WO2022158291A1 - Electrolytic silver plating bath and electrolytic silver plating method using same - Google Patents
Electrolytic silver plating bath and electrolytic silver plating method using same Download PDFInfo
- Publication number
- WO2022158291A1 WO2022158291A1 PCT/JP2022/000167 JP2022000167W WO2022158291A1 WO 2022158291 A1 WO2022158291 A1 WO 2022158291A1 JP 2022000167 W JP2022000167 W JP 2022000167W WO 2022158291 A1 WO2022158291 A1 WO 2022158291A1
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- WO
- WIPO (PCT)
- Prior art keywords
- plating bath
- silver plating
- group
- electrolytic silver
- electrolytic
- Prior art date
Links
- 238000007747 plating Methods 0.000 title claims abstract description 110
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 64
- 239000004332 silver Substances 0.000 title claims abstract description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- -1 silver ions Chemical class 0.000 claims abstract description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052783 alkali metal Chemical group 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Chemical class 0.000 claims description 11
- 239000002184 metal Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical class OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical class OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005282 brightening Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- 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
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Definitions
- the present invention relates to an electrolytic silver plating bath and an electrolytic silver plating method using the same.
- Silver plating has long been used for decorative purposes. Traditionally, silver plating has been deposited in alkaline electrolytic silver plating baths containing cyanide.
- Patent Documents 1 and 2 cyanide-free electrolytic silver plating baths that do not use cyanide have been developed.
- cyanide-free electrolytic silver plating baths contain brighteners and other additives. Continuous plating in the same plating bath using an insoluble anode will consume the brighteners and other additives rapidly and quickly. However, there is a problem in that a glossy silver plating cannot be obtained.
- Patent Document 3 a method of preventing oxidation of the additive by using a diaphragm or the like is taken as a countermeasure.
- the diaphragm surrounding the anode is Not suitable.
- an object of the present invention is to provide an electrolytic silver plating bath in which the consumption of additives such as brighteners is suppressed, and deterioration in performance of the plating bath can be suppressed even when plating is continuously performed in the same plating bath.
- An electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightener and a sacrificial reducing agent,
- the following general formula (I) as a sacrificial reducing agent [In the formula, X 1 represents hydrogen or an alkali metal.
- R 1 , R 2 and R 3 are each independently hydrogen (except when R 1 , R 2 and R 3 are hydrogen at the same time), hydroxyl group, phenyl group, C 1 -C 6 alkyl group , represents an alkenyl group or an alkynyl group, wherein the alkyl group, alkenyl group or alkynyl group may have a hydroxyl group or a carboxyl group, and R 1 and R 2 may be linked to form a cyclic alkyl or aromatic ring. .
- the present invention is an electrolytic silver plating method, characterized in that the object to be plated is immersed in the silver plating bath and electrolytically plated.
- the specific sacrificial reducing agent contained therein is preferentially oxidized with respect to the oxidizing species generated from the anode, so that the consumption of the brightening agent can be suppressed, so that the plating bath can be used continuously.
- the performance deterioration of the plating bath can be suppressed.
- FIG. 2 is a diagram showing the external appearance of an implementation product and a comparative product in Example 1 after a Hull cell test using an electrolytic silver plating bath.
- 1 is a diagram showing the state of an electrolytic silver plating bath before and after temperature rise for Hull cell test of a comparative product (fructose) in Example 1.
- FIG. 1 is a diagram showing the state of an electrolytic silver plating bath before and after temperature rise for Hull cell test of a comparative product (fructose) in Example 1.
- the electrolytic silver plating bath of the present invention (hereinafter referred to as “the plating bath of the present invention") is an electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightening agent and a sacrificial reducing agent,
- the sacrificial reducing agent contains one or more nitrogen-containing compounds represented by the following general formulas (I) and (II).
- Silver ions used in the plating bath of the present invention are not particularly limited. There is no particular limitation as long as it is silver ions generated from a silver ion source or the like. These silver ion sources may be used singly or in combination of two or more. Although the content of silver ions in the plating bath of the present invention is not particularly limited, it is, for example, 1 g/L to 80 g/L, preferably 20 g/L to 60 g/L.
- the complexing agent used in the plating bath of the present invention is not particularly limited, and examples thereof include imide compounds represented by the following general formula (III).
- B is nitrogen or carbon
- R 4 and R 5 each independently represent hydrogen or a methyl group.
- hydantoin derivatives such as succinimide, hydantoin and 5,5-dimethylhydantoin are preferred, and 5,5-dimethylhydantoin is more preferred.
- These complexing agents may be used singly or in combination of two or more.
- the content of the complexing agent in the plating bath of the present invention is not particularly limited, but is, for example, 10 g/L to 400 g/L, preferably 100 g/L to 360 g/L, particularly preferably 120 g/L to 320 g/L.
- the conductive salt used in the plating bath of the present invention is a metal salt of an inorganic acid or an organic acid, and is not particularly limited. Examples include metal salts of acids and citric acid. Among these conductive salts, sodium salts and potassium salts of carbonic acid, nitric acid and methanesulfonic acid are preferred, and potassium carbonate is more preferred. These conductive salts may be used singly or in combination of two or more.
- the content of the conductive salt in the plating bath of the present invention is not particularly limited, but is, for example, 1 g/L to 80 g/L, preferably 10 g/L to 60 g/L.
- the brightening agent used in the plating bath of the present invention is not particularly limited.
- a metal salt etc. are mentioned.
- these brighteners thiosulfate or a metal salt of thiosulfate, or thiodiglycolic acid or a metal salt thereof is preferable, and thiosulfate or a metal salt of thiosulfate is particularly preferable.
- These brightening agents may be used singly or in combination of two or more.
- the content of the brightener in the plating bath of the present invention is not particularly limited, it is, for example, 1 mg/L to 1000 mg/L, preferably 10 mg/L to 600 mg/L.
- the sacrificial reducing agents used in the plating bath of the present invention are nitrogen-containing compounds represented by the following general formulas (I) and (II).
- X1 represents hydrogen or an alkali metal.
- alkali metals lithium, sodium or potassium is preferred, and sodium or potassium is more preferred.
