JP2014139348A - Hard gold-based plating solution - Google Patents
Hard gold-based plating solution Download PDFInfo
- Publication number
- JP2014139348A JP2014139348A JP2014067301A JP2014067301A JP2014139348A JP 2014139348 A JP2014139348 A JP 2014139348A JP 2014067301 A JP2014067301 A JP 2014067301A JP 2014067301 A JP2014067301 A JP 2014067301A JP 2014139348 A JP2014139348 A JP 2014139348A
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- JP
- Japan
- Prior art keywords
- plating
- acid
- plating solution
- hard gold
- gold
- 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.)
- Pending
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- 238000007747 plating Methods 0.000 title claims abstract description 238
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 125
- 239000010931 gold Substances 0.000 title claims abstract description 125
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 124
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical group OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 30
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical group OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 23
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 239000006259 organic additive Substances 0.000 claims abstract description 7
- 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 claims abstract description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 24
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
- 125000006413 ring segment Chemical group 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 2
- 150000003378 silver Chemical class 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 235000015165 citric acid Nutrition 0.000 description 10
- 230000003247 decreasing effect Effects 0.000 description 10
- ISDDBQLTUUCGCZ-UHFFFAOYSA-N dipotassium dicyanide Chemical compound [K+].[K+].N#[C-].N#[C-] ISDDBQLTUUCGCZ-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 229910001020 Au alloy Inorganic materials 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000003353 gold alloy Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910000531 Co alloy Inorganic materials 0.000 description 5
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 4
- 229940098221 silver cyanide Drugs 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- -1 gold ion Chemical class 0.000 description 3
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- SRWFBFUYENBCGF-UHFFFAOYSA-M sodium;chloride;hydrochloride Chemical compound [Na+].Cl.[Cl-] SRWFBFUYENBCGF-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- NNNRGWOWXNCGCV-UHFFFAOYSA-N 4-(2-bromoethyl)benzonitrile Chemical compound BrCCC1=CC=C(C#N)C=C1 NNNRGWOWXNCGCV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 description 1
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940049699 cobalt gluconate Drugs 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229940116232 nickel gluconate Drugs 0.000 description 1
- DVQYNXRSNFYQRW-IYEMJOQQSA-L nickel(2+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ni+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 DVQYNXRSNFYQRW-IYEMJOQQSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- KVMLCRQYXDYXDX-UHFFFAOYSA-M potassium;chloride;hydrochloride Chemical compound Cl.[Cl-].[K+] KVMLCRQYXDYXDX-UHFFFAOYSA-M 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical group [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- KRZKNIQKJHKHPL-UHFFFAOYSA-J tripotassium;gold(1+);disulfite Chemical compound [K+].[K+].[K+].[Au+].[O-]S([O-])=O.[O-]S([O-])=O KRZKNIQKJHKHPL-UHFFFAOYSA-J 0.000 description 1
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、硬質金系めっき処理技術に関し、特に、コネクターなどの電子機器等の接点材を形成する際に好適な、硬質金めっき、硬質金合金めっきを施すための硬質金系めっき液に関する。本願における硬質金系めっきとは、硬質金めっき又は硬質金合金めっきのいずれかを指し、硬質金系めっきを施すためのめっき液を硬質金系めっき液と呼ぶ。 The present invention relates to a hard gold plating technique, and more particularly to a hard gold plating solution for performing hard gold plating and hard gold alloy plating suitable for forming contact materials for electronic devices such as connectors. The hard gold plating in the present application refers to either hard gold plating or hard gold alloy plating, and a plating solution for performing hard gold plating is referred to as a hard gold plating solution.
従来より、金めっきは、金の優れた電気特性、耐食性などの理由から、電子機器や電子部品に用いられ、電子部品などの接続端子表面を保護する用途に広く利用されている。金めっきは、半導体素子の電極端子、樹脂フィルムに形成されたリード、電子機器を接続するコネクターなどの電子部品の表面処理として用いられている。 Conventionally, gold plating has been used in electronic devices and electronic parts for reasons such as excellent electrical properties and corrosion resistance of gold, and has been widely used for applications that protect the surface of connection terminals such as electronic parts. Gold plating is used as a surface treatment for electronic components such as electrode terminals of semiconductor elements, leads formed on resin films, and connectors for connecting electronic devices.
電子機器を接続するコネクターのような電子部品では、表面処理として金めっきが用いられるが、その特性として耐食性、耐摩擦性および電気伝導性が要求されるため、硬質金系めっきを使用されることが多い。この硬質金系めっきとしては、例えば金−コバルト系合金めっき、金−ニッケル系合金めっきなど硬質金合金めっきが古くから知られている（特許文献１、特許文献２）。 Electronic parts such as connectors for connecting electronic devices use gold plating as a surface treatment, but they require hard gold plating because their properties require corrosion resistance, friction resistance, and electrical conductivity. There are many. As this hard gold plating, hard gold alloy plating such as gold-cobalt alloy plating and gold-nickel alloy plating has been known for a long time (Patent Document 1, Patent Document 2).
コネクターなどの電子部品には、一般的に銅または銅合金がその材料として用いられるが、硬質金系めっきを行う場合、通常、銅または銅合金表面にニッケルめっきを施すことが行われ、その後、ニッケルめっきの表面に硬質金系めっきが施される。 For electronic parts such as connectors, copper or copper alloy is generally used as the material. However, when performing hard gold plating, usually nickel plating is applied to the surface of copper or copper alloy, Hard gold plating is applied to the surface of the nickel plating.
このようなコネクターなどの電子部品に硬質金系めっきを行う場合、必要な部分のみに硬質金系めっきがされるように、部分的なめっき処理が要求される。つまり、必要な部分にのみ硬質金系めっきがされ、不必要な部分には、硬質金系めっきの析出が生じないことが必要とされる。その理由としては、コネクターの不必要な部分にまで硬質金系めっきがされていると、電気的な接続を行うための半田処理を行う際、その不必要な部分にも半田が這い上がり、電気的な特性が低下してしまうためである。さらに、不必要な部分に析出しなければ、使用する金量を抑制できるので少金化が可能となるからである。このような要求に対し、必要である部分にのみ選択的に硬質金系めっき処理を行える技術が提案されている（例えば、特許文献３）。 When performing hard gold plating on such an electronic component such as a connector, a partial plating process is required so that hard gold plating is performed only on necessary portions. That is, it is necessary that the hard gold plating is applied only to a necessary portion, and the hard gold plating is not deposited on an unnecessary portion. The reason for this is that if hard gold plating is applied to the unnecessary part of the connector, the solder will crawl up on the unnecessary part when soldering to make an electrical connection. This is because the typical characteristics deteriorate. Furthermore, if it does not precipitate in unnecessary parts, the amount of gold to be used can be suppressed, so that the amount of gold can be reduced. In response to such a requirement, a technique has been proposed in which hard gold plating can be selectively performed only on necessary portions (for example, Patent Document 3).
この先行技術における金コバルト合金めっき液は、コネクターなどの電子部品に対して、所望の箇所にのみ金合金めっき皮膜を析出し、必要のない箇所には析出することを抑制して、硬質金系めっきを行うことができる。 The gold-cobalt alloy plating solution in this prior art deposits a gold alloy plating film only at a desired location on an electronic component such as a connector, and suppresses the deposition at an unnecessary location, thereby producing a hard gold system. Plating can be performed.
