EP4379095A1 - White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using same - Google Patents
White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using same Download PDFInfo
- Publication number
- EP4379095A1 EP4379095A1 EP22849467.0A EP22849467A EP4379095A1 EP 4379095 A1 EP4379095 A1 EP 4379095A1 EP 22849467 A EP22849467 A EP 22849467A EP 4379095 A1 EP4379095 A1 EP 4379095A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- trivalent chromium
- plating bath
- sub
- chromium plating
- white
- 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 83
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 47
- 239000011651 chromium Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 15
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 13
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 13
- 229940081974 saccharin Drugs 0.000 claims description 12
- 235000019204 saccharin Nutrition 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 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 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 3
- ZBUUHLDYMKTVLT-UHFFFAOYSA-N 3-amino-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound NN1C(=O)CSC1=S ZBUUHLDYMKTVLT-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 3
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 3
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 3
- 239000011696 chromium(III) sulphate Substances 0.000 description 3
- 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 description 3
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 3
- -1 thiourea Chemical class 0.000 description 3
- SLYRGJDSFOCAAI-UHFFFAOYSA-N 1,3-thiazolidin-2-one Chemical compound O=C1NCCS1 SLYRGJDSFOCAAI-UHFFFAOYSA-N 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 2
- UPCYEFFISUGBRW-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCN1C(=O)CSC1=S UPCYEFFISUGBRW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-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
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JGRMXPSUZIYDRR-UHFFFAOYSA-N 2-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)acetic acid Chemical compound OC(=O)CN1C(=O)CSC1=S JGRMXPSUZIYDRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SWAHCTPCIUXXTQ-UHFFFAOYSA-N 3-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)propanoic acid Chemical compound OC(=O)CCN1C(=O)CSC1=S SWAHCTPCIUXXTQ-UHFFFAOYSA-N 0.000 description 1
- HMLWNNMYODLLJO-UHFFFAOYSA-N 3-methyl-1,3-thiazolidine-2,4-dione Chemical compound CN1C(=O)CSC1=O HMLWNNMYODLLJO-UHFFFAOYSA-N 0.000 description 1
- RGTLAJIDOSPEDH-UHFFFAOYSA-N 3-methyl-1,3-thiazolidine-2-thione Chemical compound CN1CCSC1=S RGTLAJIDOSPEDH-UHFFFAOYSA-N 0.000 description 1
- JKLZCQWVERBDEZ-UHFFFAOYSA-N 3-methyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CN1C(=O)CSC1=S JKLZCQWVERBDEZ-UHFFFAOYSA-N 0.000 description 1
- GYGUTBCTEJBRAN-UHFFFAOYSA-N 3-prop-2-enyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound C=CCN1C(=O)CSC1=S GYGUTBCTEJBRAN-UHFFFAOYSA-N 0.000 description 1
- XTSVDOIDJDJMDS-UHFFFAOYSA-N 4-sulfanylidene-1,3-thiazolidin-2-one Chemical compound O=C1NC(=S)CS1 XTSVDOIDJDJMDS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-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
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 1
- 229960002327 chloral hydrate Drugs 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 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 1
- 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
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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
- C25D3/06—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
- 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
Definitions
- the present invention relates to a white trivalent chromium plating bath and a white trivalent chromium plating method for an object to be plated using the same.
- Chromium plating is used as a coating film for decoration because it has a silver-white appearance.
- Hexavalent chromium has been used for the chromium plating, but in recent years, since this hexavalent chromium affects the environment, its use has been restricted, and there has been a shift to a technique using trivalent chromium.
- a chromium electroplating solution containing a water-soluble trivalent chromium salt, a complexing agent for trivalent chromium ions such as malic acid, a pH buffering compound, a sulfur-containing organic compound such as thiourea, and a water-soluble compound such as saccharin and having a pH of 2.8 to 4.2 is known (PTL 1).