- the compound represented by general formula (I) may be an acid or metal salt.
- compounds containing trivalent nitrogen and oxidized to pentavalent nitrogen during plating are preferred. Examples of such compounds include nitrous acid, lithium nitrite, sodium nitrite, potassium nitrite and the like.
- R 1 , R 2 and R 3 are each independently hydrogen (except when R 1 , R 2 and R 3 are simultaneously hydrogen (ammonia)), hydroxyl group, phenyl group, C 1 to C 6 It represents an alkyl group, alkenyl group or alkynyl group, and the alkyl group, alkenyl group or alkynyl group may have a hydroxyl group or a carboxyl group.
- R 1 and R 2 may be linked to form a cyclic alkyl or aromatic ring.
- the number of carbon atoms in the alkyl group and the like shown here is preferably C 1 to C 3 , more preferably C 2 .
- compounds containing trivalent nitrogen and oxidized to pentavalent nitrogen during plating are preferred.
- examples of such compounds include glycine, iminodiacetic acid, nitrilotriacetic acid, ethanolamine, 2,2'-iminodiethanol, triethanolamine, aniline and the like.
- sodium nitrite, glycine, iminodiacetic acid, nitrilotriacetic acid, ethanolamine, 2,2'-iminodiethanol and triethanolamine are preferred, and nitrous acid is preferred from the viewpoint of plating gloss and stability. More preferred are sodium, glycine, iminodiacetic acid and nitrilotriacetic acid, and particularly preferred is sodium nitrite.
- the content of the sacrificial reducing agent in the plating bath of the present invention is not particularly limited, but is, for example, 1 g/L to 100 g/L, preferably 5 g/L to 60 g/L.
- the plating bath of the present invention may further contain a known leveling agent and/or pH adjuster used in electrolytic silver plating.
- leveling agents examples include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and polyethyleneimine.
- the content of the leveling agent in the plating bath of the present invention is not particularly limited, but is, for example, 0.1 mg/L to 1000 mg/L, preferably 10 mg/L to 600 mg/L.
- pH adjusters examples include sulfuric acid, nitric acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, and the like.
- the content of the pH adjuster in the plating bath of the present invention is not particularly limited, it is adjusted to pH 6.0 to pH 12.5, preferably pH 9.0 to pH 11.5, for example.
- the plating bath of the present invention may further contain known grain refiners, discoloration inhibitors, and the like used in electrolytic silver plating.
- crystal refining agents include selenous acid, selenium and antimony compounds such as potassium antimonium tartrate, and sulfur-containing compounds such as thiourea and potassium thiocyanate.
- sulfur-containing compounds such as thiourea and potassium thiocyanate.
- discoloration inhibitors include nitrogen- or sulfur-containing compounds having a heterocyclic ring such as benzotriazole, 2-mercaptobenzothiazole, and 1,2,3-benzothiadiazole.
- the plating bath of the present invention described above can be prepared by mixing each component according to a conventional method. Since the plating bath of the present invention can be made up of only the above components, it can be a so-called cyanide-free electrolytic silver plating bath that does not contain cyanide compounds. Needless to say, the same effect can be obtained by
- the object to be plated can be electrolytically plated by immersing it in the same manner as in the conventional electrolytic silver plating bath.
- the object to be plated that can be plated with the plating bath of the present invention is not particularly limited, but examples include metals and plated objects made of copper, nickel, iron, tin, zinc, or alloys thereof. Also, the shape of the object to be plated is not particularly limited.
- the conditions for electrolytic silver plating are not particularly limited, but are, for example, a bath temperature of 20 to 70° C., a current density of 0.5 to 70 A/dm 2 and an electrolysis time of 3 seconds to 1 hour.
- Electrolytic silver plating using the plating bath of the present invention can be performed with a conventional electrolytic plating apparatus, but an apparatus using an insoluble anode as the anode is particularly preferable.
- Such equipment includes a hoop plating equipment, a sparger plating equipment, and the like.
- the specific sacrificial reducing agent contained therein is preferentially oxidized with respect to the oxidizing species generated from the anode, thereby suppressing consumption of the brightening agent. Even if it is used continuously, deterioration of the performance of the plating bath can be suppressed.
- the electrolytic silver plating obtained using the plating bath of the present invention as described above has excellent electrical properties such as low contact resistance, and is a film with excellent hardness. Therefore, this electrolytic silver plating is preferable for uses such as connectors.
- Example 1 Electrolytic silver plating An electrolytic silver plating bath was prepared by mixing the basic composition of the electrolytic silver plating bath shown in Table 1 below with one of the sacrificial reducing agents. A Hull cell test was performed using these electrolytic silver plating baths. Hull cell test conditions were as follows: copper Hull cell cathode and iridium oxide coated titanium anode, current 2 A, plating time 2.5 minutes, air stirring, bath temperature 50°C, repeated up to 5 times. gone. In addition, the silver ion source, which was reduced by plating, was replenished each time plating was performed. Fig. 1 shows the appearance after the Hull cell test.
- hydroquinone, L(+)-sodium ascorbate, benzaldehyde, and saccharides such as D(+)-glucose and maltose are examples of reducing agents that have shown decomposition.
- Phosphorous acid, sodium formate, and methanol are examples of sacrificial reducing agents that did not show the desired effect.
- the decomposition of the brightener component could be suppressed by using the sacrificial reducing agent in the electrolytic silver plating bath containing silver ions, complexing agent, conductive salt, and brightener. It was also found that sodium nitrite, iminodiacetic acid, and nitrilotriacetic acid are superior as sacrificial reducing agents in terms of plating gloss, accumulation by replenishment, and stability, and sodium nitrite is particularly superior.
- Example 2 Sparger electrolytic silver plating: Using a known sparger plating apparatus, sparger electrolytic silver plating was performed using the electrolytic silver plating bath using sodium nitrite as a sacrificial reducing agent of Example 1 above. Sparger plating is performed by using a copper plate as a test piece, and applying a plating solution jetted from a nozzle opening diameter of ⁇ 4 mm at a flow rate of 4 L / min to a mask opening of ⁇ 5.5 mm, 10 ASD to 30 ASD, 27 seconds to 9 seconds. I went with The resulting silver plating film was able to be tested with an appearance corresponding to the high current density area in the Hull cell test without oxidation of the brightener component.
