JP4139347B2 - Electroless nickel plating bath and electroless nickel alloy plating bath - Google Patents
Electroless nickel plating bath and electroless nickel alloy plating bath Download PDFInfo
- Publication number
- JP4139347B2 JP4139347B2 JP2004083111A JP2004083111A JP4139347B2 JP 4139347 B2 JP4139347 B2 JP 4139347B2 JP 2004083111 A JP2004083111 A JP 2004083111A JP 2004083111 A JP2004083111 A JP 2004083111A JP 4139347 B2 JP4139347 B2 JP 4139347B2
- Authority
- JP
- Japan
- Prior art keywords
- plating bath
- electroless nickel
- plating
- electroless
- nickel plating
- 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.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 154
- 238000007747 plating Methods 0.000 title claims description 151
- 229910052759 nickel Inorganic materials 0.000 title claims description 75
- 229910000990 Ni alloy Inorganic materials 0.000 title claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000011733 molybdenum Substances 0.000 claims description 22
- 229910052787 antimony Inorganic materials 0.000 claims description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 230000000704 physical effect Effects 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 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 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 36
- 239000000956 alloy Substances 0.000 description 36
- 230000008021 deposition Effects 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 238000007772 electroless plating Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910001453 nickel ion Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000001771 impaired 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000035404 Autolysis Diseases 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 206010057248 Cell death Diseases 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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PHJJWPXKTFKKPD-UHFFFAOYSA-N [Ni+3].[O-]P([O-])[O-] Chemical compound [Ni+3].[O-]P([O-])[O-] PHJJWPXKTFKKPD-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 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
- 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 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
- 238000011160 research Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、環境負荷の小さい無電解ニッケルめっき浴および無電解ニッケル合金めっき浴（以下、「無電解ニッケル（合金）めっき浴」と略記する）に関するものであり、更に詳細には、水銀、砒素、カドミウム、鉛等の環境負荷の大きい元素を含まず、浴安定性やめっき析出速度の優れた無電解ニッケルめっき浴および無電解ニッケル合金めっき浴に関するものである。 The present invention relates to an electroless nickel plating bath and an electroless nickel alloy plating bath (hereinafter abbreviated as “electroless nickel (alloy) plating bath”) having a low environmental load, and more particularly, mercury and arsenic. The present invention relates to an electroless nickel plating bath and an electroless nickel alloy plating bath which do not contain elements having a large environmental load such as cadmium and lead, and have excellent bath stability and plating deposition rate.
無電解めっきとは、金属イオンと還元剤が存在する溶液から、化学反応により金属イオンを還元して金属皮膜を得る技術である。そしてその中でも、無電解ニッケルめっきあるいは無電解ニッケル合金めっき（以下、これらを総称して「無電解ニッケル（合金）めっき」という）は、防錆、装飾、硬さ向上のほかに、はんだ付け性向上、はんだ濡れ性向上等の効果があり、抵抗体、磁気ディスク、電磁波シールド、更にはプリント基板やＩＴＯ基板に金めっきする際の下地めっき等に工業的に広範囲に使用されている。また、ポリテトラフルオロエチレン等の微粒子を金属皮膜に均一に分散させた複合めっき皮膜を得る為の金属マトリックスとしても使用されている。 Electroless plating is a technique for obtaining a metal film by reducing metal ions by a chemical reaction from a solution containing metal ions and a reducing agent. Among them, electroless nickel plating or electroless nickel alloy plating (hereinafter collectively referred to as “electroless nickel (alloy) plating”) is not only rust prevention, decoration, and hardness improvement, but also solderability. It has effects such as improvement and improvement in solder wettability, and is widely used industrially for resistors, magnetic disks, electromagnetic wave shields, as well as base plating for gold plating on printed circuit boards and ITO substrates. Further, it is also used as a metal matrix for obtaining a composite plating film in which fine particles such as polytetrafluoroethylene are uniformly dispersed in a metal film.
従来より、無電解ニッケル（合金）めっき液には、めっき浴の安定性維持のために、安定剤として水銀、砒素、カドミウム、鉛等の環境負荷の著しく大きい元素の水溶性の塩若しくはイオンが添加されてきた。これら安定剤の存在により、ニッケルイオンの金属への還元反応に必要な温度におけるニッケルイオンの無作為な還元反応、すなわち一般には自己分解と称される反応が抑制され、ニッケル（合金）めっき皮膜の良好な生成とめっき浴の良好な連続使用が可能だった。 Conventionally, in order to maintain the stability of the plating bath, electroless nickel (alloy) plating solutions contain water-soluble salts or ions of elements that have a significant environmental impact, such as mercury, arsenic, cadmium, and lead. Have been added. The presence of these stabilizers suppresses the random reduction of nickel ions at the temperature required for the reduction reaction of nickel ions to metal, that is, a reaction generally referred to as self-decomposition, and the nickel (alloy) plating film Good production and good continuous use of the plating bath were possible.
しかしながら、これら安定剤も無電解ニッケル（合金）めっき浴中にイオンとして存在するために、無電解ニッケルめっき浴からの還元反応によりニッケル（合金）めっき皮膜が生成される際に、これら安定剤イオンも同時に金属に還元されてニッケル皮膜中に取り込まれたり、ニッケル（合金）皮膜中に共析することが以前から知られていた。 However, since these stabilizers are also present as ions in the electroless nickel (alloy) plating bath, these stabilizer ions are produced when a nickel (alloy) plating film is formed by a reduction reaction from the electroless nickel plating bath. At the same time, it has been known that it is reduced to a metal and taken into the nickel film or co-deposited into the nickel (alloy) film.
