JP2005163107A - Method of forming black nickel film, and electroless nickel-phosphorus plating bath - Google Patents
Method of forming black nickel film, and electroless nickel-phosphorus plating bath Download PDFInfo
- Publication number
- JP2005163107A JP2005163107A JP2003403310A JP2003403310A JP2005163107A JP 2005163107 A JP2005163107 A JP 2005163107A JP 2003403310 A JP2003403310 A JP 2003403310A JP 2003403310 A JP2003403310 A JP 2003403310A JP 2005163107 A JP2005163107 A JP 2005163107A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- film
- black
- plating bath
- forming
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000007747 plating Methods 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- -1 ammonium ions Chemical class 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 238000007772 electroless plating Methods 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 49
- 230000002378 acidificating effect Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical class [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
本発明は、黒色ニッケル皮膜の形成方法及び黒色ニッケル皮膜の形成に用いる無電解ニッケル−リンめっき浴に関する。 The present invention relates to a method for forming a black nickel film and an electroless nickel-phosphorous plating bath used for forming the black nickel film.
光学部品や放熱部材の表面処理に用いられる黒色皮膜としては、黒色クロムめっき、黒色ニッケルめっきなどにより形成された皮膜が知られている。また、無電解めっきにより形成したニッケル−リン合金を酸化処理することにより黒色ニッケル皮膜を得る方法も知られている。例えば、特公昭59−22786号公報(特許文献1)、特公昭64−7153号公報(特許文献2)、特公平7−42588号公報(特許文献3)、特開平9−78256号公報(特許文献4)には、ニッケル合金皮膜を酸化処理することにより黒色皮膜を形成する方法、特開昭61−253381号公報(特許文献5)には、亜鉛又は亜鉛合金皮膜を酸化処理することにより黒化皮膜を形成する方法が記載されている。しかしながら、これら従来の方法により得られた黒色皮膜は、安定して良好な黒色皮膜を得られない場合があり、更なる改良が必要なものであり、ターン数が多くなっても安定して優れた黒色皮膜が得られる方法が望まれていた。また、黒化処理されるニッケル合金皮膜を形成するためのニッケルめっき浴にはアミノ基含有化合物を含むものがあるが、アミノ基含有化合物を含むめっき浴は、廃水処理上の問題があり経済的に不利であった。 As a black film used for the surface treatment of an optical component or a heat radiating member, a film formed by black chrome plating, black nickel plating or the like is known. Also known is a method of obtaining a black nickel film by oxidizing a nickel-phosphorus alloy formed by electroless plating. For example, JP-B-59-22786 (Patent Document 1), JP-B-64-7153 (Patent Document 2), JP-B-7-42588 (Patent Document 3), JP-A-9-78256 (Patent Document) Document 4) describes a method of forming a black film by oxidizing a nickel alloy film, and Japanese Patent Application Laid-Open No. 61-253381 (Patent Document 5) discloses a method of oxidizing black or zinc alloy film by oxidizing it. A method of forming a chemical film is described. However, the black film obtained by these conventional methods may not be able to stably obtain a good black film, and further improvement is necessary, and it is stable and excellent even when the number of turns increases. There has been a demand for a method for obtaining a black film. In addition, some nickel plating baths for forming a nickel alloy film to be blackened contain amino group-containing compounds, but plating baths containing amino group-containing compounds have problems in wastewater treatment and are economical. Was disadvantageous.
本発明は、上記事情に鑑みなされたものであり、ターン数にかかわらず良好な黒色ニッケルめっき皮膜を形成することができる黒色ニッケル皮膜の形成方法及び黒色ニッケル皮膜の形成に用いる無電解ニッケル−リンめっき浴を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a method for forming a black nickel film capable of forming a good black nickel plating film regardless of the number of turns and an electroless nickel-phosphorus used for forming the black nickel film. An object is to provide a plating bath.
本発明者は、上記問題を解決するため鋭意検討を重ねた結果、酸性処理液、好ましくは鉄、銅、銀、コバルト、マンガン及びモリブデンから選ばれる金属のイオンを1種又は2種以上含有する酸性処理液にニッケル−リン合金皮膜を接触させる処理により黒化して黒色ニッケル皮膜を形成する場合、上記ニッケル−リン合金皮膜を形成するための無電解ニッケル−リンめっき浴として、ニッケル塩、リン酸塩、有機酸及び/又はその塩、イオウ系化合物、並びにアンモニウムイオンを含有し、かつアミノ基含有化合物を含有しない無電解ニッケル−リンめっき浴を用いることで、良好な黒色ニッケル皮膜を得られると共に、補給やめっき浴の管理が容易になり、ターンにかかわらず安定して良好な黒色ニッケル皮膜が得られることを見出した。 As a result of intensive studies to solve the above problems, the inventor of the present invention contains one or more ions of an acid treatment solution, preferably a metal ion selected from iron, copper, silver, cobalt, manganese and molybdenum. In the case of forming a black nickel film by blackening by a treatment in which the nickel-phosphorus alloy film is brought into contact with an acidic treatment liquid, an electroless nickel-phosphorus plating bath for forming the nickel-phosphorus alloy film is formed of a nickel salt or phosphoric acid. By using an electroless nickel-phosphorous plating bath containing a salt, an organic acid and / or a salt thereof, a sulfur compound, and an ammonium ion and not containing an amino group-containing compound, a good black nickel film can be obtained. It was found that replenishment and plating bath management became easy and a stable and good black nickel coating could be obtained regardless of the turn.