ところで、昨今の電子部品においては、その優れた材料特性より、電気的な接続を必要とする部分に、金又は金合金めっきを施すことが非常に多くなっている。その対象部品は様々なものがあり、選択的に部分めっき処理が可能な硬質金系めっき液が要求されるものの、そのような硬質金系めっき液の種類は数少ない。つまり、特許文献３で提案されたような、選択的な部分めっき処理が可能な、新たな硬質金系めっき液を要望されているのが現状である。 By the way, in recent electronic parts, gold or gold alloy plating is very often applied to a portion requiring electrical connection because of its excellent material characteristics. There are various target parts, and although a hard gold plating solution capable of selective partial plating is required, there are few types of such hard gold plating solutions. In other words, there is a demand for a new hard gold plating solution capable of selective partial plating as proposed in Patent Document 3.
本発明は、以上のような事情を背景になされたものであり、選択的な部分めっき処理が可能で、コネクターなどの電子部品に好適な硬質金系めっき液を提供することを目的とする。 The present invention has been made in the background as described above, and an object of the present invention is to provide a hard gold plating solution that can be selectively subjected to partial plating and is suitable for electronic parts such as connectors.
本発明は、可溶性金塩または金錯体、伝導塩、キレート化剤を含み、シアンを含有する硬質金系めっき液において、１つ以上のニトロ基を有する芳香族化合物（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及び、ニトロ安息香酸、ジニトロ安息香酸、ニトロベンゼンスルホン酸を除く）を含有することを特徴とする。可溶性金塩または金錯体、伝導塩、キレート化剤を含み、シアンを含有する硬質金系めっき液に、１つ以上のニトロ基を有する芳香族化合物（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及び、ニトロ安息香酸、ジニトロ安息香酸、ニトロベンゼンスルホン酸を除く）を含有させると、硬質金系めっきによる、選択的な部分めっき処理が可能となる。 The present invention relates to an aromatic compound having one or more nitro groups (containing 1 nitrogen atom in a ring) in a hard gold plating solution containing a soluble gold salt or gold complex, a conductive salt, a chelating agent and containing cyanide. And a heterocyclic compound in which one or more nitro groups are substituted on the carbon atom in the ring, and nitrobenzoic acid, dinitrobenzoic acid, and nitrobenzenesulfonic acid are included) . An aromatic compound having one or more nitro groups (containing at least one nitrogen atom in the ring) in a hard gold plating solution containing a soluble gold salt or gold complex, a conductive salt, a chelating agent and containing cyanide Including a heterocyclic compound in which one or more nitro groups are substituted on the carbon atom in the ring, and nitrobenzoic acid, dinitrobenzoic acid, and nitrobenzenesulfonic acid). Partial plating can be performed.
本発明に係る硬質金系めっき液は、コバルト塩、ニッケル塩、銀塩の少なくとも１種の金属塩を含むことが好ましい。これらの金属塩により、めっき膜が金合金化し膜の硬質化が図れる。 The hard gold plating solution according to the present invention preferably contains at least one metal salt of a cobalt salt, a nickel salt, and a silver salt. With these metal salts, the plating film can be made into a gold alloy and the film can be hardened.
本発明に係る硬質系金めっき液は、コバルト塩、ニッケル塩、銀塩等の金属塩に代えてポリエチレンイミンの有機添加剤を含ませてもよい。ポリエチレンイミンとしては、種々の分子量を有するものを用いることができ、直鎖構造のものや分岐構造のもの等の構造は問わずに用いることができる。この有機添加剤によっても金属塩の添加と同様、めっき膜の硬質化がはかれる。 The hard gold plating solution according to the present invention may contain an organic additive of polyethyleneimine instead of a metal salt such as a cobalt salt, a nickel salt, or a silver salt. As the polyethyleneimine, those having various molecular weights can be used, and any structure such as a linear structure or a branched structure can be used. With this organic additive, the plating film is hardened in the same manner as the addition of the metal salt.
本発明に係る硬質金系めっき液において、金イオン源としては、可溶性金塩または金錯体を用いることができる。具体的には、シアン化第一金カリウム、シアン化第二金カリウム、シアン化金アンモニウム、塩化第一金カリウム、塩化第二金カリウム、塩化第一金ナトリウム、塩化第二金ナトリウム、チオ硫酸金カリウム、チオ硫酸金ナトリウム、亜硫酸金カリウム、亜硫酸金ナトリウム、およびこれら２つ以上の組み合わせを用いることができる。特に好ましいものとしては、シアン化第一金カリウムである。 In the hard gold plating solution according to the present invention, a soluble gold salt or a gold complex can be used as the gold ion source. Specifically, potassium potassium cyanide, potassium potassium cyanide, ammonium gold cyanide, potassium chloride gold, potassium chloride chloride, sodium chloride chloride, sodium chloride chloride, thiosulfuric acid Gold potassium, sodium gold thiosulfate, potassium gold sulfite, sodium gold sulfite, and combinations of two or more thereof can be used. Particularly preferable is potassium gold cyanide.
本発明の硬質金系めっき液における金濃度としては、金換算で、１ｇ／Ｌ〜２０ｇ／Ｌの範囲が望ましい。１ｇ／Ｌ未満であると、高電流密度で処理することが困難となり、高速のめっき処理が難しくなる傾向となる。また、２０ｇ／Ｌを超えると、金自体のめっき液からの持ち出し量（めっき対象物となるコネクターなどに若干のめっき液が付いて次工程へ持ち出されること。たとえば、数滴のめっき液が持ち出されたとしても、金濃度が高ければ高いほど、めっき液から金の減量が多くなる）が多くなり、製造コストの増加になるからである。より好ましい金塩濃度は、金換算で、２ｇ／Ｌ〜１６ｇ／Ｌである。 The gold concentration in the hard gold plating solution of the present invention is preferably in the range of 1 g / L to 20 g / L in terms of gold. If it is less than 1 g / L, it becomes difficult to process at a high current density, and high-speed plating tends to be difficult. If the amount exceeds 20 g / L, the amount of gold taken out from the plating solution (a slight amount of plating solution is attached to the connector to be plated, etc., and is taken out to the next process. For example, several drops of plating solution are taken out. This is because the higher the gold concentration, the greater the amount of gold lost from the plating solution), which increases the manufacturing cost. A more preferable gold salt concentration is 2 g / L to 16 g / L in terms of gold.
本発明に係る硬質金系めっき液に、コバルト塩を含有させる場合、コバルト源としては、可溶性のコバルト化合物を用いることができる。例えば、硫酸コバルト、塩化コバルト、炭酸コバルト、スルファミン酸コバルト、グルコン酸コバルトおよびこれらの２以上の組み合わせを用いることができる。好ましくは、無機コバルト塩、特に硫酸コバルトである。 When the hard gold plating solution according to the present invention contains a cobalt salt, a soluble cobalt compound can be used as the cobalt source. For example, cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt sulfamate, cobalt gluconate, and combinations of two or more thereof can be used. Preferably, it is an inorganic cobalt salt, especially cobalt sulfate.
このコバルト塩のめっき液中の濃度としては、コバルト換算で、０．０５ｇ／Ｌ〜１０ｇ／Ｌの範囲が望ましい。０．０５ｇ／Ｌ未満であると、めっき膜中のコバルトの共析量が低下し、硬質金系めっきの硬化向上が図れなくなる傾向となる。また、１０ｇ／Ｌを超えると、めっき液の安定性が低下する傾向となる。より好ましいコバルト塩濃度は、コバルト換算で、０．１ｇ／Ｌ〜３ｇ／Ｌである。 The concentration of the cobalt salt in the plating solution is preferably in the range of 0.05 g / L to 10 g / L in terms of cobalt. If it is less than 0.05 g / L, the amount of eutectoid of cobalt in the plating film decreases, and it becomes difficult to improve the hardening of the hard gold plating. Moreover, when it exceeds 10 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable cobalt salt concentration is 0.1 g / L to 3 g / L in terms of cobalt.
