JP4665244B2 - Replacement silver plating bath - Google Patents
Replacement silver plating bath Download PDFInfo
- Publication number
- JP4665244B2 JP4665244B2 JP2005139697A JP2005139697A JP4665244B2 JP 4665244 B2 JP4665244 B2 JP 4665244B2 JP 2005139697 A JP2005139697 A JP 2005139697A JP 2005139697 A JP2005139697 A JP 2005139697A JP 4665244 B2 JP4665244 B2 JP 4665244B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- silver
- plating bath
- containing compound
- mol
- 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.)
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- 238000007747 plating Methods 0.000 title claims description 121
- 229910052709 silver Inorganic materials 0.000 title claims description 112
- 239000004332 silver Substances 0.000 title claims description 112
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 81
- 150000001875 compounds Chemical class 0.000 claims description 106
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 58
- 238000006467 substitution reaction Methods 0.000 claims description 41
- 150000003378 silver Chemical class 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 235000002639 sodium chloride Nutrition 0.000 claims description 22
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- -1 dihydroxyethyl group Chemical group 0.000 claims description 21
- 125000003277 amino group Chemical group 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 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 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 10
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 150000003585 thioureas Chemical class 0.000 claims description 10
- 235000015165 citric acid Nutrition 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 7
- 229960003767 alanine Drugs 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 6
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 6
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000174 gluconic acid Substances 0.000 claims description 6
- 235000012208 gluconic acid Nutrition 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 229960003080 taurine Drugs 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 5
- 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 5
- 235000003704 aspartic acid Nutrition 0.000 claims description 5
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- LZXHHNKULPHARO-UHFFFAOYSA-M (3,4-dichlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=C(Cl)C(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LZXHHNKULPHARO-UHFFFAOYSA-M 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 4
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Amino-1-propanesulfonic acid Natural products NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 235000004279 alanine Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 3
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 claims description 3
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 claims description 3
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 3
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 claims description 3
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229960003104 ornithine Drugs 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 150000004763 sulfides Chemical class 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 description 29
- 239000000460 chlorine Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 27
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 25
- 229910052794 bromium Inorganic materials 0.000 description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- 238000002845 discoloration Methods 0.000 description 22
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 16
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 11
- 229940071536 silver acetate Drugs 0.000 description 11
- 150000003568 thioethers Chemical class 0.000 description 10
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 7
- 229940024606 amino acid Drugs 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 6
- 150000001413 amino acids Chemical class 0.000 description 6
- 229960005261 aspartic acid Drugs 0.000 description 6
- 238000004649 discoloration prevention Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229960002449 glycine Drugs 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 229960002989 glutamic acid Drugs 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical group OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- ODHCTXKNWHHXJC-UHFFFAOYSA-N 5-oxoproline Chemical compound OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229940001468 citrate Drugs 0.000 description 2
- 229940012017 ethylenediamine Drugs 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229940013688 formic acid Drugs 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 229940098895 maleic acid Drugs 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- WYCFMBAHFPUBDS-UHFFFAOYSA-L silver sulfite Chemical compound [Ag+].[Ag+].[O-]S([O-])=O WYCFMBAHFPUBDS-UHFFFAOYSA-L 0.000 description 1
- NEMJXQHXQWLYDM-JJKGCWMISA-M silver;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ag+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEMJXQHXQWLYDM-JJKGCWMISA-M 0.000 description 1
- GURNTNKIRDSILY-UHFFFAOYSA-M silver;ethanesulfonate Chemical compound [Ag+].CCS([O-])(=O)=O GURNTNKIRDSILY-UHFFFAOYSA-M 0.000 description 1
- TZMGLOFLKLBEFW-UHFFFAOYSA-M silver;sulfamate Chemical compound [Ag+].NS([O-])(=O)=O TZMGLOFLKLBEFW-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- PSVXZQVXSXSQRO-UHFFFAOYSA-N undecaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO PSVXZQVXSXSQRO-UHFFFAOYSA-N 0.000 description 1
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Description
本発明は置換銀メッキ浴に関して、皮膜の変色や色調ムラを防止して、均質で美麗な銀白色の皮膜が得られるものを提供する。 The present invention provides a substituted silver plating bath that can prevent discoloration and uneven color tone of the film and obtain a homogeneous and beautiful silver-white film.
電子部品や自動車部品などの工業メッキ分野では、スズ又はスズ合金メッキがハンダ付け性に優れることから汎用されているが、ホイスカー発生の問題がある。
銀メッキはホイスカー発生の問題がスズより少なく、ハンダ付け性も良好である。そこで、置換銀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
緻密な銀皮膜を得る目的で、可溶性銀塩と、チオ尿素類、チアゾール系化合物、ジチオカルバミン酸系化合物などの含イオウ化合物と、非イオン系界面活性剤とを含有する非シアン系の銀電気メッキ浴が開示されている（請求項１、段落８〜９参照）。
In industrial plating fields such as electronic parts and automobile parts, tin or tin alloy plating is widely used because of its excellent solderability, but there is a problem of whisker generation.
Silver plating has fewer whisker problems than tin and has good solderability. Therefore, the conventional technique of the substitution silver plating bath is as follows.
(1) Patent Document 1
Non-cyan silver electroplating containing soluble silver salts, sulfur-containing compounds such as thioureas, thiazole compounds, dithiocarbamic acid compounds, and nonionic surfactants for the purpose of obtaining a dense silver film A bath is disclosed (see claim 1, paragraphs 8-9).
(2)特許文献２
銅基材表面へのハンダ付け性を向上することを目的として（請求項１、段落８、段落１３参照）、可溶性銀塩と、酸と、脂肪族アミン（エトキシル化タローアミン、エトキシル化ココアミン等）、脂肪族アミド、脂肪酸（ステアリン酸、オレイン酸等）などの添加物とを含有する非シアン系の置換銀メッキ浴が開示されている（段落１３参照）。
(2) Patent Document 2
For the purpose of improving the solderability to the copper substrate surface (see claim 1, paragraphs 8 and 13), soluble silver salt, acid, and aliphatic amine (ethoxylated tallow amine, ethoxylated cocoamine, etc.) Non-cyan substitution silver plating baths containing additives such as aliphatic amides and fatty acids (stearic acid, oleic acid, etc.) are disclosed (see paragraph 13).
(3)特許文献３
可溶性銀塩と、ヨウ素化合物と、チオ尿素などの含イオウ化合物とを含有する非シアン系の置換銀メッキ浴が開示されている（請求項６参照）。また、実施例２には、ヨウ化銀と、チオ尿素と、ヨウ化カリウムを含有する具体的な置換銀メッキ浴が開示されている（段落２２参照）。ヨウ素化合物は銀の錯化剤として作用する（段落１２参照）。
(3) Patent Document 3
A non-cyan substitution silver plating bath containing a soluble silver salt, an iodine compound, and a sulfur-containing compound such as thiourea is disclosed (see claim 6). Example 2 discloses a specific substituted silver plating bath containing silver iodide, thiourea, and potassium iodide (see paragraph 22). The iodine compound acts as a silver complexing agent (see paragraph 12).
(4)特許文献４
銀皮膜の厚みの均一性、光沢性などの改善を目的として、可溶性銀塩と、錯化剤と、カルボン酸置換窒素含有ヘテロ環化合物を含有する置換銀メッキ浴が開示されている（請求項１、段落１１参照）。上記錯化剤としては、アミノ酸、シュウ酸、マレイン酸などのポリカルボン酸、ニトリロトリ酢酸、エチレンジアミンテトラ酢酸などのアミノカルボン酸、エチレンジアミンなどのポリアミン、クエン酸塩、酒石酸塩、グルコン酸塩、乳酸塩、クラウンエーテル、チオグリコール酸などのチオ含有配位子、エタノールアミンなどのアミノアルコールなどが挙げられる（請求項７、段落１９参照）。また、カルボン酸置換窒素含有ヘテロ環化合物としては、ピコリン酸、キノリン酸、ニコチン酸などのピリジンカルボン酸を初め、ピペリジンカルボン酸、ピペラジンカルボン酸、ピロールカルボン酸などが挙げられる（請求項４、段落２１参照）。
(4) Patent Document 4
A substituted silver plating bath containing a soluble silver salt, a complexing agent, and a carboxylic acid-substituted nitrogen-containing heterocyclic compound is disclosed for the purpose of improving the uniformity of the thickness of the silver film, glossiness, etc. (claims) 1, see paragraph 11). Examples of the complexing agent include polycarboxylic acids such as amino acids, oxalic acid and maleic acid, aminocarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyamines such as ethylenediamine, citrate, tartrate, gluconate and lactate. Thio-containing ligands such as crown ether and thioglycolic acid, amino alcohols such as ethanolamine, and the like (see claim 7, paragraph 19). Examples of the carboxylic acid-substituted nitrogen-containing heterocyclic compound include pyridinecarboxylic acid such as picolinic acid, quinolinic acid, and nicotinic acid, piperidine carboxylic acid, piperazine carboxylic acid, and pyrrole carboxylic acid. 21).
