JP4901168B2 - Replacement silver plating bath - Google Patents
Replacement silver plating bath Download PDFInfo
- Publication number
- JP4901168B2 JP4901168B2 JP2005274715A JP2005274715A JP4901168B2 JP 4901168 B2 JP4901168 B2 JP 4901168B2 JP 2005274715 A JP2005274715 A JP 2005274715A JP 2005274715 A JP2005274715 A JP 2005274715A JP 4901168 B2 JP4901168 B2 JP 4901168B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- silver
- bath
- mol
- examples
- 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 78
- 229910052709 silver Inorganic materials 0.000 title claims description 76
- 239000004332 silver Substances 0.000 title claims description 76
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 86
- 235000011007 phosphoric acid Nutrition 0.000 claims description 56
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
- 229910052717 sulfur Inorganic materials 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 22
- 150000003378 silver Chemical class 0.000 claims description 19
- 150000003585 thioureas Chemical class 0.000 claims description 17
- 150000003568 thioethers Chemical class 0.000 claims description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 12
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 5
- 235000018417 cysteine Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229930182817 methionine Natural products 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 5
- 229950006389 thiodiglycol Drugs 0.000 claims description 5
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- -1 aldehyde compound Chemical class 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 20
- 238000006467 substitution reaction Methods 0.000 description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 18
- 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 17
- 239000002253 acid Substances 0.000 description 14
- 150000003016 phosphoric acids Chemical class 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 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
- 238000012360 testing method Methods 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 8
- 235000019799 monosodium phosphate Nutrition 0.000 description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229960003237 betaine Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 230000002123 temporal effect Effects 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000006172 buffering agent Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 235000019820 disodium diphosphate Nutrition 0.000 description 3
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-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
- JTMBCYAUSCBSEY-UHFFFAOYSA-N 2-methyl-2-sulfanylpropanoic acid Chemical compound CC(C)(S)C(O)=O JTMBCYAUSCBSEY-UHFFFAOYSA-N 0.000 description 2
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
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- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- MXTMXRYBYWOAGX-UHFFFAOYSA-N dimethyl(diphenyl)azanium Chemical class C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 MXTMXRYBYWOAGX-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- ZUVOYUDQAUHLLG-OLXYHTOASA-L disilver;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Ag+].[Ag+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O ZUVOYUDQAUHLLG-OLXYHTOASA-L 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BPSQMWSZGQGXHF-UHFFFAOYSA-N dodecyl-ethyl-dimethylazanium Chemical class CCCCCCCCCCCC[N+](C)(C)CC BPSQMWSZGQGXHF-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUUOYCPDGWDPRO-UHFFFAOYSA-N ethyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC WUUOYCPDGWDPRO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NNBBQNFHCVVQHZ-UHFFFAOYSA-N methyl carbamimidothioate;sulfuric acid Chemical compound CSC(N)=N.OS(O)(=O)=O NNBBQNFHCVVQHZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- GDJYIXGPYCKDOV-UHFFFAOYSA-N n-phenylthiohydroxylamine Chemical compound SNC1=CC=CC=C1 GDJYIXGPYCKDOV-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OVLGNUHSJCCFPG-UHFFFAOYSA-N nonoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCOC1=CC=CC=C1 OVLGNUHSJCCFPG-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 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
- 229910001923 silver oxide Inorganic materials 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 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
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は置換銀メッキ浴に関して、光沢のある銀白色の美麗な銀皮膜が得られるものを提供する。 The present invention provides a substituted silver plating bath that provides a lustrous silver-white and beautiful silver coating.
電子部品や自動車部品などの工業メッキ分野では、ハンダ付け性に優れる見地からスズ又はスズ合金メッキが汎用されているが、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。
In the field of industrial plating such as electronic parts and automobile parts, tin or tin alloy plating is widely used from the viewpoint of 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)特許文献１
密着性、耐食性などの皮膜物性の向上などを目的として（段落３３）、分子内に２個のモノスルフィド基を有する含イオウ有機化合物と、次亜リン酸、亜リン酸等の次亜リン酸化合物、ホルマリン等のアルデヒド化合物、ヒドラジン、セミカルバジド等のヒドラジン誘導体、アスコルビン酸などの還元剤とを含有する無電解銀メッキ浴が開示されている（請求項１〜４）。
上記含イオウ化合物は機能的には銀の錯化剤であり（段落１０）、構造的には水酸基、カルボキシル基などを有し、２個のモノスルフィド基の間に２〜８個のメチレン基を有する化合物である（請求項２）。含イオウ化合物の具体例としては、１,２−ビス(２−ヒドロキシエチルチオ)エタン（ＨＯＣＨ2ＣＨ2−Ｓ−ＣＨ2ＣＨ2−Ｓ−ＣＨ2ＣＨ2ＯＨ）などが挙げられる（段落１８）。
(1) Patent Document 1
For the purpose of improving film properties such as adhesion and corrosion resistance (paragraph 33), sulfur-containing organic compounds having two monosulfide groups in the molecule and hypophosphorous acid such as hypophosphorous acid and phosphorous acid An electroless silver plating bath containing a compound, an aldehyde compound such as formalin, a hydrazine derivative such as hydrazine and semicarbazide, and a reducing agent such as ascorbic acid is disclosed (claims 1 to 4).
The sulfur-containing compound is functionally a silver complexing agent (paragraph 10) and structurally has a hydroxyl group, a carboxyl group, etc., and 2-8 methylene groups between two monosulfide groups. (Claim 2). Specific examples of the sulfur-containing compound include 1,2-bis (2-hydroxyethylthio) ethane (HOCH 2 CH 2 —S—CH 2 CH 2 —S—CH 2 CH 2 OH) (paragraph 18). ).
(2)特許文献２
緻密性、密着性などの外観に優れた皮膜の形成などを目的として（段落７、２９）、分子内に２個のモノスルフィド基を有する含イオウ有機化合物を含有し、ｐＨを７以下とする置換銀メッキ浴が開示されている（請求項１）。浴には、密着性を損なうことなく、析出速度を向上する（厚付けする）見地から、チオ尿素類（１〜１５０ｇ／Ｌ）を含有でき（請求項５、段落２０〜２２）、また、ｐＨ緩衝剤として、リン酸、トリポリリン酸、ホウ酸、酢酸などの塩を含有できること（段落２３）が記載されている。
(2) Patent Document 2
For the purpose of forming a film excellent in appearance such as denseness and adhesion (paragraphs 7 and 29), it contains a sulfur-containing organic compound having two monosulfide groups in the molecule, and the pH is 7 or less. A displacement silver plating bath is disclosed (claim 1). The bath can contain thioureas (1-150 g / L) from the viewpoint of improving (thickening) the deposition rate without impairing adhesion (claim 5, paragraphs 20-22), It describes that salts such as phosphoric acid, tripolyphosphoric acid, boric acid and acetic acid can be contained as a pH buffer (paragraph 23).
(3)特許文献３
チオ尿素類（Ｃ＝Ｓ結合をもつ含イオウ化合物）とヨウ素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５〜６）。
また、ピロリン酸類とチオ尿素類（Ｃ＝Ｓ結合をもつ含イオウ化合物）とヨウ素化合物を含有する置換スズ−銀合金メッキ浴が開示されている（請求項８〜９）。
(3) Patent Document 3
A substituted silver plating bath containing thioureas (a sulfur-containing compound having a C = S bond) and an iodine compound is disclosed (claims 5 to 6).
Further, a substituted tin-silver alloy plating bath containing pyrophosphoric acids, thioureas (a sulfur-containing compound having a C = S bond) and an iodine compound is disclosed (claims 8 to 9).