一方、めっき皮膜中に存在する水銀、砒素、カドミウム、鉛等の元素が環境や人体へ影響する可能性が以前から指摘されていたが、更に近年、環境意識の高まりと共に、欧州における有害物質使用制限指令（ＲｏＨＳ）、使用済み自動車指令（ＥＬＶ）、日本における、国等による環境物品等の調達に関する法律（グリーン購入法）等の法整備がなされ、日本のメーカーではグリーン調達ガイドラインにより、自主的に有害物質の使用禁止が実施されている。これら有害物質の中には、無電解めっき浴で従来から安定剤として使用されてきた、水銀、砒素、カドミウム、鉛等の安定剤元素も含まれている。 On the other hand, it has been pointed out that elements such as mercury, arsenic, cadmium, lead, etc. present in the plating film may affect the environment and the human body. Regulations such as restriction directive (RoHS), used automobile directive (ELV), and law regarding the procurement of environmental goods in Japan (Green Purchasing Law) in Japan have been established. The use of hazardous substances is prohibited. Among these harmful substances, stabilizer elements such as mercury, arsenic, cadmium, and lead, which have been conventionally used as stabilizers in electroless plating baths, are also included.
これら安定剤元素の中でも、水銀、砒素及びカドミウムは、特に有害性や環境影響が著しい為、早い時期から使用されることが少なくなったが、無電解ニッケルめっき浴の安定剤としては、鉛を使用することが一般的となっていた。しかしながら、鉛も人体や環境への影響が確認されている物質であり、鉛に代わる安定剤元素が望まれていた。 Among these stabilizer elements, mercury, arsenic, and cadmium have been used less early because they are particularly harmful and environmental impacts, but lead is used as a stabilizer for electroless nickel plating baths. It has become common to use. However, lead is a substance that has been confirmed to affect the human body and the environment, and a stabilizer element in place of lead has been desired.
現在まで、代替となる安定剤元素として、テルル、タリウム等が公表されてはいるが（非特許文献１及び非特許文献２）、それら単体ではめっき浴の安定性やめっき皮膜外観等で、何れも鉛等には及ばなかった。 To date, tellurium, thallium and the like have been published as alternative stabilizer elements (Non-Patent Document 1 and Non-Patent Document 2). However, it was not as good as lead.
また、これら無電解ニッケルめっき浴に、鉄、銅、錫、コバルト、タングステン、レニウム、マンガン、パラジウム、バナジウム、亜鉛、クロム、金、銀、白金等の金属塩を添加し、無電解ニッケル合金めっき浴とすることが知られている。しかし、これら金属はニッケルの合金化が目的であって、無電解ニッケル皮膜の硬さや耐磨耗性等の物性を向上させるものであって、安定剤としては効果が少ないものであった。
本発明はかかる技術背景に鑑みてなされたものであり、その課題は、有害物質である鉛等を実質的に含有させずに、めっき皮膜の良好な生成とめっき浴の良好な連続使用を達成できる無電解ニッケル（合金）めっき浴を提供することにある。 The present invention has been made in view of such a technical background, and its problem is to achieve good production of a plating film and good continuous use of a plating bath without substantially containing lead, which is a harmful substance. The object is to provide an electroless nickel (alloy) plating bath.
本発明者らは上記の課題を解決すべく鋭意検討を重ねた結果、特定の元素を無電解めっき浴に添加することで、かかる課題を解決できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that such problems can be solved by adding a specific element to the electroless plating bath, and the present invention has been completed.
すなわち本発明は、水溶性ニッケル塩、還元剤、モリブデン及びアンチモンを含有する無電解ニッケルめっき浴を提供するものである。 That is, the present invention provides an electroless nickel plating bath containing a water-soluble nickel salt, a reducing agent, molybdenum and antimony.
また本発明は、水溶性ニッケル塩、合金化金属塩、還元剤、モリブデン及びアンチモンを含有する無電解ニッケルめっき浴を提供するものである。 The present invention also provides an electroless nickel plating bath containing a water-soluble nickel salt, an alloyed metal salt, a reducing agent, molybdenum and antimony.
本発明によれば、有害物質である鉛等を実質的に含有させなくても、めっき被膜外観、めっき析出速度、めっき浴安定性に優れた無電解ニッケル（合金）めっき浴を提供することができる。また、無電解ニッケル（合金）めっき浴は、めっき浴の連続使用時においても、上記性能が低下しにくいので、めっき浴の更新が少なくてすみ、作業効率の向上を図ることができるものである。 According to the present invention, it is possible to provide an electroless nickel (alloy) plating bath that is excellent in plating film appearance, plating deposition rate, and plating bath stability without substantially containing harmful substances such as lead. it can. In addition, the electroless nickel (alloy) plating bath is less likely to deteriorate the performance even during continuous use of the plating bath, so that the plating bath needs to be renewed and the working efficiency can be improved. .
本発明は、少なくとも水溶性ニッケル塩、還元剤、モリブデン及びアンチモンを含有する無電解ニッケルめっき浴およびこの無電解ニッケルめっき浴に更に合金化金属塩を加えた無電解ニッケル合金めっき浴。 The present invention is an electroless nickel plating bath containing at least a water-soluble nickel salt, a reducing agent, molybdenum and antimony, and an electroless nickel alloy plating bath in which an alloying metal salt is further added to the electroless nickel plating bath.