また、特に、上記酸性処理液で処理した後、更に加熱処理すれば、黒色を退色させることなく皮膜硬度の向上を図ることができ、高い硬度を有し、かつ良好な黒色を呈する皮膜を得ることができることを見出し、本発明をなすに至った。 In particular, if the heat treatment is performed after the treatment with the acidic treatment liquid, the film hardness can be improved without fading the black color, and a film having a high hardness and a good black color can be obtained. The present inventors have found that it is possible to achieve the present invention.
即ち、本発明は、被めっき物上に、ニッケル塩、リン酸塩、有機酸及び/又はその塩、イオウ系化合物、並びにアンモニウムイオンを含有し、かつアミノ基含有化合物を含有しない無電解ニッケル−リンめっき浴を用いて無電解めっきすることによりニッケル−リン合金皮膜を形成し、次いで、該ニッケル−リン合金皮膜を酸性処理液に接触させて処理することを特徴とする黒色ニッケル皮膜の形成方法、及び
酸性処理液にニッケル−リン合金皮膜を接触させる処理により黒化して黒色ニッケル皮膜を形成するために用いる上記ニッケル−リン合金皮膜を形成するための無電解ニッケル−リンめっき浴であって、ニッケル塩、リン酸塩、有機酸及び/又はその塩、イオウ系化合物、並びにアンモニウムイオンを含有し、かつアミノ基含有化合物を含有しないことを特徴とする無電解ニッケル−リンめっき浴を提供する。
That is, the present invention provides an electroless nickel-containing nickel salt, phosphate, organic acid and / or salt thereof, a sulfur compound, and an ammonium ion on the object to be plated and containing no amino group-containing compound. Forming a nickel-phosphorus alloy film by electroless plating using a phosphorous plating bath, and then treating the nickel-phosphorous alloy film by contacting with an acidic treatment solution. And an electroless nickel-phosphorous plating bath for forming the nickel-phosphorous alloy film used to form a black nickel film by blackening by a treatment in which the nickel-phosphorus alloy film is contacted with an acidic treatment liquid, Contains nickel salts, phosphates, organic acids and / or their salts, sulfur compounds, and ammonium ions, and amino group-containing compounds Electroless nickel characterized in that it does not contain - to provide a phosphorus plating bath.
本発明によれば、黒化度が高い、皮膜表面に干渉色を発することがないなど良好な黒色を呈する皮膜が得られ、また、得られた皮膜は、被めっき物に対する密着性、硬度も良好である。更に、本発明によれば、ターン数にかかわらず良好な黒色を呈する皮膜が得られ、廃水処理上の問題もないため、経済的に有利である。 According to the present invention, a film exhibiting a good black color such as a high degree of blackening and no interference color on the surface of the film is obtained, and the obtained film also has adhesion and hardness to an object to be plated. It is good. Furthermore, according to the present invention, a film having a good black color can be obtained regardless of the number of turns, and there is no problem in wastewater treatment, which is economically advantageous.
以下、本発明について更に詳述する。
本発明の黒色ニッケル皮膜の形成方法は、被めっき物上に、ニッケル塩、リン酸塩、有機酸及び/又はその塩、イオウ系化合物、並びにアンモニウムイオンを含有し、かつアミノ基含有化合物を含有しない無電解ニッケル−リンめっき浴を用いて無電解めっきすることによりニッケル−リン合金皮膜を形成し、次いで、このニッケル−リン合金皮膜を酸性処理液に接触させて処理するものである
The present invention will be described in detail below.
The method for forming a black nickel film according to the present invention includes a nickel salt, a phosphate, an organic acid and / or salt thereof, a sulfur compound, and an ammonium ion on the object to be plated, and an amino group-containing compound. A nickel-phosphorus alloy film is formed by electroless plating using an electroless nickel-phosphorus plating bath, and the nickel-phosphorus alloy film is then contacted with an acidic treatment solution for treatment.