本発明に係る硬質金系めっき液に、ニッケル塩を含有させる場合、ニッケル源としては、可溶性のニッケル化合物を用いることができる。例えば、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、スルファミン酸ニッケル、グルコン酸ニッケル、およびこれらの２以上の組み合わせを用いることができる。好ましくは、特に硫酸ニッケルである。 When the hard gold plating solution according to the present invention contains a nickel salt, a soluble nickel compound can be used as the nickel source. For example, nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, nickel gluconate, and combinations of two or more thereof can be used. Particularly preferred is nickel sulfate.
このニッケル塩のめっき液中の濃度としては、ニッケル換算で、０．０５ｇ／Ｌ〜３０ｇ／Ｌの範囲が望ましい。０．０５ｇ／Ｌ未満であると、めっき膜中のニッケルの共析量が低下し、硬質金系めっきの硬化向上が図れなくなる傾向となる。また、３０ｇ／Ｌを超えると、めっき液の安定性が低下する傾向となる。より好ましいニッケル濃度は、ニッケル換算で、０．１ｇ／Ｌ〜２０ｇ／Ｌである。 The concentration of the nickel salt in the plating solution is preferably in the range of 0.05 g / L to 30 g / L in terms of nickel. If it is less than 0.05 g / L, the amount of eutectoid of nickel in the plating film is lowered, and the hard gold plating tends to be hardened. Moreover, when it exceeds 30 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable nickel concentration is 0.1 g / L to 20 g / L in terms of nickel.
本発明に係る硬質金系めっき液に、銀塩を含有させる場合、銀源としては、可溶性の銀化合物を用いることができる。例えば、シアン化銀及びその塩、塩化銀、炭酸銀、硝酸銀およびこれらの２以上の組み合わせを用いることができる。好ましくは、特にシアン化銀である。 When the hard gold plating solution according to the present invention contains a silver salt, a soluble silver compound can be used as the silver source. For example, silver cyanide and its salt, silver chloride, silver carbonate, silver nitrate and combinations of two or more thereof can be used. Particularly preferred is silver cyanide.
この銀塩のめっき液中の濃度としては、銀換算で、０．０５ｇ／Ｌ〜１００ｇ／Ｌの範囲が望ましい。０．０５ｇ／Ｌ未満であると、めっき膜中の銀の共析量が低下し、硬質金系めっきの硬化向上が図れなくなる傾向となる。また、１００ｇ／Ｌを超えると、めっき液の安定性が低下する傾向となる。より好ましい銀濃度は、銀換算で、０．１ｇ／Ｌ〜５０ｇ／Ｌである。 The concentration of the silver salt in the plating solution is preferably in the range of 0.05 g / L to 100 g / L in terms of silver. If it is less than 0.05 g / L, the amount of silver eutectoid in the plating film decreases, and it becomes difficult to improve the hardening of the hard gold plating. Moreover, when it exceeds 100 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable silver concentration is 0.1 g / L to 50 g / L in terms of silver.
本発明に係る硬質金系めっき液に、ポリエチレンイミンの有機添加剤を含有させる場合、めっき液中の有機添加剤の濃度としては、０．１ｇ／Ｌ〜３００ｇ／Ｌとすることが好ましい。０．１ｇ／Ｌ未満であると、硬質金系めっきの硬化向上が図れなくなる傾向となり、３００ｇ／Ｌを超えるとめっき液の安定性が低下する傾向となる。より好ましい濃度としては、１ｇ／Ｌ〜２００ｇ／Ｌである。 When the hard gold plating solution according to the present invention contains an organic additive of polyethyleneimine, the concentration of the organic additive in the plating solution is preferably 0.1 g / L to 300 g / L. If the amount is less than 0.1 g / L, the hardening of the hard gold plating tends not to be improved, and if the amount exceeds 300 g / L, the stability of the plating solution tends to decrease. A more preferable concentration is 1 g / L to 200 g / L.
本発明の硬質金系めっき液における伝導塩としては、有機化合物或いは無機化合物のどちらでも用いることができ、有機化合物としては、例えば、クエン酸、酒石酸、アジピン酸、リンゴ酸、コハク酸、乳酸、安息香酸などのカルボン酸およびその塩ならびにホスホン酸基およびその塩を含む化合物が挙げられ、無機化合物としては、リン酸、亜硫酸、亜硝酸、硝酸、硫酸等のアルカリ金属塩またはアンモニウム塩やシアン化アルカリ、シアン化アンモニウム等が挙げられる。また、これらの２種以上の組み合わせを用いることもできる。 As the conductive salt in the hard gold plating solution of the present invention, either an organic compound or an inorganic compound can be used. Examples of the organic compound include citric acid, tartaric acid, adipic acid, malic acid, succinic acid, lactic acid, Examples include carboxylic acids such as benzoic acid and salts thereof, and compounds containing phosphonic acid groups and salts thereof. Inorganic compounds include alkali metal salts such as phosphoric acid, sulfurous acid, nitrous acid, nitric acid, sulfuric acid, ammonium salts, and cyanide. Examples include alkali and ammonium cyanide. A combination of two or more of these can also be used.
この伝導塩のめっき液中の濃度としては、０．１ｇ／Ｌ〜３００ｇ／Ｌの範囲が望ましい。より好ましい濃度は、１ｇ／Ｌ〜２００ｇ／Ｌである。 The concentration of the conductive salt in the plating solution is preferably in the range of 0.1 g / L to 300 g / L. A more preferable concentration is 1 g / L to 200 g / L.
本発明の硬質金系めっき液におけるキレート化剤としては、クエン酸、クエン酸カリウム、クエン酸ナトリウム、酒石酸、シュウ酸、コハク酸などのカルボキシル基含有化合物、ホスホン酸基またはその塩を分子内に有するホスホン酸基含有化合物などを用いることができる。ホスホン酸基含有化合物としては、例えば、アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸など分子内に複数のホスホン酸基を有する化合物またはそれらのアルカリ金属塩若しくはアンモニウム塩が含まれる。また、アンモニア、エチレンジアミン、トリエタノールアミンなどの窒素化合物を補助キレート化剤としてカルボキシル基含有化合物と共に用いることもできる。キレート化剤は、２種以上の組み合わせを用いることもできる。 As a chelating agent in the hard gold plating solution of the present invention, a carboxyl group-containing compound such as citric acid, potassium citrate, sodium citrate, tartaric acid, oxalic acid and succinic acid, a phosphonic acid group or a salt thereof is contained in the molecule. The phosphonic acid group containing compound etc. which have can be used. As the phosphonic acid group-containing compound, for example, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and the like have a plurality of phosphonic acid groups in the molecule. Compounds or their alkali metal or ammonium salts are included. Moreover, nitrogen compounds, such as ammonia, ethylenediamine, and triethanolamine, can also be used with a carboxyl group-containing compound as an auxiliary chelating agent. A chelating agent can also use 2 or more types of combinations.
このキレート化剤のめっき液中の濃度としては、０．１ｇ／Ｌ〜３００ｇ／Ｌの範囲が望ましい。０．１ｇ／Ｌ未満であると、キレート化の作用が働かなくなる傾向となり、３００ｇ／Ｌを超えると、めっき液中に溶解できなくなる傾向となる。より好ましい濃度は、１ｇ／Ｌ〜２００ｇ／Ｌである。 The concentration of the chelating agent in the plating solution is preferably in the range of 0.1 g / L to 300 g / L. When the amount is less than 0.1 g / L, the chelating action tends not to work, and when the amount exceeds 300 g / L, the chelating solution tends not to be dissolved. A more preferable concentration is 1 g / L to 200 g / L.