- the present applicant has developed a practical trivalent chromium plating bath in which the plating deposition rate is high (PTL 2: a trivalent chromium plating bath including a trivalent chromium compound, a complexing agent, potassium sulfate and ammonium sulfate as conductive salts, a pH buffering agent, and a sulfur-containing organic compound, in which 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 saccharin or a salt thereof and a sulfur-containing organic compound having an allyl group are used in combination as the sulfur-containing organic compounds), and an object of the present invention is to develop a plating technique, in which the composition is simpler than the trivalent chromium plating bath, and with which an appearance also suitable for decorative applications is obtained.
- PTL 2 a trivalent chromium plating bath including a trivalent chromium compound, a complexing agent, potassium sulfate and
- the present inventors conducted intensive studies to achieve the above-mentioned object, and as a result, they found that the above-mentioned object can be achieved by incorporating a sulfur-containing organic compound having a specific structure in a white trivalent chromium plating bath, and thus completed the invention.
- the invention is directed to a white trivalent chromium plating method for an object to be plated, the method including electroplating the object to be plated in the white trivalent chromium plating bath.
- the invention is directed to a method for improving a deposition rate of white trivalent chromium plating, the method including incorporating a sulfur-containing organic compound represented by the general formula (I) in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, and a pH buffering agent.
- a sulfur-containing organic compound represented by the general formula (I) in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, and a pH buffering agent.
- white trivalent chromium plating bath of the invention enables white trivalent chromium plating with a color tone and a deposition rate equivalent to those of hexavalent chromium plating.
- the white trivalent chromium plating bath of the invention contains a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, a pH buffering agent, and a sulfur-containing organic compound.
- sulfur-containing organic compound represented by the general formula (I) include thiazolidine, rhodanine, thiazolidin-2-one, 3-methylthiazolidine-2-thione, 4-thioxo-1,3-thiazolidin-2-one, 2-mercaptothiazoline (also known as 2-thiazoline-2-thiol), 2,4-thiazolidinedione, 3-methyl-1,3-thiazolane-2,4-dione, 3-aminorhodanine, 3-methylrhodanine, 3-ethylrhodanine, 3-allylrhodanine, rhodanine-3-acetic acid, and rhodanine-3-propionic acid, and among these, rhodanine, 2,4-thiazolidinedione, 3-aminorhodanine, and 3-ethylrhodanine are preferred.
- these sulfur-containing organic compounds one type can be used, or two or more types can be used in combination.
- the content of the sulfur-containing organic compound represented by the general formula (I) or the like in the plating bath of the invention is not particularly limited, but is, for example, 1 to 500 mg/L, and preferably 5 to 100 mg/L.
- the trivalent chromium compound used in the plating bath of the invention is not particularly limited, but is, for example, basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, or chromium acetate, and is preferably basic chromium sulfate or chromium sulfate.
- these trivalent chromium compounds one type can be used, or two or more types can be used in combination.
- the content of the trivalent chromium compound in the plating bath of the invention is not particularly limited, but 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 bath of the invention is not particularly limited, and examples thereof include dicarboxylic acids such as malic acid and tartaric acid, and salts of dicarboxylic acids such as sodium malate, sodium tartrate, and diammonium tartrate, and malic acid or diammonium tartrate is preferred. Among these complexing agents, one type can be used, or two or more types can be used in combination.
- the content of the complexing agent in the plating bath of the invention is not particularly limited, but is, for example, 1 to 90 g/L, and preferably 2 to 50 g/L.
- the conductive salt used in the plating bath of the invention is a sulfate such as potassium sulfate, ammonium sulfate, or sodium sulfate.
- a sulfate such as potassium sulfate, ammonium sulfate, or sodium sulfate.
- potassium sulfate is preferred.
- these sulfates one type can be used, or two or more types can be used in combination.
- the content of the sulfate in the plating bath of the invention is not particularly limited, but is, for example, 100 to 300 g/L, and preferably 120 to 240 g/L.