本発明の無電解ニッケル（合金）めっき浴における水溶性ニッケル塩は、特に限定はなく、一般に使用される水溶性ニッケル塩、例えば、硫酸ニッケル、塩化ニッケル、酢酸ニッケル、硝酸ニッケル、次亜リン酸ニッケル等としてめっき浴中に配合される。これらは一種を単独で又は二種以上を組み合わせて用いることができる。 The water-soluble nickel salt in the electroless nickel (alloy) plating bath of the present invention is not particularly limited, and commonly used water-soluble nickel salts such as nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, hypophosphorous acid It is blended in the plating bath as nickel or the like. These can be used individually by 1 type or in combination of 2 or more types.
これら水溶性ニッケル塩の無電解ニッケル（合金）めっき浴中の配合量は、特に限定されるものではないが、ニッケルイオンの濃度として、０．１ｇ／Ｌ〜１００ｇ/Ｌであることが好ましく、１ｇ/Ｌ〜５０ｇ/Ｌであることが特に好ましい。０．１ｇ/Ｌ未満だと未反応の場合があり、１００ｇ/Ｌより多い場合は、過反応による分解が起こる場合がある。 The amount of these water-soluble nickel salts in the electroless nickel (alloy) plating bath is not particularly limited, but the nickel ion concentration is preferably 0.1 g / L to 100 g / L, It is particularly preferably 1 to 50 g / L. If it is less than 0.1 g / L, it may be unreacted, and if it is more than 100 g / L, decomposition due to overreaction may occur.
また、本発明の無電解ニッケル（合金）めっき浴で使用できる還元剤も、特に限定されるものではないが、好ましい例としては、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム等の次亜リン酸（塩）類；ジメチルアミンボラン、トリメチルアミンボラン等のアミンボラン類；ヒドラジン等のヒドラジン（塩）類；水素化ホウ素ナトリウム等が挙げられる。これらは一種を単独で又は二種以上を組み合わせて用いることができる。 Further, the reducing agent that can be used in the electroless nickel (alloy) plating bath of the present invention is not particularly limited. Preferred examples include hypophosphorous acid, sodium hypophosphite, and potassium hypophosphite. Hypophosphorous acid (salt) such as dimethylamine borane, amine borane such as trimethylamine borane; hydrazine (salt) such as hydrazine; sodium borohydride and the like. These can be used individually by 1 type or in combination of 2 or more types.
この還元剤の、無電解ニッケル（合金）めっき浴中での濃度は、使用する還元剤の種類や必要とする析出速度により相違するが、めっき浴全体に対し、１ｇ/Ｌ〜１００ｇ/Ｌが好ましく、２ｇ/Ｌ〜５０ｇ/Ｌが特に好ましい。１ｇ/Ｌ未満だと未反応の場合があり、１００ｇ/Ｌより多い場合は、過反応による分解が起こる場合がある。 The concentration of this reducing agent in the electroless nickel (alloy) plating bath varies depending on the type of reducing agent used and the required deposition rate, but is 1 g / L to 100 g / L for the entire plating bath. 2g / L to 50g / L is particularly preferable. If it is less than 1 g / L, it may be unreacted, and if it is more than 100 g / L, decomposition due to overreaction may occur.
本発明の無電解ニッケル（合金）めっきの特徴は、その組成中に、モリブデンとアンチモンの両方を含有する点である。 A feature of the electroless nickel (alloy) plating of the present invention is that it contains both molybdenum and antimony in its composition.
モリブデンの無電解ニッケル（合金）めっき浴中での形態には特に限定はないが、モリブデン酸イオン又はモリブデンイオンの形態をとることが好ましい。このモリブデンは、例えば、モリブデン酸ナトリウム、モリブデン酸カリウム、モリブデン酸アンモン等のモリブデン酸塩；それらモリブデン酸塩水和物；モリブデン酸等の形で無電解ニッケル（合金）めっき浴中に添加することができ、これらは一種を単独で又は二種以上を組み合わせて用いることができる。 Although there is no particular limitation on the form of molybdenum in the electroless nickel (alloy) plating bath, it is preferable to take the form of molybdate or molybdenum ions. The molybdenum may be added to the electroless nickel (alloy) plating bath in the form of molybdate such as sodium molybdate, potassium molybdate, and ammonium molybdate; These can be used singly or in combination of two or more.
上記モリブデンのめっき浴全体に対する含有量は特に限定はないが、モリブデン金属に換算して、０．１ｍｇ/Ｌ〜１ｇ/Ｌであることが好ましく、１０ｍｇ/Ｌ〜５００ｍｇ/Ｌであることが特に好ましい。また、２０ｍｇ/Ｌ〜２００ｍｇ/Ｌであることが更に好ましい。０．１ｍｇ/Ｌ未満だと自己分解する場合があり、１ｇ/Ｌより多い場合は、めっき外観不良や反応停止する場合がある。 The content of the molybdenum with respect to the entire plating bath is not particularly limited, but is preferably 0.1 mg / L to 1 g / L in terms of molybdenum metal, and particularly preferably 10 mg / L to 500 mg / L. preferable. Further, it is more preferably 20 mg / L to 200 mg / L. If it is less than 0.1 mg / L, it may self-decompose, and if it is more than 1 g / L, it may cause poor plating appearance or stop the reaction.
