JP6909072B2 - Electroless nickel-phosphorus plating film and electroless nickel-phosphorus plating bath - Google Patents
Electroless nickel-phosphorus plating film and electroless nickel-phosphorus plating bath Download PDFInfo
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- JP6909072B2 JP6909072B2 JP2017123414A JP2017123414A JP6909072B2 JP 6909072 B2 JP6909072 B2 JP 6909072B2 JP 2017123414 A JP2017123414 A JP 2017123414A JP 2017123414 A JP2017123414 A JP 2017123414A JP 6909072 B2 JP6909072 B2 JP 6909072B2
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- Prior art keywords
- plating film
- plating
- electroless nickel
- phosphorus
- nickel
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- 238000007747 plating Methods 0.000 title claims description 174
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title claims description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052716 thallium Inorganic materials 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 8
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- XNMUCIILODALDI-UHFFFAOYSA-N nickel phosphoric acid Chemical compound [Ni].P(O)(O)(O)=O XNMUCIILODALDI-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 150000003464 sulfur compounds Chemical class 0.000 description 15
- 239000008139 complexing agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 238000000879 optical micrograph Methods 0.000 description 8
- 150000003475 thallium Chemical class 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 4
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 3
- 229940119523 thallium sulfate Drugs 0.000 description 3
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 2
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 2
- 229940103494 thiosalicylic acid Drugs 0.000 description 2
- GQGHFSJGSKEKJZ-UHFFFAOYSA-N 2-(dimethylamino)ethanethioamide Chemical compound CN(C)CC(N)=S GQGHFSJGSKEKJZ-UHFFFAOYSA-N 0.000 description 1
- UYRFJJJSEKLZRY-UHFFFAOYSA-N 4-pyridin-3-ylbutanimidamide Chemical compound NC(=N)CCCC1=CC=CN=C1 UYRFJJJSEKLZRY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
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- 239000000853 adhesive Substances 0.000 description 1
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- 235000004279 alanine Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
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- 235000009697 arginine Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids 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
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、無電解ニッケルめっき皮膜及び無電解ニッケル−リンめっき浴に関する。 The present invention relates to an electroless nickel plating film and an electroless nickel-phosphorus plating bath.
従来、電子部品分野において、フレキシブル基板やシリコンウェハ基板のAlやCuパターン上に無電解ニッケルめっき皮膜を形成することが行われている。 Conventionally, in the field of electronic components, an electroless nickel plating film has been formed on an Al or Cu pattern of a flexible substrate or a silicon wafer substrate.
無電解ニッケルめっき法は、電気めっき法と異なり、めっき液中に被めっき物を浸漬するだけで、被めっき物の表面に金属ニッケル皮膜を形成することができる方法であり、素材の形状や種類にかかわらず均一な厚みの皮膜が得られるため、複雑な形状や精密な部品のめっき加工処理に適している。この無電解ニッケルめっき皮膜としては、例えば、ニッケルイオンと、ニッケルイオンの還元剤としてリン化合物を含有する無電解ニッケル−リンめっき液に、被めっき物を浸漬することにより,当該被めっき物の表面上に形成された無電解ニッケル−リンめっき皮膜が開示されている(例えば、特許文献1参照)。 Unlike the electroplating method, the electroless nickel plating method is a method that can form a metallic nickel film on the surface of the object to be plated simply by immersing the object to be plated in the plating solution, and the shape and type of the material. Regardless of this, a film with a uniform thickness can be obtained, making it suitable for plating complex shapes and precision parts. The electroless nickel plating film is obtained by immersing the object to be plated in, for example, an electroless nickel-phosphorus plating solution containing nickel ions and a phosphorus compound as a reducing agent for nickel ions. The electroless nickel-phosphorus plating film formed above is disclosed (see, for example, Patent Document 1).
ここで、近年、上述の無電解ニッケル−リンめっき皮膜は、車載部品等に数多く用いられており、ニッケルめっき加工後に、様々な形状に折り曲げ加工されている。従って、折り曲げ加工等に対してクラックが発生ないような耐折性に優れた無電解ニッケル−リンめっき皮膜が求められている。 Here, in recent years, the above-mentioned electroless nickel-phosphorus plating film has been widely used for in-vehicle parts and the like, and is bent into various shapes after the nickel plating process. Therefore, there is a demand for an electroless nickel-phosphorus plating film having excellent folding resistance so that cracks do not occur during bending or the like.
しかし、上記従来の無電解ニッケル−リンめっき皮膜は、電気ニッケルめっき皮膜に比し、耐折性がかなり劣っているため、折り曲げ加工される部品への適用が困難であるという問題があった。 However, since the conventional electroless nickel-phosphorus plating film is considerably inferior in folding resistance to the electronickel plating film, there is a problem that it is difficult to apply it to a part to be bent.
