WO2006016603A1 - Tin-zinc alloy electroplating method - Google Patents
Tin-zinc alloy electroplating method Download PDFInfo
- Publication number
- WO2006016603A1 WO2006016603A1 PCT/JP2005/014648 JP2005014648W WO2006016603A1 WO 2006016603 A1 WO2006016603 A1 WO 2006016603A1 JP 2005014648 W JP2005014648 W JP 2005014648W WO 2006016603 A1 WO2006016603 A1 WO 2006016603A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tin
- zinc alloy
- plating bath
- acid
- zinc
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 30
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000009713 electroplating Methods 0.000 title claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 75
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 4
- -1 organic acid ester Chemical class 0.000 claims description 36
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940044654 phenolsulfonic acid Drugs 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 2
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QPNXDYIIMODUQF-UHFFFAOYSA-N 1,3-dichloropropane-1,2,3-triol Chemical compound OC(Cl)C(O)C(O)Cl QPNXDYIIMODUQF-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- HQNBJNDMPLEUDS-UHFFFAOYSA-N 1,5-dimethylimidazole Chemical compound CC1=CN=CN1C HQNBJNDMPLEUDS-UHFFFAOYSA-N 0.000 description 1
- NYYVCPHBKQYINK-UHFFFAOYSA-N 1-ethyl-2-methylimidazole Chemical compound CCN1C=CN=C1C NYYVCPHBKQYINK-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
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- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PVRATXCXJDHJJN-UHFFFAOYSA-N dimethyl 2,3-dihydroxybutanedioate Chemical compound COC(=O)C(O)C(O)C(=O)OC PVRATXCXJDHJJN-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- RAHHITDKGXOSCO-UHFFFAOYSA-N ethene;hydrochloride Chemical compound Cl.C=C RAHHITDKGXOSCO-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ROBFUDYVXSDBQM-UHFFFAOYSA-L hydroxymalonate(2-) Chemical compound [O-]C(=O)C(O)C([O-])=O ROBFUDYVXSDBQM-UHFFFAOYSA-L 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- FIYXUOWXHWJDAM-UHFFFAOYSA-N methyl sulfamate Chemical compound COS(N)(=O)=O FIYXUOWXHWJDAM-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- WWJZZUYNODNLMZ-UHFFFAOYSA-M potassium;2,3-dihydroxybenzenesulfonate Chemical compound [K+].OC1=CC=CC(S([O-])(=O)=O)=C1O WWJZZUYNODNLMZ-UHFFFAOYSA-M 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MKRZFOIRSLOYCE-UHFFFAOYSA-L zinc;methanesulfonate Chemical compound [Zn+2].CS([O-])(=O)=O.CS([O-])(=O)=O MKRZFOIRSLOYCE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- 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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- 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
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
Definitions
- the present invention relates to a tin-zinc alloy electroplating method.
- tin-zinc alloy electroplating Since tin-zinc alloy electroplating is excellent in corrosion resistance, workability, and solderability, it has been attracting attention and widely used as an industrial plating for automobile parts and electronic parts.
- As the baths used for the tin-zinc alloy electroplating alkali cyan baths, phosphoric acid phosphate baths, borofluoride baths, sulfonic acid baths, carboxylic acid baths, etc. have been proposed and partially put into practical use. Has reached.
- An object of the present invention is to provide an electroplating method that enables processing in a short time, which has been difficult with conventional tin-zinc alloy electroplating.
- the present invention makes it possible to electroplat tin-zinc alloy in a short time by using a specific tin-zinc alloy plating bath with the plating bath temperature and plating solution stirring speed set to a predetermined level or higher. It was made based on the knowledge.
- the present invention provides a plating bath temperature of 30 to 90 ° C., and a plating solution stirring speed of 5 to 300 mZ.
- tin-zinc alloy can be electroplated in a short time by setting the plating bath temperature and the stirring speed of the plating solution to a predetermined level or more and using a specific tin-palladium alloy plating bath. Can be.
- the plating bath temperature is 30 to 90 ° C, preferably 40 to 60 ° C
- the stirring speed of the plating solution is 5 to 300 mZmin, preferably 10 to 100 mZmin.
- the stirring of the plating solution can be applied by a jet type plating device or a steel plate plating device in which the solution is circulated by a pump.
- the plating equipment is made of a heat-resistant and chemical-resistant material, metals such as stainless steel and titanium, salt vinyl, Teflon (registered trademark), and ABS resin can be used.
- an apparatus capable of obtaining a uniform plating solution stirring speed over the entire object to be plated is desirable.
- any plating bath known to those skilled in the art can be used.
- it contains a hydroxycarboxylic acid or a salt thereof. It is a bathing bath.
- hydroxycarboxylic acid a compound having 1 or 2 or more hydroxy groups and 1 or 2 or more carboxyl groups in one molecule is preferable! /.
- hydroxycarboxylic acids include citrate, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, ⁇ -hydroxypropionic acid and darconic acid.
- citrate, tartaric acid, malic acid and darconic acid are used.
- hydroxycarboxylates include alkali metal salts (sodium, potassium, lithium salts) of the above hydroxycarboxylic acids, alkaline earth metal salts (magnesium, calcium, barium salts, etc.), and divalent tin salts.
- Zinc salts, ammonium salts and organic amine salts (monomethylamine, dimethylamine, trimethylamine, ethylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.).
- These hydroxycarboxylic acids and salts thereof may be used alone or
- the concentration in the plating bath in which two or more kinds may be used in combination is 0.25 to 3 molZL, preferably 0.3 to 1.5 molZL.
- hydroxycarboxylic acid which is a counter ion of the metal ion, also constitutes a part of the above concentration.
- the pH of the bath containing hydroxycarboxylic acid or a salt thereof is preferably 2 to 10, more preferably 3 to 9.
- the pH of the plating bath can be adjusted using an alkaline compound such as a hydroxide or carbonate or an acidic compound such as an inorganic acid or an organic acid.
- alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, aqueous ammonia, sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid.
- acidic compounds such as phenolsulfonic acid.
- a group comprising a water-soluble compound obtained by reacting an aliphatic amine, an organic acid ester and phthalic anhydride, and an amphoteric surfactant. It is also possible to use a bath with one or more selected power. Specifically, for example, 0.2 to 3 mol of an organic acid ester is reacted at a temperature of 50 to 99 ° C. for 10 to 60 minutes per 1 mol of an aliphatic amine, and the reactive product 1 obtained by weight ratio is reacted.
- Examples thereof include water-soluble compounds obtained by reacting phthalic anhydride 0.1 to 1 at a temperature of 60 to 130 ° C for 30 to 180 minutes.
- Examples of amphoteric surfactants include imidazoline type, betaine type, alanine type, glycine type and amide type.
- Examples of the aliphatic amine used for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isoptylamine, 3-methoxypropylamine, iminobispropylamine, jetylamine, hexamethyltetramine, dimethylaminopropylamine and the like.
- organic acid ester examples include dimethyl malonate, cetyl succinate, methyl maleate, dimethyl fumarate, dimethyl tartrate, dimethyl malate, and jetyl tartronate. These water-soluble compounds and amphoteric surfactants may be used alone or in admixture of two or more.
- the content in the plating bath is 0.001 to 50 g ZL, preferably 0.01 to 30 g. / L.
- the pH of the bath containing one or more kinds selected from the group power consisting of a surfactant is preferably 2 to 10, more preferably 3 to 9.
- the pH of the plating bath can be adjusted by using an alkaline compound such as hydroxide or carbonate, or an acidic compound such as inorganic acid or organic acid.
- alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, aqueous ammonia, sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, fluoric acid, And acidic compounds such as ⁇ -nolusulfonic acid.
- a bath containing one or more selected from the group consisting of tertiary amine compounds and quaternary amine compounds may be used. it can.
- tertiary amine compounds include imidazole compounds and aliphatic amine compounds.
- quaternary amine compounds include reaction products of tertiary amine compounds and alkyl halides.
- Specific examples of the tertiary amine compound include imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole.
- 1oxymethylimidazole, 1 bwisemidazole and 1,5 dimethylimidazole, and aliphatic amines include monoethanolamine, jetanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispamine. Examples include oral pinoleamine, triethylenetetramine, tetraethylenepentamine, and N, N bis (3aminopropyl) ethylenediamine.