- the present invention can be used for silver plating.
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Abstract
This electrolytic silver plating bath contains silver ions, a complexing agent, a conductive salt, a brightening agent, and a sacrificial reductant, and is characterized by containing, as the sacrificial reductant, one or more kinds of nitrogen-containing compounds expressed by general formula (I) [In the formula, X1 represents hydrogen or an alkali metal.] and general formula (II) [In the formula, R1, R2, and R3 independently represent a hydrogen (provided that a case where R1, R2, and R3 are hydrogen at the same time is excluded), a hydroxyl group, a phenyl group, a C1-C 6 alkyl group, an alkenyl group, or an alkynyl group, wherein the alkyl group, the alkenyl group, or the alkynyl group may have a hydroxyl group or a carboxyl group, and R1 and R2 may be linked to form cyclic alkyl or an aromatic ring.]. Accordingly, with this electrolytic silver plating bath, consumption of an additive, such as a brightening agent, can be suppressed and performance degradation of the plating bath even when plating is continuously carried out using the same plating bath can be suppressed.
Description
本発明は、電解銀めっき浴およびこれを用いた電解銀めっき方法に関する。
The present invention relates to an electrolytic silver plating bath and an electrolytic silver plating method using the same.
銀めっきは、昔から装飾用等の用途に用いられている。これまで銀めっきは、シアン化物を含有するアルカリ性の電解銀めっき浴で析出させていた。
Silver plating has long been used for decorative purposes. Traditionally, silver plating has been deposited in alkaline electrolytic silver plating baths containing cyanide.
しかしながら、シアン化物は毒性が強く、排水処理をする必要もあるため、このシアン化物を使用しない、いわゆるノーシアン電解銀めっき浴が開発されてきている（特許文献１、２）。
However, cyanide is highly toxic and requires wastewater treatment, so so-called cyanide-free electrolytic silver plating baths that do not use cyanide have been developed (Patent Documents 1 and 2).
一般にノーシアン電解銀めっき浴には、光沢剤等の添加剤が含有されるが、不溶性のアノードを用いて同じめっき浴で連続的にめっきをすると、光沢剤等の添加剤の消耗が激しく、すぐに光沢のある銀めっきが得られなくなるという問題があった。
In general, cyanide-free electrolytic silver plating baths contain brighteners and other additives. Continuous plating in the same plating bath using an insoluble anode will consume the brighteners and other additives rapidly and quickly. However, there is a problem in that a glossy silver plating cannot be obtained.
通常、不溶性アノードを用いる場合は隔膜などを用いて添加剤の酸化を防止する方法が対策としてとられる（特許文献３）。
Usually, when using an insoluble anode, a method of preventing oxidation of the additive by using a diaphragm or the like is taken as a countermeasure (Patent Document 3).
しかし、スパージャーめっきやフープめっきのような、高電流密度を用いためっきや、不溶性アノードをめっき液が通過をする、あるいは高速でアノードせん断する液流れが必要な場合にはアノードを囲む隔膜は適していない。
However, for plating using high current densities, such as sparger plating and hoop plating, where the plating solution passes through the insoluble anode, or when the solution flow requires high-speed anodic shear, the diaphragm surrounding the anode is Not suitable.
従って、本発明の課題は、光沢剤等の添加剤の消耗が抑制され、同じめっき浴で連続的にめっきしてもめっき浴の性能低下が抑制できる電解銀めっき浴を提供することである。
Therefore, an object of the present invention is to provide an electrolytic silver plating bath in which the consumption of additives such as brighteners is suppressed, and deterioration in performance of the plating bath can be suppressed even when plating is continuously performed in the same plating bath.
本発明者らは上記課題を解決するために鋭意研究した結果、光沢剤等の添加剤を含有する電解銀めっき浴と、特定の犠牲還元剤を組み合わせることにより、上記課題を解決できることを見出し、本発明を完成させた。
As a result of intensive research to solve the above problems, the present inventors found that the above problems can be solved by combining an electrolytic silver plating bath containing additives such as brighteners with a specific sacrificial reducing agent. I completed the present invention.
銀イオン、錯化剤、伝導塩、光沢剤および犠牲還元剤を含有する電解銀めっき浴であって、
犠牲還元剤として下記一般式（I）
［式中、Ｘ１は水素あるいはアルカリ金属を表す。］
および一般式（II）
［式中、Ｒ１、Ｒ２、Ｒ３はそれぞれ独立に水素（ただし、Ｒ１、Ｒ２、Ｒ３が同時に水素のものを除く）、水酸基、フェニル基、Ｃ１～Ｃ６のアルキル基、アルケニル基あるいはアルキニル基を表し、前記アルキル基、アルケニル基あるいはアルキニル基は水酸基あるいはカルボキシル基を持っていてもよく、Ｒ１とＲ２は繋がって環状のアルキルあるいは芳香環を形成してもよい。］
で表される含窒素化合物の１種または２種以上を含むことを特徴とする電解銀めっき浴である。 An electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightener and a sacrificial reducing agent,
The following general formula (I) as a sacrificial reducing agent
[In the formula, X 1 represents hydrogen or an alkali metal. ]
and general formula (II)
[wherein R 1 , R 2 and R 3 are each independently hydrogen (except when R 1 , R 2 and R 3 are hydrogen at the same time), hydroxyl group, phenyl group, C 1 -C 6 alkyl group , represents an alkenyl group or an alkynyl group, wherein the alkyl group, alkenyl group or alkynyl group may have a hydroxyl group or a carboxyl group, and R 1 and R 2 may be linked to form a cyclic alkyl or aromatic ring. . ]
It is an electrolytic silver plating bath characterized by containing one or more nitrogen-containing compounds represented by.
