JP2009235456A - Solution for use in electrolytically treating trivalent-chromium plated film - Google Patents
Solution for use in electrolytically treating trivalent-chromium plated film Download PDFInfo
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- JP2009235456A JP2009235456A JP2008080755A JP2008080755A JP2009235456A JP 2009235456 A JP2009235456 A JP 2009235456A JP 2008080755 A JP2008080755 A JP 2008080755A JP 2008080755 A JP2008080755 A JP 2008080755A JP 2009235456 A JP2009235456 A JP 2009235456A
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- chromium
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- trivalent chromium
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- 239000011651 chromium Substances 0.000 title claims abstract description 75
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000007747 plating Methods 0.000 claims description 73
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 68
- 229910001430 chromium ion Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 230000003139 buffering effect Effects 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 12
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 aliphatic monocarboxylic acids Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-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 Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 2
- 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 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
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004471 Glycine 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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910003086 Ti–Pt Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、３価クロムめっき液から形成されたクロムめっき皮膜用の電解処理液、及び該電解処理液を用いる電解処理方法に関する。 The present invention relates to an electrolytic treatment solution for a chromium plating film formed from a trivalent chromium plating solution, and an electrolytic treatment method using the electrolytic treatment solution.
クロムめっきは、装飾用、工業用など各種の分野で広く利用されており、従来から、主として、クロム成分として６価クロムを多量に含有するクロムめっき浴を用いてめっき処理が行われている。 Chromium plating is widely used in various fields such as decoration and industrial use. Conventionally, plating is performed mainly using a chromium plating bath containing a large amount of hexavalent chromium as a chromium component.
しかしながら、６価クロムを含有するめっき浴を用いる場合には、めっき時に発生する６価クロムを含有するミストの有害性が問題となっており、作業環境の改善や廃水処理の効率などを考慮して、毒性の少ない３価クロム化合物を用いた３価めっき浴が普及してきている（下記非特許文献１参照）。 However, when using a plating bath containing hexavalent chromium, the harmfulness of the mist containing hexavalent chromium generated during plating is a problem, considering the improvement of the working environment and the efficiency of wastewater treatment. Therefore, a trivalent plating bath using a trivalent chromium compound with less toxicity has been widespread (see Non-Patent Document 1 below).
しかしながら，３価クロムめっき浴から得られるクロムめっき皮膜（３価クロムめっき皮膜）は、従来の６価クロムを含むめっき浴から得られるクロムめっき皮膜（６価クロムめっき皮膜）と比較した場合、耐食性については一般的にやや劣ることが知られている（下記特許文献１参照）。また，３価クロムめっき浴はそれ自身にクロメート皮膜を形成する働きがないため，パイプ内部などクロムめっきが析出しない部分の耐食性が６価クロムめっきに比較して劣るという問題点がある（下記非特許文献１参照）。 However, the chromium plating film obtained from a trivalent chromium plating bath (trivalent chromium plating film) is more resistant to corrosion when compared with a chromium plating film obtained from a conventional plating bath containing hexavalent chromium (hexavalent chromium plating film). Is generally known to be slightly inferior (see Patent Document 1 below). In addition, since the trivalent chromium plating bath itself does not function to form a chromate film, there is a problem that the corrosion resistance of the portion where the chromium plating does not deposit, such as the inside of the pipe, is inferior to that of the hexavalent chromium plating. Patent Document 1).
このため，現状では、３価クロムめっき皮膜の耐食性を向上させる目的で、クロメート皮膜を形成する働きを有する６価のクロム塩であるクロム酸（CrO3）水溶液への浸漬処理や重クロム酸（K2Cr2O7）水溶液中での陰極電解処理（電解クロメート）等を行なうことが多い。 For this reason, at present, for the purpose of improving the corrosion resistance of the trivalent chromium plating film, it is immersed in a chromic acid (CrO 3 ) aqueous solution, which is a hexavalent chromium salt having a function of forming a chromate film, and dichromic acid ( K 2 Cr 2 O 7 ) Cathodic electrolytic treatment (electrolytic chromate) in aqueous solution is often performed.
