US20210317589A1 - Trivalent chromium plating solution and chromium plating method using same - Google Patents
Trivalent chromium plating solution and chromium plating method using same Download PDFInfo
- Publication number
- US20210317589A1 US20210317589A1 US17/257,348 US201917257348A US2021317589A1 US 20210317589 A1 US20210317589 A1 US 20210317589A1 US 201917257348 A US201917257348 A US 201917257348A US 2021317589 A1 US2021317589 A1 US 2021317589A1
- Authority
- US
- United States
- Prior art keywords
- chromium plating
- trivalent chromium
- plating solution
- organic compound
- salt
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 135
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 70
- 239000011651 chromium Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 12
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 238000005260 corrosion Methods 0.000 claims abstract description 26
- 230000007797 corrosion Effects 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 17
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 12
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 238000009713 electroplating Methods 0.000 claims description 13
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 11
- -1 carbamimidoylthio group Chemical group 0.000 claims description 10
- 229960002327 chloral hydrate Drugs 0.000 claims description 10
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- NGPGDYLVALNKEG-OLXYHTOASA-N diammonium L-tartrate Chemical compound [NH4+].[NH4+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O NGPGDYLVALNKEG-OLXYHTOASA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
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- 229940081974 saccharin Drugs 0.000 claims description 6
- 235000019204 saccharin Nutrition 0.000 claims description 6
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 6
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
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- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 58
- 235000002639 sodium chloride Nutrition 0.000 description 34
- 229910052759 nickel Inorganic materials 0.000 description 29
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 8
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 8
- 239000011696 chromium(III) sulphate Substances 0.000 description 8
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 230000001105 regulatory effect Effects 0.000 description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- HYMJHROUVPWYNQ-UHFFFAOYSA-N 2-amino-1,3-thiazol-4-one Chemical compound NC1=NC(=O)CS1 HYMJHROUVPWYNQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 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
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 239000011780 sodium chloride Substances 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
- BWUNQEXPLIAUOU-UHFFFAOYSA-N 2-[amino(azaniumylidene)methyl]sulfanylacetate Chemical compound NC(=N)SCC(O)=O BWUNQEXPLIAUOU-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- YSHYSAKBZQCSQY-UHFFFAOYSA-N 2-amino-5,6-dihydro-1,3-thiazin-4-one Chemical compound NC1=NC(=O)CCS1 YSHYSAKBZQCSQY-UHFFFAOYSA-N 0.000 description 1
- ICCLGNPZARKJKF-UHFFFAOYSA-N 3-[amino(azaniumylidene)methyl]sulfanylpropanoate Chemical compound NC(=N)SCCC(O)=O ICCLGNPZARKJKF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 description 1
- NOGBENJVEVQHKG-UHFFFAOYSA-K [Cr+3].NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O Chemical compound [Cr+3].NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O NOGBENJVEVQHKG-UHFFFAOYSA-K 0.000 description 1
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- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
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- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
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- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
Definitions
- the present invention relates to a trivalent chromium plating solution and a chromium plating method using the same.
- a chromium plating has been used as a decorative coating film due to the silver-white appearance thereof.
- Hexavalent chromium has been used for the chromium plating, but the use of hexavalent chromium is being restricted in recent years since hexavalent chromium adversely affects the environments, and the technologies are being shifted to the use of trivalent chromium.
- a trivalent chromium plating is inferior in corrosion resistance to a hexavalent chromium plating.
- the techniques for enhancing the corrosion resistance of the trivalent chromium plating have been reported.
- PTL 1 reports the technique of the enhancement of corrosion resistance in a calcium chloride environment.
- this trivalent chromium plating is still inferior in CASS corrosion resistance to the hexavalent chromium plating, and is not practical.
- a problem of the present invention is to provide a practical trivalent chromium plating with enhanced corrosion resistance as compared to the ordinary trivalent chromium plating.
- the present invention relates to a trivalent chromium plating solution containing a trivalent chromium compound, a complexing agent, a conductive salt, and a pH-buffering agent,
- the trivalent chromium plating solution further containing an organic compound having 2-4 carbon atoms and three or more chloro groups.
- the present invention also relates to an additive for a trivalent chromium plating solution, containing an organic compound having 2-4 carbon atoms and three or more chloro groups as an active ingredient.
- the present invention further relates to a chromium plating method for an article to be plated, including electroplating the article to be plated with the trivalent chromium plating solution.
- the present invention still further relates to a method for enhancing corrosion resistance of an article to be plated, including electroplating the article to be plated with the trivalent chromium plating solution.
- the present invention still further relates to a chromium plated product obtained by electroplating an article to be plated with the trivalent chromium plating solution.
- the trivalent chromium plating solution of the present invention can provide a plating that has an appearance equivalent to a plating formed by using hexavalent chromium, irrespective of the use of trivalent chromium, and further has enhanced corrosion resistance and practicality.
