JP6803502B2 - Alkaline Substitution Tinning Bath on Aluminum Base - Google Patents
Alkaline Substitution Tinning Bath on Aluminum Base Download PDFInfo
- Publication number
- JP6803502B2 JP6803502B2 JP2016250083A JP2016250083A JP6803502B2 JP 6803502 B2 JP6803502 B2 JP 6803502B2 JP 2016250083 A JP2016250083 A JP 2016250083A JP 2016250083 A JP2016250083 A JP 2016250083A JP 6803502 B2 JP6803502 B2 JP 6803502B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- bath
- hydroxide
- acid
- alkaline
- 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
- 229910052782 aluminium Inorganic materials 0.000 title claims description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 57
- 238000006467 substitution reaction Methods 0.000 title description 22
- 238000007747 plating Methods 0.000 claims description 99
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 95
- 229910052718 tin Inorganic materials 0.000 claims description 92
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- 239000008139 complexing agent Substances 0.000 claims description 47
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 31
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229960003330 pentetic acid Drugs 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 21
- -1 alkali metal succinate Chemical class 0.000 claims description 20
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 claims description 19
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 claims description 18
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 6
- 229940074404 sodium succinate Drugs 0.000 claims description 6
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- PBUBJNYXWIDFMU-UHFFFAOYSA-L calcium;butanedioate Chemical compound [Ca+2].[O-]C(=O)CCC([O-])=O PBUBJNYXWIDFMU-UHFFFAOYSA-L 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- HFAQXXPQBRIXGD-UHFFFAOYSA-L barium(2+);butanedioate Chemical compound [Ba+2].[O-]C(=O)CCC([O-])=O HFAQXXPQBRIXGD-UHFFFAOYSA-L 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 2
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical compound CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 claims description 2
- 208000030452 Transient pseudohypoaldosteronism Diseases 0.000 claims 2
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 40
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 29
- 239000000463 material Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 15
- 229910000838 Al alloy Inorganic materials 0.000 description 12
- 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 12
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 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 9
- 239000000174 gluconic acid Substances 0.000 description 9
- 235000012208 gluconic acid Nutrition 0.000 description 9
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 8
- 229940071182 stannate Drugs 0.000 description 8
- 125000005402 stannate group Chemical group 0.000 description 8
- 229960002989 glutamic acid Drugs 0.000 description 7
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000013922 glutamic acid Nutrition 0.000 description 6
- 239000004220 glutamic acid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002332 glycine derivatives Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 235000001968 nicotinic acid Nutrition 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 description 2
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229940050410 gluconate Drugs 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- IYNGLSRZLOHZJA-UHFFFAOYSA-N 1,4,7-triazabicyclo[5.2.2]undecane Chemical compound C1CN2CCN1CCNCC2 IYNGLSRZLOHZJA-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- TWFSYIOOAAYYAL-UHFFFAOYSA-N 2,4,6-trichlorobenzaldehyde Chemical compound ClC1=CC(Cl)=C(C=O)C(Cl)=C1 TWFSYIOOAAYYAL-UHFFFAOYSA-N 0.000 description 1
- XHANCLXYCNTZMM-UHFFFAOYSA-N 2,5-dimethyl-1,3-benzothiazole Chemical compound CC1=CC=C2SC(C)=NC2=C1 XHANCLXYCNTZMM-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
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- HNQGTZYKXIXXST-UHFFFAOYSA-N calcium;dioxido(oxo)tin Chemical compound [Ca+2].[O-][Sn]([O-])=O HNQGTZYKXIXXST-UHFFFAOYSA-N 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
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Landscapes
- Chemically Coating (AREA)
Description
本発明はアルミニウム基材にスズ皮膜を形成するためのアルカリ性置換スズメッキ浴に関して、作業時に白濁の発生がないメッキ浴の安定性と基材へのスズ皮膜の密着性に優れるものを提供する。 The present invention provides an alkaline substituted tin-plated bath for forming a tin film on an aluminum base material, which is excellent in stability of the plating bath without causing white turbidity during work and adhesion of the tin film to the base material.
アルミニウム材は容易に表面酸化されるので表面処理は難しい。酸性の置換スズはチオ尿素を使用するが、酸性置換ではスズが析出しても粉状を呈する場合が多く、均質なスズ皮膜を得ることは容易でない。
従って、実際にはアルカリ性の置換スズが直接メッキ可能なほぼ唯一の方法である。
このアルカリ性の置換スズではチオ尿素が作用しないため、アルミニウムとスズの単純な電位差を利用した置換メッキが基本原理となる。
Surface treatment is difficult because the surface of aluminum is easily oxidized. Thiourea is used as the acidic substituted tin, but in the acidic substitution, even if tin is precipitated, it often becomes powdery, and it is not easy to obtain a homogeneous tin film.
Therefore, in practice, alkaline substituted tin is almost the only method that can be directly plated.
Since thiourea does not act on this alkaline substituted tin, substitution plating using a simple potential difference between aluminum and tin is the basic principle.
そこで、アルミニウム基材に対するアルカリ性置換スズメッキ浴の従来技術を挙げると、次の通りである。
（1）特許文献１
アミノカルボン酸系及びポリヒドロキシカルボン酸系の錯化剤（ジョングキンドキレート剤（＝ヨンキント錯化剤））と、スズ酸ナトリウム及びスズ酸カリウムから選ばれたスズ酸塩とを含有する水溶液中にアルミニウム（アルミニウム合金を含む）を浸漬して、アルミニウム上にスズ皮膜を形成する。
上記アミノカルボン酸系錯化剤にはエチレンジアミン四酢酸（ＥＤＴＡ）、ジヒドロキシエチルエチレンジアミン３酢酸、ジヒドロキシエチルグリシン（ＤＨＥＧ）の各種塩、グルコン酸、グルコヘプトン酸、グリセリン酸、糖類の酸、酒石酸の各種塩が挙げられる（第５欄第２１行〜第６欄第１２行、第７欄第２〜３３行）。
Therefore, the prior art of the alkaline substitution tin plating bath for the aluminum base material is as follows.
(1) Patent Document 1
In an aqueous solution containing an aminocarboxylic acid-based and polyhydroxycarboxylic acid-based complexing agent (Johngkind chelating agent (= Youngkinto complexing agent)) and a stannate selected from sodium succinate and potassium succinate. Immerse aluminum (including aluminum alloy) to form a tin film on the aluminum.
The aminocarboxylic acid-based complexing agent includes various salts of ethylenediaminetetraacetic acid (EDTA), dihydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine (DHEG), gluconic acid, glucoheptonic acid, glyceric acid, saccharide acid, and tartrate acid. (Column 5, line 21 to column 6, line 12, column 7, line 2-33).
（2）特許文献２
リン酸化合物、シアン化物及びフッ素イオンを含まない水系アルカリ性ｐＨ液浸スズコーティング組成物であって、スズイオン源と、スラッジ抑制剤と、付着性促進に有効な量のモリブデンイオンと、緩衝作用に有効な量の無機緩衝剤と、付着性促進に有効な量の有機ポリヒドロキシ化合物とを含有するコーティング組成物である。
上記スズイオン源はスズ酸カリウム、スズ酸ナトリウムなどである（第７頁）。
上記スラッジ抑制剤は有機錯化剤であり、ＥＤＴＡ、ニトリロ３酢酸（ＮＴＡ）、ＤＨＥＧ、グリシン、アスパラギン酸、グルタミン酸などのアミノカルボン酸及びその塩、ジエチレンジアミン、トリエチレンジアミン、テトラエチレントリアミンなどである（第７頁）。
上記無機緩衝剤はホウ酸化合物、炭酸化合物などである（第８頁）。
上記ポリヒドロキシ化合物はエチレングリコール、プロピレングリコール、グルコン酸などである（第８頁）。
(2) Patent Document 2
An aqueous alkaline pH solution tin coating composition free of phosphate compounds, cyanides and fluorine ions, which is effective for a tin ion source, a sludge inhibitor, an amount of molybdenum ion effective for promoting adhesion, and a buffering action. A coating composition containing a large amount of an inorganic buffer and an amount of an organic polyhydroxy compound effective for promoting adhesion.
The tin ion source is potassium succinate, sodium succinate, etc. (page 7).
The sludge inhibitor is an organic complexing agent, and is an aminocarboxylic acid such as EDTA, nitrilotriacetic acid (NTA), DHEG, glycine, aspartic acid, glutamic acid and a salt thereof, diethylenediamine, triethylenediamine, tetraethylenetriamine and the like. (Page 7).
The inorganic buffering agent is a boric acid compound, a carbonic acid compound, or the like (page 8).
The polyhydroxy compound is ethylene glycol, propylene glycol, gluconic acid and the like (page 8).
（3）特許文献３
均一で摺動性に優れたスズ皮膜を形成する目的で、スズ酸アルカリ金属塩と、アミノ酸類と、及び２価の銅塩とを各所定量で含有する水溶液からなるアルミニウム合金上へのスズ置換液である（請求項１、段落６〜７）。
上記アミノ酸はグリシン、グルタミン酸、リジンなどである（請求項２）。
比較例１〜４には、ＥＤＴＡの塩、グルコン酸塩、クエン酸、ＥＤＴＡと酒石酸の混合物を夫々錯化剤に用いたスズ置換液が開示される（段落３４〜４０）。
(3) Patent Document 3
For the purpose of forming a uniform and highly slidable tin film, tin substitution on an aluminum alloy consisting of an aqueous solution containing an alkali metal tinic acid salt, amino acids, and a divalent copper salt in predetermined amounts of each. It is a liquid (claim 1, paragraphs 6-7).