しかしながら、これらの処理方法を採用する場合には、３価クロムを含むめっき液を用いてめっき皮膜を形成した場合であっても、後処理工程において６価クロムを含む処理液を用いるために、やはり作業環境上問題がある。
本発明は、上記した従来技術の問題点に鑑みてなされてものであり、その主な目的は、
６価クロム化合物を用いることなく３価クロムめっき皮膜の耐食性を大きく向上させることが可能な、新規な３価クロムめっき皮膜の処理液及び処理方法を提供することである。
The present invention has been made in view of the above-mentioned problems of the prior art, and its main purpose is as follows.
It is an object to provide a novel trivalent chromium plating film treatment liquid and treatment method capable of greatly improving the corrosion resistance of a trivalent chromium plating film without using a hexavalent chromium compound.
本発明者は、上記した目的を達成すべく鋭意研究を重ねた結果、３価クロムめっき皮膜を有する物品を３価クロム化合物を含有する水溶液中で比較的低い電流密度で陰極電解処理することによって、６価クロム化合物を用いることなく、３価クロムめっき皮膜の耐食性を大きく向上させることが可能となることを見出し、ここに本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventor has carried out a cathodic electrolytic treatment of an article having a trivalent chromium plating film in an aqueous solution containing a trivalent chromium compound at a relatively low current density. It was found that the corrosion resistance of the trivalent chromium plating film can be greatly improved without using a hexavalent chromium compound, and the present invention has been completed here.
即ち、本発明は、３価クロムめっき液から形成されたクロムめっき皮膜用の電解処理液、及び該電解処理液を用いる電解処理方法を提供するものである。
１． 水溶性３価クロム化合物を含有する水溶液からなる、３価クロムめっき液から形成されたクロムめっき皮膜用電解処理液。
２． 水溶性３価クロム化合物を３価クロムイオン濃度として５〜５０ｇ／Ｌ含有するｐＨ２〜８の水溶液である上記項１に記載の電解処理液。
３． 更に、ｐＨ緩衝能力を有する化合物を含有することを特徴とする上記項１又は２に記載の電解処理液。
４． 上記項１〜３のいずれかに記載の電解処理液中において、３価クロムめっき液から形成されたクロムめっき皮膜を有する物品を陰極電解することを特徴とする、３価クロムめっき液から形成されたクロムめっき皮膜の電解処理方法。
５． 陰極電流密度０．１〜５Ａ／ｄｍ２で陰極電解処理を行う上記項４に記載の方法。
That is, the present invention provides an electrolytic treatment solution for a chromium plating film formed from a trivalent chromium plating solution, and an electrolytic treatment method using the electrolytic treatment solution.
1. An electrolytic treatment solution for a chromium plating film formed from a trivalent chromium plating solution comprising an aqueous solution containing a water-soluble trivalent chromium compound.
2. Item 2. The electrolytic treatment solution according to Item 1, which is an aqueous solution having a pH of 2 to 8 and containing 5 to 50 g / L of a water-soluble trivalent chromium compound as a trivalent chromium ion concentration.
3. 3. The electrolytic treatment solution according to item 1 or 2, further comprising a compound having a pH buffering ability.
4). The electrolytic treatment solution according to any one of the above items 1 to 3, wherein an article having a chromium plating film formed from a trivalent chromium plating solution is catholyzed and is formed from a trivalent chromium plating solution. Electrolytic treatment method for chrome plating film.
5. The method according to Item 4 for cathodic electrolysis treatment with cathode current density 0.1~5A / dm 2.
以下、本発明の電解処理液及び電解処理方法について具体的に説明する。 Hereinafter, the electrolytic treatment solution and the electrolytic treatment method of the present invention will be specifically described.
