EP1811063B1 - Tin-zinc alloy electroplating method - Google Patents
Tin-zinc alloy electroplating method Download PDFInfo
- Publication number
- EP1811063B1 EP1811063B1 EP05770802.6A EP05770802A EP1811063B1 EP 1811063 B1 EP1811063 B1 EP 1811063B1 EP 05770802 A EP05770802 A EP 05770802A EP 1811063 B1 EP1811063 B1 EP 1811063B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- plating bath
- acid
- zinc alloy
- zinc
- 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.)
- Active
Links
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 25
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims description 25
- 238000009713 electroplating Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 22
- 238000007747 plating Methods 0.000 claims description 77
- -1 organic acid ester Chemical class 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000011701 zinc Substances 0.000 description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 235000011118 potassium hydroxide Nutrition 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 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
- 229940098779 methanesulfonic 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
- 241000894007 species Species 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 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
- 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 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
- 239000000654 additive Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 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
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 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
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GWHRFNPTPGZQIC-UHFFFAOYSA-L [Sn+].[Sn+].[O-]S([O-])(=O)=O Chemical compound [Sn+].[Sn+].[O-]S([O-])(=O)=O GWHRFNPTPGZQIC-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 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
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-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
- 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
- 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
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 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
- 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
- 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
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-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
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-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
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-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
- BWDPPMPQZZILAG-UHFFFAOYSA-N 3-(chloromethyl)aniline Chemical compound NC1=CC=CC(CCl)=C1 BWDPPMPQZZILAG-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
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical compound CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 239000004471 Glycine Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 229960003237 betaine 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
- 238000004532 chromating Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 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
- VXZQTXSCMRPKMH-UHFFFAOYSA-N diethyl 2-hydroxypropanedioate Chemical compound CCOC(=O)C(O)C(=O)OCC VXZQTXSCMRPKMH-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 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
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011147 inorganic material 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
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-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
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides 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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 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
- 159000000001 potassium salts Chemical class 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
- 238000001556 precipitation Methods 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
- 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
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 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
- 238000005406 washing Methods 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 method for electroplating with a tin-zinc alloy.
- the systems that are still used include a rack system (maximum current density about 3 A/dm 2 ) in which the articles to be plated are treated upon mounting them on a jig and a barrel system (maximum current density 1 A/dm 2 ) in which the articles to be plated are treated in a barrel.
- the present invention is based on a discovery that electroplating with a tin-zinc alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
- the present invention provides a method for electroplating with a tin-zinc alloy according to claim 1.
- electroplating with a tin-zinc alloy can be carried out within a short interval by using a specific tin-zinc alloy plating bath at a plating bath temperature and plating bath stirring rate above the predetermined values.
- the temperature of the plating bath in the electroplating method in accordance with the present invention is 30 to 90°C, preferably 40 to 60°C, and the stirring rate of the plating solution is 5 to 300 m/min, preferably 10 to 100 m/min.
- Stirring of the plating solution is specifically carried out by a plating apparatus of a jet flow system in which the solution is circulated with a pump or by a plating apparatus for steel sheets.
- the plating apparatus can be made from any material, provided it has heat resistance and chemical resistance, and metals such as stainless steel and titanium or polyvinyl chloride, Teflon (registered trade name), and an ABS resin can be used.
- a device enabling the stirring of the plating solution that is uniform with respect to the entire plated article is preferred from the standpoint of increasing the uniformity of the plated alloy composition and plated film thickness.
- a compound having one or more hydroxyl groups and one or more carboxyl groups in a molecule is preferred as the hydroxycarboxylic acid.
- hydroxycarboxylic acids include citric acid, tartaric acid, malic acid, glycolic acid, glyceric acid, lactic acid, ⁇ -hydroxypropionic acid, and gluconic acid.
- citric acid, tartaric acid, malic acid, and gluconic acid are preferred among them.