The amino acids include glycine, glutamic acid, lysine and the like (claim 2).
Comparative Examples 1 to 4 disclose tin substitution solutions using EDTA salts, gluconates, citric acid, and mixtures of EDTA and tartaric acid as complexing agents, respectively (paragraphs 34-40).
（4）特許文献４
均一で摺動性に優れたスズ皮膜を形成する目的で、スズ酸アルカリ金属塩と、ピロリン酸塩と、２価の銅塩とを各所定量で含有する水溶液からなるアルミニウム合金上へのスズ置換液である（請求項１、段落６〜７）。
上記特許文献３と同様に、比較例１〜４には、ＥＤＴＡの塩、グルコン酸塩、クエン酸、ＥＤＴＡと酒石酸の混合物を夫々錯化剤に用いたスズ置換液が開示される（段落２９〜３５）。
(4) Patent Document 4
For the purpose of forming a uniform tin film with excellent slidability, tin substitution on an aluminum alloy consisting of an aqueous solution containing an alkali metal tinic acid salt, a pyrophosphate, and a divalent copper salt in predetermined amounts of each. It is a liquid (claim 1, paragraphs 6-7).
Similar to Patent Document 3, Comparative Examples 1 to 4 disclose tin substituents using a salt of EDTA, gluconate, citric acid, and a mixture of EDTA and tartaric acid as complexing agents, respectively (paragraph 29). ~ 35).
（5）特許文献５
アルミニウム基材に置換スズ皮膜を形成することに関して、スズ酸塩（スズ酸ナトリウム塩、同カリウム塩）とヨンキント錯化剤を含む置換スズメッキ浴が開示される。前記先行文献１に先行する特許である。
上記ヨンキント錯化剤としては、前記先行文献１と同じく、アミノカルボン酸系錯化剤（ＥＤＴＡ、ジヒドロキシエチルグリシン（ＤＨＥＧ）、ヒドロキシエチルエチレンジアミン三酢酸など）とポリヒドロキシカルボン酸系錯化剤（グルコン酸塩、グルコヘプトン酸塩、グリセリン酸塩など）が開示される。
尚、米国特許第３６１６２９１号には、アルミニウム基材上に電気メッキでスズ皮膜を形成することが開示される。
(5) Patent Document 5
Regarding the formation of a substituted tin film on an aluminum substrate, a substituted tin plating bath containing a stannate (sodium chlorate salt, potassium salt) and a yonkinto complexing agent is disclosed. This is a patent that precedes the prior document 1.
The Yonkinto complexing agent includes an aminocarboxylic acid-based complexing agent (EDTA, dihydroxyethylglycine (DHEG), hydroxyethylethylenediamine triacetic acid, etc.) and a polyhydroxycarboxylic acid-based complexing agent (glucon) as in the prior document 1. Acidates, glucoheptates, glycerates, etc.) are disclosed.
U.S. Pat. No. 3,616,291 discloses that a tin film is formed on an aluminum substrate by electroplating.
（6）特許文献６
アルミニウム基材に置換スズ皮膜を形成することに関して、スズ酸塩（スズ酸ナトリウム塩、同カリウム塩）とヨンキント錯化剤を含む置換スズメッキ浴が開示される。前記先行文献５に先行する特許である。
上記ヨンキント錯化剤としては、前記特許文献１のうち、ポリヒドロキシカルボン酸系錯化剤（グルコン酸塩、グルコヘプトン酸塩、グリセリン酸塩、糖類酸の塩、酒石酸塩など）が開示される。
(6) Patent Document 6
Regarding the formation of a substituted tin film on an aluminum substrate, a substituted tin plating bath containing a stannate (sodium chlorate salt, potassium salt) and a yonkinto complexing agent is disclosed. This is a patent that precedes the prior document 5.
As the Yonkinto complexing agent, a polyhydroxycarboxylic acid-based complexing agent (gluconate, glucoheptonate, glycerate, saccharide acid salt, tartaric acid, etc.) is disclosed in Patent Document 1.
（7）その他の特許文献
以下は参考的な文献であり、アルミニウム基材上への置換又は無電解メッキであってスズメッキを含むもの、或は、スズイオン含有液による前処理に関するものである。
特開平７−３４２５４号公報には、アルミニウム系材料上に、亜鉛又はスズを主成分とする置換液で皮膜を形成し、次いで、還元剤を含有する水溶液で処理を行なった後、無電解メッキ処理をするアルミニウム系材料への無電解めっき方法が開示される（請求項１）。還元剤を含有する水溶液により金属置換皮膜の表面を均一に活性化でき、形成された無電解皮膜の外観性、密着性などを改善できる（段落７）。スズ置換液はスズ酸ナトリウムと水酸化ナトリウムを含有する（段落１５）。
特開２００９−１２７１０１号公報には、少なくともアルミニウムと置換可能な金属の塩と、アルカリ化合物（水酸化第４級アンモニウム）とを含有するアルミニウム合金上への金属置換処理液が開示される。上記金属は亜鉛、スズ、ニッケル、銅などであり（請求項４、段落１６）、置換はジンケート処理が中心であり、スズ置換の例示はない。
特開２０１６−１４８０８６号公報には、アルミニウム系基材に置換スズメッキ処理（＝スタネート処理）又はジンケート処理からなるメッキ促進処理をした後、スズ−銅合金メッキ皮膜及びスズ皮膜を順次形成することが開示される（請求項１〜３）。但し、上記置換スズメッキ浴の組成は不明である（段落２１）。
特開２００２−０７９７７１号公報には、陽極酸化処理をしたアルミニウム系基材に無電解メッキにてスズの下地皮膜を形成した後、銅皮膜を形成することが開示されるが、無電解スズメッキ浴の組成は不明である（段落２９〜３０）。
特開２０１２−０４１５７９号公報はアルミニウム系基材の表面加工方法及び前処理液に関して、アルミニウム合金材をスズ酸カリウムと酸化亜鉛と水酸化ナトリウムの含有液で前処理して所定の皮膜を形成した後（段落６２）、エッチングにより粗化処理することが開示される（請求項１）。
特開２０１４−０４３６３２号公報には、アルミニウム系基材にジンケート処理で亜鉛皮膜を形成した後、置換スズメッキ処理を施すことが開示される（請求項１）。置換スズ浴には錯化剤として奥野製薬のサブスターＡＳ−２５が用いられる（段落３０）。
(7) Other Patent Documents The following are reference documents, which relate to substitution on an aluminum substrate or electroless plating including tin plating, or pretreatment with a tin ion-containing liquid.
In Japanese Patent Application Laid-Open No. 7-34254, a film is formed on an aluminum-based material with a substitution solution containing zinc or tin as a main component, and then treated with an aqueous solution containing a reducing agent, followed by electroless plating. An electroless plating method for an aluminum-based material to be treated is disclosed (claim 1). The surface of the metal substitution film can be uniformly activated by the aqueous solution containing the reducing agent, and the appearance and adhesion of the formed electroless film can be improved (paragraph 7). The tin replacement solution contains sodium tinate and sodium hydroxide (paragraph 15).
Japanese Unexamined Patent Publication No. 2009-127101 discloses a metal substitution treatment liquid on an aluminum alloy containing at least a salt of a metal substitutable for aluminum and an alkaline compound (quaternary ammonium hydroxide). The metal is zinc, tin, nickel, copper or the like (claim 4, paragraph 16), and the substitution is mainly zincate treatment, and there is no example of tin substitution.
According to Japanese Patent Application Laid-Open No. 2016-148806, a tin-copper alloy plating film and a tin film are sequentially formed after performing a plating acceleration treatment consisting of a substitution tin plating treatment (= stnate treatment) or a zincate treatment on an aluminum-based base material. It is disclosed (claims 1 to 3). However, the composition of the substituted tin-plated bath is unknown (paragraph 21).
Japanese Unexamined Patent Publication No. 2002-079771 discloses that a copper film is formed after forming a tin base film by electroless plating on an anodicated aluminum-based substrate. The composition of is unknown (paragraphs 29-30).
Japanese Patent Application Laid-Open No. 2012-041579 describes a surface processing method for an aluminum-based base material and a pretreatment liquid, in which an aluminum alloy material is pretreated with a liquid containing potassium stannate, zinc oxide and sodium hydroxide to form a predetermined film. Later (paragraph 62), it is disclosed that the roughening treatment is performed by etching (claim 1).
Japanese Unexamined Patent Publication No. 2014-043632 discloses that a zinc film is formed on an aluminum-based base material by a zincate treatment, and then a substitution tin plating treatment is performed (claim 1). Okuno Pharmaceutical's Substar AS-25 is used as a complexing agent in the substituted tin bath (paragraph 30).