- halogenated alkyl to be reacted with the tertiary amine compound examples include monochloroacetic acid, benzyl chloride, chloracetamide, 3-aminobenzyl chloride, aryl chloride, dichloroethane, monochloropropane, dichloroglycerin, ethylene chlorohydride. Examples include phosphorus and epichlorohydrin. These tertiary amine compounds and quaternary amine compounds may be used alone or in admixture of two or more.
- the content of the plating bath is 0.1 to 30 g / L, preferably Is 0.2 ⁇ 20g / L
- a tertiary amine and a quaternary amine compound are also selected.
- the pH of the hot water bath containing one or more is preferably 10 to 14, more preferably 12 to 14.
- the pH of the bath can be adjusted using alkaline compounds such as hydroxides and carbonates. it can. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and aqueous ammonia.
- the tanning bath used in the electroplating method of the present invention further includes at least one surface activity selected from the group force consisting of a nonionic surfactant, a ionic surfactant and a cationic surfactant.
- An agent can also be contained. By containing these surfactants, precipitation at a high current density can be made dense, so that the electroplating method of the present invention can be smoothly carried out.
- the tin ion concentration of the plating bath used in the plating method of the present invention is 1 to 10 OgZL, preferably 5 to 80 gZL for divalent ions, and the zinc ion concentration is 0.2 to 80 gZL, preferably l. ⁇ 50gZL.
- these metal ion sources include hydroxide, oxide, sulfate, hydrochloride, sulfamate, pyrophosphate, hydroxycarboxylate, sulfonate, and amino acid salt of each metal. .
- Preferred are oxides, sulfates, hydrochlorides, and hydroxides of each metal.
- Specific examples of the hydroxycarboxylate include those exemplified above.
- the sulfonate include alkane sulfonate, alkane sulfonate, and phenol sulfonate.
- alkanesulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid and hexanesulfonic acid.
- Specific examples of the acid include 2-hydroxyethane sulfonic acid, 3-hydroxypropane sulfonic acid, and 2-hydroxybutane sulfonic acid.
- phenol sulfonic acid examples include phenol sulfonic acid, cresol sulfonic acid, and dimethyl phenol sulfonic acid.
- amino acids include glycine, glutamic acid, and alanine.
- sulfuric acid In the tanning bath used in the electroplating method of the present invention, sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxide, carbon Alkali metal salts (sodium, potassium, lithium salts), alkaline earth metal salts (magnesium, calcium, norlium salts), ammonium salts, organic amine salts (monomethylamine, dimethylamine, trimethyl) Amin, ethylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.).
- the content of these salts is 10 to 300 gZL, preferably 50 to 200 gZL.
- the tanning bath used in the electroplating method of the present invention can also contain additives used as tin and zinc brighteners in addition to the above-mentioned components.
- additives used as tin and zinc brighteners for example, synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, etc.), ketones (benzal acetone, acetophenone, etc.), aliphatic aldehydes (formalin, acetoaldehyde, crotonaldehyde, etc.), Aromatic aldehydes (vanillin, salicylaldehyde, olsochlorbenzaldehyde, etc.), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, etc.), Cu, Ni, Mn, Bi, In etc.
- additives contain 0.001 to 5 Og / preferably 0.005 to 30 g ZL.
- hydroxyphenol compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate, and salts thereof, L-corcorbic acid, sorbitol, and the like can also be used as antioxidants for tin.
- the object to be plated in the plating method of the present invention is a metal material of Fe, Ni, Cu, or an alloy based on these, and this is used as a cathode.
- a tin-zinc alloy or a Ti material in which Pt plating is applied, an insoluble electrode, a force-bonded electrode, or the like can be used.
- an insoluble anode the above-mentioned method of directly dissolving the tin and zinc metal salts in the sag solution or replenishing an aqueous solution in which the tin and zinc metal salts are dissolved at a high concentration is used.
- the metal concentration of the bath can be maintained.
- This high-concentration aqueous solution of the metal may contain the above hydroxycarboxylic acid or a salt thereof and a hydroxy-alkali compound.
- the cathode current density is 5 to 200 A / dm 2 , preferably 10 to 120 A / dm 2 , and the film thickness can be in a wide range, but is generally 0.5 to 500 ⁇ m, preferably 2 to 20 ⁇ m.
- tin-zinc alloy plating with a wide range of compositions can be applied.
- an electronic component can be tinned with a zinc content of 3 to 15%, which particularly enhances saltwater resistance and corrosion resistance.
- tin-zinc alloy plating with a zinc content of 15 to 45% can be applied.
- tin-zinc alloy plating with a zinc content of 50 to 90% can be applied.
- the object to be covered is subjected to a plating step after pretreatment by a conventional method.
- a pretreatment process at least one operation of immersion degreasing, pickling, electrolytic cleaning and activation is performed.
- the resulting film can be washed with water and dried, followed by conventional chromate treatment and chemical conversion treatment, or coating treatment with inorganic and organic substances.
- the present invention will be described by way of examples.
- the present invention is not limited thereto, and the plating solution temperature, the plating solution flow rate, and the composition of the bath used can be arbitrarily changed according to the purpose. it can.
- plating bath temperature 60 ° C.
- plating solution stirring speed 50 mZmin.
- Zinc oxide (as zinc) 5 g /
- electroplating was performed using the following plating bath under the conditions of plating bath temperature: 50 ° C. and plating solution stirring speed: 60 mZmin.
- Zinc methanesulfonate (Zinc and 15 g /
- the plating bath temperature of 23 ° C. and the plating solution stirring speed: 50 mZmin were applied using the plating bath of Example 1.
- the plating bath of Example 1 was used, and the plating bath temperature was 60 ° C., and the plating solution was stirred at a rate of 2 mZmin.
- the plating bath of Example 3 was used, and the plating bath temperature was 60 ° C., and the plating solution was stirred at a rate of 3 mZmin.
- Tables 1 and 2 show the precipitation states of Examples 1 to 5 and Comparative Examples 1 to 3, the alloy composition (% by weight) of the deposited film, the treatment time, and the film thickness.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Disclosed is an electroplating method realizing short-time processing which has been difficult for conventional tin-zinc alloy electroplating methods. Specifically disclosed is a method for performing tin-zinc alloy electroplating under the following conditions: the plating liquid temperature is 30-90˚C; the stirring rate of the plating liquid is 5-300 m/min; and the cathode current density is 5-200 A/dm2. Preferably, the divalent tin ion concentration in the tin-zinc alloy plating bath is 1-100 g/L, while the zinc ion concentration is 0.2-80 g/L.
Description
明 細 書 Specification
錫一亜鉛合金電気めつき方法 Tin-zinc alloy electroplating method
技術分野 Technical field
[0001] 本発明は錫—亜鉛合金電気めつき方法に関するものである。 [0001] The present invention relates to a tin-zinc alloy electroplating method.
背景技術 Background art
[0002] 錫—亜鉛合金電気めつきは耐食性、加工性、ハンダ付け性に優れているため自動 車部品や電子部品等の工業用めつきとして注目され広く使用されるようになってきた 。この錫一亜鉛合金電気めつきに使用されるめつき浴としては、アルカリシアン浴、ピ 口リン酸浴、ホウフッ化浴、スルホン酸浴、カルボン酸浴等が提案され、一部実用化さ れるに至っている。 [0002] Since tin-zinc alloy electroplating is excellent in corrosion resistance, workability, and solderability, it has been attracting attention and widely used as an industrial plating for automobile parts and electronic parts. As the baths used for the tin-zinc alloy electroplating, alkali cyan baths, phosphoric acid phosphate baths, borofluoride baths, sulfonic acid baths, carboxylic acid baths, etc. have been proposed and partially put into practical use. Has reached.