一方、アンチモンのめっき浴中での形態にも特に限定はないが、アンチモン酸イオン又はアンチモンイオンの形態をとることが好ましい。このアンチモンは、例えば、アンチモン酸ナトリウム、アンチモン酸カリウム、アンチモン酸アンモン等のアンチモン酸塩；それらアンチモン酸塩水和物；アンチモン酸；アンチモニル−Ｌ−酒石酸、酒石酸アンチモニルカリウム等の形で無電解ニッケル（合金）めっき浴中に添加することができ、これらは一種を単独で又は二種以上を組み合わせて用いることができる。 On the other hand, the form of antimony in the plating bath is not particularly limited, but it is preferably in the form of antimonate ions or antimony ions. This antimony includes, for example, antimonic acid salts such as sodium antimonate, potassium antimonate, and ammonium antimonate; their antimonate hydrates; antimonic acid; antimonyl-L-tartaric acid, and antimonyl potassium tartrate. (Alloy) It can be added to the plating bath, and these can be used alone or in combination of two or more.
アンチモンのめっき浴全体に対する含有量は特に限定はないが、アンチモン金属に換算して、０．１ｍｇ/Ｌ〜１ｇ/Ｌであることが好ましく、０．５ｍｇ/Ｌ〜２００ｍｇ/Ｌであることが特に好ましい。また、１ｍｇ/Ｌ〜１００ｍｇ/Ｌであることが更に好ましい。０．１ｍｇ/Ｌ未満だと自己分解する場合があり、１ｇ/Ｌより多い場合は、めっき外観不良や反応停止する場合がある。 The content of antimony with respect to the entire plating bath is not particularly limited, but in terms of antimony metal, it is preferably 0.1 mg / L to 1 g / L, and preferably 0.5 mg / L to 200 mg / L. Particularly preferred. Further, it is more preferably 1 mg / L to 100 mg / L. If it is less than 0.1 mg / L, it may self-decompose, and if it is more than 1 g / L, it may cause poor plating appearance or stop the reaction.
更に、モリブデンとアンチモンの配合比率は特に限定はないが、モリブデン１００重量部に対して、アンチモン０．５〜２０重量部が好ましい。特に好ましくは１〜１０重量部である。０．５重量部未満だと自己分解する場合があり、２０重量部より多い場合は、めっき外観不良や反応停止する場合がある。また、モリブデンとアンチモンの合計の、めっき浴全体に対する含有量は特に限定はないが、２５ｍｇ/Ｌ〜１ｇ/Ｌであることが好ましく、５０ｍｇ/Ｌ〜２００ｍｇ/Ｌであることが特に好ましい。 Further, the mixing ratio of molybdenum and antimony is not particularly limited, but 0.5 to 20 parts by weight of antimony is preferable with respect to 100 parts by weight of molybdenum. Particularly preferred is 1 to 10 parts by weight. If it is less than 0.5 part by weight, it may be self-decomposed. If it is more than 20 part by weight, the plating appearance may be poor or the reaction may be stopped. Further, the content of the total of molybdenum and antimony with respect to the entire plating bath is not particularly limited, but is preferably 25 mg / L to 1 g / L, and particularly preferably 50 mg / L to 200 mg / L.
本発明の無電解ニッケル（合金）めっき浴が、無電解ニッケル合金めっき浴である場合は、更に、合金化金属塩を含有させることが必要である。この合金化金属塩は、めっき皮膜の硬さ、磁性、延展性、電気抵抗、靭性等の物性を改善させるために添加されるものであり、特に限定されるものではないが、好ましい合金化金属としては、鉄、銅、スズ、コバルト、タングステン、レニウム、マンガン、パラジウム、バナジウム、亜鉛、クロム、金、銀、白金等が挙げられる。これら合金化金属塩は、一種を単独で又は二種以上を組み合わせて用いることができる。 When the electroless nickel (alloy) plating bath of the present invention is an electroless nickel alloy plating bath, it is necessary to further contain an alloying metal salt. This alloyed metal salt is added to improve physical properties such as hardness, magnetism, spreadability, electrical resistance, and toughness of the plating film, and is not particularly limited. Examples thereof include iron, copper, tin, cobalt, tungsten, rhenium, manganese, palladium, vanadium, zinc, chromium, gold, silver, platinum, and the like. These alloyed metal salts can be used singly or in combination of two or more.
上記合金化金属塩の無電解ニッケル合金めっき浴全体に対する含有量は、水溶性合金化金属塩として、０．１ｇ/Ｌ〜１００ｇ/Ｌであることが好ましく、１ｇ/Ｌ〜５０ｇ/Ｌであることが特に好ましい。 The content of the alloyed metal salt with respect to the entire electroless nickel alloy plating bath is preferably 0.1 g / L to 100 g / L as a water-soluble alloyed metal salt, and preferably 1 g / L to 50 g / L. It is particularly preferred.
本発明の無電解ニッケル（合金）めっき浴には、上記各必須成分の他、必要により、種々の成分を配合することができる。このうち、錯化剤として、種々の無機酸および有機酸が好ましく使用される。具体的には、これに限定されるものではないが、ホウ酸、ホウ砂等のホウ素化合物；酢酸、プロピオン酸、リンゴ酸、乳酸、コハク酸、マロン酸、アジピン酸、クエン酸、グルコン酸、グリコール酸等のモノカルボン酸化合物、ジカルボン酸化合物又はヒドロキシカルボン酸化合物；グリシン等のアミノ酸類等が挙げられる。これらは一種を単独で又は二種以上を組み合わせて用いることができる。 In the electroless nickel (alloy) plating bath of the present invention, various components can be blended as necessary in addition to the above-described essential components. Of these, various inorganic acids and organic acids are preferably used as complexing agents. Specifically, but not limited to, boron compounds such as boric acid and borax; acetic acid, propionic acid, malic acid, lactic acid, succinic acid, malonic acid, adipic acid, citric acid, gluconic acid, Examples thereof include monocarboxylic acid compounds such as glycolic acid, dicarboxylic acid compounds or hydroxycarboxylic acid compounds; amino acids such as glycine. These can be used individually by 1 type or in combination of 2 or more types.
