JP2015067849A - Regeneration apparatus for trivalent chromium plating solution, trivalent chromium plating system with the regeneration apparatus, and regeneration method of trivalent chromium solution - Google Patents
Regeneration apparatus for trivalent chromium plating solution, trivalent chromium plating system with the regeneration apparatus, and regeneration method of trivalent chromium solution Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 254
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 239000011651 chromium Substances 0.000 title claims abstract description 234
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 233
- 238000011069 regeneration method Methods 0.000 title claims abstract description 63
- 230000008929 regeneration Effects 0.000 title claims abstract description 61
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 83
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 230000001172 regenerating effect Effects 0.000 claims description 9
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 75
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 23
- 238000011282 treatment Methods 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- MILMJAFFMWCPLL-UHFFFAOYSA-J sodium;chromium(3+);disulfate Chemical compound [Na+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MILMJAFFMWCPLL-UHFFFAOYSA-J 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical compound [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- 238000002845 discoloration Methods 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
- 238000005530 etching Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 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
- -1 potassium tetrahydroborate Chemical compound 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、３価クロムめっき液中で生成する６価クロムイオン濃度を減少させるために用いられる３価クロムめっき液の再生装置、当該再生装置を備えた３価クロムめっきシステム、及び３価クロムめっき液中で生成する６価クロムイオン濃度を減少させるための３価クロムめっき液の再生方法に関するものである。 The present invention relates to a regeneration device for a trivalent chromium plating solution used for reducing the concentration of hexavalent chromium ions generated in a trivalent chromium plating solution, a trivalent chromium plating system including the regeneration device, and trivalent chromium. The present invention relates to a method for regenerating a trivalent chromium plating solution for reducing the concentration of hexavalent chromium ions generated in the plating solution.
金属、樹脂、セラミックなどの素材表面の装飾性を高めたり、防錆性、防食性、耐摩耗性、耐熱性、装飾性等各種性能を付与したりするために、素材表面の表面処理技術の一つとしてめっき処理が行われている。その中でも、皮膜が固くて安定であり、変色や腐食に強くて鏡面光沢を有するクロムめっきは、耐摩耗性や光沢性に優れており、銅やニッケルめっきを下地としためっき層に装飾性を付与するための仕上げの最上層めっきとして使用されている。 In order to enhance the surface decoration of materials such as metal, resin, ceramic, etc., and to provide various performances such as rust prevention, corrosion resistance, wear resistance, heat resistance, decoration, etc. One example is plating. Among these, chromium plating that has a hard and stable coating, is resistant to discoloration and corrosion, and has a specular gloss is excellent in wear resistance and gloss, and has a decorative property on the plating layer based on copper or nickel plating. Used as the top layer plating for finishing.
多くの工業製品の表面処理にこうした装飾クロムめっきを施す場合、従来では、防錆性、防食性に優れた被膜特性を有し、また、めっき浴管理も容易であることから、６価クロムめっきが幅広く使用されてきた。しかし、６価クロムは人体に影響を与える有害物質であることから環境面における問題があり、環境基本法等によっても排水規制が行われている。そこで近年では、人体や環境への悪影響に対応するため、６価クロムめっきの代替法として３価クロムめっきの利用が進められてきている。 When such decorative chrome plating is applied to the surface treatment of many industrial products, it has traditionally had coating properties with excellent rust and corrosion resistance, and it is easy to manage the plating bath. Has been widely used. However, hexavalent chromium is an environmental problem because it is a harmful substance that affects the human body, and wastewater is regulated by the Basic Environmental Law. In recent years, therefore, the use of trivalent chromium plating has been promoted as an alternative to hexavalent chromium plating in order to cope with adverse effects on the human body and the environment.
３価クロムめっきは、例えば、陽極電極として鉛合金電極を用い、塩化クロム、硫酸クロムナトリウム等の３価クロム源、錯化剤、電導塩、ｐＨ緩衝剤、及び界面活性剤等を含有する浴中で、比較的低電流密度で行われるものが知られている。こういった３価クロムめっきは、６価クロムめっきと比べて浴安定性が低いことから、良好なめっき層を安定して得ることが難しかったものの、近年では、浴の改良が進んで６価クロムめっきの代替法として定着してきている。 Trivalent chromium plating uses, for example, a lead alloy electrode as an anode electrode, and a bath containing a trivalent chromium source such as chromium chloride and sodium chromium sulfate, a complexing agent, a conductive salt, a pH buffer, and a surfactant. Among them, those performed at a relatively low current density are known. Such trivalent chromium plating has low bath stability compared to hexavalent chromium plating, and thus it has been difficult to stably obtain a good plating layer. It has become established as an alternative to chrome plating.
しかし、その一方で、３価クロムめっき浴中で陰極側の製品に対する金属クロムの析出が進行すると、陽極電極側では、３価クロムイオンが酸化されて６価クロムイオンが生成し、生成した６価クロムイオンが製品の基材表面の状態を変質させるといった問題がある。こういった基材表面の変質現象は、６価クロムイオン濃度が所定濃度を超えると観察され、また、電流密度が高い部分、つまり、陽極電極に近い部分で生じやすい。そして、基材表面の変質が起こると基材表面に対する金属クロムの付着性が悪くなり、基材表面にはヤケが生じてしまうため、結果として製造された製品の色調が悪くなって外観不良を起こす要因となっていた。 On the other hand, however, when deposition of metallic chromium on the cathode side product proceeds in the trivalent chromium plating bath, trivalent chromium ions are oxidized on the anode electrode side to produce hexavalent chromium ions. There is a problem that the chromium ion changes the state of the surface of the substrate of the product. Such alteration of the surface of the substrate is observed when the hexavalent chromium ion concentration exceeds a predetermined concentration, and tends to occur in a portion where the current density is high, that is, a portion close to the anode electrode. And if the surface of the base material changes, the adhesion of metallic chromium to the surface of the base material will deteriorate, and the surface of the base material will be burnt. As a result, the color tone of the manufactured product will deteriorate, resulting in poor appearance. It was a cause.