また、従来、折り曲げ加工に対してクラックが発生しにくく、耐折性が良好な電気ニッケルめっき処理が行われているが、例えば、パイプ部品等では、その内部においてもめっき処理を行う必要があるため、生産性が低下するとともに、生産コストが増大するという問題があった。 Further, conventionally, an electronickel plating process is performed in which cracks are less likely to occur in the bending process and the folding resistance is good. However, for example, in a pipe part or the like, it is necessary to perform a plating process inside the pipe parts or the like. Therefore, there is a problem that the productivity is lowered and the production cost is increased.
そこで、本発明は、上述の問題に鑑み、電気ニッケルめっき皮膜と同等の耐折性を有する無電解ニッケル−リンめっき皮膜を提供することを目的とする。 Therefore, in view of the above problems, an object of the present invention is to provide an electroless nickel-phosphorus plating film having the same folding resistance as an electronickel plating film.
上記目的を達成するために、本発明に係る無電解ニッケル−リンめっき皮膜は、被めっき物上に形成された無電解ニッケル−リンめっき皮膜であって、リンの含有量が0.1〜4.0質量%であり、タリウムと硫黄とを含有することを特徴とする。 In order to achieve the above object, the electroless nickel-phosphorus plating film according to the present invention is an electroless nickel-phosphorus plating film formed on an object to be plated, and has a phosphorus content of 0.1 to 4. It is 0.0% by mass and is characterized by containing tarium and sulfur.
本発明によれば、電気ニッケルめっき皮膜と同等の耐折性を有する無電解ニッケル−リンめっき皮膜を提供することができる。 According to the present invention, it is possible to provide an electroless nickel-phosphorus plating film having a folding resistance equivalent to that of an electronickel plating film.
以下、本実施形態における無電解ニッケル−リンめっき皮膜及び無電解ニッケル−リンめっき浴について説明する。 Hereinafter, the electroless nickel-phosphorus plating film and the electroless nickel-phosphorus plating bath in the present embodiment will be described.
<無電解ニッケル−リンめっき皮膜>
本実施形態の無電解ニッケル−リンめっき皮膜(以下、単に「めっき皮膜」という場合がある。)は、被めっき物上に形成された無電解ニッケル−リンめっき皮膜である。本実施形態のめっき皮膜が形成される被めっき物としては、特に限定されないが、例えば、鉄やアルミニウム、亜鉛等の金属または金属の合金が挙げられ、特に、めっき処理後にプレス加工(特に、絞り加工や曲げ加工)により所望の形状に成型される板材、管材、棒材等料が挙げられる。
<Electroless nickel-phosphorus plating film>
The electroless nickel-phosphorus plating film of the present embodiment (hereinafter, may be simply referred to as “plating film”) is an electroless nickel-phosphorus plating film formed on an object to be plated. The object to be plated on which the plating film of the present embodiment is formed is not particularly limited, and examples thereof include metals such as iron, aluminum, and zinc, or alloys of metals, and in particular, press working (particularly, drawing) after the plating treatment. Examples thereof include plate materials, pipe materials, bar materials, etc. that are molded into a desired shape by processing (processing or bending).
また、本発明の無電解ニッケル−リンめっき皮膜においては、リンの含有量が0.1〜4.0質量%であり、1.0〜2.0質量%が特に好ましい。リンの含有量を0.1〜4.0質量%とすることにより、無電解ニッケル−リンめっき皮膜が結晶質構造となるため、めっき皮膜の耐折性が向上する。 Further, in the electroless nickel-phosphorus plating film of the present invention, the phosphorus content is 0.1 to 4.0% by mass, and 1.0 to 2.0% by mass is particularly preferable. By setting the phosphorus content to 0.1 to 4.0% by mass, the electroless nickel-phosphorus plating film has a crystalline structure, so that the folding resistance of the plating film is improved.
また、本発明の無電解ニッケル−リンめっき皮膜は硫黄を含有しており、皮膜中に硫黄を配合することにより、めっき皮膜の伸び率が向上(即ち、皮膜の柔軟性が向上)するため、めっき皮膜が折り曲げに対して追随できるようになる。その結果、無電解ニッケル−リンめっき皮膜の耐折性が向上することになる。 Further, the electroless nickel-phosphorus plating film of the present invention contains sulfur, and by blending sulfur in the film, the elongation rate of the plating film is improved (that is, the flexibility of the film is improved). The plating film can follow the bending. As a result, the folding resistance of the electroless nickel-phosphorus plating film is improved.
また、無電解ニッケル−リンめっき皮膜における硫黄の含有率は0.01〜0.3質量%が好ましく、特に、0.05〜0.2質量%の場合、上述のめっき皮膜の伸び率がより一層向上するため、好ましい。 The sulfur content in the electroless nickel-phosphorus plating film is preferably 0.01 to 0.3% by mass, and particularly in the case of 0.05 to 0.2% by mass, the elongation rate of the above-mentioned plating film is higher. It is preferable because it is further improved.