これらの電気めつき浴を使用した従来の方法では、処理時間を短縮するために高 電流密度で処理した場合、めっきの粗析出、ャケ、コゲ等が発生し、錫—亜鉛合金 めっきの特性を損なうため高速電気めつきの実用化は困難であった。実際、被めつき 物を治具に装着して処理するラック方式 (最大電流密度 3AZdm2程度)や被めつき 物をバレルに入れ処理するバレル方式 (最大電流密度 lAZdm2)が実用化されるに 留まっている。また、錫—亜鉛合金めつきを短時間で行う場合には、錫と亜鉛を各々 別個に電気めつきし合金化する方法や錫 亜鉛合金の溶融塩による溶融めつき法 が用いられてきた。 In the conventional methods using these electroplating baths, when the treatment is performed at a high current density in order to shorten the treatment time, rough deposition of the plating, cracks, burns, etc. occur and the characteristics of the tin-zinc alloy plating It was difficult to put high-speed electric plating into practical use. Actually, the rack method (maximum current density 3 AZdm 2 ) for mounting the object to be attached to a jig for processing and the barrel method (maximum current density lAZdm 2 ) for processing the object to be attached in a barrel are put into practical use. Stays on. Moreover, when tin-zinc alloy plating is performed in a short time, a method of separately plating tin and zinc to form an alloy and a method of melting tin tin alloy with a molten salt have been used.
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0003] 本発明は、従来の錫 亜鉛合金電気めつきでは困難であった短時間での処理を 可能にする電気めつき方法を提供することを目的とする。 [0003] An object of the present invention is to provide an electroplating method that enables processing in a short time, which has been difficult with conventional tin-zinc alloy electroplating.
課題を解決するための手段 Means for solving the problem
[0004] 本発明は、めっき浴温、めっき液の攪拌速度を所定以上とし、特定の錫—亜鉛合 金めつき浴を使用することで、短時間で錫 亜鉛合金電気めつきが可能であるとの 知見に基づきなされたものである。 [0004] The present invention makes it possible to electroplat tin-zinc alloy in a short time by using a specific tin-zinc alloy plating bath with the plating bath temperature and plating solution stirring speed set to a predetermined level or higher. It was made based on the knowledge.
すなわち、本発明は、めっき浴温： 30〜90°C、めっき液の攪拌速度： 5〜300mZ
min及び陰極電流密度： 5〜200AZdm2の条件下で錫—亜鉛合金電気めつきを行 う方法を提供する。 That is, the present invention provides a plating bath temperature of 30 to 90 ° C., and a plating solution stirring speed of 5 to 300 mZ. Provided is a method for electroplating a tin-zinc alloy under conditions of min and cathode current density: 5 to 200 AZdm 2 .
発明の効果 The invention's effect
[0005] 本発明によれば、めっき浴温、めっき液の攪拌速度を所定以上とし、特定の錫 亜 鉛合金めつき浴を使用することにより、短時間で錫 亜鉛合金の電気めつきを可能 にすることができる。 [0005] According to the present invention, tin-zinc alloy can be electroplated in a short time by setting the plating bath temperature and the stirring speed of the plating solution to a predetermined level or more and using a specific tin-palladium alloy plating bath. Can be.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0006] 本発明の電気めつき方法におけるめっき浴温は、 30〜90°C、好ましくは 40〜60°C であり、めっき液の攪拌速度は 5〜300mZmin、好ましくは 10〜100mZminであ る。めっき液の撹拌は、具体的にはポンプにより液循環させる噴流式のめっき装置や 鋼板のめっき装置などが適用できる。めっき装置は耐熱、耐薬品性の材質のもので あれば何れもよぐステンレス、チタンなどの金属や塩ィ匕ビニル、テフロン (登録商標） 、 ABS榭脂などが使用できる。また、めっき膜厚及びめつき合金組成の均一性を向 上させるため、被めつき物全体に対して均一なめっき液の攪拌速度が得られる装置 が望ましい。 [0006] In the electroplating method of the present invention, the plating bath temperature is 30 to 90 ° C, preferably 40 to 60 ° C, and the stirring speed of the plating solution is 5 to 300 mZmin, preferably 10 to 100 mZmin. . Specifically, the stirring of the plating solution can be applied by a jet type plating device or a steel plate plating device in which the solution is circulated by a pump. As long as the plating equipment is made of a heat-resistant and chemical-resistant material, metals such as stainless steel and titanium, salt vinyl, Teflon (registered trademark), and ABS resin can be used. In addition, in order to improve the uniformity of the plating film thickness and the plating alloy composition, an apparatus capable of obtaining a uniform plating solution stirring speed over the entire object to be plated is desirable.
[0007] 本発明の電気めつき方法に使用する錫 亜鉛合金電気めつき浴としては、当業者 に公知のいずれのめっき浴も使用することができる力 好ましくはヒドロキシカルボン 酸又はその塩を含有するめつき浴である。 [0007] As a tin-zinc alloy electroplating bath used in the electroplating method of the present invention, any plating bath known to those skilled in the art can be used. Preferably, it contains a hydroxycarboxylic acid or a salt thereof. It is a bathing bath.
ヒドロキシカルボン酸としては、 1分子内に 1又は 2以上のヒドロキシ基と 1又は 2以上 のカルボキシル基を有する化合物が好まし!/、。具体的なヒドロキシカルボン酸の例と しては、クェン酸、酒石酸、リンゴ酸、グリコール酸、グリセリン酸、乳酸、 βーヒドロキ シプロピオン酸及びダルコン酸が挙げられる。好ましくは、クェン酸、酒石酸、リンゴ 酸及びダルコン酸である。また、ヒドロキシカルボン酸塩の具体例としては、上記ヒドロ キシカルボン酸のアルカリ金属塩 (ナトリウム、カリウム、リチウム塩）、アルカリ土類金 属塩（マグネシウム、カルシウム、バリウム塩等）、 2価の錫塩、亜鉛塩、アンモ-ゥム 塩及び有機アミン塩 (モノメチルァミン、ジメチルァミン、トリメチルァミン、ェチルァミン 、イソプロピルァミン、エチレンジァミン、ジエチレントリアミン等）が挙げられる。好まし くは、クェン酸、酒石酸、リンゴ酸又はダルコン酸のナトリウム、カリウム、リチウム塩、 2
価の錫及び亜鉛塩である。これらヒドロキシカルボン酸及びその塩は、単独で、又はAs the hydroxycarboxylic acid, a compound having 1 or 2 or more hydroxy groups and 1 or 2 or more carboxyl groups in one molecule is preferable! /. Specific examples of hydroxycarboxylic acids include citrate, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, β-hydroxypropionic acid and darconic acid. Preferably, citrate, tartaric acid, malic acid and darconic acid are used. Specific examples of hydroxycarboxylates include alkali metal salts (sodium, potassium, lithium salts) of the above hydroxycarboxylic acids, alkaline earth metal salts (magnesium, calcium, barium salts, etc.), and divalent tin salts. Zinc salts, ammonium salts and organic amine salts (monomethylamine, dimethylamine, trimethylamine, ethylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.). Preferably, sodium, potassium, lithium salts of citrate, tartaric acid, malic acid or darconic acid, 2 Valent tin and zinc salts. These hydroxycarboxylic acids and salts thereof may be used alone or
2種類以上を混合して使用してもよぐめっき浴における濃度は 0. 25〜3molZL、 好ましくは、 0. 3〜1. 5molZLである。なお、 2価の錫塩及び Z又は亜鉛塩としてヒ ドロキシカルボン酸塩を使用した場合は、金属イオンの対イオンであるヒドロキシカル ボン酸も上記の濃度の一部を構成する。 The concentration in the plating bath in which two or more kinds may be used in combination is 0.25 to 3 molZL, preferably 0.3 to 1.5 molZL. In addition, when a hydroxycarboxylate is used as the divalent tin salt and Z or zinc salt, hydroxycarboxylic acid, which is a counter ion of the metal ion, also constitutes a part of the above concentration.