- FIG. 1 is a figure showing results of a corrosion resistance test (CASS test) performed (Examples 1 to 5).
- FIG. 2 is a figure showing results of the corrosion resistance test (CASS test) performed (Comparative Examples 1 and 2 and Reference Example).
- FIG. 3 is a figure showing results of the corrosion resistance test (CRSS test) performed (Examples 6 to 8).
- the trivalent chromium plating solution of the present invention (hereinafter referred to as a “plating solution of the present invention”) is obtained by adding an organic compound having 2-4 carbon atoms and three or more chloro groups, to a trivalent chromium plating solution containing a trivalent chromium compound, a complexing agent, a conductive salt, and a pH-buffering agent.
- the organic compound having 2-4 carbon atoms and three or more chloro groups used in the plating solution of the present invention (which may be hereinafter referred simply to as an “organic compound”) is not particularly limited, and examples of which include chloral hydrate, trichloroethylene, trichloroacetic acid, trichloroacetonitrile, and trichloroethanol.
- the organic compound may be used alone, or two or more kinds thereof may be used. Among these organic compounds, chloral hydrate and/or trichloroethylene are preferred, and chloral hydrate is more preferred.
- the content of the organic compound in the plating solution of the present invention is not particularly limited, and is, for example, 10 to 5,000 mg/L, preferably 20 to 2,000 mg/L, and more preferably 50 to 1,000 mg/L.
- the organic compound can form an additive for a trivalent chromium plating solution using the organic compound as an active ingredient.
- the additive for a trivalent chromium plating solution may be added to the ordinary trivalent chromium plating solution.
- the trivalent chromium compound used in the plating solution of the present invention is not particularly limited, examples of which include basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, and chromium acetate, and basic chromium sulfate and chromium sulfate are preferred.
- the trivalent chromium compound may be used alone, or two or more kinds thereof may be used in combination.
- the content of the trivalent chromium compound in the plating solution of the present invention is not particularly limited, and is, for example, 1 to 25 g/L, and preferably 1 to 15 g/L, in terms of metallic chromium.
- the complexing agent used in the plating solution of the present invention is not particularly limited, examples of which include an aliphatic monocarboxylic acid, such as formic acid, ammonium formate, and potassium formate, an aliphatic dicarboxylic acid, such as succinic acid, maleic acid, malic acid, citric acid, and triammonium citrate, and a carboxylic acid having two or more hydroxy groups and two or more carboxy groups, such as tartaric acid, diammonium tartrate, and sodium tartrate.
- the complexing agent may be used alone, or two or more kinds thereof may be used in combination.
- the content of the complexing agent in the plating solution of the present invention is not particularly limited, and is, for example, 0.1 to 50 g/L, and preferably 1 to 30 g/L.
- the conductive salt used in the plating solution of the present invention is not particularly limited, examples of which include a sulfate, such as potassium sulfate, ammonium sulfate, and sodium sulfate, a chloride, such as potassium chloride, ammonium chloride, and sodium chloride, and a sulfamate, such as potassium sulfamate, ammonium sulfamate, and sodium sulfamate.
- a sulfate such as potassium sulfate, ammonium sulfate, and sodium chloride
- a chloride such as potassium chloride, ammonium chloride, and sodium chloride
- a sulfamate such as potassium sulfamate, ammonium sulfamate, and sodium sulfamate.
- the conductive salt may be used alone, or two or more kinds thereof may be used in combination.
- the content of the conductive salt in the plating solution of the present invention is not particularly limited, and is, for example, 100 to 500 g/L, and preferably 150 to 300 g/L.
- the pH-buffering agent used in the plating solution of the present invention is not particularly limited, and may be boric acid, sodium borate, potassium borate, phosphoric acid, dipotassium hydrogen phosphate, or the like. Among these, boric acid and sodium borate are preferred.
- the pH-buffering agent may be used alone, or two or more kinds thereof may be used in combination.
- the content of the pH-buffering agent in the plating solution of the present invention is not particularly limited, and is, for example, 25 to 200 g/L, and preferably 50 to 100 g/L.
- the plating solution of the present invention may further contain ascorbic acid, sodium ascorbate, hydrogen peroxide, polyethylene glycol, a tin salt, such as tin sulfate and tin chloride, and the like.
- the pH of the plating solution of the present invention is not particularly limited, as far as the pH is in an acidic range, and is, for example, preferably 2 to 4.5, and more preferably 2.5 to 4.0.
- the complexing agent used is preferably a carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof.
- the complexing agent include the carboxylic acid, such as tartaric acid, and the salt of the carboxylic acid, such as diammonium tartrate, Rochelle salt, and sodium tartrate.
- tartaric acid and diammonium tartrate are preferred, and diammonium tartrate is more preferred.