また、本発明の無電解ニッケル−リンめっき皮膜はタリウムを含有しており、皮膜中にタリウムを配合することにより、ニッケル−リンの結晶粒界にタリウムが取り込まれ、当該結晶粒界において、タリウムが、粒界間を接着する接着剤的な役割を果たすことになる。従って、ニッケル−リンの結晶粒界におけるクラックの発生が抑制されるため、無電解ニッケル−リンめっき皮膜の耐折性が向上する。 Further, the electroless nickel-phosphorus plating film of the present invention contains thallium, and by blending thallium in the film, thallium is incorporated into the grain boundaries of nickel-phosphorus, and thallium is incorporated at the grain boundaries. However, it plays a role as an adhesive that adheres between grain boundaries. Therefore, the generation of cracks at the grain boundaries of nickel-phosphorus is suppressed, and the folding resistance of the electroless nickel-phosphorus plating film is improved.
また、無電解ニッケル−リンめっき皮膜におけるタリウムの含有量は0.1〜5.0質量%が好ましく、特に、1.0〜3.0質量%の場合、上述のニッケル−リンの結晶粒界におけるクラックの発生がより一層抑制されるため、好ましい。 The content of tallium in the electroless nickel-phosphorus plating film is preferably 0.1 to 5.0% by mass, and particularly when it is 1.0 to 3.0% by mass, the above-mentioned nickel-phosphorus crystal grain boundaries. It is preferable because the occurrence of cracks in the above is further suppressed.
以上のように、本実施形態の無電解ニッケル−リンめっき皮膜においては、リンの含有量が0.1〜4.0質量%であり、かつ、タリウムと硫黄とを含有しているため、無電解ニッケル−リンめっき皮膜において、タリウムと硫黄が共析し、結果として、電気ニッケルめっき皮膜と同等の優れた耐折性を実現することが可能になる。 As described above, in the electroless nickel-phosphorus plating film of the present embodiment, the phosphorus content is 0.1 to 4.0% by mass, and talium and sulfur are contained, so that there is no phosphorus. In the electrolytic nickel-phosphorus plating film, tallium and sulfur are co-deposited, and as a result, it becomes possible to realize excellent folding resistance equivalent to that of the electroless nickel plating film.
また、耐折性に優れためっき皮膜を形成する際に、電解めっき法を使用する場合に比し、生産性を向上させることができるとともに、生産コストを抑制することが可能になる。 Further, when forming a plating film having excellent folding resistance, productivity can be improved and production cost can be suppressed as compared with the case where an electrolytic plating method is used.
なお、ここで言う「耐折性」とは、めっき皮膜に対してプレス加工(特に、絞り加工、曲げ加工)を行う場合に、めっき皮膜におけるヒビや割れ(即ち、クラック)の発生が抑制される特性のことをいう。 The term "folding resistance" as used herein means that the occurrence of cracks and cracks (that is, cracks) in the plating film is suppressed when the plating film is pressed (particularly drawing and bending). Refers to the characteristics of
なお、めっき皮膜の厚みは、1〜10μmが好ましく、3〜7μmが、特に好ましい。これは、めっき皮膜が薄すぎると、耐食性の低下等、めっき本来の機能を発揮できない場合があり、めっき皮膜が厚すぎると、クラック等が発生しやすくなるためである。 The thickness of the plating film is preferably 1 to 10 μm, particularly preferably 3 to 7 μm. This is because if the plating film is too thin, the original functions of plating such as deterioration of corrosion resistance may not be exhibited, and if the plating film is too thick, cracks and the like are likely to occur.
<無電解ニッケル−リンめっき浴>
本実施形態の無電解ニッケル−リンめっき皮膜は、水溶性ニッケル塩と、還元剤である次亜リン酸塩と、硫黄含有化合物と、タリウム塩と、錯化剤とを含有する無電解ニッケル−リンめっき浴(以下、単に「めっき浴」という場合がある。)を用いてめっき処理を行うことにより、被めっき物上に形成することができる。
<Electroless nickel-phosphorus plating bath>
The electroless nickel-phosphorus plating film of the present embodiment is an electroless nickel containing a water-soluble nickel salt, a hypophosphate which is a reducing agent, a sulfur-containing compound, a tarium salt, and a complexing agent. It can be formed on an object to be plated by performing a plating treatment using a phosphorus plating bath (hereinafter, may be simply referred to as a "plating bath").