(5)特許文献５
マイグレーション（電解移行）の防止を主目的として、可溶性銀塩と、錯化剤と、フッ素系界面活性剤を含有する置換銀メッキ浴が開示されている（請求項１、段落５参照）。錯化剤としてはピロリドン化合物が挙げられ（請求項２と４参照）、フッ素系界面活性剤としては、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルリン酸エステル、パーフルオロアルキルアミンオキシドなどが挙げられる（請求項５、段落９参照）。
また、具体的に、試料４には、銀錯化剤として２−ピロリドン−５−カルボン酸、フッ素系界面活性剤としてパーフルオロアルキルカルボン酸塩を含有する銀メッキ浴が、試料７には、銀錯化剤として２−ピロリドン−５−カルボン酸、フッ素系界面活性剤としてパーフルオロアルキルアミンオキシドを含有する銀メッキ浴が夫々開示されている（表１参照）。
(5) Patent Document 5
A displacement silver plating bath containing a soluble silver salt, a complexing agent, and a fluorosurfactant has been disclosed mainly for the purpose of preventing migration (electrolytic migration) (see claim 1, paragraph 5). Examples of complexing agents include pyrrolidone compounds (see claims 2 and 4), and examples of fluorosurfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoro And alkylamine oxides (see claim 5, paragraph 9).
Specifically, Sample 4 includes a silver plating bath containing 2-pyrrolidone-5-carboxylic acid as a silver complexing agent and perfluoroalkylcarboxylate as a fluorine-based surfactant, and Sample 7 includes A silver plating bath containing 2-pyrrolidone-5-carboxylic acid as a silver complexing agent and perfluoroalkylamine oxide as a fluorosurfactant is disclosed (see Table 1).
(6)特許文献６
浴安定性や皮膜の密着性などの改善を目的として、可溶性銀塩と、分子内に２個のモノスルフィド基を有する水溶性含イオウ有機化合物を含有する置換銀メッキ浴が開示されている（請求項１、段落６参照）。この含イオウ有機化合物は、分子内にスルフィド基の外に、カルボキシル基、アミノ基、スルホン酸基、ホスホン酸基などの水溶性基を有し、具体的には、１,２−ビス（２−ヒドロキシエチルチオ）エタン、２,２′−（エチレンジチオ）ジエタンチオールなどである（段落１４参照）。
また、メッキ浴の安定剤として酒石酸、クエン酸、グルコン酸などを添加でき（段落１８参照）、さらに、必要に応じて、皮膜の密着性などの向上のために、チオ尿素類を添加しても良いことが開示されている（段落２０参照）。
(6) Patent Document 6
For the purpose of improving bath stability and film adhesion, a substituted silver plating bath containing a soluble silver salt and a water-soluble sulfur-containing organic compound having two monosulfide groups in the molecule is disclosed ( (See claim 1, paragraph 6). This sulfur-containing organic compound has a water-soluble group such as a carboxyl group, an amino group, a sulfonic acid group, and a phosphonic acid group in addition to a sulfide group in the molecule. Specifically, 1,2-bis (2 -Hydroxyethylthio) ethane, 2,2 '-(ethylenedithio) diethanethiol and the like (see paragraph 14).
In addition, tartaric acid, citric acid, gluconic acid and the like can be added as stabilizers for the plating bath (see paragraph 18), and thioureas can be added as necessary to improve the adhesion of the film. (See paragraph 20).
(7)特許文献７
皮膜の密着性、ハンダ付け性の改善を目的として、可溶性銀塩と、第一錯化剤のニトロ芳香族化合物と、第二錯化剤のアミノカルボン酸化合物、ヒドロキシカルボン酸化合物又はトリアゾール化合物とを含有する置換銀メッキ浴が開示されている（請求項１、段落６参照）。
上記第一錯化剤は、ニトロフェノール、ニトロベンゼンアルコール、ニトロアニリン、ニトロフェノールスルホン酸、ニトロ安息香酸などであり、第二錯化剤は、グリシン、ニトリロ酢酸、エチレンジアミンテトラ酢酸、乳酸、クエン酸、サリチル酸などである（段落１１〜１２参照）。
(7) Patent Document 7
For the purpose of improving adhesion and solderability of the film, a soluble silver salt, a nitroaromatic compound as a first complexing agent, an aminocarboxylic acid compound, a hydroxycarboxylic acid compound or a triazole compound as a second complexing agent A substituted silver plating bath containing is disclosed (see claim 1, paragraph 6).
The first complexing agent is nitrophenol, nitrobenzene alcohol, nitroaniline, nitrophenol sulfonic acid, nitrobenzoic acid, etc., and the second complexing agent is glycine, nitriloacetic acid, ethylenediaminetetraacetic acid, lactic acid, citric acid, Salicylic acid and the like (see paragraphs 11 to 12).
(8)特許文献８
浴の経時安定性、皮膜外観の改善を目的として、可溶性銀塩と、特定のスルフィド化合物とを含有する置換銀メッキ浴が開示されている（請求項１〜２、段落６参照）。また、当該銀メッキ浴には、チオ尿素類、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸などのアミノカルボン酸類、エチレンジアミン、ジエチリントリアミンなどのポリアミン類、酒石酸、クエン酸、グルコン酸などのオキシカルボン酸類を添加しても良いことが記載されている（請求項３、段落２５参照）。
(8) Patent Document 8
A substituted silver plating bath containing a soluble silver salt and a specific sulfide compound has been disclosed for the purpose of improving bath stability over time and coating appearance (see claims 1 and 2, paragraph 6). In addition, aminocarboxylic acids such as thioureas, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid, polyamines such as ethylenediamine and diethylintriamine, and oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid are added to the silver plating bath. (See claim 3, paragraph 25).
(9)特許文献９
可溶性銀塩と、アミノ酸、アミノ酢酸、ポリカルボン酸、クエン酸塩、酒石酸塩などの錯化剤とを含有する置換銀メッキ浴が開示されている（請求項６、段落４１参照）。また、当該銀メッキ浴には、界面活性剤（ノニオン系が好適；段落４５参照）、エトキシ化アルキルアミン（第三級アミン）等の変色防止剤などを添加できることが記載されている（段落４７参照）。但し、ハロゲン化物イオンは実質的に含まないことが好ましい点が記載されている（段落５０参照）。
(9) Patent Document 9
A substituted silver plating bath containing a soluble silver salt and a complexing agent such as amino acid, aminoacetic acid, polycarboxylic acid, citrate, and tartrate is disclosed (see claim 6, paragraph 41). In addition, it is described that a surfactant (preferably nonionic type; see paragraph 45), an anti-discoloring agent such as ethoxylated alkylamine (tertiary amine) and the like can be added to the silver plating bath (paragraph 47). reference). However, it is described that it is preferable that halide ions are not substantially contained (see paragraph 50).
銀メッキ皮膜は美麗で光沢のある銀白色の皮膜を理想とするが、可溶性銀塩とチオ尿素を基本組成とする置換銀浴を用いてメッキを行うと、チオ尿素中のイオウ元素の吸着が原因と推定される変色（黄変）が発生するという弊害があり、この黄変はハンダ付け性にも悪影響を及ぼす恐れがある。
また、たとえ、変色のない皮膜が得られても、部分的にくすんだ銀白色を呈した、いわゆるメッキむらが生じる問題が依然として残り、全体に均質で美麗な銀白色のメッキ皮膜を得ることは容易でない。
The silver-plated film is ideally a beautiful and shiny silver-white film, but when plating is performed using a substitution silver bath based on a soluble silver salt and thiourea, adsorption of sulfur elements in thiourea can be achieved. There is an adverse effect of discoloration (yellowing) presumed to be the cause, and this yellowing may adversely affect solderability.
Moreover, even if a film without discoloration is obtained, there still remains a problem that the so-called plating unevenness with a partially dull silver white color remains, and it is possible to obtain a uniform and beautiful silver white plating film as a whole. Not easy.
本発明は、置換銀メッキにおいて、変色及び色調ムラを防止して、均質で美麗な光沢の銀メッキ皮膜を得ることを技術的課題とする。 An object of the present invention is to obtain a uniform and beautiful glossy silver plating film by preventing discoloration and uneven color tone in substitution silver plating.