前記錯化剤の含有量は、本発明の効果を損なわない範囲であれば特に限定はないが、無電解ニッケル（合金）めっき浴全体に対して、１ｇ/Ｌ〜１００ｇ/Ｌが好ましく、１０ｇ/Ｌ〜４０ｇ/Ｌが特に好ましい。１ｇ/Ｌ未満だと、自己分解をしたり、次亜リン酸塩を還元剤として用いた場合には亜リン酸ニッケルが生成する場合がある。また、１００ｇ/Ｌより多い場合は、未反応や充分な反応速度が得られない場合がある。 The content of the complexing agent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 1 g / L to 100 g / L with respect to the entire electroless nickel (alloy) plating bath. / L to 40 g / L is particularly preferable. If it is less than 1 g / L, it may undergo autolysis or nickel phosphite may be produced when hypophosphite is used as a reducing agent. Moreover, when more than 100 g / L, unreacted and sufficient reaction rate may not be obtained.
本発明の無電解ニッケル（合金）めっき浴には、更に、反応促進剤を含有させることができる。この反応促進剤としては、特に限定されるものではないが、有機硫黄化合物又は無機硫黄化合物が好ましく使用される。具体的には、チオ硫酸塩、チオン酸塩、ポリチオン酸塩、チオ尿素、チオシアン酸塩、チオスルホン酸塩、チオ炭酸塩、チオカルバミン酸塩、チオセミカルバジド、スルフィド、ジスルフィド、チオール、メルカプタン等又はこれらの誘導体等が挙げられ、これらは一種を単独で又は二種以上を組み合わせて用いることができる。 The electroless nickel (alloy) plating bath of the present invention may further contain a reaction accelerator. The reaction accelerator is not particularly limited, but an organic sulfur compound or an inorganic sulfur compound is preferably used. Specifically, thiosulfate, thionate, polythionate, thiourea, thiocyanate, thiosulfonate, thiocarbonate, thiocarbamate, thiosemicarbazide, sulfide, disulfide, thiol, mercaptan, etc. These can be used singly or in combination of two or more.
前記反応促進剤の含有量は、本発明の効果を損なわない範囲であれば特に限定はないが、無電解ニッケル（合金）めっき浴全体に対して、０．００１ｍｇ/Ｌ〜１０００ｍｇ/Ｌが好ましく、０．０１ｍｇ/Ｌ〜１００ｍｇ/Ｌが特に好ましい。０．００１ｍｇ/Ｌ未満だと反応促進効果が得られない場合があり、１０００ｍｇ/Ｌより多い場合は、めっき外観不良や反応停止する場合がある。 The content of the reaction accelerator is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.001 mg / L to 1000 mg / L with respect to the entire electroless nickel (alloy) plating bath. 0.01 mg / L to 100 mg / L is particularly preferable. When the amount is less than 0.001 mg / L, the reaction promoting effect may not be obtained. When the amount is more than 1000 mg / L, the plating appearance may be poor or the reaction may be stopped.
本発明の無電解ニッケル（合金）めっき浴には、更に、被膜物性改善剤を含有させることができる。被膜物性改善剤としては特に限定はないが、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、フッ化ピッチ等のフッ素樹脂若しくはフッ化化合物；ナイロン、ポリエチレン等の有機ポリマー；黒鉛、フッ化黒鉛、二硫化モリブデン、窒化ホウ素、炭化ケイ素、酸化チタン、ダイヤモンド等の無機物；カーボンナノチューブ等、一般に無電解複合めっき浴に用いられる水不溶性の微粒子や短繊維を、一種単独又は二種以上を組み合わせて用いることができる。 The electroless nickel (alloy) plating bath of the present invention may further contain a film property improving agent. Although there is no limitation in particular as a film physical property improving agent, Polytetrafluoroethylene (PTFE), Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), Fluorine resin or fluoride compound such as fluoride pitch; Nylon, polyethylene Organic polymers such as: graphite, fluorinated graphite, molybdenum disulfide, boron nitride, silicon carbide, titanium oxide, diamond and other inorganic materials; carbon nanotubes, etc., water-insoluble fine particles and short fibers generally used in electroless composite plating baths These can be used singly or in combination of two or more.
被膜物性改善剤の含有量は、本発明の効果を損なわない範囲であれば特に限定はないが、無電解ニッケル（合金）めっき浴全体に対して、０〜５００ｇ/Ｌが好ましく、１ｇ/Ｌ〜１０ｇ/Ｌが特に好ましい。５００ｇ/Ｌより多い場合は、めっき皮膜の良好な析出が得られず、また被膜物性改善剤の被膜中での均一な分散が得られない場合がある。 The content of the film physical property improving agent is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0 to 500 g / L with respect to the entire electroless nickel (alloy) plating bath, and 1 g / L. 10 g / L is particularly preferred. When the amount is more than 500 g / L, good deposition of the plating film cannot be obtained, and uniform dispersion of the film property improving agent in the film may not be obtained.
本発明の無電解ニッケル（合金）めっき浴には、水銀、ヒ素、カドミウム又は鉛を実質的に含有しないが、本発明は、環境や人体にほとんど影響を及ぼす可能性がなく、規制、ガイドライン等の対象とならない程度の極微量のそれら金属の含有を排除するものではない。 The electroless nickel (alloy) plating bath of the present invention does not substantially contain mercury, arsenic, cadmium or lead, but the present invention has little possibility of affecting the environment and the human body, and regulations, guidelines, etc. It does not exclude the inclusion of such trace amounts of metals that are not subject to the above.