電解処理液
本発明の電解処理液は、水溶性３価クロム化合物を含有する水溶液からなるものである。
水溶性３価クロム化合物としては、クロム成分として３価クロムを含む水溶液化合物であれば特に限定なく使用できる。このような 水溶液３価クロム化合物としては、硫酸クロム、塩基性硫酸クロム、硝酸クロム、酢酸クロム、塩化クロム、リン酸クロムなどを例示できる。これらの水溶性３価クロム化合物は、一種単独または二種以上混合して用いることができる。
Electrolytic treatment liquid The electrolytic treatment liquid of the present invention comprises an aqueous solution containing a water-soluble trivalent chromium compound.
The water-soluble trivalent chromium compound can be used without particular limitation as long as it is an aqueous solution compound containing trivalent chromium as a chromium component. Examples of such an aqueous trivalent chromium compound include chromium sulfate, basic chromium sulfate, chromium nitrate, chromium acetate, chromium chloride, and chromium phosphate. These water-soluble trivalent chromium compounds can be used singly or in combination of two or more.
本発明の電解処理液では、３価クロムイオン濃度が低すぎる場合には、後述する条件で電解処理を行った場合であっても３価クロムめっき皮膜の耐食性を十分に向上させることができない。また、３価クロムイオン濃度を高くすることにより、電解処理によって良好な耐食性を付与することが可能となるが、濃度が高すぎると、クロムめっき皮膜の表面が黄色の変色が生じて外観が損なわれることがある。よって、この様な観点から、水溶性３価クロム化合物の濃度は、３価クロムイオンの濃度として、５〜５０ｇ／Ｌ程度とすることが好ましく、１０〜３０ｇ／Ｌ程度とすることがより好ましい。 In the electrolytic treatment solution of the present invention, when the trivalent chromium ion concentration is too low, the corrosion resistance of the trivalent chromium plating film cannot be sufficiently improved even when electrolytic treatment is performed under the conditions described later. In addition, by increasing the trivalent chromium ion concentration, it is possible to impart good corrosion resistance by electrolytic treatment. However, if the concentration is too high, the surface of the chromium plating film is discolored yellow and the appearance is impaired. May be. Therefore, from such a viewpoint, the concentration of the water-soluble trivalent chromium compound is preferably about 5 to 50 g / L, more preferably about 10 to 30 g / L as the concentration of the trivalent chromium ions. .
本発明の電解処理液は、ｐＨが２〜８程度の範囲内にあることが好ましい。ｐＨがこの範囲内にある場合には、後述する条件で陰極電解処理を行うことによって、めっき皮膜の外観などを損なうことなく、良好な耐食性を付与できる。これに対して、ｐＨが低すぎると、３価クロムめっき皮膜が処理液中に溶解する可能性があるので好ましくない。一方、ｐＨが高すぎる場合には、陰極電解によって被処理物の表面に緑色のクロム酸化物が付着することがあるので、やはり好ましくない。 The electrolytic treatment solution of the present invention preferably has a pH in the range of about 2-8. When the pH is within this range, good corrosion resistance can be imparted without deteriorating the appearance of the plating film by performing cathodic electrolysis under the conditions described later. On the other hand, if the pH is too low, the trivalent chromium plating film may be dissolved in the treatment liquid, which is not preferable. On the other hand, if the pH is too high, green chromium oxide may adhere to the surface of the object to be treated by cathodic electrolysis, which is also not preferable.