本発明者らは、可溶性銀塩とチオ尿素を基本組成とする置換銀浴において、塩素又は臭素イオンを含有すると、銀皮膜の変色が有効に防止できることを突き止めた。しかしながら、この塩素又は臭素イオンを含有した置換銀メッキ浴では、変色のない銀皮膜を形成できる反面、部分的にくすんだ銀白色のメッキむらが生じ易いという問題が発生し、その改善を鋭意検討した。
その結果、乳酸、ギ酸、アスパラギン酸などのアミノ基含有化合物又はカルボキシル基含有化合物をさらに含有させると、このメッキむらが改善され、均質で光沢のある銀白色のメッキ皮膜が得られることを見い出して、本発明を完成した。
The present inventors have found that discoloration of the silver film can be effectively prevented when chlorine or bromine ions are contained in a substituted silver bath having a soluble silver salt and thiourea as a basic composition. However, while this substitution silver plating bath containing chlorine or bromine ions can form a silver film without discoloration, it has a problem that it is likely to cause partially dull silver-white plating unevenness. did.
As a result, it was found that when an amino group-containing compound or carboxyl group-containing compound such as lactic acid, formic acid, or aspartic acid was further added, this plating unevenness was improved, and a uniform and glossy silver-white plating film was obtained. The present invention has been completed.
即ち、本発明１は、可溶性銀塩と、チオ尿素類、スルフィド類、メルカプタン類などの含イオウ化合物からなる錯化剤とを含有する置換銀メッキ浴において、
(Ａ)ハロゲン含有化合物と、
(Ｂ)アミノ基含有化合物及びカルボキシル基含有化合物の少なくとも一種
とを含有し、
上記成分(Ｂ)が、乳酸、クエン酸、酒石酸、リンゴ酸、グルコン酸、アスコルビン酸よりなるオキシカルボン酸、ギ酸、酢酸、マレイン酸よりなるカルボン酸、アラニン、アスパラギン酸、グリシン、オルニチン、グルタミン酸よりなるアミノ酸、アミノメタンスルホン酸、タウリン、Ｎ−メチルタウリン、３−アミノ−１−プロパンスルホン酸よりなるアミノスルホン酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、ニトリロトリ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、Ｎ,Ｎ−ジカルボキシメチル−Ｌ−アラニン、ヒドロキシエチルイミノジ酢酸、１,３−プロパンジアミンテトラ酢酸、１,３−ジアミノ−２−ヒドロキシプロパンテトラ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸よりなるアミノカルボン酸、ヒドロキシエチリデンジホスホン酸、ニトリロトリス（メチレンホスホン酸）、ホスホノブタントリカルボン酸、Ｎ,Ｎ,Ｎ′,Ｎ′-テトラキス（ホスホノメチル）エチレンジアミンよりなるアミノホスホン酸、及びこれらの塩よりなる群から選ばれた化合物であることを特徴とする置換銀メッキ浴である。
That is, the present invention 1 is a substitution silver plating bath containing a soluble silver salt and a complexing agent comprising a sulfur-containing compound such as thioureas, sulfides, mercaptans, etc.
(A) a halogen-containing compound;
(B) containing at least one of an amino group-containing compound and a carboxyl group-containing compound ,
The component (B) is oxycarboxylic acid composed of lactic acid, citric acid, tartaric acid, malic acid, gluconic acid, ascorbic acid, carboxylic acid composed of formic acid, acetic acid, maleic acid, alanine, aspartic acid, glycine, ornithine, glutamic acid Amino sulfonic acid, aminomethanesulfonic acid, taurine, N-methyltaurine, aminosulfonic acid consisting of 3-amino-1-propanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetramine Hexaacetic acid, N, N-dicarboxymethyl-L-alanine, hydroxyethyliminodiacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethyl group Aminocarboxylic acid consisting of syn, glycol ether diamine tetraacetic acid, hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), phosphonobutanetricarboxylic acid, N, N, N ', N'-tetrakis (phosphonomethyl) ethylenediamine It is a substituted silver plating bath characterized by being a compound selected from the group consisting of aminophosphonic acid and salts thereof .
本発明２は、上記本発明１において、含イオウ化合物がチオ尿素類であることを特徴とす置換銀メッキ浴である。 Invention 2 is a substituted silver plating bath according to Invention 1, wherein the sulfur-containing compound is a thiourea .
本発明３は、上記本発明１又は２において、ハロゲン含有化合物(Ａ)が、塩化ナトリウム、塩化カリウム、塩化アンモニウム、臭化ナトリウム、臭化カリウム、塩素アニオン、臭素アニオン又はヨウ素アニオンを含むカチオン系界面活性剤、ヨウ化ナトリウム、ヨウ化カリウムであることを特徴とする置換銀メッキ浴である。 Invention 3 is a cation system according to Invention 1 or 2, wherein the halogen-containing compound (A) contains sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, chlorine anion, bromine anion or iodine anion. A substituted silver plating bath characterized by being a surfactant , sodium iodide, and potassium iodide .
本発明４は、上記本発明１〜３のいずれかにおいて、ハロゲン含有化合物(Ａ)のメッキ浴に対する含有量が、１０-6〜１００ｇ／Ｌであることを特徴とする置換銀メッキ浴である。 The present invention 4 is the substitution silver plating bath according to any one of the present inventions 1 to 3, wherein the content of the halogen-containing compound (A) with respect to the plating bath is 10 −6 to 100 g / L. .
本発明５は、上記本発明１〜４のいずれかにおいて、成分(Ｂ)のメッキ浴に対する含有量が、１０-4〜５モル／Ｌであることを特徴とする置換銀メッキ浴。 Invention 5 is a substituted silver plating bath according to any one of Inventions 1 to 4, wherein the content of component (B) in the plating bath is 10 −4 to 5 mol / L.
銀塩と銀の錯化剤を基本組成とする置換銀メッキ浴に塩素含有化合物又は臭素含有化合物を添加すると、メッキ皮膜の変色を防止して、銀白色の皮膜を得ることができるが、メッキむらが生じ易い。
そこで、本発明１のように、上記基本組成の置換銀メッキ浴に、塩素、臭素などのハロゲンを含有する化合物に加えて、さらに特定のアミノ基含有化合物又はカルボキシル基含有化合物とを併用添加すると、銀メッキ皮膜の変色を防止しながら、皮膜の色調ムラを抑制して均質で光沢のある銀白色の銀皮膜を得ることができる。
The addition of chlorine-containing compound or bromine-containing compound to substituted silver plating bath having a basic composition of a silver salt and silver complexing agent, to prevent discoloration of the plating film, but silver-white film can be obtained, plated Unevenness is likely to occur.
Therefore, as in the case of the present invention 1, in addition to the compound containing halogen such as chlorine and bromine, in addition to the compound containing halogen such as chlorine and bromine, the specific amino group-containing compound or carboxyl group-containing compound is added to the substitution silver plating bath having the above basic composition. In addition, while preventing the discoloration of the silver plating film, it is possible to obtain a homogeneous and glossy silver-white silver film by suppressing the uneven color tone of the film.
本発明は、可溶性銀塩と、チオ尿素類、スルフィド類、メルカプタン類などの含イオウ化合物からなる錯化剤とを基本組成とするメッキ浴に、(Ａ)ハロゲン含有化合物と、(Ｂ)特定のアミノ基含有化合物及びカルボキシル基含有化合物の少なくとも一種とを含有する置換銀メッキ浴である。 The present invention provides a plating bath comprising a soluble silver salt and a complexing agent comprising a sulfur-containing compound such as thioureas, sulfides, and mercaptans as a basic composition , (A) a halogen-containing compound, (B) a specific a substituted silver plating bath containing at least one amino group-containing compound and a carboxyl group-containing compound.
本発明の置換銀メッキ浴に含有する可溶性銀塩は、浴中でＡｇ+を生成する可溶性の塩類であれば任意のものが使用でき、特段の制約はなく、難溶性塩をも排除するものではない。
可溶性銀塩としては、硫酸銀、亜硫酸銀、炭酸銀、酢酸銀、乳酸銀、スルホコハク酸銀、硝酸銀、有機スルホン酸銀、ホウフッ化銀、クエン酸銀、酒石酸銀、グルコン酸銀、スルファミン酸銀、シュウ酸銀、酸化銀などの可溶性塩が使用でき、また、本来は難溶性であるが、スルフィド系化合物などの作用によりある程度の溶解性を確保できる塩化銀なども使用できる。銀塩の好ましい具体例としては、メタンスルホン酸銀、エタンスルホン酸銀、酢酸銀、乳酸銀、クエン酸銀などが挙げられる。
メッキ浴に対する当該可溶性銀塩の金属塩換算の含有量は、０.０００１〜２００ｇ／Ｌであり、好ましくは１〜３０ｇ／Ｌである。
As the soluble silver salt contained in the substituted silver plating bath of the present invention, any soluble salt can be used as long as it is a soluble salt that produces Ag + in the bath, and there is no particular limitation, and even a hardly soluble salt is excluded. is not.