本発明の硬質金系めっき液における、１つ以上のニトロ基を有する芳香族化合物（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及び、ニトロ安息香酸、ジニトロ安息香酸、ニトロベンゼンスルホン酸を除く）は、めっき液に添加すると、選択的な部分めっき処理が可能となり、不必要な部分への硬質金系めっきの析出が効果的に抑制される。 An aromatic compound having one or more nitro groups in the hard gold plating solution of the present invention (having one or more nitrogen atoms in the ring, and at least one nitro group is substituted on the carbon atom in the ring) (Excluding nitrobenzoic acid, dinitrobenzoic acid, and nitrobenzenesulfonic acid), selective partial plating is possible when added to the plating solution, and hard gold plating is applied to unnecessary parts. Precipitation is effectively suppressed.
この１つ以上のニトロ基を有する芳香族化合物（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及び、ニトロ安息香酸、ジニトロ安息香酸、ニトロベンゼンスルホン酸を除く）のめっき液中の濃度としては、０．０１ｇ／Ｌ〜３０ｇ／Ｌの範囲が望ましい。０．０１ｇ／Ｌ未満であると、不必要な部分への金合金めっきの析出が生じやすくなる。また、３０ｇ／Ｌを超えると、めっき析出量が全体的に抑制され過ぎて、必要個所への硬質金系めっきが困難となる傾向となる。より好ましい濃度は、０．０５ｇ／Ｌ〜１５ｇ／Ｌである。 An aromatic compound having one or more nitro groups (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, and nitrobenzoic acid) The concentration in the plating solution of acid, dinitrobenzoic acid and nitrobenzenesulfonic acid is preferably in the range of 0.01 g / L to 30 g / L. If it is less than 0.01 g / L, deposition of gold alloy plating on unnecessary portions tends to occur. On the other hand, if it exceeds 30 g / L, the plating deposition amount is excessively suppressed as a whole, and it becomes difficult to perform hard gold plating on a necessary portion. A more preferable concentration is 0.05 g / L to 15 g / L.
本発明における硬質金系めっき液は、上記した基本組成に加え、ｐＨ調整剤、緩衝剤などを含むことも可能である。ｐＨ調整剤としては、アルカリ金属水酸化物、例えば、クエン酸カリウム、水酸化カリウムなど、または酸性物質、例えばクエン酸、燐酸などを用いることができる。また、緩衝剤としては、クエン酸、酒石酸、シュウ酸、コハク酸、リン酸、亜硫酸またはこれらの塩などを用いることができる。 In addition to the basic composition described above, the hard gold plating solution in the present invention can also contain a pH adjusting agent, a buffering agent and the like. As the pH adjuster, alkali metal hydroxides such as potassium citrate and potassium hydroxide, or acidic substances such as citric acid and phosphoric acid can be used. As the buffer, citric acid, tartaric acid, oxalic acid, succinic acid, phosphoric acid, sulfurous acid, or a salt thereof can be used.
上記した本発明に係る硬質金系めっき液は、そのめっき処理条件として、めっき液ｐＨをｐＨ３以上にすることが好ましく、液温５℃〜９０℃で行うことが好ましい。ｐＨ３未満であると、シアンガスの発生が生じやすくなる傾向となる。より好ましいめっき処理条件は、ｐＨ４以上、液温２０℃〜７０℃である。めっき処理時の電流密度については、その適用範囲が広く、めっき対象物、めっき装置、めっき液流量などの条件に合わせて、最適な電流密度値を選択することができる。本発明に係る硬質金系めっき液は、特に、高速めっき処理のような高電流密度のめっき処理条件に対応可能である。 The above-described hard gold plating solution according to the present invention preferably has a plating solution pH of 3 or more, and preferably at a solution temperature of 5 ° C. to 90 ° C. as the plating treatment condition. If the pH is less than 3, cyan gas is likely to be generated. More preferable plating treatment conditions are pH 4 or higher and a liquid temperature of 20 ° C to 70 ° C. About the current density at the time of a plating process, the applicable range is wide and it can select an optimal current density value according to conditions, such as a plating target object, a plating apparatus, and a plating solution flow rate. The hard gold plating solution according to the present invention is particularly applicable to high current density plating treatment conditions such as high-speed plating treatment.
本発明は、上記した本願発明の硬質金系めっき液を用いて、ニッケルめっきを施した下地表面に、めっき処理が必要な部分へ選択的に硬質金系めっき処理を行うことを特徴とする硬質金系めっき方法に関する。本発明に係る硬質金系
めっき液によれば、コネクターなどの電子部品において、必要な部分にのみ、硬質金系めっき処理を行うことが可能となり、良好な電気的な特性を有した電子部品を製造でき、使用する金量を抑制してコストの抑制が可能となる。
The present invention is characterized in that a hard gold plating process is selectively performed on a nickel plating-plated base surface using a hard gold plating solution of the present invention described above to a portion that needs to be plated. The present invention relates to a gold plating method. According to the hard gold-based plating solution according to the present invention, it is possible to perform a hard gold-based plating process only on a necessary portion in an electronic component such as a connector, and an electronic component having good electrical characteristics can be obtained. It can be manufactured and the amount of gold to be used can be suppressed to reduce costs.
本発明に係る硬質金系めっき液によれば、コネクターなどの電子部品において、必要な部分にのみ、硬質金系めっき処理が行うことが可能となる。特に、下地にニッケルめっきを施したものの表面に、硬質金系めっきを行う場合、選択的に部分めっき処理を行うことが可能となる。 According to the hard gold plating solution according to the present invention, it is possible to perform a hard gold plating process only on a necessary portion of an electronic component such as a connector. In particular, when hard gold plating is performed on the surface of the base plated with nickel, it is possible to selectively perform partial plating.
以下に、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
第一実施形態：本実施形態では、金−コバルト合金の硬質金系めっき液について、そのめっき特性を調査した結果について説明する。 1st embodiment: This embodiment demonstrates the result of having investigated the plating characteristic about the hard gold type plating solution of a gold-cobalt alloy.
この実施例１では、１つ以上のニトロ基を有する芳香族化合物として、ジニトロ安息香酸を用いて、ハルセル試験を行うことにより、その電着特性を調べた結果について説明する。硬質金系めっき液の組成は、以下のようにした。 In this Example 1, the results of examining the electrodeposition characteristics by conducting a Hull cell test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups will be described. The composition of the hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
硫酸コバルト ３．６ｇ／Ｌ（コバルト換算で０．７６ｇ／Ｌ）
クエン酸 １５０ｇ／Ｌ
水酸化カリウム ２０ｇ／Ｌ
ジニトロ安息香酸 １ｇ／Ｌ、５ｇ／Ｌ
ｐＨ ４．４
液温 ６０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Cobalt sulfate 3.6 g / L (0.76 g / L in terms of cobalt)
Citric acid 150g / L
Potassium hydroxide 20g / L
Dinitrobenzoic acid 1g / L, 5g / L
pH 4.4
Liquid temperature 60 ℃
ハルセル試験は、市販のハルセル試験器（山本鍍金試験器社製）を用い、めっき対象の基材は、真鍮製ハルセル板（縦７０ｍｍ、横１００ｍｍ、厚さ０．３ｍｍ）にニッケルめっき（厚さ１０μｍ）を両面に施したものを使用した。めっき処理時間は、３０秒間で、通電電流を３Ａとした。また、めっき処理中は、めっき液を強撹拌した。 The hull cell test uses a commercially available hull cell tester (manufactured by Yamamoto Kakin Tester Co., Ltd.), and the substrate to be plated is nickel-plated (thickness 70 mm, width 100 mm, thickness 0.3 mm) on a brass hull cell plate. 10 μm) was used on both sides. The plating treatment time was 30 seconds, and the energization current was 3A. During the plating process, the plating solution was vigorously stirred.