本発明の電解処理液には、必要に応じて、所定のｐＨ範囲においてｐＨ緩衝能力を有する化合物を添加することによって、電解処理液のｐＨ変動を抑制することができる。この様なｐＨ緩衝能力を有する化合物としては、水溶性脂肪族カルボン酸、ホウ酸、硼砂、リン酸、リン酸２水素カリウム、グリシン、酒石酸、フタル酸等を例示できる。特に、水溶性脂肪族カルボン酸類は、ｐＨ緩衝剤としての作用と同時に、３価クロムイオンの錯化剤として作用してｐＨ調整の際の水酸化物の生成を抑制できる。この様な脂肪族カルボン酸類としては、例えばギ酸，酢酸などの脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸などの脂肪族ジカルボン酸；グルコン酸などの脂肪族ヒドロキシモノカルボン酸；リンゴ酸などの脂肪族ヒドロキシジカルボン酸；クエン酸などの脂肪族ヒドロキシトリカルボン酸などのカルボン酸；これらカルボン酸の水溶性塩、例えばナトリウム塩、カリウム塩などを例示できる。これらの水溶液脂肪族カルボン酸類は、一種単独又は二種以上混合して用いることができる。 If necessary, the electrolytic treatment solution of the present invention can suppress pH fluctuation of the electrolytic treatment solution by adding a compound having a pH buffering ability in a predetermined pH range. Examples of the compound having such pH buffering ability include water-soluble aliphatic carboxylic acid, boric acid, borax, phosphoric acid, potassium dihydrogen phosphate, glycine, tartaric acid, phthalic acid and the like. In particular, the water-soluble aliphatic carboxylic acids can act as a pH buffering agent and simultaneously act as a complexing agent for trivalent chromium ions to suppress the formation of hydroxide during pH adjustment. Examples of such aliphatic carboxylic acids include aliphatic monocarboxylic acids such as formic acid and acetic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid and succinic acid; aliphatic hydroxymonocarboxylic acids such as gluconic acid; malic acid Examples thereof include aliphatic hydroxydicarboxylic acids such as carboxylic acids; carboxylic acids such as aliphatic hydroxytricarboxylic acids such as citric acid; and water-soluble salts of these carboxylic acids such as sodium salts and potassium salts. These aqueous aliphatic carboxylic acids can be used singly or in combination of two or more.
ｐＨ緩衝能力を有する化合物の添加量については特に限定的ではないが、通常、10〜200g/L程度とすることができ、20〜100g/L程度とすることが好ましい。 The addition amount of the compound having pH buffering ability is not particularly limited, but can be usually about 10 to 200 g / L, preferably about 20 to 100 g / L.
更に、本発明の電解処理液は、弱酸性領域（pHが2.0〜8.0の範囲）で陰極電解を行うことから、浴電圧の上昇を抑制するために、電導性塩、例えば硫酸ナトリウム、硫酸カリウム、塩化カリウム、塩化ナトリウム、硫酸アンモニウムなどを添加してもよい。これらの導電性塩の添加量については、特に限定的ではないが、通常、5〜100g/L程度とすることが好ましく、10〜50g/L程度とすることがより好ましい。 Furthermore, the electrolytic treatment solution of the present invention performs cathodic electrolysis in a weakly acidic region (pH is in the range of 2.0 to 8.0). Potassium chloride, sodium chloride, ammonium sulfate and the like may be added. The amount of these conductive salts added is not particularly limited, but is usually preferably about 5 to 100 g / L, and more preferably about 10 to 50 g / L.
電解処理方法
本発明の電解処理方法では、被処理物としては、３価クロムめっき液から形成されたクロムめっき皮膜を有する物品を用いる。
Electrolytic treatment method In the electrolytic treatment method of the present invention, an article having a chromium plating film formed from a trivalent chromium plating solution is used as an object to be treated.