Soluble silver salts include silver sulfate, silver sulfite, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver nitrate, silver organic sulfonate, silver borofluoride, silver citrate, silver tartrate, silver gluconate, silver sulfamate Soluble salts such as silver oxalate and silver oxide can be used, and silver chloride which is originally poorly soluble but can ensure a certain degree of solubility by the action of sulfide compounds and the like can also be used. Preferable specific examples of the silver salt include silver methanesulfonate, silver ethanesulfonate, silver acetate, silver lactate, and silver citrate.
The content of the soluble silver salt in terms of metal salt with respect to the plating bath is 0.0001 to 200 g / L, preferably 1 to 30 g / L.
本発明の置換銀メッキ浴では、浴中の銀イオンを安定化するために錯化剤を含有する。当該錯化剤はチオ尿素類、スルフィド類、メルカプタン類などの含イオウ化合物からなる。これらの含イオウ化合物は夫々を単用又は併用でき、或は、異種を複用（例えば、チオ尿素とスルフィド類とを複用）できる。メッキ浴に対する含イオウ化合物の添加量は０.０００１〜５モル／Ｌであり、０.０３〜２モル／Ｌである。 The substituted silver plating bath of the present invention contains a complexing agent to stabilize silver ions in the bath. The complexing agent comprises a sulfur-containing compound such as thioureas, sulfides, mercaptans and the like. These sulfur-containing compounds can be used singly or in combination, or different types can be used together (for example, thiourea and sulfides can be used together). The amount of the sulfur-containing compound added to the plating bath is 0.0001 to 5 mol / L and 0.03 to 2 mol / L.
上記チオ尿素類はチオ尿素及びチオ誘導体である。チオ尿素誘導体には、１,３―ジメチルチオ尿素、トリメチルチオ尿素、ジエチルチオ尿素(例えば、１,３―ジエチルチオ尿素)、１,３―ジイソプロピルチオ尿素、アリルチオ尿素、アセチルチオ尿素、エチレンチオ尿素、１,３―ジフェニルチオ尿素、二酸化チオ尿素、チオセミカルバジド、Ｓ−メチルイソチオ尿素硫酸塩、トリブチルチオ尿素、塩酸ベンジルイソチオ尿素、１,３−ジブチルチオ尿素、１−ナフチルチオ尿素、テトラメチルチオ尿素、１−フェニルチオ尿素、１−メチルチオ尿素等が挙げられる。 The thioureas are thiourea and thio derivatives. The thiourea derivatives include 1,3-dimethylthiourea, trimethylthiourea, diethylthiourea (for example, 1,3-diethylthiourea), 1,3-diisopropylthiourea, allylthiourea, acetylthiourea, ethylenethiourea, 1,3. -Diphenylthiourea, thiourea dioxide, thiosemicarbazide, S-methylisothiourea sulfate, tributylthiourea, benzylisothiourea hydrochloride, 1,3-dibutylthiourea, 1-naphthylthiourea, tetramethylthiourea, 1-phenylthiourea, 1-methylthiourea etc. are mentioned.
上記メルカプタン類には、システイン、Ｎ−アセチルシステイン、チオグリコール、メルカプトコハク酸、メルカプトイソ酪酸、メルカプト酢酸、ジメルカプト酢酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、２,３−ジメルカプトコハク酸、メルカプトアニリン、メルカプトピリジンなどが挙げられる。 The mercaptans include cysteine, N-acetylcysteine, thioglycol, mercaptosuccinic acid, mercaptoisobutyric acid, mercaptoacetic acid, dimercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and 2,3-dimercaptosuccinic acid. , Mercaptoaniline, mercaptopyridine and the like.
上記スルフィド類には、メチオニン、エチオニン、シスチン、チオジグリコール酸、チオジグリコール、２,２′−チオビス(エチルアミン)、チオジプロピオン酸、チオジエタンスルホン酸、チオジプロパノール、３,３′−チオビス(プロピルアミン)、チオジ酪酸、チオジプロパンスルホン酸、ビス(ウンデカエチレングリコール)チオエーテル、ビス(ドデカエチレングリコール)チオエーテル、ビス(ペンタデカエチレングリコール)チオエーテル、ビス(トリエチレングリコール)チオエーテル、４,７,１０−トリチアトリデカン−１,２,１２,１３−テトラオール、６,９,１２−トリチア−３,１５−ジオキサヘプタデカン−１,１７−ジオール、３,６−ジチアオクタン−１,８―ジオール、４,７−ジチアデカン−１,１０−ジオール、３,６,９−トリチアウンデカン−１,１１−ジオール、３,６−ジチアオクタン−１,８―ジアミン、３,６−ジチアオクタン−１,８―ジカルボン酸、４,７,１０−トリチアトリデカン−１,１３−ジスルホン酸ジナトリウム、３,６,９−トリチアウンデカン−１,１１−ジスルホン酸、４,７,１０,１３−テトラチアヘキサデカン−１,１６−ジスルホン酸、１,８−ビス（２−ピリジル）−３,６−ジチアオクタンなどが挙げられる。 The sulfides include methionine, ethionine, cystine, thiodiglycolic acid, thiodiglycol, 2,2'-thiobis (ethylamine), thiodipropionic acid, thiodiethanesulfonic acid, thiodipropanol, 3,3 '. -Thiobis (propylamine), thiodibutyric acid, thiodipropanesulfonic acid, bis (undecaethylene glycol) thioether, bis (dodecaethylene glycol) thioether, bis (pentadecaethylene glycol) thioether, bis (triethylene glycol) thioether, 4,7,10-trithiatridecane-1,2,12,13-tetraol, 6,9,12-trithia-3,15-dioxaheptadecane-1,17-diol, 3,6-dithiaoctane- 1,8-diol, 4,7-dithiadecane-1,10-diol, 3,6,9-triti Undecane-1,11-diol, 3,6-dithiaoctane-1,8-diamine, 3,6-dithiaoctane-1,8-dicarboxylic acid, 4,7,10-trithiatridecane-1,13-disulfonic acid diester Sodium, 3,6,9-trithiaundecane-1,11-disulfonic acid, 4,7,10,13-tetrathiahexadecane-1,16-disulfonic acid, 1,8-bis (2-pyridyl) -3 , 6-dithiaoctane and the like.
本発明の置換銀メッキ浴は有機酸、無機酸、或はその塩をベース酸としても良いし、可溶性銀塩、錯化剤を水に溶解させて建浴しても良い。
有機酸としては、排水処理が比較的容易なアルカンスルホン酸、アルカノールスルホン酸、芳香族スルホン酸等の有機スルホン酸、或は、脂肪族カルボン酸などが好ましい。
無機酸としては、ホウフッ化水素酸、ケイフッ化水素酸、スルファミン酸、塩酸、硫酸、硝酸、過塩素酸等が挙げられる。
上記の酸（又は塩）は単用又は併用でき、その含有量は０.１〜３００ｇ／Ｌであり、好ましくは２０〜１２０ｇ／Ｌである。
The substituted silver plating bath of the present invention may be an organic acid, an inorganic acid, or a salt thereof as a base acid, or may be constructed by dissolving a soluble silver salt or a complexing agent in water.
The organic acid is preferably an organic sulfonic acid such as alkane sulfonic acid, alkanol sulfonic acid or aromatic sulfonic acid, which is relatively easy to treat waste water, or an aliphatic carboxylic acid.
Examples of inorganic acids include borohydrofluoric acid, silicohydrofluoric acid, sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, and the like.
The above acid (or salt) can be used singly or in combination, and its content is 0.1 to 300 g / L, preferably 20 to 120 g / L.
本発明１の置換銀メッキ浴は、(Ａ)ハロゲン含有化合物と、(Ｂ)アミノ基含有化合物とカルボキシル基含有化合物の少なくとも一種とを含有して、銀メッキ皮膜の変色とメッキむらを防止することを特徴とする。
上記ハロゲン含有化合物(Ａ)は、ハロゲンがイオン結合又は共有結合した化合物であり、具体的には、塩素含有化合物や臭素含有化合物を初め、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ素イオンを含むカチオン系界面活性剤であり（本発明３参照）、また、冒述の特許文献５のフッ素含系界面活性剤などを排除するものではない。
上記塩素含有化合物は、具体的には、塩化ナトリウム、塩化カリウム、塩化アンモニウム、塩素アニオンを含むカチオン系界面活性剤などが挙げられ、塩素アニオンを含むカチオン系界面活性剤が好ましい（本発明３参照）。臭素含有化合物も同様に、臭化ナトリウム、臭化カリウム、臭化アンモニウム、臭素アニオンを含むカチオン系界面活性剤などが挙げられる（本発明３参照）。
上記ハロゲン含有化合物は単用又は併用でき、また、例えば、塩素含有化合物と臭素含有化合物を複用しても良い。
ハロゲン含有化合物のメッキ浴に対する含有量は１０-6〜１００ｇ／Ｌが適量であり、０.０１〜１０ｇ／Ｌが好ましい。適正範囲より少ないと、銀皮膜の変色防止効果が損なわれ、多過ぎても効果にあまり差異がなく、コストの無駄である（本発明４参照）。
The substituted silver plating bath of the present invention 1 contains (A) a halogen-containing compound, (B) at least one of an amino group-containing compound and a carboxyl group-containing compound to prevent discoloration and plating unevenness of the silver plating film. It is characterized by that.
