換していない複素環式化合物を用いた。なお、ｐＨは２０質量％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。 As the “comparative compound”, hexamethylenetetramine, a benzene ring compound in which one or more nitro groups were substituted on the carbon atom in the ring, and a heterocyclic compound in which the nitro group was not substituted were used. In addition, pH was adjusted with 20 mass% potassium hydroxide aqueous solution and a citric acid, the bath temperature of the electrolytic gold plating solution was set to 50 degreeC, and the following evaluation was performed.
実施例１１
コバルト塩、ニッケル塩、鉄塩等の金塩以外の金属塩を含有しない以外は、実施例１と同様に電解金めっき液を調製し、実施例１と同様に電解金めっきを施し、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 no metal salt other than a gold salt such as a cobalt salt, a nickel salt, or an iron salt was contained, and electrolytic gold plating was performed in the same manner as in Example 1. The following evaluation was performed.
＜電解金めっきの方法＞
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、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攪拌しながら（以下、「ジェット噴流式金めっき法」とする）、電流密度を５Ａ／ｄｍ２、４０Ａ／ｄｍ２の２水準で各１０秒間ずつ電解金めっき処理した。<Method of electrolytic gold plating>
Using the electrolytic gold plating solution prepared in each example and each 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. did. Electrolytic gold plating is carried out by stirring the electrolytic gold plating solution from a circular jet port having a diameter of 8 mm at a flow rate of 18 L / min with a pump (hereinafter referred to as “jet jet gold plating method”), and a current density of 5 A. Electrolytic gold plating was performed for 10 seconds each at two levels of / dm 2 and 40 A / dm 2 .
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にめっきした。すなわち、市販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 plated to a thickness of 2.0 μm using the following electrolytic nickel plating solution A. That is, commercially available nickel sulfamate plating solution (manufactured by Murata Co., Ltd., SN Conque (trade name)) 500 mL / L, commercially available nickel chloride 10 g / L, commercially available boric acid 30 g / L, and pit inhibitor (Ebara Eugelite Co. The product was made at a concentration of 2 mL / L, made by company, pit inhibitor # 82 (trade name) to obtain “electrolytic nickel plating solution A”.
＜金皮膜の膜厚の測定方法と金選択析出性能の評価方法＞
円状に電解金めっき処理された中心付近を、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 and evaluation method of gold selective deposition performance>
The thickness of the gold film was measured according to a conventional method using a fluorescent X-ray analyzer (SFT 9255, manufactured by Seiko Instruments Inc.) in the vicinity of the center subjected to electrolytic gold plating in a circular shape. The results are shown in Table 3.
電流密度５Ａ／ｄｍ２で電解金めっき処理した場合の金皮膜の膜厚が０．１μｍ以下であるものを金選択析出性能に優れたニッケルバリアめっき技術に最適な電解金めっき液と判定した。０．１μｍ以下を「良」とし、０．１μｍより厚いものを「不良」とし、結果を表３に示す。A gold film having a gold film thickness of 0.1 μm or less when subjected to electrolytic gold plating at a current density of 5 A / dm 2 was determined to be an electrolytic gold plating solution optimal for nickel barrier plating technology having excellent gold selective deposition performance. The result is shown in Table 3 as “good” when 0.1 μm or less and “bad” when thicker than 0.1 μm.
また、電流密度４０Ａ／ｄｍ２で電解金めっき処理した場合の金皮膜の膜厚が電流密度５Ａ／ｄｍ２で電解金めっき処理した場合の金皮膜の膜厚の５倍以上であるものを金選択析出性能に優れたニッケルバリアめっき技術に最適な電解金めっき液と判定した。５倍以上を「良」とし、５倍未満を「不良」とし、結果を表３に示す。In addition, a gold film having a gold film thickness of 5 times or more than the gold film thickness when electrolytic gold plating treatment is performed at a current density of 5 A / dm 2 when gold plating is performed at a current density of 40 A / dm 2 is used. The electrolytic gold plating solution was judged to be optimal for nickel barrier plating technology with excellent selective deposition performance. 5 times or more is “good”, less than 5 times is “bad”, and the results are shown in Table 3.