犠牲還元剤として下記一般式（I）
および一般式（II）
で表される含窒素化合物の１種または２種以上を含むことを特徴とする電解銀めっき浴である。 An electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightener and a sacrificial reducing agent,
The following general formula (I) as a sacrificial reducing agent
and general formula (II)
It is an electrolytic silver plating bath characterized by containing one or more nitrogen-containing compounds represented by.
また、本発明は、被めっき物を、上記銀めっき浴に浸漬して電解めっきすることを特徴とする電解銀めっき方法である。
Further, the present invention is an electrolytic silver plating method, characterized in that the object to be plated is immersed in the silver plating bath and electrolytically plated.
本発明の電解銀めっき浴は、これに含まれる特定の犠牲還元剤がアノードから発生する酸化種に対して優先的に酸化されることで光沢剤の消耗を抑制できるため、めっき浴を連続使用してもめっき浴の性能低下が抑制できる。
In the electrolytic silver plating bath of the present invention, the specific sacrificial reducing agent contained therein is preferentially oxidized with respect to the oxidizing species generated from the anode, so that the consumption of the brightening agent can be suppressed, so that the plating bath can be used continuously. However, the performance deterioration of the plating bath can be suppressed.
本発明の電解銀めっき浴（以下、「本発明めっき浴」という）は、銀イオン、錯化剤、伝導塩、光沢剤および犠牲還元剤を含有する電解銀めっき浴であって、
犠牲還元剤として下記一般式（I）および一般式（II）で表される含窒素化合物の１種または２種以上を含むものである。 The electrolytic silver plating bath of the present invention (hereinafter referred to as "the plating bath of the present invention") is an electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightening agent and a sacrificial reducing agent,
The sacrificial reducing agent contains one or more nitrogen-containing compounds represented by the following general formulas (I) and (II).
犠牲還元剤として下記一般式（I）および一般式（II）で表される含窒素化合物の１種または２種以上を含むものである。 The electrolytic silver plating bath of the present invention (hereinafter referred to as "the plating bath of the present invention") is an electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightening agent and a sacrificial reducing agent,
The sacrificial reducing agent contains one or more nitrogen-containing compounds represented by the following general formulas (I) and (II).
本発明めっき浴に用いられる銀イオンは、特に限定されず、例えば、硝酸銀、硫酸銀、酢酸銀、乳酸銀、くえん酸銀、酸化銀、リン酸銀、アルカンスルホン酸銀、ハロゲン化銀等の銀イオン源等から発生する銀イオンであれば特に限定されない。これら銀イオン源は１種または２種以上を組み合わせてもよい。本発明めっき浴における銀イオンの含有量は特に限定されないが、例えば、１ｇ／Ｌ～８０ｇ／Ｌ、好ましくは２０ｇ／Ｌ～６０ｇ／Ｌである。
Silver ions used in the plating bath of the present invention are not particularly limited. There is no particular limitation as long as it is silver ions generated from a silver ion source or the like. These silver ion sources may be used singly or in combination of two or more. Although the content of silver ions in the plating bath of the present invention is not particularly limited, it is, for example, 1 g/L to 80 g/L, preferably 20 g/L to 60 g/L.
本発明めっき浴に用いられる錯化剤は、特に限定されず、例えば、下記一般式（III）で表されるイミド化合物等が挙げられる。
The complexing agent used in the plating bath of the present invention is not particularly limited, and examples thereof include imide compounds represented by the following general formula (III).
［式中のＢは窒素あるいは炭素であり、Ｒ４、Ｒ５はそれぞれ独立に水素あるいはメチル基を表す。］これらの錯化剤の中でもコハク酸イミド、ヒダントイン、５，５－ジメチルヒダントイン等のヒダントイン誘導体が好ましく、５，５－ジメチルヒダントインがより好ましい。これら錯化剤は１種または２種以上を組み合わせてもよい。本発明めっき浴における錯化剤の含有量は特に限定されないが、例えば、１０ｇ／Ｌ～４００ｇ／Ｌ、好ましくは１００ｇ／Ｌ～３６０ｇ／Ｌ、特に好ましくは１２０ｇ／Ｌ～３２０ｇ／Ｌである。
[In the formula, B is nitrogen or carbon, and R 4 and R 5 each independently represent hydrogen or a methyl group. ] Among these complexing agents, hydantoin derivatives such as succinimide, hydantoin and 5,5-dimethylhydantoin are preferred, and 5,5-dimethylhydantoin is more preferred. These complexing agents may be used singly or in combination of two or more. The content of the complexing agent in the plating bath of the present invention is not particularly limited, but is, for example, 10 g/L to 400 g/L, preferably 100 g/L to 360 g/L, particularly preferably 120 g/L to 320 g/L.
本発明めっき浴に用いられる伝導塩は無機酸および有機酸の金属塩で、特に限定されず、例えば、硫酸、硝酸、塩酸、リン酸、スルファミン酸、炭酸、ホウ酸、酢酸、乳酸、メタンスルホン酸、くえん酸の金属塩等が挙げられる。これらの伝導塩の中でも炭酸、硝酸、メタンスルホン酸のナトリウム塩およびカリウム塩等が好ましく、炭酸カリウムがより好ましい。これら伝導塩は１種または２種以上を組み合わせてもよい。本発明めっき浴における伝導塩の含有量は特に限定されないが、例えば、１ｇ／Ｌ～８０ｇ／Ｌ、好ましくは１０ｇ／Ｌ～６０ｇ／Ｌである。
The conductive salt used in the plating bath of the present invention is a metal salt of an inorganic acid or an organic acid, and is not particularly limited. Examples include metal salts of acids and citric acid. Among these conductive salts, sodium salts and potassium salts of carbonic acid, nitric acid and methanesulfonic acid are preferred, and potassium carbonate is more preferred. These conductive salts may be used singly or in combination of two or more. The content of the conductive salt in the plating bath of the present invention is not particularly limited, but is, for example, 1 g/L to 80 g/L, preferably 10 g/L to 60 g/L.