- the pH buffering agent used in the plating bath of the invention is not particularly limited, and examples thereof include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate, and among these, boric acid and sodium borate are preferred. Among these pH buffering agents, one type can be used, or two or more types can be used in combination.
- the content of the pH buffering agent in the plating bath of the invention is not particularly limited, but is, for example, 30 to 150 g/L, and preferably 50 to 110 g/L.
- saccharin or a salt thereof in order to stabilize the deposition of chromium.
- the saccharin or a salt thereof include saccharin and sodium saccharinate.
- saccharin or a salt thereof one type can be used, or two or more types can be used in combination.
- the content of saccharin or a salt thereof in the plating bath of the invention is not particularly limited, but is, for example, 0.5 to 10 g/L, and preferably 2 to 8 g/L. Naturally, the content of saccharin in the plating bath of the invention is not included in the content of the sulfur-containing organic compound represented by the general formula (I) or the like.
- the plating bath of the invention in a preferred aspect may be, for example, a plating bath containing the above-mentioned components, but it goes without saying that it may be a plating bath containing only the above-mentioned components (a plating bath composed of the above-mentioned components).
- the plating bath of the invention may further contain a polymer compound such as polyethylene glycol, ascorbic acid, sodium ascorbate, hydrogen peroxide, a surfactant, chloral hydrate, iminodiacetic acid, or the like as long as the effects of the invention are not impaired.
- a polymer compound such as polyethylene glycol, ascorbic acid, sodium ascorbate, hydrogen peroxide, a surfactant, chloral hydrate, iminodiacetic acid, or the like as long as the effects of the invention are not impaired.
- the pH of the plating bath of the invention is not particularly limited as long as it is acidic, and is preferably, for example, 2 to 4.5, and more preferably 3 to 4.5.
- the method for preparing the plating bath of the invention is not particularly limited, and the plating bath can be prepared, for example, by adding and mixing a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and a sulfur-containing organic compound (saccharin or a salt thereof if necessary) in water at 50 to 60°C, and finally adjusting the pH with sulfuric acid, aqueous ammonia, or the like if necessary.
- the plating bath of the invention enables white trivalent chromium plating on an object to be plated by electroplating the object to be plated in the plating bath of the invention in the same manner as in a conventional chromium plating bath.
- Electroplating conditions are not particularly limited, but for example, electroplating may be performed at a bath temperature of 30 to 60°C using carbon or iridium oxide as an anode at a cathode current density of 2 to 20 A/dm 2 for 1 to 15 minutes.
- Examples of the object to be plated that can be electroplated include metals such as iron, stainless steel, and brass, and resins such as ABS and PC/ABS.
- the object to be plated may be subjected to a treatment such as copper plating or nickel plating in advance before being plated in the plating bath of the invention.
- the deposition rate is 0.03 to 0.17 um/min, preferably 0.04 to 0.13 um/min, which is equal to or higher than the deposition rate when conventional hexavalent chromium plating is performed.
- the deposition rate of white trivalent chromium plating can be improved by incorporating the sulfur-containing organic compound represented by the general formula (I) or the like in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, and a pH buffering agent.
- a chromium-plated product thus obtained is white, and has an L* value of 80 or more, preferably 82 or more, more preferably 83 or more, and particularly preferably 83 to 84, as measured using a color difference meter, and the color tone is equivalent to that of hexavalent chromium plating.
- the white chromium-plated product can be used for the same applications as conventional hexavalent chromium-plated products, but is particularly suitable for products for decorative applications such as cars, motorcycles, and metal fittings.
- a trivalent chromium plating bath was prepared by dissolving the components shown in Table 1 in water and adjusting the pH with aqueous ammonia.