(4)特許文献４
皮膜外観の向上などを目的として、１個のモノ又はジスルフィド結合と、１個以上の水酸基とを分子内に有する脂肪族スルフィド系化合物を錯化剤に含有する無電解銀メッキ浴が開示されている（請求項１）。脂肪族スルフィド系化合物は、ビス(トリエチレングリコール)チオエーテル（Ｈ−(ＯＣＨ2ＣＨ2)3−Ｓ−(ＣＨ2ＣＨ2Ｏ)3−Ｈ）、ビス(ドデカエチレングリコール)チオエーテル（Ｈ−(ＯＣＨ2ＣＨ2)12−Ｓ−(ＣＨ2ＣＨ2Ｏ)12−Ｈ）などである（段落１５）。
当該浴には、チオ尿素類を含有でき（請求項３、段落２５）、また、還元剤として次亜リン酸、亜リン酸などを含有できること（段落２７）が記載されている。
(4) Patent Document 4
An electroless silver plating bath containing an aliphatic sulfide compound having one mono- or disulfide bond and one or more hydroxyl groups in the molecule as a complexing agent is disclosed for the purpose of improving the appearance of the film. (Claim 1). Aliphatic sulfide compounds include bis (triethylene glycol) thioether (H— (OCH 2 CH 2 ) 3 —S— (CH 2 CH 2 O) 3 —H), bis (dodecaethylene glycol) thioether (H— ( and the like OCH 2 CH 2) 12 -S- ( CH 2 CH 2 O) 12 -H) ( paragraph 15).
It is described that the bath can contain thioureas (Claim 3, Paragraph 25) and can contain hypophosphorous acid, phosphorous acid, etc. as a reducing agent (paragraph 27).
(5)特許文献５
チオグリコール酸、チオジグリコール酸、チオリンゴ酸、チオ尿素などの含イオウ化合物を安定剤として、また、次亜リン酸塩、ロッセル塩、ヒドラジン、ギ酸塩などを還元剤として含有する繊維用の無電解銀メッキ浴が開示されている（請求項１）。
(5) Patent Document 5
For fibers containing sulfur-containing compounds such as thioglycolic acid, thiodiglycolic acid, thiomalic acid and thiourea as stabilizers, and hypophosphites, rossell salts, hydrazines, formates as reducing agents. An electrolytic silver plating bath is disclosed (claim 1).
(6)特許文献６
銀、スズを含む合金の無電解メッキ浴が開示され（請求項２３〜２４）、当該メッキ浴には、還元剤としてリン含有化合物（次亜リン酸類）、チオール類、チオ尿素類、窒素含有化合物、ホウ素含有化合物などを含有でき（請求項３、５）、また、安定化剤として含イオウ化合物（メルカプトカルボン酸、チオジカルボン酸等）、チオ尿素類、含ヨウ素化合物、ポリアルキレングリコール、アゾール類などを含有できること（請求項６〜９）が記載されている。
(6) Patent Document 6
An electroless plating bath of an alloy containing silver and tin is disclosed (Claims 23 to 24), and the plating bath contains phosphorus-containing compounds (hypophosphites), thiols, thioureas, and nitrogen as a reducing agent. Compounds, boron-containing compounds, etc. (Claims 3 and 5), sulfur-containing compounds (mercaptocarboxylic acid, thiodicarboxylic acid, etc.), thioureas, iodine-containing compounds, polyalkylene glycols, azoles as stabilizers (Claims 6 to 9) are described.
(7)特許文献７
スズ又はスズ合金上に銀皮膜を形成することを目的として（請求項１）、酸根又は銀の錯化剤として、(Ａ)硝酸イオンなどの無機酸イオン、(Ｃ)酢酸イオン、(Ｄ)スルホン酸イオン、(Ｅ)チオ尿素類、(Ｈ)チオカルボン酸又はチオスルホン酸などを含有する置換銀メッキ浴が開示されている（請求項１）。
さらに、当該銀メッキ浴には、置換溶出したスズの沈殿を防止するためのスズの錯化剤として、(ａ)脂肪族ジカルボン酸、(ｄ)環状エステル化合物、(ｆ)脂肪族メルカプトカルボン酸、(ｇ)アミンカルボン酸、(ｉ)縮合リン酸などを含有できることが記載されている（請求項２）。
(7) Patent Document 7
For the purpose of forming a silver film on tin or a tin alloy (claim 1), (A) inorganic acid ions such as nitrate ions, (C) acetate ions, (D) A substituted silver plating bath containing sulfonate ions, (E) thioureas, (H) thiocarboxylic acid or thiosulfonic acid is disclosed (claim 1).
Further, the silver plating bath includes (a) an aliphatic dicarboxylic acid, (d) a cyclic ester compound, (f) an aliphatic mercaptocarboxylic acid as a tin complexing agent for preventing precipitation of displacement-eluting tin. (G) amine carboxylic acid, (i) condensed phosphoric acid and the like can be contained (claim 2).
(8)特許文献８
緩衝剤として水酸化アルカリ、リン酸水素２カリウムなどのアルカリ塩２０〜１００ｇ／Ｌと、チオ尿素誘導体又はチオサリチル酸、チオールなどの環状イオウ化合物０.１〜１０ｇ／Ｌとを含有するシアン系の置換銀メッキ浴が開示されている（請求項９〜１０）。
(8) Patent Document 8
Cyanide containing 20 to 100 g / L of alkali salt such as alkali hydroxide and dipotassium hydrogen phosphate as buffering agent and 0.1 to 10 g / L of cyclic sulfur compound such as thiourea derivative or thiosalicylic acid and thiol A displacement silver plating bath is disclosed (claims 9-10).
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、黒色の粗い粒子状を呈したり、或は、チオ尿素中のイオウ元素の吸着が原因と推定されるメッキむらが発生するという弊害があり、この皮膜の外観不良はハンダ付け性にも悪影響を及ぼす恐れがある。
上記特許文献１〜８においても、光沢性のある銀白色のメッキ皮膜を得るという点では、いまだ満足できる水準ではない。
特に、初期浴から銀白色のメッキ皮膜が得られれても、建浴から時間を置いた後の浴（経時浴）では、置換反応により素地金属が溶出などして初期の浴組成にはない余剰成分が混入して来るため、初期浴から得られるものと同様の銀白色の皮膜を獲得することは難しい。
The silver plating film is ideally a beautiful and glossy silver-white film, but when plating is performed using a substitution silver bath based on a soluble silver salt and thiourea, black coarse particles are formed, Or, there is an adverse effect that unevenness of plating presumably caused by adsorption of sulfur element in thiourea occurs, and this poor appearance of the film may adversely affect solderability.
In the above Patent Documents 1 to 8, it is still not a satisfactory level in terms of obtaining a glossy silver-white plating film.
In particular, even if a silver-white plating film is obtained from the initial bath, in the bath after aging from the building bath (aging bath), the base metal elutes due to the substitution reaction, etc., which is not in the initial bath composition Since the components come in, it is difficult to obtain a silvery white film similar to that obtained from the initial bath.
本発明は、置換銀メッキにおいて、初期浴のみならず、経時浴にあっても銀白色の美麗な銀メッキ皮膜を得ることを技術的課題とする。 It is a technical object of the present invention to obtain a beautiful silver-white silver plating film not only in an initial bath but also in a time-lapse bath in substitution silver plating.
上記特許文献１、４〜６などには、浴への添加成分として酸化防止機能を有する次亜リン酸類又は亜リン酸類が開示されている。
本発明者らは、これら次亜リン酸などと同様にリン酸類に属しながら、しかし、種類の異なるオルトリン酸、或は、ピロリン酸、ポリリン酸などの縮合リン酸又はこれらの塩よりなる群から選ばれた特定のリン酸類に着目し、可溶性銀塩と銀の錯化剤を基本組成とする置換銀浴において、当該特定のリン酸類を含有し、且つ、これら特定のリン酸類を所定濃度以上で含有すると、銀の皮膜外観を有効に改善できること、特に、初期浴から得られる皮膜外観だけではなく、経時浴から得られる皮膜外観についても概ね優れることを突き止め、本発明を完成した。
Patent Documents 1, 4 to 6 and the like disclose hypophosphorous acids or phosphorous acids having an antioxidant function as an additive component to the bath.