- the complexing agent may be used alone, or two or more kinds thereof may be used in combination.
- the content of the carboxylic acid or the salt thereof in the plating solution of the present invention is not particularly limited, and is, for example, 0.1 to 90 g/L, and preferably 1 to 60 g/L.
- a hydroxy group in the carboxy group is not counted as the hydroxy group.
- a carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof is preferably used in combination with the complexing agent.
- the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof include a carboxylic acid, such as adipic acid, phthalic acid, pimelic acid, and sebacic acid, and salts of the carboxylic acids.
- the complexing agent may be used alone, or two or more kinds thereof may be used in combination, and phthalic acid and/or adipic acid are preferred.
- the content of the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof in the plating solution of the present invention is not particularly limited, and the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof may be used as a part of the carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof within the range of the content thereof.
- the use of the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof enhances the corrosion resistance without a chromate treatment described later performed.
- a sulfur-containing organic compound is preferably contained.
- the sulfur-containing organic compound used in the plating solution of the present invention is not particularly limited, and examples of which include saccharin or a salt thereof, a sulfur-containing organic compound having an allyl group, a carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof, thiourea, and sodium thiocyanate.
- saccharin or a salt thereof examples include saccharin and sodium saccharate. Among these, sodium saccharate is preferred.
- sulfur-containing organic compound having an allyl group examples include sodium allylsulfonate, allylthiourea, ammonium 2-methylallylsulfonate, and allyl isothiocyanate. Among these, sodium allylsulfonate and/or allylthiourea are preferred.
- Examples of the carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof include a carboxylic acid having a carbamimidoylthio group represented by the general formula (1) and a dehydration reaction product of a carboxylic acid having a carbamimidoylthio group represented by the general formula (2).
- n represents an integer of 1 to 5, preferably 1 to 2.
- n represents an integer of 1 or 2.
- carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof include [[amino(imino)methyl]thio]acetic acid, 3-[[amino(imino)methyl]thio]propanoic acid, 2-iminothiazolidin-4-one, and 2-amino-5,6-dihydro-4H-1,3-thiazin-4-one.
- the sulfur-containing organic compound may be used alone, or two or more kinds thereof may be used in combination.
- a combination of saccharin or a salt thereof and one or more kind selected from the group consisting of a sulfur-containing organic compound having an allyl group and a carboxylic acid having a carbamimidoylthio group and/or a dehydration reaction product thereof is preferred, and a combination of sodium saccharate and sodium allylsulfonate is particularly preferred.
- the content of the sulfur-containing organic compound in the plating solution of the present invention is not particularly limited, and is, for example, 0.5 to 10 g/L, and preferably 2 to 8 g/L.
- the conductive salt of the plating solution of the present invention is a sulfate
- a carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof is used as the complexing agent, and a combination of saccharin or a salt thereof and one or more kind selected from the group consisting of a sulfur-containing organic compound having an allyl group and a carboxylic acid having a carbamimidoylthio group and/or a dehydration reaction product thereof is used as the sulfur-containing organic compound.
- the preparation method of the plating solution of the present invention described above is not particularly limited, and the plating solution may be prepared, for example, in such a manner that the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent are added to water at 40 to 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and depending on necessity the sulfur-containing organic compound are added thereto and mixed therein, and finally the pH is regulated with sulfuric acid, aqueous ammonia, or the like.
- the plating solution of the present invention can provide a chromium plating on an article to be plated by electroplating the article to be plated with the plating solution of the present invention, similarly to the ordinary chromium plating solution. Further, corrosion resistance is enhanced by the electroplating.
- the condition of the electroplating is not particularly limited, and the electroplating may be performed, for example, at a bath temperature of 30 to 60° C., with an anode formed of carbon or iridium oxide, at a cathode current density of 2 to 20 A/dm 2 , for 1 to 15 minutes.
- Examples of the article to be plated capable of being electroplated include a metal, such as iron, stainless steel, and brass, and a resin, such as ABS and PC/ABS.
- the article to be plated may be subjected to a treatment, such as copper plating and nickel plating, in advance before the treatment with the plating solution of the present invention.
- the article to be plated is subjected to a nickel plating treatment
- three layers or four layers of nickel plating layers are preferably provided by the ordinary method.
- a semibright nickel plating, a bright nickel plating, and a microporous nickel plating may be provided in this order.
- the potential differences among the layers are not particularly limited, and for example, it is preferred that the potential difference of the bright nickel plating is ⁇ 200 to ⁇ 60 mV with respect to the semibright nickel plating, and the potential difference of the microporous nickel plating is 20 to 100 mV with respect to the bright nickel plating.
- a semibright nickel plating, a high sulfur content nickel plating, a bright nickel plating, and a microporous nickel plating may be provided in this order.