本発明めっき浴に用いられる光沢剤は、特に限定されず、例えば、チオ硫酸、２－メルカプトエタンスルホン酸、３－メルカプトプロパンスルホン酸、チオジグリコール酸、ジチオジグリコール酸、チオ尿素もしくはこれらの金属塩等が挙げられる。これらの光沢剤の中でもチオ硫酸またはチオ硫酸の金属塩、もしくはチオジグリコール酸またはその金属塩が好ましく、特にチオ硫酸またはチオ硫酸の金属塩が好ましい。これら光沢剤は１種または２種以上を組み合わせてもよい。本発明めっき浴における光沢剤の含有量は特に限定されないが、例えば、１ｍｇ／Ｌ～１０００ｍｇ／Ｌ、好ましくは１０ｍｇ／Ｌ～６００ｍｇ／Ｌである。
The brightening agent used in the plating bath of the present invention is not particularly limited. A metal salt etc. are mentioned. Among these brighteners, thiosulfate or a metal salt of thiosulfate, or thiodiglycolic acid or a metal salt thereof is preferable, and thiosulfate or a metal salt of thiosulfate is particularly preferable. These brightening agents may be used singly or in combination of two or more. Although the content of the brightener in the plating bath of the present invention is not particularly limited, it is, for example, 1 mg/L to 1000 mg/L, preferably 10 mg/L to 600 mg/L.
本発明めっき浴に用いられる犠牲還元剤は、下記一般式（I）および（II）で表される含窒素化合物である。
The sacrificial reducing agents used in the plating bath of the present invention are nitrogen-containing compounds represented by the following general formulas (I) and (II).
式中、Ｘ１は水素あるいはアルカリ金属を表す。アルカリ金属の中でも、好ましくはリチウム、ナトリウムあるいはカリウムであり、より好ましくはナトリウムあるいはカリウムである。一般式（I）で表される化合物は酸あるいは金属塩となっていてもよい。この式で表される化合物の中でも３価の窒素を含む化合物であり、めっき中に５価に酸化される化合物が好ましい。このような化合物としては、例えば、亜硝酸、亜硝酸リチウム、亜硝酸ナトリウム、亜硝酸カリウム等が挙げられる。
In the formula, X1 represents hydrogen or an alkali metal. Among alkali metals, lithium, sodium or potassium is preferred, and sodium or potassium is more preferred. The compound represented by general formula (I) may be an acid or metal salt. Among the compounds represented by this formula, compounds containing trivalent nitrogen and oxidized to pentavalent nitrogen during plating are preferred. Examples of such compounds include nitrous acid, lithium nitrite, sodium nitrite, potassium nitrite and the like.
式中、Ｒ１、Ｒ２、Ｒ３はそれぞれ独立に水素（ただし、Ｒ１、Ｒ２、Ｒ３が同時に水素のもの（アンモニア）を除く）、水酸基、フェニル基、Ｃ１～Ｃ６のアルキル基、アルケニル基あるいはアルキニル基を表し、アルキル基、アルケニル基、アルキニル基は水酸基あるいはカルボキシル基を持っていてもよい。Ｒ１とＲ２は繋がって環状のアルキルあるいは芳香環を形成してもよい。ここで示すアルキル基等の炭素数は、好ましくはＣ１～Ｃ３で、より好ましくはＣ２である。この式で表される化合物の中でも３価の窒素を含む化合物であり、めっき中に５価に酸化される化合物が好ましい。このような化合物としては、例えば、グリシン、イミノ二酢酸、ニトリロ三酢酸、エタノールアミン、２,２’－イミノジエタノール、トリエタノールアミン、アニリン等が挙げられる。
In the formula, R 1 , R 2 and R 3 are each independently hydrogen (except when R 1 , R 2 and R 3 are simultaneously hydrogen (ammonia)), hydroxyl group, phenyl group, C 1 to C 6 It represents an alkyl group, alkenyl group or alkynyl group, and the alkyl group, alkenyl group or alkynyl group may have a hydroxyl group or a carboxyl group. R 1 and R 2 may be linked to form a cyclic alkyl or aromatic ring. The number of carbon atoms in the alkyl group and the like shown here is preferably C 1 to C 3 , more preferably C 2 . Among the compounds represented by this formula, compounds containing trivalent nitrogen and oxidized to pentavalent nitrogen during plating are preferred. Examples of such compounds include glycine, iminodiacetic acid, nitrilotriacetic acid, ethanolamine, 2,2'-iminodiethanol, triethanolamine, aniline and the like.
上記した含窒素化合物の中でも、亜硝酸ナトリウム、グリシン、イミノ二酢酸、ニトリロ三酢酸、エタノールアミン、 ２,２’－イミノジエタノールおよびトリエタノールアミンが好ましく、めっきの光沢や安定性の面から亜硝酸ナトリウム、グリシン、イミノ二酢酸、ニトリロ三酢酸がより好ましく、特に亜硝酸ナトリウムが好ましい。
Among the above nitrogen-containing compounds, sodium nitrite, glycine, iminodiacetic acid, nitrilotriacetic acid, ethanolamine, 2,2'-iminodiethanol and triethanolamine are preferred, and nitrous acid is preferred from the viewpoint of plating gloss and stability. More preferred are sodium, glycine, iminodiacetic acid and nitrilotriacetic acid, and particularly preferred is sodium nitrite.
本発明めっき浴には上記した含窒素化合物は１種または２種以上を用いることができる。また、本発明めっき浴における犠牲還元剤の含有量は特に限定されないが、例えば、１ｇ／Ｌ～１００ｇ／Ｌ、好ましくは５ｇ／Ｌ～６０ｇ／Ｌである。
One or more of the above nitrogen-containing compounds can be used in the plating bath of the present invention. Also, the content of the sacrificial reducing agent in the plating bath of the present invention is not particularly limited, but is, for example, 1 g/L to 100 g/L, preferably 5 g/L to 60 g/L.
本発明めっき浴には、更に、電解銀めっきに用いられる公知のレベリング剤および／またはｐＨ調整剤を含有させてもよい。
The plating bath of the present invention may further contain a known leveling agent and/or pH adjuster used in electrolytic silver plating.