特許文献１には、３価クロムめっき浴中での６価クロムイオンの生成を抑制して長期にわたって安定した３価クロムめっきを可能とするためのクロムめっき方法が記載されている。ここでは、陽極電極として酸化イリジウムからなる電極触媒の被覆を形成した電極を使用すること、或いは、陽極電極をクロムめっき浴中でイオン交換膜で区画した陽極室に設けること、が記載されている。 Patent Document 1 describes a chromium plating method for suppressing the generation of hexavalent chromium ions in a trivalent chromium plating bath and enabling stable trivalent chromium plating over a long period of time. Here, it is described that an electrode having an electrode catalyst coating made of iridium oxide is used as the anode electrode, or that the anode electrode is provided in an anode chamber partitioned by an ion exchange membrane in a chromium plating bath. .
特許文献２には、建浴段階で還元剤を加えて、６価クロムイオンを３価クロムイオンに還元させるための３価クロムクロメート液の調整方法が記載されている。 Patent Document 2 describes a method for adjusting a trivalent chromium chromate solution for reducing a hexavalent chromium ion to a trivalent chromium ion by adding a reducing agent in the building bath stage.
しかし、特許文献１に記載されるクロムめっき方法において、酸化イリジウムからなる電極触媒の被覆を形成した電極を使用して３価クロムめっきを行った場合には、６価クロムイオンの生成を抑制することはできるものの、その抑制量は十分ではなく、なお改善の余地があるものであった。また、陽極電極をイオン交換膜で区画した場合には、生成した６価クロムイオンによる基材表面の変質を抑制することはできるものの、６価クロムイオン自体の生成を抑制するものではないため、根本的な解決となるものではなかった。 However, in the chromium plating method described in Patent Document 1, when trivalent chromium plating is performed using an electrode formed with an electrode catalyst coating made of iridium oxide, the generation of hexavalent chromium ions is suppressed. Although it was possible, the amount of suppression was not sufficient and there was still room for improvement. In addition, when the anode electrode is partitioned by an ion exchange membrane, although it is possible to suppress deterioration of the substrate surface due to the generated hexavalent chromium ions, it does not suppress the generation of hexavalent chromium ions themselves, It was not a fundamental solution.
特許文献２に記載される３価クロムめっきでは、還元剤による反応率向上のために浴温を高温に維持するものであり、高温では還元反応は効率的に進行するものの、３価クロムめっきの浴安定性は悪くなり、３価クロムめっき自体の効率が損なわれるといった問題があった。 In the trivalent chromium plating described in Patent Document 2, the bath temperature is maintained at a high temperature in order to improve the reaction rate by the reducing agent, and the reduction reaction proceeds efficiently at a high temperature. There was a problem that the bath stability deteriorated and the efficiency of the trivalent chromium plating itself was impaired.
本発明は、こういった問題点を解決するためになされたものであり、その目的は、３価クロムめっき液中に生成する６価クロムイオン濃度を減少させることである。 The present invention has been made to solve these problems, and its object is to reduce the concentration of hexavalent chromium ions generated in the trivalent chromium plating solution.
前記目的を達成するために、請求項１に記載の３価クロムめっき液の再生装置の発明では、３価クロムイオンと還元剤とを含有する３価クロムめっき液を循環する再生装置であって、３価クロムめっき後の３価クロムめっき液が供給される再生槽と、該再生槽から３価クロムめっき液が供給される冷却槽とを備え、前記再生槽の温度は、３価クロムめっき温度より高く設定され、前記冷却槽の温度は、前記３価クロムめっき温度以上であって、前記再生槽の温度より低く設定されていることを要旨とする。 In order to achieve the above object, the invention of the regeneration device for a trivalent chromium plating solution according to claim 1 is a regeneration device for circulating a trivalent chromium plating solution containing a trivalent chromium ion and a reducing agent. A regeneration tank to which a trivalent chromium plating solution after the trivalent chromium plating is supplied; and a cooling tank to which the trivalent chromium plating solution is supplied from the regeneration tank. The gist of the invention is that the temperature is set higher than the temperature, and the temperature of the cooling tank is equal to or higher than the trivalent chromium plating temperature and lower than the temperature of the regeneration tank.
この発明によれば、３価クロムめっき温度より高く設定された再生槽に３価クロムめっき液が循環されることにより、３価クロムめっき液中に含有される還元剤の反応速度を増大させることができる。これにより、３価クロムめっき液中で生成した６価クロムイオンを効率的に還元することが可能であり、金属クロムの付着性に影響のない濃度範囲にまで６価クロムイオンを減少させることができる。したがって、再生槽で６価クロムイオン濃度が減少した３価クロムめっき液を３価クロムめっき処理槽に再度供給することができる。また、このとき、再生槽の３価クロムめっき液を冷却槽に供給することから、再生槽で６価クロムイオンが減少した３価クロムめっき液を、冷却槽で効率的に冷却して３価クロムめっき処理槽に供給することができる。したがって、冷却槽内の３価クロムめっき液の温度が、３価クロムめっき処理の至適温度からはずれることが抑制される。 According to the present invention, the reaction rate of the reducing agent contained in the trivalent chromium plating solution is increased by circulating the trivalent chromium plating solution in the regeneration tank set higher than the trivalent chromium plating temperature. Can do. As a result, hexavalent chromium ions generated in the trivalent chromium plating solution can be efficiently reduced, and the hexavalent chromium ions can be reduced to a concentration range that does not affect the adhesion of metallic chromium. it can. Therefore, the trivalent chromium plating solution in which the hexavalent chromium ion concentration is reduced in the regeneration tank can be supplied again to the trivalent chromium plating treatment tank. At this time, since the trivalent chromium plating solution in the regeneration tank is supplied to the cooling tank, the trivalent chromium plating solution in which hexavalent chromium ions are reduced in the regeneration tank is efficiently cooled in the cooling tank to obtain the trivalent chromium. It can be supplied to a chrome plating tank. Therefore, the temperature of the trivalent chromium plating solution in the cooling tank is prevented from deviating from the optimum temperature for the trivalent chromium plating process.