また、本発明の無電解ニッケル−リンめっき浴は、酸性処理液にニッケル−リン合金皮膜を接触させる処理により黒化して黒色ニッケル皮膜を形成するために用いる上記ニッケル−リン合金皮膜を形成するための無電解ニッケル−リンめっき浴であり、ニッケル塩、リン酸塩、有機酸及び/又はその塩、イオウ系化合物、並びにアンモニウムイオンを含有し、かつアミノ基含有化合物を含有しないものである。 In addition, the electroless nickel-phosphorous plating bath of the present invention forms the nickel-phosphorous alloy film used to form a black nickel film by blackening by a treatment in which the nickel-phosphorous alloy film is brought into contact with an acidic treatment liquid. Electroless nickel-phosphorus plating bath, which contains a nickel salt, phosphate, organic acid and / or salt thereof, a sulfur compound, and ammonium ion, and does not contain an amino group-containing compound.
本発明においてニッケル−リン合金皮膜を形成するために用いる無電解ニッケル−リンめっき浴には、ニッケル塩及びリン酸塩が含まれる。ニッケル塩としては、硝酸ニッケル、塩化ニッケル、酢酸ニッケル等が好ましく、そのめっき浴中の濃度は0.01〜0.2mol/Lであることが好ましい。また、リン酸塩としては、次亜リン酸カリウム、次亜リン酸ナトリウム等の次亜リン酸塩、亜リン酸カリウム、亜リン酸ナトリウム等の亜リン酸塩が好ましく、特に、次亜リン酸塩が好ましい。また、そのめっき浴中の濃度は0.1〜2mol/L、特に0.1〜1mol/Lであることが好ましい。 The electroless nickel-phosphorous plating bath used to form the nickel-phosphorus alloy film in the present invention contains a nickel salt and a phosphate. The nickel salt is preferably nickel nitrate, nickel chloride, nickel acetate or the like, and the concentration in the plating bath is preferably 0.01 to 0.2 mol / L. The phosphate is preferably a hypophosphite such as potassium hypophosphite or sodium hypophosphite, or a phosphite such as potassium phosphite or sodium phosphite. Acid salts are preferred. Moreover, it is preferable that the density | concentration in the plating bath is 0.1-2 mol / L, especially 0.1-1 mol / L.
また、本発明の無電解ニッケル−リンめっき浴は、めっき浴中のニッケルイオンを錯化する及び/又はpH変動を抑制する目的で有機酸及び/又はその塩を含有する。有機酸、有機酸塩としては、ギ酸、酢酸、プロピオン酸、フマル酸、マロン酸、コハク酸、アジピン酸等のカルボン酸、上記カルボン酸の塩(ナトリウム塩、カリウム塩、アンモニウム塩等)、乳酸、クエン酸、リンゴ酸、グリコール酸、酒石酸、グルコン酸等のオキシカルボン酸、上記オキシカルボン酸の塩(ナトリウム塩、カリウム塩、アンモニウム塩等)が挙げられる。これら有機酸及び/又はその塩は、1種単独で又は2種以上を併用して含有させることが可能である。また、後述するアンモニウムイオンの供給源として、上記有機酸塩としてアンモニウム塩を用いることも可能である。この有機酸及び/又はその塩のめっき浴中の濃度は、0.1〜2mol/L、特に0.1〜1mol/Lであることが好ましい。有機酸及び/又はその塩の濃度が0.1mol/L未満の場合、めっき浴の安定性が悪くなり、ターンが進むにつれて安定して黒色ニッケル皮膜が得られなくなる場合がある。また、2mol/Lより高いとめっきが進行しないおそれがある。 The electroless nickel-phosphorous plating bath of the present invention contains an organic acid and / or a salt thereof for the purpose of complexing nickel ions in the plating bath and / or suppressing pH fluctuation. Organic acids and organic acid salts include formic acid, acetic acid, propionic acid, fumaric acid, malonic acid, succinic acid, adipic acid and other carboxylic acids, carboxylic acid salts (sodium salt, potassium salt, ammonium salt, etc.), lactic acid And oxycarboxylic acids such as citric acid, malic acid, glycolic acid, tartaric acid and gluconic acid, and salts of the above oxycarboxylic acids (sodium salt, potassium salt, ammonium salt and the like). These organic acids and / or salts thereof can be contained alone or in combination of two or more. Moreover, it is also possible to use ammonium salt as said organic acid salt as a supply source of ammonium ion mentioned later. The concentration of the organic acid and / or salt thereof in the plating bath is preferably 0.1 to 2 mol / L, particularly preferably 0.1 to 1 mol / L. When the concentration of the organic acid and / or salt thereof is less than 0.1 mol / L, the stability of the plating bath is deteriorated, and the black nickel film may not be stably obtained as the turn proceeds. If it is higher than 2 mol / L, the plating may not proceed.