- a Hull cell test was performed on the trivalent chromium plating bath using a nickel-plated brass plate. The Hull cell test conditions are as follows: current: 5 A; and plating time: 3 minutes. After plating, the film thickness of the brass plate was measured with X-ray fluorescence at a point where the current density is 10 A/dm 2 , and the deposition rate was calculated. Further, the appearance after plating was evaluated based on an L* value, an a* value, and a b* value obtained using a color difference meter (manufactured by Konica Minolta, Inc.).
- the plating bath of the invention can be used for various applications in the same manner as white plating using hexavalent chromium.
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Abstract
A white trivalent chromium plating bath including a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and one type or two or more types of sulfur-containing organic compounds represented by the following general formula (I) (in which R represents -H, -NH<sub>2</sub>, -OH, -CH<sub>3</sub>, -(CH<sub>2</sub>)<sub>n</sub>-CH<sub>3</sub>, or -(CH<sub>2</sub>)<sub>n</sub>-COOH, n represents an integer of 1 to 4, and X and Y each independently represent CH<sub>2</sub>, C=O, or C=S), and a white trivalent chromium plating method using the white trivalent chromium plating bath enable a high plating deposition rate in the trivalent chromium plating bath, and provide an appearance suitable for decorative applications.
Description
- The present invention relates to a white trivalent chromium plating bath and a white trivalent chromium plating method for an object to be plated using the same.
- Chromium plating is used as a coating film for decoration because it has a silver-white appearance. Hexavalent chromium has been used for the chromium plating, but in recent years, since this hexavalent chromium affects the environment, its use has been restricted, and there has been a shift to a technique using trivalent chromium.
- Many techniques using trivalent chromium in this manner have been reported. For example, a chromium electroplating solution containing a water-soluble trivalent chromium salt, a complexing agent for trivalent chromium ions such as malic acid, a pH buffering compound, a sulfur-containing organic compound such as thiourea, and a water-soluble compound such as saccharin and having a pH of 2.8 to 4.2 is known (PTL 1).
- However, this trivalent chromium plating bath is not practical because the plating deposition rate is low.
-
- PTL 1:
JP5696134B - PTL 2:
WO2019/117178 - The present applicant has developed a practical trivalent chromium plating bath in which the plating deposition rate is high (PTL 2: a trivalent chromium plating bath including a trivalent chromium compound, a complexing agent, potassium sulfate and ammonium sulfate as conductive salts, a pH buffering agent, and a sulfur-containing organic compound, in which 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 saccharin or a salt thereof and a sulfur-containing organic compound having an allyl group are used in combination as the sulfur-containing organic compounds), and an object of the present invention is to develop a plating technique, in which the composition is simpler than the trivalent chromium plating bath, and with which an appearance also suitable for decorative applications is obtained.
- The present inventors conducted intensive studies to achieve the above-mentioned object, and as a result, they found that the above-mentioned object can be achieved by incorporating a sulfur-containing organic compound having a specific structure in a white trivalent chromium plating bath, and thus completed the invention.
- That is, the invention is directed to a white trivalent chromium plating bath including a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and one type or two or more types of sulfur-containing organic compounds represented by the following general formula (I):
- In addition, the invention is directed to a white trivalent chromium plating method for an object to be plated, the method including electroplating the object to be plated in the white trivalent chromium plating bath.
- Further, the invention is directed to a method for improving a deposition rate of white trivalent chromium plating, the method including incorporating a sulfur-containing organic compound represented by the general formula (I) in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, and a pH buffering agent.
- Use of the white trivalent chromium plating bath of the invention enables white trivalent chromium plating with a color tone and a deposition rate equivalent to those of hexavalent chromium plating.
- The white trivalent chromium plating bath of the invention (hereinafter referred to as "the plating bath of the invention") contains a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, a pH buffering agent, and a sulfur-containing organic compound.
