JP2023018744A - White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using the same - Google Patents
White trivalent chromium plating bath and white trivalent chromium plating method for object to be plated using the same Download PDFInfo
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- trivalent chromium
- plating bath
- chromium plating
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- 238000007747 plating Methods 0.000 title claims abstract description 80
- 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 46
- 239000011651 chromium Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 12
- 239000006174 pH buffer Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 235000019204 saccharin Nutrition 0.000 claims description 10
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 10
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 9
- 229940081974 saccharin Drugs 0.000 claims description 9
- 238000009713 electroplating Methods 0.000 claims description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 150000001875 compounds Chemical class 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
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-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
- ZBUUHLDYMKTVLT-UHFFFAOYSA-N 3-amino-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound NN1C(=O)CSC1=S ZBUUHLDYMKTVLT-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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 2
- SLYRGJDSFOCAAI-UHFFFAOYSA-N 1,3-thiazolidin-2-one Chemical compound O=C1NCCS1 SLYRGJDSFOCAAI-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 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
- 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
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 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
- 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
- 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 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
- 230000000694 effects Effects 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
- 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
- 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
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate 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
- 230000000087 stabilizing effect Effects 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
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、白色３価クロムめっき浴およびこれを利用した被めっき物への白色３価クロムめっき方法に関する。 TECHNICAL FIELD 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 white trivalent chromium plating bath.
クロムめっきは、銀白色の外観を有するため装飾用のコーティング膜として用いられている。このクロムめっきには６価のクロムが用いられていたが、近年ではこの６価のクロムが環境に影響を及ぼすため、その使用が制限されてきていて、３価のクロムを用いる技術へシフトしてきている。 Chrome plating is used as a decorative coating film because it has a silvery white appearance. Hexavalent chromium was used for this chromium plating, but in recent years this hexavalent chromium affects the environment, so its use has been restricted, and there has been a shift to technology that uses trivalent chromium. ing.
このような３価のクロムを用いる技術としては、多数報告されていて、例えば、水溶性３価クロム塩、リンゴ酸等の３価クロムイオン用錯化剤、ｐＨ緩衝化合物、チオ尿素等の硫黄含有有機化合物およびサッカリン等の水溶性化合物を含有し、ｐＨが２．８～４．２のクロム電解めっき溶液が知られている（特許文献１）。 Many techniques using such trivalent chromium have been reported. A chromium electroplating solution containing an organic compound and a water-soluble compound such as saccharin and having a pH of 2.8 to 4.2 is known (Patent Document 1).
しかしながら、この３価のクロムめっき浴は、めっきの析出速度が遅く、実用的なものではなかった。 However, this trivalent chromium plating bath has a slow plating deposition rate and is not practical.
本出願人は、３価のクロムめっき浴においてめっきの析出速度が速く、実用的なものを開発したが（特許文献２：３価クロム化合物、錯化剤、伝導性塩として硫酸カリウムおよび硫酸アンモニウム、ｐＨ緩衝剤、硫黄含有有機化合物を含有する３価クロムめっき浴であって、錯化剤として、ヒドロキシ基を２つ以上、カルボキシ基を２つ以上有するカルボン酸またはその塩を用い、硫黄含有有機化合物として、サッカリンまたはその塩と、アリル基を有する硫黄含有有機化合物を組み合わせて用いることを特徴とする３価クロムめっき浴）、これよりも組成が単純で、装飾用途としても適するような外観が得られるめっき技術を開発することを課題とした。 The present applicant has developed a practical trivalent chromium plating bath with a high deposition rate of plating (Patent Document 2: trivalent chromium compound, complexing agent, potassium sulfate and ammonium sulfate as conductive salts, A trivalent chromium plating bath containing a pH buffer and a sulfur-containing organic compound, wherein a carboxylic acid or a salt thereof having two or more hydroxyl groups and two or more carboxy groups is used as a complexing agent, and a sulfur-containing organic compound is used. A trivalent chromium plating bath characterized by using a combination of saccharin or a salt thereof and a sulfur-containing organic compound having an allyl group as a compound), which has a simpler composition and an appearance suitable for decorative purposes. The task was to develop the plating technology that can be obtained.