ヒドロキシカルボン酸又はその塩を含有するめつき浴の pHは、好ましくは 2〜 10で あり、より好ましくは 3〜9である。めっき浴の pHは水酸ィ匕物及び炭酸ィ匕物等のアル カリ性化合物や無機酸、有機酸等の酸性化合物等を用いて調整することができる。 具体的には、水酸化ナトリウム、水酸ィ匕カリウム、水酸化リチウム、炭酸ナトリウム、炭 酸カリウム、炭酸リチウム、アンモニア水等のアルカリ性ィ匕合物や硫酸、塩酸、スルフ アミン酸、メタンスルホン酸、フエノールスルホン酸等の酸性化合物が挙げられる。 また、本発明の電気めつき方法に使用する錫—亜鉛合金電気めつき浴として、脂 肪族ァミンと有機酸エステルと無水フタル酸を反応させた水溶性化合物及び両性界 面活性剤からなる群力 選ばれる 1種類以上を含有するめつき浴を使用することもで きる。具体的には、例えば脂肪族ァミン 1モル当たりに有機酸エステル 0. 2〜3モル を温度 50〜99°Cで 10〜60分反応させ、重量比で得られた反応性生成物 1に対し 無水フタル酸 0. 1〜 1を温度 60〜 130°Cにおいて 30〜 180分反応させた水溶性化 合物が挙げられる。また、両性界面活性剤としては、イミダゾリン型、ベタイン型、ァラ ニン型、グリシン型及びアマイド型等が挙げられる。水溶性化合物の反応に用いる脂 肪族ァミンとしては、例えばエチレンジァミン、トリエチレンテトラミン、イソプチルァミン 、 3—メトキシプロピルァミン、イミノビスプロピルァミン、ジェチルァミン、へキサメチレ ンテトラミン、ジメチルァミノプロピルアミン等が挙げられ、有機酸エステルとしては、例 えばマロン酸ジメチル、コハク酸ジェチル、マレイン酸ジェチル、フマル酸ジメチル、 酒石酸ジェチル、リンゴ酸ジメチル、タルトロン酸ジェチルなどが挙げられる。これら 水溶性ィ匕合物と両性界面活性剤は、単独で、又は 2種類以上を混合して使用しても よぐめっき浴における含有量は 0. 001〜50gZL、好ましくは 0. 01〜30g/Lであ る。 The pH of the bath containing hydroxycarboxylic acid or a salt thereof is preferably 2 to 10, more preferably 3 to 9. The pH of the plating bath can be adjusted using an alkaline compound such as a hydroxide or carbonate or an acidic compound such as an inorganic acid or an organic acid. Specific examples include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, aqueous ammonia, sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid. And acidic compounds such as phenolsulfonic acid. In addition, as a tin-zinc alloy electroplating bath used in the electroplating method of the present invention, a group comprising a water-soluble compound obtained by reacting an aliphatic amine, an organic acid ester and phthalic anhydride, and an amphoteric surfactant. It is also possible to use a bath with one or more selected power. Specifically, for example, 0.2 to 3 mol of an organic acid ester is reacted at a temperature of 50 to 99 ° C. for 10 to 60 minutes per 1 mol of an aliphatic amine, and the reactive product 1 obtained by weight ratio is reacted. Examples thereof include water-soluble compounds obtained by reacting phthalic anhydride 0.1 to 1 at a temperature of 60 to 130 ° C for 30 to 180 minutes. Examples of amphoteric surfactants include imidazoline type, betaine type, alanine type, glycine type and amide type. Examples of the aliphatic amine used for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isoptylamine, 3-methoxypropylamine, iminobispropylamine, jetylamine, hexamethyltetramine, dimethylaminopropylamine and the like. Examples of the organic acid ester include dimethyl malonate, cetyl succinate, methyl maleate, dimethyl fumarate, dimethyl tartrate, dimethyl malate, and jetyl tartronate. These water-soluble compounds and amphoteric surfactants may be used alone or in admixture of two or more. The content in the plating bath is 0.001 to 50 g ZL, preferably 0.01 to 30 g. / L.
脂肪族ァミンと有機酸エステルと無水フタル酸を反応させた水溶性化合物及び両
性界面活性剤からなる群力 選ばれる 1種類以上を含有するめつき浴の pHは、好ま しくは 2〜 10であり、より好ましくは 3〜9である。めっき浴の pHは水酸ィ匕物及び炭酸 化物等のアルカリ性化合物や無機酸、有機酸等の酸性化合物等を用いて調整する ことができる。具体的には、水酸化ナトリウム、水酸ィ匕カリウム、水酸化リチウム、炭酸 ナトリウム、炭酸カリウム、炭酸リチウム、アンモニア水等のアルカリ性ィ匕合物や硫酸、 塩酸、スルファミン酸、メタンスルホン酸、フヱノールスルホン酸等の酸性化合物が挙 げられる。 Water-soluble compounds obtained by reacting aliphatic amines, organic acid esters and phthalic anhydride, and both The pH of the bath containing one or more kinds selected from the group power consisting of a surfactant is preferably 2 to 10, more preferably 3 to 9. The pH of the plating bath can be adjusted by using an alkaline compound such as hydroxide or carbonate, or an acidic compound such as inorganic acid or organic acid. Specifically, alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, aqueous ammonia, sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, fluoric acid, And acidic compounds such as ヱ -nolusulfonic acid.
また、本発明の電気めつき方法に使用する錫—亜鉛合金電気めつき浴として、 3級 ァミン化合物及び 4級ァミン化合物からなる群から選ばれる 1種類以上を含有するめ つき浴を使用することもできる。 3級アミンィ匕合物としては、例えばイミダゾ—ル系化合 物、脂肪族ァミン化合物が挙げられ、 4級アミンィ匕合物としては、例えば 3級アミンィ匕 合物とハロゲン化アルキルの反応生成物が挙げられる。具体的な 3級アミンィ匕合物と しては、例えばイミダゾ—ル系化合物として、イミダゾ—ル、 1—メチルイミダゾ—ル、 1 ェチルイミダゾール、 2—メチルイミダゾール、 1 ェチル 2—メチルイミダゾ ル 、 1 ォキシメチルイミダゾール、 1 ビュルイミダゾ ル及び 1, 5 ジメチルイミダゾ —ルが挙げられ、脂肪族ァミンとしてはモノエタノ一ルァミン、ジェタノ一ルァミン、トリ ェタノ一ルァミン、ジメチルァミン、エチレンジァミン、ジエチレントリァミン、イミノビスプ 口ピノレアミン、トリエチレンテトラミン、テトラエチレンペンタミン、 N, N ビス一（3ァミノ プロピル)エチレンジァミンなどが挙げられる。また、 3級ァミン化合物と反応させるハ ロゲン化アルキルとしては、例えばモノクロル酢酸、ベンジルクロライド、クロルァセト アミド、 3—ァミノべンジルクロライド、ァリルクロライド、ジクロルェタン、モノクロルプロ パン、ジクロログリセリン、エチレンクロルヒドリン、ェピクロルヒドリンが挙げられる。これ ら 3級アミンィ匕合物及び 4級アミンィ匕合物は、単独で、又は 2種類以上を混合して使 用してもよぐめっき浴に含有量は 0. l〜30g/L、好ましくは 0. 2〜20g/Lである Further, as the tin-zinc alloy electroplating bath used in the electroplating method of the present invention, a bath containing one or more selected from the group consisting of tertiary amine compounds and quaternary amine compounds may be used. it can. Examples of tertiary amine compounds include imidazole compounds and aliphatic amine compounds. Examples of quaternary amine compounds include reaction products of tertiary amine compounds and alkyl halides. Can be mentioned. Specific examples of the tertiary amine compound include imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole. , 1oxymethylimidazole, 1 buluimidazole and 1,5 dimethylimidazole, and aliphatic amines include monoethanolamine, jetanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispamine. Examples include oral pinoleamine, triethylenetetramine, tetraethylenepentamine, and N, N bis (3aminopropyl) ethylenediamine. Examples of the halogenated alkyl to be reacted with the tertiary amine compound include monochloroacetic acid, benzyl chloride, chloracetamide, 3-aminobenzyl chloride, aryl chloride, dichloroethane, monochloropropane, dichloroglycerin, ethylene chlorohydride. Examples include phosphorus and epichlorohydrin. These tertiary amine compounds and quaternary amine compounds may be used alone or in admixture of two or more. The content of the plating bath is 0.1 to 30 g / L, preferably Is 0.2 ~ 20g / L
3級アミンィ匕合物及び 4級アミンィ匕合物力もなる群力も選ばれる 1種類以上を含有 するめつき浴の pHは、好ましくは 10〜14であり、より好ましくは 12〜14である。めつ き浴の pHは水酸ィ匕物及び炭酸ィ匕物等のアルカリ性ィ匕合物を用いて調整することが
できる。具体的には、水酸化ナトリウム、水酸ィ匕カリウム、水酸化リチウム、炭酸ナトリウ ム、炭酸カリウム、炭酸リチウム、アンモニア水などが挙げられる。 A tertiary amine and a quaternary amine compound are also selected. The pH of the hot water bath containing one or more is preferably 10 to 14, more preferably 12 to 14. The pH of the bath can be adjusted using alkaline compounds such as hydroxides and carbonates. it can. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and aqueous ammonia.