前述した通り、アルミニウム基材上へのアルカリ性置換スズメッキは単純な電位差を利用したものであるが、チオ尿素に代わる錯化剤は必要であり、上記特許文献に見るように、グルコン酸、グルコヘプトン酸などのヒドロキシカルボン酸系錯化剤、或は、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）などのアミノカルボン酸系錯化剤が使用される。
アルカリ性置換スズメッキ浴において、錯化剤に上記特許文献に開示されたグルコン酸などのヒドロキシカルボン酸を使用すると、ランニングによりスラッジが発生してメッキ浴が白濁するうえ、アルミニウム基材への密着性も高くなく、メッキ浴の安定性と皮膜の密着性の両面で問題が多い。
また、上記特許文献に開示されたＮＴＡ、ＥＤＴＡなどのアミノカルボン酸系錯化剤は、グルコン酸などのヒドロキシカルボン酸系列の錯化剤より安定性は少し改善されるが、依然として白濁が生じるうえ、白濁に起因して密着性も良くないという問題がある。
As described above, alkaline substituted tin plating on an aluminum substrate utilizes a simple potential difference, but a complexing agent instead of thiourea is required, and as seen in the above patent documents, gluconic acid and glucoheptoic acid Hydroxycarboxylic acid-based complexing agents such as, or aminocarboxylic acid-based complexing agents such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) are used.
When a hydroxycarboxylic acid such as gluconic acid disclosed in the above patent document is used as a complexing agent in an alkaline substituted tin plating bath, sludge is generated by running, the plating bath becomes cloudy, and adhesion to an aluminum substrate is also improved. It is not expensive, and there are many problems in terms of both the stability of the plating bath and the adhesion of the film.
Further, the aminocarboxylic acid-based complexing agents such as NTA and EDTA disclosed in the above patent documents have slightly improved stability as compared with the hydroxycarboxylic acid-based complexing agents such as gluconic acid, but white turbidity still occurs. There is a problem that the adhesion is not good due to cloudiness.
本発明は、アルミニウム基材上へのアルカリ性置換スズメッキに際して、メッキ作業時の白濁を防止してメッキ浴の安定性を向上し、且つ、スズ皮膜をアルミニウム基材に対して強固に密着することを技術的課題とする。 According to the present invention, when performing alkaline substitution tin plating on an aluminum base material, it is possible to prevent white turbidity during plating work, improve the stability of the plating bath, and firmly adhere the tin film to the aluminum base material. Make it a technical issue.
本発明者らは、アルミニウム基材上へのアルカリ性置換スズメッキにおいて、当該スズメッキ浴に使用されるアミノカルボン酸系錯化剤に着目し、上記特許文献に開示されたＥＤＴＡやＮＴＡではなく、ジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）などの特定のアミノカルボン酸類を上記置換スズメッキ浴に適用すると、アミノカルボン酸類に属する同じ系列の錯化剤であっても、上記文献公知のＥＤＴＡ、ＮＴＡに対して、ＤＴＰＡ、ＴＴＨＡのような分子内に５個以上の酢酸基が結合したアミノカルボン酸類では、作業時のスズメッキ浴の性状、並びに、当該浴から得られるスズ皮膜のアルミニウム基材に対する性質に顕著な優位性があるという予測外の知見を得た。
即ち、ＤＴＰＡ、ＴＴＨＡなどで代表される分子内に５個以上の酢酸基が結合したアミノカルボン酸類を上記アルカリ性置換スズメッキ浴に適用すると、メッキ作業時の白濁を防止して浴の安定性が飛躍的に改善すること、また、浴から得られるスズ皮膜をアルミニウム基材に強固に密着できることを見い出して、本発明を完成した。
The present inventors have focused on the aminocarboxylic acid-based complexing agent used in the tin-plated bath in alkaline-substituted tin plating on an aluminum substrate, and instead of EDTA and NTA disclosed in the above patent documents, diethylenetriamine-5 When specific aminocarboxylic acids such as acetic acid (DTPA) and triethylenetetraminehexacetic acid (TTHA) are applied to the substituted tin plating bath, EDTA is known in the above literature even if it is a complexing agent of the same series belonging to the aminocarboxylic acids. , NTA, DTPA, TTHA, and other aminocarboxylic acids in which 5 or more acetic acid groups are bonded in the molecule, the properties of the tin-plated bath during work, and the tin-coated aluminum base material obtained from the bath. We obtained the unexpected finding that there is a significant advantage in the properties against.
That is, when aminocarboxylic acids in which five or more acetic acid groups are bonded in a molecule represented by DTPA, TTHA, etc. are applied to the above alkaline substituted tin plating bath, white turbidity during plating work is prevented and the stability of the bath is dramatically improved. The present invention has been completed by finding that the tin film obtained from the bath can be firmly adhered to the aluminum base material.
即ち、本発明１は、アルミニウム基材に対して置換スズ皮膜を形成するメッキ浴であり、
上記置換スズメッキ浴が、
(ａ)可溶性第二スズ塩と、
(ｂ)錯化剤と、
(ｃ)水酸化物とを含有するアルカリ性置換スズメッキ浴であって、
上記錯化剤（ｂ）が、分子内に５個以上の酢酸基が結合したアミノカルボン酸類であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴である。
That is, the present invention 1 is a plating bath that forms a substituted tin film on an aluminum base material.
The above replacement tin-plated bath
(a) Soluble stannic salt and
(b) Coordinator and
(c) An alkaline substituted tin-plated bath containing hydroxide.
The complexing agent (b) is an alkaline substitution tin plating bath on an aluminum base material, which is an aminocarboxylic acid having 5 or more acetic acid groups bonded in the molecule.
本発明２は、上記本発明１において、上記アミノカルボン酸類(ｂ)がジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、テトラエチレンペンタミン七酢酸（ＴＰＨＡ）、ペンタエチレンヘキサミン八酢酸、ヘキサエチレンヘプタミン九酢酸、ヘプタエチレンオクタミン十酢酸及びその塩の少なくとも一種であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴である。 In the present invention 2, the aminocarboxylic acids (b) are diethylenetriamine pentaacetic acid (DTPA), triethylenetetramine hexaacetic acid (TTHA), tetraethylenepentamine hepacetic acid (TPHA), pentaethylenehexamine octaacetic acid in the present invention 1. , Hexaethylene heptamin nine acetic acid, heptaethylene octamine deacetic acid and at least one of salts thereof, which is an alkaline substitution tin plating bath on an aluminum base material.
本発明３は、上記本発明１又は２において、上記アミノカルボン酸類(ｂ)がＤＴＰＡ、ＴＴＨＡ、ＴＰＨＡ及びその塩の少なくとも一種であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴である。 The present invention 3 is an alkaline-substituted tin-plated bath on an aluminum substrate, wherein the aminocarboxylic acids (b) are at least one of DTPA, TTHA, TPHA and a salt thereof in the present invention 1 or 2. ..
本発明４は、上記本発明１〜３のいずれかにおいて、上記成分(ａ)がスズ酸カリウム、スズ酸ナトリウムから選ばれたスズ酸アルカリ金属塩、スズ酸カルシウム、スズ酸マグネシウム、スズ酸バリウムから選ばれたスズ酸アルカリ土類金属塩の少なくとも一種であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴である。 In the present invention 4, in any one of the above inventions 1 to 3, the above component (a) is an alkali metal succinate selected from potassium succinate and sodium succinate, calcium succinate, magnesium succinate, barium succinate. It is an alkaline substitution tin plating bath on an aluminum base material, which is characterized by being at least one kind of an alkaline earth metal salt of tin acid selected from.
本発明５は、上記本発明１〜４のいずれかにおいて、上記水酸化物(ｃ)が水酸化リチウム、水酸化ナトリウム、水酸化カリウムから選ばれたアルカリ金属の水酸化物、並びに水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化ストロンチウムから選ばれたアルカリ土類金属の水酸化物、水酸化アンモニウムの少なくとも一種であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴である。 In the present invention 5, in any one of the above inventions 1 to 4, the hydroxide (c) is an alkali metal hydroxide selected from lithium hydroxide, sodium hydroxide and potassium hydroxide, and magnesium hydroxide. , A hydroxide of an alkaline earth metal selected from calcium hydroxide, barium hydroxide, and strontium hydroxide, and an alkaline substitution tin plating bath on an aluminum base material, which is at least one of ammonium hydroxide.
本発明では、アルカリ性置換スズメッキ浴において、前記特許文献に開示されたＥＤＴＡ、ＮＴＡに代えて、ＤＴＰＡ、ＴＴＨＡなどの分子内に５個以上の酢酸基が結合したアミノカルボン酸類系列の錯化剤を使用するので、メッキ作業時にスラッジが発生せず、メッキ浴が白濁することがないため、メッキ作業に際してスズ浴の安定性に優れる。
また、当該白濁の防止も一つの理由と思われるが、上記特許文献に開示されたＥＤＴＡ、ＮＴＡを錯化剤に用いた場合に比べて、メッキ浴から得られるスズ皮膜をアルミニウム基材に対して強固に密着できる。
このように、アルカリ性置換スズメッキに際して、同じアミノカルボン酸類の系列に属しながら、ＤＴＰＡ、ＴＴＨＡのような分子内に５個以上の酢酸基が結合したアミノカルボン酸類を上記置換スズメッキ浴の錯化剤に選択すると、作業時のメッキ浴の安定性とアルミニウム基材へのスズ皮膜の密着性との両面で、ＥＤＴＡ、ＮＴＡのような４個以下の酢酸基が結合したアミノカルボン酸類を選択した場合に比べて、顕著な優位性を発揮する。
In the present invention, in the alkaline-substituted tin-plated bath, instead of EDTA and NTA disclosed in the above patent document, an aminocarboxylic acid-series complexing agent in which five or more acetic acid groups are bonded in a molecule such as DTPA and TTHA is used. Since it is used, sludge is not generated during the plating work and the plating bath does not become cloudy, so that the tin bath is excellent in stability during the plating work.