処理対象の物品にクロムめっき皮膜を形成するために用いる３価クロムめっき液としては、クロム成分として３価クロム化合物を含むクロムめっき浴であればよく、具体的な組成については特に限定はない。３価クロムめっき浴の一例を挙げると、クロム成分として、硫酸クロム，塩基性硫酸クロム，塩化クロム，酢酸クロムなどの水溶液３価クロム化合物を含み、電導性塩として、硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、塩化ナトリウム、塩化カリウム、塩化アンモニウムなどを含み、錯化剤として、ギ酸，酢酸等のモノカルボン酸又はその塩，シュウ酸、マロン酸、マレイン酸等のジカルボン酸、クエン酸、リンゴ酸、グリコール酸などのヒドロキシカルボン酸又はその塩等、尿素、チオシアン、シアン酸などの無機化合物等を含むめっき浴を例示できる。更に、ｐＨ緩衝剤として、ホウ酸、ホウ酸ナトリウム、塩化アルミニウムなどを含んでいても良い。これらの各成分の濃度については、特に限定的ではないが、例えば、３価クロム化合物については、１０〜１００g/L程度、電導性塩については、３０〜３００g/L程度、錯化剤については、５〜５０g/L程度、ｐＨ緩衝剤については、１０〜１００g/L 程度の３価クロムめっき浴を例示できる。クロムめっき皮膜を形成する条件についても特に限定はなく、使用する３価クロムめっき液に応じてめっき条件を決めればよい。 The trivalent chromium plating solution used to form a chromium plating film on the article to be treated may be a chromium plating bath containing a trivalent chromium compound as a chromium component, and the specific composition is not particularly limited. An example of a trivalent chromium plating bath includes an aqueous trivalent chromium compound such as chromium sulfate, basic chromium sulfate, chromium chloride, and chromium acetate as a chromium component, and sodium sulfate, potassium sulfate, and ammonium sulfate as conductive salts. , Sodium chloride, potassium chloride, ammonium chloride, etc. As complexing agents, monocarboxylic acids such as formic acid and acetic acid or salts thereof, dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, citric acid, malic acid, glycol Examples thereof include a plating bath containing a hydroxycarboxylic acid such as an acid or a salt thereof, an inorganic compound such as urea, thiocyanate, and cyanic acid. Further, boric acid, sodium borate, aluminum chloride or the like may be included as a pH buffer. The concentration of each of these components is not particularly limited, but for example, about 10 to 100 g / L for trivalent chromium compounds, about 30 to 300 g / L for conductive salts, and about complexing agents. About 5 to 50 g / L, and a pH buffering agent, a trivalent chromium plating bath of about 10 to 100 g / L can be exemplified. The conditions for forming the chromium plating film are not particularly limited, and the plating conditions may be determined according to the trivalent chromium plating solution used.
本発明の電解処理方法では、上記した３価クロムめっき液から形成されたクロムめっき皮膜を有する物品を被処理物として用い、前述した電解処理液中に被処理物を浸漬し、被処理物を陰極として電解処理を行えばよい。これにより、被処理物のクロムめっき皮膜の耐食性を大きく向上させることができる。 In the electrolytic treatment method of the present invention, an article having a chromium plating film formed from the above-described trivalent chromium plating solution is used as an object to be processed, and the object to be processed is immersed in the above-described electrolytic treatment liquid. Electrolytic treatment may be performed as a cathode. Thereby, the corrosion resistance of the chromium plating film of a to-be-processed object can be improved significantly.
電解条件については特に限定されないが、電解処理液中から金属クロムが析出しない電流密度あるいは電位を適応することが望ましい。また、金属クロムが析出しない電流密度範囲であっても、電流密度が高すぎると被処理物表面に黄色の皮膜が形成され外観が損なわれることがある。このため、陰極電流密度は、0.1〜5A/dm２程度とすることが好ましく、0.3〜2A/dm２程度とすることがより好ましい。 The electrolysis conditions are not particularly limited, but it is desirable to apply a current density or potential at which metal chromium does not precipitate from the electrolytic treatment solution. Even in the current density range where metallic chromium does not precipitate, if the current density is too high, a yellow film may be formed on the surface of the object to be processed and the appearance may be impaired. Therefore, the cathode current density is preferably in a 0.1~5A / dm 2 about, and more preferably a 0.3~2A / dm 2 about.
電解処理温度については特に限定されないが、例えば、20℃〜60℃程度の温度範囲とすればよい。 Although there is no particular limitation on the electrolytic treatment temperature, for example, a temperature range of about 20 ° C to 60 ° C may be used.