The halogen-containing compound (A) is a compound in which halogen is ion-bonded or covalently bonded, and specifically, a cation system containing chlorine-containing compound or bromine-containing compound, sodium iodide, potassium iodide, or iodine ion. It is a surfactant (see the present invention 3), and does not exclude the fluorine-containing surfactant described in Patent Document 5 mentioned above.
Specific examples of the chlorine-containing compound include sodium chloride, potassium chloride, ammonium chloride, and a cationic surfactant containing a chlorine anion, and a cationic surfactant containing a chlorine anion is preferable (see Invention 3) . ). Similarly, examples of the bromine-containing compound include sodium bromide, potassium bromide, ammonium bromide, and a cationic surfactant containing a bromine anion (see Invention 3 ).
The halogen-containing compounds can be used alone or in combination. For example, a chlorine-containing compound and a bromine-containing compound may be used in combination.
The appropriate content of the halogen-containing compound in the plating bath is 10 −6 to 100 g / L, preferably 0.01 to 10 g / L. When the amount is less than the appropriate range, discoloration prevention effect of the silver film is impaired, not very difference in effect even multi only a waste of cost (see present invention 4).
上記塩素アニオン又は臭素アニオンを含むカチオン系界面活性剤としては、例えば、下記の一般式(ａ)で表される第４級アンモニウム塩
(Ｒ1・Ｒ2・Ｒ3・Ｒ4Ｎ)+・Ｘ- …(ａ)
(式(ａ)中、Ｘは塩素、臭素、Ｒ1、Ｒ2、Ｒ3及びＲ4は同一又は異なるＣ1〜Ｃ20アルキル、アリール又はベンジルを示す。)或は、
下記の一般式(ｂ)で表されるピリジニウム塩などが挙げられる。
Ｒ6−(Ｃ5Ｈ4Ｎ−Ｒ5)+・Ｘ- …(ｂ)
(式(ｂ)中、Ｃ5Ｈ4Ｎはピリジン環、Ｘは塩素、臭素、Ｒ5はＣ1〜Ｃ20アルキル、Ｒ6はＨ又はＣ1〜Ｃ10アルキルを示す。)
Examples of the cationic surfactant containing the chlorine anion or bromine anion include, for example, a quaternary ammonium salt represented by the following general formula (a):
(R 1 · R 2 · R 3 · R 4 N) + · X - ... (a)
(In the formula (a), X represents chlorine, bromine, R 1 , R 2 , R 3 and R 4 are the same or different C 1 to C 20 alkyl, aryl or benzyl.)
Examples thereof include pyridinium salts represented by the following general formula (b).
R 6- (C 5 H 4 N-R 5 ) + · X − (b)
(In the formula (b), C 5 H 4 N represents a pyridine ring, X represents chlorine and bromine, R 5 represents C 1 to C 20 alkyl, and R 6 represents H or C 1 to C 10 alkyl.)
塩の形態のカチオン系界面活性剤の例としては、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、ラウリルジメチルエチルアンモニウム塩、オクタデシルジメチルエチルアンモニウム塩、ジメチルベンジルラウリルアンモニウム塩、セチルジメチルベンジルアンモニウム塩、オクタデシルジメチルベンジルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリエチルベンジルアンモニウム塩、ジメチルジフェニルアンモニウム塩、ベンジルジメチルフェニルアンモニウム塩、ヘキサデシルピリジニウム塩、ラウリルピリジニウム塩、ドデシルピリジニウム塩、ステアリルアミンアセテート、ラウリルアミンアセテート、オクタデシルアミンアセテートなどが挙げられる。
前述したように、可溶性銀塩とチオ尿素を基本組成とする置換銀浴に塩素又は臭素イオンを含有すると、銀皮膜の変色を防止できるが、この置換銀メッキ浴の代表例は、可溶性銀塩と、チオ尿素類と、塩素アニオンを含むカチオン系界面活性剤とを含有するメッキ浴である。
Examples of cationic surfactants in the form of salts include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl Benzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyldimethylphenylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, octadecylamine acetate, etc. Is mentioned.
As described above, discoloration of the silver film can be prevented when chlorine or bromine ions are contained in a substituted silver bath based on a soluble silver salt and thiourea, but a typical example of this substituted silver plating bath is a soluble silver salt. And a plating bath containing thioureas and a cationic surfactant containing a chlorine anion .
また、上記本発明１の成分(Ｂ)は、乳酸、ギ酸、クエン酸、酒石酸、リンゴ酸、グルコン酸、Ｌ−アスコルビン酸などのようなカルボキシル基を有する化合物、アラニン、Ｌ−アスパラギン酸、グリシンなどのようなアミノ基とカルボキシル基を兼備するアミノ酸類、アミノメタンスルホン酸、タウリン、３−アミノ−１−プロパンスルホン酸などのアミノスルホン酸類、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、ニトリロトリ酢酸などのアミノカルボン酸類、ヒドロキシエチリデンジホスホン酸、ニトリロトリス（メチレンホスホン酸）、ホスホノブタントリカルボン酸などのようにアミノ基とホスホノ基を兼備するアミノホスホン酸類のうちから選択される。
成分(Ｂ)は、具体的には、乳酸、クエン酸、酒石酸、リンゴ酸、グルコン酸、アスコルビン酸よりなるオキシカルボン酸、ギ酸、酢酸、マレイン酸よりなるカルボン酸、アラニン、アスパラギン酸、グリシン、オルニチン、グルタミン酸よりなるアミノ酸、アミノメタンスルホン酸、タウリン、Ｎ−メチルタウリン、３−アミノ−１−プロパンスルホン酸よりなるアミノスルホン酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、ニトリロトリ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、Ｎ,Ｎ−ジカルボキシメチル−Ｌ−アラニン、ヒドロキシエチルイミノジ酢酸、１,３−プロパンジアミンテトラ酢酸、１,３−ジアミノ−２−ヒドロキシプロパンテトラ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸よりなるアミノカルボン酸、ヒドロキシエチリデンジホスホン酸、ニトリロトリス（メチレンホスホン酸）、ホスホノブタントリカルボン酸、Ｎ,Ｎ,Ｎ′,Ｎ′-テトラキス（ホスホノメチル）エチレンジアミンよりなるアミノホスホン酸、及びこれらの塩よりなる群から選ばれた化合物である。
上記成分(Ｂ)としては、アミノ基含有化合物又はカルボキシル基含有化合物を夫々単用又は併用でき、両者を複用しても良い。上記アミノ酸類、アミノカルボン酸類を使用すると、アミノ基含有化合物とカルボキシル基含有化合物を複用することになる。
上記成分(Ｂ)のメッキ浴に対する含有量は０.０００１〜５モル／Ｌが適量であり、０.０３〜２モル／Ｌが好ましい。適正範囲より少ないと、銀皮膜のメッキむら防止効果が損なわれ、多過ぎても効果にあまり差異がなく、コストの無駄である（本発明５参照）。
本発明の置換銀メッキ浴の代表例を挙げると、可溶性銀塩と、チオ尿素類と、塩素アニオンを含むカチオン系界面活性剤と、乳酸、ギ酸、タウリンのうちの少なくとも一種とを含有するメッキ浴である。
本発明の置換銀メッキ浴には、上記成分以外に、必要に応じて、光沢剤、界面活性剤などの各種添加剤を含有できる。また、本発明の置換銀メッキ浴を、プリント回路板、半導体集積回路、抵抗、可変抵抗、コンデンサー、フィルター、インダクター、サーミスター、水晶振動子、スイッチ、リード線などの電子部品に適用して、これらの素地上に銀メッキ皮膜を形成できることはいうまでもない。
The component (B) of the present invention 1 is a compound having a carboxyl group such as lactic acid, formic acid, citric acid, tartaric acid, malic acid, gluconic acid, L-ascorbic acid, alanine, L-aspartic acid, glycine. amino acids having both an amino group and a carboxyl group, such as, amino methanesulfonic acid, taurine, amino sulfonic acids such as 3-amino-1-propanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, amino such as nitrilotriacetic acid It is selected from aminophosphonic acids having both an amino group and a phosphono group, such as carboxylic acids, hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), and phosphonobutanetricarboxylic acid.