Further, the prevention of the white turbidity seems to be one reason, but as compared with the case where EDTA and NTA disclosed in the above patent document are used as the complexing agent, the tin film obtained from the plating bath is applied to the aluminum base material. Can be firmly attached.
As described above, in the case of alkaline substituted tin plating, aminocarboxylic acids such as DTPA and TTHA in which five or more acetic acid groups are bonded in the molecule while belonging to the same series of aminocarboxylic acids are used as the complexing agent for the substituted tin plating bath. When selected, amino carboxylic acids such as EDTA and NTA to which 4 or less acetic acid groups are bonded are selected in terms of both the stability of the plating bath during work and the adhesion of the tin film to the aluminum substrate. In comparison, it demonstrates a remarkable advantage.
本発明は可溶性第二スズ塩と錯化剤と水酸化物を含有するアルミニウム基材用のアルカリ性置換スズメッキ浴であって、分子内に５個以上の酢酸基が結合したアミノカルボン酸類を上記錯化剤に選択したスズ浴である。
上記アルミニウム基材は純アルミニウム、アルミニウム合金を包含する概念である。当該アルミニウム合金はアルミニウムと他の金属との各種合金が製品化されているが、アルミニウムとシリコンからなるアルミニウム−シリコン系合金が本発明の置換スズ浴には好適である。ちなみに、同じアルミニウム材であってもアルミニウム合金とアルミダイキャストはＪＩＳ規格では別々に分類されるが、本発明に好適な上記アルミニウム−シリコン系合金は、ＪＩＳ規格において４０００番台の系列に分類されるアルミニウム合金、並びに、アルミニウム及びシリコンに加えて、さらに銅などの他種金属成分を含むアルミダイキャストの両方を包含するものである（後述の評価試験例の試料１〜２参照）。
The present invention is an alkaline substituted tin-plated bath for an aluminum substrate containing a soluble stannic salt, a complexing agent and a hydroxide, in which aminocarboxylic acids having five or more acetic acid groups bonded in the molecule are combined. The tin bath selected as the agent.
The aluminum base material is a concept including pure aluminum and an aluminum alloy. Various alloys of aluminum and other metals have been commercialized as the aluminum alloy, and an aluminum-silicon alloy composed of aluminum and silicon is suitable for the substituted tin bath of the present invention. By the way, even if the same aluminum material is used, aluminum alloys and aluminum die casts are classified separately in the JIS standard, but the aluminum-silicon alloys suitable for the present invention are classified in the 4000 series in the JIS standard. It includes both an aluminum alloy and an aluminum die cast containing other metal components such as copper in addition to aluminum and silicon (see Samples 1 and 2 of the evaluation test example described later).
上述したように、本発明のアルカリ性置換スズメッキ浴は、アルミニウム基材に対して置換スズ皮膜を形成するためのメッキ浴であって、
(ａ)可溶性第二スズ塩と、
(ｂ)所定のアミノカルボン酸類からなるスズイオンの錯化剤と、
(ｃ)水酸化物とを含有する。
上記可溶性第二スズ塩（ａ）は４価のスズ塩であり、基本的にスズ酸アルカリ金属塩、スズ酸アルカリ土類金属塩から選ばれ、これらを単用又は併用できる。
上記スズ酸アルカリ金属塩としてはスズ酸カリウム、スズ酸ナトリウムなどが挙げられ、上記スズ酸アルカリ土類金属塩としてはスズ酸カルシウム、スズ酸マグネシウム、スズ酸バリウムなどが挙げられる。
上記可溶性第二スズ塩（ａ）のメッキ浴に対する含有量は０.２０〜０.８０モル／Ｌ、好ましくは０.３０〜０.６０モル／Ｌ、より好ましくは０.４０〜０.６０モル／Ｌである。
As described above, the alkaline substituted tin plating bath of the present invention is a plating bath for forming a substituted tin film on an aluminum substrate.
(a) Soluble stannic salt and
(b) A tin ion complexing agent composed of predetermined aminocarboxylic acids and
(c) Contains hydroxide.
The soluble ditin salt (a) is a tetravalent tin salt, and is basically selected from an alkali metal tin acid salt and an alkaline earth metal tin acid salt, and these can be used alone or in combination.
Examples of the alkali metal tinic acid salt include potassium tinate and sodium tinate, and examples of the alkaline earth metal tinate salt include calcium tinate, magnesium nitrate, barium tinate and the like.
The content of the soluble stannic salt (a) in the plating bath is 0.20 to 0.80 mol / L, preferably 0.30 to 0.60 mol / L, and more preferably 0.40 to 0.60. Molar / L.
上記水酸化物（ｃ）はメッキ浴をアルカリ性に調整するためのもので、具体的には、水酸化リチウム、水酸化ナトリウム、水酸化カリウムから選ばれたアルカリ金属の水酸化物、並びに水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化ストロンチウムから選ばれたアルカリ土類金属の水酸化物、或は水酸化アンモニウムなどを単用又は併用できる。
上記水酸化物（ｃ）のメッキ浴に対する含有量は０.０１〜０.３０モル／Ｌ、好ましくは０.０３〜０.１０モル／Ｌ、より好ましくは０.０５〜０.１０モル／Ｌである。
The hydroxide (c) is for adjusting the plating bath to be alkaline. Specifically, an alkali metal hydroxide selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, and hydroxide. Hydroxides of alkaline earth metals selected from magnesium, calcium hydroxide, barium hydroxide, and strontium hydroxide, or ammonium hydroxide can be used alone or in combination.
The content of the hydroxide (c) in the plating bath is 0.01 to 0.30 mol / L, preferably 0.03 to 0.10 mol / L, and more preferably 0.05 to 0.10 mol / L. It is L.
本発明の置換スズメッキ浴の最大の特徴は、上述の通り、錯化剤に前記特許文献に開示されたＥＤＴＡやＮＴＡではなく、上記（ｂ）で特定されたアミノカルボン酸類を使用する点にある。
即ち、本発明の置換スズメッキ浴で用いるアミノカルボン酸類(ｂ)は、分子内に５個以上の酢酸基が結合したアミノカルボン酸及びその塩に限定され、これらを必須の錯化剤成分とするものである。従って、分子内に４個以下の酢酸基が結合したＥＤＴＡやＮＴＡなどのアミノカルボン酸類、或は、分子内にプロピオン酸基などが結合したアミノカルボン酸類は本発明の錯化剤（ｂ）の適用外である。
但し、本発明の置換スズメッキ浴では、上記アミノカルボン酸類(ｂ)に加えて、従来のＥＤＴＡやＮＴＡ、或はグルコン酸、酒石酸などのオキシカルボン酸類との併用まで排除するものではない。
上記アミノカルボン酸類(ｂ)としては、ジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、テトラエチレンペンタミン七酢酸（ＴＰＨＡ）、ペンタエチレンヘキサミン八酢酸、ヘキサエチレンヘプタミン九酢酸、ヘプタエチレンオクタミン十酢酸及びその塩を単用又は併用でき、ＤＴＰＡ、ＴＴＨＡ、ＴＰＨＡ及びその塩が好ましく、より好ましくはＤＴＰＡ、ＴＴＨＡ及びその塩である。
即ち、本発明にあっては、分子内の酢酸基の結合数が５〜１０個のアミノカルボン酸類（ｂ）のうち、酢酸基の結合数が５〜７個のアミノカルボン酸類が好ましい。
上記アミノカルボン酸類(ｂ)のメッキ浴に対する含有量は０.０３〜０.３０モル／Ｌ、好ましくは０.０５〜０.１５モル／Ｌである。
As described above, the greatest feature of the substituted tin-plated bath of the present invention is that the aminocarboxylic acids specified in (b) above are used as the complexing agent instead of EDTA and NTA disclosed in the patent document. ..
That is, the aminocarboxylic acids (b) used in the substituted tin plating bath of the present invention are limited to aminocarboxylic acids having 5 or more acetic acid groups bonded in the molecule and salts thereof, and these are essential complexing agent components. It is a thing. Therefore, aminocarboxylic acids such as EDTA and NTA in which 4 or less acetic acid groups are bonded in the molecule, or aminocarboxylic acids in which propionic acid groups and the like are bonded in the molecule are the complexing agents (b) of the present invention. Not applicable.
However, in the substituted tin-plated bath of the present invention, in addition to the above aminocarboxylic acids (b), the combined use with conventional EDTA, NTA, or oxycarboxylic acids such as gluconic acid and tartaric acid is not excluded.