[0010] 本発明の電気めつき方法で使用する上記めつき浴には、さらに、ノニオン界面活性 剤、ァ-オン界面活性剤及びカチオン界面活性剤からなる群力 選ばれる 1種以上 の界面活性剤を含有することもできる。これらの界面活性剤を含有させることにより、 高電流密度での析出を緻密にすることができるので、本発明の電気めつき方法を円 滑に実施することができる。 [0010] The tanning bath used in the electroplating method of the present invention further includes at least one surface activity selected from the group force consisting of a nonionic surfactant, a ionic surfactant and a cationic surfactant. An agent can also be contained. By containing these surfactants, precipitation at a high current density can be made dense, so that the electroplating method of the present invention can be smoothly carried out.
[0011] 本発明のめっき方法に使用するめつき浴の錫イオン濃度は、 2価のイオンが 1〜10 OgZL、好ましくは 5〜80gZLであり、亜鉛イオン濃度は 0. 2〜80gZL、好ましくは l〜50gZLである。これら金属イオン源としては、例えば各々の金属の水酸ィ匕物、酸 化物、硫酸塩、塩酸塩、スルファミン酸塩、ピロリン酸塩、ヒドロキシカルボン酸塩、ス ルホン酸塩及びアミノ酸塩が挙げられる。好ましくは、各々の金属の酸化物、硫酸塩 、塩酸塩、水酸ィ匕物である。ヒドロキシカルボン酸塩の具体例としては、上記に例示し たものが挙げられる。スルホン酸塩の具体例としては、アルカンスルホン酸塩、アル力 ノールスルホン酸塩、フエノールスルホン酸塩が挙げられる。このうち、アルカンスル ホン酸の具体例としてはメタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ィ ソプロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸及びへキサンスルホン 酸を挙げることができ、アルカノ一ルスルホン酸の具体例としては 2—ヒドロキシェタン スルホン酸、 3—ヒドロキシプロパンスルホン酸、 2—ヒドロキシブタンスルホン酸を挙 げることができる。フエノ一ルスルホン酸の具体例としては、フエノ一ルスルホン酸、ク レゾ一ルスルホン酸及びジメチルフエノ一ルスルホン酸を挙げることができる。また、 アミノ酸の具体例としては、グリシン、グルタミン酸、ァラニンを挙げることができる。 The tin ion concentration of the plating bath used in the plating method of the present invention is 1 to 10 OgZL, preferably 5 to 80 gZL for divalent ions, and the zinc ion concentration is 0.2 to 80 gZL, preferably l. ~ 50gZL. Examples of these metal ion sources include hydroxide, oxide, sulfate, hydrochloride, sulfamate, pyrophosphate, hydroxycarboxylate, sulfonate, and amino acid salt of each metal. . Preferred are oxides, sulfates, hydrochlorides, and hydroxides of each metal. Specific examples of the hydroxycarboxylate include those exemplified above. Specific examples of the sulfonate include alkane sulfonate, alkane sulfonate, and phenol sulfonate. Among these, specific examples of alkanesulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid and hexanesulfonic acid. Specific examples of the acid include 2-hydroxyethane sulfonic acid, 3-hydroxypropane sulfonic acid, and 2-hydroxybutane sulfonic acid. Specific examples of phenol sulfonic acid include phenol sulfonic acid, cresol sulfonic acid, and dimethyl phenol sulfonic acid. Specific examples of amino acids include glycine, glutamic acid, and alanine.
[0012] 本発明の電気めつき方法に使用するめつき浴には、めっき時の通電性を良好にす るために、さらに硫酸、塩酸、スルファミン酸、ピロリン酸、スルホン酸、水酸化物、炭 酸ィ匕物のアルカリ金属塩 (ナトリウム、カリウム、リチウム塩）、アルカリ土類金属塩 (マ グネシゥム、カルシウム、ノ リウム塩）、アンモ-ゥム塩、有機アミン塩（モノメチルァミン 、ジメチルァミン、トリメチルァミン、ェチルァミン、イソプロピルァミン、エチレンジァミン 、ジエチレントリアミン等）を含有させることができる。具体的には硫酸アンモ-ゥム、
塩ィ匕アンモ-ゥム、ピロリン酸ナトリウム、スルファミン酸モノメチル、水酸化ナトリウム、 水酸ィ匕カリウム、炭酸ナトリウム、炭酸カリウム等が挙げられ、硫酸アンモ-ゥム、塩ィ匕 アンモ-ゥム、水酸ィ匕カリウム、炭酸カリウムが特に望ましい。これら塩の含有量は 10 〜300gZL、好ましくは 50〜200gZLである。 [0012] In the tanning bath used in the electroplating method of the present invention, sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxide, carbon Alkali metal salts (sodium, potassium, lithium salts), alkaline earth metal salts (magnesium, calcium, norlium salts), ammonium salts, organic amine salts (monomethylamine, dimethylamine, trimethyl) Amin, ethylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.). Specifically, ammonium sulfate, Salt ammonium, sodium pyrophosphate, monomethyl sulfamate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., ammonium sulfate, salt ammonium, Particularly preferred are potassium hydroxide and potassium carbonate. The content of these salts is 10 to 300 gZL, preferably 50 to 200 gZL.
[0013] 本発明の電気めつき方法で使用するめつき浴は上記含有成分以外を水とすること ができる力 錫及び亜鉛の光沢剤として用いられている添加剤を含有することもでき る。例えば、合成高分子（ポリビニルアルコ—ル、ポリビニルピロリドン、ポリエチレング リコ—ル等）、ケトン類 (ベンザ—ルアセトン、ァセトフ ノン等）、脂肪族アルデヒド (ホ ルマリン、ァセトアルデヒド、クロトンアルデヒド等）、芳香族アルデヒド (バニリン、サリ チルアルデヒド、ォルソークロルべンズアルデヒド等）、不飽和脂肪族アルデヒドとアミ ン系化合物による反応生成物、硫黄ィ匕合物（チォ尿素、メルカプトべンズイミダゾー ル等）、また、 Cu、 Ni、 Mn、 Bi、 Inなどが挙げられる。これらの添加剤は 0. 001〜5 Og/ 好ましくは、 0. 005〜30gZL含有するのが望ましい。また、錫の酸化防止 剤としてカテコール、ピロガロール、ヒドロキノン、スルホサリチル酸、ジヒドロキシベン ゼンスルホン酸カリウムなどのヒドロキシフヱ-ル化合物及びその塩や L ァスコルビ ン酸、ソルビト—ル等を使用することもできる。 [0013] The tanning bath used in the electroplating method of the present invention can also contain additives used as tin and zinc brighteners in addition to the above-mentioned components. For example, synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, etc.), ketones (benzal acetone, acetophenone, etc.), aliphatic aldehydes (formalin, acetoaldehyde, crotonaldehyde, etc.), Aromatic aldehydes (vanillin, salicylaldehyde, olsochlorbenzaldehyde, etc.), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, etc.), Cu, Ni, Mn, Bi, In etc. These additives contain 0.001 to 5 Og / preferably 0.005 to 30 g ZL. In addition, hydroxyphenol compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate, and salts thereof, L-corcorbic acid, sorbitol, and the like can also be used as antioxidants for tin.
[0014] 本発明のめっき方法における被めつき物は Fe、 Ni、 Cuやこれらを基にした合金の 金属材料であり、これを陰極としてめつきを行う。この対極には、錫—亜鉛合金又は T i材に Ptめっきを施した不溶性電極、力一ボン電極などを使用することができる。不溶 性陽極を使用する場合は、上記の錫及び亜鉛の金属塩を直接めつき液に溶解する 方法又は錫及び亜鉛の金属塩を高濃度で溶解した水溶液を補給することで使用す るめつき浴の金属濃度を維持することができる。この金属の高濃度水溶液は上記のヒ ドロキシカルボン酸又はその塩及び水酸ィ匕アルカリ化合物を含有してもよい。 [0014] The object to be plated in the plating method of the present invention is a metal material of Fe, Ni, Cu, or an alloy based on these, and this is used as a cathode. As the counter electrode, a tin-zinc alloy or a Ti material in which Pt plating is applied, an insoluble electrode, a force-bonded electrode, or the like can be used. When using an insoluble anode, the above-mentioned method of directly dissolving the tin and zinc metal salts in the sag solution or replenishing an aqueous solution in which the tin and zinc metal salts are dissolved at a high concentration is used. The metal concentration of the bath can be maintained. This high-concentration aqueous solution of the metal may contain the above hydroxycarboxylic acid or a salt thereof and a hydroxy-alkali compound.