また、本発明の無電解ニッケル−リンめっき浴にはイオウ系化合物が含まれる。イオウ系化合物としては、チオエーテル化合物、チオシアン化合物、チオカルボニル化合物、チオール化合物、チオ硫酸及びチオ硫酸塩から選ばれる1種又は2種以上が好ましい。具体的には、チオエーテル化合物としては、メチオニン、ジメチルスルホキシド、チオジグリコール酸、ベンゾチアゾール等、チオシアン化合物としては、チオシアン酸、チオシアン酸カリウム、チオシアン酸ナトリウム、チオシアン酸アンモニウム等、チオカルボニル化合物としては、チオ尿素又はその誘導体、チオール化合物としてはシステイン、チオ乳酸、チオグリコール酸、メルカプトエタノール、ブタンチオール等、チオ硫酸塩としては、チオ硫酸ナトリウム等が挙げられ、そのめっき浴中の濃度は0.0001〜1g/Lであることが好ましい。 The electroless nickel-phosphorous plating bath of the present invention contains a sulfur compound. The sulfur compound is preferably one or more selected from thioether compounds, thiocyan compounds, thiocarbonyl compounds, thiol compounds, thiosulfuric acid and thiosulfate. Specifically, thioether compounds include methionine, dimethyl sulfoxide, thiodiglycolic acid, benzothiazole, and thiocyanate compounds include thiocyanic acid, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, and the like. Thiourea or derivatives thereof, thiol compounds such as cysteine, thiolactic acid, thioglycolic acid, mercaptoethanol, butanethiol and the like, and thiosulfate include sodium thiosulfate, and the concentration in the plating bath is 0. It is preferable that it is 0001-1g / L.
なかでも、メチオニン、ジメチルスルホキシド、チオジグリコール酸、ベンゾチアゾール等のチオエーテル化合物、及びチオシアン酸、チオシアン酸塩(チオシアン酸カリウム、チオシアン酸ナトリウム、チオシアン酸アンモニウム)等のチオシアン化合物から選ばれる1種又は2種以上が好ましい。チオエーテル化合物又はチオシアン化合物を用いることにより、干渉色のないより良好な黒色ニッケル皮膜が得られる。 Among them, one kind selected from thioether compounds such as methionine, dimethyl sulfoxide, thiodiglycolic acid and benzothiazole, and thiocyanate such as thiocyanic acid and thiocyanate (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate) Two or more are preferred. By using a thioether compound or a thiocyan compound, a better black nickel film having no interference color can be obtained.
本発明において、無電解ニッケル−リンめっき浴には、アンモニウムイオンが含まれる。アンモニウムイオンをめっき浴中に含有させるには、アンモニア水又はアンモニウム塩を添加する方法を採用し得る。この場合、アンモニア水、塩化アンモニウム、水酸化アンモニウム等を用いることができる。また、有機酸のアンモニウム塩を用いることによりアンモニウムイオンを含有させることも可能である。なお、このアンモニウムイオンのめっき浴中の濃度は0.1〜10mol/Lであることが好ましい。 In the present invention, the electroless nickel-phosphorous plating bath contains ammonium ions. In order to contain ammonium ions in the plating bath, a method of adding aqueous ammonia or ammonium salt can be employed. In this case, aqueous ammonia, ammonium chloride, ammonium hydroxide or the like can be used. It is also possible to contain ammonium ions by using an ammonium salt of an organic acid. In addition, it is preferable that the density | concentration in the plating bath of this ammonium ion is 0.1-10 mol / L.
アンモニウムイオンを上記範囲で含有させることにより、無電解ニッケル−リンめっき浴を、一般に必須とされるアミノ基含有化合物を含まない構成とすることができ、経済的で、廃水処理上有利なものとすることができる。また、アンモニウムイオンと上述した有機酸及び/又は有機酸塩とイオウ系化合物とを併用することにより、ターン数にかかわらず、干渉色のない良好な黒色ニッケル皮膜が得られる。更に、有機酸として、カルボン酸及び/又はその塩とオキシカルボン酸/又はその塩とを含有させることにより、補給やめっき浴の管理が容易になる上、含有するイオウ系化合物の種類にかかわりなく形成されるニッケル−リン合金皮膜中のリン含有量を後述する黒色ニッケル皮膜を得るのに最適な範囲に安定して保つことができる。 By containing ammonium ions in the above range, the electroless nickel-phosphorous plating bath can be configured to contain no generally required amino group-containing compound, which is economical and advantageous for wastewater treatment. can do. In addition, by using ammonium ions, the above-described organic acid and / or organic acid salt, and a sulfur compound in combination, a good black nickel film having no interference color can be obtained regardless of the number of turns. Furthermore, by adding a carboxylic acid and / or salt thereof and an oxycarboxylic acid / or salt as an organic acid, replenishment and management of the plating bath are facilitated, regardless of the type of sulfur compound contained. The phosphorus content in the nickel-phosphorus alloy film to be formed can be stably maintained in an optimum range for obtaining a black nickel film described later.