- hydroxycarboxylic acid salts include alkali metal salts (sodium, potassium, lithium salts) alkaline earth metal salts (magnesium, calcium, barium salts, and the like), divalent tin salts, zinc salts, ammonium salts, and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.) of the aforementioned hydroxycarboxylic acids.
- alkali metal salts sodium, potassium, lithium salts
- divalent tin salts alkaline earth metal salts (magnesium, calcium, barium salts, and the like
- organic amine salts monomethylamine, dimethylamine, trimethylamine, methylamine, isopropylamine, ethylenediamine, diethylenetriamine, etc.
- the preferred among them are sodium salts, potassium salts, lithium salts, divalent tin salts, and zinc salts of citric acid, tartaric
- hydroxycarboxylic acids and salts thereof may be used individually or in a mixture of two or more thereof, and the concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
- concentration thereof in the plating bath is 0.25 to 3 mol/L, preferably 0.3 to 1.5 mol/L.
- the hydroxycarboxylic acid which is a counterion of the metal ions also constitutes part of the aforementioned concentration.
- the pH of the plating bath comprising the hydroxycarboxylic acid or salt thereof is 2 to 10, preferably 3 to 9.
- the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
- suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
- a plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine an organic acid ester, and phthalic anhydride also can be utilized as the tin-zinc alloy electroplating bath used in the electroplating method in accordance with the present invention. More specifically, for example, a water-soluble compound can be used that is obtained by reacting 0.2 to 3 moles of an organic acid ester per 1 mole of an aliphatic amine for 10 to 60 min. at a temperature of 50 to 99°C and then reacting phthalic anhydride with the obtained reactive product at a weight ratio of 0.1 to 1 ; 1 for 30 to 180 min at a temperature of 60 to 130°C.
- amphoteric surfactants include imidazoline-type, betaine-type, alanine-type, glycine-type, and amide-type surfactants.
- aliphatic amines suitable for the reaction of the water-soluble compound include ethylenediamine, triethylenetetramine, isobutylamine, 3-methoxypropylamine, iminobispropylamine, diethylamine, hexamethylenetetramine, and dimethylaminopropylamine.
- suitable organic acid esters include dimethyl manolate, diethyl succinate, diethyl maleate, dimethyl fumarate, diethyl tartarate, dimethyl malate, and diethyl tartronate.
- These water-soluble compounds and amphoteric surfactants may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.001 to 50 g/L, preferably 0.01 to 30 g/L.
- the pH of the plating bath comprising at least one species selected from the group consisting of amphoteric surfactants and water-soluble compounds obtained by a reaction of an aliphatic amine, an organic acid ester, and phthalic anhydride 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 a hydroxide and carbonate, or an acidic compound such as an inorganic acid or organic acid.
- suitable compounds include alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water and acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
- alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water
- acidic compounds such as sulfuric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, and phenolsulfonic acid.
- a plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds also can be used as the tin-zinc alloy electroplating bath employed in the electroplating method in accordance with the present invention.
- tertiary amine compounds include imidazole compounds and aliphatic amine compounds
- examples of quaternary amine compounds include reaction products of tertiary amine compounds and halogenated alkyls.
- tertiary amine compounds include imidazole compounds, such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole, and aliphatic amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine, and N,N-bis-(3-aminopropyl)ethylenediamine.
- imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, and 1, 5-dimethylimidazole
- tertiary amine compounds and quaternary amine compounds may be used individually or in a mixture of two or more thereof, and the content thereof in the plating bath is 0.1 to 30 g/L, preferably 0.2 to 20 g/L.
- the pH of the plating bath comprising at least one species selected from the group consisting of tertiary amine compounds and quaternary amine compounds is preferably 10 to 14, more preferably 12 to 14.
- the pH of the plating bath can be adjusted by using an alkaline compound such as a hydroxide and carbonate.
- suitable compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and ammonia water.