Specifically, the component (B) is composed of lactic acid, citric acid, tartaric acid, malic acid, gluconic acid, oxycarboxylic acid composed of ascorbic acid, carboxylic acid composed of formic acid, acetic acid, maleic acid, alanine, aspartic acid, glycine, Ornithine, amino acid consisting of glutamic acid, aminomethanesulfonic acid, taurine, N-methyltaurine, aminosulfonic acid consisting of 3-amino-1-propanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid , Triethylenetetramine hexaacetic acid, N, N-dicarboxymethyl-L-alanine, hydroxyethyliminodiacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxy Containing aminocarboxylic acid consisting of tilglycine, glycol etherdiaminetetraacetic acid, hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), phosphonobutanetricarboxylic acid, N, N, N ', N'-tetrakis (phosphonomethyl) ethylenediamine It is a compound selected from the group consisting of aminophosphonic acid and salts thereof .
As the component (B), an amino group-containing compound or a carboxyl group-containing compound can be used singly or in combination, and both may be used in combination. When the amino acids and aminocarboxylic acids are used, the amino group-containing compound and the carboxyl group-containing compound are used in combination.
The content of the component (B) in the plating bath is suitably 0.0001 to 5 mol / L, and preferably 0.03 to 2 mol / L. When the amount is less than the appropriate range, the plated uneven effect of preventing the silver film is impaired, not very difference in effect even multi only a waste of cost (see present invention 5).
A representative example of the substituted silver plating bath of the present invention is a plating containing a soluble silver salt, a thiourea, a cationic surfactant containing a chlorine anion, and at least one of lactic acid, formic acid, and taurine. It is a bath.
In addition to the above components, the substituted silver plating bath of the present invention can contain various additives such as brighteners and surfactants as necessary. In addition, the substitution silver plating bath of the present invention is applied to electronic components such as printed circuit boards, semiconductor integrated circuits, resistors, variable resistors, capacitors, filters, inductors, thermistors, crystal resonators, switches, lead wires, Needless to say, a silver plating film can be formed on these substrates.
以下、本発明の置換銀メッキ浴の実施例、当該メッキ浴から得られた銀皮膜の外観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 substitution silver plating bath of the present invention and appearance evaluation test examples of the silver film obtained from the plating bath will be described in order.
The present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
先ず、可溶性銀塩とチオ尿素を基本組成とし、塩素含有化合物又は臭素含有化合物を添加した置換銀メッキ浴を参考例として、浴から得られる銀メッキ皮膜の変色防止能の度合を試験評価した。
《塩素含有化合物又は臭素含有化合物を添加した置換銀メッキ浴の参考例》
参考例１〜８のうち、参考例１〜３、５〜６は塩素含有化合物を添加した例、参考例４と７は臭素含有化合物を添加した例、参考例８は塩素含有化合物と臭素含有化合物を併用添加した例である。参考例４〜６は塩素アニオン又は臭素アニオンを含むカチオン系界面活性剤を添加した例、その他の参考例は塩化カリウム、塩化ナトリウムなどのイオン結合化合物を添加した例である。
また、比較参考例１〜２は塩素含有化合物又は臭素含有化合物を添加しないブランク例である。
First, the degree of discoloration prevention ability of a silver plating film obtained from the bath was evaluated by taking a substituted silver plating bath having a soluble silver salt and thiourea as a basic composition and added with a chlorine-containing compound or a bromine-containing compound as a reference example .
<< Reference Example of Substitution Silver Plating Bath with Addition of Chlorine-containing Compound or Bromine-containing Compound >>
Of Reference Example 1-8, Example Reference Example 1～3,5～6 the addition of chlorine-containing compounds, examples Reference Example 4 and 7 with the addition of bromine-containing compounds, Reference Example 8 chlorine-containing compounds and bromine-containing This is an example in which a compound is added in combination. Reference Examples 4 to 6 are examples in which a cationic surfactant containing a chlorine anion or bromine anion is added, and other reference examples are examples in which an ion-binding compound such as potassium chloride or sodium chloride is added.
Comparative Reference Examples 1 and 2 are blank examples in which no chlorine-containing compound or bromine-containing compound is added.
(1)参考例１
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
塩化カリウム ０.０１モル／Ｌ
(1) Reference example 1
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Thiourea 0.30 mol / L
Potassium chloride 0.01 mol / L
(2)参考例２
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.５０モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
(2) Reference example 2
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Thiourea 0.50 mol / L
Sodium chloride 0.01 mol / L
(3)参考例３
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.０５モル／Ｌ
酢酸（遊離酸として） １.００モル／Ｌ
チオ尿素 ０.５０モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
(3) Reference example 3
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Acetic acid (as free acid) 1.00 mol / L
Thiourea 0.50 mol / L
Sodium chloride 0.01 mol / L
(4)参考例４
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.１０モル／Ｌ
１,３−ジエチルチオ尿素 ０.４０モル／Ｌ
ヘキサデシルトリメチルアンモニウムブロマイド １０ｇ／Ｌ
(4) Reference example 4
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.10 mol / L
1,3-diethylthiourea 0.40 mol / L
Hexadecyltrimethylammonium bromide 10g / L
(5)参考例５
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.２０モル／Ｌ
メタンスルホン酸(遊離酸として) ０.８０モル／Ｌ
メルカプトコハク酸 ０.１０モル／Ｌ
テトラブチルアンモニウムクロライド １０ｇ／Ｌ
(5) Reference example 5
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.20 mol / L
Methanesulfonic acid (as free acid) 0.80 mol / L
Mercaptosuccinic acid 0.10 mol / L
Tetrabutylammonium chloride 10g / L
(6)参考例６
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
デシルジメチルベンジルアンモニウムクロライド １０ｇ／Ｌ
(6) Reference example 6
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.05 mol / L
Thiourea 0.30 mol / L
Decyldimethylbenzylammonium chloride 10g / L
(7)参考例７
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
臭化ナトリウム ０.０１モル／Ｌ
(7) Reference example 7
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.10 mol / L
Thiourea 0.30 mol / L
Sodium bromide 0.01 mol / L
(8)参考例８
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
臭化ナトリウム ０.０１モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
(8) Reference example 8
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.10 mol / L
Thiourea 0.30 mol / L
Sodium bromide 0.01 mol / L
Sodium chloride 0.01 mol / L
(9)比較参考例１
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
(9) Comparative Reference Example 1
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Thiourea 0.30 mol / L
(10)比較参考例２
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.１０モル／Ｌ
１,３−ジエチルチオ尿素 ０.５０モル／Ｌ
(10) Comparative Reference Example 2
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.10 mol / L
1,3-diethylthiourea 0.50 mol / L
《銀メッキ皮膜の変色防止能評価試験例》
そこで、上記参考例１〜８及び比較参考例１〜２の各置換銀メッキ浴について、25×25mmの圧延銅板の試験片をメッキ温度５０℃、１分間の条件で浸漬することにより、銅板表面に置換銀メッキを施し、メッキ直後と５日経過後の銀メッキ皮膜を夫々目視観察して、当該皮膜外観の変色防止能の優劣を下記の基準で評価した。
○：光沢のある銀白色を呈した。
△：淡黄色を呈した。
×：黄変した。
<Example of evaluation test for discoloration prevention ability of silver plating film>
Then, about each substitution silver plating bath of the said reference examples 1-8 and comparative reference examples 1-2, a copper plate surface is obtained by immersing the test piece of a 25x25mm rolled copper plate on the conditions of 50 degreeC of plating temperature, and 1 minute. Substituted silver plating was applied, and the silver plating film immediately after plating and after 5 days were visually observed, and the superiority or inferiority of the discoloration preventing ability of the film appearance was evaluated according to the following criteria.
○: Glossy silver-white color was exhibited.
Δ: Light yellow.
X: Yellowed.
試験結果は下表の通りである。
変色防止能評価 変色防止能評価
直後 ５日後 直後 ５日後
参考例１ ○ ○ 比較参考例１ △ ×
参考例２ ○ ○ 比較参考例２ △ ×
参考例３ ○ ○
参考例４ ○ ○
参考例５ ○ ○
参考例６ ○ ○
参考例７ ○ ○
参考例８ ○ ○
The test results are as shown in the table below.
Discoloration prevention evaluation Evaluation of discoloration prevention
Immediately 5 days later Immediately 5 days later
Reference Example 1 ○ ○ Comparative Reference Example 1 △ ×
Reference Example 2 ○ ○ Comparative Reference Example 2 △ ×
Reference Example 3 ○ ○
Reference example 4
Reference Example 5 ○ ○
Reference Example 6 ○ ○
Reference Example 7 ○ ○
Reference Example 8 ○ ○
上表によると、塩素含有化合物又は臭素含有化合物を添加した参考例では、５日経過後の時点でも銀皮膜の変色は認められず、光沢のある銀白色の皮膜が得られた。この場合、カチオン系界面活性剤の形態で添加しても、塩化ナトリウムなどの形態で添加しても銀皮膜の変色を防止する能力に変わりはなかった。
これに対して、塩素含有化合物又は臭素含有化合物を添加しない比較参考例１〜２では、メッキ直後に既に皮膜は淡黄色を呈し、５日後には皮膜はさらに黄変したことから、銀白色のメッキ皮膜は得られなかった。
According to the above table, in the reference example to which the chlorine-containing compound or bromine-containing compound was added, no discoloration of the silver film was observed even after 5 days, and a glossy silver-white film was obtained. In this case, the ability to prevent discoloration of the silver film was not changed even when added in the form of a cationic surfactant or in the form of sodium chloride.