- the potential differences among the layers are not particularly limited, and for example, it is preferred that the potential difference of the bright nickel plating is ⁇ 200 to ⁇ 60 mV with respect to the semibright nickel plating, the potential difference of the high sulfur content nickel plating is ⁇ 50 to ⁇ 5 mV with respect to the bright nickel plating, and the potential difference of the microporous nickel plating is 20 to 100 mV with respect to the bright nickel plating.
- the chromium plated product thus obtained has enhanced corrosion resistance.
- the enhancement of the corrosion resistance herein means that the rating number (R. N.) is enhanced in the evaluation according to JIS H8502.
- the chromium plating may be further subjected to a chromate treatment, and thereby the corrosion resistance is further enhanced.
- the condition of the chromate treatment is not particularly limited, and for example, electroplating may be performed at a bath temperature of 25 to 70° C., with an insoluble anode, such as a lead-tin alloy, as an anode, at a cathode current density of 0.1 to 1 A/dm 2 , for 1 minute.
- an insoluble anode such as a lead-tin alloy
- the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 1 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and the sulfur-containing organic compound were added thereto and mixed therein, and finally the pH was regulated with sulfuric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution.
- a chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITE #88”, produced by JCU Corporation), and a microporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 1 and a current density of 10 A/dm 2 for 3 minutes, so as to provide a test piece.
- the test piece was subjected to a CASS test (JIS H8502).
- the micrographs of the test pieces after the CASS test for 80 hours are shown in FIGS. 1 and 2 .
- Example Example Example Comparative Comparative Reference Composition of plating solution 1 2 3 4 5
- Example 1 Example 2
- the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 2 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and the sulfur-containing organic compound were added thereto and mixed therein, and finally the pH was regulated with sulfuric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution.
- a chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITS #88”, produced by JCU Corporation), and a microporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 2 and a current density of 10 A/dm 2 for 3 minutes, so as to provide a test piece.
- the test piece was subjected to a CASS test (JIS H8502).
- the micrographs of the test pieces after the CASS test for 80 hours are shown in FIG. 3 .
- the rating numbers (R. N.) shown in the figure are evaluation in terms of total corrosion rate. The results are also shown in Table 2.
- the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in the following compositions 1 to 3 were added to water at 50° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups was added thereto and mixed therein, and finally the pH was regulated with hydrochloric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution.
- the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 3 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups was added thereto and mixed therein, and finally the pH was regulated with hydrochloric acid or aqueous ammonia, thereby preparing a trivalent chromium plating solution.
- a chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITE #88”, produced by JCU Corporation), and a macroporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 3 and a current density of 10 A/dm 2 for 3 minutes, so as to provide a test piece.
- the test piece was subjected to a CASS test (JIS H8502).
- the rating numbers (R. N.) after the CASS test for 80 hours are evaluation in terms of total corrosion rate.
- the results are also shown in Table 3.
- the chromate treatment was performed with “EBACHRO-500”, produced by JCU Corporation, under condition of a bath temperature of 40° C. and a cathode current density of 0.2 A/dm 2 for 1 minute.
- the trivalent chromium plating solution of the present invention can be applied to various purposes similarly to a plating using hexavalent chromium.
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Abstract
Description
- The present invention relates to a trivalent chromium plating solution and a chromium plating method using the same.
- A chromium plating has been used as a decorative coating film due to the silver-white appearance thereof. Hexavalent chromium has been used for the chromium plating, but the use of hexavalent chromium is being restricted in recent years since hexavalent chromium adversely affects the environments, and the technologies are being shifted to the use of trivalent chromium.
- However, a trivalent chromium plating is inferior in corrosion resistance to a hexavalent chromium plating. Under the circumstances, the techniques for enhancing the corrosion resistance of the trivalent chromium plating have been reported. For example,
PTL 1 reports the technique of the enhancement of corrosion resistance in a calcium chloride environment. - However, this trivalent chromium plating is still inferior in CASS corrosion resistance to the hexavalent chromium plating, and is not practical.
- PTL 1: JP-A-2012-521495
- A problem of the present invention is to provide a practical trivalent chromium plating with enhanced corrosion resistance as compared to the ordinary trivalent chromium plating.
- As a result of earnest investigations for solving the problem by the present inventors, it has been found that a trivalent chromium plating obtained with a trivalent chromium plating solution having added thereto an organic compound having 2-4 carbon atoms and three or more chloro groups has high corrosion resistance and is practical, and thus the present invention has been completed.
- The present invention relates to a trivalent chromium plating solution containing a trivalent chromium compound, a complexing agent, a conductive salt, and a pH-buffering agent,
- the trivalent chromium plating solution further containing an organic compound having 2-4 carbon atoms and three or more chloro groups.
- The present invention also relates to an additive for a trivalent chromium plating solution, containing an organic compound having 2-4 carbon atoms and three or more chloro groups as an active ingredient.