本発明者らは、上記課題を解決するために鋭意研究した結果、白色３価クロムめっき浴に特定の構造の硫黄含有有機化合物を含有させることにより上記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive research to solve the above problems, the present inventors found that the above problems can be solved by adding a sulfur-containing organic compound having a specific structure to the white trivalent chromium plating bath, and completed the present invention. let me
すわなち、本発明は、３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤、 下記一般式（I）
で表される硫黄含有有機化合物の１種または２種以上を含有することを特徴とする白色３価クロムめっき浴である。
That is, the present invention provides a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, a pH buffer, and the following general formula (I):
A white trivalent chromium plating bath characterized by containing one or more sulfur-containing organic compounds represented by
また、本発明は、被めっき物を上記白色３価クロムめっき浴で電気めっきすることを特徴とする被めっき物への白色３価クロムめっき方法である。 The present invention also provides a white trivalent chromium plating method for an object to be plated, characterized by electroplating the object to be plated with the white trivalent chromium plating bath.
更に、本発明は、上記一般式（I）で表される硫黄含有有機化合物を、３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤を含有する白色３価クロムめっき浴に含有させることを特徴とする白色３価クロムめっきの析出速度向上方法である。 Further, the present invention provides a white trivalent chromium plating containing a sulfur-containing organic compound represented by the above general formula (I), a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, and a pH buffer. A method for improving the deposition rate of white trivalent chromium plating, characterized by containing it in a bath.
本発明の白色３価クロムめっき浴を用いれば、６価クロムめっきと比べて色調や析出速度が同等の白色の３価クロムめっきをすることができる。 By using the white trivalent chromium plating bath of the present invention, white trivalent chromium plating having a color tone and deposition rate equivalent to those of hexavalent chromium plating can be obtained.
本発明の白色３価クロムめっき浴（以下、「本発明めっき浴」という）は、３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤、硫黄含有有機化合物を含有するものである。 The white trivalent chromium plating bath of the present invention (hereinafter referred to as "the plating bath of the present invention") contains a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, a pH buffer, and a sulfur-containing organic compound. It is a thing.
上記硫黄含有有機化合物は、下記一般式（I）
上記一般式（I）で表される硫黄含有有機化合物で好ましいものとしては、下記一般式（II）
一般式（I）で表される硫黄含有有機化合物のより好ましいものとしては、例えば、チアゾリジン、ロダニン、チアゾリジン－２－オン、３－メチルチアゾリジン－２－チオン、４－チオキソ－１，３－チアゾリジン－２－オン、２－メルカプトチアゾリン（別名：２－チアゾリン－２－チオール）、２，４－チアゾリジンジオン、３－メチル－１，３－チアゾラン－２，４－ジオン、３－アミノロダニン、３－メチルロダニン、３－エチルロダニン、３－アリルロダニン、ロダニン－３－酢酸、ロダニン－３－プロピオン酸等が挙げられ、これらの中でもロダニン、２，４－チアゾリジンジオン、３－アミノロダニン、３－エチルロダニンが好ましい。これら硫黄含有有機化合物は１種または２種以上を組み合わせて用いることができる。 More preferred sulfur-containing organic compounds represented by general formula (I) include, for example, thiazolidine, rhodanine, thiazolidin-2-one, 3-methylthiazolidine-2-thione, 4-thioxo-1,3-thiazolidine -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, rhodanine-3-propionic acid and the like, among which rhodanine, 2,4-thiazolidinedione, 3-aminorhodanine and 3-ethylrhodanine are preferred. These sulfur-containing organic compounds can be used singly or in combination of two or more.
本発明めっき浴における、一般式（I）等で表される硫黄含有有機化合物の含有量は特に限定されないが、例えば、１～５００ｍｇ／Ｌ、好ましくは５～１００ｍｇ／Ｌである。 The content of the sulfur-containing organic compound represented by general formula (I) or the like in the plating bath of the present invention is not particularly limited, but is, for example, 1 to 500 mg/L, preferably 5 to 100 mg/L.