上記構成において、前記再生槽の温度は、４０℃を超えて１００℃未満であることが好ましい。
前記目的を達成するために、請求項３に記載の３価クロムめっきシステムの発明では、請求項１又は２記載の３価クロムめっき液の再生装置を備え、３価クロムめっきを施すための本槽と、前記本槽との間で３価クロムめっき液を循環して前記本槽に３価クロムめっき液を供給するためのサブ槽とを備え、前記サブ槽内の３価クロムめっき液を前記再生装置に循環することを要旨とする。
The said structure WHEREIN: It is preferable that the temperature of the said regeneration tank exceeds 40 degreeC and is less than 100 degreeC.
In order to achieve the object, the invention of the trivalent chromium plating system according to claim 3 includes the regenerating device for the trivalent chromium plating solution according to claim 1 or 2, and a book for performing trivalent chromium plating. A sub tank for circulating the trivalent chromium plating solution between the tank and the main tank and supplying the trivalent chromium plating solution to the main tank; and the trivalent chromium plating solution in the sub tank The gist is to circulate to the playback device.
３価クロムめっき液を本槽との間で循環して供給するサブ槽内の３価クロムめっき液には、３価クロムめっきにより生成した６価クロムイオンが存在している。請求項３に記載の３価クロムめっきシステムによれば、高温に設定された再生槽を備えた再生装置に３価クロムめっき液を循環することにより、３価クロムめっき液中の還元剤による反応を促進させて６価クロムイオンを還元することができる。これにより、本槽内の３価クロムめっき液中の６価クロムイオンを、金属クロムの付着性に影響のない濃度にまで減少させることができるため、製品に対する付着むらを抑制することが可能な３価クロムめっきシステムを構築することが可能となる。 In the trivalent chromium plating solution in the sub-tank supplied by circulating the trivalent chromium plating solution to and from the main tank, hexavalent chromium ions generated by the trivalent chromium plating are present. According to the trivalent chromium plating system according to claim 3, the reaction by the reducing agent in the trivalent chromium plating solution is performed by circulating the trivalent chromium plating solution through a regeneration device having a regeneration tank set at a high temperature. Can be promoted to reduce hexavalent chromium ions. As a result, hexavalent chromium ions in the trivalent chromium plating solution in the main tank can be reduced to a concentration that does not affect the adhesion of metal chromium, so that uneven adhesion to the product can be suppressed. It becomes possible to construct a trivalent chromium plating system.
また、３価クロムめっきを実際に行う本槽とは別に設けられた再生装置の再生槽の温度を、３価クロムめっき温度より高温に設定していることから、３価クロムめっき処理と、３価クロムめっき液の再生とを異なる温度で行うことができる。それぞれの反応の至適温度に各槽を設定することができるため、各反応を効率的に行うことができる。 In addition, since the temperature of the regeneration tank of the regeneration apparatus provided separately from the main tank that actually performs the trivalent chromium plating is set higher than the trivalent chromium plating temperature, The regeneration of the valent chromium plating solution can be performed at different temperatures. Since each tank can be set to the optimum temperature for each reaction, each reaction can be performed efficiently.
前記目的を達成するために、請求項４に記載の３価クロムめっき液の再生方法の発明では、３価クロムめっきを施す本槽から取り出した３価クロムめっき液を、３価クロムめっき温度より高い温度まで加熱する加熱工程と、加熱された前記３価クロムめっき液を前記３価クロムめっき温度まで冷却して前記本槽に戻す冷却工程と、を含むことを要旨とする。 In order to achieve the above object, in the invention of the method for regenerating a trivalent chromium plating solution according to claim 4, the trivalent chromium plating solution taken out from the main tank to which the trivalent chromium plating is applied is determined from the trivalent chromium plating temperature. The gist includes a heating step of heating to a high temperature and a cooling step of cooling the heated trivalent chromium plating solution to the trivalent chromium plating temperature and returning it to the main tank.
上記構成において、前記加熱工程は、４０℃を超えて１００℃未満の温度で前記３価クロムめっき液を加熱することを要旨とする。 The said structure WHEREIN: The said heating process makes it a summary to heat the said trivalent chromium plating solution at the temperature exceeding 40 degreeC and less than 100 degreeC.
本発明の３価クロムめっき液の再生装置、当該再生装置を備えた３価クロムめっきシステム、及び３価クロムめっき液の再生方法によれば、３価クロムめっき液中に生成する６価クロムイオン濃度を減少させることができる。 According to the trivalent chromium plating solution regeneration apparatus, trivalent chromium plating system including the regeneration apparatus, and trivalent chromium plating liquid regeneration method of the present invention, hexavalent chromium ions generated in the trivalent chromium plating liquid The concentration can be reduced.
以下、本発明を具体化した一実施形態としての３価クロムめっきシステムについて説明する。
本実施形態の３価クロムめっきシステムは、銅やニッケルめっきを下地とした金属めっき層に、装飾性を付与するための仕上げのめっきとして、製品の最上層に積層される装飾３価クロムめっき処理に適用されるものである。
Hereinafter, a trivalent chromium plating system as an embodiment embodying the present invention will be described.
The trivalent chromium plating system of the present embodiment is a decorative trivalent chromium plating process that is laminated on the top layer of a product as a finish plating for imparting decorative properties to a metal plating layer based on copper or nickel plating. Applies to
３価クロムめっき処理に供される基材は、従来公知の方法によって表面処理されたものを使用することができる。基材の素材としては、従来公知の樹脂素材或いは金属素材を適宜選択して使用することができる。３価クロムめっき処理を施す前の一般的な表面処理も従来公知の方法で行えばよい。 As the base material to be subjected to the trivalent chrome plating treatment, those subjected to surface treatment by a conventionally known method can be used. As a material for the base material, a conventionally known resin material or metal material can be appropriately selected and used. A general surface treatment before the trivalent chromium plating treatment may be performed by a conventionally known method.