- the plating bath used in the electroplating method in accordance with the present invention can additionally contain at least one surfactant selected from the group consisting of a nonionic surfactant, anionic surfactant, and cationic surfactant. Introducing such surfactants into the plating bath enables denser precipitation at a high current density and, therefore, makes it possible to implement more smoothly the electroplating method in accordance with the present invention.
- the divalent tin ion concentration is 1 to 100 g/L, preferably 5 to 80 g/L, and the zinc ion concentration is 0.2 to 80 g/L, preferably 1 to 50 g/L.
- sources of such metal ions include various metal hydroxides, oxides, sulfates, chlorides, sulfamates, pyrophosphates, hydroxycarboxylates, sulfonates, and amino acid salts.
- Various metal oxides, sulfates, chlorides, and hydroxides are preferred. Specific examples of hydroxycarboxylic acid salts are presented hereinabove.
- sulfonates include alkanesulfonates, alkanolsulfonates, and phenolsulfonates.
- alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, and hexanesulfonic acid.
- alkanolsulfonic acids include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, and 2-hydroxybutanesulfonic acid.
- phenolsulfonic acids include phenolsulfonic acid, cresolsulfonic acid, and dimethylphenolsulfonic acid.
- amino acids include glycine, glutamic acid, and alanine.
- alkali metal salts sodium, potassium, lithium salts
- alkaline earth metal salts magnesium, calcium, barium salts
- ammonium salts and organic amine salts (monomethylamine, dimethylamine, trimethylamine, methylamine, ispropylamine, ethylenediamine, diethylenetriamine, etc.) of sulfuric acid, hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
- sulfuric acid hydrochloric acid, sulfamic acid, pyrophosphoric acid, sulfonic acid, hydroxides and carbonates
- salts include ammonium sulfate, ammonium chloride, sodium pyrophosphate, monomethyl sulfamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and among these especially preferred are ammonium sulfate, ammonium chloride, potassium hydroxide, and potassium carbonate.
- the content of these salts is 10 to 300 g/L, preferably 50 to 200 g/L.
- the plating bath used in the electroplating method in accordance with the present invention can contain water in addition to the above-described components and also can contain additives that have been used as a brightener for tin and zinc.
- suitable additives include synthetic polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, and the like), ketones (benzalacetone, acetophenone, and the like), aliphatic aldehydes (formalin, acetaldehyde, crotonaldehyde, and the like), aromatic aldehydes (vanillin, salicylaldehyde, orthochlorobenzaldehyde, and the like), reaction products of unsaturated aliphatic aldehydes and amine compounds, sulfur compounds (thiourea, mercaptobenzimidazole, and the like), and also Cu, Ni, Mn, Bi, In, and the like.
- additives are contained at 0.001 to 50 g/L, preferably 0.005 to 30 g/L.
- hydroxyphenyl compounds such as catechol, pyrogallol, hydroquinone, sulfosalicylic acid, potassium dihydroxybenzenesulfonate and salts thereof and L-ascorbic acid, sorbitol and the like also can be used as oxidation preventing agents for tin.
- the articles to be plated by the plating method in accordance with the present invention are metal materials such as Fe, Ni, Cu, or alloys based thereon, and the plating is carried out by using them as cathodes.
- a carbon electrode and insoluble electrode obtained by plating Pt on a Ti material or tin-zinc alloy can be used as a counter electrode thereof.
- the concentration of metals in the plating bath that is being used can be maintained by directly dissolving the aforementioned tin and zinc salts in the plating bath or by supplying an aqueous solution in which tin and zinc salts are dissolved into a high concentration.
- the high-concentration aqueous solution of the metals may contain the above-described hydroxycarboxylic acid or salt thereof and an alkali hydroxide compound.
- the cathode current density is 10 to 120 A/dm 2 .
- the film thickness can be within a wide range, but is generally 0.5 to 500 ⁇ m, preferably 2 to 20 ⁇ m.