本発明めっき浴に用いられる３価クロム化合物は、特に限定されないが、例えば、塩基性硫酸クロム、硫酸クロム、塩化クロム、スルファミン酸クロム、酢酸クロムであり、好ましくは塩基性硫酸クロム、硫酸クロムである。これら３価クロム化合物は１種または２種以上を組み合わせて用いることができる。本発明めっき浴における３価クロム化合物の含有量は特に限定されないが、例えば金属クロムとして１～２５ｇ／Ｌであり、好ましくは１～１５ｇ／Ｌである。 The trivalent chromium compound used in the plating bath of the present invention is not particularly limited. be. These trivalent chromium compounds can be used singly or in combination of two or more. Although the content of the trivalent chromium compound in the plating bath of the present invention is not particularly limited, it is, for example, 1 to 25 g/L, preferably 1 to 15 g/L as metallic chromium.
本発明めっき浴に用いられる錯化剤は、特に限定されないが、例えば、リンゴ酸、酒石酸等のジカルボン酸や、リンゴ酸ナトリウム、酒石酸ナトリウム、酒石酸ジアンモニウム等のジカルボン酸の塩等が挙げられ、好ましくはリンゴ酸または酒石酸ジアンモニウムである。これら錯化剤は１種または２種以上を組み合わせて用いることができる。本発明めっき浴における錯化剤の含有量は特に限定されないが、例えば、１～９０ｇ／Ｌであり、好ましくは２～５０ｇ／Ｌである。 The complexing agent used in the plating bath of the present invention is not particularly limited. Malic acid or diammonium tartrate is preferred. These complexing agents can be used singly or in combination of two or more. Although the content of the complexing agent in the plating bath of the present invention is not particularly limited, it is, for example, 1 to 90 g/L, preferably 2 to 50 g/L.
本発明めっき浴に用いられる伝導性塩は、硫酸カリウム、硫酸アンモニウム、硫酸ナトリウム等の硫酸塩である。これら硫酸塩の中でも硫酸カリウムが好ましい。これら硫酸塩は１種または２種以上を組み合わせて用いることができる。本発明めっき浴における硫酸塩の含有量は特に限定されないが、例えば、１００～３００ｇ／Ｌであり、好ましくは１２０～２４０ｇ／Ｌである。 The conductive salts used in the plating bath of the present invention are sulfates such as potassium sulfate, ammonium sulfate and sodium sulfate. Among these sulfates, potassium sulfate is preferred. These sulfates can be used singly or in combination of two or more. Although the content of sulfate in the plating bath of the present invention is not particularly limited, it is, for example, 100 to 300 g/L, preferably 120 to 240 g/L.
本発明めっき浴に用いられるｐＨ緩衝剤は、特に限定されないが、例えば、ホウ酸、ホウ酸ナトリウム、ホウ酸カリウム、リン酸、リン酸水素２カリウム等が挙げられ、これらの中でもホウ酸、ホウ酸ナトリウムが好ましい。これらｐＨ緩衝剤は１種または２種以上を組み合わせて用いることができる。本発明めっき浴におけるｐＨ緩衝剤の含有量は特に限定されないが、例えば、３０～１５０ｇ／Ｌであり、好ましくは５０～１１０ｇ／Ｌである。 The pH buffering agent used in the plating bath of the present invention is not particularly limited, and examples thereof include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate. Sodium phosphate is preferred. These pH buffers can be used singly or in combination of two or more. Although the content of the pH buffering agent in the plating bath of the present invention is not particularly limited, it is, for example, 30 to 150 g/L, preferably 50 to 110 g/L.
本発明めっき浴には、更に、サッカリンまたはその塩を含有させることが、クロムの析出を安定化させるために好ましい。サッカリンまたはその塩としては、例えば、サッカリン、サッカリン酸ナトリウム等が挙げられる。これらサッカリンまたはその塩は１種または２種以上を組み合わせて用いることができる。本発明めっき浴におけるサッカリンまたはその塩の含有量は特に限定されないが、例えば、０．５～１０ｇ／Ｌであり、好ましくは２～８ｇ／Ｌである。なお、当然ながら本発明めっき浴におけるサッカリンの含有量は上記した一般式（I）等で表される硫黄含有有機化合物の含有量には含まれない。 The plating bath of the present invention preferably further contains saccharin or a salt thereof for stabilizing the deposition of chromium. Examples of saccharin or salts thereof include saccharin, sodium saccharinate and the like. These saccharins or salts thereof can be used singly or in combination of two or more. Although the content of saccharin or a salt thereof in the plating bath of the present invention is not particularly limited, it is, for example, 0.5 to 10 g/L, preferably 2 to 8 g/L. Of course, the content of saccharin in the plating bath of the present invention is not included in the content of sulfur-containing organic compounds represented by the general formula (I).