Examples of the aminocarboxylic acids (b) include diethylenetriamine pentaacetic acid (DTPA), triethylenetetramine hexaacetic acid (TTHA), tetraethylenepentamine seven acetic acid (TPHA), pentaethylene hexamine octaacetic acid, hexaethylene heptamine nine acetic acid, and hepta. Ethylene octamine deacetic acid and salts thereof can be used alone or in combination, and DTPA, TTHA, TPHA and salts thereof are preferable, and DTPA, TTHA and salts thereof are more preferable.
That is, in the present invention, among the aminocarboxylic acids (b) having 5 to 10 acetic acid group bonds in the molecule, aminocarboxylic acids having 5 to 7 acetic acid group bonds are preferable.
The content of the aminocarboxylic acids (b) in the plating bath is 0.03 to 0.30 mol / L, preferably 0.05 to 0.15 mol / L.
本発明の置換スズメッキ浴には、界面活性剤、光沢剤、半光沢剤、防腐剤などの各種添加剤を含有することができる。
上記界面活性剤には通常のノニオン系、アニオン系、両性、或はカチオン系などの各種界面活性剤が挙げられ、メッキ皮膜の外観、緻密性、平滑性、密着性などの改善に寄与する。
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩などが挙げられる。カチオン系界面活性剤としては、モノ〜トリアルキルアミン塩、ジメチルジアルキルアンモニウム塩、トリメチルアルキルアンモニウム塩などが挙げられる。ノニオン系界面活性剤としては、Ｃ1〜Ｃ20アルカノール、フェノール、ナフトール、ビスフェノール類、Ｃ1〜Ｃ25アルキルフェノール、アリールアルキルフェノール、Ｃ1〜Ｃ25アルキルナフトール、Ｃ1〜Ｃ25アルコキシルリン酸(塩)、ソルビタンエステル、ポリアルキレングリコール、Ｃ1〜Ｃ22脂肪族アミドなどにエチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を２〜３００モル付加縮合させたものなどが挙げられる。両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、スルホベタイン、アミノカルボン酸などが挙げられる。
当該界面活性剤のメッキ浴に対する含有量は０.０１〜１００ｇ／Ｌ、好ましくは０.１〜５０ｇ／Ｌである。
The substituted tin-plated bath of the present invention can contain various additives such as surfactants, brighteners, semi-brighteners and preservatives.
Examples of the above-mentioned surfactant include various surfactants such as ordinary nonionic, anionic, amphoteric, and cationic surfactants, which contribute to the improvement of the appearance, denseness, smoothness, adhesion and the like of the plating film.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates and the like. Examples of the cationic surfactant include mono-trialkylamine salts, dimethyldialkylammonium salts, trimethylalkylammonium salts and the like. Examples of the nonionic surfactant, C 1 -C 20 alkanols, phenol, naphthol, bisphenol, C 1 -C 25 alkyl phenols, aryl phenols, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxyl phosphoric acid (salt ), Sorbitane ester, polyalkylene glycol, C 1 to C 22 aliphatic amide and the like, and 2 to 300 mol of ethylene oxide (EO) and / or propylene oxide (PO) are added and condensed. Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, aminocarboxylic acid and the like.
The content of the surfactant in the plating bath is 0.01 to 100 g / L, preferably 0.1 to 50 g / L.
上記光沢剤、或は半光沢剤としては、ベンズアルデヒド、ｏ−クロロベンズアルデヒド、２,４,６−トリクロロベンズアルデヒド、ｍ−クロロベンズアルデヒド、ｐ−ニトロベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、フルフラール、１−ナフトアルデヒド、２−ナフトアルデヒド、２−ヒドロキシ−１−ナフトアルデヒド、３−アセナフトアルデヒド、ベンジリデンアセトン、ピリジデンアセトン、フルフリルデンアセトン、シンナムアルデヒド、アニスアルデヒド、サリチルアルデヒド、クロトンアルデヒド、アクロレイン、グルタルアルデヒド、パラアルデヒド、バニリンなどの各種アルデヒド、トリアジン、イミダゾール、インドール、キノリン、２−ビニルピリジン、アニリン、フェナントロリン、ネオクプロイン、ピコリン酸、チオ尿素類、Ｎ―(３―ヒドロキシブチリデン)―ｐ―スルファニル酸、Ｎ―ブチリデンスルファニル酸、Ｎ―シンナモイリデンスルファニル酸、２,４―ジアミノ―６―(２′―メチルイミダゾリル(１′))エチル―１,３,５―トリアジン、２,４―ジアミノ―６―(２′―エチル―４―メチルイミダゾリル(１′))エチル―１,３,５―トリアジン、２,４―ジアミノ―６―(２′―ウンデシルイミダゾリル(１′))エチル―１,３,５―トリアジン、サリチル酸フェニル、或は、ベンゾチアゾール、２―メルカプトベンゾチアゾール、２―メチルベンゾチアゾール、２―アミノベンゾチアゾール、２―アミノ―６―メトキシベンゾチアゾール、２―メチル―５―クロロベンゾチアゾール、２―ヒドロキシベンゾチアゾール、２―アミノ―６―メチルベンゾチアゾール、２―クロロベンゾチアゾール、２,５―ジメチルベンゾチアゾール、５―ヒドロキシ―２―メチルベンゾチアゾール等のベンゾチアゾール類などが挙げられる。 Examples of the brightener or semi-brightener include benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, and the like. 2-Naftaldehyde, 2-Hydroxy-1-naphthaldehyde, 3-acenaftaldehyde, benzilidenacetone, pyrididenacetone, furfuryldenacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, achlorine, glutaaldehyde, para Various aldehydes such as aldehydes and vanillins, triazine, imidazole, indol, quinoline, 2-vinylpyridine, aniline, phenanthroline, neocuproin, picolinic acid, thioureas, N- (3-hydroxybutylidene) -p-sulfanyl acid, N -Buchilidene sulfanyl acid, N-cinnamoilidene sulfanyl acid, 2,4-diamino-6- (2'-methylimidazolyl (1')) ethyl-1,3,5-triazine, 2,4-diamino-6 -(2'-Ethyl-4-methylimidazolyl (1')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-undecylimidazolyl (1')) ethyl-1, 3,5-Triazine, phenyl salicylate, or benzothiazole, 2-mercaptobenzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chloro Examples include benzothiazoles such as benzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 5-hydroxy-2-methylbenzothiazole and the like. Be done.
上記防腐剤としては、ホウ酸、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、塩化ベンザルコニウム、フェノール、フェノールポリエトキシレート、チモール、レゾルシン、イソプロピルアミン、グアヤコールなどが挙げられる。
上記置換スズメッキ浴では添加する可溶性第二スズ塩、水酸化物によってアルカリ性に調整されるので、ｐＨ調整剤を用いる必要はないが、別途、塩基を加えてｐＨを適正に調整しても良い。
また、本発明のアルカリ性置換スズメッキ浴で使用するスズ酸塩は４価のスズであって浴中で安定であるため、２価スズ塩を用いた場合のようにアスコルビン酸又はその塩、ハイドロキノン、カテコールなどの酸化防止剤は不要である。
Examples of the preservative include boric acid, 5-chloro-2-methyl-4-isothiazolin-3-one, benzalkonium chloride, phenol, phenolpolyethoxylate, thymol, resorcin, isopropylamine, guayacol and the like.
In the above-mentioned substituted tin plating bath, the pH is adjusted to be alkaline by the soluble stannic salt and hydroxide added, so it is not necessary to use a pH adjuster, but the pH may be adjusted appropriately by adding a base separately.
Further, since the stannate used in the alkaline substituted tin plating bath of the present invention is tetravalent tin and is stable in the bath, ascorbic acid or a salt thereof, hydroquinone, as in the case of using a divalent tin salt, No antioxidant such as catechol is required.
置換スズメッキの条件は任意であるが、浴温は４５〜９０℃が好ましく、析出速度を増す見地から５０〜７０℃がより好ましい。浸漬時間は３０秒〜３０分が好ましいが、浴温にも左右される。 The conditions for the substituted tin plating are arbitrary, but the bath temperature is preferably 45 to 90 ° C., more preferably 50 to 70 ° C. from the viewpoint of increasing the precipitation rate. The immersion time is preferably 30 seconds to 30 minutes, but it also depends on the bath temperature.
以下、本発明のアルカリ性置換スズメッキ浴の実施例、当該スズメッキ浴を用いてアルミニウム基材に置換メッキした直後の初期密着性並びにメッキ作業時の浴安定性の評価試験例を順次説明する。
尚、本発明は下記の実施例、試験例に拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
Hereinafter, examples of the alkaline substitution tin plating bath of the present invention, initial adhesion immediately after substitution plating on an aluminum base material using the tin plating bath, and evaluation test examples of bath stability during plating work will be sequentially described.
It should be noted that the present invention is not limited to the following examples and test examples, and it goes without saying that any modification can be made within the scope of the technical idea of the present invention.