(水溶性ニッケル塩)
水溶性ニッケル塩としては、めっき浴に可溶性で、所定の濃度の水溶液が得られるものであれば、特に限定されない。例えば、硫酸ニッケル、塩化ニッケル、次亜リン酸ニッケル等の無機の水溶性ニッケル塩、及び酢酸ニッケル、リンゴ酸ニッケル等の有機の水溶性ニッケル塩等を用いることができる。なお、これらの水溶性ニッケル塩は単独で、あるいは2種以上を混合して用いることができる。
(Water-soluble nickel salt)
The water-soluble nickel salt is not particularly limited as long as it is soluble in a plating bath and an aqueous solution having a predetermined concentration can be obtained. For example, inorganic water-soluble nickel salts such as nickel sulfate, nickel chloride and nickel hypophosphate, and organic water-soluble nickel salts such as nickel acetate and nickel malate can be used. These water-soluble nickel salts can be used alone or in combination of two or more.
また、めっき浴中のニッケルイオンの濃度は、例えば、金属ニッケルとして3〜7g/Lが好ましく、より好ましくは4〜6g/Lである。ニッケル濃度が低過ぎると、めっき速度が遅くなる場合があるため、好ましくない。また、ニッケル濃度が高過ぎると、めっき浴において白濁が生じる場合や、めっき浴の粘度が高くなる場合があるため、均一析出性が低下し、形成後のめっき皮膜にピットが生じる場合があるため、好ましくない。 The concentration of nickel ions in the plating bath is, for example, preferably 3 to 7 g / L as metallic nickel, and more preferably 4 to 6 g / L. If the nickel concentration is too low, the plating rate may slow down, which is not preferable. Further, if the nickel concentration is too high, white turbidity may occur in the plating bath or the viscosity of the plating bath may increase, so that the uniform precipitation property may decrease and pits may occur in the plating film after formation. , Not preferable.
(次亜リン酸塩)
還元剤としての次亜リン酸塩としては、例えば、次亜リン酸ナトリウム(次亜リン酸ソーダ)や次亜リン酸カリウム等が挙げられる。
(Hypophosphate)
Examples of the hypophosphite as a reducing agent include sodium hypophosphite (sodium hypophosphate) and potassium hypophosphite.
また、めっき浴における還元剤の濃度は、使用する錯化剤の種類により異なるが、例えば10〜30g/Lが好ましく、より好ましくは15〜25g/Lである。還元剤の濃度が低過ぎると、めっき速度が遅くなる場合があるため、好ましくない。また、還元剤の濃度が高過ぎると、皮膜におけるリンの含有率が上述の4質量%よりも多くなることに起因して非昌質構造となる場合があり、また、浴安定性も低下するため、めっき液が分解する場合があり、好ましくない。 The concentration of the reducing agent in the plating bath varies depending on the type of complexing agent used, but is preferably 10 to 30 g / L, more preferably 15 to 25 g / L, for example. If the concentration of the reducing agent is too low, the plating rate may slow down, which is not preferable. In addition, if the concentration of the reducing agent is too high, the phosphorus content in the film may be higher than the above-mentioned 4% by mass, resulting in a non-changing structure, and the bath stability is also lowered. Therefore, the plating solution may decompose, which is not preferable.
なお、還元剤として、次亜リン酸塩を使用することにより、少なくとも0.1質量%以上のリンが共析する。 By using hypophosphate as a reducing agent, at least 0.1% by mass or more of phosphorus is co-deposited.
(硫黄含有化合物)
硫黄含有化合物としては、無電解ニッケルめっき浴に使用する一般的なものであれば、特に限定されない。例えば、−SH(メルカプト基)、−COSH(チオカルボキシル基)、>C=S(チオケトン基)、−S−(スルフィド)、−S−S−(ジスルフィド)、−SCN(チオシアネート基)、−CSNH2(チオアミド基)やこれら誘導体からなる1種または2種以上の硫黄化合物が挙げられる。具体的には、チオ尿素、グルタチオン、チオ酢酸、チオリンゴ酸、3,3-ジチオジプロピオン酸、システイン、チオアセトアミド、ジメチルアミノチオアセトアミド、チオバルビツール酸、メチオニン、チオサリチル酸、2-メルカプト-1-イミダゾール、チオジグリコール酸、チオシアン酸ナトリウム、チオシアン酸カリウム、エチレンチオ尿素、1-アセチル-2-チオ尿素、メチルエチルスルフィド、メチルフェニルスルフィド、ジメチルスルフィド、ジメチルジスルフィド、ジフェニルジスルフィド、メルカプトエタノール、チオ硫酸ナトリウム、チオ硫酸カリウム及びシスタミン等を用いることができる。
(Sulfur-containing compound)
The sulfur-containing compound is not particularly limited as long as it is a general compound used in an electroless nickel plating bath. For example, -SH (mercapto group), -COSH (thiocarboxyl group),> C = S (thioketone group), -S- (sulfide), -S-S- (disulfide), -SCN (thiocyanate group),- Examples thereof include one or more sulfur compounds composed of CSNH 2 (thioamide group) and derivatives thereof. Specifically, thiourea, glutathione, thioacetic acid, thioannic acid, 3,3-dithiodipropionic acid, cysteine, thioacetamide, dimethylaminothioacetamide, thiobarbituric acid, methionine, thiosalicylic acid, 2-mercapto-1. -Imidazole, thiodiglycolic acid, sodium thiocyanate, potassium thiocyanate, ethylene thiourea, 1-acetyl-2-thiourea, methyl ethyl sulfide, methyl phenyl sulfide, dimethyl sulfide, dimethyl disulfide, diphenyl disulfide, mercaptoethanol, thiosulfate Sodium, potassium thiosulfate, cystamine and the like can be used.