以上のようにして得られる本発明の無電解ニッケル（合金）めっき浴の使用方法は、通常の無電解めっき浴の使用方法と同様であれば良く、特に限定はされないが、好ましい使用方法としては、以下のような条件の使用が挙げられる。 The method of using the electroless nickel (alloy) plating bath of the present invention obtained as described above is not particularly limited as long as it is the same as the method of using a normal electroless plating bath. The use of the following conditions is mentioned.
すなわち、本発明の無電解ニッケル（合金）めっき浴を建浴し、この中に脱脂、水洗、活性化等を行った被めっき物を浸漬すればよい。この無電解ニッケル（合金）めっき浴のｐＨは特に限定はないが、めっき時には、ｐＨ３〜１０とすることが好ましく、ｐＨ４〜９とすることが特に好ましい。無電解めっき浴のｐＨをこの範囲とすることにより、効率的な金属イオンの還元反応が進行し、無電解めっき皮膜の析出速度が良好となる効果が得られる。めっき浴のｐＨ調整には、塩酸、硫酸、スルファミン酸等の酸や、水酸化ナトリウム、水酸化アンモニウム等のアルカリを、好ましくは水で希釈して適宜添加することができる。 That is, the electroless nickel (alloy) plating bath of the present invention is constructed, and the object to be plated that has been degreased, washed with water, activated, etc. may be immersed therein. The pH of the electroless nickel (alloy) plating bath is not particularly limited, but is preferably 3 to 10, and particularly preferably 4 to 9 during plating. By setting the pH of the electroless plating bath to this range, an efficient reduction reaction of metal ions proceeds, and the effect of improving the deposition rate of the electroless plating film can be obtained. For adjusting the pH of the plating bath, an acid such as hydrochloric acid, sulfuric acid or sulfamic acid, or an alkali such as sodium hydroxide or ammonium hydroxide, preferably diluted with water, can be added as appropriate.
また、本発明の無電解ニッケル（合金）めっき浴のめっき時の浴の温度については、ニッケルイオンの還元反応が行なわれる温度であれば特に限定はないが、効率の良い還元反応を起こさせるために、１５〜９８℃が好ましく、２５〜９０℃が特に好ましい。 Further, the temperature of the bath during plating of the electroless nickel (alloy) plating bath of the present invention is not particularly limited as long as it is a temperature at which nickel ion reduction reaction is carried out, but in order to cause an efficient reduction reaction. 15-98 degreeC is preferable and 25-90 degreeC is especially preferable.
更に、本発明の無電解ニッケル（合金）めっき浴を用いて無電解ニッケル（合金）めっきを行なうにあたっては、めっきの進行により、金属イオンが還元剤によって金属に還元される結果、めっき液中の金属イオン濃度、還元剤濃度が低下し、またｐＨも低下することになる。従って、連続的に又は適当な時間ごとに、無電解ニッケル（合金）めっき浴中に、水溶性ニッケル塩、還元剤、錯化剤、モリブデン、アンチモン、ｐＨ調整剤等を補給して、それらの濃度をもとの濃度に戻すことが好ましい。連続的に又は適当な時間ごとに、めっき液中の金属イオン濃度、還元剤濃度やｐＨを測定し、その測定結果に応じて、それらを補給することも好ましい。 Furthermore, in performing electroless nickel (alloy) plating using the electroless nickel (alloy) plating bath of the present invention, as a result of the progress of plating, metal ions are reduced to metal by a reducing agent, The metal ion concentration and the reducing agent concentration are lowered, and the pH is also lowered. Therefore, water-soluble nickel salt, reducing agent, complexing agent, molybdenum, antimony, pH adjusting agent, etc. are replenished continuously or at appropriate times in an electroless nickel (alloy) plating bath. It is preferable to return the concentration to the original concentration. It is also preferable to measure the metal ion concentration, the reducing agent concentration and the pH in the plating solution continuously or at appropriate time intervals, and replenish them according to the measurement results.
次に、実施例を挙げて本発明を更に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited to these Examples.
実 施 例 １
［無電解ニッケルめっき浴の初期性能の評価］
下記組成で、安定化剤としてモリブデンおよびアンチモンを含む本発明無電解ニッケルめっき浴を常法に従って調製した。また、比較としてモリブデンまたはアンチモンの一方のみを含むもの、および鉛を含むものを用いた。なお、表１において、モリブデン、アンチモン、鉛の含有量は、金属としての含有量である。
Example 1
[Evaluation of initial performance of electroless nickel plating bath]
An electroless nickel plating bath of the present invention having the following composition and containing molybdenum and antimony as stabilizers was prepared according to a conventional method. For comparison, a material containing only one of molybdenum and antimony and a material containing lead were used. In Table 1, the contents of molybdenum, antimony, and lead are the contents as metals.
＜無電解ニッケルめっき浴組成＞
硫酸ニッケル七水和物 ２５ｇ／Ｌ
次亜リン酸ナトリウム一水和物 ２０ｇ／Ｌ
ＤＬ−リンゴ酸 ２５ｇ／Ｌ
乳酸 １０ｇ／Ｌ
酢酸 ５ｇ／Ｌ
安定化剤 表１に記載の量
界面活性剤 適宜
<Electroless nickel plating bath composition>
Nickel sulfate heptahydrate 25g / L
Sodium hypophosphite monohydrate 20g / L
DL-malic acid 25g / L
Lactic acid 10g / L
Acetic acid 5g / L
Stabilizer Amounts listed in Table 1 Surfactant as appropriate
被めっき試験片として、ＳＰＣＣ−ＳＢの鉄板（サイズ：０．３ｍｍ×５０ｍｍ×５０ｍｍ）を用い、上記各無電解ニッケルめっき浴１Ｌ中に、下記めっき条件のもとで浸漬し、無電解ニッケルめっきを行った。 An SPCC-SB iron plate (size: 0.3 mm x 50 mm x 50 mm) was used as the specimen to be plated, and immersed in each electroless nickel plating bath 1L under the following plating conditions, and electroless nickel plated Went.