- The present invention further relates to a chromium plating method for an article to be plated, including electroplating the article to be plated with the trivalent chromium plating solution.
- The present invention still further relates to a method for enhancing corrosion resistance of an article to be plated, including electroplating the article to be plated with the trivalent chromium plating solution.
- The present invention still further relates to a chromium plated product obtained by electroplating an article to be plated with the trivalent chromium plating solution.
- The trivalent chromium plating solution of the present invention can provide a plating that has an appearance equivalent to a plating formed by using hexavalent chromium, irrespective of the use of trivalent chromium, and further has enhanced corrosion resistance and practicality.
-
FIG. 1 is a figure showing results of a corrosion resistance test (CASS test) performed (Examples 1 to 5). -
FIG. 2 is a figure showing results of the corrosion resistance test (CASS test) performed (Comparative Examples 1 and 2 and Reference Example). -
FIG. 3 is a figure showing results of the corrosion resistance test (CRSS test) performed (Examples 6 to 8). - The trivalent chromium plating solution of the present invention (hereinafter referred to as a “plating solution of the present invention”) is obtained by adding an organic compound having 2-4 carbon atoms and three or more chloro groups, to a trivalent chromium plating solution containing a trivalent chromium compound, a complexing agent, a conductive salt, and a pH-buffering agent.
- The organic compound having 2-4 carbon atoms and three or more chloro groups used in the plating solution of the present invention (which may be hereinafter referred simply to as an “organic compound”) is not particularly limited, and examples of which include chloral hydrate, trichloroethylene, trichloroacetic acid, trichloroacetonitrile, and trichloroethanol. The organic compound may be used alone, or two or more kinds thereof may be used. Among these organic compounds, chloral hydrate and/or trichloroethylene are preferred, and chloral hydrate is more preferred. The content of the organic compound in the plating solution of the present invention is not particularly limited, and is, for example, 10 to 5,000 mg/L, preferably 20 to 2,000 mg/L, and more preferably 50 to 1,000 mg/L.
- The organic compound can form an additive for a trivalent chromium plating solution using the organic compound as an active ingredient. The additive for a trivalent chromium plating solution may be added to the ordinary trivalent chromium plating solution.
- The trivalent chromium compound used in the plating solution of the present invention is not particularly limited, examples of which include basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, and chromium acetate, and basic chromium sulfate and chromium sulfate are preferred. The trivalent chromium compound may be used alone, or two or more kinds thereof may be used in combination. The content of the trivalent chromium compound in the plating solution of the present invention is not particularly limited, and is, for example, 1 to 25 g/L, and preferably 1 to 15 g/L, in terms of metallic chromium.
- The complexing agent used in the plating solution of the present invention is not particularly limited, examples of which include an aliphatic monocarboxylic acid, such as formic acid, ammonium formate, and potassium formate, an aliphatic dicarboxylic acid, such as succinic acid, maleic acid, malic acid, citric acid, and triammonium citrate, and a carboxylic acid having two or more hydroxy groups and two or more carboxy groups, such as tartaric acid, diammonium tartrate, and sodium tartrate. The complexing agent may be used alone, or two or more kinds thereof may be used in combination. The content of the complexing agent in the plating solution of the present invention is not particularly limited, and is, for example, 0.1 to 50 g/L, and preferably 1 to 30 g/L.
- The conductive salt used in the plating solution of the present invention is not particularly limited, examples of which include a sulfate, such as potassium sulfate, ammonium sulfate, and sodium sulfate, a chloride, such as potassium chloride, ammonium chloride, and sodium chloride, and a sulfamate, such as potassium sulfamate, ammonium sulfamate, and sodium sulfamate. These conductive salts are used as each of the groups, for example, groups of sulfates, chlorides, and the like. Among the conductive salts, a sulfate and a chloride are preferred. The conductive salt may be used alone, or two or more kinds thereof may be used in combination. The content of the conductive salt in the plating solution of the present invention is not particularly limited, and is, for example, 100 to 500 g/L, and preferably 150 to 300 g/L.
- The pH-buffering agent used in the plating solution of the present invention is not particularly limited, and may be boric acid, sodium borate, potassium borate, phosphoric acid, dipotassium hydrogen phosphate, or the like. Among these, boric acid and sodium borate are preferred. The pH-buffering agent may be used alone, or two or more kinds thereof may be used in combination. The content of the pH-buffering agent in the plating solution of the present invention is not particularly limited, and is, for example, 25 to 200 g/L, and preferably 50 to 100 g/L.
- The plating solution of the present invention may further contain ascorbic acid, sodium ascorbate, hydrogen peroxide, polyethylene glycol, a tin salt, such as tin sulfate and tin chloride, and the like.
- The pH of the plating solution of the present invention is not particularly limited, as far as the pH is in an acidic range, and is, for example, preferably 2 to 4.5, and more preferably 2.5 to 4.0.