電解処理時間については、処理時間が極端に短い場合には十分な耐食性の向上が認められない。また，処理時間が必要以上に長い場合には、クロムめっき皮膜表面に黄色い膜が形成されて皮膜外観を損なうことがあるので好ましくない。このため、通常は、10秒〜10分程度の電解処理時間とすればよく、30秒〜2分程度の電解処理時間とすることが好ましい。 Regarding the electrolytic treatment time, when the treatment time is extremely short, sufficient improvement in corrosion resistance is not recognized. In addition, when the treatment time is longer than necessary, a yellow film is formed on the surface of the chromium plating film, which may be unfavorable. For this reason, the electrolytic treatment time is usually about 10 seconds to 10 minutes, preferably about 30 seconds to 2 minutes.
電解処理に用いるアノードについては特に限定されないが、ステンレス鋼などを用いると、長期間の電解処理により電解処理液中に金属成分（Fe，Ni，Crなど）の溶出が起こることがある。溶出した各種金属成分（特にFe，Ni）は、クロムより貴な金属であるため、電解処理時にカソード側の３価クロムめっき皮膜表面への析出が懸念される。このことから、アノードとしては、不溶解性アノードの使用が望ましく、例えば、カーボン、Ti-Pt、DSA電極（Ru酸化物系，Ir酸化物系）等の不溶性電極を用いることが好ましい。 The anode used for the electrolytic treatment is not particularly limited. However, when stainless steel or the like is used, elution of metal components (Fe, Ni, Cr, etc.) may occur in the electrolytic treatment solution due to long-term electrolytic treatment. Since the eluted various metal components (especially Fe, Ni) are noble metals than chromium, there is a concern about deposition on the surface of the trivalent chromium plating film on the cathode side during the electrolytic treatment. For this reason, it is desirable to use an insoluble anode as the anode. For example, insoluble electrodes such as carbon, Ti—Pt, and DSA electrodes (Ru oxide type, Ir oxide type) are preferably used.
本発明の電解処理方法では、陰極電解処理を行うことにより、処理液のｐＨが低下する傾向がある。このため、連続的に電解処理を行う場合には、電解処理液のｐＨが２〜８の範囲内となるようにｐＨを管理することが必要となる。この場合、ｐＨの調整には、ＮａＯＨ等のアルカリ水溶液を用いることができるが、アルカリ水溶液を添加する際に、クロムの水酸化物生成を抑制できるように徐々に添加することが必要である。 In the electrolytic treatment method of the present invention, the pH of the treatment liquid tends to be lowered by performing the cathode electrolytic treatment. For this reason, when performing electrolytic treatment continuously, it is necessary to control the pH so that the pH of the electrolytic treatment solution is in the range of 2-8. In this case, an alkaline aqueous solution such as NaOH can be used to adjust the pH, but when adding the alkaline aqueous solution, it is necessary to gradually add it so as to suppress the formation of chromium hydroxide.
本発明の電解処理液は、６価クロム化合物を含まない処理液であって、３価クロムめっき液から形成されたクロムめっき皮膜に対して、外観を損なうことなく、良好な耐食性を付与できる。 The electrolytic treatment solution of the present invention is a treatment solution that does not contain a hexavalent chromium compound, and can impart good corrosion resistance to the chromium plating film formed from the trivalent chromium plating solution without impairing the appearance.
よって、３価クロムめっき液から形成されたクロムメッキ皮膜に対して、本発明の電解処理液を用いて電解処理を行うことによって、６価クロムフリーのめっきプロセスによって、外観及び耐食性に優れたクロムめっき皮膜を形成することが可能となる。 Therefore, chromium having excellent appearance and corrosion resistance can be obtained by a hexavalent chromium-free plating process by subjecting a chromium plating film formed from a trivalent chromium plating solution to electrolytic treatment using the electrolytic treatment solution of the present invention. A plating film can be formed.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１〜４
膜厚５μｍの光沢ニッケルめっき皮膜を形成した真鍮板に、市販の３価クロムめっき液（商標名：トップファインクロム、奥野製薬工業（株）製）を用いて、液温４５℃、電流密度８Ａ／ｄｍ２の条件で膜厚約０．１μｍの３価クロムめっき皮膜を形成した。
Examples 1-4
Using a commercially available trivalent chromium plating solution (trade name: Top Fine Chrome, manufactured by Okuno Pharmaceutical Co., Ltd.) on a brass plate on which a bright nickel plating film with a film thickness of 5 μm is formed, the liquid temperature is 45 ° C., and the current density is 8 A. A trivalent chromium plating film having a film thickness of about 0.1 μm was formed under the conditions of / dm 2 .