On the other hand, in Comparative Reference Examples 1 and 2 in which no chlorine-containing compound or bromine-containing compound was added, the film already showed a pale yellow color immediately after plating, and the film was further yellowed after 5 days. A plating film was not obtained.
冒述したように、塩素含有化合物などを添加した置換銀メッキ浴では、銀皮膜の変色を防止して、銀白色の皮膜が得られる反面、くすんだ銀白色が部分的に見られる、いわゆるメッキむらが銀皮膜に生じ易くなる。
そこで、塩素含有化合物を初めとするハロゲン含有化合物(Ａ)に、アミノ基含有化合物又はカルボキシル基含有化合物(Ｂ)をさらに併用添加した置換銀メッキ浴の実施例を説明して、浴から得られる銀皮膜の変色防止能力とメッキむら防止能力とを総合的に評価試験した。
As described above, a substituted silver plating bath to which a chlorine-containing compound or the like is added prevents discoloration of the silver film to obtain a silver-white film, but on the other hand, a so-called plating in which a dull silver-white color is partially seen Unevenness is likely to occur in the silver film.
Therefore, an example of a substituted silver plating bath in which an amino group-containing compound or a carboxyl group-containing compound (B) is further added to a halogen-containing compound (A) such as a chlorine-containing compound will be described and obtained from the bath. The ability to prevent discoloration of the silver film and the ability to prevent uneven plating were comprehensively evaluated and tested.
《成分(Ａ)及び(Ｂ)を添加した置換銀メッキの実施例》
実施例１〜８のうち、実施例１〜２は塩素含有化合物とカルボキシル基含有化合物を併用添加した例、実施例７は臭素含有化合物とカルボキシル基含有化合物を併用添加した例、実施例６は塩素含有化合物とアミノ基含有化合物を併用添加した例、実施例３〜５は塩素含有化合物とカルボキシル基含有化合物とアミノ基含有化合物を併用添加した例、実施例８は塩素含有化合物と臭素含有化合物とカルボキシル基含有化合物とアミノ基含有化合物を併用添加した例である。
また、比較例１〜２は塩素含有化合物又は臭素含有化合物を添加し、カルボキシル基含有化合物又はアミノ基含有化合物を添加しない例（成分(Ｂ)のブランク例）である。比較例３〜５はカルボキシル基含有化合物を添加し、塩素含有化合物又は臭素含有化合物を添加しない例（成分(Ａ)のブランク例）である。
<< Example of Substitution Silver Plating with Addition of Components (A) and (B) >>
Among Examples 1 to 8 , Examples 1 to 2 are examples in which a chlorine-containing compound and a carboxyl group-containing compound are added together, Example 7 is an example in which a bromine-containing compound and a carboxyl group-containing compound are added in combination, and Example 6 is Examples in which a chlorine-containing compound and an amino group-containing compound were added together, Examples 3 to 5 were examples in which a chlorine-containing compound, a carboxyl group-containing compound and an amino group-containing compound were added together, and Example 8 was a chlorine-containing compound and a bromine-containing compound This is an example in which a carboxyl group-containing compound and an amino group-containing compound are added in combination.
Comparative Examples 1 and 2 are examples in which a chlorine-containing compound or a bromine-containing compound is added and a carboxyl group-containing compound or an amino group-containing compound is not added (blank example of component (B)). Comparative Examples 3 to 5 are examples in which a carboxyl group-containing compound is added and a chlorine-containing compound or a bromine-containing compound is not added (blank example of component (A)).
(1)実施例１
下記の組成で置換銀メッキ浴を建浴した。
酸化銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
塩化カリウム ０.０１モル／Ｌ
ギ酸 ０.２０モル／Ｌ
(1) Example 1
A substitution silver plating bath was constructed with the following composition.
Silver oxide (as Ag + ) 0.05 mol / L
Thiourea 0.30 mol / L
Potassium chloride 0.01 mol / L
Formic acid 0.20 mol / L
(2)実施例２
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.０１モル／Ｌ
チオ尿素 ０.１０モル／Ｌ
塩化カリウム ０.０１モル／Ｌ
酒石酸 ０.０５モル／Ｌ
(2) Example 2
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.01 mol / L
Thiourea 0.10 mol / L
Potassium chloride 0.01 mol / L
Tartaric acid 0.05mol / L
(3)実施例３
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.５０モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
アスパラギン酸 ０.４０モル／Ｌ
(3) Example 3
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.10 mol / L
Thiourea 0.50 mol / L
Sodium chloride 0.01 mol / L
Aspartic acid 0.40 mol / L
(4)実施例４
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.５０モル／Ｌ
メルカプトコハク酸 １.００モル／Ｌ
ニトリロトリ酢酸 ０.５０モル／Ｌ
トリエチルベンジルアンモニウムクロライド １０ｇ／Ｌ
(4) Example 4
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.50 mol / L
Mercaptosuccinic acid 1.00 mol / L
Nitrilotriacetic acid 0.50 mol / L
Triethylbenzylammonium chloride 10g / L
(5)実施例５
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.４０モル／Ｌ
メタンスルホン酸(遊離酸として) １.００モル／Ｌ
メルカプトコハク酸 ０.５０モル／Ｌ
ニトリロトリ酢酸 ０.５０モル／Ｌ
トリエチルベンジルアンモニウムクロライド １５ｇ／Ｌ
(5) Example 5
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.40 mol / L
Methanesulfonic acid (as free acid) 1.00 mol / L
Mercaptosuccinic acid 0.50 mol / L
Nitrilotriacetic acid 0.50 mol / L
Triethylbenzylammonium chloride 15g / L
(6)実施例６
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
タウリン ０.２０モル／Ｌ
ヘキサデシルピリジニウムクロライド １０ｇ／Ｌ
(6) Example 6
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.05 mol / L
Thiourea 0.30 mol / L
Taurine 0.20 mol / L
Hexadecylpyridinium chloride 10g / L
(7)実施例７
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) １.００モル／Ｌ
チオ尿素 １.５０モル／Ｌ
乳酸 ２.００モル／Ｌ
ギ酸ナトリウム １.００モル／Ｌ
臭化ナトリウム １０ｇ／Ｌ
(7) Example 7
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 1.00 mol / L
Thiourea 1.50 mol / L
Lactic acid 2.00 mol / L
Sodium formate 1.00 mol / L
Sodium bromide 10g / L
(8)実施例８
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
クエン酸 ０.３０モル／Ｌ
グルタミン酸 ０.３０モル／Ｌ
臭化ナトリウム ０.０１モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
(8) Example 8
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.10 mol / L
Thiourea 0.30 mol / L
Citric acid 0.30 mol / L
Glutamic acid 0.30 mol / L
Sodium bromide 0.01 mol / L
Sodium chloride 0.01 mol / L
(9)比較例１
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.０５モル／Ｌ
チオ尿素 ０.５０モル／Ｌ
塩化ナトリウム ０.０１モル／Ｌ
(9) Comparative Example 1
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Thiourea 0.50 mol / L
Sodium chloride 0.01 mol / L
(10)比較例２
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
臭化ナトリウム ０.０１モル／Ｌ
(10) Comparative example 2
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.10 mol / L
Thiourea 0.30 mol / L
Sodium bromide 0.01 mol / L
(11)比較例３
下記の組成で置換銀メッキ浴を建浴した。
酢酸銀(Ａｇ+として) ０.１０モル／Ｌ
１,３−ジエチルチオ尿素 ０.３０モル／Ｌ
酒石酸 ０.２０モル／Ｌ
(11) Comparative Example 3
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.10 mol / L
1,3-diethylthiourea 0.30 mol / L
Tartaric acid 0.20 mol / L
(12)比較例４
下記の組成で置換銀メッキ浴を建浴した。
乳酸銀(Ａｇ+として) ０.３０モル／Ｌ
チオ尿素 ０.６０モル／Ｌ
クエン酸 ０.２０モル／Ｌ
(12) Comparative Example 4
A substitution silver plating bath was constructed with the following composition.