なお、本発明の無電解ニッケル−リンめっき浴には、その他適宜Pb,Tl等の安定剤や界面活性剤などの各種公知の添加物を含有させることができるが、アミノ基含有化合物は含有させないことが好ましい。また、めっき浴のpHは5〜8、特に6〜7であることが好ましい。 The electroless nickel-phosphorous plating bath of the present invention may contain various other known additives such as stabilizers such as Pb and Tl and surfactants as appropriate, but does not contain an amino group-containing compound. It is preferable. Moreover, it is preferable that pH of a plating bath is 5-8, especially 6-7.
また、本発明の無電解ニッケル−リンめっき浴は、アミノ基含有化合物を含有しないものである。アミノ基含有化合物を含有すると、廃水処理上の問題が生じて不経済となる上、干渉色が発生しやすくなる。上記アミノ基含有化合物としては、モノエタノールアミン等の第1級アミン、ジメチルアミン等の第2級アミン、TEA(トリエタノールアミン)等の第3級アミン、グリシン等のアミノ酸又はそれらの塩が挙げられる。 Moreover, the electroless nickel-phosphorus plating bath of the present invention does not contain an amino group-containing compound. When the amino group-containing compound is contained, problems in wastewater treatment occur, which is uneconomical, and interference colors are easily generated. Examples of the amino group-containing compound include primary amines such as monoethanolamine, secondary amines such as dimethylamine, tertiary amines such as TEA (triethanolamine), amino acids such as glycine, and salts thereof. It is done.
本発明においては、被めっき物上に、上記無電解ニッケル−リンめっき浴を用いてニッケル−リン合金皮膜を形成し、次いでこのニッケル−リン合金皮膜を酸性処理液により処理することにより黒化して黒色ニッケル皮膜を形成するが、ニッケル−リン合金皮膜の黒化は、このニッケル−リン合金皮膜を酸性処理液で処理することによりニッケル−リン合金皮膜が酸化されて酸化ニッケルとなって黒化が達成されるものと推定される。そのため、良好な黒色ニッケル皮膜を得るためには、皮膜に対して効果的かつ効率的に酸化反応を進行させて黒化する必要があるが、上記無電解ニッケル−リンめっき浴を用いることにより形成したニッケル−リン合金皮膜は、酸性処理液により効果的かつ効率的に黒化することができる。なお、ニッケル−リン合金皮膜中のリン含有量は2〜7質量%、特に3〜5質量%であることが好ましい。 In the present invention, a nickel-phosphorous alloy film is formed on the object to be plated using the electroless nickel-phosphorous plating bath, and then the nickel-phosphorous alloy film is blackened by treating with an acidic treatment liquid. A black nickel film is formed. The nickel-phosphorus alloy film is blackened by treating the nickel-phosphorous alloy film with an acid treatment solution to oxidize the nickel-phosphorus alloy film to nickel oxide. Estimated to be achieved. Therefore, in order to obtain a good black nickel coating, it is necessary to effectively and efficiently cause the coating to blacken, but it is formed by using the above electroless nickel-phosphorous plating bath. The nickel-phosphorus alloy film can be blackened effectively and efficiently by the acidic treatment liquid. In addition, it is preferable that the phosphorus content in a nickel-phosphorus alloy film is 2-7 mass%, especially 3-5 mass%.
本発明の無電解ニッケル−リンめっき浴によるめっき温度及びめっき時間は、めっき浴の組成や、形成するニッケル−リン合金皮膜の厚さ等により適宜決定され、特に制限されるものではないが、60〜95℃、特に70〜95℃のめっき温度、0.1〜5時間のめっき時間が好適に適用し得る。 The plating temperature and plating time in the electroless nickel-phosphorous plating bath of the present invention are appropriately determined depending on the composition of the plating bath, the thickness of the nickel-phosphorous alloy film to be formed, and the like, but are not particularly limited. A plating temperature of ˜95 ° C., particularly 70 to 95 ° C., and a plating time of 0.1 to 5 hours can be suitably applied.
なお、本発明においては、ニッケル−リン合金皮膜を形成する前に、無電解ニッケルめっき等により基板上に、好ましくは0.1〜20μmの厚さの下地層を形成してからニッケル−リン合金皮膜を形成することが好ましい。下地層を形成することにより、基板表面の荒れ等の影響を低減することができ、黒化された皮膜がより優れた物性を有するもの、特に優れた黒色を呈するものになることから好ましい。この下地層は、その上に形成される上述したニッケル−リン合金皮膜とは異なり、酸性処理液によって直接処理されるものではないため、従来公知のめっき法により形成することが可能であり、例えば、従来公知の無電解ニッケルめっき浴を用いて形成することが可能である。 In the present invention, before the nickel-phosphorus alloy film is formed, a nickel-phosphorus alloy is preferably formed after an underlayer having a thickness of preferably 0.1 to 20 μm is formed on the substrate by electroless nickel plating or the like. It is preferable to form a film. By forming the underlayer, it is possible to reduce the influence of roughness of the substrate surface and the like, and the blackened film is preferable because it has more excellent physical properties, particularly excellent black color. Unlike the above-described nickel-phosphorus alloy film formed thereon, this underlayer is not directly treated with an acidic treatment solution, and can be formed by a conventionally known plating method, for example, It can be formed using a conventionally known electroless nickel plating bath.