Although the present inventors belong to phosphoric acids as well as these hypophosphorous acids, etc., they are different from orthophosphoric acid, or condensed phosphoric acid such as pyrophosphoric acid and polyphosphoric acid, or a salt thereof. Paying attention to the selected specific phosphoric acid, the substituted silver bath having a basic composition of a soluble silver salt and a silver complexing agent contains the specific phosphoric acid, and the specific phosphoric acid is at a predetermined concentration or more. In the present invention, it was found that the silver film appearance can be effectively improved, and in particular, not only the film appearance obtained from the initial bath, but also the film appearance obtained from the aging bath is generally excellent.
即ち、本発明１は、可溶性銀塩と、チオ尿素類、スルフィド類、メルカプタン類より選ばれた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、
オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸及びこれらの塩よりなる群から選ばれたリン酸類の少なくとも一種を含有し、且つ、当該リン酸類の含有量が０.５〜１０モル／Ｌ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 substituted silver plating bath containing a soluble silver salt and a complexing agent comprising a sulfur-containing compound selected from thioureas, sulfides, and mercaptans.
Contains at least one phosphoric acid selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and salts thereof, and the content of the phosphoric acid is 0.5 to 10 mol / L This is a substituted silver plating bath.
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、チオグリコール、チオジグリコール、システイン、メチオニンの少なくとも一種であることを特徴とする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 at least one of thioureas , thioglycol, thiodiglycol , cysteine, and methionine.
本発明３は、上記本発明１又は２において、さらに、アニオン系、カチオン系、ノニオン系、両性の界面活性剤の少なくとも一種を含有することを特徴とする置換銀メッキ浴である。 The present invention 3 is the substitution silver plating bath according to the present invention 1 or 2 , further comprising at least one of anionic, cationic, nonionic and amphoteric surfactants.
本発明４は、上記本発明１〜３のいずれかにおいて、置換銀メッキ浴が、４２アロイ、ニッケル、鉄及び銅から選ばれた素地表面に銀メッキ皮膜を形成するための浴であることを特徴とする置換銀メッキ浴である。 Invention 4 is that in any one of Inventions 1 to 3 , the replacement silver plating bath is a bath for forming a silver plating film on the substrate surface selected from 42 alloy, nickel, iron and copper. This is a featured substitution silver plating bath.
銀塩と銀の錯化剤を基本組成とする従来の置換銀メッキ浴では、得られる銀皮膜が粗い粒子状となって黒変したり、色調むらが発生する弊害があった。
本発明では、上記基本組成のメッキ浴にオルトリン酸、縮合リン酸及びこれらの塩より選ばれた特定のリン酸類を含有し、且つ、これら特定のリン酸類を所定濃度以上で含有することにより、従来の銀皮膜の弊害を解消して、均質で光沢のある銀白色の美麗な銀皮膜を得ることができる。
しかも、本発明の置換銀浴では、初期浴のみならず、経時浴においても初期浴から得られるものと同様の銀白色、或はそれに近い銀皮膜を得ることができ、皮膜の経時安定性にも優れる。
In a conventional substitution silver plating bath having a basic composition of a silver salt and a silver complexing agent, the resulting silver film has coarse particles and turns black or has uneven color.
In the present invention, the plating bath having the above basic composition contains specific phosphoric acids selected from orthophosphoric acid, condensed phosphoric acid and salts thereof, and contains these specific phosphoric acids at a predetermined concentration or more. By eliminating the negative effects of conventional silver films, it is possible to obtain a beautiful silver film that is homogeneous and glossy silver-white.
Moreover, in the substituted silver bath of the present invention, not only the initial bath, but also a aging bath can obtain a silver-white color similar to or similar to that obtained from the initial bath, and the aging stability of the coating can be improved. Also excellent.
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、オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸及びこれらの塩よりなる群から選ばれた特定のリン酸類を含有し、且つ、当該リン酸類の含有量を０.５〜１０モル／Ｌとした置換銀メッキ浴である。 The present invention provides a plating bath having a basic composition of a soluble silver salt and a complexing agent comprising a sulfur-containing compound such as thioureas, sulfides, mercaptans, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and It is a substituted silver plating bath containing specific phosphoric acids selected from the group consisting of these salts and having a content of the phosphoric acids of 0.5 to 10 mol / L.
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換算の含有量は０.０００１〜１モル／Ｌであり、好ましくは０.００１〜０.５モル／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. Preferable specific examples of the silver salt include silver methanesulfonate, silver ethanesulfonate, silver acetate, silver lactate, and silver citrate.
The metal equivalent content of the soluble silver salt with respect to the plating bath is 0.0001 to 1 mol / L, preferably 0.001 to 0.5 mol / 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。
含イオウ化合物のメッキ浴に対する含有量は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).
Content with respect to the plating bath of a sulfur-containing compound is 0.0001-5 mol / L, and is 0.03-2 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. Thiourea derivatives include 1,3-dimethylthiourea, trimethylthiourea, diethylthiourea (eg, 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（チオグリコール酸）、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 (thioglycolic 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。
含イオウ化合物にあっては、光沢のある銀白色のメッキ皮膜をより効果的に得る見地から、メチオニン、エチオニン、シスチン、チオジグリコール酸、チオジグリコールなどのスルフィド類、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（チオグリコール酸）などのメルカプタン類が好ましい。
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.
In the case of sulfur-containing compounds, from the viewpoint of more effectively obtaining a bright silver-white plating film, sulfides such as methionine, ethionine, cystine, thiodiglycolic acid, thiodiglycol, cysteine, N-acetylcysteine Mercaptans such as thioglycol, mercaptosuccinic acid, mercaptoisobutyric acid, mercaptoacetic acid (thioglycolic acid) are preferred.
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することを基本にするが、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 substitution silver plating bath of the present invention is based on an organic acid, an inorganic acid, or a salt thereof as a base acid, but a soluble silver salt or a complexing agent may be dissolved in water to build a bath.
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.
本発明の置換銀メッキ浴には、オルトリン酸（正リン酸）、縮合リン酸及びこれらの塩よりなる群から選ばれた特定のリン酸類を含有することが必要である。
縮合リン酸はピロリン酸、トリポリリン酸、ポリリン酸（縮合度がトリポリリン酸より大きいもの）、連鎖状或は環状のメタリン酸などをいう。
これらのリン酸塩は、ナトリウム、カリウム、カルシウム、マグネシウム、アンモニウム、アミン、スルホネートなどの各種塩をいう。
本発明では、上記特定のリン酸類は、オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸及びこれらの塩よりなる群から選択される。
上記特定のリン酸類は単用又は併用でき、その含有量は０.５〜１０モル／Ｌであり、好ましくは０.５〜５モル／Ｌである。含有量が０.５モル／Ｌより少ないと、銀メッキ皮膜に銀白色の美麗な外観を付与することが困難になり、黒変し易くなる。
The substituted silver plating bath of the present invention needs to contain a specific phosphoric acid selected from the group consisting of orthophosphoric acid (normal phosphoric acid), condensed phosphoric acid and salts thereof.
The condensed phosphoric acid refers to pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid (having a degree of condensation larger than tripolyphosphoric acid), chained or cyclic metaphosphoric acid, and the like.
These phosphates refer to various salts such as sodium, potassium, calcium, magnesium, ammonium, amine, sulfonate and the like.
In the present invention, the specific phosphoric acid is selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, and salts thereof.
The specific phosphoric acids can be used alone or in combination, and the content thereof is 0.5 to 10 mol / L, preferably 0.5 to 5 mol / L. When the content is less than 0.5 mol / L, it is difficult to impart a beautiful silver-white appearance to the silver plating film, and blackening is likely to occur.