また、めっき浴における硫黄含有化合物の濃度は、0.1〜1000mg/Lが好ましく、より好ましくは10〜100mg/Lである。硫黄含有化合物の濃度が高すぎると、めっき反応が停止する場合があるため、好ましくない。従って、上述のごとく、皮膜中には、硫黄を0.3質量%までしか含有させることができない。また、硫黄含有化合物の濃度が低すぎると、上述のめっき皮膜の伸び率が低下し、十分な耐折性を得られない場合があるため、好ましくない。 The concentration of the sulfur-containing compound in the plating bath is preferably 0.1 to 1000 mg / L, more preferably 10 to 100 mg / L. If the concentration of the sulfur-containing compound is too high, the plating reaction may stop, which is not preferable. Therefore, as described above, the film can contain only up to 0.3% by mass of sulfur. Further, if the concentration of the sulfur-containing compound is too low, the elongation rate of the above-mentioned plating film is lowered, and sufficient folding resistance may not be obtained, which is not preferable.
(タリウム塩)
タリウム塩としては、例えば、硫酸タリウムや硝酸タリウム等が挙げられを用いることができる。
(Thallium salt)
Examples of the thallium salt include thallium sulfate and thallium nitrate.
また、めっき浴におけるタリウム塩の濃度は、1〜1000mg/Lが好ましく、より好ましくは、10〜100mg/Lである。タリウム塩の濃度が高すぎると、めっき反応が停止する場合があるため、好ましくない。従って、上述のごとく、皮膜中には、タリウムを5.0質量%までしか含有させることができない。また、タリウム塩の濃度が低すぎると、上述の結晶粒界におけるクラックの抑制効果が低下し、十分な耐折性を得られない場合があるため、好ましくない。 The concentration of the thallium salt in the plating bath is preferably 1 to 1000 mg / L, more preferably 10 to 100 mg / L. If the concentration of thallium salt is too high, the plating reaction may stop, which is not preferable. Therefore, as described above, the film can contain only up to 5.0% by mass of thallium. Further, if the concentration of the thallium salt is too low, the effect of suppressing cracks at the above-mentioned grain boundaries is lowered, and sufficient folding resistance may not be obtained, which is not preferable.
(錯化剤)
錯化剤としては、公知の無電解ニッケルめっき浴において用いられている各種の錯化剤を用いることができる。錯化剤の具体例としては、グリシン、アラニン、アルギニン、アスパラギン酸、グルタミン酸等のアミノ酸、乳酸、プロピオン酸、グリコール酸、グルコン酸等のモノカルボン酸、酒石酸、シュウ酸、コハク酸、リンゴ酸等のジカルボン酸、クエン酸等のトリカルボン酸などが挙げられる。また、これらの塩、例えば、ナトリウム塩、カリウム塩等も錯化剤として使用可能である。なお、これらの錯化剤は、単独で、または2種以上混合して用いることができる。
(Coordinating agent)
As the complexing agent, various complexing agents used in known electroless nickel plating baths can be used. Specific examples of the complexing agent include amino acids such as glycine, alanine, arginine, aspartic acid and glutamic acid, monocarboxylic acids such as lactic acid, propionic acid, glycolic acid and gluconic acid, tartrate acid, oxalic acid, succinic acid and malic acid. Dicarboxylic acid, tricarboxylic acid such as citric acid and the like can be mentioned. Further, these salts such as sodium salt and potassium salt can also be used as a complexing agent. These complexing agents can be used alone or in combination of two or more.
また、めっき浴における錯化剤の濃度は、使用する錯化剤の種類により異なるが、10〜200g/Lが好ましく、より好ましくは30〜100g/Lである。錯化剤濃度が低すぎると、水酸化ニッケルの沈殿が生じやすくなるため好ましくない。また、錯化剤濃度が高すぎると、めっき液の粘度が高くなるため、均一析出性の低下が生じる場合があるため、好ましくない。 The concentration of the complexing agent in the plating bath varies depending on the type of complexing agent used, but is preferably 10 to 200 g / L, more preferably 30 to 100 g / L. If the concentration of the complexing agent is too low, nickel hydroxide is likely to precipitate, which is not preferable. Further, if the concentration of the complexing agent is too high, the viscosity of the plating solution becomes high, which may cause a decrease in uniform precipitation, which is not preferable.