例えば、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ）樹脂を使用する場合、脱脂工程、エッチング工程、触媒付与工程、及び酸活性化工程によって、ＡＢＳ樹脂基材表面を前処理した後、無電解ニッケルめっき処理によって素材表面に導電性を付与する。その後、銅めっき処理、ニッケルめっき処理を経て、３価クロムめっきを最上層に積層するようにすればよい。これら前処理、銅めっき処理、及びニッケルめっき処理のいずれも従来公知の方法により行うことができる。 For example, when using an acrylonitrile / butadiene / styrene copolymer (ABS) resin, the surface of the ABS resin substrate is pretreated by a degreasing process, an etching process, a catalyst application process, and an acid activation process, and then electroless nickel is used. Conductivity is imparted to the material surface by plating. Thereafter, trivalent chromium plating may be laminated on the uppermost layer through copper plating treatment and nickel plating treatment. Any of these pretreatments, copper plating treatments, and nickel plating treatments can be performed by a conventionally known method.
図１に示すように、本実施形態の３価クロムめっきシステム１は、３価クロムめっき処理を施すための本槽２と、本槽２との間で３価クロムめっき液を循環して本槽２に３価クロムイオンを供給するためのサブ槽３と、再生装置４とで構成されている。再生装置４は、本槽２で３価クロムめっきが進行したときに生成した６価クロムイオンを還元するための装置であり、３価クロムめっき液中に存在する還元剤の反応を促進して６価クロムイオン濃度を減少させるものである。 As shown in FIG. 1, the trivalent chromium plating system 1 of the present embodiment circulates a trivalent chromium plating solution between a main tank 2 and a main tank 2 for performing a trivalent chromium plating process. A sub-tank 3 for supplying trivalent chromium ions to the tank 2 and a regenerator 4 are configured. The regeneration device 4 is a device for reducing hexavalent chromium ions generated when trivalent chromium plating proceeds in the main tank 2, and promotes the reaction of the reducing agent present in the trivalent chromium plating solution. This is to reduce the hexavalent chromium ion concentration.
本実施形態の３価クロムめっきシステム１に設けられる再生装置４は、３価クロムめっき液を加熱するための再生槽５と、加熱された３価クロムめっき液を冷却するための冷却槽６とを備えている。本槽２、サブ槽３、再生槽５、及び冷却槽６の間は、図示しないポンプによって３価クロムめっき液が循環するようになっている。図１に示すように、本槽２とサブ槽３との間で循環している３価クロムめっき液は、再生槽５、冷却槽６の順に供給された後、サブ槽３を介して本槽２に戻される。 The regeneration device 4 provided in the trivalent chromium plating system 1 of the present embodiment includes a regeneration tank 5 for heating the trivalent chromium plating solution, and a cooling tank 6 for cooling the heated trivalent chromium plating solution. It has. A trivalent chromium plating solution is circulated between the main tank 2, the sub tank 3, the regeneration tank 5 and the cooling tank 6 by a pump (not shown). As shown in FIG. 1, the trivalent chromium plating solution circulating between the main tank 2 and the sub tank 3 is supplied in the order of the regeneration tank 5 and the cooling tank 6, and then is supplied through the sub tank 3. Returned to tank 2.
本槽２では、３価クロムめっきを施す基材を陰極２１にセットし、カーボン或いは鉛ースズ合金等からなる陽極電極２２と陰極２１との間で通電を行うことで３価クロムめっき処理を行うものである。３価クロムめっき処理は、従来公知の３価クロムめっき液にて従来公知の条件下で行うことができる。例えば、塩化クロム、硫酸クロムナトリウム等をクロム供給源とし、ギ酸カリウム、リンゴ酸ナトリウム等の錯化剤、塩化アンモニウム、硫酸カリウム、硫酸ナトリウム等の電導塩、ｐＨ緩衝剤、析出促進剤等を含有するめっき浴に浸漬することによって行うことができる。 In this tank 2, a base material to be subjected to trivalent chromium plating is set on the cathode 21, and trivalent chromium plating is performed by energizing between the anode 21 made of carbon or a lead-soot alloy and the cathode 21. Is. The trivalent chromium plating treatment can be performed with a conventionally known trivalent chromium plating solution under a conventionally known condition. For example, chromium chloride, sodium chromium sulfate, etc. are used as the chromium source, and complexing agents such as potassium formate and sodium malate, conductive salts such as ammonium chloride, potassium sulfate and sodium sulfate, pH buffering agents, precipitation accelerators, etc. It can be performed by immersing in a plating bath.
ここで、３価クロムめっき液中には、還元剤が含有されていることが必須である。３価クロムめっき液中では、浴液中に含有される３価クロムイオンが陽極電極２２側で酸化されて６価クロムイオンの生成が進むことが観察される。そして、浴液中の６価クロムイオンが所定濃度以上となると、製品表面の色調が悪くなって外観不良が生じる場合がある。これは、６価クロムイオンの存在が基材表面の変質を引き起こすことによるものであると考えられ、こういった基材表面の変質によって金属クロムの付着性が悪くなるためであると考えられる。 Here, it is essential that the trivalent chromium plating solution contains a reducing agent. In the trivalent chromium plating solution, it is observed that trivalent chromium ions contained in the bath solution are oxidized on the anode electrode 22 side and the generation of hexavalent chromium ions proceeds. And when the hexavalent chromium ion in a bath liquid becomes more than predetermined concentration, the color tone of a product surface may worsen and an external appearance defect may arise. This is considered to be due to the presence of hexavalent chromium ions causing the surface of the base material to be altered, and this is thought to be due to the deterioration of the adhesion of the metal chromium due to such alteration of the surface of the base material.
還元剤の種類としては、特に限定されるものではない。例えば、リンゴ酸、クエン酸等の有機酸系の還元剤、ホウ水素化ナトリウム、テトラヒドロホウ酸カリウム、ジメチルアミンボラン等の水素化ホウ素系の還元剤、亜リン酸、次亜リン酸等の亜リン酸系の還元剤、重亜硫酸ナトリウム、亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の亜硫酸系の還元剤、或いは、ヒドラジン、ホルムアルデヒドといった従来公知の還元剤を適宜使用することができる。還元剤は１種類であってもよく、複数種類を適宜組み合わせて使用することもできる。 The type of reducing agent is not particularly limited. For example, organic acid reducing agents such as malic acid and citric acid, borohydride reducing agents such as sodium borohydride, potassium tetrahydroborate, dimethylamine borane, phosphorous acid, hypophosphorous acid, etc. A phosphoric acid-based reducing agent, a sulfite-based reducing agent such as sodium bisulfite, sodium sulfite, or sodium metabisulfite, or a conventionally known reducing agent such as hydrazine or formaldehyde can be appropriately used. One type of reducing agent may be used, and a plurality of types may be used in combination as appropriate.