本発明の置換銀メッキ浴には、上述の成分以外に、目的に応じて公知の界面活性剤、ｐＨ調整剤、緩衝剤などの各種添加剤を含有できることはいうまでもない。
上記界面活性剤は、析出する銀皮膜の緻密性、平滑性、密着性などの補助的改善を目的として含有され、ノニオン系界面活性剤、両性界面活性剤、カチオン系界面活性剤、或はアニオン系界面活性剤を単用又は併用できる（本発明３参照）。
その含有量は０.０１〜１００ｇ／Ｌ、好ましくは０.１〜５０ｇ／Ｌである。
It goes without saying that the substituted silver plating bath of the present invention can contain various additives such as known surfactants, pH adjusters, and buffering agents in addition to the above-described components.
The surfactant is contained for the purpose of assisting improvement of the denseness, smoothness, adhesion, etc. of the deposited silver film, and is a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or an anion. A system surfactant can be used alone or in combination (see the present invention 3 ).
Its content is 0.01-100 g / L, preferably 0.1-50 g / L.
当該ノニオン系界面活性剤の具体例としては、Ｃ1〜Ｃ20アルカノール、フェノール、ナフトール、ビスフェノール類、（ポリ）Ｃ1〜Ｃ25アルキルフェノール、（ポリ）アリールアルキルフェノール、Ｃ1〜Ｃ25アルキルナフトール、Ｃ1〜Ｃ25アルコキシル化リン酸(塩)、ソルビタンエステル、ポリアルキレングリコール、Ｃ1〜Ｃ22脂肪族アミン、Ｃ1〜Ｃ22脂肪族アミドなどにエチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を２〜３００モル付加縮合させたものや、Ｃ1〜Ｃ25アルコキシル化リン酸(塩)などが挙げられる。 Specific examples of the nonionic surface active agent, C 1 -C 20 alkanols, phenols, naphthols, bisphenols, (poly) C 1 -C 25 alkyl phenol, (poly) aryl phenol, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxylated phosphoric acid (salt), sorbitan ester, polyalkylene glycol, C 1 -C 22 aliphatic amine, C 1 -C 22 aliphatic amide and the like with ethylene oxide (EO) and / or propylene oxide (PO ) a and those engaged 2-300 mol adduct condensation, and the like C 1 -C 25 alkoxylated phosphoric acid (salt).
上記エチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を付加縮合させるＣ1〜Ｃ20アルカノールとしては、メタノール、エタノール、ｎ−ブタノール、ｔ−ブタノール、ｎ−ヘキサノール、オクタノール、デカノール、ラウリルアルコール、テトラデカノール、ヘキサデカノール、ステアリルアルコール、エイコサノール、オレイルアルコール、ドコサノールなどが挙げられる。同じく上記ビスフェノール類としては、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＦなどが挙げられる。上記（ポリ）Ｃ1〜Ｃ25アルキルフェノールとしては、モノ、ジ、若しくはトリアルキル置換フェノール、例えば、ｐ−メチルフェノール、ｐ−ブチルフェノール、ｐ−イソオクチルフェノール、ｐ−ノニルフェノール、ｐ−ヘキシルフェノール、２,４−ジブチルフェノール、２,４,６−トリブチルフェノール、ジノニルフェノール、ｐ−ドデシルフェノール、ｐ−ラウリルフェノール、ｐ−ステアリルフェノールなどが挙げられる。上記アリールアルキルフェノールとしては、２−フェニルイソプロピルフェノール、クミルフェノール、(モノ、ジ又はトリ)スチレン化フェノール、(モノ、ジ又はトリ)ベンジルフェノールなどが挙げられる。上記Ｃ1〜Ｃ25アルキルナフトールのアルキル基としては、メチル、エチル、プロピル、ブチル、ヘキシル、オクチル、デシル、ドデシル、オクタデシルなどが挙げられ、ナフタレン核の任意の位置にあって良い。上記ポリアルキレングリコールとしては、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシエチレンポリオキシプロピレン・コポリマーなどが挙げられる。 The C 1 -C 20 alkanol addition condensation of the above ethylene oxide (EO) and / or propylene oxide (PO), methanol, ethanol, n- butanol, t-butanol, n- hexanol, octanol, decanol, lauryl alcohol, tetra Examples include decanol, hexadecanol, stearyl alcohol, eicosanol, oleyl alcohol, docosanol and the like. Similarly, examples of the bisphenols include bisphenol A, bisphenol B, and bisphenol F. Examples of the (poly) C 1 -C 25 alkylphenol include mono-, di-, or trialkyl-substituted phenols such as p-methylphenol, p-butylphenol, p-isooctylphenol, p-nonylphenol, p-hexylphenol, 2, Examples include 4-dibutylphenol, 2,4,6-tributylphenol, dinonylphenol, p-dodecylphenol, p-laurylphenol, and p-stearylphenol. Examples of the arylalkylphenol include 2-phenylisopropylphenol, cumylphenol, (mono, di or tri) styrenated phenol, (mono, di or tri) benzylphenol and the like. Examples of the alkyl group of the C 1 -C 25 alkyl naphthol include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like, and may be at any position of the naphthalene nucleus. Examples of the polyalkylene glycol include polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene copolymer.
上記Ｃ1〜Ｃ25アルコキシル化リン酸(塩)は、下記の一般式(ａ)で表されるものである。
Ｒa・Ｒb・(ＭＯ)Ｐ＝Ｏ …(ａ)
(式(ａ)中、Ｒa及びＲbは同一又は異なるＣ1〜Ｃ25アルキル、但し、一方がＨであっても良い。ＭはＨ又はアルカリ金属を示す。)
The C 1 -C 25 alkoxylated phosphoric acid (salt) is represented by the following general formula (a).
Ra, Rb, (MO) P = O (a)
(In the formula (a), Ra and Rb are the same or different C 1 -C 25 alkyl, provided that one of them may be H. M represents H or an alkali metal.)
上記ソルビタンエステルとしては、モノ、ジ又はトリエステル化した１,４−、１,５−又は３,６−ソルビタン、例えばソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンジステアレート、ソルビタンジオレエート、ソルビタン混合脂肪酸エステルなどが挙げられる。上記Ｃ1〜Ｃ22脂肪族アミンとしては、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ラウリルアミン、ミリスチルアミン、ステアリルアミン、オレイルアミン、牛脂アミン、エチレンジアミン、プロピレンジアミンなどの飽和及び不飽和脂肪酸アミンなどが挙げられる。上記Ｃ1〜Ｃ22脂肪族アミドとしては、プロピオン酸、酪酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘン酸、ヤシ油脂肪酸、牛脂脂肪酸などのアミドが挙げられる。 Examples of the sorbitan ester include mono-, di- or triesterized 1,4-, 1,5- or 3,6-sorbitan such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dioleate And sorbitan mixed fatty acid ester. Examples of the C 1 to C 22 aliphatic amine include saturated and unsaturated fatty acids such as propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, myristylamine, stearylamine, oleylamine, beef tallow amine, ethylenediamine, and propylenediamine. An amine etc. are mentioned. Examples of the C 1 -C 22 aliphatic amide include amides such as propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, coconut oil fatty acid, and beef tallow fatty acid. Is mentioned.
更に、上記ノニオン系界面活性剤としては、
Ｒ1Ｎ(Ｒ2)2→Ｏ
(上式中、Ｒ1はＣ5〜Ｃ25アルキル又はＲＣＯＮＨＲ3（Ｒ3はＣ1〜Ｃ5アルキレンを示す)、Ｒ2は同一又は異なるＣ1〜Ｃ5アルキルを示す。)などで示されるアミンオキシドを用いることができる。
Furthermore, as the nonionic surfactant,
R 1 N (R 2 ) 2 → O
(In the above formula, R 1 represents C 5 to C 25 alkyl or RCONHR 3 (R 3 represents C 1 to C 5 alkylene), R 2 represents the same or different C 1 to C 5 alkyl) and the like. Amine oxides can be used.