- Tin-zinc alloy plating can be performed within a wide range of alloy compositions by changing the ratio of tin ions and zinc ions in the plating bath that is being used.
- tin-zinc alloy coatings with a zinc content of 3 to 15% can be obtained on electronic components.
- a tin-zinc alloy coating with a zinc content of 15 to 45% can be obtained.
- a tin-zinc alloy coating with a zinc content of 50 to 90% can be produced.
- the article to be plated is subjected to plating after a pretreatment conducted by the usual method. At least one operation selected from immersion degreasing, pickling, electrolytic washing, and activation is performed in the pretreatment process.
- the film obtained may be washed with water and dried, or can be further coated by a chromating and conversion treatment, or with an inorganic or organic material by the usual method.
- the present invention will be described below based on embodiments thereof, but the present invention is not limited to the embodiments, and the plating solution temperature, flow rate of the plating solution, and the composition of the plating bath can be freely changed according to the article to be plated.
- a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 50 m/min.
- Tin (I) sulfate (as tin) 30 g/L
- Zinc sulfate (as zinc) 25 g/L
- Product obtained by reacting 1 mole of ethylene diamine and 1 mole of dimethyl malonate for 60 mins. at 85°C and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 90 mins. at 95°C pH 4 (adjusted with ammonia water) 10 mL/L
- a steel sheet was pretreated, Nymin NAG-1001 manufactured by Nippon Oils & Fats Co., Ltd. was added as a nonionic surfactant at 5 g/L to the plating solution of Embodiment 1, and electroplating was conducted under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 30 m/min.
- a steel sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 30 m/min.
- Potassium stannate (as tin) 55 g/L
- Zinc oxide (as zinc) 5 g/L
- Potassium hydroxide 80 g/L
- Potassium carbonate 100 g/L Product obtained by reacting 1 mole of 1-methyl imidazole and 1 mole of benzyl chloride for 180 mins. at 85°C 1 g/L Product obtained by reacting 1 mole of diethylene triamine and 1 mole of ethylene chlorhydrine for 90 mins. at 100°C 1 g/L pH 14
- a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 50°C and a plating bath stirring rate of 60 m/min.
- Citric acid 120 g/L (0.57 mole/L)
- Product obtained by reacting 1 mole of triethylene tetramine and 1.2 mole of diethyl succinate for 40 mins. at 80°C and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.7:1 for 120 mins. at 90°C 10 mL/L
- a phosphorus bronze sheet was pretreated and then electroplated by using the following plating solution under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 60 m/min.
- Tin methanesulfonate (as tin) 30 g/L
- Zinc methanesulfonate (as zinc) 15 g/L
- Sodium gluconate 150 g/L (0.69 mole/L)
- Methanesulfonic acid 100 g/L
- Product obtained by reacting 1 mole of ethylene diamine and 1 mole of dimethyl maleate for 60 mins. at 90°C and then reacting phthalic anhydride with the obtained product at a weight ratio of 0.5:1 for 150 mins. at 110°C 8 mL/L Salicylaldehyde pH 6.2 (adjusted with sodium hydroxide) 0.05 g/L
- a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 23°C and a plating bath stirring rate of 50 m/min.
- a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 1 under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 2 m/min.
- a steel sheet was pretreated and then electroplated by using the plating solution of Embodiment 3 under the conditions of a plating bath temperature of 60°C and a plating bath stirring rate of 3 m/min.