＜めっき条件＞
めっき液のｐＨ ４．９
浴温 ９０℃
攪拌 空気攪拌
めっき時間 ２０分
<Plating conditions>
PH of plating solution 4.9
Bath temperature 90 ° C
Agitation Air agitation Plating time 20 minutes
得られた無電解ニッケルめっき皮膜について、下記の判定条件により、めっき皮膜外観を評価した。また、析出速度を測定し、めっき浴安定性を評価した。この結果を表２に示す。 About the obtained electroless nickel plating film | membrane, the plating film external appearance was evaluated on condition of the following. Further, the deposition rate was measured to evaluate the plating bath stability. The results are shown in Table 2.
＜めっき皮膜外観の評価方法＞
判 定 めっき皮膜外観
◎ ： 光沢のある均一な外観
○ ： 光沢の弱い均一な外観
△ ： 光沢がなく白っぽい外観
× ： 不均一で未析出部分のある外観
<Evaluation method of plating film appearance>
Judgment Appearance of plating film ◎: Uniform appearance with gloss ○: Uniform appearance with low gloss
△: Non-glossy and whitish appearance ×: Non-uniform appearance with undeposited parts
＜析出速度の評価方法＞
判 定 析出速度
◎ ： １５μｍ/ｈｒ以上
○ ： １５〜１２μｍ/ｈｒ
△ ： １２〜１０μｍ/ｈｒ
× ： １０μｍ/ｈｒ以下
<Evaluation method of precipitation rate>
Judgment Deposition rate ◎: 15 μm / hr or more ○: 15-12 μm / hr
Δ: 12 to 10 μm / hr
×: 10 μm / hr or less
＜めっき浴安定性の評価方法＞
めっき時のめっき槽底面の析出物を目視で確認した。
判 定 析出物目視確認
◎ ： 直径１ｍｍ以下の点状析出物が、析出なし
○ ： 直径１ｍｍ以下の点状析出物が、１個以上５個以下確認できた
△ ： 直径１ｍｍ以下の点状析出物が、６個以上２０個以下確認できた
× ： 直径１ｍｍ以下の点状析出物が、２１個以上確認できた
<Method for evaluating plating bath stability>
The deposit on the bottom of the plating tank during plating was visually confirmed.
Judgment Preliminary confirmation of precipitates ◎: No dotted precipitate with a diameter of 1 mm or less
○: 1 to 5 spot-like precipitates having a diameter of 1 mm or less were confirmed. Δ: 6 to 20 spot-like precipitates having a diameter of 1 mm or less were confirmed. More than 21 deposits were confirmed.
表２の結果より、モリブデン１００ｍｇ/Ｌ及びアンチモン５ｍｇ/Ｌを含有する本発明めっき浴（１）の場合、鉛を配合したのと同等以上の効果を示すことが確認された。更に、モリブデンは１０〜１００ｍｇ/Ｌの濃度で、上記評価項目については、極めて優れた効果を示すことが確認された。 From the results of Table 2, it was confirmed that in the case of the plating bath (1) of the present invention containing 100 mg / L of molybdenum and 5 mg / L of antimony, the effect is equal to or better than that of lead. Furthermore, it was confirmed that molybdenum has a concentration of 10 to 100 mg / L and exhibits extremely excellent effects for the above evaluation items.
実 施 例 ２
［無電解ニッケルめっき浴の連続使用試験］
表１及び表２の結果から、めっき被膜外観、析出速度、めっき浴安定性の全てで、鉛と同等以上の性能が確認された本発明めっき浴（１）、比較めっき浴（２）、比較めっき浴（３）及び比較めっき浴（７）について、連続使用試験を行なった。連続使用試験は、無電解ニッケルめっき浴を、１、２、３、４、５、６ターン連続使用して無電解めっきを行い、各ターン毎のめっき皮膜外観、めっき浴安定性を実施例１と同様の方法で評価を行なった。
Example 2
[Continuous use test of electroless nickel plating bath]
From the results of Tables 1 and 2, the plating bath of the present invention (1), comparative plating bath (2), and comparisons in which the performance equal to or higher than that of lead was confirmed in all aspects of plating film appearance, deposition rate, and plating bath stability. A continuous use test was performed on the plating bath (3) and the comparative plating bath (7). In the continuous use test, an electroless nickel plating bath was used continuously for 1, 2, 3, 4, 5, 6 turns, and electroless plating was performed. Evaluation was carried out in the same manner as above.
また、相対析出速度を以下の判定条件を用いて評価した。
＜相対析出速度＞
各ターン連続使用時の析出速度を、実施例１と同様の方法でそれぞれ測定し、この測定値を下記の判定基準を用いて、実施例１で得られた初期の析出速度に対する各ターン時の析出速度の低下割合を評価した。
判定 析出速度
◎ ： ０％〜１０％低下した
○ ： １０％〜２０％低下した
△ ： ２０％〜５０％低下した
× ： ５０％以上低下した
Moreover, the relative precipitation rate was evaluated using the following judgment conditions.