上記カチオン系界面活性剤としては、下記の一般式(ｂ)で表される第４級アンモニウム塩
(Ｒ1・Ｒ2・Ｒ3・Ｒ4Ｎ)+・Ｘ- …(ｂ)
(式(ｂ)中、Ｘはハロゲン、ヒドロキシ、Ｃ1〜Ｃ5アルカンスルホン酸又は硫酸、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(ｃ)で表されるピリジニウム塩などが挙げられる。
Ｒ6−(Ｃ5Ｈ4Ｎ−Ｒ5)+・Ｘ- …(ｃ)
(式(ｃ)中、Ｃ5Ｈ4Ｎはピリジン環、Ｘはハロゲン、ヒドロキシ、Ｃ1〜Ｃ5アルカンスルホン酸又は硫酸、Ｒ5はＣ1〜Ｃ20アルキル、Ｒ6はＨ又はＣ1〜Ｃ10アルキルを示す。)
As the cationic surfactant, a quaternary ammonium salt represented by the following general formula (b)
(R 1 · R 2 · R 3 · R 4 N) + · X - ... (b)
(In the formula (b), X is halogen, hydroxy, C 1 -C 5 alkanesulfonic acid or sulfuric acid, R 1 , R 2 , R 3 and R 4 are the same or different C 1 -C 20 alkyl, aryl or benzyl. Or a pyridinium salt represented by the following general formula (c).
R 6- (C 5 H 4 N-R 5 ) + · X − (c)
(In the formula (c), C 5 H 4 N is a pyridine ring, X is halogen, hydroxy, C 1 -C 5 alkanesulfonic acid or sulfuric acid, R 5 is C 1 -C 20 alkyl, R 6 is H or C 1. ~C 10 represents an 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。 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.
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、｛(モノ、ジ、トリ)アルキル｝ナフタレンスルホン酸塩などが挙げられる。アルキル硫酸塩としては、ラウリル硫酸ナトリウム、オレイル硫酸ナトリウムなどが挙げられる。ポリオキシエチレンアルキルエーテル硫酸塩としては、ポリオキシエチレン(ＥＯ５)ノニルエーテル硫酸ナトリウム、ポリオキシエチレン(ＥＯ１５)ドデシルエーテル硫酸ナトリウムなどが挙げられる。ポリオキシエチレンアルキルフェニルエーテル硫酸塩としては、ポリオキシエチレン(ＥＯ１５)ノニルフェニルエーテル硫酸塩などが挙げられる。アルキルベンゼンスルホン酸塩としては、ドデシルベンゼンスルホン酸ナトリウムなどが挙げられる。また、｛(モノ、ジ、トリ)アルキル｝ナフタレンスルホン酸塩としては、ナフタレンスルホン酸塩、ジブチルナフタレンスルホン酸ナトリウム、ナフタレンスルホン酸ホルマリン縮合物などが挙げられる。 Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, {(mono, di, tri) alkyl} naphthalene sulfonates, etc. Is mentioned. Examples of the alkyl sulfate include sodium lauryl sulfate and sodium oleyl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include sodium polyoxyethylene (EO5) nonyl ether sulfate and sodium polyoxyethylene (EO15) dodecyl ether sulfate. Examples of the polyoxyethylene alkylphenyl ether sulfate include polyoxyethylene (EO15) nonylphenyl ether sulfate. Examples of the alkyl benzene sulfonate include sodium dodecylbenzene sulfonate. Examples of the {(mono, di, tri) alkyl} naphthalene sulfonate include naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, and naphthalene sulfonate formalin condensate.
上記両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、スルホベタイン、アミノカルボン酸などが挙げられる。また、エチレンオキシド及び／又はプロピレンオキシドとアルキルアミン又はジアミンとの縮合生成物の硫酸化、或はスルホン酸化付加物も使用できる。 Examples of the amphoteric surfactant include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. In addition, sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
代表的なカルボキシベタイン、或はイミダゾリンベタインは、ラウリルジメチルアミノ酢酸ベタイン、ミリスチルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、２−ウンデシル−１−カルボキシメチル−１−ヒドロキシエチルイミダゾリニウムベタイン、２−オクチル−１−カルボキシメチル−１−カルボキシエチルイミダゾリニウムベタインなどが挙げられ、硫酸化及びスルホン酸化付加物としてはエトキシル化アルキルアミンの硫酸付加物、スルホン酸化ラウリル酸誘導体ナトリウム塩などが挙げられる。 Representative carboxybetaines or imidazoline betaines are lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, 2-undecyl-1-carboxymethyl-1 -Hydroxyethyl imidazolinium betaine, 2-octyl-1-carboxymethyl-1-carboxyethyl imidazolinium betaine, and the like. Sulfated and sulfonated adducts include sulfated adducts of ethoxylated alkylamines, sulfonated Examples thereof include lauric acid derivative sodium salt.
上記スルホベタインとしては、ヤシ油脂肪酸アミドプロピルジメチルアンモニウム−２−ヒドロキシプロパンスルホン酸、Ｎ−ココイルメチルタウリンナトリウム、Ｎ−パルミトイルメチルタウリンナトリウムなどが挙げられる。アミノカルボン酸としては、ジオクチルアミノエチルグリシン、Ｎ−ラウリルアミノプロピオン酸、オクチルジ(アミノエチル)グリシンナトリウム塩などが挙げられる。 Examples of the sulfobetaines include coconut oil fatty acid amidopropyldimethylammonium-2-hydroxypropanesulfonic acid, N-cocoylmethyl taurine sodium, and N-palmitoylmethyl taurine sodium. Examples of the aminocarboxylic acid include dioctylaminoethylglycine, N-laurylaminopropionic acid, octyldi (aminoethyl) glycine sodium salt, and the like.
上記ｐＨ調整剤としては、塩酸、硫酸等の各種の酸、アンモニア水、水酸化カリウム、水酸化ナトリウム等の各種の塩基などが挙げられる。
上記緩衝剤としては、ホウ酸類、ホスフィン酸やホスホン酸、シュウ酸、コハク酸などのジカルボン酸類、乳酸、酒石酸などのオキシカルボン酸類など塩化アンモニウム、硫酸アンモニウムなどが挙げられる。また、本発明で添加する特定のリン酸類により当該緩衝剤を兼用することもできる。
Examples of the pH adjuster include various acids such as hydrochloric acid and sulfuric acid, various bases such as aqueous ammonia, potassium hydroxide, and sodium hydroxide.
Examples of the buffer include dicarboxylic acids such as boric acid, phosphinic acid, phosphonic acid, oxalic acid, and succinic acid, and oxycarboxylic acids such as lactic acid and tartaric acid, and ammonium chloride and ammonium sulfate. Moreover, the said buffering agent can also be combined with the specific phosphoric acids added by this invention.
本発明の置換銀メッキは、基本的に、被メッキ物をメッキ液に通常１秒〜３０分間浸漬し、所望の膜厚までメッキ皮膜を析出させることにより行う。ＰＨは８.０以下が好ましく、浴の撹拌は必要に応じて行う場合もある。また、浴温は１０〜８０℃程度であり、メッキ時間は膜厚に依存して決定される。
本発明の置換銀メッキ浴を適用する被メッキ物（即ち、素地表面）は任意であり特に制限はないが、本発明４に示すように、４２アロイ、ニッケル、鉄又は銅から選ぶことが好ましい。従って、プリント回路板、半導体集積回路、フィルムキャリア、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銀皮膜を形成する場合、本発明の置換銀メッキ浴は好適である。 但し、本発明の置換銀メッキ浴を４２アロイ、ニッケル、鉄の素地表面に適用すると、他の素地を選択した場合に比べて、得られる銀皮膜をより美麗な銀白色の色調へと促進できる。従って、本発明の置換銀メッキ浴を適用すべき素地表面としては、４２アロイ、ニッケル、鉄がより好ましい。
The substitution silver plating of the present invention is basically performed by immersing the object to be plated in a plating solution usually for 1 second to 30 minutes to deposit a plating film to a desired film thickness. The pH is preferably 8.0 or less, and the bath may be stirred as necessary. The bath temperature is about 10 to 80 ° C., and the plating time is determined depending on the film thickness.