- Example 1 Example 2
- Example 3 Plated precip itate state Sn/Zn (wt.%) Treatment time Film thickness ( ⁇ m) Plated precip itate state Sn/Zn (wt.%) Treatment time Film thickness ( ⁇ m) Plated precip itate state Sn/Zn (wt.%) Treatment time Film thickness ( ⁇ m) 10A/dm 2 ⁇ 70/30 120 8.8 ⁇ 70/30 120 8.8 ⁇ 45/55 240 7.0 20A/dm 2 ⁇ 70/30 60 8.8 ⁇ 70/30 60 8.8 ⁇ 45/55 120 6.5 30A/dm 2 ⁇ 70/30 40 8.8 ⁇ 70/30 40 8.8 ⁇ 40/60 80 4.9 40A/dm 2 ⁇ 72/28 30 8.9 ⁇ 70/30 30 8.8 ⁇ 40/60 60 3.5 50A/dm
- Example 5 Plated precipitate state Sn/Zn (wt.%) Treatment time Film thickness ( ⁇ m) Plated precipitate state Sn/Zn (wt.%) Treatment time Film thickness ( ⁇ m) 10A/dm 2 ⁇ 88/12 120 9.4 ⁇ 85/15 120 9.0 20A/dm 2 ⁇ 90/10 60 9.2 ⁇ 80/20 60 8.5 30A/dm 2 ⁇ 90/10 40 9.2 ⁇ 80/20 40 8.5 40A/dm 2 ⁇ 90/10 30 9.2 ⁇ 80/20 30 8.0 50A/dm 2 ⁇ 90/10 25 9.0 ⁇ 80/20 25 7.9 60A/dm 2 ⁇ 90/10 20 8.6 ⁇ 85/15 20 7.6 70A/dm 2 ⁇ 91/9 17 7.2 ⁇ 84/16 17 7.3 80A/dm 2 ⁇ 91/9 15 6.4 ⁇ 88/12 15 6.0 90A/dm 2
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004233633A JP4594672B2 (ja) | 2004-08-10 | 2004-08-10 | 錫−亜鉛合金電気めっき方法 |
PCT/JP2005/014648 WO2006016603A1 (ja) | 2004-08-10 | 2005-08-10 | 錫-亜鉛合金電気めっき方法 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1811063A1 EP1811063A1 (en) | 2007-07-25 |
EP1811063A4 EP1811063A4 (en) | 2009-03-04 |
EP1811063B1 true EP1811063B1 (en) | 2014-12-03 |
Family
ID=35839372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05770802.6A Active EP1811063B1 (en) | 2004-08-10 | 2005-08-10 | Tin-zinc alloy electroplating method |
Country Status (8)
Country | Link |
---|---|
US (1) | US20070199827A1 (ko) |
EP (1) | EP1811063B1 (ko) |
JP (1) | JP4594672B2 (ko) |
KR (1) | KR100929761B1 (ko) |
CN (1) | CN101001982B (ko) |
BR (1) | BRPI0514210B1 (ko) |
ES (1) | ES2526430T3 (ko) |
WO (1) | WO2006016603A1 (ko) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634827B (zh) * | 2012-05-07 | 2015-04-08 | 东莞市闻誉实业有限公司 | 一种锡-锌合金电镀方法 |
CN102690975B (zh) * | 2012-06-11 | 2014-12-03 | 东莞市闻誉实业有限公司 | 一种三元锡-锌合金及其电镀方法 |
CN104213159A (zh) * | 2014-09-17 | 2014-12-17 | 朱忠良 | 电镀液及电镀方法 |
CN104357884A (zh) * | 2014-11-14 | 2015-02-18 | 无锡伊佩克科技有限公司 | 一种钢铁材料镀锌锡合金方法 |
CN105002526A (zh) * | 2015-06-30 | 2015-10-28 | 安徽飞达新材料科技股份有限公司 | 一种冷轧钢板光亮剂 |
CN105350056B (zh) * | 2015-11-24 | 2017-12-01 | 安徽天思朴超精密模具股份有限公司 | 耐磨损电镀液材料组合物和耐磨损电镀液的制备方法及应用 |
KR101678013B1 (ko) * | 2016-02-15 | 2016-11-21 | 주식회사 베프스 | 금속성분의 액중 농도 지시체를 포함하는 도금액 및 이를 이용한 도금 방법 |
KR102621912B1 (ko) * | 2018-12-24 | 2024-01-05 | 현대자동차주식회사 | 휘스커 저항성이 우수한 전기전자부품용 아연 도금 방법 및 아연 도금 강판 |
CN111188069A (zh) * | 2019-12-31 | 2020-05-22 | 大连长丰实业总公司 | 一种镀锡铋合金溶液及其制备方法 |
CN111394734A (zh) * | 2020-05-06 | 2020-07-10 | 苏州清飙科技有限公司 | 压铸锌合金用脱膜抛光液及其制备方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5175632A (en) * | 1974-12-27 | 1976-06-30 | Dipsol Chem | Kotakusuzu aengokindenkimetsukyotenkabutsu |
JPS5175633A (en) * | 1974-12-27 | 1976-06-30 | Dipsol Chem | Suzu aengokinmetsukyoku |