<Relative precipitation rate>
The deposition rate at the time of continuous use for each turn was measured by the same method as in Example 1, and the measured value was measured for each turn with respect to the initial deposition rate obtained in Example 1 using the following criteria. The reduction rate of the deposition rate was evaluated.
Judgment Precipitation rate ◎: Decreased by 0-10% ○: Decreased by 10-20% △: Decreased by 20-50% ×: Decreased by 50% or more
なおここで１ターン連続使用とは、無電解ニッケルめっき浴中の初期のニッケルイオン濃度に相当する量のニッケル金属がめっきされるまで連続してめっきを行うことをいう。例えば、無電解ニッケルめっき浴中の初期ニッケルイオン濃度が、Ｍ［ｇ／Ｌ］であるとした場合、Ｍ［ｇ／Ｌ］のニッケルがめっきにより析出した時点を１ターンとするものである。よって、この場合には、５ターン連続使用とは、５×Ｍ［ｇ／Ｌ］のニッケルめっきがなされるまで連続してめっきすることをいう。 Here, the one-turn continuous use means that plating is continuously performed until an amount of nickel metal corresponding to the initial nickel ion concentration in the electroless nickel plating bath is plated. For example, if the initial nickel ion concentration in the electroless nickel plating bath is M [g / L], the time when nickel of M [g / L] is deposited by plating is one turn. Therefore, in this case, continuous use of 5 turns means continuous plating until nickel plating of 5 × M [g / L] is performed.
比較めっき浴（２）は、連続使用試験開始後間もなく自己分解が発生したため、連続使用試験を中止した。比較めっき浴（３）も、２ターン経過後に自己分解が発生したため、連続使用試験を中止した。 Since the comparative plating bath (2) self-decomposed soon after the start of the continuous use test, the continuous use test was stopped. Since the comparative plating bath (3) also self-decomposed after 2 turns, the continuous use test was stopped.
実施例２で評価しためっき浴の中で、本発明めっき浴（１）が最も良好であった。すなわち、本発明めっき浴（１）は、６ターンまで良好に無電解ニッケルめっきを続けることができ、連続的に使用しても、めっき皮膜外観の低下や析出速度の低下が少なく、浴安定性にも優れたものであった。また、モリブデンだけでなく、アンチモンを併用することによって、連続使用試験の結果が著しく良好になった。 Among the plating baths evaluated in Example 2, the present plating bath (1) was the best. That is, the plating bath (1) of the present invention can continue electroless nickel plating well up to 6 turns, and even when continuously used, there is little decrease in the appearance of the plating film and decrease in the deposition rate, and the bath stability. It was also excellent. In addition, not only molybdenum but also antimony was used together, the results of the continuous use test were remarkably improved.
更に、本発明めっき浴（１）は、鉛使用の比較めっき浴（７）に比べても、ターン進行時におけるめっき皮膜外観に優れていた。また、析出速度の低下も少ないことが確認され、めっき浴安定性において、めっき浴中の析出物の生成も少なく、鉛と比較しても遜色のない性能であることが確認された。 Furthermore, the plating bath (1) of the present invention was excellent in the appearance of the plating film when the turn proceeded, as compared with the comparative plating bath (7) using lead. In addition, it was confirmed that the decrease in the deposition rate was small, and in the plating bath stability, the generation of precipitates in the plating bath was small, and it was confirmed that the performance was comparable to lead.
本発明によれば、有害物質である鉛等を実質的に含有させなくても、めっき被膜外観、析出速度、めっき浴安定性に優れた無電解ニッケル（合金）めっき浴を提供することができる。そして、この無電解ニッケル（合金）めっき浴は、その連続使用時においても上記優れた性能が低下しにくいので、めっき浴の更新が少なくてすみ、作業効率の向上ができる。 According to the present invention, an electroless nickel (alloy) plating bath excellent in plating film appearance, deposition rate, and plating bath stability can be provided without substantially containing harmful substances such as lead. . The electroless nickel (alloy) plating bath is less likely to deteriorate the excellent performance even during continuous use, so that the plating bath needs to be renewed and work efficiency can be improved.
従って、本発明の無電解ニッケル（合金）めっき浴は、抵抗体、磁気ディスク、電磁波シールド、金めっきの下地めっき、微粒子含有複合めっき皮膜の金属マトリックス等の用途に広範囲に好適に使用できるものである。
以 上
Therefore, the electroless nickel (alloy) plating bath of the present invention can be suitably used in a wide range of applications such as resistors, magnetic disks, electromagnetic wave shields, gold plating base plating, and fine metal-containing composite plating films. is there.
more than
Claims (12)
An electroless nickel plating method or an electroless nickel alloy plating method using the electroless nickel plating bath or electroless nickel alloy plating bath according to any one of claims 1 to 11.
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| CN101831643B (en) * | 2010-05-24 | 2012-09-19 | 深圳市华傲创表面技术有限公司 | Chemical nickel-plating stabilizer and chemical nickel plating solution |
| JP2012087386A (en) * | 2010-10-21 | 2012-05-10 | Toyota Motor Corp | Electroless nickel plating bath and electroless nickel plating method using the same |
| KR101447110B1 (en) | 2012-11-08 | 2014-10-08 | 한국생산기술연구원 | Lead-free and cadmium-free electroless plating solution, method of electroless plating using the same, and nickel plating layer using the same |
| JP2015163726A (en) * | 2014-02-28 | 2015-09-10 | 住友金属鉱山株式会社 | Method of producing nickel powder |
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