通常、３価クロムめっき処理は浴温度が３０〜５０℃に管理されており、比較的低温領域で行われる。このような浴温度では、浴液中に含有される還元剤による還元作用が十分とは言えず、３価クロムめっき液中で生成する６価クロムイオン量に比べて、６価クロムイオンの還元量が少ないものとなる。３価クロムめっき液中に含有される還元剤による還元作用を効果的に発現させるために、３価クロムめっきを行う本槽２とは別に再生装置４を備えている。再生装置４では、再生槽５で、循環された３価クロムめっき液を３価クロムめっきの浴温度より高温に加熱することで、３価クロムめっき液中で生成した６価クロムイオンの還元反応を効率的に進めるとともに、冷却槽６で３価クロムめっき液を３価クロムめっき処理の浴温度まで冷却して、サブ槽３を介して本槽２へ戻すようにしているものである。 Usually, the trivalent chromium plating treatment is performed at a bath temperature of 30 to 50 ° C. and is performed in a relatively low temperature region. At such a bath temperature, it cannot be said that the reducing action of the reducing agent contained in the bath solution is sufficient, and the reduction of hexavalent chromium ions compared to the amount of hexavalent chromium ions produced in the trivalent chromium plating solution. The amount will be small. In order to effectively express the reducing action by the reducing agent contained in the trivalent chromium plating solution, the regenerator 4 is provided separately from the main tank 2 for performing the trivalent chromium plating. In the regenerator 4, the reduction reaction of hexavalent chromium ions generated in the trivalent chromium plating solution by heating the circulating trivalent chromium plating solution to a temperature higher than the bath temperature of the trivalent chromium plating in the regeneration tank 5. The trivalent chromium plating solution is cooled to the bath temperature of the trivalent chromium plating process in the cooling tank 6 and returned to the main tank 2 through the sub tank 3.
３価クロムめっきシステム１を構成する各槽における温度について説明する。本槽２における３価クロムめっき液の温度は、３価クロムめっき処理のための至適温度であればよいが、３０〜５０℃であることが好ましい。本槽２内の３価クロムめっき液を循環して、本槽２に３価クロムめっき液を供給するためのサブ槽３についても本槽２とほぼ同じ温度に保持されていることが好ましい。図１に示した例では、本槽２、サブ槽３ともに、３価クロムめっき液の浴温度が４０℃となるように管理されている。 The temperature in each tank constituting the trivalent chromium plating system 1 will be described. The temperature of the trivalent chromium plating solution in the main tank 2 may be an optimum temperature for the trivalent chromium plating treatment, but is preferably 30 to 50 ° C. It is preferable that the sub tank 3 for circulating the trivalent chromium plating solution in the main tank 2 to supply the trivalent chromium plating solution to the main tank 2 is maintained at substantially the same temperature as the main tank 2. In the example shown in FIG. 1, both the main tank 2 and the sub tank 3 are managed so that the bath temperature of the trivalent chromium plating solution is 40 ° C.
循環された３価クロムめっき液を加熱するための再生槽５の温度は、３価クロムめっき液に含まれる還元剤によって浴液中の６価クロムイオン濃度を減少させることができる温度であることが必要である。つまり、還元剤の還元反応を進行させるために十分な温度であることが必要である。再生槽５の温度は、３価クロムめっき処理の温度より高く設定されており、３価クロムめっき液の浴温度を４０℃に設定している場合には、４０℃を超えて１００℃未満であることが好ましい。４０℃以下の低温であると還元剤による還元反応が起こりにくくなり、１００℃以上の高温であると３価クロムめっき液の溶媒である水が沸騰してしまうため好ましくない。５０〜８０℃であることがより好ましく、６０〜７０℃であることがさらに好ましい。図１に示した例では、再生槽５の温度が７０℃となるように管理されている。 The temperature of the regeneration tank 5 for heating the circulated trivalent chromium plating solution is a temperature at which the concentration of hexavalent chromium ions in the bath solution can be reduced by the reducing agent contained in the trivalent chromium plating solution. is necessary. That is, it is necessary that the temperature is sufficient to cause the reduction reaction of the reducing agent to proceed. The temperature of the regeneration tank 5 is set higher than the temperature of the trivalent chromium plating treatment. When the bath temperature of the trivalent chromium plating solution is set to 40 ° C., it exceeds 40 ° C. and less than 100 ° C. Preferably there is. When the temperature is 40 ° C. or lower, the reduction reaction due to the reducing agent hardly occurs, and when the temperature is 100 ° C. or higher, water as a solvent for the trivalent chromium plating solution is boiled. More preferably, it is 50-80 degreeC, and it is further more preferable that it is 60-70 degreeC. In the example shown in FIG. 1, the temperature of the regeneration tank 5 is managed so as to be 70 ° C.
また、再生槽５により加熱された３価クロムめっき液を冷却するための冷却槽６の温度は、本槽２の温度以上であって、前記再生槽５の温度より低く設定されていることが好ましい。３価クロムめっき液を冷却してサブ槽３を経て本槽２へ供給することを考慮して、本槽２の温度、つまり、３価クロムめっき処理における処理温度に、より近いことが好ましい。例えば、図１に示した例では、冷却槽６の温度を４３℃に設定して、３価クロムめっき液の浴温度４０℃に近い温度としている。これにより、３価クロムめっき液をサブ槽３を介して本槽２に供給したときに、本槽２内の３価クロムめっき液の温度を過度に上昇させることがなく、加熱された３価クロムめっき液による３価クロムめっき処理への影響を抑制することができる。 Further, the temperature of the cooling tank 6 for cooling the trivalent chromium plating solution heated by the regeneration tank 5 is set to be equal to or higher than the temperature of the main tank 2 and lower than the temperature of the regeneration tank 5. preferable. In consideration of cooling the trivalent chromium plating solution and supplying it to the main tank 2 through the sub tank 3, it is preferable that the temperature of the main tank 2 is closer to the processing temperature in the trivalent chromium plating process. For example, in the example shown in FIG. 1, the temperature of the cooling bath 6 is set to 43 ° C., and the temperature is close to the bath temperature of 40 ° C. of the trivalent chromium plating solution. As a result, when the trivalent chromium plating solution is supplied to the main tank 2 via the sub tank 3, the temperature of the trivalent chromium plating solution in the main tank 2 is not excessively increased and is heated. The influence on the trivalent chromium plating process by the chromium plating solution can be suppressed.