次に、このニッケル−リン合金皮膜を酸性処理液で処理することにより黒色ニッケル皮膜を形成する。本発明においては、この酸性処理液による処理を、上述したようにして得られたニッケル−リン合金皮膜に加熱処理を施すことなく実施する。皮膜の加熱処理は、皮膜硬度を向上させることができる点で有効であるが、従来の黒色皮膜の形成方法では、黒化させた後に加熱処理すると退色が起こってしまい、また、加熱処理した皮膜に黒化処理しても十分な黒色が得られないという問題があった。これに対して、本発明により得られる黒色ニッケル皮膜は、後述するように、黒化処理後の加熱処理により黒色を退色させることなく皮膜硬度を向上させることができることから、この段階での加熱処理は不要である。 Next, this nickel-phosphorus alloy film is treated with an acidic treatment liquid to form a black nickel film. In the present invention, the treatment with the acidic treatment liquid is performed without subjecting the nickel-phosphorus alloy film obtained as described above to heat treatment. Heat treatment of the film is effective in that the film hardness can be improved, but in the conventional method of forming a black film, discoloration occurs when heat treatment is performed after blackening, and the heat-treated film However, there was a problem that sufficient black color could not be obtained even when blackening treatment was performed. On the other hand, the black nickel film obtained by the present invention can improve the film hardness without fading black by the heat treatment after the blackening treatment, as will be described later. Is unnecessary.
本発明において、酸性処理液としては、硝酸、塩酸、硫酸、過硫酸、過酸化水素の1種又は2種以上の水溶液が挙げられ、その酸性処理液中の濃度は10〜800g/Lであることが好ましい。なお、酸性処理液のpHは4以下、特に2以下が好ましい。 In the present invention, examples of the acidic treatment liquid include one or more aqueous solutions of nitric acid, hydrochloric acid, sulfuric acid, persulfuric acid, and hydrogen peroxide, and the concentration in the acidic treatment liquid is 10 to 800 g / L. It is preferable. The pH of the acidic treatment liquid is preferably 4 or less, particularly 2 or less.
また、本発明においては、上記酸性処理液が、鉄、銅、銀、コバルト、マンガン及びモリブデン、特に銅及び鉄から選ばれる金属のイオンを1種又は2種以上含んでいることが好ましい。金属のイオンとしては、例えばCu2+,Fe3+等の金属元素のみからなるイオンの他、上記金属を含む錯イオンが挙げられる。この場合、酸性処理液中の上記金属のイオンの濃度は0.1〜10mol/Lであることが好ましい。 Moreover, in this invention, it is preferable that the said acidic process liquid contains the 1 type (s) or 2 or more types of metal ion chosen from iron, copper, silver, cobalt, manganese, and molybdenum, especially copper and iron. Examples of metal ions include ions composed only of metal elements such as Cu 2+ and Fe 3+ , and complex ions containing the above metals. In this case, the concentration of the metal ions in the acidic treatment liquid is preferably 0.1 to 10 mol / L.
酸性処理液中に上記金属のイオンを含有させることにより、黒化処理における酸化反応と共に、金属の置換反応によってもニッケル−リン合金皮膜の黒化を進行させることが可能である。上述した本発明の無電解ニッケル−リンめっき浴により形成されたニッケル−リン合金皮膜は、この金属の置換反応に対しても効果的かつ効率的であるためこの点においても好適である。 By including the metal ions in the acidic treatment liquid, it is possible to advance the blackening of the nickel-phosphorus alloy film by the metal substitution reaction as well as the oxidation reaction in the blackening treatment. The above-described nickel-phosphorus alloy film formed by the electroless nickel-phosphorus plating bath of the present invention is also effective in this metal substitution reaction and is also suitable in this respect.