《本発明のアルカリ性置換スズメッキ浴の実施例》
下記の実施例１〜１０のうち、実施例１はスズ酸カリウム（可溶性第二スズ塩）とＤＴＰＡ（錯化剤）と水酸化カリウム（水酸化物）を含有する置換スズメッキ浴である。実施例２は当該実施例１を基本として錯化剤をＴＴＨＡに変更した例、実施例３は同じくＴＰＨＡに変更した例である。実施例４は実施例１を基本としてスズ酸塩をスズ酸ナトリウムに変更した例、実施例５は実施例２を基本としてスズ酸塩をスズ酸カルシウムに変更した例である。実施例６は実施例１を基本として水酸化物を水酸化ナトリウムに変更した例、実施例７は同じく上記実施例２を基本として水酸化物を水酸化カルシウムに変更した例である。実施例８は上記実施例３を基本としてスズ酸塩にスズ酸カリウムとスズ酸ナトリウムを併用した例、実施例９は上記実施例１を基本として水酸化物に水酸化カリウムと水酸化ナトリウムを併用した例である。実施例１０は実施例１を基本として錯化剤にＤＴＰＡとＴＴＨＡを併用した例である。
特に、上記実施例１〜３では、本発明の成分（ａ）と（ｃ）の種類と含有量を固定し、錯化剤（ｂ）の種類を変えながら、その含有量を０.０５〜０.１５モル／Ｌの範囲で変化させている。
<< Examples of the Alkaline Substituted Tinning Bath of the Present Invention >>
Of the following Examples 1 to 10, Example 1 is a substituted tin plating bath containing potassium stannate (soluble stannic salt), DTPA (complexing agent) and potassium hydroxide (hydroxide). Example 2 is an example in which the complexing agent is changed to TTHA based on the first example, and Example 3 is an example in which the complexing agent is also changed to TPHA. Example 4 is an example in which the stannate is changed to sodium stannate based on Example 1, and Example 5 is an example in which the stannate is changed to calcium stannate based on Example 2. Example 6 is an example in which the hydroxide is changed to sodium hydroxide based on Example 1, and Example 7 is an example in which the hydroxide is changed to calcium hydroxide based on the same Example 2. Example 8 is an example in which potassium nitrate and sodium stannate are used in combination as a stannate based on the above-mentioned Example 3, and Example 9 is an example in which potassium hydroxide and sodium hydroxide are added to the hydroxide based on the above-mentioned Example 1. This is an example of combined use. Example 10 is an example in which DTPA and TTHA are used in combination as a complexing agent based on Example 1.
In particular, in Examples 1 to 3 above, the types and contents of the components (a) and (c) of the present invention are fixed, and the content is changed from 0.05 to while changing the type of the complexing agent (b). It is changed in the range of 0.15 mol / L.
一方、比較例１〜６は冒述の特許文献１〜６に準拠した例であり、比較例１は上記実施例１を基本として錯化剤にＥＤＴＡを用いた例（特に特許文献１〜２、５）、比較例２は同じくＮＴＡを用いた例（特に特許文献１〜２）、比較例３は同じくグリシン誘導体であるＤＨＥＧを用いた例（特に特許文献２、５）である。比較例４は上記実施例１を基本として錯化剤にグルコン酸を用いた例（特に特許文献２、５〜６）、比較例５は同じくアミノ酸としてのグルタミン酸を用いた例（特に特許文献２〜３）、比較例６は同じくピロリン酸を用いた例（特に特許文献４）である。 On the other hand, Comparative Examples 1 to 6 are examples based on the above-mentioned Patent Documents 1 to 6, and Comparative Example 1 is an example in which EDTA is used as a complexing agent based on the above Example 1 (particularly Patent Documents 1 to 2). 5), Comparative Example 2 is an example using NTA (particularly Patent Documents 1 and 2), and Comparative Example 3 is an example using DHEG, which is also a glycine derivative (particularly Patent Documents 2 and 5). Comparative Example 4 is an example in which gluconic acid is used as a complexing agent based on Example 1 above (particularly Patent Documents 2 and 5 to 6), and Comparative Example 5 is an example in which glutamic acid is also used as an amino acid (particularly Patent Document 2). ~ 3), Comparative Example 6 is also an example using glutamic acid (particularly Patent Document 4).
（1）実施例１
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジエチレントリアミン五酢酸（ＤＴＰＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.０μｍ
(1) Example 1
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Diethylenetriamine pentaacetic acid (DTPA) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.0 μm
（2）実施例２
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
トリエチレンテトラミン六酢酸（ＴＴＨＡ） ０.１５モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.２μｍ
(2) Example 2
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Triethylenetetramine hexaacetic acid (THA) 0.15 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.2 μm
（3）実施例３
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
テトラエチレンペンタミン七酢酸（ＴＰＨＡ） ０.０５モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.１μｍ
(3) Example 3
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Tetraethylene pentamine hepatic acetic acid (TPHA) 0.05 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.1 μm
（4）実施例４
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸ナトリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジエチレントリアミン五酢酸（ＤＴＰＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.９μｍ
(4) Example 4
An alkaline substituted tin-plated bath was constructed with the following composition.
Sodium succinate (as Sn4 +) 0.40 mol / L
Diethylenetriamine pentaacetic acid (DTPA) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.9 μm
（5）実施例５
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カルシウム（Ｓｎ4+として） ０.３５モル／Ｌ
トリエチレンテトラミン六酢酸（ＴＴＨＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.０μｍ
(5) Example 5
An alkaline substituted tin-plated bath was constructed with the following composition.
Calcium succinate (as Sn4 +) 0.35 mol / L
Triethylenetetramine hexaacetic acid (THA) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.0 μm
（6）実施例６
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジエチレントリアミン五酢酸（ＤＴＰＡ） ０.１０モル／Ｌ
水酸化ナトリウム ０.０６モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.０μｍ
(6) Example 6
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Diethylenetriamine pentaacetic acid (DTPA) 0.10 mol / L
Sodium hydroxide 0.06 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.0 μm
（7）実施例７
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
トリエチレンテトラミン六酢酸（ＴＴＨＡ） ０.１０モル／Ｌ
水酸化カルシウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.１μｍ
(7) Example 7
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Triethylenetetramine hexaacetic acid (THA) 0.10 mol / L
Calcium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.1 μm
（8）実施例８
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.３０モル／Ｌ
スズ酸ナトリウム（Ｓｎ4+として） ０.２０モル／Ｌ
テトラエチレンペンタミン七酢酸（ＴＰＨＡ） ０.０５モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.０μｍ
(8) Example 8
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.30 mol / L
Sodium succinate (as Sn4 +) 0.20 mol / L
Tetraethylene pentamine hepatic acetic acid (TPHA) 0.05 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.0 μm
（9）実施例９
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジエチレントリアミン五酢酸（ＤＴＰＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０３モル／Ｌ
水酸化ナトリウム ０.０３モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.９μｍ
(9) Example 9
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Diethylenetriamine pentaacetic acid (DTPA) 0.10 mol / L
Potassium hydroxide 0.03 mol / L
Sodium hydroxide 0.03 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.9 μm
（10）実施例１０
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジエチレントリアミン五酢酸（ＤＴＰＡ） ０.０５モル／Ｌ
トリチレンテトラミン六酢酸（ＴＴＨＡ） ０.０５モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.２μｍ
(10) Example 10
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Diethylenetriamine pentaacetic acid (DTPA) 0.05 mol / L
Tritylenetetramine hexaacetic acid (THA) 0.05 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.2 μm
（11）比較例１
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
エチレンジアミン四酢酸（ＥＤＴＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.９μｍ
(11) Comparative Example 1
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Ethylenediaminetetraacetic acid (EDTA) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.9 μm
（12）比較例２
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ニトリロ三酢酸（ＮＴＡ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.９μｍ
(12) Comparative Example 2
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Nitrilotriacetic acid (NTA) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.9 μm
（13）比較例３
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ジヒドロキシエチルグリシン（ＤＨＥＧ） ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 １.０μｍ
(13) Comparative Example 3
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Dihydroxyethylglycine (DHEG) 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 1.0 μm
（14）比較例４
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
グルコン酸 ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.７μｍ
(14) Comparative Example 4
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Gluconic acid 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.7 μm
（15）比較例５
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
グルタミン酸 ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.８μｍ
(15) Comparative Example 5
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Glutamic acid 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.8 μm
（16）比較例６
下記の組成でアルカリ性置換スズメッキ浴を建浴した。
スズ酸カリウム（Ｓｎ4+として） ０.４０モル／Ｌ
ピロリン酸 ０.１０モル／Ｌ
水酸化カリウム ０.０５モル／Ｌ
ｐＨ １３.０
［メッキ条件］
浴温 ６０℃
メッキ膜厚 ０.６μｍ
(16) Comparative Example 6
An alkaline substituted tin-plated bath was constructed with the following composition.