An object to be plated (that is, the substrate surface) to which the substitution silver plating bath of the present invention is applied is arbitrary and is not particularly limited, but is preferably selected from 42 alloy, nickel, iron or copper as shown in the present invention 4. . Therefore, when forming a silver film on electronic parts such as printed circuit boards, semiconductor integrated circuits, film carriers, resistors, variable resistors, capacitors, filters, inductors, thermistors, crystal resonators, switches, lead wires, etc. A displacement silver plating bath is preferred. However, when the substitution silver plating bath of the present invention is applied to the surface of a 42 alloy, nickel, or iron substrate, the resulting silver film can be promoted to a more beautiful silver-white color than when other substrates are selected. . Therefore, as the substrate surface to which the substituted silver plating bath of the present invention is applied, 42 alloy, nickel and iron are more preferable.
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.
《置換銀メッキ浴の実施例》
実施例１〜１３のうち、実施例１〜４、６、８〜１０、１３は特定のリン酸類にオルトリン酸又はその塩を使用した例、その他の実施例は縮合リン酸又はその塩を使用した例である。実施例１〜６、９〜１０、１３は含イオウ化合物としてメルカプタン類を使用した例、実施例８、１１は同じくスルフィド類を使用した例、実施例７、１２は同じくチオ尿素を使用した例である。実施例１〜３はメルカプタン類の濃度を一定にしてリン酸塩の濃度を変化させた例である。実施例３〜４は逆にリン酸塩の濃度を一定にしてメルカプタン類の濃度を変化させた例である。
一方、比較例１〜５のうち、比較例１は含イオウ化合物のみを含み、特定のリン酸類を含まないブランク例である。比較例２〜３はリン酸類のみを含み、含イオウ化合物を含まないブランク例である。比較例４〜５は含イオウ化合物とリン酸類の両方を含むが、リン酸類の濃度が０.５モル／Ｌより少ない例である。
<< Example of Substitution Silver Plating Bath >>
Among Examples 1 to 13, Examples 1 to 4, 6, 8 to 10 and 13 are examples using orthophosphoric acid or a salt thereof as a specific phosphoric acid, and other examples are using condensed phosphoric acid or a salt thereof. This is an example. Examples 1 to 6, 9 to 10 and 13 are examples using mercaptans as sulfur-containing compounds, Examples 8 and 11 are examples using sulfides, Examples 7 and 12 are examples using thiourea It is. Examples 1 to 3 are examples in which the concentration of phosphate was changed while the concentration of mercaptans was kept constant. Examples 3 to 4 are examples in which the concentration of the mercaptans was changed while keeping the concentration of phosphate constant.
On the other hand, among Comparative Examples 1 to 5, Comparative Example 1 is a blank example containing only a sulfur-containing compound and no specific phosphoric acid. Comparative Examples 2-3 are blank examples containing only phosphoric acids and no sulfur-containing compounds. Comparative Examples 4 to 5 include both sulfur-containing compounds and phosphoric acids, but the phosphoric acid concentration is less than 0.5 mol / L.
(1)実施例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
リン酸２水素ナトリウム ０.５０モル／Ｌ
チオグリコール ０.３０モル／Ｌ
(1) Example 1
A substitution silver plating bath was constructed with the following composition.
Silver acetate (as Ag + ) 0.05 mol / L
Sodium dihydrogen phosphate 0.50 mol / L
Thioglycol 0.30 mol / L
(2)実施例２
酢酸銀（Ａｇ+として） ０.０５モル／Ｌ
リン酸２水素ナトリウム １.００モル／Ｌ
チオグリコール ０.３０モル／Ｌ
(2) Example 2
Silver acetate (as Ag + ) 0.05 mol / L
Sodium dihydrogen phosphate 1.00 mol / L
Thioglycol 0.30 mol / L
(3)実施例３
酢酸銀（Ａｇ+として） ０.０５モル／Ｌ
リン酸２水素ナトリウム ２.００モル／Ｌ
チオグリコール ０.３０モル／Ｌ
(3) Example 3
Silver acetate (as Ag + ) 0.05 mol / L
Sodium dihydrogen phosphate 2.00 mol / L
Thioglycol 0.30 mol / L
(4)実施例４
酢酸銀（Ａｇ+として） ０.０５モル／Ｌ
リン酸２水素ナトリウム ２.００モル／Ｌ
チオグリコール １.００モル／Ｌ
(4) Example 4
Silver acetate (as Ag + ) 0.05 mol / L
Sodium dihydrogen phosphate 2.00 mol / L
Thioglycol 1.00 mol / L
(5)実施例５
メタンスルホン酸銀（Ａｇ+として） ０.１０モル／Ｌ
ピロリン酸２水素２ナトリウム １.００モル／Ｌ
システイン ０.１０モル／Ｌ
(5) Example 5
Silver methanesulfonate (as Ag + ) 0.10 mol / L
Disodium dihydrogen pyrophosphate 1.00 mol / L
Cysteine 0.10 mol / L
(6)実施例６
メタンスルホン酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸 ２.００モル／Ｌ
システイン ０.５０モル／Ｌ
(6) Example 6
Silver methanesulfonate (as Ag + ) 0.10 mol / L
Phosphoric acid 2.00 mol / L
Cysteine 0.50 mol / L
(7)実施例７
乳酸銀（Ａｇ+として） ０.１０モル／Ｌ
メタリン酸 ０.５０モル／Ｌ
チオ尿素 ０.３０モル／Ｌ
(7) Example 7
Silver lactate (as Ag + ) 0.10 mol / L
Metaphosphoric acid 0.50 mol / L
Thiourea 0.30 mol / L
(8)実施例８
メタンスルホン酸銀（Ａｇ+として） ０.０５モル／Ｌ
リン酸 ２.００モル／Ｌ
メチオニン ０.３０モル／Ｌ
(8) Example 8
Silver methanesulfonate (as Ag + ) 0.05 mol / L
Phosphoric acid 2.00 mol / L
Methionine 0.30 mol / L
(9)実施例９
メタンスルホン酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸 １.００モル／Ｌ
チオグリコール酸 ０.３０モル／Ｌ
(9) Example 9
Silver methanesulfonate (as Ag + ) 0.10 mol / L
Phosphoric acid 1.00 mol / L
Thioglycolic acid 0.30 mol / L
(10)実施例１０
メタンスルホン酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸 １.００モル／Ｌ
２−メルカプトベンゾチアゾール ０.３０モル／Ｌ
ポリオキシエチレンアルキルエーテル
−硫酸エステル塩（EO10モル） １０.０ｇ／Ｌ
(10) Example 10
Silver methanesulfonate (as Ag + ) 0.10 mol / L
Phosphoric acid 1.00 mol / L
2-mercaptobenzothiazole 0.30 mol / L
Polyoxyethylene alkyl ether
-Sulfate ester salt (EO10 mol) 10.0 g / L
(11)実施例１１
酢酸銀（Ａｇ+として） ０.１０モル／Ｌ
ピロリン酸２水素２ナトリウム １.００モル／Ｌ
チオジグリコール ０.３０モル／Ｌ
ジブチル−β−ナフトールポリエトキシレート(EO8モル)１０.０ｇ／Ｌ
(11) Example 11
Silver acetate (as Ag + ) 0.10 mol / L
Disodium dihydrogen pyrophosphate 1.00 mol / L
Thiodiglycol 0.30 mol / L
Dibutyl-β-naphthol polyethoxylate (EO8 mol) 10.0 g / L
(12)実施例１２
酢酸銀（Ａｇ+として） ０.１０モル／Ｌ
ピロリン酸２水素２ナトリウム １.００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
(12) Example 12
Silver acetate (as Ag + ) 0.10 mol / L