特に、上述した金属のイオンを含む酸性処理液としては、更に、ニッケルのイオンを含むものが好ましい。ニッケルのイオンとしては、ニッケルイオン(Ni2+)の他、ニッケル錯イオンが挙げられる。上述した金属のイオンと共に、ニッケルのイオンを共存させることにより、ニッケルのイオンと共存する金属のイオンによる皮膜の置換反応を促進することが可能である。この場合、酸性処理液中の上記ニッケルのイオンの濃度は0.001〜1mol/Lであることが好ましい。 In particular, the acidic treatment liquid containing metal ions described above preferably further contains nickel ions. Nickel ions include nickel ions (Ni 2+ ) and nickel complex ions. By making nickel ions coexist with the metal ions described above, it is possible to promote the substitution reaction of the film with the metal ions coexisting with the nickel ions. In this case, the concentration of the nickel ions in the acidic treatment liquid is preferably 0.001 to 1 mol / L.
本発明において、酸性処理液による処理温度及び処理時間は、酸性処理液の組成や形成されたニッケル−リン合金皮膜(ニッケル−リン合金皮膜の形成に用いた無電解ニッケル−リンめっき浴の組成)等により適宜決定され、特に制限されるものではないが、0〜60℃、好ましくは20〜60℃の処理温度、0.1〜10分の処理時間が好適に適用し得る。 In the present invention, the treatment temperature and treatment time of the acidic treatment liquid are the composition of the acidic treatment liquid and the formed nickel-phosphorus alloy film (composition of the electroless nickel-phosphorous plating bath used for forming the nickel-phosphorus alloy film). Although it determines suitably by etc. and it does not restrict | limit in particular, 0-60 degreeC, Preferably the processing temperature of 20-60 degreeC and the processing time for 0.1-10 minutes can be applied suitably.
また、酸性処理液により処理して得られた皮膜は、酸性処理液で処理した後、更に加熱処理することが可能である。酸性処理液で処理しただけの皮膜であっても、従来に比べて優れた物性を有するものであるが、得られた皮膜は、加熱処理により黒色を退色させることなく皮膜硬度を向上させることができることから、加熱処理により、更に、高い硬度を有しつつ、良好な黒色を呈する皮膜を得ることが可能である。この場合、加熱処理条件としては、例えば、大気下(空気雰囲気下)、100〜400℃で、0.1〜100分加熱処理することが効果的である。 Moreover, the film obtained by the treatment with the acidic treatment liquid can be further heat-treated after being treated with the acidic treatment liquid. Even if the film is only treated with an acidic treatment solution, it has excellent physical properties compared to the conventional one, but the obtained film can improve the film hardness without fading black by heat treatment. Therefore, it is possible to obtain a film exhibiting a good black color while having a higher hardness by heat treatment. In this case, as heat treatment conditions, for example, it is effective to heat-treat at 100 to 400 ° C. for 0.1 to 100 minutes in the air (under air atmosphere).
本発明によれば、形成する黒色ニッケル皮膜の膜厚が薄い場合であっても干渉色がない良好な黒色ニッケル皮膜を得ることが可能であり、本発明は100μm以下、特に0.1〜10μm程度の黒色ニッケル皮膜を形成する場合に好適である。 According to the present invention, it is possible to obtain a good black nickel film having no interference color even when the thickness of the formed black nickel film is thin, and the present invention is 100 μm or less, particularly 0.1 to 10 μm. It is suitable for forming a black nickel film of a degree.
以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example.
[実施例1〜5、比較例1]
被めっき物としてAl板(JIS1050)を用い、このAl板に前処理として以下の処理を順に施した。
UA−68(上村工業株式会社製)に50℃にて5分浸漬
AZ−102(上村工業株式会社製)に60℃にて1分浸漬
(1:1)硝酸に20℃にて30秒浸漬
AZ−301(上村工業株式会社製)に25℃にて30秒浸漬
(1:1)硝酸に20℃にて20秒浸漬
AZ−301(上村工業株式会社製)に25℃にて20秒浸漬
[Examples 1 to 5, Comparative Example 1]
An Al plate (JIS1050) was used as an object to be plated, and the following treatments were sequentially performed as pretreatment on the Al plate.
Immerse in UA-68 (manufactured by Uemura Kogyo Co., Ltd.) for 5 minutes at 50 ° C. Immerse in AZ-102 (manufactured by Uemura Kogyo Co., Ltd.) for 1 minute at 60 ° C. (1: 1) Immerse in nitric acid for 30 seconds at 20 ° C. Immerse in AZ-301 (manufactured by Uemura Kogyo Co., Ltd.) for 30 seconds at 25 ° C. (1: 1) Soak in nitric acid for 20 seconds at 20 ° C. Soak in AZ-301 (manufactured by Uemura Kogyo Co., Ltd.) for 20 seconds at 25 ° C.
次に、硝酸ニッケル0.1mol/L、次亜リン酸ナトリウム0.1mol/L及びクエン酸0.2mol/Lを含有し、pHが4.5である無電解ニッケル−リンめっき浴に、上記前処理を施したAl板を90℃にて10分浸漬して下地層を形成した。 Next, in an electroless nickel-phosphorous plating bath containing nickel nitrate 0.1 mol / L, sodium hypophosphite 0.1 mol / L and citric acid 0.2 mol / L and having a pH of 4.5, The pretreated Al plate was immersed at 90 ° C. for 10 minutes to form an underlayer.