Potassium succinate (as Sn4 +) 0.40 mol / L
Pyrophosphoric acid 0.10 mol / L
Potassium hydroxide 0.05 mol / L
pH 13.0
[Plating conditions]
Bath temperature 60 ℃
Plating film thickness 0.6 μm
そこで、上記実施例１〜１０並びに比較例１〜６の各アルカリ性置換スズメッキ浴を２種類のアルミニウム基材に適用して、基材に対するスズ皮膜の初期密着性並びにメッキ作業時のスズ浴の安定性の各評価試験例を述べる。
《メッキ浴から得られたスズ皮膜の初期密着性の評価試験例》
［置換スズメッキ方法］
先ず、下記(ｉ)及び(ii)で示す２種類のアルミニウム基材を試料として用意した。
（ｉ）試料１：アルミニウム合金／Ａｌ−Ｓｉ系（Ａ４０３２；ＪＩＳ規格）
（ii）試料２：アルミダイキャスト／Ａｌ−Ｓｉ−Ｃｕ系（ＡＤＣ１２；ＪＩＳ規格）
次いで、上記各試料１〜２を水酸化ナトリウム水溶液（２重量％）で２５℃、３分の条件でアルカリ脱脂し、実施例及び比較例に示す各置換スズメッキ浴に６０℃、３分間の条件で浸漬した後、２５℃、約３０秒の条件で水洗し、乾燥して置換スズ皮膜を得た（スズ皮膜の膜厚は各実施例、比較例に示した）。
［評価方法］
得られたスズ皮膜について、JIS K5600クロスカット法（２５マス）に準拠して、スズ皮膜の初期密着性の優劣を試料ごとに評価した。
尚、上記初期密着性とはメッキ直後のスズ皮膜の密着性を意味し、メッキ作業終了から時間を経た後の皮膜の密着性を評価したものではない。
初期密着性の評価基準は次の通りである。
◎ ：スズ皮膜に切り込みを入れた２５マスの全てが試料から剥離しなかった。
△ ：スズ皮膜の上記２５マスのうち、１〜１５マスが試料から剥離した。
× ：スズ皮膜の上記２５マスのうち、１６〜２４マスが試料から剥離した。
××：スズ皮膜の上記２５マスの全てが試料から剥離した。
Therefore, the alkaline substituted tin-plated baths of Examples 1 to 10 and Comparative Examples 1 to 6 are applied to two types of aluminum base materials to provide the initial adhesion of the tin film to the base materials and the stability of the tin bath during the plating operation. Examples of each sex evaluation test are described.
<< Example of evaluation test of initial adhesion of tin film obtained from plating bath >>
[Replacement tin plating method]
First, two types of aluminum substrates shown in (i) and (ii) below were prepared as samples.
(I) Sample 1: Aluminum alloy / Al—Si system (A4032; JIS standard)
(Ii) Sample 2: Aluminum die-cast / Al-Si-Cu system (ADC12; JIS standard)
Next, each of the above samples 1 and 2 was alkaline degreased with an aqueous sodium hydroxide solution (2% by weight) at 25 ° C. for 3 minutes, and each of the substituted tin plating baths shown in Examples and Comparative Examples was subjected to the conditions of 60 ° C. for 3 minutes. After immersion in, the mixture was washed with water at 25 ° C. for about 30 seconds and dried to obtain a substituted tin film (the film thickness of the tin film is shown in each example and comparative example).
[Evaluation method]
Regarding the obtained tin film, the superiority or inferiority of the initial adhesion of the tin film was evaluated for each sample in accordance with the JIS K5600 cross-cut method (25 squares).
The initial adhesion means the adhesion of the tin film immediately after plating, and does not evaluate the adhesion of the film after a lapse of time from the end of the plating work.
The evaluation criteria for initial adhesion are as follows.
⊚: All 25 squares in which the tin film was cut did not peel off from the sample.
Δ: Of the above 25 cells of the tin film, 1 to 15 cells were peeled from the sample.
X: Of the above 25 cells of the tin film, 16 to 24 cells were peeled from the sample.
XX: All of the above 25 cells of the tin film were peeled off from the sample.
一方、置換スズメッキ浴を用いてメッキ作業を行った場合、浴の白濁の有無、或は白濁の発生度合に基づいて当該スズ浴の安定性を評価した。
《置換スズメッキ浴の安定性の評価試験例》
上記白濁の発生度合は試料をメッキ処理する面積量で違い、一般に、メッキ浴に浸漬するＡｌ合金試料の面積が増すほど白濁の発生度合は高くなるため、処理面積で比較を行った。
スズ浴の安定性の評価基準は次の通りである。
〇：３０ｄｍ2／Ｌの処理を行った時点で、白濁の発生がなかった。
△：１５〜２０ｄｍ2／Ｌの処理を行った時点で、白濁が発生した。
×：１０〜１５ｄｍ2／Ｌの処理を行った時点で、白濁が発生した。
この場合、例えば、上記「○」の評価は、１ｄｍ2のＡｌ合金試料を３０枚用意し、１Ｌのメッキ浴にこれらの試料を１枚ごとに順次３０回浸漬し続けても白濁しなかったことを意味する。
On the other hand, when the plating work was performed using the substituted tin plating bath, the stability of the tin bath was evaluated based on the presence or absence of white turbidity in the bath or the degree of occurrence of white turbidity.
<< Example of evaluation test of stability of replacement tin-plated bath >>
The degree of white turbidity generated differs depending on the amount of area where the sample is plated. Generally, the degree of white turbidity generated increases as the area of the Al alloy sample immersed in the plating bath increases. Therefore, comparisons were made based on the treated area.
The evaluation criteria for the stability of the tin bath are as follows.
〇: At the time of performing the treatment of 30 dm2 / L, no cloudiness occurred.
Δ: White turbidity occurred at the time of performing the treatment of 15 to 20 dm2 / L.
X: White turbidity occurred when the treatment of 10 to 15 dm2 / L was performed.
In this case, for example, in the evaluation of "○" above, 30 1 dm2 Al alloy samples were prepared, and these samples were continuously immersed in a 1 L plating bath 30 times in sequence without becoming cloudy. Means.
《スズ皮膜の初期密着性とスズメッキ浴の安定性の試験結果》
下表Ａはその試験結果である。
但し、前述の通り、初期密着性の評価試験は試料１〜２ごとに行ったが、各実施例及び比較例ともに、前記４段階評価（◎〜××）に基づく試験結果は試料１と試料２の間で差異はなかった。例えば、実施例１において、試料１の評価は◎、試料２でも◎であった（他の実施例、比較例も同じ）。従って、下表では試料１と２に分けて結果を示すことはせず、初期密着性は試料１〜２の間で同じ評価であることを表している。
<< Test results of initial adhesion of tin film and stability of tin-plated bath >>
Table A below shows the test results.
However, as described above, the initial adhesion evaluation test was performed for each sample 1 and 2, but in each example and comparative example, the test results based on the above-mentioned four-stage evaluation (◎ to XX) are sample 1 and sample. There was no difference between the two. For example, in Example 1, the evaluation of Sample 1 was ⊚, and that of Sample 2 was ⊚ (the same applies to other Examples and Comparative Examples). Therefore, in the table below, the results are not shown separately for Samples 1 and 2, indicating that the initial adhesion is the same evaluation between Samples 1 and 2.
［表Ａ］ 初期密着性 浴の安定性 初期密着性 浴の安定性
実施例１ ◎ ○ 比較例１ △ △
実施例２ ◎ ○ 比較例２ △ △
実施例３ ◎ ○ 比較例３ × ×
実施例４ ◎ ○ 比較例４ ×× ×
実施例５ ◎ ○ 比較例５ ×× ×
実施例６ ◎ ○ 比較例６ ×× ×
実施例７ ◎ ○
実施例８ ◎ ○
実施例９ ◎ ○
実施例10 ◎ ○
[Table A] Initial Adhesion Bath Stability Initial Adhesion Bath Stability Example 1 ◎ ○ Comparative Example 1 △△
Example 2 ◎ ○ Comparative Example 2 △△
Example 3 ◎ ○ Comparative Example 3 ××
Example 4 ◎ ○ Comparative Example 4 ×××
Example 5 ◎ ○ Comparative Example 5 ×××
Example 6 ◎ ○ Comparative Example 6 ×××
Example 7 ◎ ○
Example 8 ◎ ○
Example 9 ◎ ○
Example 10 ◎ ○
《スズ皮膜の初期密着性とスズ浴の安定性の総合評価》
上表Ａを見ると、冒述の特許文献２、５〜６に開示されたヒドロキシカルボン酸類であるグルコン酸を錯化剤に用いた比較例４、同じく冒述の特許文献２〜３に開示されたグルタミン酸を比較例５、或は同じく特許文献４に開示されたピロリン酸を用いた比較例６では、共にスズ皮膜のアルミニウム基材に対する初期密着性は××であり、また、スズ浴は顕著に白濁しており、浴の安定性は×であった。
冒述の特許文献２、５に開示されたグリシン誘導体であるＤＨＥＧを錯化剤に用いた比較例３では、初期密着性は×、スズ浴の安定性は×であって、浴の安定性は上記比較例４〜６と変わらないが、初期密着性は比較例４〜６より少しだけ改善傾向が見られた。
また、冒述の特許文献１〜２、５に開示されたＥＤＴＡ、ＮＴＡを錯化剤に用いた比較例１〜２では、上記比較例３より初期密着性及び浴安定性の両面で更なる改善傾向が見られたが、評価は共に△にとどまった。
これらに対して、分子内に５個以上の酢酸基が結合したアミノカルボン酸類であるＤＴＰＡ、ＴＴＨＡ、ＴＰＨＡを錯化剤に用いた実施例１〜１０では、２５マスの全てがアルミニウム基材に強固に密着しており、初期密着性の評価は◎であるとともに、メッキ浴についても白濁は認められず、浴の安定性も○であった。
従って、グルタミン酸、ピロリン酸を錯化剤に用いた比較例５〜６はもとより、メッキ浴の錯化剤として比較的多用されるグルコン酸を用いた比較例４に比べても、実施例１〜１０は初期密着性と浴安定性の両面で顕著な優位性を示した。
《Comprehensive evaluation of initial adhesion of tin film and stability of tin bath》
Looking at Table A above, Comparative Example 4 in which gluconic acid, which is a hydroxycarboxylic acid disclosed in Patent Documents 2 and 5-6, was used as a complexing agent, and Patent Documents 2 and 3 also disclosed in the above. In Comparative Example 5 using the obtained glutamic acid, or in Comparative Example 6 using pyrophosphate also disclosed in Patent Document 4, the initial adhesion of the tin film to the aluminum substrate was XX, and the tin bath was It was significantly cloudy and the stability of the bath was x.