ハルセル評価は、めっき処理したハルセル板の９個所のめっき膜厚を測定することにより行った。このハルセル板の９個所は、ハルセル試験器の内部底面に接したハルセル板底辺から約２ｃｍ上側の部分（めっき液に浸せきした部分）で、水平方向に、ハルセル板幅方向に所定間隔を明けて選択した。また、めっき膜厚は、蛍光Ｘ線膜厚測定器（エスアイアイ・ナノテクノロジー（株）社製）によって測定した。膜厚を測定した９個所の各ポイント（Ｎｏ．１〜９）における、おおよその各電流密度値は、Ｎｏ．１が０．３Ａ／ｄｍ２、Ｎｏ．２が１Ａ／ｄｍ２、Ｎｏ．３が２Ａ／ｄｍ２、Ｎｏ．４が３Ａ／ｄｍ２、Ｎｏ．５が４Ａ／ｄｍ２、Ｎｏ．６が５．５Ａ／ｄｍ２、Ｎｏ．７が７．５Ａ／ｄｍ２、Ｎｏ．８が１０Ａ／ｄｍ２、Ｎｏ．９が１３．５Ａ／ｄｍ２であった。このハルセル評価は、めっき処理がされたハルセル板表面と、その裏面との両面について行った。表１に各ポイントの膜厚を測定した結果を示す。尚、上記した９個所の電流密度値は、ハルセル板の表面側の電流密度を示すもので、ハルセル板の裏面側の電流密度値は不明である。ハルセル板の裏面側では、表面側に比べ、かなり低い電流密度値となる。 Hull cell evaluation was performed by measuring the plating film thickness of nine places of the plated hull cell plate. Nine locations on this Hull cell plate are the portion about 2 cm above the bottom of the Hull cell plate that touches the inner bottom surface of the Hull cell tester (the portion immersed in the plating solution), with a predetermined interval in the horizontal direction and in the width direction of the hull cell plate. Selected. Moreover, the plating film thickness was measured with a fluorescent X-ray film thickness measuring device (manufactured by SII Nanotechnology Co., Ltd.). The approximate current density values at the nine points (Nos. 1 to 9) at which the film thickness was measured are 1 is 0.3 A / dm 2 , No. 1 2 is 1 A / dm 2 , No. 2 3 is 2 A / dm 2 , No. 3 4 is 3 A / dm 2 , No. 4 5 is 4 A / dm 2 , No. 5 6 is 5.5 A / dm 2 , No. 6 7 is 7.5 A / dm 2 , No. 7 8 is 10 A / dm 2 , No. 8 9 was 13.5 A / dm 2 . This hull cell evaluation was performed on both the surface of the hull cell plate subjected to plating and the back surface thereof. Table 1 shows the results of measuring the film thickness at each point. The above nine current density values indicate the current density on the front side of the hull cell plate, and the current density value on the back side of the hull cell plate is unknown. On the back side of the hull cell plate, the current density value is considerably lower than that on the front side.
表１には、比較のために、ジニトロ安息香酸を添加していないブランクの硬質金系めっき液の結果も示している。この表１に示す１〜９の番号は、ハルセル板の９個所において測定ポイントを示しており、ハイフンの列の結果がブランクの硬質金系めっき液の結果であり、１ｇ／Ｌ、５ｇ／Ｌの各列が、その濃度のジニトロ安息香酸を含む硬質金系めっき液の結果である（以下に示すハルセル板の膜厚測定結果の表についても同様である）。ハルセル板表面の膜厚測定の結果を見ると判るように、ジニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。また、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。さらに、ブランクの場合では、ハルセル板裏面側にも硬質金系めっきがされていたが、ジニトロ安息香酸を添加すると、裏面側にはほとんどめっき処理がされないことが判明した。 Table 1 also shows the results of a blank hard gold plating solution to which no dinitrobenzoic acid was added for comparison. The numbers 1 to 9 shown in Table 1 indicate the measurement points at nine locations on the Hull cell plate, and the result of the hyphen row is the result of the blank hard gold plating solution. 1 g / L, 5 g / L Are the results of the hard gold-based plating solution containing dinitrobenzoic acid at that concentration (the same applies to the table of film thickness measurement results of the hull cell plate shown below). As can be seen from the results of the film thickness measurement on the surface of the Hull cell plate, it was found that the addition of dinitrobenzoic acid sharply decreased the plating film thickness on the low current density side. Further, it was found that when the addition amount is 5 g / L, plating on the low current density side is further suppressed. Further, in the case of the blank, hard gold plating was also performed on the back side of the hull cell plate, but it was found that when dinitrobenzoic acid was added, the back side was hardly plated.
この実施例２では、１つ以上のニトロ基を有する芳香族化合物として、ニトロ安息香酸を用いた。この実施例２の硬質金系めっき液の組成は、実施例１と同じで、実施例１のジニトロ安息香酸の替わりにニトロ安息香酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価も実施例１と同様とした。表２に、実施例２による各ポイントの膜厚を測定した結果を示す。 In Example 2, nitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 2 is the same as that of Example 1, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 1. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 2 shows the results of measuring the film thickness at each point according to Example 2.
表２に示す結果を見ると判るように、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 2, when nitrobenzoic acid was added, it was found that the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzoic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例３では、１つ以上のニトロ基を有する芳香族化合物としてニトロベンゼンスルホン酸を用いた。この実施例３の硬質金系めっき液の組成は、実施例１と同じで、実施例１のジニトロ安息香酸の替わりに、ニトロベンゼンスルホン酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価も実施例１と同様とした。表３に、実施例３による各ポイントの膜厚を測定した結果を示す。 In Example 3, nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 3 is the same as that of Example 1, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 1. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 3 shows the results of measuring the film thickness at each point according to Example 3.
表３に示す結果を見ると判るように、ニトロベンゼンスルホン酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロベンゼンスルホン酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 3, it was found that when nitrobenzene sulfonic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzenesulfonic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例４では、１つ以上のニトロ基を有する芳香族化合物としてジニトロ安息香酸を用いて、高速部分めっき試験を行うことにより、その電着特性を調べた結果について説明する。金−コバルト合金の硬質金系めっき液の組成は、以下のようにした。 In Example 4, the results of examining the electrodeposition characteristics of a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups will be described. The composition of the gold-cobalt alloy hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
硫酸コバルト ３．６ｇ／Ｌ（コバルト換算で０．７６ｇ／Ｌ）
クエン酸 １５０ｇ／Ｌ
水酸化カリウム ２０ｇ／Ｌ
ジニトロ安息香酸 ０．５ｇ／Ｌ、１．０ｇ／Ｌ、
１．５ｇ／Ｌ、２．０ｇ／Ｌ、
３．０ｇ／Ｌ、５．０ｇ／Ｌ
ｐＨ ４．４
液温 ６０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Cobalt sulfate 3.6 g / L (0.76 g / L in terms of cobalt)
Citric acid 150g / L
Potassium hydroxide 20g / L
Dinitrobenzoic acid 0.5 g / L, 1.0 g / L,
1.5 g / L, 2.0 g / L,
3.0g / L, 5.0g / L
pH 4.4
Liquid temperature 60 ℃
高速部分めっき試験では、被めっき物として真鍮板にニッケルめっき（１０μｍ厚）を施したものを使用した。金めっき皮膜の析出選択性を確認するために、直径９ｍｍの円形の部分が露出した状態となるように、シリコンパッキンにより液密的にシールされるようにした。ただし、円形の露出した部分の一端から延びる溝（幅２ｍｍ、長さ２０ｍｍ、深さ３mm）を、ニッケルめっきとシリコンパッキンのマスクとの間に形成した。シリコンパッキンでマスクされていない露出した円形部分に対してめっき液を噴流すると、円形部分にめっきが形成され、めっき液は溝部分に形成された間隙を通過して、溝部分の終端側から排出されるようになっている。この溝部分はマスクがその上部に存在するため、マスクのない円形の露出部分に比較して、電解時には低電流密度部分となるものである。従って、この高速部分めっき装置によりめっき処理をした場合、円形部分にのみにめっき処理がされて、溝部分にはめっき処理が施されないことが理想的なめっき処理となる。 In the high-speed partial plating test, a brass plate subjected to nickel plating (10 μm thickness) was used as an object to be plated. In order to confirm the deposition selectivity of the gold plating film, it was liquid-tightly sealed with silicon packing so that a circular portion having a diameter of 9 mm was exposed. However, a groove (width 2 mm, length 20 mm, depth 3 mm) extending from one end of the circular exposed portion was formed between the nickel plating and the silicon packing mask. When the plating solution is jetted onto an exposed circular portion that is not masked with silicon packing, plating is formed in the circular portion, and the plating solution passes through the gap formed in the groove portion and is discharged from the end side of the groove portion. It has come to be. Since this groove portion has a mask above it, it becomes a low current density portion during electrolysis as compared with a circular exposed portion without a mask. Therefore, when plating is performed by this high-speed partial plating apparatus, it is an ideal plating process that only the circular portion is plated and the groove portion is not plated.