US4183799A (en) * | 1978-08-31 | 1980-01-15 | Production Machinery Corporation | Apparatus for plating a layer onto a metal strip |
US4749626A (en) * | 1985-08-05 | 1988-06-07 | Olin Corporation | Whisker resistant tin coatings and baths and methods for making such coatings |
JPH02175894A (ja) * | 1988-12-28 | 1990-07-09 | Kosaku:Kk | スズ、スズ合金電気めっき方法及び同電気めっき装置 |
JP3279353B2 (ja) * | 1992-09-25 | 2002-04-30 | ディップソール株式会社 | 錫−亜鉛合金電気めっき浴 |
JPH06228786A (ja) * | 1993-01-29 | 1994-08-16 | Deitsupusoole Kk | 錫−亜鉛合金めっき浴及びそれを使用するめっき方法 |
JP3233784B2 (ja) * | 1994-08-01 | 2001-11-26 | 日本鋼管株式会社 | 優れた外観を有する電気亜鉛めっき鋼板 |
US5985106A (en) * | 1995-07-14 | 1999-11-16 | Velasquez; Geronimo Z. | Continuous rack plater |
JP3609565B2 (ja) * | 1996-12-09 | 2005-01-12 | 株式会社大和化成研究所 | 錫−亜鉛合金めっき浴 |
JP3366851B2 (ja) * | 1997-12-18 | 2003-01-14 | 株式会社ジャパンエナジー | 錫合金電気めっき液およびめっき方法 |
JP4249292B2 (ja) * | 1998-07-10 | 2009-04-02 | 株式会社大和化成研究所 | 錫及び錫合金メッキ浴 |
US6322686B1 (en) * | 2000-03-31 | 2001-11-27 | Shipley Company, L.L.C. | Tin electrolyte |
JP2002275678A (ja) * | 2001-01-11 | 2002-09-25 | Nikko Materials Co Ltd | ウィスカーフリー錫及び錫合金めっき液、めっき被膜並びにめっき物 |
JP4441726B2 (ja) * | 2003-01-24 | 2010-03-31 | 石原薬品株式会社 | スズ又はスズ合金の脂肪族スルホン酸メッキ浴の製造方法 |
-
2004
- 2004-08-10 JP JP2004233633A patent/JP4594672B2/ja active Active
-
2005
- 2005-08-10 CN CN2005800271252A patent/CN101001982B/zh active Active
- 2005-08-10 ES ES05770802.6T patent/ES2526430T3/es active Active
- 2005-08-10 WO PCT/JP2005/014648 patent/WO2006016603A1/ja active Application Filing
- 2005-08-10 BR BRPI0514210A patent/BRPI0514210B1/pt not_active IP Right Cessation
- 2005-08-10 KR KR1020077002958A patent/KR100929761B1/ko active IP Right Grant
- 2005-08-10 EP EP05770802.6A patent/EP1811063B1/en active Active
-
2007
- 2007-02-09 US US11/704,805 patent/US20070199827A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1811063A4 (en) | 2009-03-04 |
JP2006052431A (ja) | 2006-02-23 |
BRPI0514210B1 (pt) | 2016-05-03 |
CN101001982A (zh) | 2007-07-18 |
EP1811063A1 (en) | 2007-07-25 |
KR100929761B1 (ko) | 2009-12-03 |
WO2006016603A1 (ja) | 2006-02-16 |
KR20070031442A (ko) | 2007-03-19 |
JP4594672B2 (ja) | 2010-12-08 |
CN101001982B (zh) | 2010-09-08 |
ES2526430T3 (es) | 2015-01-12 |
US20070199827A1 (en) | 2007-08-30 |
BRPI0514210A2 (pt) | 2009-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1811063B1 (en) | Tin-zinc alloy electroplating method | |
US6129830A (en) | Process for the electrolytic deposition of copper layers | |
KR101609171B1 (ko) | 구리-주석 합금의 무-시안화물 침착을 위한 피로인산염-함유 욕 | |
US4889602A (en) | Electroplating bath and method for forming zinc-nickel alloy coating | |
EP0770711B1 (en) | Sn-Bi alloy-plating bath and method for forming plated Sn-Bi alloy film | |
EP1138805A2 (en) | Tin electolyte | |
TWI439580B (zh) | 用於電鍍錫合金層之焦磷酸鹽基浴 | |
WO2007147605A2 (de) | Tripyridinium-verbindungen als zusätze in wässrigen alkalischen, cyanidfreien bädern zur galvanischen abscheidung von zink- und zinklegierungsüberzügen | |
GB2075063A (en) | Process for plating polumeric substrates | |