本発明めっき浴の好ましい態様としては、例えば、上記成分を含有するものでもよいが、上記成分のみを含有するもの（上記成分からなるもの）でもよいことは言うまでもない。 As a preferred embodiment of the plating bath of the present invention, for example, it may contain the above components, but it goes without saying that it may contain only the above components (consisting of the above components).
本発明めっき浴には、更に、本発明の効果を損なわない範囲で、ポリエチレングリコール等の高分子化合物、アスコルビン酸、アスコルビン酸ナトリウム、過酸化水素、界面活性剤、抱水クロラール、イミノジ酢酸等を含有させても良い。 The plating bath of the present invention further contains polymer compounds such as polyethylene glycol, ascorbic acid, sodium ascorbate, hydrogen peroxide, surfactants, chloral hydrate, iminodiacetic acid, etc., to the extent that the effects of the present invention are not impaired. may be included.
本発明めっき浴のｐＨは酸性であれば特に限定されず、例えば、２～４．５が好ましく、３～４．５がより好ましい。 The pH of the plating bath of the present invention is not particularly limited as long as it is acidic, and is preferably 2 to 4.5, more preferably 3 to 4.5.
本発明めっき浴の調製法は特に限定されず、例えば、５０～６０℃の水に３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤、硫黄含有有機化合物（必要によりサッカリンまたはその塩）を添加、混合し、最後に必要により硫酸、アンモニア水等でｐＨを調整することにより、調製することができる。 The method of preparing the plating bath of the present invention is not particularly limited. saccharin or a salt thereof) are added and mixed, and finally, if necessary, the pH is adjusted with sulfuric acid, aqueous ammonia or the like.
本発明めっき浴は、従来のクロムめっき浴と同様に、被めっき物を本発明めっき浴で電気めっきすることにより被めっき物へ白色３価クロムめっきをすることができる。 In the plating bath of the present invention, white trivalent chromium plating can be applied to the article to be plated by electroplating the article to be plated with the plating bath of the present invention in the same manner as the conventional chromium plating bath.
電気めっきの条件は特に限定されないが、例えば、浴温が３０～６０℃、アノードがカーボンあるいは酸化イリジウム、陰極電流密度が２～２０Ａ／ｄｍ２で１～１５分間電気めっきを行えばよい。 Electroplating conditions are not particularly limited. For example, electroplating may be performed at a bath temperature of 30 to 60° C., an anode of carbon or iridium oxide, and a cathode current density of 2 to 20 A/dm 2 for 1 to 15 minutes.
電気めっきすることのできる被めっき物としては、例えば、鉄、ステンレス、真鍮等の金属、ＡＢＳ、ＰＣ／ＡＢＳ等の樹脂が挙げられる。なお、この被めっき物は本発明のめっき浴でめっきする前に予め銅めっき、ニッケルめっき等の処理をしておいてもよい。 Examples of objects to 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 copper plating, nickel plating, or the like in advance before being plated with the plating bath of the present invention.
このように本発明めっき浴を用いて白色３価クロムめっきをすると析出速度は、０．０３～０．１７μｍ／分、好ましくは０．０４～０．１３μｍ／分となり、従来の６価クロムめっきと比べて析出速度が同等以上である。 When white trivalent chromium plating is performed using the plating bath of the present invention in this way, the deposition rate is 0.03 to 0.17 μm/minute, preferably 0.04 to 0.13 μm/minute, which is comparable to conventional hexavalent chromium plating. The deposition rate is equal or higher than that of
そのため、上記した一般式（I）等で表される硫黄含有有機化合物は、３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤を含有する白色３価クロムめっき浴に含有させることにより白色３価クロムめっきの析出速度を向上させることができる。 Therefore, the sulfur-containing organic compound represented by the above general formula (I) etc. is used in a white trivalent chromium plating bath containing a trivalent chromium compound, a complexing agent, a sulfate as a conductive salt, and a pH buffer. By containing it, the deposition rate of white trivalent chromium plating can be improved.