レベリング剤としては、例えば、ポリエチレングリコール、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンイミン等が挙げられる。本発明めっき浴におけるレベリング剤の含有量は特に限定されないが、例えば、０．１ｍｇ／Ｌ～１０００ｍｇ／Ｌ、好ましくは１０ｍｇ／Ｌ～６００ｍｇ／Ｌである。
Examples of leveling agents include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and polyethyleneimine. The content of the leveling agent in the plating bath of the present invention is not particularly limited, but is, for example, 0.1 mg/L to 1000 mg/L, preferably 10 mg/L to 600 mg/L.
ｐＨ調整剤としては、例えば、硫酸、硝酸、メタンスルホン酸、水酸化ナトリウム、水酸化カリウム等が挙げられる。本発明めっき浴におけるｐＨ調整剤の含有量は特に限定されないが、例えば、ｐＨ６．０～ｐＨ１２．５、好ましくはｐＨ９．０～ｐＨ１１．５に調整されることである。
Examples of pH adjusters include sulfuric acid, nitric acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, and the like. Although the content of the pH adjuster in the plating bath of the present invention is not particularly limited, it is adjusted to pH 6.0 to pH 12.5, preferably pH 9.0 to pH 11.5, for example.
本発明めっき浴には、更に、電解銀めっきに用いられる公知の結晶微粒化剤、変色防止剤等を含有させてもよい。結晶微粒化剤としては、例えば、亜セレン酸や、酒石酸カリウムアンチモニウムといったセレン、アンチモン化合物の他、チオ尿素、チオシアン酸カリウムといった含硫黄化合物等が挙げられる。また、変色防止剤としては、例えば、ベンゾトリアゾール、２－メルカプトベンゾチアゾール、１，２，３－ベンゾチアジアゾールといった複素環を有する含窒素もしくは含硫黄化合物等が挙げられる。
The plating bath of the present invention may further contain known grain refiners, discoloration inhibitors, and the like used in electrolytic silver plating. Examples of crystal refining agents include selenous acid, selenium and antimony compounds such as potassium antimonium tartrate, and sulfur-containing compounds such as thiourea and potassium thiocyanate. Examples of discoloration inhibitors include nitrogen- or sulfur-containing compounds having a heterocyclic ring such as benzotriazole, 2-mercaptobenzothiazole, and 1,2,3-benzothiadiazole.
以上説明した本発明めっき浴は、常法に従って各成分を混合することにより調製することができる。なお、本発明めっき浴は、上記成分だけで建浴できるので、シアン化合物を含まない、いわゆるノーシアン電解銀めっき浴とすることができるが、従来銀めっき浴に用いられていたシアン化合物を含ませても同様の効果を得られることは言うまでもない。
The plating bath of the present invention described above can be prepared by mixing each component according to a conventional method. Since the plating bath of the present invention can be made up of only the above components, it can be a so-called cyanide-free electrolytic silver plating bath that does not contain cyanide compounds. Needless to say, the same effect can be obtained by
本発明めっき浴は、従来の電解銀めっき浴と同様に、被めっき物をこれに浸漬して電解めっきすることにより、被めっき物へ電解銀めっきをすることができる。
In the plating bath of the present invention, the object to be plated can be electrolytically plated by immersing it in the same manner as in the conventional electrolytic silver plating bath.
本発明めっき浴でめっきをすることのできる被めっき物は特に限定されないが、例えば、銅、ニッケル、鉄、錫、亜鉛あるいはこれらの合金による金属およびめっき物等が挙げられる。また、被めっき物の形状も特に限定されない。
The object to be plated that can be plated with the plating bath of the present invention is not particularly limited, but examples include metals and plated objects made of copper, nickel, iron, tin, zinc, or alloys thereof. Also, the shape of the object to be plated is not particularly limited.
電解銀めっきの条件は特に限定されないが、例えば、２０～７０℃の浴温、０．５～７０Ａ／ｄｍ２の電流密度、３秒～１時間の電解時間である。
The conditions for electrolytic silver plating are not particularly limited, but are, for example, a bath temperature of 20 to 70° C., a current density of 0.5 to 70 A/dm 2 and an electrolysis time of 3 seconds to 1 hour.
本発明めっき浴を用いた電解銀めっきは従来の電解めっき装置で行うことができるが、特にアノードとして不溶性アノードを用いる装置が好ましい。このような装置としては、フープめっき装置、スパージャーめっき装置等が挙げられる。
Electrolytic silver plating using the plating bath of the present invention can be performed with a conventional electrolytic plating apparatus, but an apparatus using an insoluble anode as the anode is particularly preferable. Such equipment includes a hoop plating equipment, a sparger plating equipment, and the like.
なお、本発明の電解銀めっき浴は、これに含まれる特定の犠牲還元剤がアノードから発生する酸化種に対して優先的に酸化されることで光沢剤の消耗を抑制できるため、めっき浴を連続使用してもめっき浴の性能低下が抑制できる。
In the electrolytic silver plating bath of the present invention, the specific sacrificial reducing agent contained therein is preferentially oxidized with respect to the oxidizing species generated from the anode, thereby suppressing consumption of the brightening agent. Even if it is used continuously, deterioration of the performance of the plating bath can be suppressed.
上記のようにして本発明めっき浴を用いて得られる電解銀めっきは、接触抵抗が低いといった電気特性に優れ、硬さに優れた皮膜である。そのため、この電解銀めっきは、コネクター等の用途に好ましい。
The electrolytic silver plating obtained using the plating bath of the present invention as described above has excellent electrical properties such as low contact resistance, and is a film with excellent hardness. Therefore, this electrolytic silver plating is preferable for uses such as connectors.
以下、本発明の実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。
Although the present invention will be described in detail below with reference to examples, the present invention is not limited to these examples.