- In the case where the conductive salt of the plating solution of the present invention is a sulfate, the complexing agent used is preferably a carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof. Examples of the complexing agent include the carboxylic acid, such as tartaric acid, and the salt of the carboxylic acid, such as diammonium tartrate, Rochelle salt, and sodium tartrate. Among these complexing agents, tartaric acid and diammonium tartrate are preferred, and diammonium tartrate is more preferred. The complexing agent may be used alone, or two or more kinds thereof may be used in combination. The content of the carboxylic acid or the salt thereof in the plating solution of the present invention is not particularly limited, and is, for example, 0.1 to 90 g/L, and preferably 1 to 60 g/L. In the present invention, a hydroxy group in the carboxy group is not counted as the hydroxy group.
- In the case where the conductive salt of the plating solution of the present invention is a sulfate, furthermore, a carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof is preferably used in combination with the complexing agent. Examples of the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof include a carboxylic acid, such as adipic acid, phthalic acid, pimelic acid, and sebacic acid, and salts of the carboxylic acids. The complexing agent may be used alone, or two or more kinds thereof may be used in combination, and phthalic acid and/or adipic acid are preferred. The content of the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof in the plating solution of the present invention is not particularly limited, and the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof may be used as a part of the carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof within the range of the content thereof. The use of the carboxylic acid having two or more carboxy groups and 4 or more carbon atoms or a salt thereof enhances the corrosion resistance without a chromate treatment described later performed.
- In the case where the conductive salt of the plating solution of the present invention is a sulfate, furthermore, a sulfur-containing organic compound is preferably contained. The sulfur-containing organic compound used in the plating solution of the present invention is not particularly limited, and examples of which include saccharin or a salt thereof, a sulfur-containing organic compound having an allyl group, a carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof, thiourea, and sodium thiocyanate.
- Examples of the saccharin or a salt thereof include saccharin and sodium saccharate. Among these, sodium saccharate is preferred.
- Examples of the sulfur-containing organic compound having an allyl group include sodium allylsulfonate, allylthiourea, ammonium 2-methylallylsulfonate, and allyl isothiocyanate. Among these, sodium allylsulfonate and/or allylthiourea are preferred.
- Examples of the carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof include a carboxylic acid having a carbamimidoylthio group represented by the general formula (1) and a dehydration reaction product of a carboxylic acid having a carbamimidoylthio group represented by the general formula (2).
- In the formula (1), n represents an integer of 1 to 5, preferably 1 to 2.
- In the formula (2), m represents an integer of 1 or 2.
- Specific examples of the carboxylic acid having a carbamimidoylthio group and a dehydration reaction product thereof include [[amino(imino)methyl]thio]acetic acid, 3-[[amino(imino)methyl]thio]propanoic acid, 2-iminothiazolidin-4-one, and 2-amino-5,6-dihydro-4H-1,3-thiazin-4-one.
- The sulfur-containing organic compound may be used alone, or two or more kinds thereof may be used in combination. Among the sulfur-containing organic compounds, a combination of saccharin or a salt thereof and one or more kind selected from the group consisting of a sulfur-containing organic compound having an allyl group and a carboxylic acid having a carbamimidoylthio group and/or a dehydration reaction product thereof is preferred, and a combination of sodium saccharate and sodium allylsulfonate is particularly preferred. The content of the sulfur-containing organic compound in the plating solution of the present invention is not particularly limited, and is, for example, 0.5 to 10 g/L, and preferably 2 to 8 g/L.
- In the case where the conductive salt of the plating solution of the present invention is a sulfate, it is particularly preferred that a carboxylic acid having two or more hydroxy groups and two or more carboxy groups or a salt thereof is used as the complexing agent, and a combination of saccharin or a salt thereof and one or more kind selected from the group consisting of a sulfur-containing organic compound having an allyl group and a carboxylic acid having a carbamimidoylthio group and/or a dehydration reaction product thereof is used as the sulfur-containing organic compound.
- The preparation method of the plating solution of the present invention described above is not particularly limited, and the plating solution may be prepared, for example, in such a manner that the trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent are added to water at 40 to 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and depending on necessity the sulfur-containing organic compound are added thereto and mixed therein, and finally the pH is regulated with sulfuric acid, aqueous ammonia, or the like.
- The plating solution of the present invention can provide a chromium plating on an article to be plated by electroplating the article to be plated with the plating solution of the present invention, similarly to the ordinary chromium plating solution. Further, corrosion resistance is enhanced by the electroplating.
- The condition of the electroplating is not particularly limited, and the electroplating may be performed, for example, at a bath temperature of 30 to 60° C., with an anode formed of carbon or iridium oxide, at a cathode current density of 2 to 20 A/dm2, for 1 to 15 minutes.