US5169514A (en) | Plating compositions and processes | |
KR20110011613A (ko) | 개질된 구리-주석 전해액, 및 청동 층의 침착 방법 | |
EP0715003A1 (en) | Sn-Bi alloy-plating bath and plating method using the same | |
EP1292724B1 (en) | Zinc-nickel electroplating | |
US6755960B1 (en) | Zinc-nickel electroplating | |
EP2350355B1 (en) | Zinc alloy electroplating baths and processes | |
KR20130098304A (ko) | 구리-주석 합금 층들을 전착시키기 위한 전해질 및 공정 | |
WO2004108995A1 (en) | Zinc and zinc-alloy electroplating | |
EP0663460A1 (en) | Tin-zinc alloy electroplating bath and method for electroplating using the same | |
US6387229B1 (en) | Alloy plating | |
US20070023280A1 (en) | Zinc and zinc-alloy electroplating | |
JP7121390B2 (ja) | すず合金電気めっき浴及びそれを用いためっき方法 | |
JP2997072B2 (ja) | 亜鉛−ニッケル合金めっき浴及び被めっき物上の黒色析出を防止する方法 | |
CN103806046A (zh) | 一种通过外加磁场提高电镀层沉积速率的方法 | |
JPS6319600B2 (ko) | ||
KR20020013873A (ko) | 합금 도금 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20070209 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20090204 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25D 3/60 20060101AFI20090129BHEP Ipc: C25D 5/08 20060101ALI20090129BHEP Ipc: C25D 21/10 20060101ALI20090129BHEP |
|
17Q | First examination report despatched |
Effective date: 20090507 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140130 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140627 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 699438 Country of ref document: AT Kind code of ref document: T Effective date: 20141215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602005045355 Country of ref document: DE Effective date: 20150108 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2526430 Country of ref document: ES Kind code of ref document: T3 Effective date: 20150112 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 699438 Country of ref document: AT Kind code of ref document: T Effective date: 20141203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150304 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150403 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602005045355 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
26N | No opposition filed |
Effective date: 20150904 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150810 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150831 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20050810 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141203 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CZ Payment date: 20190617 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20190612 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20190904 Year of fee payment: 15 Ref country code: IT Payment date: 20190715 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20190827 Year of fee payment: 15 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20220114 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200811 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230821 Year of fee payment: 19 |