実 施 例 １
電解銀めっき：
以下の表１の電解銀めっき浴の基本組成と、犠牲還元剤の一つずつを混合して、電解銀めっき浴を調製した。これらの電解銀めっき浴を用いてハルセル試験を行った。ハルセル試験の条件は、銅のハルセルカソードと酸化イリジウムコーティングをされたチタンアノードを用いて、電流２Ａ、めっき時間２．５分、空気攪拌中、浴温５０℃で行い、これを繰り返し５回まで行った。なお、めっきを１回行うごとに、めっきで減少する銀イオン源を補給した。ハルセル試験後の外観を図１に示した。 Example 1
Electrolytic silver plating:
An electrolytic silver plating bath was prepared by mixing the basic composition of the electrolytic silver plating bath shown in Table 1 below with one of the sacrificial reducing agents. A Hull cell test was performed using these electrolytic silver plating baths. Hull cell test conditions were as follows: copper Hull cell cathode and iridium oxide coated titanium anode, current 2 A, plating time 2.5 minutes, air stirring, bath temperature 50°C, repeated up to 5 times. gone. In addition, the silver ion source, which was reduced by plating, was replenished each time plating was performed. Fig. 1 shows the appearance after the Hull cell test.
電解銀めっき：
以下の表１の電解銀めっき浴の基本組成と、犠牲還元剤の一つずつを混合して、電解銀めっき浴を調製した。これらの電解銀めっき浴を用いてハルセル試験を行った。ハルセル試験の条件は、銅のハルセルカソードと酸化イリジウムコーティングをされたチタンアノードを用いて、電流２Ａ、めっき時間２．５分、空気攪拌中、浴温５０℃で行い、これを繰り返し５回まで行った。なお、めっきを１回行うごとに、めっきで減少する銀イオン源を補給した。ハルセル試験後の外観を図１に示した。 Example 1
Electrolytic silver plating:
An electrolytic silver plating bath was prepared by mixing the basic composition of the electrolytic silver plating bath shown in Table 1 below with one of the sacrificial reducing agents. A Hull cell test was performed using these electrolytic silver plating baths. Hull cell test conditions were as follows: copper Hull cell cathode and iridium oxide coated titanium anode, current 2 A, plating time 2.5 minutes, air stirring, bath temperature 50°C, repeated up to 5 times. gone. In addition, the silver ion source, which was reduced by plating, was replenished each time plating was performed. Fig. 1 shows the appearance after the Hull cell test.
※２ 各組成の溶解およびｐＨの調整のために適当な量の水酸化カリウムを加えた。
*2 An appropriate amount of potassium hydroxide was added to dissolve each composition and adjust the pH.
図１に示したハルセル試験の通り、犠牲還元剤を含まない場合、連続２回目までは半光沢のはっきりとした白色外観が得られるが、連続３回目に低電流密度に特徴的な曇りを示し始め、５回目ではやや黄色味を帯びた銀のめっきがされることから、光沢剤成分の減少が確認できる。表１に示した犠牲還元剤を含むめっき浴で試験を行うと、５回目まで連続でめっきを行っても１回目と同等の外観を示す事から、光沢剤成分が損なわれないことが分かった。
As shown in the Hull cell test shown in FIG. 1, without the sacrificial reducing agent, a semi-glossy, distinctly white appearance is obtained for the first two consecutive runs, but the haze characteristic of low current densities is exhibited by the third successive run. From the beginning, silver plating with a slightly yellowish tint is formed at the fifth time, so it can be confirmed that the amount of the brightener component has decreased. When the test was carried out using a plating bath containing the sacrificial reducing agents shown in Table 1, even if plating was performed continuously up to the fifth time, the appearance was the same as that of the first time, indicating that the brightener component was not impaired. .
また、次亜リン酸ナトリウムおよびホルムアルデヒドではハルセル試験の回数を重ねることで外観が変わり、目的の効果が得られないことが分かった。一方、フルクトースに関しては、ハルセル試験の結果の上では一定の効果が見られるが、図２に示す通り、ハルセル試験を行う前の昇温の段階でめっき浴が分解するため、それが浴中に舞って濁ったり、めっき後にめっき槽に析出してしまう。このような還元力が強い不適当な物質を犠牲還元剤として用いると工業用途としては不適切である。
In addition, it was found that the appearance of sodium hypophosphite and formaldehyde changed with repeated Hull cell tests, and the desired effect could not be obtained. On the other hand, with regard to fructose, a certain effect can be seen in the results of the Hull cell test, but as shown in Fig. 2, the plating bath decomposes during the heating stage before the Hull cell test, so it is It dances and becomes turbid, or precipitates in the plating tank after plating. If such an unsuitable substance with strong reducing power is used as a sacrificial reducing agent, it is unsuitable for industrial use.
上記で述べた犠牲還元剤以外にも、分解を示した還元剤としてヒドロキノン、Ｌ（＋）－アスコルビン酸ナトリウム、ベンズアルデヒド、およびＤ（＋）－グルコース、マルトース等の糖類が挙げられる。また、目的の効果を示さなかった犠牲還元剤として亜リン酸、ギ酸ナトリウム、メタノールが挙げられる。
In addition to the sacrificial reducing agents mentioned above, hydroquinone, L(+)-sodium ascorbate, benzaldehyde, and saccharides such as D(+)-glucose and maltose are examples of reducing agents that have shown decomposition. Phosphorous acid, sodium formate, and methanol are examples of sacrificial reducing agents that did not show the desired effect.
以上の結果より、銀イオン、錯化剤、伝導塩、光沢剤を含有する電解銀めっき浴において、犠牲還元剤を用いることにより、光沢剤成分の分解を抑制できていることが分かった。また、めっきの光沢や補給による蓄積、安定性の面から、犠牲還元剤としては亜硝酸ナトリウム、イミノ二酢酸、ニトリロ三酢酸が優れていて、特に亜硝酸ナトリウムが優れていることも分かった。
From the above results, it was found that the decomposition of the brightener component could be suppressed by using the sacrificial reducing agent in the electrolytic silver plating bath containing silver ions, complexing agent, conductive salt, and brightener. It was also found that sodium nitrite, iminodiacetic acid, and nitrilotriacetic acid are superior as sacrificial reducing agents in terms of plating gloss, accumulation by replenishment, and stability, and sodium nitrite is particularly superior.