次に、表1に示される無電解ニッケル−リンめっき浴に、下地層を形成したAl板を、80℃にて、形成するニッケル−リン合金皮膜の膜厚が15μmとなるように時間を調整して浸漬して、無電解ニッケル−リン合金めっき皮膜を形成した。 Next, adjust the time so that the thickness of the nickel-phosphorus alloy film to be formed on the Al plate on which the base layer is formed in the electroless nickel-phosphorous plating bath shown in Table 1 is 80 ° C. And dipped to form an electroless nickel-phosphorus alloy plating film.
次いで、各めっき浴につき、この操作を繰り返し、各々1ターン目、3ターン目、5ターン目に当たる無電解ニッケル−リンめっき皮膜を形成したAl板について、塩化第二鉄100g/L(Fe3+として約0.37mol/L)、及び塩酸200g/Lを含有する酸性処理液を用い、酸性処理液中に25℃で1分浸漬する黒化処理を施して黒色ニッケル皮膜を得た。得られた黒色ニッケル皮膜の明度、干渉色の有無を下記の方法で評価した。結果を表2に示す。 Subsequently, this operation was repeated for each plating bath, and 100 g / L of ferric chloride (Fe 3+ About 0.37 mol / L) and an acidic treatment liquid containing 200 g / L of hydrochloric acid, and a black nickel treatment was performed by immersion in the acidic treatment liquid at 25 ° C. for 1 minute to obtain a black nickel film. The brightness of the resulting black nickel coating and the presence or absence of interference colors were evaluated by the following methods. The results are shown in Table 2.
明度(L値)
分光式色差計(日本電色製:SQ−2000)を用い光源(C/10)にて測定した。
干渉色の有無
皮膜に蛍光灯の光を照射して目視し、虹色が確認されたものを干渉色「有」とした。
Lightness (L value)
It measured with the light source (C / 10) using the spectroscopic color difference meter (Nippon Denshoku: SQ-2000).
The film with or without an interference color was observed by irradiating the fluorescent lamp with light from a fluorescent lamp.
[実施例6〜8]
酸性処理液を下記表3のA(実施例6)、B(実施例7)、C(実施例8)に換えて黒化処理した以外は実施例5と同様の方法で黒色ニッケル皮膜を形成し、得られた黒色ニッケル皮膜について、実施例1と同様の方法で評価した。結果を表4に示す。
[Examples 6 to 8]
A black nickel film was formed in the same manner as in Example 5 except that the acidic treatment solution was blackened in place of A (Example 6), B (Example 7), and C (Example 8) in Table 3 below. Then, the obtained black nickel film was evaluated in the same manner as in Example 1. The results are shown in Table 4.
[実施例9、比較例2]
実施例5及び比較例1の各々と同様の方法でAl板を前処理し、下地層及び無電解ニッケル−リン合金めっき皮膜を形成した1ターン目の皮膜について、黒化処理を施した後、更に300℃で60分加熱処理を施して黒色ニッケル皮膜を得た。得られた黒色ニッケル皮膜について、明度、干渉色の有無を実施例1と同様の方法で、また、皮膜硬度を下記の方法で評価した。結果を表5に示す。
[Example 9, Comparative Example 2]
After pre-treating the Al plate by the same method as in each of Example 5 and Comparative Example 1, the first turn film on which the underlayer and the electroless nickel-phosphorus alloy plating film were formed was subjected to blackening treatment, Further, a heat treatment was performed at 300 ° C. for 60 minutes to obtain a black nickel film. About the obtained black nickel membrane | film | coat, the brightness | luminance and the presence or absence of the interference color were evaluated by the method similar to Example 1, and coating hardness was evaluated by the following method. The results are shown in Table 5.
皮膜硬度
微小硬さ試験機(アカシ製:HM−124)を用いビッカース硬さを測定した。
The Vickers hardness was measured using a film hardness microhardness tester (Akashi: HM-124).
[実施例10〜19]
ベンゾチアゾールの代わりに表6に示される化合物を表6に示される量で用いた以外は実施例5と同様の方法で黒色ニッケル皮膜を形成し、得られた黒色ニッケル皮膜について、実施例1と同様の方法で評価した。結果を表7に示す。
[Examples 10 to 19]
A black nickel film was formed in the same manner as in Example 5 except that the compounds shown in Table 6 were used in the amounts shown in Table 6 instead of benzothiazole. Evaluation was made in the same manner. The results are shown in Table 7.
Claims (9)
9. The electroless nickel-phosphorous plating bath according to claim 8, wherein the acidic treatment liquid further contains nickel ions.
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