＜金皮膜の金純度の測定法＞
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作成し、硝酸にて銅素材及びニッケルめっき皮膜を溶解して金箔を作成した。作成した金箔の重量を測った後、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、析出金質量と不純物質量から金純度を算出した。結果を表３に示す。表３中、「％」は「質量％」を示す。<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. An electrolytic gold plating film of 50 μm was prepared at dm 2 by a jet-jet gold plating method, and a copper material and a nickel plating film were dissolved in nitric acid to prepare a gold foil. After measuring the weight of the prepared gold foil, the gold foil was dissolved in 20 mL of aqua regia and quantitative analysis of Cu, Ni, Co, and Fe as impurity elements was performed with an ICP emission spectroscopic analyzer (Seiko Instruments Inc., SPS3000). The gold purity was calculated from the deposited gold mass and the impurity mass. The results are shown in Table 3. In Table 3, “%” indicates “mass%”.
＜電流密度と金皮膜の膜厚との関係＞
汎用の「特定複素環式化合物を含有していない電解金めっき液」と「本発明の上記実施例１の電解金めっき液」を用い、何れの電解金めっき液も金換算の濃度９ｇ／Ｌとし、浴温を５０℃に昇温して、上記した表２記載の工程で、１０ｍｍ×１０ｍｍの銅板上の１次光沢ニッケルめっき皮膜２．０μｍ上に金めっきを施した。金めっきは、上記ジェット噴流式金めっき法により、電流密度を１Ａ／ｄｍ２、５Ａ／ｄｍ２、１０Ａ／ｄｍ２、１５Ａ／ｄｍ２（実施例１の電解金めっき液のみ）、２０Ａ／ｄｍ２、３０Ａ／ｄｍ２、４０Ａ／ｄｍ２、５０Ａ／ｄｍ２、６０Ａ／ｄｍ２と変化させて１０秒間ずつ電解金めっきをし、円状に金めっき処理された中心付近を上記した方法で金皮膜の膜厚を測定した。測定結果をプロットしたグラフを図１に示す。<Relationship between current density and film thickness of gold film>
Using general-purpose “electrolytic gold plating solution not containing a specific heterocyclic compound” and “electrolytic gold plating solution of Example 1 of the present invention”, each electrolytic gold plating solution has a gold equivalent concentration of 9 g / L. Then, the bath temperature was raised to 50 ° C., and gold plating was performed on 2.0 μm of the primary bright nickel plating film on the 10 mm × 10 mm copper plate in the process described in Table 2 above. In the gold plating, the current density is 1 A / dm 2 , 5 A / dm 2 , 10 A / dm 2 , 15 A / dm 2 (only the electrolytic gold plating solution of Example 1), 20 A / dm by the jet jet gold plating method. 2 , 30 A / dm 2 , 40 A / dm 2 , 50 A / dm 2 , 60 A / dm 2 , followed by electrolytic gold plating for 10 seconds each, and the gold was plated in the vicinity of the center by the above method. The film thickness of the film was measured. A graph plotting the measurement results is shown in FIG.
０Ａ／ｄｍ２から５Ａ／ｄｍ２（低電流密度域）において、実施例１の電解金めっき液では、金皮膜の膜厚は非常に薄かったが、汎用の電解金めっき液では、厚い金皮膜が形成されてしまった。また、２０Ａ／ｄｍ２から６０Ａ／ｄｍ２（高電流密度域）においては、実施例１の電解金めっき液は、汎用の電解金めっき液と同等以上の膜厚の金皮膜を形成することができた。In 0A / dm 2 to 5 A / dm 2 (low current density range), in the electrolytic gold plating solution of Example 1, the film thickness of the gold film was very thin. Has formed. In addition, in 20 A / dm 2 to 60 A / dm 2 (high current density region), the electrolytic gold plating solution of Example 1 may form a gold film having a film thickness equal to or greater than that of a general-purpose electrolytic gold plating solution. did it.