実 施 例 ２
スパージャー電解銀めっき：
上記実施例１の亜硝酸ナトリウムを犠牲還元剤として使用した電解銀めっき浴を用いて公知のスパージャーめっき装置を用いて、スパージャー電解銀めっきを行った。スパージャーめっきは、銅板を試験片とし、マスクの開口φ５．５ｍｍに対してノズル開口径φ４ｍｍから流量４Ｌ／ｍｉｎで噴流しためっき液を当てながら、１０ＡＳＤ～３０ＡＳＤ、２７秒～９秒とする条件で行った。得られた銀めっき皮膜は、光沢剤成分が酸化されることなく、ハルセル試験における高電流密度部に相当する外観で行うことができた。 Example 2
Sparger electrolytic silver plating:
Using a known sparger plating apparatus, sparger electrolytic silver plating was performed using the electrolytic silver plating bath using sodium nitrite as a sacrificial reducing agent of Example 1 above. Sparger plating is performed by using a copper plate as a test piece, and applying a plating solution jetted from a nozzle opening diameter of φ4 mm at a flow rate of 4 L / min to a mask opening of φ5.5 mm, 10 ASD to 30 ASD, 27 seconds to 9 seconds. I went with The resulting silver plating film was able to be tested with an appearance corresponding to the high current density area in the Hull cell test without oxidation of the brightener component.
スパージャー電解銀めっき：
上記実施例１の亜硝酸ナトリウムを犠牲還元剤として使用した電解銀めっき浴を用いて公知のスパージャーめっき装置を用いて、スパージャー電解銀めっきを行った。スパージャーめっきは、銅板を試験片とし、マスクの開口φ５．５ｍｍに対してノズル開口径φ４ｍｍから流量４Ｌ／ｍｉｎで噴流しためっき液を当てながら、１０ＡＳＤ～３０ＡＳＤ、２７秒～９秒とする条件で行った。得られた銀めっき皮膜は、光沢剤成分が酸化されることなく、ハルセル試験における高電流密度部に相当する外観で行うことができた。 Example 2
Sparger electrolytic silver plating:
Using a known sparger plating apparatus, sparger electrolytic silver plating was performed using the electrolytic silver plating bath using sodium nitrite as a sacrificial reducing agent of Example 1 above. Sparger plating is performed by using a copper plate as a test piece, and applying a plating solution jetted from a nozzle opening diameter of φ4 mm at a flow rate of 4 L / min to a mask opening of φ5.5 mm, 10 ASD to 30 ASD, 27 seconds to 9 seconds. I went with The resulting silver plating film was able to be tested with an appearance corresponding to the high current density area in the Hull cell test without oxidation of the brightener component.
本発明は、銀めっきに利用することができる。
The present invention can be used for silver plating.
Claims (9)
- 銀イオン、錯化剤、伝導塩、光沢剤および犠牲還元剤を含有する電解銀めっき浴であって、
犠牲還元剤として下記一般式（I）
および一般式（II）
で表される含窒素化合物の１種または２種以上を含むことを特徴とする電解銀めっき浴。 An electrolytic silver plating bath containing silver ions, a complexing agent, a conductive salt, a brightener and a sacrificial reducing agent,
The following general formula (I) as a sacrificial reducing agent
and general formula (II)
An electrolytic silver plating bath characterized by containing one or more nitrogen-containing compounds represented by: - 犠牲還元剤が、３価の窒素を含む化合物であり、めっき中に５価に酸化される化合物である請求項１記載の電解銀めっき浴。 The electrolytic silver plating bath according to claim 1, wherein the sacrificial reducing agent is a compound containing trivalent nitrogen that is oxidized to pentavalent nitrogen during plating.
- 光沢剤が、チオ硫酸またはチオ硫酸の金属塩、もしくはチオジグリコール酸またはその金属塩である請求項１または２記載の電解銀めっき浴。 The electrolytic silver plating bath according to claim 1 or 2, wherein the brightener is thiosulfuric acid or a metal salt of thiosulfuric acid, or thiodiglycolic acid or a metal salt thereof.
- 錯化剤が、下記一般式（III）
で表されるイミド化合物である請求項１～３の何れかに記載の電解銀めっき浴。 The complexing agent has the following general formula (III)
The electrolytic silver plating bath according to any one of claims 1 to 3, which is an imide compound represented by: - 伝導塩が、無機酸あるいは有機酸の金属塩である請求項１～４の何れかに記載の電解銀めっき浴。 The electrolytic silver plating bath according to any one of claims 1 to 4, wherein the conductive salt is a metal salt of an inorganic acid or an organic acid.
- 更に、レベリング剤および／またはｐＨ調整剤を含有するものである請求項１～５の何れかに記載の電解銀めっき浴。 The electrolytic silver plating bath according to any one of claims 1 to 5, which further contains a leveling agent and/or a pH adjuster.
- 不溶性アノードを用いる銀めっき用である請求項１～６の何れかに記載の電解銀めっき浴。 The electrolytic silver plating bath according to any one of claims 1 to 6, which is for silver plating using an insoluble anode.
- 被めっき物を、請求項１～６の何れかに記載の銀めっき浴に浸漬して電解めっきすることを特徴とする電解銀めっき方法。 An electrolytic silver plating method, characterized in that an object to be plated is immersed in the silver plating bath according to any one of claims 1 to 6 for electrolytic plating.
- 電解めっきに用いるアノードとして不溶性アノードを用いるものである請求項８記載の電解銀めっき方法。 The electrolytic silver plating method according to claim 8, wherein an insoluble anode is used as the anode for electrolytic plating.
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| CN202280008609.6A CN116710600A (en) | 2021-01-20 | 2022-01-06 | Electrolytic silver plating bath and electrolytic silver plating method using same |
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| JP5247142B2 (en) | 2007-12-19 | 2013-07-24 | 株式会社大和化成研究所 | Silver plating method |
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2022
- 2022-01-06 CN CN202280008609.6A patent/CN116710600A/en active Pending
- 2022-01-06 WO PCT/JP2022/000167 patent/WO2022158291A1/en active Application Filing
- 2022-01-06 KR KR1020237026048A patent/KR20230131873A/en unknown
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| TW202237904A (en) | 2022-10-01 |
| CN116710600A (en) | 2023-09-05 |
| JP2022111432A (en) | 2022-08-01 |
| KR20230131873A (en) | 2023-09-14 |
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