[0015] 陰極電流密度は 5〜200A/dm2、好ましくは 10〜120A/dm2であり、膜厚は広 い範囲で可能であるが一般に、 0. 5〜500 μ m、好ましくは 2〜20 μ mである。 The cathode current density is 5 to 200 A / dm 2 , preferably 10 to 120 A / dm 2 , and the film thickness can be in a wide range, but is generally 0.5 to 500 μm, preferably 2 to 20 μm.
使用するめつき浴中の錫イオンと亜鉛イオンの比率を変動させることにより、幅広い 組成の錫—亜鉛合金めつきを施すことができる。例えば、電子部品には亜鉛含有率 3〜 15%の錫—亜鉛合金めつきを施すことができ、耐塩水性や耐食性を特に強化す
る場合には亜鉛含有率 15〜45%の錫—亜鉛合金めつきを施すことができる。更に 大気暴露性を考慮した高!ヽ耐食性の皮膜を得ようとする場合には、亜鉛含有率 50 〜90%の錫一亜鉛合金めつきを施すことができる。 By varying the ratio of tin ions to zinc ions in the bath used, tin-zinc alloy plating with a wide range of compositions can be applied. For example, an electronic component can be tinned with a zinc content of 3 to 15%, which particularly enhances saltwater resistance and corrosion resistance. In this case, tin-zinc alloy plating with a zinc content of 15 to 45% can be applied. Furthermore, in order to obtain a highly corrosion-resistant film in consideration of atmospheric exposure, tin-zinc alloy plating with a zinc content of 50 to 90% can be applied.
本発明のめっき方法では被めつき物は常法により前処理した後にめっき工程に付 される。前処理工程では、浸漬脱脂、酸洗、電解洗浄及び活性化の少なくとも 1つの 操作が行われる。めっき後は得られた皮膜を水洗浄して乾燥すればよぐ常法による クロメート処理及び化成処理又は無機及び有機物によるコーティング処理をすること ちでさる。 In the plating method of the present invention, the object to be covered is subjected to a plating step after pretreatment by a conventional method. In the pretreatment process, at least one operation of immersion degreasing, pickling, electrolytic cleaning and activation is performed. After plating, the resulting film can be washed with water and dried, followed by conventional chromate treatment and chemical conversion treatment, or coating treatment with inorganic and organic substances.
次に実施例により本発明を説明するが、本発明はこれに限定されるものではなぐ 目的に応じて、めっき液温度、めっき液の流速及び使用するめつき浴の組成を任意 に変更することができる。 EXAMPLES Next, the present invention will be described by way of examples. However, the present invention is not limited thereto, and the plating solution temperature, the plating solution flow rate, and the composition of the bath used can be arbitrarily changed according to the purpose. it can.
実施例 Example
[0016] (実施例 1) [0016] (Example 1)
鋼板を前処理後、下記のめっき浴を使用し、めっき浴温: 60°C、めっき液の攪拌速 度： 50mZminの条件下で電気めつき処理を施した。 After pretreatment of the steel sheet, the following plating bath was used, and electroplating was performed under the conditions of plating bath temperature: 60 ° C. and plating solution stirring speed: 50 mZmin.
硫酸第一錕 （錫として） 30 g7L 1st sulfuric acid (as tin) 30 g7L
硫酸亜鉛 （亜鉛として） 25 g/L Zinc sulfate (as zinc) 25 g / L
クェン酸 1 50 g / L (0. 7 1モノレ ZL) Chenic acid 1 50 g / L (0.7 7 1 Monore ZL)
硫酸アンモニゥム 1 00 g/L Ammonium sulfate 1 00 g / L
エチレンジァミ ン 1モノレとマロン酸ジ 1 0m l /L Ethylenediamine 1 monole and malonate di 10 ml / L
メチル 1モルを 8 5。じで 60分反応さ Methyl 1 mole 8 5. Reacts for 60 minutes
せた生成物 1に対し、 重量比で 0. 5の 0.5 weight ratio to the product 1
無水フタル酸を 9 5 °Cで 90分反応さ React phthalic anhydride at 95 ° C for 90 minutes
せた生成物 Product
p H 4 (アンモニア水で調整） pH 4 (adjusted with ammonia water)
[0017] (実施例 2) [0017] (Example 2)
鋼板を前処理後、実施例 1のめつき浴に、ノ-オン界面活性剤として日本油脂 (株） 製のナイミーン NAG— 1001を 5g/L添カ卩し、めっき浴温： 60°C、めっき液の攪拌速 度： 30mZminの条件下で電気めつき処理を施した。 After pre-treating the steel plate, add 5g / L of Niimen NAG-1001 made by Nippon Oil & Fats Co., Ltd. as a non-ionic surfactant to the dip bath of Example 1, and the bath temperature: 60 ° C. The plating solution was stirred at a rate of 30 mZmin.
[0018] (実施例 3) [0018] (Example 3)
鋼板を前処理後、下記のめっき浴を使用し、めっき浴温: 60°C、めっき液の攪拌速 度： 30mZminの条件下で電気めつき処理を施した。
錫酸力リ ウム （錫として） 5 5 g / After pretreatment of the steel sheet, the following plating bath was used, and electroplating was performed under the conditions of plating bath temperature: 60 ° C. and plating solution stirring speed: 30 mZmin. Lithium stannate (as tin) 5 5 g /
酸化亜鉛 （亜鉛として） 5 g / Zinc oxide (as zinc) 5 g /
水酸化力リウム 8 0 g / Hydroxyl hydroxide 8 0 g /
炭酸力リ ゥム 1 0 0 g / Carbonated Lithium 1 0 0 g /
1ーメチノレイミダゾ一ノレ 1モノレとベン■ジ 1 g / 1-Metinoreididazonore 1 Monore and Ben ■ Di 1 g /
ルクロライ ド lモルを 8 5 °Cで 1 8 0分 Luclolide lmol at 85 ° C for 1 80 minutes
反応させた生成物 Reacted product
ジェチレント リアミン 1モノレとエチレン Jet Rent Reamine 1 Monore and Ethylene
クロルヒ ドリン 1モルを 1 0 0 °Cで 9 0 Chlorhydrin 1 mole 9 0 at 100 ° C
分反応させた生成物 Product reacted in minutes
p H 1 4 (実施例 4) pH 1 4 (Example 4)
リン青銅板を前処理後、下記のめっき浴を使用し、めっき浴温： 50°C、めっき液の 攪拌速度： 60mZminの条件下で電気めつき処理を施した。 After pretreatment of the phosphor bronze plate, electroplating was performed using the following plating bath under the conditions of plating bath temperature: 50 ° C. and plating solution stirring speed: 60 mZmin.