めっき処理条件は、流量は１５Ｌ／ｍｉｎ、電流密度５０Ａ／ｄｍ２に調整し、厚み０．５μｍの金−コバルト合金めっき膜を形成した。 The plating treatment conditions were adjusted to a flow rate of 15 L / min and a current density of 50 A / dm 2 to form a gold-cobalt alloy plating film having a thickness of 0.5 μm.
めっき液中のジニトロ安息香酸の濃度を変えた時のめっき状態を外観にて観察したところ、ジニトロ安息香酸の添加量が多くなるほど、溝部分にはめっき処理がされないようになることが判明した。 When the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, it was found that as the amount of dinitrobenzoic acid added increased, the groove portion was not plated.
そこで、各濃度でめっき処理した試験サンプルについて、その溝部分の４個所のめっき膜厚を測定し、その平均めっき膜厚を調査した。その結果を表４に示す。このめっき膜厚は、蛍光Ｘ線膜厚測定器（エスアイアイ・ナノテクノロジー（株）社製）によって測定した。 Then, about the test sample plated with each density | concentration, the plating film thickness of four places of the groove part was measured, and the average plating film thickness was investigated. The results are shown in Table 4. This plating film thickness was measured with a fluorescent X-ray film thickness measuring instrument (manufactured by SII Nanotechnology Inc.).
表４の結果より、めっき液中のジニトロ安息香酸の濃度が大きくなると、基板の円形めっき部分に選択的にめっき処理が進行し、めっき処理の不必要な部分の溝部分にはめっき処理がされないことが判明した。 From the results shown in Table 4, when the concentration of dinitrobenzoic acid in the plating solution increases, the plating process proceeds selectively to the circular plating part of the substrate, and the groove part of the unnecessary part of the plating process is not plated. It has been found.
第二実施形態：本実施形態では、金−ニッケル合金の硬質金系めっき液について、そのめっき特性を調査した結果について説明する。 Second Embodiment: In this embodiment, the results of investigating the plating characteristics of a hard gold plating solution of a gold-nickel alloy will be described.
この実施例５では、１つ以上のニトロ基を有する芳香族化合物として、ジニトロ安息香酸を用いた。硬質金系めっき液の組成は、以下のようにした。 In Example 5, dinitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
硫酸ニッケル ９ｇ／Ｌ（ニッケル換算で２ｇ／Ｌ）
クエン酸 １５０ｇ／Ｌ
水酸化カリウム ２０ｇ／Ｌ
ジニトロ安息香酸 １ｇ／Ｌ、５ｇ／Ｌ
ｐＨ ４．４
液温 ６０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Nickel sulfate 9g / L (2g / L in terms of nickel)
Citric acid 150g / L
Potassium hydroxide 20g / L
Dinitrobenzoic acid 1g / L, 5g / L
pH 4.4
Liquid temperature 60 ℃
ハルセル試験条件及び評価は実施例１と同様とした。表５に、実施例５による各ポイントの膜厚を測定した結果を示す。 The Hull cell test conditions and evaluation were the same as in Example 1. Table 5 shows the results of measuring the film thickness at each point according to Example 5.
表５には、比較のために、ジニトロ安息香酸を添加していないブランクの硬質金系めっき液の結果も示している。表５に示す結果を見ると判るように、上記第一実施形態の場合と同様に、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合では、ハルセル板裏面側にも硬質金系めっきがされていたが、ジニトロ安息香酸を添加すると、裏面側にはほとんどめっき処理がされないことが判明した。 Table 5 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison. As can be seen from the results shown in Table 5, when nitrobenzoic acid was added, the plating film thickness on the low current density side was abruptly reduced as in the case of the first embodiment. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. In the case of the blank, hard gold plating was also performed on the back side of the hull cell plate, but it was found that when dinitrobenzoic acid was added, the back side was hardly plated.
この実施例６では、１つ以上のニトロ基を有する芳香族化合物として、ニトロ安息香酸を用いた。この実施例６の硬質金系めっき液の組成は、実施例５と同じで、実施例５のジニトロ安息香酸の替わりに、ニトロ安息香酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価は実施例１と同様とした。表６に、実施例６による各ポイントの膜厚を測定した結果を示す。 In Example 6, nitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 6 is the same as that of Example 5 except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 5. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 6 shows the results of measuring the film thickness at each point according to Example 6.
表６に示す結果を見ると判るように、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 6, it was found that when nitrobenzoic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzoic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例７では、１つ以上のニトロ基を有する芳香族化合物としてニトロベンゼンスルホン酸を用いた。この実施例７の硬質金系めっき液の組成は、実施例５と同じで、実施例５のジニトロ安息香酸の替わりに、ニトロベンゼンスルホン酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価も実施例１と同様とした。表７に、実施例７による各ポイントの膜厚を測定した結果を示す。 In Example 7, nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 7 is the same as that of Example 5, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 5. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 7 shows the results of measuring the film thickness at each point according to Example 7.
表７に示す結果を見ると判るように、ニトロベンゼンスルホン酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロベンゼンスルホン酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 7, it was found that when nitrobenzenesulfonic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzenesulfonic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例８では、上記実施例４と同様に、１つ以上のニトロ基を有する芳香族化合物としてジニトロ安息香酸を用いて、高速部分めっき試験を行うことにより、その電着特性を調べた結果について説明する。金−ニッケル合金の硬質金系めっき液の組成は、以下のようにした。 In this Example 8, as in Example 4, the electrodeposition characteristics were examined by conducting a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described. The composition of the gold-nickel alloy hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
硫酸ニッケル ９ｇ／Ｌ（ニッケル換算で２ｇ／Ｌ）
クエン酸 １５０ｇ／Ｌ
水酸化カリウム ２０ｇ／Ｌ
ジニトロ安息香酸 ０．５ｇ／Ｌ、１．０ｇ／Ｌ、
１．５ｇ／Ｌ、２．０ｇ／Ｌ、
３．０ｇ／Ｌ、５．０ｇ／Ｌ
ｐＨ ４．４
液温 ６０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Nickel sulfate 9g / L (2g / L in terms of nickel)
Citric acid 150g / L
Potassium hydroxide 20g / L
Dinitrobenzoic acid 0.5 g / L, 1.0 g / L,
1.5 g / L, 2.0 g / L,
3.0g / L, 5.0g / L
pH 4.4
Liquid temperature 60 ℃
高速部分めっき試験の試験サンプル、装置、めっき条件等については、実施例４と同様にした。 The test sample, apparatus, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
この実施例８においても、めっき液中のジニトロ安息香酸の濃度を変えた時のめっき状態を外観にて観察したところ、ジニトロ安息香酸の添加量が多くなるほど、溝部分にはめっき処理がされないようになることが判明した。 In Example 8 as well, when the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, as the amount of dinitrobenzoic acid added increased, the groove portion was not plated. Turned out to be.