上記した方法で３価クロムめっき皮膜を形成した試料を試験片として用い、下記表１に記載した組成を有する実施例１〜４の各電解処理液中に浸漬して、表１に記載の条件で電解処理を行った。 Using the sample on which the trivalent chromium plating film was formed by the above-described method as a test piece, it was immersed in each electrolytic treatment solution of Examples 1 to 4 having the composition described in Table 1 below, and the conditions described in Table 1 The electrolytic treatment was performed.
次いで、電解処理後の各試験片について、JIS 2371に従った塩水噴霧試験法によって耐食性試験を行い、白サビ発生までの時間により耐食性を評価した。尚、電解処理を行なっていない試料では、塩水噴霧試験開始後72時間で白サビが発生した。 Subsequently, each test piece after the electrolytic treatment was subjected to a corrosion resistance test by a salt spray test method according to JIS 2371, and the corrosion resistance was evaluated by the time until the occurrence of white rust. In the sample not subjected to electrolytic treatment, white rust was generated 72 hours after the start of the salt spray test.
また、目視により電解処理後のクロムめっき皮膜の外観を評価した。めっきした状態と変化のない試験片を○、電解処理後に僅かに黄色く変色した試験片を△、電解処理後に茶色く変色した試験片を×で示す。 Moreover, the external appearance of the chromium plating film after electrolytic treatment was evaluated visually. A test piece that is not changed from the plated state is indicated by ◯, a test piece that is slightly yellowed after electrolytic treatment is indicated by Δ, and a test piece that is turned brown after electrolytic treatment is indicated by ×.
以上の結果を下記表１に記載する。 The above results are shown in Table 1 below.
以上の結果から明らかなように、実施例１〜４の電解処理液を用いて電解処理を行った場合には、塩水噴霧試験法によって白サビが発生するまでの時間が１６８時間以上となった。これに対して、電解処理を行わなかった場合には、塩水噴霧試験開始後７２時間程度で３価クロムめっき皮膜に白サビが発生しており、本発明の電解処理液を用いて電解処理を行うことによって３価クロムめっき皮膜の耐食性を大きく向上できることが確認できた。 As is clear from the above results, when electrolytic treatment was performed using the electrolytic treatment liquids of Examples 1 to 4, the time until white rust was generated by the salt spray test method was 168 hours or more. . On the other hand, when the electrolytic treatment was not performed, white rust was generated in the trivalent chromium plating film about 72 hours after the start of the salt spray test, and the electrolytic treatment was performed using the electrolytic treatment solution of the present invention. It was confirmed that the corrosion resistance of the trivalent chromium plating film can be greatly improved by carrying out the process.
また、電解処理時間を延長した実施例３及び４では、白サビ発生までの時間は２１６時間となり、耐食性を更に大幅に延長できることが確認できた。 Further, in Examples 3 and 4 in which the electrolytic treatment time was extended, the time until the occurrence of white rust was 216 hours, and it was confirmed that the corrosion resistance could be further greatly extended.
また、実施例１〜４では、いずれも電解処理後の皮膜外観は良好であった。 In Examples 1 to 4, the film appearance after the electrolytic treatment was good.
よって、本発明の電解処理液を用いて電解処理を行うことによって、３価クロムめっき皮膜の外観を低下させることなく、耐食性を大きく向上できることが明らかである。 Therefore, it is clear that by performing the electrolytic treatment using the electrolytic treatment solution of the present invention, the corrosion resistance can be greatly improved without deteriorating the appearance of the trivalent chromium plating film.
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