斯くして得られるクロムめっき製品は、白色で有り、色彩色差計を用いて測定されるＬ＊値が８０以上、好ましくは８２以上、より好ましくは８３以上、特に好ましくは８３～８４となり、６価クロムめっきと比べて色調が同等のものとなる。 The 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, particularly preferably 83 to 84, as measured using a colorimeter. The color tone is equivalent to that of valent chromium plating.
この白色のクロムめっき製品は、従来の６価クロムめっき製品と同様の用途に用いることができるが、特に、車、オートバイ、金具等の装飾用途の製品に好適である。 This white chromium-plated product can be used for the same applications as conventional hexavalent chromium-plated products, but is particularly suitable for decorative products such as cars, motorcycles, and metal fittings.
以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples.
実 施 例 １
白色クロムめっき：
表１に記載の成分を水に溶解して、ｐＨをアンモニア水で調整して３価クロムめっき浴を調製した。この３価クロムめっき浴について、ニッケルめっきを施した真鍮板を用いてハルセル試験を行った。ハルセル試験の条件は電流５Ａ、めっき時間３分である。めっき後、真鍮板の電流密度１０Ａ／ｄｍ２に該当する箇所の膜厚を蛍光Ｘ線で測定し、析出速度を算出した。更に、めっき後の外観は色彩色差計（コニカミノルタ社製）を用いてＬ＊値、ａ＊値、ｂ＊値により評価した。それらの結果も表１に示した。
Example 1
White chrome plating:
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 this trivalent chromium plating bath using a nickel-plated brass plate. The Hull cell test conditions are a current of 5 A and a plating time of 3 minutes. After plating, the film thickness was measured by fluorescent X-rays at a portion of the brass plate corresponding to a current density of 10 A/dm 2 , and the deposition rate was calculated. Furthermore, the appearance after plating was evaluated by L * value, a * value, and b * value using a color difference meter (manufactured by Konica Minolta). Those results are also shown in Table 1.
この結果から、本発明めっき浴は、硫黄含有有機化合物として一般式（I）のものを用いることにより、めっきの析出速度が速く、外観が白色でＬ＊値が８０以上となることが分かった。特に硫黄含有有機化合物として一般式（II）のものを用いることにより、めっきの析出速度が速く、外観が白色でＬ＊値が８３以上となることが分かった。また、本発明めっき浴に、更にサッカリンまたはその塩を含有させることによりクロムの析出が安定化することも分かった。 From this result, it was found that the plating bath of the present invention, by using the sulfur-containing organic compound represented by the general formula (I), has a high plating deposition rate, a white appearance, and an L * value of 80 or more. . In particular, it has been found that the use of the sulfur-containing organic compound represented by the general formula (II) results in a fast 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 adding saccharin or a salt thereof to the plating bath of the present invention.
本発明めっき浴は、６価のクロムを用いた白色めっきと同様に各種用途に用いることができる。 The plating bath of the present invention can be used for various purposes like white plating using hexavalent chromium.
Claims (7)
で表される硫黄含有有機化合物の１種または２種以上を含有することを特徴とする白色３価クロムめっき浴。 trivalent chromium compound, complexing agent, sulfate as conductive salt, pH buffer, general formula (I) below
White trivalent chromium plating bath characterized by containing one or more sulfur-containing organic compounds represented by.
で表される硫黄含有有機化合物の１種または２種以上を含有することを特徴とする白色３価クロムめっき浴。 Trivalent chromium compound, complexing agent, sulfate as conductive salt, pH buffer, general formula (II) below
White trivalent chromium plating bath characterized by containing one or more sulfur-containing organic compounds represented by.
で表される硫黄含有有機化合物を、３価クロム化合物、錯化剤、伝導性塩としての硫酸塩、ｐＨ緩衝剤を含有する白色３価クロムめっき浴に含有させることを特徴とする白色３価クロムめっきの析出速度向上方法。 The following general formula (I)
A white trivalent chromium plating bath containing a sulfur-containing organic compound represented by a trivalent chromium compound, a complexing agent, a sulfate salt as a conductive salt, and a pH buffer. A method for improving the deposition rate of chromium plating.
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| CN202280049583.XA CN117642528A (en) | 2021-07-28 | 2022-07-26 | White trivalent chromium plating bath and method for plating 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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