(pH)
また、十分な耐折性を有する良好なめっき皮膜を得るとの観点から、本実施形態のめっき浴のpHは5.0〜8.0であることが好ましい。なお、pHは、アンモニア水、水酸化ナトリウム(苛性ソーダ)等のアルカリ、硫酸、塩酸、硝酸等の酸で調整可能である。
(PH)
Further, from the viewpoint of obtaining a good plating film having sufficient folding resistance, the pH of the plating bath of the present embodiment is preferably 5.0 to 8.0. The pH can be adjusted with aqueous ammonia, alkalis such as sodium hydroxide (caustic soda), and acids such as sulfuric acid, hydrochloric acid, and nitric acid.
(めっき浴の温度)
また、使用するめっき浴の温度は、70〜95℃が好ましく、80〜90℃が、特に好ましい。めっき浴の温度が高すぎると、めっき液自体が熱分解する場合があり、また、めっき浴の温度が低すぎると、めっき反応が低下する場合があるため、好ましくない。なお、めっき処理時間は、形成するめっき皮膜の膜厚によって適宜、変更可能であるが、10〜60分が一般的である。
(Plating bath temperature)
The temperature of the plating bath used is preferably 70 to 95 ° C, particularly preferably 80 to 90 ° C. If the temperature of the plating bath is too high, the plating solution itself may be thermally decomposed, and if the temperature of the plating bath is too low, the plating reaction may be lowered, which is not preferable. The plating treatment time can be appropriately changed depending on the film thickness of the plating film to be formed, but is generally 10 to 60 minutes.
以下、実施例及び比較例に基づき本出願に係る発明をさらに具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 Hereinafter, the invention according to the present application will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
(実施例1)
(めっき浴の調製)
水溶性ニッケル塩である硫酸ニッケルと、還元剤である次亜リン酸ナトリウム、硫黄化合物であるチオ尿素、タリウム塩である炭酸タリウムと、錯化剤であるグリシン及び乳酸と、pH調製剤である苛性ソーダとを、表1に示す濃度となるように混合して攪拌することにより、本実施例のめっき浴を調製した。なお、めっき浴の温度を80℃、pHを7.0に設定した。
(Example 1)
(Preparation of plating bath)
Nickel sulfate, which is a water-soluble nickel salt, sodium hypophosphate, which is a reducing agent, thiourea, which is a sulfur compound, talium carbonate, which is a tarium salt, glycine and lactic acid, which are complex agents, and a pH adjuster. The plating bath of this example was prepared by mixing and stirring caustic soda to the concentrations shown in Table 1. The temperature of the plating bath was set to 80 ° C. and the pH was set to 7.0.
(めっき処理)
次に、調製しためっき浴に、被めっき物であるSPCC−SB板(サイズ:50mm×50mm、厚み:0.4mm)を25分間、浸漬し、被めっき物上に5μmの厚みを有する無電解ニッケル−リンめっき皮膜を形成した。
(Plating process)
Next, the SPCC-SB plate (size: 50 mm × 50 mm, thickness: 0.4 mm) to be plated is immersed in the prepared plating bath for 25 minutes, and electroless electroless having a thickness of 5 μm is placed on the object to be plated. A nickel-phosphorus plating film was formed.
(めっき皮膜の組成分析)
次に、形成しためっき皮膜の組成を分析した。より具体的には、めっき析出した無電解ニッケルーリンめっき皮膜を硝酸に溶解させ、この溶解液をICP(HORIBA製、商品名:Ultima Expert)にてリン、硫黄、及びタリウムの定量分析を行い、溶解しためっき皮膜の重量から、皮膜中の各成分の重量%を算出した。以上の結果を表3に示す。
(Composition analysis of plating film)
Next, the composition of the formed plating film was analyzed. More specifically, the electroless nickel-phosphorus plating film deposited by plating is dissolved in nitrate, and this solution is quantitatively analyzed for phosphorus, sulfur, and tarium by ICP (manufactured by HORIBA, trade name: Ultima Expert). From the weight of the dissolved plating film, the weight% of each component in the film was calculated. The above results are shown in Table 3.
(耐折性評価)
次に、JIS Z2247:2006に準拠して、エリクセン試験機を用いて、SPCC−SB板のめっき皮膜側の面から、試験速度60mm/分、押し込み深さ5mmの条件下で押し込み加工を行った後、SPCC−SB板のめっき皮膜側の面を光学顕微鏡(Lasertec製、商品名:OPTELICS C130)にて観察し、以下の基準で、めっき皮膜の耐折性を評価した。以上の結果を表3に示す。
(Fold resistance evaluation)
Next, in accordance with JIS Z2247: 2006, a pressing process was performed from the surface of the SPCC-SB plate on the plating film side using an Ericssen testing machine under the conditions of a test speed of 60 mm / min and a pressing depth of 5 mm. After that, the surface of the SPCC-SB plate on the plating film side was observed with an optical microscope (Lasertec, trade name: OPTELICS C130), and the folding resistance of the plating film was evaluated according to the following criteria. The above results are shown in Table 3.