- Examples of the article to be plated capable of being electroplated include a metal, such as iron, stainless steel, and brass, and a resin, such as ABS and PC/ABS. The article to be plated may be subjected to a treatment, such as copper plating and nickel plating, in advance before the treatment with the plating solution of the present invention.
- In the case where the article to be plated is subjected to a nickel plating treatment, three layers or four layers of nickel plating layers are preferably provided by the ordinary method. In the case of three layers, a semibright nickel plating, a bright nickel plating, and a microporous nickel plating may be provided in this order. In this case, the potential differences among the layers are not particularly limited, and for example, it is preferred that the potential difference of the bright nickel plating is −200 to −60 mV with respect to the semibright nickel plating, and the potential difference of the microporous nickel plating is 20 to 100 mV with respect to the bright nickel plating. In the case of four layers, a semibright nickel plating, a high sulfur content nickel plating, a bright nickel plating, and a microporous nickel plating may be provided in this order. In this case, the potential differences among the layers are not particularly limited, and for example, it is preferred that the potential difference of the bright nickel plating is −200 to −60 mV with respect to the semibright nickel plating, the potential difference of the high sulfur content nickel plating is −50 to −5 mV with respect to the bright nickel plating, and the potential difference of the microporous nickel plating is 20 to 100 mV with respect to the bright nickel plating.
- The chromium plated product thus obtained has enhanced corrosion resistance. The enhancement of the corrosion resistance herein means that the rating number (R. N.) is enhanced in the evaluation according to JIS H8502.
- The chromium plating may be further subjected to a chromate treatment, and thereby the corrosion resistance is further enhanced.
- The condition of the chromate treatment is not particularly limited, and for example, electroplating may be performed at a bath temperature of 25 to 70° C., with an insoluble anode, such as a lead-tin alloy, as an anode, at a cathode current density of 0.1 to 1 A/dm2, for 1 minute.
- The present invention will be described in detail with reference to examples below, but the present invention is not limited to the examples.
- The trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 1 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and the sulfur-containing organic compound were added thereto and mixed therein, and finally the pH was regulated with sulfuric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution. A chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITE #88”, produced by JCU Corporation), and a microporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 1 and a current density of 10 A/dm2 for 3 minutes, so as to provide a test piece. The test piece was subjected to a CASS test (JIS H8502). The micrographs of the test pieces after the CASS test for 80 hours are shown in
FIGS. 1 and 2 . The rating numbers (R. N.) shown in the figures are evaluation in terms of total corrosion rate. The chromate treatment was performed with “EBACHRO-500”, produced by JCU Corporation, under condition of a bath temperature of 40° C. and a cathode current density of 0.2 A/dm2 for 1 minute. -
TABLE 1 Example Example Example Example Example Comparative Comparative Reference Composition of plating solution 1 2 3 4 5 Example 1 Example 2 Example Basic chromium sulfate g/L 64 64 64 64 64 64 64 — Chromium anhydride g/L — — — — — — — 250 Sulfuric acid (98%) g/L — — — — — — — 2.5 Malic acid g/L 15 — — — — 15 — — Diammonium tartrate g/L — 30 30 30 30 — 30 — Adipic acid g/L — — — 1 — — — — Sodium sulfate g/L 35 — — — — 35 — — Potassium sulfate g/L 140 150 150 150 150 — 150 — Ammonium sulfate g/L 30 20 20 20 20 30 20 — Boric acid g/L 90 80 80 80 80 90 80 — Sodium saccharate g/L 2.5 4 4 4 4 2.5 4 — Thiourea mg/L 10 — — — — 10 — — Sodium allylsulfonate (36%) mL/L — 2 2 2 2 — 2 — Chloral hydrate (810 g/L) mL/L 0.1 0.1 0.1 0.1 — — — — Trichloroethylene mL/L — — — — 26 — — — pH of plating solution 3.4 3.4 3.4 3.4 3.4 3.4 3.4 — Bath temperature ° C. 60 55 55 55 55 60 45 40 Chromate treatment no no yes no no no yes — - It was understood from the results of the CASS test that the addition of the organic compound having 2-4 carbon atoms and three or more chloro groups to the trivalent chromium plating solution enhanced the corrosion resistance. Some of the plating solutions of the present invention provided a high corrosion resistant film without the chromate treatment performed.