In Comparative Example 3 in which DHEG, which is a glycine derivative disclosed in Patent Documents 2 and 5 described above, was used as a complexing agent, the initial adhesion was ×, the tin bath stability was ×, and the bath stability. Is the same as that of Comparative Examples 4 to 6, but the initial adhesion tends to be slightly improved as compared with Comparative Examples 4 to 6.
Further, in Comparative Examples 1 and 2 in which EDTA and NTA disclosed in Patent Documents 1 and 2 and 5 described above are used as a complexing agent, both initial adhesion and bath stability are further improved as compared with Comparative Example 3 above. Although there was an improvement trend, both evaluations remained at △.
On the other hand, in Examples 1 to 10 in which DTPA, TTHA, and TPHA, which are aminocarboxylic acids having 5 or more acetic acid groups bonded in the molecule, were used as the complexing agent, all 25 cells were made of an aluminum base material. The adhesion was strong, and the initial adhesion was evaluated as ⊚, no cloudiness was observed in the plating bath, and the stability of the bath was also ◯.
Therefore, not only in Comparative Examples 5 to 6 in which glutamic acid and pyrophosphoric acid were used as the complexing agent, but also in Comparative Examples 1 to 4 in which gluconic acid, which is relatively frequently used as the complexing agent in the plating bath, was used. 10 showed a remarkable advantage in both initial adhesion and bath stability.
次いで、実施例の優位性は、グリシン誘導体であるＤＨＥＧを用いた比較例３に対しても同じであるが、特に、ＥＤＴＡ、ＮＴＡを用いた比較例１〜２に対して、実施例１〜１０は、ＥＤＴＡなどと同じ系列に属するアミノカルボン酸類を用いながら、想定外の顕著な優位性を示すことに注目すべきである。
ＥＤＴＡ、ＮＴＡを用いた比較例１〜２では、メッキ浴の安定性が低く浴が白濁して、アルミニウム基材に対する密着性自体を発現しなかったが、実施例１〜１０ではメッキ浴に白濁がなく浴安定性に優れる点がＥＤＴＡやＮＴＡに対する特段の相違であり、また、アルミニウム基材への初期密着性もＥＤＴＡやＮＴＡに比べて飛躍的に向上した。おそらく、実施例１〜１０では、メッキ浴の高い安定性に起因して強力な密着機能を発現したものと推定される。
以上のように、最も明解な比較例１〜２との対比で実施例１〜１０を考察すると、同じ系列のアミノカルボン酸類をアルカリ性置換スズメッキに適用した場合であっても、アミノカルボン酸類の分子内における酢酸基の結合数がスズ浴の安定性、並びにスズ皮膜の初期密着性に顕著な影響を及ぼし、ＤＴＰＡ、ＴＴＨＡ、ＴＰＨＡのような分子内に５個以上の酢酸基が結合したアミノカルボン酸類は、ＥＤＴＡ、ＮＴＡのような４個以下の酢酸基が結合したアミノカルボン酸類とは異なる特異な錯化機能を果たすことが推定でき、浴安定性と初期密着性の両方について、酢酸基の結合数が５個以上のアミノカルボン酸類の顕著な優位性が裏付けられた。
Next, the superiority of Examples is the same as that of Comparative Example 3 using DHEG, which is a glycine derivative, but in particular, Examples 1 to 2 are compared with Comparative Examples 1 and 2 using EDTA and NTA. It should be noted that 10 shows an unexpectedly remarkable advantage while using aminocarboxylic acids belonging to the same series as EDTA and the like.
In Comparative Examples 1 and 2 using EDTA and NTA, the stability of the plating bath was low and the bath became cloudy and did not exhibit the adhesion itself to the aluminum substrate, but in Examples 1 to 10, the plating bath became cloudy. It is a special difference from EDTA and NTA in that it is excellent in bath stability, and the initial adhesion to the aluminum base material is also dramatically improved as compared with EDTA and NTA. Presumably, in Examples 1 to 10, a strong adhesion function was exhibited due to the high stability of the plating bath.
As described above, considering Examples 1 to 10 in comparison with the most obvious Comparative Examples 1 and 2, the molecules of aminocarboxylic acids are molecules even when the same series of aminocarboxylic acids are applied to alkaline substituted tin plating. The number of acetic acid groups bonded within has a significant effect on the stability of the tin bath and the initial adhesion of the tin film, and aminocarboxylics in which 5 or more acetic acid groups are bonded in the molecule such as DTPA, TTHA, and TPHA. It can be presumed that the acids perform a unique complexing function different from aminocarboxylic acids in which 4 or less acetic acid groups are bound, such as EDTA and NTA, and the acetic acid groups have both bath stability and initial adhesion. The remarkable superiority of aminocarboxylic acids having 5 or more bonds was confirmed.
以下、実施例１〜１０を詳細に考察する。
ＤＴＰＡ、ＴＴＨＡ、ＴＰＨＡを夫々用いた実施例１〜３では、初期密着性と浴安定性は共に同じ評価であるため、アミノカルボン酸類の分子内における酢酸基の結合数が５個以上であれば、これら両面の有効性に差異はないことが分かる。また、実施例１０のように、本発明の錯化剤であるアミノカルボン酸類（ｂ）を併用しても、有効性は変わらないことが分かる。
実施例３ではＴＰＨＡの含有量は０.０５モル／Ｌであり、実施例２ではＴＴＨＡの含有量は０.１５モル／Ｌであるが、初期密着性と浴安定性の評価は両者間で同じであるため、本発明の錯化剤（ｂ）の含有量は０.０５モル／Ｌ前後の少量でも有効であり、過剰の含有量は必要ないことが判断できる。
実施例１、４、５、８を対比すると、スズ酸塩をアルカリ金属塩、アルカリ土類金属の間で変更し或は併用しても、初期密着性及び浴安定性の有効性に変わりはなく、実施例６〜７、９を対比すると、水酸化物をアルカリ金属の水酸化物、アルカリ土類金属の水酸化物の間で変更し或は併用しても、初期密着性及び浴安定性の有効性に変わりはないことが判断できる。
Hereinafter, Examples 1 to 10 will be considered in detail.
In Examples 1 to 3 using DTPA, TTHA, and TPHA, respectively, the initial adhesion and bath stability are all evaluated in the same manner. Therefore, if the number of acetic acid groups in the molecule of aminocarboxylic acids is 5 or more. , It can be seen that there is no difference in the effectiveness of both sides. Further, it can be seen that the effectiveness does not change even when the aminocarboxylic acids (b) which are the complexing agents of the present invention are used in combination as in Example 10.
In Example 3, the TPHA content was 0.05 mol / L, and in Example 2, the TTHA content was 0.15 mol / L, but the initial adhesion and bath stability were evaluated between the two. Therefore, since the content of the complexing agent (b) of the present invention is effective even in a small amount of about 0.05 mol / L, it can be determined that an excessive content is not necessary.
Comparing Examples 1, 4, 5 and 8, even if the stannate is changed or used in combination with the alkali metal salt and the alkaline earth metal, the effectiveness of the initial adhesion and the bath stability does not change. However, when comparing Examples 6 to 7 and 9, even if the hydroxide is changed between the alkali metal hydroxide and the alkaline earth metal hydroxide or used in combination, the initial adhesion and bath stability It can be judged that there is no change in the effectiveness of sex.
Claims (5)
上記置換スズメッキ浴が、
(ａ)可溶性第二スズ塩と、
(ｂ)錯化剤と、
(ｃ)水酸化物とを含有するアルカリ性置換スズメッキ浴であって、
上記錯化剤（ｂ）が、分子内に５個以上の酢酸基が結合したアミノカルボン酸類であることを特徴とするアルミニウム基材へのアルカリ性置換スズメッキ浴。 A plating bath that forms a substituted tin film on an aluminum substrate.
The above replacement tin-plated bath
(a) Soluble stannic salt and
(b) Coordinator and
(c) An alkaline substituted tin-plated bath containing hydroxide.
An alkaline-substituted tin-plated bath on an aluminum substrate, wherein the complexing agent (b) is an aminocarboxylic acid having five or more acetic acid groups bonded in the molecule.
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