- The sulfur-containing organic compound is represented by the following general formula (I):
- Preferred examples of the sulfur-containing organic compound represented by the general formula (I) include a compound represented by the following general formula (II):
- More preferred examples of the sulfur-containing organic compound represented by the general formula (I) include thiazolidine, rhodanine, thiazolidin-2-one, 3-methylthiazolidine-2-thione, 4-thioxo-1,3-thiazolidin-2-one, 2-mercaptothiazoline (also known as 2-thiazoline-2-thiol), 2,4-thiazolidinedione, 3-methyl-1,3-thiazolane-2,4-dione, 3-aminorhodanine, 3-methylrhodanine, 3-ethylrhodanine, 3-allylrhodanine, rhodanine-3-acetic acid, and rhodanine-3-propionic acid, and among these, rhodanine, 2,4-thiazolidinedione, 3-aminorhodanine, and 3-ethylrhodanine are preferred. Among these sulfur-containing organic compounds, one type can be used, or two or more types can be used in combination.
- The content of the sulfur-containing organic compound represented by the general formula (I) or the like in the plating bath of the invention is not particularly limited, but is, for example, 1 to 500 mg/L, and preferably 5 to 100 mg/L.
- The trivalent chromium compound used in the plating bath of the invention is not particularly limited, but is, for example, basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, or chromium acetate, and is preferably basic chromium sulfate or chromium sulfate. Among these trivalent chromium compounds, one type can be used, or two or more types can be used in combination. The content of the trivalent chromium compound in the plating bath of the invention is not particularly limited, but 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 bath of the invention is not particularly limited, and examples thereof include dicarboxylic acids such as malic acid and tartaric acid, and salts of dicarboxylic acids such as sodium malate, sodium tartrate, and diammonium tartrate, and malic acid or diammonium tartrate is preferred. Among these complexing agents, one type can be used, or two or more types can be used in combination. The content of the complexing agent in the plating bath of the invention is not particularly limited, but is, for example, 1 to 90 g/L, and preferably 2 to 50 g/L.
- The conductive salt used in the plating bath of the invention is a sulfate such as potassium sulfate, ammonium sulfate, or sodium sulfate. Among these sulfates, potassium sulfate is preferred. Among these sulfates, one type can be used, or two or more types can be used in combination. The content of the sulfate in the plating bath of the invention is not particularly limited, but is, for example, 100 to 300 g/L, and preferably 120 to 240 g/L.
- The pH buffering agent used in the plating bath of the invention is not particularly limited, and examples thereof include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate, and among these, boric acid and sodium borate are preferred. Among these pH buffering agents, one type can be used, or two or more types can be used in combination. The content of the pH buffering agent in the plating bath of the invention is not particularly limited, but is, for example, 30 to 150 g/L, and preferably 50 to 110 g/L.
- It is preferred to further incorporate saccharin or a salt thereof in the plating bath of the invention in order to stabilize the deposition of chromium. Examples of the saccharin or a salt thereof include saccharin and sodium saccharinate. As such saccharin or a salt thereof, one type can be used, or two or more types can be used in combination. The content of saccharin or a salt thereof in the plating bath of the invention is not particularly limited, but is, for example, 0.5 to 10 g/L, and preferably 2 to 8 g/L. Naturally, the content of saccharin in the plating bath of the invention is not included in the content of the sulfur-containing organic compound represented by the general formula (I) or the like.
- The plating bath of the invention in a preferred aspect may be, for example, a plating bath containing the above-mentioned components, but it goes without saying that it may be a plating bath containing only the above-mentioned components (a plating bath composed of the above-mentioned components).
- The plating bath of the invention may further contain a polymer compound such as polyethylene glycol, ascorbic acid, sodium ascorbate, hydrogen peroxide, a surfactant, chloral hydrate, iminodiacetic acid, or the like as long as the effects of the invention are not impaired.
- The pH of the plating bath of the invention is not particularly limited as long as it is acidic, and is preferably, for example, 2 to 4.5, and more preferably 3 to 4.5.