このように構成された本実施形態の３価クロムめっきシステム１では、本槽２で３価クロムめっき処理が行われると、陽極電極２２側で６価クロムイオンが生成し、６価クロムイオンが所定濃度以上になると、陰極２１側の基材表面状態に影響を及ぼすことが考えられる。本槽２との間で３価クロムめっき液を循環させて本槽２へ３価クロムイオンを供給するサブ槽３から、再生装置４の再生槽５側へ３価クロムめっき液を循環させて、再生槽５内で３価クロムめっき液を加熱する。これにより、３価クロムめっき液中で生成した６価クロムイオンが、浴液中に含まれる還元剤によって３価クロムイオンに還元される。６価クロムイオン濃度が減少した３価クロムめっき液は、冷却槽６において３価クロムめっき処理の処理温度近くまで冷却されて、サブ槽３を介して本槽２へ戻される。このようにして、本実施形態の３価クロムめっきシステム１では、３価クロムめっき処理中に生成した６価クロムイオン濃度を減少させて、好適な３価クロムめっき処理を長期間にわたって行うことができる。 In the trivalent chromium plating system 1 of the present embodiment configured as described above, when trivalent chromium plating processing is performed in the main tank 2, hexavalent chromium ions are generated on the anode electrode 22 side, and the hexavalent chromium ions are generated. If the concentration is higher than a predetermined concentration, it is considered that the substrate surface state on the cathode 21 side is affected. The trivalent chromium plating solution is circulated from the sub tank 3 that circulates the trivalent chromium plating solution to the main tank 2 and supplies the trivalent chromium ions to the main tank 2 to the regeneration tank 5 side of the reproducing device 4. The trivalent chromium plating solution is heated in the regeneration tank 5. As a result, hexavalent chromium ions generated in the trivalent chromium plating solution are reduced to trivalent chromium ions by the reducing agent contained in the bath solution. The trivalent chromium plating solution having a reduced hexavalent chromium ion concentration is cooled to near the processing temperature of the trivalent chromium plating process in the cooling tank 6 and returned to the main tank 2 via the sub tank 3. Thus, in the trivalent chromium plating system 1 of the present embodiment, the concentration of the hexavalent chromium ions generated during the trivalent chromium plating process can be reduced, and a suitable trivalent chromium plating process can be performed over a long period of time. it can.
次に、本実施形態の３価クロムめっきシステム１の作用について記載する。
本実施形態の３価クロムめっきシステム１では、本槽２における３価クロムめっき処理によって、陽極電極２２側で生成した６価クロムイオンを含む３価クロムめっき液が、図示しないポンプによって吸引されて、サブ槽３を介して再生装置４の再生槽５に供給される。再生槽５は、３価クロムめっき処理の処理温度である４０℃より高い７０℃に保持されていることから、３価クロムめっき液が加熱されて、３価クロムめっき液中に含まれる還元剤の還元作用が増大する。これによって、３価クロムめっき液中に生成した６価クロムイオンが還元されて３価クロムイオンとなり、浴液中の６価クロムイオン濃度が減少するように作用する。
Next, the operation of the trivalent chromium plating system 1 of the present embodiment will be described.
In the trivalent chromium plating system 1 of the present embodiment, the trivalent chromium plating solution containing hexavalent chromium ions generated on the anode electrode 22 side by the trivalent chromium plating process in the main tank 2 is sucked by a pump (not shown). Then, it is supplied to the regeneration tank 5 of the regeneration apparatus 4 through the sub tank 3. Since the regeneration tank 5 is maintained at 70 ° C. which is higher than 40 ° C. which is the treatment temperature of the trivalent chromium plating treatment, the trivalent chromium plating solution is heated and the reducing agent contained in the trivalent chromium plating solution The reduction action of increases. As a result, the hexavalent chromium ions generated in the trivalent chromium plating solution are reduced to become trivalent chromium ions, and the concentration of the hexavalent chromium ions in the bath solution is reduced.
また、加熱されて６価クロムイオン濃度が減少した３価クロムめっき液は、図示しないポンプによって吸引されて、冷却槽６に供給される。冷却槽６は、再生槽５より低い温度であって３価クロムめっき処理の処理温度に近い４３℃に保持されていることから、再生槽５で加熱された３価クロムめっき液が冷却される。これによって、冷却された３価クロムめっき液は、サブ槽３を介して本槽２に供給されたときに、本槽２内の３価クロムめっき液の温度を過度に上昇させないように作用する。 Further, the trivalent chromium plating solution whose hexavalent chromium ion concentration is reduced by heating is sucked by a pump (not shown) and supplied to the cooling tank 6. Since the cooling tank 6 is maintained at 43 ° C., which is lower than the regeneration tank 5 and close to the processing temperature of the trivalent chromium plating process, the trivalent chromium plating solution heated in the regeneration tank 5 is cooled. . Thus, the cooled trivalent chromium plating solution acts so as not to excessively increase the temperature of the trivalent chromium plating solution in the main tank 2 when supplied to the main tank 2 through the sub tank 3. .