この実施例８において、上記実施例４と同様に溝部分の平均めっき膜厚を調査した結果を表８に示す。この膜厚調査に関しても、上記実施例４と同様にして行った。 In this Example 8, the results of investigating the average plating film thickness of the groove portions as in Example 4 are shown in Table 8. This film thickness investigation was performed in the same manner as in Example 4 above.
表８の結果より、上記実施例４と同様に、めっき液中のジニトロ安息香酸の濃度が大きくなると、基板の円形めっき部分に選択的にめっき処理が進行し、めっき処理の不必要な部分の溝部分にはめっき処理がされないことが判明した。 From the results of Table 8, as in Example 4 above, when the concentration of dinitrobenzoic acid in the plating solution increases, the plating process proceeds selectively to the circular plating part of the substrate, and the unnecessary part of the plating process is obtained. It was found that the groove was not plated.
第三実施形態：本実施形態では、金−銀合金の硬質金系めっき液について、そのめっき特性を調査した結果について説明する。 Third Embodiment: In this embodiment, the results of investigating the plating characteristics of a hard gold plating solution of a gold-silver alloy will be described.
この実施例９では、１つ以上のニトロ基を有する芳香族化合物として、ジニトロ安息香酸を用いた。硬質金系めっき液の組成は、以下のようにした。 In Example 9, dinitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
シアン化銀 １０ｇ／Ｌ（銀換算で８ｇ／Ｌ）
シアン化カリウム ５０ｇ／Ｌ
ジニトロ安息香酸 １ｇ／Ｌ、５ｇ／Ｌ
ｐＨ １２
液温 ２０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Silver cyanide 10g / L (8g / L in terms of silver)
Potassium cyanide 50g / L
Dinitrobenzoic acid 1g / L, 5g / L
pH 12
Liquid temperature 20 ℃
ハルセル試験条件及び評価は実施例１と同様とした。表９に、実施例９による各ポイントの膜厚を測定した結果を示す。 The Hull cell test conditions and evaluation were the same as in Example 1. Table 9 shows the results of measuring the film thickness at each point according to Example 9.
表９には、比較のために、ジニトロ安息香酸を添加していないブランクの硬質金系めっき液の結果も示している。表９に示す結果を見ると判るように、上記第一実施形態の場合と同様に、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ジニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 Table 9 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison. As can be seen from the results shown in Table 9, when nitrobenzoic acid was added, the plating film thickness on the low current density side was abruptly reduced as in the case of the first embodiment. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank case, it was found that when dinitrobenzoic acid was added, there was almost no plating treatment on the back side of the hull cell plate.
この実施例１０では、１つ以上のニトロ基を有する芳香族化合物として、ニトロ安息香酸を用いた。この実施例１０の硬質金系めっき液の組成は、実施例９と同じで、実施例１０のジニトロ安息香酸の替わりに、ニトロ安息香酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価は実施例１と同様とした。表１０に、実施例１０における各ポイントの膜厚を測定した結果を示す。 In Example 10, nitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 10 is the same as that of Example 9, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 10. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 10, the result of having measured the film thickness of each point in Example 10 is shown.
表１０に示す結果を見ると判るように、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 10, it was found that when nitrobenzoic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzoic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例１１では、１つ以上のニトロ基を有する芳香族化合物としてニトロベンゼンスルホン酸を用いた。この実施例１１の硬質金系めっき液の組成は、実施例９と同じで、実施例９のジニトロ安息香酸の替わりに、ニトロベンゼンスルホン酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価も実施例１と同様とした。表１１に、実施例１１における各ポイントの膜厚を測定した結果を示す。 In Example 11, nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 11 is the same as that of Example 9, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 9. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 11, the result of having measured the film thickness of each point in Example 11 is shown.
表１１に示す結果を見ると判るように、ニトロベンゼンスルホン酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロベンゼンスルホン酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 11, when nitrobenzenesulfonic acid was added, it was found that the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzenesulfonic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例１２では、上記実施例４と同様に、１つ以上のニトロ基を有する芳香族化合物としてジニトロ安息香酸を用いて、高速部分めっき試験を行うことにより、その電着特性を調べた結果について説明する。金−銀合金の硬質金系めっき液の組成は、以下のようにした。 In this Example 12, as in Example 4, the electrodeposition characteristics were examined by conducting a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described. The composition of the gold-silver alloy hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
シアン化銀 １０ｇ／Ｌ（銀換算で８ｇ／Ｌ）
シアン化カリウム ５０ｇ／Ｌ
ジニトロ安息香酸 ０．５ｇ／Ｌ、１．０ｇ／Ｌ、
１．５ｇ／Ｌ、２．０ｇ／Ｌ、
３．０ｇ／Ｌ、５．０ｇ／Ｌ
ｐＨ １２
液温 ２０℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Silver cyanide 10g / L (8g / L in terms of silver)
Potassium cyanide 50g / L
Dinitrobenzoic acid 0.5 g / L, 1.0 g / L,
1.5 g / L, 2.0 g / L,
3.0g / L, 5.0g / L
pH 12
Liquid temperature 20 ℃
高速部分めっき試験の試験サンプル、装置、めっき条件等については、実施例４と同様にした。 The test sample, apparatus, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
この実施例１２においても、めっき液中のジニトロ安息香酸の濃度を変えた時のめっき状態を外観にて観察したところ、ジニトロ安息香酸の添加量が多くなるほど、溝部分にはめっき処理がされないようになることが判明した。 Also in this Example 12, when the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, as the amount of dinitrobenzoic acid added increased, the groove portion was not plated. Turned out to be.
この実施例１２において、上記実施例４と同様に溝部分の平均めっき膜厚を調査した結果を表１２に示す。この膜厚調査に関しても、上記実施例４と同様にして行った。 In this Example 12, the results of investigating the average plating film thickness of the groove portions as in Example 4 are shown in Table 12. This film thickness investigation was performed in the same manner as in Example 4 above.
表１２の結果より、上記実施例４と同様に、めっき液中のジニトロ安息香酸の濃度が大きくなると、基板の円形めっき部分に選択的にめっき処理が進行し、めっき処理の不必要な部分の溝部分にはめっき処理がされないことが判明した。 From the results of Table 12, as in Example 4 above, when the concentration of dinitrobenzoic acid in the plating solution increases, the plating process proceeds selectively to the circular plating part of the substrate, and the unnecessary part of the plating process is obtained. It was found that the groove was not plated.
第四実施形態：本実施形態では、金のみの硬質金系めっき液について、そのめっき特性を調査した結果について説明する。硬質化に寄与する有機添加剤としてはポリエチレンアミンを用いた。 Fourth Embodiment: In this embodiment, the results of investigating the plating characteristics of a hard gold plating solution containing only gold will be described. Polyethyleneamine was used as an organic additive that contributes to hardening.