Disodium dihydrogen pyrophosphate 1.00 mol / L
Thiourea 0.30 mol / L
Decyldimethylbenzylammonium chloride 10g / L
(13)実施例１３
硝酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸２水素ナトリウム １.００モル／Ｌ
システイン ０.３０モル／Ｌ
ポリオキシエチレンノニルフェニルエーテル(EO10モル) １０.０ｇ／Ｌ
(13) Example 13
Silver nitrate (as Ag + ) 0.10 mol / L
Sodium dihydrogen phosphate 1.00 mol / L
Cysteine 0.30 mol / L
Polyoxyethylene nonylphenyl ether (EO10 mol) 10.0 g / L
(14)比較例１
酢酸銀（Ａｇ+として） ０.０５モル／Ｌ
チオグリコール ０.３０モル／Ｌ
(14) Comparative Example 1
Silver acetate (as Ag + ) 0.05 mol / L
Thioglycol 0.30 mol / L
(15)比較例２
硝酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸２水素ナトリウム ０.５０モル／Ｌ
(15) Comparative example 2
Silver nitrate (as Ag + ) 0.10 mol / L
Sodium dihydrogen phosphate 0.50 mol / L
(16)比較例３
酢酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸 ０.５０モル／Ｌ
(16) Comparative Example 3
Silver acetate (as Ag + ) 0.10 mol / L
Phosphoric acid 0.50 mol / L
(17)比較例４
酢酸銀（Ａｇ+として） ０.１０モル／Ｌ
ピロリン酸 ０.４０モル／Ｌ
チオグリコール ０.３０モル／Ｌ
(17) Comparative example 4
Silver acetate (as Ag + ) 0.10 mol / L
Pyrophosphate 0.40 mol / L
Thioglycol 0.30 mol / L
(18)比較例５
乳酸銀（Ａｇ+として） ０.１０モル／Ｌ
リン酸 ０.３０モル／Ｌ
システイン ０.２０モル／Ｌ
(18) Comparative Example 5
Silver lactate (as Ag + ) 0.10 mol / L
Phosphoric acid 0.30 mol / L
Cysteine 0.20 mol / L
《置換銀メッキによる皮膜外観評価試験例》
そこで、上記実施例１〜１３及び比較例１〜５の各置換銀メッキ浴について、25mm×25mmの形状で４２アロイ製の試験板をメッキ温度５０℃、３０秒の条件で浸漬することにより、試験板表面に置換銀メッキを施し、下記の試験評価(ａ)〜(ｃ)を行った。
(ａ)初期浴から得られるメッキ皮膜の外観評価試験
建浴直後の銀浴（初期浴）から得られるメッキ皮膜の外観を夫々目視観察して、当該皮膜外観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。
×：黒色を呈し、或は色調むらが生じた。
<< Example of film appearance evaluation test by substitution silver plating >>
Then, about each substitution silver plating bath of the said Examples 1-13 and Comparative Examples 1-5, by immersing the test plate made from 42 alloy in the shape of 25 mm x 25 mm on the conditions of plating temperature 50 degreeC and 30 second, The surface of the test plate was subjected to substitution silver plating, and the following test evaluations (a) to (c) were performed.
(a) Appearance evaluation test of the plating film obtained from the initial bath The appearance of the plating film obtained from the silver bath immediately after the construction bath (initial bath) was visually observed, and the superiority or inferiority of the appearance of the film was evaluated according to the following criteria. .
○: Glossy silver-white color was exhibited.
X: Black color was exhibited or color unevenness occurred.
(ｂ)皮膜外観の経時安定性評価試験
初期浴と、建浴から時間を置いた後の銀浴（経時浴）とから得られる各メッキ皮膜の外観を対比観察して、メッキ浴の経時変化に伴う皮膜外観の安定性（皮膜外観の経時安定性という）の優劣を下記の基準により評価した。
尚、上記経時浴は、建浴からの時間の経過に伴って置換反応により素地金属が溶解するなどして、初期組成にない余剰成分が混入した状態の浴をいう。
○：経時浴から得られたメッキ皮膜の外観が初期浴から得られた皮膜外観に比べて変化がなかった。
△：経時浴から得られたメッキ皮膜の外観が初期浴から得られた皮膜外観に比べて、銀白色から少し黒味を帯びた銀色に変化した。
(b) Evaluating stability of coating appearance over time Observing the appearance of each plating coating obtained from an initial bath and a silver bath (aging bath) after a period of time from the building bath, the change over time of the plating bath The superiority or inferiority of the stability of the film appearance (referred to as the stability of the film appearance over time) associated with was evaluated according to the following criteria.
The time-lapse bath refers to a bath in which surplus components not in the initial composition are mixed because the base metal is dissolved by a substitution reaction with the passage of time from the building bath.
○: The appearance of the plating film obtained from the time-lapse bath was not changed compared to the appearance of the film obtained from the initial bath.
(Triangle | delta): The external appearance of the plating film obtained from the time-lapse | temporal bath changed from silver white to the silver color with a little blackishness compared with the film external appearance obtained from the initial stage bath.
(ｃ)皮膜外観の総合評価
上記メッキ皮膜（初期浴から得られる皮膜）の外観試験(ａ)と、皮膜外観の経時安定性試験(ｂ)との結果を下記の基準により総合的に評価した。
○：初期浴から得られる皮膜外観に優れるとともに、皮膜外観の経時安定性にも優れる。
△：初期浴から得られる皮膜外観には優れるが、皮膜外観の経時安定性は少し後退した。
×：初期浴から得られる皮膜外観に劣る。
但し、上記初期浴から得られる皮膜外観の評価が×である例については、当然ながら経時浴での評価が初期浴以上になることはまず考えられないことに鑑みて、皮膜外観の経時安定性試験は行わず、従って、総合評価も×とした。
(c) Comprehensive evaluation of film appearance The results of the appearance test (a) of the plating film (the film obtained from the initial bath) and the temporal stability test (b) of the film appearance were comprehensively evaluated according to the following criteria. .
○: Excellent in the appearance of the film obtained from the initial bath and excellent in the temporal stability of the appearance of the film.
Δ: The film appearance obtained from the initial bath is excellent, but the temporal stability of the film appearance is slightly retreated.
X: The film appearance obtained from the initial bath is inferior.
However, in the case where the evaluation of the film appearance obtained from the above initial bath is x, it is natural that the evaluation with the aging bath is not considered to be more than the initial bath. The test was not conducted, and therefore, the overall evaluation was x.
下表はその試験結果である。
初期浴の皮膜外観 経時安定性 総合評価
実施例１ ○ ○ ○
実施例２ ○ ○ ○
実施例３ ○ ○ ○
実施例４ ○ ○ ○
実施例５ ○ ○ ○
実施例６ ○ ○ ○
実施例７ ○ △ △
実施例８ ○ ○ ○
実施例９ ○ ○ ○
実施例10 ○ ○ ○
実施例11 ○ ○ ○
実施例12 ○ △ △
実施例13 ○ ○ ○
比較例１ × −− ×
比較例２ × −− ×
比較例３ × −− ×
比較例４ × −− ×
比較例５ × −− ×
The table below shows the test results.