本発明で見出されたように、ニッケルバリアめっき技術において、低電流密度域は金めっきを施さない部分に相当し、高電流密度域は金めっきを施す部分に相当すると考えられるので、低電流密度域での金皮膜の膜厚は薄ければ薄いほど、高電流密度域での金皮膜の膜厚は厚ければ厚いほどニッケルバリア特性が良好になる。従って、特定複素環式化合物を含有する実施例１の電解金めっき液は、図１に示した性質と上記理由から、「ニッケルバリアめっき技術に適応した優れた性能」を有するものになった。 As found in the present invention, in the nickel barrier plating technology, the low current density region corresponds to a portion not subjected to gold plating, and the high current density region is considered to correspond to a portion subjected to gold plating. The thinner the gold film in the density region, the better the nickel barrier properties the thicker the gold film in the high current density region. Therefore, the electrolytic gold plating solution of Example 1 containing the specific heterocyclic compound has “excellent performance adapted to the nickel barrier plating technique” because of the properties shown in FIG. 1 and the above reasons.
＜高精度コネクターへの適用＞
実施例１及び比較例１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、高精度コネクターの銅上に１次光沢ニッケルめっき皮膜２．０μｍを施した。次いで、その上に、図２に示すように、電解金めっきを施したくない部分（ニッケルバリア−部分）のみに、常法に従ってシリコンゴム部材を押しつけて、５０℃で平均の陰極電流密度４０Ａ／ｄｍ２にて１０秒間、電解金めっき皮膜をジェット噴流式金めっき法で作成した。上記で用いたニッケルバリアめっき技術におけるコネクターの形態を図２に示し、実施例１で調製した電解金めっき液を用いたときの、図２に対応した位置の膜厚分布を図３に示す。<Application to high precision connectors>
Using the electrolytic gold plating solution prepared in Example 1 and Comparative Example 1, a primary bright nickel plating film of 2.0 μm was applied on the copper of the high-precision connector in the steps shown in Table 2. Next, as shown in FIG. 2, a silicon rubber member is pressed only on a portion (nickel barrier portion) that is not desired to be subjected to electrolytic gold plating according to a conventional method, and an average cathode current density of 40 A / 50 ° C. An electrolytic gold plating film was prepared by jet jet gold plating at
実施例１の電解金めっき液を用いた場合、電解金めっきを施したくない部分（ニッケルバリア−部分）（シリコンゴム部材を押しつけた部分）には、縁の部分であっても常に０．０５μｍ以下の金皮膜しか形成されていなかったが、電解金めっきを施したい部分（シリコンゴム部材を押しつけていない部分）は、全域にわたって平均０．６７μｍの金皮膜が形成されていた。また、シリコンゴム部材を押しつけた部分の側面にも、常に０．０３μｍ以下の金皮膜しか形成されていなかった。ニッケルバリア−部分にはたとえ縁であっても殆ど金皮膜が形成されていなかったため、はんだのにじみが見られなかった。 When the electrolytic gold plating solution of Example 1 was used, the portion (nickel barrier portion) where the electrolytic gold plating is not desired (the portion where the silicon rubber member was pressed) was always 0.05 μm even at the edge portion. Only the following gold film was formed, but the gold film with an average of 0.67 μm was formed over the entire area where the electrolytic gold plating was desired (the part where the silicon rubber member was not pressed). Also, only a gold film of 0.03 μm or less was always formed on the side surface of the portion where the silicon rubber member was pressed. Even though the nickel barrier portion was an edge, almost no gold film was formed, so no solder bleeding was observed.