◎:めっき皮膜にヒビや割れが認められない(クラックが発生していない)
○:めっき皮膜にヒビや割れが僅かに認められる(クラックが殆ど発生していない)
△:めっき皮膜にヒビや割れが少し認められる(クラックが少し発生している)
×:めっき皮膜にヒビや割れが多数認められる(クラックが、多数、発生している)
⊚: No cracks or cracks are found in the plating film (no cracks have occurred)
◯: Slight cracks and cracks are observed in the plating film (almost no cracks occur)
Δ: Some cracks and cracks are observed in the plating film (some cracks are generated).
X: Many cracks and cracks are observed in the plating film (many cracks are generated)
また、上述の、めっき皮膜が形成されたSPCC−SB板を手動により、180度、折り曲げた後、その折り曲げ部分を光学顕微鏡にて観察し、上述のエリクセン試験と同様の基準により、めっき皮膜の耐折性を評価した。以上の結果を表3に示す。 Further, after manually bending the SPCC-SB plate on which the plating film is formed 180 degrees, the bent portion is observed with an optical microscope, and the plating film is formed according to the same criteria as in the Eriksen test described above. The folding resistance was evaluated. The above results are shown in Table 3.
なお、実施例1のめっき皮膜における折り曲げ部分の光学顕微鏡写真を図1に示す。 An optical micrograph of a bent portion of the plating film of Example 1 is shown in FIG.
(実施例2)
表1に示すように、硫黄化合物として、チオ尿素の代わりに3,3-ジチオジプロピオン酸を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 2)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that 3,3-dithiodipropionic acid was used instead of thiourea as the sulfur compound. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例3)
表1に示すように、タリウム塩として、炭酸タリウムの代わりに硫酸タリウムを使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 3)
As shown in Table 1, the plating bath was prepared in the same manner as in Example 1 except that thallium sulfate was used instead of thallium carbonate as the thallium salt. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例4)
表1に示すように、硫黄化合物として、チオ尿素の代わりに3,3-ジチオジプロピオン酸を使用するとともに、タリウム塩として、炭酸タリウムの代わりに硫酸タリウムを使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 4)
As shown in Table 1, Example 1 except that 3,3-dithiodipropionic acid was used instead of thiourea as the sulfur compound and thallium sulfate was used instead of thallium carbonate as the thallium salt. The plating bath was prepared in the same manner as in the above. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例5)
表1に示すように、硫黄化合物として、チオ尿素の代わりにL-システインを使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。なお、実施例5のめっき皮膜における折り曲げ部分の光学顕微鏡写真を図2に示す。
(Example 5)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that L-cysteine was used as the sulfur compound instead of thiourea. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3. An optical micrograph of a bent portion of the plating film of Example 5 is shown in FIG.
(実施例6)
表1に示すように、硫黄化合物として、チオ尿素の代わりに2−チオバルビツール酸を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 6)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that 2-thiobarbituric acid was used instead of thiourea as the sulfur compound. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例7)
表1に示すように、硫黄化合物として、チオ尿素の代わりにチオサリチル酸を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 7)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that thiosalicylic acid was used instead of thiourea as the sulfur compound. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例8)
表1に示すように、硫黄化合物として、チオ尿素の代わりにチオジグリコール酸を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 8)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that thiodiglycolic acid was used instead of thiourea as the sulfur compound. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例9)
表1に示すように、硫黄化合物として、チオ尿素の代わりにチオシアン酸ナトリウムを使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 9)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that sodium thiocyanate was used as the sulfur compound instead of thiourea. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例10)
表1に示すように、硫黄化合物として、チオ尿素の代わりに1−アセチル−2−チオ尿素を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 10)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that 1-acetyl-2-thiourea was used as the sulfur compound instead of thiourea. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例11)
表1に示すように、硫黄化合物として、チオ尿素の代わりにシスタミン硫酸塩を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 11)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that cystamine sulfate was used as the sulfur compound instead of thiourea. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(実施例12)
表1に示すように、硫黄化合物として、チオ尿素の代わりにエチレンチオ尿素を使用したこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表3に示す。
(Example 12)
As shown in Table 1, a plating bath was prepared in the same manner as in Example 1 except that ethylene thiourea was used instead of thiourea as the sulfur compound. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 3.
(比較例1)
表2に示すように、硫黄化合物であるチオ尿素、及びタリウム塩である炭酸タリウムを使用しなかったこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表4に示す。
(Comparative Example 1)
As shown in Table 2, a plating bath was prepared in the same manner as in Example 1 except that thiourea, which is a sulfur compound, and thallium carbonate, which is a thallium salt, were not used. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 4.
なお、比較例1のめっき皮膜における折り曲げ部分の光学顕微鏡写真を図3に示す。 An optical micrograph of the bent portion of the plating film of Comparative Example 1 is shown in FIG.