硫酸第一錫 （錫として） 2 0 g / L Stannous sulfate (as tin) 20 g / L
硫酸亜鉛 （亜鉛として） 7 g / L Zinc sulfate (as zinc) 7 g / L
クェン酸 1 2 0 g / L ( 0 Chenic acid 1 2 0 g / L (0
硫酸アンモェゥム 8 0 g / L Ammonium sulfate 8 0 g / L
トリエチレンテトラミン 1 モノレとコハク 1 0 m l / L Triethylenetetramine 1 monole and amber 10 ml / L
酸ジェチル 1 . 2モルを 8 0 °Cで 4 0分反 Jetyl acid 1.2 mols 40 minutes at 80 ° C
応させた生成物 1に対し、 重量比で 0 . 7 0.7% by weight with respect to the adjusted product 1
の無水フタル酸を 9 0 °Cで 1 2 0分反応 Of phthalic anhydride at 90 ° C for 120 minutes
させた生成物 Product
ャシ油ァノレキノレー N 力ノレボキシェチノレ 5 g / L Pear oil ano rekinolé N force rebochetinore 5 g / L
N— ヒ ドロキシェチルイミダゾリゥム N—Hydroxicheil imidazolium
ベタインナトリウム Betaine sodium
p H 5 . 5 (水酸化ナトリウムで調整） pH 5.5 (adjusted with sodium hydroxide)
(実施例 5) (Example 5)
リン青銅板を前処理後、下記のめっき浴を使用し、めっき浴温: 60°C、めっき液の 攪拌速度： 60mZminの条件下で電気めつき処理を施した。
メタンスルホン酸錫 (錫として) 3 0 g / After pretreatment of the phosphor bronze plate, electroplating was performed using the following plating bath under the conditions of plating bath temperature: 60 ° C. and plating solution stirring speed: 60 mZmin. Tin methanesulfonate (as tin) 30 g /
メタンスルホン酸亜鉛 (亜鉛と 1 5 g / Zinc methanesulfonate (Zinc and 15 g /
ダルコン酸ナトリ ウム 1 5 0 g / ( 0 . 6 9モ L ) メタンスノレホン酸 1 0 0 g / Sodium dulconate 150 g / (0.69 mol L) Methanesulphonic acid 100 g /
ェチレンジァ ミ ン 1 モノレとマレイン酸ジ 8 m 1 L Ethylenediamine 1 monole and dimaleic acid 8 m 1 L
メチル 1モルを 9 0。じで 6 0分反応させ 1 mole of methyl is 90. Let it react for 60 minutes
た生成物 1に対し、 重量比で 0 . 5の無水 0.5 weight ratio of anhydrous product 1
フタル酸を 1 1 0 °Cで 1 5 0分反応させ Reaction of phthalic acid at 1 1 0 ° C for 1 50 minutes
た生成物 Product
サリチルアルデヒ ド 0 . 0 5 g / L Salicylaldehyde 0.05 g / L
p H 6 . 2 (水酸化ナトリ ウムで調整） pH 6.2 (adjusted with sodium hydroxide)
[0021] (比較例 1) [Comparative Example 1]
鋼板を前処理後、実施例 1のめつき浴を使用し、めっき浴温： 23°C、めっき液の攪 拌速度： 50mZminの条件下で電気めつき処理を施した。 After the pretreatment of the steel sheet, the plating bath temperature of 23 ° C. and the plating solution stirring speed: 50 mZmin were applied using the plating bath of Example 1.
[0022] (比較例 2) [0022] (Comparative Example 2)
鋼板を前処理後、実施例 1のめつき浴を使用し、めっき浴温: 60°C、めっき液の攪 拌速度： 2mZminの条件下で電気めつき処理を施した。 After the steel plate was pretreated, the plating bath of Example 1 was used, and the plating bath temperature was 60 ° C., and the plating solution was stirred at a rate of 2 mZmin.
[0023] (比較例 3) [0023] (Comparative Example 3)
鋼板を前処理後、実施例 3のめつき浴を使用し、めっき浴温: 60°C、めっき液の攪 拌速度： 3mZminの条件下で電気めつき処理を施した。 After the steel plate was pretreated, the plating bath of Example 3 was used, and the plating bath temperature was 60 ° C., and the plating solution was stirred at a rate of 3 mZmin.
[0024] 実施例 1〜5、比較例 1〜3のめつき析出状態、析出皮膜の合金組成 (重量％)、処 理時間及び膜厚を表 1〜2に示す。 [0024] Tables 1 and 2 show the precipitation states of Examples 1 to 5 and Comparative Examples 1 to 3, the alloy composition (% by weight) of the deposited film, the treatment time, and the film thickness.
[0025] [0025]
実施例 1 実施例 2 実施例 3 Example 1 Example 2 Example 3
析 Sn/Zn 処 膜厚 析 Sn/Zn 処 膜厚 析 Sn/Zn 処 膜厚 出 ( t%) 理 ( 11 m) 出 (wt%) 理 ( m) 出 ( t%) 理 ( μ m) 状 時 状 時 状 時 態 間 態 間 態 間 lOA/dm2 〇 70/ 30 120 8. 8 〇 70/30 120 8. 8 O 45/ 55 240 7. 0Sn / Zn treatment film thickness Analysis Sn / Zn treatment film thickness Analysis Sn / Zn treatment film thickness Output (t%) Process (11m) Process (wt%) Process (m) Process (t%) Process (μm) Status Time Status Time Status Status Status lOA / dm 2 ○ 70/30 120 8. 8 ○ 70/30 120 8.8 O 45/55 240 7. 0
20A/dm2 〇 70/ 30 60 8. 8 〇 70/30 60 8. 8 O 45/ 55 120 6. 520A / dm 2 ○ 70/30 60 8. 8 ○ 70/30 60 8. 8 O 45/55 120 6. 5
30A/dm2 〇 70/ 30 40 8. 8 〇 70/30 40 8. 8 o 40/60 80 4. 9 / dm2 〇 72/28 30 8. 9 〇 70/30 30 8. 8 Δ 40/60 60 3. 530A / dm 2 ○ 70/30 40 8. 8 ○ 70/30 40 8. 8 o 40/60 80 4. 9 / dm 2 ○ 72/28 30 8. 9 ○ 70/30 30 8. 8 Δ 40 / 60 60 3.5
50A/dm2 〇 72/28 25 8. 9 〇 70/30 25 8. 7 X 4850A / dm 2 ○ 72/28 25 8. 9 ○ 70/30 25 8. 7 X 48
60A/dm2 〇 75/25 20 8. 0 〇 75/25 20 8. 1 X 4060A / dm 2 ○ 75/25 20 8. 0 ○ 75/25 20 8. 1 X 40
70A/dm2 〇 75/25 17 7. 8 〇 75/25 17 8. 0 X 34 ― 腸/ dm2 O 75/25 15 7. 6 〇 75/25 15 7. 8 X 3070A / dm 2 ○ 75/25 17 7. 8 ○ 75/25 17 8. 0 X 34 ― Intestine / dm 2 O 75/25 15 7.6 ○ 75/25 15 7. 8 X 30
90A/dm2 Δ 85/ 15 13 7. 4 〇 82/ 18 13 7. 6 X 27 ― lOOA/ dm2 △ 85/ 15 12 6. 9 O 82/ 18 12 7. 2 X 24
処理時間の単位はすべて sec.である 90A / dm 2 Δ 85/15 13 7. 4 ○ 82/18 13 7. 6 X 27 ― lOOA / dm 2 Δ 85/15 12 6. 9 O 82/18 12 7. 2 X 24 All processing time units are sec.
〇 o：緻密で平滑な析出 O: Dense and smooth precipitation
△:部分的に粗析出の発生 Δ: Rough precipitation occurs partially
X：粉末状の粗い析出 X: coarse powdery precipitation
[0026] 表 2 [0026] Table 2
〇：緻密で平滑な析出 ○: Precise and smooth precipitation
△:部分的に粗析出の発生 Δ: Rough precipitation occurs partially
X：粉末状の粗い析出 X: coarse powdery precipitation
[0027] 表 3 [0027] Table 3
比較例 1 比較例 2 比較例 3 Comparative Example 1 Comparative Example 2 Comparative Example 3
析 Sn/ ζ,η 処 膜厚 析 Sn/ ζ,η 処 膜厚 析 Sn/Zn 処 膜厚 出 (wt%) 理 ( IX m) 出 (wt%) 理 ( 11 m) 出 (wt%) 理 ( m) 状 時 状 時 状 時 態 間 態 間 態 間 Sn / ζ, η film thickness Analysis Sn / ζ, η film thickness Analysis Sn / Zn film thickness Output (wt%) Process (IX m) Output (wt%) Process (11 m) Output (wt%) (M) Status Time Status Time Status Status Status
〇 48/52 120 5. 6 〇 66/34 120 4. 2 Δ 45/55 120 3. 2○ 48/52 120 5. 6 ○ 66/34 120 4. 2 Δ 45/55 120 3. 2
20A/dm2 〇 52/48 60 4. 2 X 60 X 6020A / dm 2 ○ 52/48 60 4. 2 X 60 X 60
30A/dm2 Δ 52/48 40 2. 9 X 40 X 4030A / dm 2 Δ 52/48 40 2. 9 X 40 X 40
40A/dm2 X 30 X 30 X 3040A / dm 2 X 30 X 30 X 30
50A/dm2 X 25 X 25 X 2550A / dm 2 X 25 X 25 X 25
60A/dm2 X 20 X 20 X 2060A / dm 2 X 20 X 20 X 20
70A/dm2 X 17 X 17 X 1770A / dm 2 X 17 X 17 X 17
80A/dm2 X 15 X 15 X 1580A / dm 2 X 15 X 15 X 15
90A/dm2 X 13 X 13 X 13 lOOA/ dm2 X 12 X 12 X 12
処理時間の単位はすべて sec.である 〇：緻密で平滑な析出 90A / dm 2 X 13 X 13 X 13 lOOA / dm 2 X 12 X 12 X 12 All processing time units are sec. 〇: Dense and smooth precipitation
△:部分的に粗析出の発生 Δ: Rough precipitation occurs partially
X：粉末状の粗い析出
X: coarse powdery precipitation
Claims
[1] 以下の条件下で行う錫 亜鉛合金電気めつき方法。 [1] A tin-zinc alloy electroplating method performed under the following conditions.