- The trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 2 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups and the sulfur-containing organic compound were added thereto and mixed therein, and finally the pH was regulated with sulfuric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution. A chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITS #88”, produced by JCU Corporation), and a microporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 2 and a current density of 10 A/dm2 for 3 minutes, so as to provide a test piece. The test piece was subjected to a CASS test (JIS H8502). The micrographs of the test pieces after the CASS test for 80 hours are shown in
FIG. 3 . The rating numbers (R. N.) shown in the figure are evaluation in terms of total corrosion rate. The results are also shown in Table 2. -
TABLE 2 Composition of plating Example Example Example Comparative solution 6 7 8 Example 3 Basic chromium sulfate g/L 19.5 19.5 19.5 19.5 Diammonium tartrate g/ L 3 3 3 3 Potassium sulfate g/L 150 150 150 150 Boric acid g/L 70 70 70 70 Sodium saccharate g/ L 3 3 3 3 [[amino(imino)methyl] 50 — 20 50 thio]acetic acid mg/L 2-Iminothiazolidin-4-one — 50 30 — mg/L Chloral hydrate (810 g/L) 0.25 0.25 0.25 — mL/L pH of plating solution 3.7 3.7 3.7 3.7 Bath temperature ° C. 55 55 55 55 Chromate treatment no no no no Rating number (R. N.) 9 9 9 8 - It was understood from the results of the CASS test that the corrosion pitting was smaller in Example 6 than in Comparative Example 3. The similar result was obtained in Examples 7 and 8. It was understood therefrom that the addition of the organic compound having 2-4 carbon atoms and three or more chloro groups to the trivalent chromium plating solution enhanced the corrosion resistance.
- The trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in the following
compositions 1 to 3 were added to water at 50° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups was added thereto and mixed therein, and finally the pH was regulated with hydrochloric acid, aqueous ammonia, or the like, thereby preparing a trivalent chromium plating solution. -
-
Basic chromium sulfate 64 g/L Ammonium formate 16 g/L Potassium chloride 165 g/L Ammonium chloride 100 g/L Ammonium bromide 6 g/L Boric acid 67 g/L Chloral hydrate (810 g/L) 0.1 mL/L -
-
Basic chromium sulfate 64 g/L Ammonium formate 16 g/L Sodium chloride 75 g/L Potassium chloride 165 g/L Ammonium chloride 100 g/L Ammonium bromide 6 g/L Boric acid 67 g/L Chloral hydrate (810 g/L) 0.1 mL/L -
-
Basic chromium sulfate 64 g/L Ammonium tartrate 30 g/L Potassium sulfate 150 g/L Ammonium sulfate 20 g/L Boric acid 80 g/L Chloral hydrate (810 g/L) 0.1 mL/L - The trivalent chromium compound, the complexing agent, the conductive salt, and the pH-buffering agent shown in Table 3 were added to water at 60° C. and mixed and dissolved therein, then the organic compound having 2-4 carbon atoms and three or more chloro groups was added thereto and mixed therein, and finally the pH was regulated with hydrochloric acid or aqueous ammonia, thereby preparing a trivalent chromium plating solution. A chromium plating was formed on an article of an ABS resin having formed thereon a copper plating (“CU-BRITE EP-30”, produced by JCU Corporation), a semibright nickel plating (“CF-24T”, produced by JCU Corporation), a bright nickel plating (“HI-BRITE #88”, produced by JCU Corporation), and a macroporous nickel plating (“MP-NI 308”, produced by JCU Corporation) under condition of the bath temperature shown in Table 3 and a current density of 10 A/dm2 for 3 minutes, so as to provide a test piece. The test piece was subjected to a CASS test (JIS H8502). The rating numbers (R. N.) after the CASS test for 80 hours are evaluation in terms of total corrosion rate. The results are also shown in Table 3. The chromate treatment was performed with “EBACHRO-500”, produced by JCU Corporation, under condition of a bath temperature of 40° C. and a cathode current density of 0.2 A/dm2 for 1 minute.
-
TABLE 3 Composition of plating Example Example Comparative Comparative solution 10 11 Example 4 Example 5 Basic chromium sulfate 64 64 64 64 g/L Ammonium formate g/L 16 16 16 16 Sodium chloride g/L 70 70 70 70 Potassium chloride g/L 140 140 140 140 Ammonium chloride g/L 85 85 85 85 Ammonium bromide g/ L 6 6 6 6 Boric acid g/L 67 67 67 67 Chloral hydrate 0.8 0.8 — — (810 g/L) mL/L pH of plating solution 2.7 2.7 2.7 2.7 Bath temperature ° C. 32 32 32 32 Chromate treatment no yes no yes Rating number (R. N.) 9 9.3 8 9 - It was understood from the results of the CASS test that the addition of the organic compound having 2-4 carbon atoms and three or more chloro groups to the trivalent chromium plating solution enhanced the corrosion resistance.
- The trivalent chromium plating solution of the present invention can be applied to various purposes similarly to a plating using hexavalent chromium.
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US4092226A (en) * | 1974-12-11 | 1978-05-30 | Nikolaus Laing | Process for the treatment of metal surfaces by electro-deposition of metal coatings at high current densities |
US4472249A (en) * | 1981-08-24 | 1984-09-18 | M&T Chemicals Inc. | Bright chromium plating baths and process |
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