(比較例2)
表2に示すように、硫黄化合物であるチオ尿素を使用しなかったこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表4に示す。
(Comparative Example 2)
As shown in Table 2, a plating bath was prepared in the same manner as in Example 1 except that thiourea, which is a sulfur compound, was not used. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 4.
(比較例3)
表2に示すように、タリウム塩である炭酸タリウムを使用しなかったこと以外は、実施例1と同様にしてめっき浴の調製を行った。その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表4に示す。
(Comparative Example 3)
As shown in Table 2, the plating bath was prepared in the same manner as in Example 1 except that thallium carbonate, which is a thallium salt, was not used. Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 4.
(比較例4)
水溶性ニッケル塩である硫酸ニッケルと、還元剤である次亜リン酸ナトリウム、硫黄化合物であるチオ尿素、タリウム塩である炭酸タリウムと、錯化剤であるリンゴ酸及び乳酸とを、表2に示す濃度となるように混合して攪拌することにより、本比較例のめっき浴を調製した。なお、めっき浴の温度を80℃、pHを5.3に設定した。
(Comparative Example 4)
Table 2 shows nickel sulfate, which is a water-soluble nickel salt, sodium hypophosphite, which is a reducing agent, thiourea, which is a sulfur compound, talium carbonate, which is a tarium salt, and malic acid and lactic acid, which are complexing agents. The plating bath of this comparative example was prepared by mixing and stirring to obtain the indicated concentrations. The temperature of the plating bath was set to 80 ° C. and the pH was set to 5.3.
その後、実施例1と同様にして、めっき処理、めっき皮膜の組成分析、及び耐折性評価を行った。以上の結果を表4に示す。 Then, in the same manner as in Example 1, the plating treatment, the composition analysis of the plating film, and the folding resistance evaluation were performed. The above results are shown in Table 4.
なお、比較例4のめっき皮膜における折り曲げ部分の光学顕微鏡写真を図4に示す。 An optical micrograph of the bent portion of the plating film of Comparative Example 4 is shown in FIG.
表3、表4に示すように、リンの含有量が0.1〜4.0質量%であり、タリウムと硫黄とを含有する実施例1〜12においては、めっき皮膜におけるクラックの発生が抑制されており、電気ニッケルめっき皮膜と同等の優れた耐折性を有することが分かる。 As shown in Tables 3 and 4, the phosphorus content is 0.1 to 4.0% by mass, and in Examples 1 to 12 containing thallium and sulfur, the occurrence of cracks in the plating film is suppressed. It can be seen that it has excellent folding resistance equivalent to that of the electro-nickel plating film.
一方、比較例1〜4においては、めっき皮膜において多数のクラックが発生しており、実施例1〜12のめっき皮膜に比し、耐折性に劣ることが分かる。 On the other hand, in Comparative Examples 1 to 4, a large number of cracks were generated in the plating film, and it can be seen that the folding resistance was inferior to that of the plating films of Examples 1 to 12.
本実施形態の無電解ニッケル−リンめっき皮膜は、無電解めっき処理後にプレス加工される部品等に好適に使用される。 The electroless nickel-phosphorus plating film of the present embodiment is suitably used for parts and the like that are press-processed after the electroless plating treatment.
Claims (5)
リンの含有量が0.1〜4.0質量%であり、
タリウムと硫黄とを含有する
ことを特徴とする無電解ニッケル−リンめっき皮膜。 An electroless nickel-phosphorus plating film formed on the object to be plated.
The phosphorus content is 0.1-4.0% by mass.
An electroless nickel-phosphorus plating film characterized by containing thallium and sulfur.
前記硫黄の含有量が0.01〜0.3質量%である
ことを特徴とする請求項1に記載の無電解ニッケル−リンめっき皮膜。 The content of the thallium is 0.1 to 5.0% by mass.
The electroless nickel-phosphorus plating film according to claim 1, wherein the sulfur content is 0.01 to 0.3% by mass.
水溶性ニッケル塩と、次亜リン酸塩と、タリウム塩と、硫黄含有化合物と、グリシンとを含有し、前記次亜リン酸塩の濃度が10〜30g/Lであり、前記タリウム塩の濃度が1〜10000mg/Lであり、前記硫黄含有化合物の濃度が0.1〜1000mg/Lであることを特徴とする無電解ニッケル−リンめっき浴。 An electroless nickel-phosphorus plating bath for forming an electroless nickel-phosphorus plating film.
It contains a water-soluble nickel salt, a hypophosphate, a tarium salt, a sulfur-containing compound, and glycine, and the concentration of the hypophosphate is 10 to 30 g / L, and the concentration of the tarium salt. Is 1-1,000 mg / L, and the concentration of the sulfur-containing compound is 0.1 to 1000 mg / L, which is an electroless nickel-phosphoric acid plating bath.
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