めっき浴温： 30〜90°C、 Plating bath temperature: 30-90 ° C,
めっき液の攪拌速度： 5〜300mZmin、及び Agitation rate of plating solution: 5-300mZmin, and
陰極電流密度： 5〜200AZdm2。 Cathode current density: 5 to 200 AZdm 2 .
[2] 錫—亜鉛合金めつき浴力ヒドロキシカルボン酸又はその塩を含有し、かつ錫—亜鉛 合金めつき浴の pHが 2〜： LOである、請求項 1記載の方法。 [2] The method according to claim 1, wherein the tin-zinc alloy plating bath hydroxycarboxylic acid or a salt thereof is contained, and the tin-zinc alloy plating bath has a pH of 2 to LO.
[3] 錫—亜鉛合金めつき浴が脂肪族ァミンと有機酸エステルと無水フタル酸を反応させ た水溶性ィ匕合物及び両性界面活性剤カゝらなる群カゝら選ばれる 1種類以上を含有し、 かつ錫—亜鉛合金めつき浴の pHが 2〜 10である、請求項 1記載の方法。 [3] One or more selected from the group consisting of a water-soluble compound obtained by reacting an aliphatic amine, an organic acid ester, and phthalic anhydride, and an amphoteric surfactant. The method according to claim 1, wherein the pH of the tin-zinc alloy plating bath is 2-10.
[4] 錫—亜鉛合金めつき浴が 3級アミンィ匕合物及び 4級ァミン化合物力 なる群力 選 ばれる 1種類以上を含有し、かつ錫—亜鉛合金めつき浴の pHが 10〜 14である、請 求項 1記載の方法。 [4] The tin-zinc alloy plating bath contains at least one selected group power consisting of tertiary amine compounds and quaternary amine compounds. The tin-zinc alloy plating bath has a pH of 10-14. The method according to claim 1, wherein:
[5] 錫—亜鉛合金めつき浴が、ノ-オン界面活性剤、ァ-オン界面活性剤及びカチォ ン界面活性剤力もなる群力も選ばれる 1種以上を含有する、請求項 1〜4のいずれか 1項記載の方法。 [5] The tin-zinc alloy plating bath contains at least one selected from the group force including a non-ionic surfactant, a char-on surfactant, and a cationic surfactant. The method according to any one of the above.
[6] 錫—亜鉛合金めつき浴中の 2価の錫イオン濃度が 1〜： LOOgZLであり、かつ亜鉛ィ オン濃度が 0. 2〜80gZLである、請求項 1〜5のいずれか 1項記載の方法。
[6] The divalent tin ion concentration in the tin-zinc alloy plating bath is 1 to: LOOgZL, and the zinc ion concentration is 0.2 to 80 gZL. The method described.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0514210A BRPI0514210B1 (en) | 2004-08-10 | 2005-08-10 | tin-zinc alloy electrodeposition method |
| KR1020077002958A KR100929761B1 (en) | 2004-08-10 | 2005-08-10 | Tin-Zinc Alloy Electroplating Method |
| ES05770802.6T ES2526430T3 (en) | 2004-08-10 | 2005-08-10 | Electroplating method with a tin and zinc alloy |
| EP05770802.6A EP1811063B1 (en) | 2004-08-10 | 2005-08-10 | Tin-zinc alloy electroplating method |
| CN2005800271252A CN101001982B (en) | 2004-08-10 | 2005-08-10 | Tin-zinc alloy electroplating method |
| US11/704,805 US20070199827A1 (en) | 2004-08-10 | 2007-02-09 | Method for electroplating with tin-zinc alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004-233633 | 2004-08-10 | ||
| JP2004233633A JP4594672B2 (en) | 2004-08-10 | 2004-08-10 | Tin-zinc alloy electroplating method |
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| US11/704,805 Continuation US20070199827A1 (en) | 2004-08-10 | 2007-02-09 | Method for electroplating with tin-zinc alloy |
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| WO2006016603A1 true WO2006016603A1 (en) | 2006-02-16 |
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| PCT/JP2005/014648 WO2006016603A1 (en) | 2004-08-10 | 2005-08-10 | Tin-zinc alloy electroplating method |
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|---|---|
| US (1) | US20070199827A1 (en) |
| EP (1) | EP1811063B1 (en) |
| JP (1) | JP4594672B2 (en) |
| KR (1) | KR100929761B1 (en) |
| CN (1) | CN101001982B (en) |
| BR (1) | BRPI0514210B1 (en) |
| ES (1) | ES2526430T3 (en) |
| WO (1) | WO2006016603A1 (en) |
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| CN102634827B (en) * | 2012-05-07 | 2015-04-08 | 东莞市闻誉实业有限公司 | Tin-zinc alloy electroplating method |
| CN102690975B (en) * | 2012-06-11 | 2014-12-03 | 东莞市闻誉实业有限公司 | Ternary tin-zinc alloy and electroplating method thereof |
| CN104213159A (en) * | 2014-09-17 | 2014-12-17 | 朱忠良 | Electroplating liquid and electroplating method |
| CN104357884A (en) * | 2014-11-14 | 2015-02-18 | 无锡伊佩克科技有限公司 | Method for plating zinc-tin alloy on ferrous material |
| CN105002526A (en) * | 2015-06-30 | 2015-10-28 | 安徽飞达新材料科技股份有限公司 | Cold-rolled steel plate brightener |
| CN105350056B (en) * | 2015-11-24 | 2017-12-01 | 安徽天思朴超精密模具股份有限公司 | The preparation method and application of wear-resistant electroplate liquid material compositions and wear-resistant electroplate liquid |
| KR101678013B1 (en) * | 2016-02-15 | 2016-11-21 | 주식회사 베프스 | A plating solution with concentration-detecting indicators for determing supplement time of metal component and plating method of therewith |
| KR102621912B1 (en) * | 2018-12-24 | 2024-01-05 | 현대자동차주식회사 | Excellent activation whisker resistant zinc coating method for electrical and electronic components |
| CN111188069A (en) * | 2019-12-31 | 2020-05-22 | 大连长丰实业总公司 | Tin-plated bismuth alloy solution and preparation method thereof |
| CN111394734A (en) * | 2020-05-06 | 2020-07-10 | 苏州清飙科技有限公司 | Stripping polishing solution for die-casting zinc alloy and preparation method thereof |
| CN114927677B (en) * | 2022-05-31 | 2024-05-24 | 山东大学 | Flexible sodium battery anode material and green preparation method and application thereof |
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- 2005-08-10 CN CN2005800271252A patent/CN101001982B/en active Active
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| JPH02175894A (en) * | 1988-12-28 | 1990-07-09 | Kosaku:Kk | Method and device for tin or tin alloy electroplating |
| JPH06122991A (en) * | 1992-09-25 | 1994-05-06 | Deitsupusoole Kk | Tin-zinc alloy electroplating bath |
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0514210A2 (en) | 2009-04-28 |
| EP1811063A4 (en) | 2009-03-04 |
| EP1811063A1 (en) | 2007-07-25 |
| ES2526430T3 (en) | 2015-01-12 |
| US20070199827A1 (en) | 2007-08-30 |
| BRPI0514210B1 (en) | 2016-05-03 |
| JP2006052431A (en) | 2006-02-23 |
| CN101001982B (en) | 2010-09-08 |
| JP4594672B2 (en) | 2010-12-08 |
| EP1811063B1 (en) | 2014-12-03 |
| KR20070031442A (en) | 2007-03-19 |
| KR100929761B1 (en) | 2009-12-03 |
| CN101001982A (en) | 2007-07-18 |
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