一方、比較例１の電解金めっき液を用いた場合、シリコンゴム部材を押しつけた部分であっても、特に縁の部分は０．２μｍの金皮膜が形成されてしまった部分があった。また、シリコンゴム部材を押しつけた部分の側面にも、０．２μｍの金皮膜が形成されてしまった部分が存在した。従って、電解金めっきを施したくない部分であっても、薄く金皮膜が形成されてしまったため、ニッケルのバリアー効果が十分でなく、はんだのにじみが見られた。 On the other hand, when the electrolytic gold plating solution of Comparative Example 1 was used, even in the portion where the silicon rubber member was pressed, there was a portion in which a 0.2 μm gold film was formed particularly in the edge portion. Also, there was a portion where a 0.2 μm gold film was formed on the side surface of the portion where the silicon rubber member was pressed. Therefore, even in a portion where electrolytic gold plating is not desired, a thin gold film was formed, so that the barrier effect of nickel was not sufficient and solder bleeding was observed.
＜実施例と比較例のまとめ＞
本発明の電解金めっき液を使用した実施例１〜実施例１１は、電流密度５Ａ／ｄｍ２での金膜厚が何れも０．１μｍ以下であり、かつ電流密度５Ａ／ｄｍ２での金皮膜の膜厚と電流密度４０Ａ／ｄｍ２での金皮膜の膜厚の比が何れも１：５以上であり、金選択析出性能は全てが「良」で、ニッケルバリアめっきに最適な金めっき液であることが分かった。<Summary of Examples and Comparative Examples>
In Examples 1 to 11 using the electrolytic gold plating solution of the present invention, the gold film thickness at a current density of 5 A / dm 2 is 0.1 μm or less, and the gold at a current density of 5 A / dm 2 is used. The ratio of the film thickness to the gold film thickness at a current density of 40 A / dm 2 is 1: 5 or more, and the gold selective deposition performance is all “good”, which is optimal for nickel barrier plating. It turned out to be a liquid.
また、実施例１〜実施例１１の本発明の電解金めっき液を使用して得られた金皮膜は、優れた耐摩耗性等の機械特性、耐食性及び電気特性を有していた。特に、実施例１〜実施例１０の電解金合金めっき液を使用して得られた金合金皮膜は、優れた耐摩耗性等の機械特性を有していた。 Moreover, the gold film obtained using the electrolytic gold plating solution of the present invention of Examples 1 to 11 had excellent mechanical properties such as wear resistance, corrosion resistance, and electrical properties. In particular, the gold alloy film obtained using the electrolytic gold alloy plating solutions of Examples 1 to 10 had excellent mechanical properties such as wear resistance.
これに対して、比較例１〜比較例１２では、電流密度５Ａ／ｄｍ２での金皮膜の膜厚が何れも０．１μｍを大きく上回り、更に電流密度５Ａ／ｄｍ２での金皮膜の膜厚と電流密度４０Ａ／ｄｍ２での金膜厚の比が何れも１：５未満であり、低電流密度域での金析出膜厚と高電流密度域での金析出膜厚の差が小さく、何れも金選択析出性能が悪く、ニッケルバリアめっきには適さないことが分かった。On the other hand, in Comparative Examples 1 to 12, the film thickness of the gold film at a current density of 5 A / dm 2 is significantly higher than 0.1 μm, and the film of the gold film at a current density of 5 A / dm 2 is further obtained. The ratio between the thickness and the gold film thickness at a current density of 40 A / dm 2 is less than 1: 5, and the difference between the gold film thickness in the low current density area and the gold film thickness in the high current density area is small. , All showed poor gold selective deposition performance and were not suitable for nickel barrier plating.
実際のコネクターに適用したところ、低電流密度域での金析出膜厚と高電流密度域での金析出膜厚の差が大きいと、ニッケルバリアめっきに適した電解金めっき液であることが確認でき、実施例１〜１１の電解金めっき液はニッケルバリアめっきに適したものであることが分かった。 When applied to an actual connector, if the difference between the gold deposition film thickness in the low current density region and the gold deposition film thickness in the high current density region is large, it is confirmed that the electrolytic gold plating solution is suitable for nickel barrier plating. The electrolytic gold plating solutions of Examples 1 to 11 were found to be suitable for nickel barrier plating.