次に、本実施形態の３価クロムめっきシステム１の効果について記載する。
（１）３価クロムめっきを行う本槽２は３価クロムめっき処理に最適な温度に保持される一方で、本槽２とは別に設けられた再生装置４は、３価クロムめっき液を高温に加熱している。これにより、３価クロムめっき液中に含まれる還元剤による還元作用を好適に発揮させることができる。３価クロムめっき処理を行う本槽２と、６価クロムイオンの還元反応を進める再生装置４とを別構成とすることで、３価クロムめっき処理に影響を与えることなく、６価クロムイオンの還元反応を効率的に行うことができる。そして、３価クロムめっき液中の６価クロムイオン濃度を、金属クロム皮膜の形成に影響を与えないレベルまで減少させることが可能な３価クロムめっきシステム１を構築することができる。
Next, the effect of the trivalent chromium plating system 1 of this embodiment will be described.
(1) While the main tank 2 for performing the trivalent chromium plating is maintained at an optimum temperature for the trivalent chromium plating treatment, the regenerating device 4 provided separately from the main tank 2 allows the trivalent chromium plating solution to be heated at a high temperature. Is heated. Thereby, the reducing action by the reducing agent contained in the trivalent chromium plating solution can be suitably exhibited. By making the main tank 2 for performing the trivalent chromium plating process and the regenerating apparatus 4 for proceeding the reduction reaction of the hexavalent chromium ions separately, the hexavalent chromium ions can be produced without affecting the trivalent chromium plating process. The reduction reaction can be performed efficiently. And the trivalent chromium plating system 1 which can reduce the hexavalent chromium ion density | concentration in a trivalent chromium plating solution to the level which does not affect formation of a metal chromium membrane | film | coat can be constructed | assembled.
（２）再生装置４を、３価クロムめっき液を加熱する再生槽５と、加熱された３価クロムめっき液を冷却する冷却槽６で構成している。還元剤の還元反応を効率的に進めるとともに、本槽２内の３価クロムめっき液の温度管理を容易に行うことができる。 (2) The regeneration device 4 is constituted by a regeneration tank 5 for heating the trivalent chromium plating solution and a cooling tank 6 for cooling the heated trivalent chromium plating solution. While reducing reaction of a reducing agent efficiently, temperature control of the trivalent chromium plating solution in the main tank 2 can be easily performed.
なお、上記実施形態は、以下のように変更してもよい。また、以下に示す変更例をそれぞれ組み合わせてもよい。
・ 本実施形態では、本槽２及びサブ槽３の温度を４０℃とし、再生槽５の温度を７０℃とし、冷却槽６の温度を４３℃としたが、これに限定されるものではない。３価クロムめっき液の成分、還元剤の種類、基材の性状等に応じて適宜設定温度を変更することができる。
In addition, you may change the said embodiment as follows. Further, the following modifications may be combined.
In the present embodiment, the temperature of the main tank 2 and the sub tank 3 is 40 ° C., the temperature of the regeneration tank 5 is 70 ° C., and the temperature of the cooling tank 6 is 43 ° C., but is not limited thereto. . The set temperature can be changed as appropriate according to the components of the trivalent chromium plating solution, the type of reducing agent, the properties of the substrate, and the like.
・ 冷却槽６を省略してもよい。この場合、再生槽５の容積を大きくすることで、再生槽５の加熱温度を低く保持したとしても、還元剤による６価クロムイオンの還元反応を進めて６価クロムイオン量を減少させることが可能である。 -The cooling tank 6 may be omitted. In this case, by increasing the volume of the regeneration tank 5, even if the heating temperature of the regeneration tank 5 is kept low, the amount of hexavalent chromium ions can be reduced by advancing the reduction reaction of hexavalent chromium ions by the reducing agent. Is possible.
・ 本実施形態では、３価クロムめっきシステムを装飾クロムめっきとしての３価クロムめっき処理に適用したが、工業用クロムめっきとしての３価クロムめっき処理に適用することもできる。また、めっき製品の最上層に積層される３価クロムめっき処理に適用したが、中間層に積層される３価クロムめっき処理に適用することもできる。 In the present embodiment, the trivalent chrome plating system is applied to the trivalent chrome plating process as the decorative chrome plating, but can also be applied to the trivalent chrome plating process as the industrial chrome plating. Moreover, although applied to the trivalent chromium plating process laminated | stacked on the uppermost layer of plating product, it can also be applied to the trivalent chromium plating process laminated | stacked on an intermediate | middle layer.
・ 一般的な装飾クロムめっき工程として、本実施形態では、樹脂基材表面を前処理した後、銅めっき処理、ニッケルめっき処理を行った後、３価クロムめっき処理を行う場合を記載したが、装飾３価クロムめっき処理までの各工程は、これに限定されるものではない。基材の性状、求められる製品の用途、機能等に応じて各めっき処理を適宜選択することができる。 -As a general decorative chrome plating process, in the present embodiment, after pre-treating the resin base material surface, copper plating treatment, nickel plating treatment, and then trivalent chromium plating treatment is described, Each process until the decoration trivalent chromium plating process is not limited to this. Each plating treatment can be appropriately selected according to the properties of the substrate, the intended use and function of the product.
以下、実施例により本発明をさらに詳細に説明する。
（３価クロムめっき液の違いによる６価クロムイオン生成の検討）
市販されている３価クロムめっき液を使用して、３価クロムめっき処理時の６価クロムイオン生成の有無を検討した。
Hereinafter, the present invention will be described in more detail with reference to examples.
(Examination of hexavalent chromium ion generation by the difference of trivalent chromium plating solution)
Using a commercially available trivalent chromium plating solution, the presence or absence of hexavalent chromium ion generation during the trivalent chromium plating treatment was examined.