Silver lactate (as Ag + ) 0.30 mol / L
Thiourea 0.60 mol / L
Citric acid 0.20 mol / L
(13)比較例５
下記の組成で置換銀メッキ浴を建浴した。
メタンスルホン酸銀(Ａｇ+として) ０.１０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
ギ酸 ０.１０モル／Ｌ
(13) Comparative Example 5
A substitution silver plating bath was constructed with the following composition.
Silver methanesulfonate (as Ag + ) 0.10 mol / L
Thiourea 0.30 mol / L
Formic acid 0.10 mol / L
《銀メッキ皮膜の変色防止能とメッキむら防止能の総合評価試験例》
そこで、上記実施例１〜８及び比較例１〜５の各置換銀メッキ浴について、25×25mmの圧延銅板の試験片をメッキ温度５０℃、１分間の条件で浸漬することにより、銅板表面に置換銀メッキを施し、５日経過後の銀メッキ皮膜を目視観察して、当該皮膜外観の変色防止能とメッキむらの優劣を統合的にまとめて、下記の基準で総合評価した。
◎：変色は認められず、均質で光沢のある銀白色を呈した。
△：変色は認められなかったが、部分的にくすんだ銀白色を呈した。
×：黄変し、メッキむらも認められた。
<< Comprehensive evaluation test example of ability to prevent discoloration and uneven plating of silver plating film >>
Then, about each substitution silver plating bath of the said Examples 1-8 and Comparative Examples 1-5 , by immersing the test piece of a 25x25mm rolled copper plate on the conditions of plating temperature 50 degreeC and 1 minute, it is on the copper plate surface. Substitution silver plating was performed, and the silver plating film after the lapse of 5 days was visually observed to comprehensively evaluate the discoloration prevention ability of the film appearance and the superiority or inferiority of the plating unevenness based on the following criteria.
(Double-circle): Discoloration was not recognized but it was homogeneous and glossy silver white.
(Triangle | delta): Although discoloration was not recognized, it showed the dull silver white partially.
X: Yellowing and uneven plating were observed.
下表はその試験結果である。
総合評価 総合評価
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 ◎
実施例７ ◎
実施例８ ◎
The table below shows the test results.
Comprehensive evaluation Comprehensive evaluation 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
Example 7
Example 8
上表によると、カルボキシル基含有化合物又はアミノ基含有化合物(Ｂ)を添加して、塩素含有化合物又は臭素含有化合物(Ａ)を添加しない比較例３〜５では、変色により実用的な銀皮膜が得られないうえ、メッキむらも認められた。また、塩素含有化合物又は臭素含有化合物(Ａ)を添加して、カルボキシル基含有化合物又はアミノ基含有化合物(Ｂ)を添加しない比較例１〜２では、皮膜の変色は認められなかったが、くすんだ銀白色が部分的に認められ、いわゆるメッキむらが発生した。
これに対して、成分(Ａ)と成分(Ｂ)を共存させた実施例１〜８では全てに亘り変色とメッキむらは認められず、均一で光沢のある銀白色の美麗な銀皮膜が得られ、総合評価は◎であった。
この場合、成分(Ａ)は塩素含有化合物であっても、臭素含有化合物でも有効であり、また、成分(Ｂ)はカルボキシル基含有化合物であっても、アミノ基含有化合物でも、或はこれらの両官能基を有する化合物（例えば、アスパラギン酸やグルタミン酸等のアミノ酸など）でも有効であり、銀皮膜の変色を防止するとともに、メッキむらのない均質な皮膜を形成することができる。
According to the above table, in Comparative Examples 3 to 5 in which the carboxyl group-containing compound or the amino group-containing compound (B) is added and the chlorine-containing compound or the bromine-containing compound (A) is not added, a practical silver film is formed by discoloration. In addition, plating unevenness was also observed. Further, in Comparative Examples 1 and 2 in which the chlorine-containing compound or the bromine-containing compound (A) was added and the carboxyl group-containing compound or amino group-containing compound (B) was not added, no discoloration of the film was observed. The silver-white color was partially recognized and so-called uneven plating occurred.
On the other hand, in Examples 1 to 8 in which the component (A) and the component (B) coexisted, discoloration and plating unevenness were not observed in all, and a uniform and glossy silver-white beautiful silver film was obtained. The overall evaluation was ◎.
In this case, component (A) may be a chlorine-containing compound or a bromine-containing compound, and component (B) may be a carboxyl group-containing compound, an amino group-containing compound, or any of these. A compound having both functional groups (for example, amino acids such as aspartic acid and glutamic acid) is also effective, and can prevent discoloration of the silver film and form a uniform film without uneven plating.
Claims (5)
(Ａ)ハロゲン含有化合物と、
(Ｂ)アミノ基含有化合物及びカルボキシル基含有化合物の少なくとも一種
とを含有し、
上記成分(Ｂ)が、乳酸、クエン酸、酒石酸、リンゴ酸、グルコン酸、アスコルビン酸よりなるオキシカルボン酸、ギ酸、酢酸、マレイン酸よりなるカルボン酸、アラニン、アスパラギン酸、グリシン、オルニチン、グルタミン酸よりなるアミノ酸、アミノメタンスルホン酸、タウリン、Ｎ−メチルタウリン、３−アミノ−１−プロパンスルホン酸よりなるアミノスルホン酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、ニトリロトリ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、Ｎ,Ｎ−ジカルボキシメチル−Ｌ−アラニン、ヒドロキシエチルイミノジ酢酸、１,３−プロパンジアミンテトラ酢酸、１,３−ジアミノ−２−ヒドロキシプロパンテトラ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸よりなるアミノカルボン酸、ヒドロキシエチリデンジホスホン酸、ニトリロトリス（メチレンホスホン酸）、ホスホノブタントリカルボン酸、Ｎ,Ｎ,Ｎ′,Ｎ′-テトラキス（ホスホノメチル）エチレンジアミンよりなるアミノホスホン酸、及びこれらの塩よりなる群から選ばれた化合物であることを特徴とする置換銀メッキ浴。 In a substituted silver plating bath containing a soluble silver salt and a complexing agent comprising a sulfur-containing compound such as thioureas, sulfides, and mercaptans,
(A) a halogen-containing compound;
(B) containing at least one of an amino group-containing compound and a carboxyl group-containing compound ,
The component (B) is oxycarboxylic acid composed of lactic acid, citric acid, tartaric acid, malic acid, gluconic acid, ascorbic acid, carboxylic acid composed of formic acid, acetic acid, maleic acid, alanine, aspartic acid, glycine, ornithine, glutamic acid Amino sulfonic acid, aminomethanesulfonic acid, taurine, N-methyltaurine, aminosulfonic acid consisting of 3-amino-1-propanesulfonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetramine Hexaacetic acid, N, N-dicarboxymethyl-L-alanine, hydroxyethyliminodiacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethyl group Aminocarboxylic acid consisting of syn, glycol ether diamine tetraacetic acid, hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), phosphonobutanetricarboxylic acid, N, N, N ', N'-tetrakis (phosphonomethyl) ethylenediamine A substituted silver plating bath , which is a compound selected from the group consisting of aminophosphonic acid and salts thereof .
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| JPH09302476A (en) * | 1996-05-10 | 1997-11-25 | Daiwa Kasei Kenkyusho:Kk | Electroless tin-silver alloy plating bath |
| JPH10130855A (en) * | 1996-10-25 | 1998-05-19 | Daiwa Kasei Kenkyusho:Kk | Non-cyanide displacement silver plating bath |
| JPH1161426A (en) * | 1997-08-22 | 1999-03-05 | Ishihara Chem Co Ltd | Electroless tin and tin alloy plating bath, electroless plating and electronic part coated with tin or tin alloy film in the electroless plating bath |
| JP2000160351A (en) * | 1998-11-26 | 2000-06-13 | Nippon Kojundo Kagaku Kk | Electroless silver plating solution for electronic parts |
| JP2002245783A (en) * | 2001-02-20 | 2002-08-30 | Hitachi Ltd | Semiconductor integrated circuit device |
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| JPH09302476A (en) * | 1996-05-10 | 1997-11-25 | Daiwa Kasei Kenkyusho:Kk | Electroless tin-silver alloy plating bath |
| JPH10130855A (en) * | 1996-10-25 | 1998-05-19 | Daiwa Kasei Kenkyusho:Kk | Non-cyanide displacement silver plating bath |
| JPH1161426A (en) * | 1997-08-22 | 1999-03-05 | Ishihara Chem Co Ltd | Electroless tin and tin alloy plating bath, electroless plating and electronic part coated with tin or tin alloy film in the electroless plating bath |
| JP2000160351A (en) * | 1998-11-26 | 2000-06-13 | Nippon Kojundo Kagaku Kk | Electroless silver plating solution for electronic parts |
| JP2002245783A (en) * | 2001-02-20 | 2002-08-30 | Hitachi Ltd | Semiconductor integrated circuit device |
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