本発明の電解金めっき液を用いて得られた金皮膜は、優れた機械特性、耐食性及び電気特性を有しており、更に、金選択析出性能に優れるため、現在、電子機器の接点部材等に実用化されているニッケルバリアめっきに最適であり、今までニッケルバリアめっきが非常に難しいとされてきた複雑な形状のコネクターや微小化されたコネクター等にニッケルバリアめっきを施すことが可能となり、この分野に広く利用されるものである。 The gold film obtained using the electrolytic gold plating solution of the present invention has excellent mechanical properties, corrosion resistance, and electrical properties, and further has excellent gold selective deposition performance. It is ideal for nickel barrier plating that has been put to practical use in the past, and it is possible to apply nickel barrier plating to connectors with complicated shapes and miniaturized connectors that have been considered extremely difficult until now. It is widely used in this field.
本願は、２００８年６月１１日に出願した日本の特許出願である特願２００８−１５３１８８に基づくものであり、その出願の全ての内容はここに引用し、本願発明の明細書の開示として取り込まれるものである。 This application is based on Japanese Patent Application No. 2008-153188, a Japanese patent application filed on June 11, 2008, the entire contents of which are hereby incorporated by reference as the disclosure of the specification of the present invention. It is what
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| US10577704B2 (en) | 2015-06-26 | 2020-03-03 | Metalor Technologies Corporation | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
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| JP5513784B2 (en) * | 2008-08-25 | 2014-06-04 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Hard gold plating solution |
| JP2011021217A (en) * | 2009-07-14 | 2011-02-03 | Ne Chemcat Corp | Electrolytic hard-gold-plating liquid and plating method using the same |
| US8608931B2 (en) * | 2009-09-25 | 2013-12-17 | Rohm And Haas Electronic Materials Llc | Anti-displacement hard gold compositions |
| JP2011122192A (en) * | 2009-12-09 | 2011-06-23 | Ne Chemcat Corp | Electrolytic hard gold plating liquid and plating method using the same |
| JP5731802B2 (en) * | 2010-11-25 | 2015-06-10 | ローム・アンド・ハース電子材料株式会社 | Gold plating solution |
| JP2013177654A (en) * | 2012-02-28 | 2013-09-09 | Matex Japan Co Ltd | Electrolytic hard gold plating liquid, plating method, and manufacturing method of gold-iron alloy film |
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| DE102013109400A1 (en) * | 2013-08-29 | 2015-03-05 | Harting Kgaa | Contact element with gold coating |
| CN103741180B (en) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | Non-cyanide bright electrogilding additive and application thereof |
| EP2990507A1 (en) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Composition, use thereof and method for electrodepositing gold containing layers |
| CN106637307B (en) * | 2017-01-04 | 2019-01-01 | 中国地质大学（武汉） | A kind of additive for gold without cyanogen electroforming process |
| JP7079016B2 (en) * | 2017-05-30 | 2022-06-01 | オリエンタル鍍金株式会社 | PCB terminal manufacturing method and PCB terminal |
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| KR102610613B1 (en) * | 2021-11-30 | 2023-12-07 | (주)엠케이켐앤텍 | Plating solution for conductive particles used in semiconductor test socket, plating method thereof, and conductive particles plated using the same |
| CN116240597B (en) * | 2022-12-29 | 2024-03-26 | 华为技术有限公司 | Electroplating solution and application thereof |
| CN115821341B (en) * | 2023-01-06 | 2023-04-28 | 深圳创智芯联科技股份有限公司 | Environment-friendly cyanide-free electroplating solution and electroplating process thereof |
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| KR20110022576A (en) | 2011-03-07 |
| CN102105623A (en) | 2011-06-22 |
| CN102105623B (en) | 2013-10-02 |
| WO2009150915A1 (en) | 2009-12-17 |
| JPWO2009150915A1 (en) | 2011-11-10 |
| TW201009125A (en) | 2010-03-01 |
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