- The method for preparing the plating bath of the invention is not particularly limited, and the plating bath can be prepared, for example, by adding and mixing a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and a sulfur-containing organic compound (saccharin or a salt thereof if necessary) in water at 50 to 60°C, and finally adjusting the pH with sulfuric acid, aqueous ammonia, or the like if necessary.
- The plating bath of the invention enables white trivalent chromium plating on an object to be plated by electroplating the object to be plated in the plating bath of the invention in the same manner as in a conventional chromium plating bath.
- Electroplating conditions are not particularly limited, but for example, electroplating may be performed at a bath temperature of 30 to 60°C using carbon or iridium oxide as an anode at a cathode current density of 2 to 20 A/dm2 for 1 to 15 minutes.
- Examples of the object to be plated that can be electroplated include metals such as iron, stainless steel, and brass, and resins such as ABS and PC/ABS. The object to be plated may be subjected to a treatment such as copper plating or nickel plating in advance before being plated in the plating bath of the invention.
- When white trivalent chromium plating is performed using the plating bath of the invention in this manner, the deposition rate is 0.03 to 0.17 um/min, preferably 0.04 to 0.13 um/min, which is equal to or higher than the deposition rate when conventional hexavalent chromium plating is performed.
- Therefore, the deposition rate of white trivalent chromium plating can be improved by incorporating the sulfur-containing organic compound represented by the general formula (I) or the like in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, and a pH buffering agent.
- A chromium-plated product thus obtained is white, and has an L* value of 80 or more, preferably 82 or more, more preferably 83 or more, and particularly preferably 83 to 84, as measured using a color difference meter, and the color tone is equivalent to that of hexavalent chromium plating.
- The white chromium-plated product can be used for the same applications as conventional hexavalent chromium-plated products, but is particularly suitable for products for decorative applications such as cars, motorcycles, and metal fittings.
- Hereinafter, the invention will be described in detail with reference to Examples, but the invention is by no means limited to these Examples.
- A trivalent chromium plating bath was prepared by dissolving the components shown in Table 1 in water and adjusting the pH with aqueous ammonia. A Hull cell test was performed on the trivalent chromium plating bath using a nickel-plated brass plate. The Hull cell test conditions are as follows: current: 5 A; and plating time: 3 minutes. After plating, the film thickness of the brass plate was measured with X-ray fluorescence at a point where the current density is 10 A/dm2, and the deposition rate was calculated. Further, the appearance after plating was evaluated based on an L* value, an a* value, and a b* value obtained using a color difference meter (manufactured by Konica Minolta, Inc.). These results are also shown in Table 1.
[Table 1] Comparative Product 1 Example Product 1 Example Product 2 Example Product 3 Comparative Product 2 Example Product 4 Example Product 5 Example Product 6 Comparative Product 3 Example Product 7 Comparative Product 4 Example Product 8 Basic chromium sulfate (g/L) 19.5 19.5 19.5 19.5 19.5 19.5 19.5 19.5 64 64 64 64 Chromium concentration (g/L) 3 3 3 3 3 3 3 3 10 10 10 10 Malic acid (g/L) 3 3 3 3 Diammonium tartrate (g/L) 4 4 4 4 30 30 30 30 Potassium sulfate (g/L) 150 150 150 150 150 150 150 150 150 150 150 150 Boric acid (g/L) 70 70 70 70 70 70 70 70 70 70 70 70 Saccharin (g/L) 3 3 3 3 3 3 3 3 3 3 Thiazolidine (mg/L) 10 Rhodanine (mg/L) 20 30 2,4-Thiazolidinedione (mg/L) 20 3-Aminorhodanine (mg/L) 10 20 20 Thiazolidin-2-one (mg/L) 10 pH 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Bath temperature (°C) 55 55 55 55 55 55 55 55 55 55 55 55 Color tone L* 83.45 83.45 83.24 83.01 82.9 80.24 83.17 82.14 82.97 83.47 80.57 83.62 Color tone a* -0.7 -0.66 -0.68 -0.81 -0.81 -0.65 -0.61 -0.66 -0.82 -0.58 -0.52 -0.5 Color tone b* -0.13 -0.74 -0.55 -0.68 0.1 0.53 -0.58 -0.32 0.05 -0.68 0.8 -1.12 Film thickness (µm) 0.061 0.131 0.15 0.27 0.093 0.158 0.332 0.169 0.104 0.234 0.04 0.178 Deposition rate (µm/min) 0.020 0.044 0.050 0.090 0.031 0.053 0.110 0.056 0.035 0.078 0.013 0.059 - From these results, it was found that use of the compound represented by the general formula (I) as the sulfur-containing organic compound in the plating bath of the invention enables a high plating deposition rate, a white appearance, and an L* value of 80 or more. In particular, it was found that use of the compound represented by the general formula (II) as the sulfur-containing organic compound enables a high plating deposition rate, a white appearance, and an L* value of 83 or more. It was also found that the deposition of chromium is stabilized by further incorporating saccharin or a salt thereof in the plating bath of the invention.