Film appearance of initial bath Stability over time Comprehensive evaluation Example 1 ○ ○ ○
Example 2 ○ ○ ○
Example 3 ○ ○ ○
Example 4 ○ ○ ○
Example 5 ○ ○ ○
Example 6 ○ ○ ○
Example 7 ○ △ △
Example 8 ○ ○ ○
Example 9 ○ ○ ○
Example 10 ○ ○ ○
Example 11 ○ ○ ○
Example 12 ○ △ △
Example 13 ○ ○ ○
Comparative Example 1 × −− ×
Comparative Example 2 × −− ×
Comparative Example 3 × −− ×
Comparative Example 4 × −− ×
Comparative Example 5 × −− ×
上表により初期浴での皮膜外観を検討すると、含イオウ化合物のみを含み、特定のリン酸類を含まない比較例１では、皮膜外観の評価は劣っていた。特定のリン酸類のみを含み、含イオウ化合物を含まない比較例２〜３でも、同様に皮膜外観の評価は劣った。
これに対して、実施例１〜１３ではいずれも光沢のある美麗な銀白色のメッキ皮膜が得られ、皮膜外観に優れることが認められた。従って、光沢のある銀白色のメッキ皮膜を得るためには、銀の錯化剤である含イオウ化合物と特定のリン酸類を共存させる必要があることが確認できた。
また、比較例４〜５は本発明と同様に含イオウ化合物と特定のリン酸類との両成分を含むが、リン酸類の濃度が０.３０〜０.４０モル／Ｌであり、皮膜外観の評価は劣った。従って、比較例４〜５を実施例に対比すると、銀皮膜の外観を向上するには、リン酸類を含イオウ化合物と共存させるだけでは十分でなく、リン酸類の濃度を０.５０モル／Ｌ以上に増大させる必要があることが確認できた。
When the appearance of the film in the initial bath was examined according to the above table, the evaluation of the appearance of the film was inferior in Comparative Example 1 that contained only the sulfur-containing compound and no specific phosphoric acid. Even in Comparative Examples 2 to 3 containing only specific phosphoric acids and no sulfur-containing compound, the evaluation of the film appearance was similarly inferior.
On the other hand, in Examples 1 to 13, a glossy and beautiful silver-white plating film was obtained, and it was recognized that the film appearance was excellent. Therefore, in order to obtain a glossy silver-white plating film, it was confirmed that a sulfur-containing compound that is a complexing agent of silver and a specific phosphoric acid need to coexist.
Comparative Examples 4 to 5 contain both components of a sulfur-containing compound and specific phosphoric acids as in the present invention, but the concentration of phosphoric acids is 0.30 to 0.40 mol / L, and the appearance of the film is Evaluation was inferior. Therefore, when Comparative Examples 4 to 5 are compared with Examples, it is not sufficient to make phosphoric acid coexist with a sulfur-containing compound in order to improve the appearance of the silver film, and the concentration of phosphoric acid is 0.50 mol / L. It was confirmed that it was necessary to increase the above.
実施例１〜３はメルカプタン類（チオグリコール）の濃度を一定にしてリン酸塩（リン酸２水素ナトリウム）の濃度を０.５０〜２.００モル／Ｌに変化させた例であるが、初期浴での皮膜外観の評価はいずれも優れていたことから、リン酸類の濃度は０.５０モル／Ｌ以上であれば、光沢のある銀白色のメッキ皮膜が得られることが分かる。
一方、実施例３〜４は逆にリン酸塩（リン酸２水素ナトリウム）の濃度を一定にしてメルカプタン類（チオグリコール）の濃度を０.３０〜１.００モル／Ｌに変化させた例であり、また、実施例５ではメルカプタン類（システイン）の濃度は０.１０モル／Ｌであることから、光沢のある銀白色のメッキ皮膜を得るためには、含イオウ化合物の濃度はリン酸類の濃度水準で含む必要はなく、少なくても良いことが分かる。
Examples 1 to 3 are examples in which the concentration of mercaptans (thioglycol) was kept constant and the concentration of phosphate (sodium dihydrogen phosphate) was changed to 0.50 to 2.00 mol / L. Since the evaluation of the film appearance in the initial bath was excellent, it can be seen that if the concentration of phosphoric acid is 0.50 mol / L or more, a shiny silver-white plating film can be obtained.
On the other hand, Examples 3 to 4 are examples in which the concentration of the phosphate (sodium dihydrogen phosphate) was kept constant and the concentration of the mercaptans (thioglycol) was changed from 0.30 to 1.00 mol / L. In Example 5, the concentration of mercaptans (cysteine) is 0.10 mol / L. Therefore, in order to obtain a shiny silver-white plating film, the concentration of the sulfur-containing compound is phosphoric acids. It is understood that it is not necessary to include it at the concentration level, and it may be small.
実施例は初期浴での皮膜外観に優れるだけではなく、概ね、経時浴から得られるスズ皮膜も初期浴での皮膜と変わらず光沢のある銀白色であり、皮膜の経時安定性の面でも優れることが分かった。
この点を詳述すると、含イオウ化合物にメルカプタン類やスルフィド類を使用した実施例１〜６、８〜１１、１３では、初期浴での皮膜外観に優れるだけではなく、皮膜の経時安定性にも優れる。但し、含イオウ化合物にチオ尿素を使用した実施例７と１２では、銀イオンへの錯化効果に優れることでメッキ浴自体の安定性は良好であったが、経時浴から得られる銀皮膜は少し黒みを帯びた銀色を呈した。
従って、実施例１〜１３を初期浴での皮膜外観と皮膜の経時安定性との両面で総合的に評価すると、含イオウ化合物と特定のリン酸類を共存させる条件下で、当該含イオウ化合物にメルカプタン類やスルフィド類を選択した場合にはこの総合評価に優れ、その一方で、含イオウ化合物にチオ尿素類を選択した場合には、総合評価が多少後退することが分かった。
他方、経時浴での皮膜外観の評価は初期浴での評価以上になることはまず考えられないため、初期浴での皮膜外観の評価に劣る比較例１〜５では経時浴での評価は行わず、従って、比較例１〜５の総合評価は低かった。
The examples are not only excellent in the appearance of the film in the initial bath, but generally, the tin film obtained from the aging bath is also glossy silver-white, which is the same as the film in the initial bath, and is excellent in terms of the aging stability of the film. I understood that.
In detail, in Examples 1-6, 8-11, and 13 using mercaptans and sulfides as the sulfur-containing compound, not only the film appearance in the initial bath is excellent, but also the stability of the film over time. Also excellent. However, in Examples 7 and 12, in which thiourea was used as the sulfur-containing compound, the stability of the plating bath itself was good due to the excellent complexing effect to silver ions, but the silver film obtained from the aging bath was Slightly blackish silver.
Therefore, when Examples 1 to 13 were comprehensively evaluated in terms of both the appearance of the film in the initial bath and the stability over time of the film, the sulfur-containing compound was subjected to the conditions under which the sulfur-containing compound and the specific phosphoric acid coexist. It was found that when mercaptans and sulfides were selected, the overall evaluation was excellent, while when thioureas were selected as the sulfur-containing compound, the overall evaluation was somewhat retreated.
On the other hand, since it is unlikely that the evaluation of the film appearance in the aging bath is more than the evaluation in the initial bath, in Comparative Examples 1 to 5 inferior to the evaluation of the film appearance in the initial bath, the evaluation in the aging bath is performed. Therefore, the overall evaluation of Comparative Examples 1 to 5 was low.
Claims (4)
オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸及びこれらの塩よりなる群から選ばれたリン酸類の少なくとも一種を含有し、且つ、当該リン酸類の含有量が０.５〜１０モル／Ｌ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 selected from thioureas, sulfides, and mercaptans,
Contains at least one phosphoric acid selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and salts thereof, and the content of the phosphoric acid is 0.5 to 10 mol / L A substituted silver plating bath characterized by that.
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| JP2000309875A (en) * | 1999-04-23 | 2000-11-07 | Okuno Chem Ind Co Ltd | Substitution type electroless silver plating solution |
| JP2002266077A (en) * | 2001-03-07 | 2002-09-18 | Shinko Electric Ind Co Ltd | Substitution type electroless plating bath for tin, silver and tin-silver alloy |
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