この実施例１３では、１つ以上のニトロ基を有する芳香族化合物としてジニトロ安息香酸を用いた。金のみの硬質金系めっき液の組成は、以下のようにした。 In Example 13, dinitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution containing only gold was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
ポリエチレンアミン １０ｇ／Ｌ
クエン酸 １５０ｇ／Ｌ
ジニトロ安息香酸 １ｇ／Ｌ、５ｇ／Ｌ
ｐＨ ７
液温 ６５℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Polyethyleneamine 10g / L
Citric acid 150g / L
Dinitrobenzoic acid 1g / L, 5g / L
pH 7
Liquid temperature 65 ℃
ハルセル試験条件及び評価は実施例１と同様とした。表１３に、実施例１３による各ポイントの膜厚を測定した結果を示す。 The Hull cell test conditions and evaluation were the same as in Example 1. Table 13 shows the results of measuring the film thickness at each point according to Example 13.
表１３には、比較のために、ジニトロ安息香酸を添加していないブランクの硬質金系めっき液の結果も示している。表１３に示す結果を見ると判るように、上記第一実施形態の場合と同様に、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ジニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 Table 13 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison. As can be seen from the results shown in Table 13, as in the case of the first embodiment described above, it was found that when nitrobenzoic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank case, it was found that when dinitrobenzoic acid was added, there was almost no plating treatment on the back side of the hull cell plate.
この実施例１４では、１つ以上のニトロ基を有する芳香族化合物として、ニトロ安息香酸を用いた。この実施例１４の硬質金系めっき液の組成は、実施例１３と同じで、実施例１３のジニトロ安息香酸の替わりに、ニトロ安息香酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価は実施例１と同様とした。表１４に、実施例１３における各ポイントの膜厚を測定した結果を示す。 In Example 14, nitrobenzoic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 14 is the same as that of Example 13, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 13. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 14, the result of having measured the film thickness of each point in Example 13 is shown.
表１４に示す結果を見ると判るように、ニトロ安息香酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロ安息香酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 14, it was found that when nitrobenzoic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzoic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例１５では、１つ以上のニトロ基を有する芳香族化合物としてニトロベンゼンスルホン酸を用いた。この実施例１５の硬質金系めっき液の組成は、実施例１３と同じで、実施例９のジニトロ安息香酸の替わりに、ニトロベンゼンスルホン酸を用いた点のみが異なる。また、ハルセル試験条件及びその評価も実施例１と同様とした。表１５に、実施例１５における各ポイントの膜厚を測定した結果を示す。 In Example 15, nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups. The composition of the hard gold plating solution of Example 15 is the same as that of Example 13 except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 9. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 15 shows the results of measuring the film thickness at each point in Example 15.
表１５に示す結果を見ると判るように、ニトロベンゼンスルホン酸を添加すると、低電流密度側のめっき膜厚が急激に減少することが判明した。そして、その添加量を５ｇ／Ｌにすると、低電流密度側のめっきがさらに抑制されることが判った。また、ブランクの場合と異なり、ニトロベンゼンスルホン酸を添加すると、ハルセル板裏面側にはほとんどめっき処理がされないことが判明した。 As can be seen from the results shown in Table 15, it was found that when nitrobenzene sulfonic acid was added, the plating film thickness on the low current density side rapidly decreased. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed. Also, unlike the blank, it was found that when nitrobenzenesulfonic acid was added, the Hull cell plate was hardly plated on the back side.
この実施例１６では、上記実施例４と同様に、１つ以上のニトロ基を有する芳香族化合物としてジニトロ安息香酸を用いて、高速部分めっき試験を行うことにより、その電着特性を調べた結果について説明する。硬質金系めっき液の組成は、以下のようにした。 In Example 16, as in Example 4, the electrodeposition characteristics were examined by performing a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described. The composition of the hard gold plating solution was as follows.
シアン化第一金カリウム １２ｇ／Ｌ（金換算で８ｇ／Ｌ）
ポリエチレンアミン １０ｇ／Ｌ
クエン酸 １５０ｇ／Ｌ
ジニトロ安息香酸 ０．５ｇ／Ｌ、１．０ｇ／Ｌ、
１．５ｇ／Ｌ、２．０ｇ／Ｌ、
３．０ｇ／Ｌ、５．０ｇ／Ｌ
ｐＨ ７
液温 ６５℃
Potassium cyanide potassium 12g / L (8g / L in terms of gold)
Polyethyleneamine 10g / L
Citric acid 150g / L
Dinitrobenzoic acid 0.5 g / L, 1.0 g / L,
1.5 g / L, 2.0 g / L,
3.0g / L, 5.0g / L
pH 7
Liquid temperature 65 ℃
高速部分めっき試験の試験サンプル、装置、めっき条件等については、実施例４と同様にした。 The test sample, apparatus, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
この実施例１６においても、めっき液中のジニトロ安息香酸の濃度を変えた時のめっき状態を外観にて観察したところ、ジニトロ安息香酸の添加量が多くなるほど、溝部分にはめっき処理がされないようになることが判明した。 In Example 16 as well, when the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, as the amount of dinitrobenzoic acid added increased, the groove portion was not plated. Turned out to be.
この実施例１６において、上記実施例４と同様に溝部分の平均めっき膜厚を調査した結果を表１６に示す。この膜厚調査に関しても、上記実施例４と同様にして行った。 In this Example 16, the results of investigating the average plating film thickness of the groove portions as in Example 4 are shown in Table 16. This film thickness investigation was performed in the same manner as in Example 4 above.
表１６の結果より、上記実施例４と同様に、めっき液中のジニトロ安息香酸の濃度が大きくなると、基板の円形めっき部分に選択的にめっき処理が進行し、めっき処理の不必要な部分の溝部分にはめっき処理がされないことが判明した。 From the results of Table 16, as in Example 4 above, when the concentration of dinitrobenzoic acid in the plating solution increases, the plating process proceeds selectively to the circular plating part of the substrate, and the unnecessary part of the plating process is obtained. It was found that the groove was not plated.
本発明によれば、コネクターなどの電子部品において、必要な部分にのみ、硬質金系めっき処理が行うことが可能となる。特に、下地にニッケルめっきを施したものの表面に、硬質金系めっきを行う場合、選択的に部分めっき処理を行うことが可能となる。 According to the present invention, in an electronic component such as a connector, it is possible to perform a hard gold plating process only on a necessary portion. In particular, when hard gold plating is performed on the surface of the base plated with nickel, it is possible to selectively perform partial plating.
Claims (4)
１つ以上のニトロ基を有する芳香族化合物（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及び、ニトロ安息香酸、ジニトロ安息香酸、ニトロベンゼンスルホン酸を除く）を含有することを特徴とする硬質金系めっき液。 In a hard gold plating solution containing a soluble gold salt or gold complex, a conductive salt, a chelating agent and containing cyanide,
Aromatic compounds having one or more nitro groups (heterocyclic compounds having one or more nitrogen atoms in the ring, and one or more nitro groups substituted on carbon atoms in the ring, and nitrobenzoic acid And a hard gold plating solution characterized by containing dinitrobenzoic acid and nitrobenzenesulfonic acid).
ニッケルめっきを施した下地表面に、めっき処理が必要な部分へ選択的に硬質金系めっき処理を行うことを特徴とする硬質金系めっき方法。 An aromatic compound containing a soluble gold salt or gold complex, a conductive salt, a chelating agent, and cyanide and having one or more nitro groups (having one or more nitrogen atoms in the ring, and carbon atoms in the ring) A hard gold plating method using a hard gold plating solution containing a heterocyclic compound in which at least one nitro group is substituted in
A hard gold plating method, characterized in that a hard gold plating process is selectively performed on a portion that needs to be plated on a nickel-plated base surface.
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| JP2016117946A (en) * | 2014-11-21 | 2016-06-30 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Environmentally friendly gold electroplating compositions and methods |
| WO2022039171A1 (en) * | 2020-08-19 | 2022-02-24 | 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 | Cyanide-based silver alloy electroplating solution |
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