- The plating bath of the invention can be used for various applications in the same manner as white plating using hexavalent chromium.
Claims (7)
- A white trivalent chromium plating bath comprising a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and one type or two or more types of sulfur-containing organic compounds represented by the following general formula (I) :
- A white trivalent chromium plating bath comprising a trivalent chromium compound, a complexing agent, a sulfate serving as a conductive salt, a pH buffering agent, and one type or two or more types of sulfur-containing organic compounds represented by the following general formula (II) :
- The white trivalent chromium plating bath according to claim 1 or 2, wherein the complexing agent is a dicarboxylic acid or a salt thereof.
- The white trivalent chromium plating bath according to claim 3, wherein the dicarboxylic acid is malic acid and/or tartaric acid.
- The white trivalent chromium plating bath according to any one of claims 1 to 4, further comprising saccharin or a salt thereof.
- A white trivalent chromium plating method for an object to be plated, the method comprising electroplating the object to be plated in the white trivalent chromium plating bath according to any one of claims 1 to 5.
- A method for improving a deposition rate of white trivalent chromium plating, the method comprising incorporating a sulfur-containing organic compound represented by the following general formula (I):
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| JP2021122970A JP2023018744A (en) | 2021-07-28 | 2021-07-28 | White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using the same |
| PCT/JP2022/028711 WO2023008406A1 (en) | 2021-07-28 | 2022-07-26 | White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using same |
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| GB2093861B (en) * | 1981-02-09 | 1984-08-22 | Canning Materials W Ltd | Bath for electrodeposition of chromium |
| MX2010003543A (en) * | 2007-10-02 | 2010-05-17 | Atotech Deutschland Gmbh | Crystalline chromium alloy deposit. |
| US9765437B2 (en) * | 2009-03-24 | 2017-09-19 | Roderick D. Herdman | Chromium alloy coating with enhanced resistance to corrosion in calcium chloride environments |
| ES2578503T3 (en) * | 2011-05-03 | 2016-07-27 | Atotech Deutschland Gmbh | Electrometallized bath and method to produce dark chrome layers |
| US11047064B2 (en) * | 2013-01-10 | 2021-06-29 | Coventya, Inc. | Apparatus and method to maintaining trivalent chromium bath plating |
| EP3147388A1 (en) * | 2015-09-25 | 2017-03-29 | Enthone, Incorporated | Flexible color adjustment for dark cr(iii)-platings |
| WO2019117178A1 (en) * | 2017-12-13 | 2019-06-20 | 株式会社Ｊｃｕ | Trivalent chromium plating solution and method for chromium-plating using same |
| US20210317589A1 (en) * | 2018-07-03 | 2021-10-14 | Jcu Corporation | Trivalent chromium plating solution and chromium plating method using same |
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