３価クロムめっき液を、電流５Ａで０、５、１５、３０、４０、５０、６０分間、及び電流１０、１５Ａで５分間のハルセル試験を行って、３価クロムめっき液中で生成する６価クロムイオン濃度を調べた。３価クロムめっき液は、市販されているＣＰ−３００（日本マクダーミット株式会社製）、ＴＧＹ（SurTec MMC Japan K.K.製）、ＥＸＭ（SurTec MMC Japan K.K.製）の３種類のものを使用した。また、陽極板としては、チタニウム基板上にイリジウム等の白金族原料を焼成コーティングした３価クロムめっき用不溶性陽極を使用した。 A trivalent chromium plating solution is produced in a trivalent chromium plating solution by performing a hull cell test for 0, 5, 15, 30, 40, 50, 60 minutes at a current of 5 A and for 5 minutes at a current of 10, 15 A. 6 The valent chromium ion concentration was examined. As the trivalent chromium plating solution, three types of commercially available CP-300 (manufactured by Nihon Mcdermit Co., Ltd.), TGY (manufactured by SurTec MMC Japan K.K.), and EXM (manufactured by SurTec MMC Japan K.K.) were used. Further, as the anode plate, an insoluble anode for trivalent chromium plating in which a platinum group material such as iridium was baked and coated on a titanium substrate was used.
なお、６価クロムイオン濃度の測定には、ジフェニルカルバジド吸光光度法の発色原理を用いた６価クロム簡易測定キットである株式会社共立理化学研究所製の６価クロムパックテスト 型式ＷＡＫ−Ｃｒ６＋を使用した。 For the measurement of hexavalent chromium ion concentration, a hexavalent chromium pack test model WAK-Cr 6+ manufactured by Kyoritsu Riken Co., Ltd., which is a simple hexavalent chromium measurement kit using the coloring principle of diphenylcarbazide absorptiometry. It was used.
６価クロムイオン濃度の測定結果を表１に示す。 The measurement results of the hexavalent chromium ion concentration are shown in Table 1.
（３価クロムめっき液加熱後の６価クロムイオン濃度の検討）
次に、電流５Ａで６０分間ハルセル試験を行った後の３価クロムめっき液を、加熱温度７５℃で、１、２、２４時間加熱して、６価クロムイオン濃度の変化を調べた。加熱後の３価クロムめっき液中の６価クロムイオン濃度の測定結果を表２に示す。
(Examination of hexavalent chromium ion concentration after heating the trivalent chromium plating solution)
Next, the trivalent chromium plating solution after performing the hull cell test at a current of 5 A for 60 minutes was heated at a heating temperature of 75 ° C. for 1, 24 hours, and the change in hexavalent chromium ion concentration was examined. Table 2 shows the measurement results of the hexavalent chromium ion concentration in the trivalent chromium plating solution after heating.
（３価クロムめっき液加熱温度の検討）
次に、電流５Ａで６０分間ハルセル試験を行った後の３価クロムめっき液を、加熱温度を４０、５０、６０、７５℃と変えて、１、２、５、９、１２、１５時間加熱したときの、６価クロムイオン濃度の変化を調べた。加熱後の３価クロムめっき液中の６価クロムイオン濃度の測定結果を表３に示す。
(Examination of heating temperature of trivalent chromium plating solution)
Next, the trivalent chromium plating solution after the Hull Cell test at a current of 5 A for 60 minutes was heated for 1, 2, 5, 9, 12, and 15 hours while changing the heating temperature to 40, 50, 60, and 75 ° C. The change in the hexavalent chromium ion concentration was investigated. Table 3 shows the measurement results of the hexavalent chromium ion concentration in the trivalent chromium plating solution after heating.
（３価クロムめっき液の加熱温度の違いによる６価クロムイオンの還元速度の検討）
各温度での１時間当たりの還元速度を計算したものを表４に示す。ここで、１時間当たりの還元速度は、表３において、加熱前の６価クロムイオン濃度を、６価クロムイオン濃度が０になったときの加熱時間で割った値として表した。
(Examination of the reduction rate of hexavalent chromium ions depending on the heating temperature of the trivalent chromium plating solution)
Table 4 shows the calculated reduction rate per hour at each temperature. Here, the reduction rate per hour is represented as a value obtained by dividing the hexavalent chromium ion concentration before heating by the heating time when the hexavalent chromium ion concentration becomes 0 in Table 3.
以上の結果より、いずれの３価クロムめっき液においても６価クロムイオンの生成が観察されるものの、３価クロムめっき処理槽とは別個の槽内で加熱処理を行うことにより、生成した６価クロムイオン濃度をゼロとすることが可能であることがわかった。３価クロムめっき処理を行う本槽とは別に、３価クロムめっき液を循環して加熱処理を行う再生装置を設けた３価クロムめっきシステムにより、３価クロムめっき液の効率的な再生が可能であり、３価クロムめっき処理に影響のないレベルにまで３価クロムめっき液中の６価クロムイオンを減少させることができる。 Although the generation of hexavalent chromium ions is observed in any of the trivalent chromium plating solutions from the above results, the hexavalent produced by heat treatment in a tank separate from the trivalent chromium plating treatment tank. It was found that the chromium ion concentration can be made zero. A trivalent chromium plating system equipped with a regeneration device that circulates a trivalent chromium plating solution and heats it separately from the main tank that performs the trivalent chromium plating treatment enables efficient regeneration of the trivalent chromium plating solution. The hexavalent chromium ions in the trivalent chromium plating solution can be reduced to a level that does not affect the trivalent chromium plating treatment.
１…３価クロムめっきシステム、２…本槽、３…サブ槽、４…再生装置、５…再生槽、６…冷却槽、２１…陰極、２２…陽極電極。 DESCRIPTION OF SYMBOLS 1 ... Trivalent chromium plating system, 2 ... Main tank, 3 ... Sub tank, 4 ... Regeneration apparatus, 5 ... Regeneration tank, 6 ... Cooling tank, 21 ... Cathode, 22 ... Anode electrode.
Claims (5)
３価クロムめっき後の３価クロムめっき液が供給される再生槽と、該再生槽から３価クロムめっき液が供給される冷却槽とを備え、
前記再生槽の温度は、３価クロムめっき温度より高く設定され、
前記冷却槽の温度は、前記３価クロムめっき温度以上であって、前記再生槽の温度より低く設定されていることを特徴とする３価クロムめっき液の再生装置。 A device for regenerating a trivalent chromium plating solution for circulating a trivalent chromium plating solution containing a trivalent chromium ion and a reducing agent,
A regeneration tank to which the trivalent chromium plating solution after the trivalent chromium plating is supplied, and a cooling tank to which the trivalent chromium plating solution is supplied from the regeneration tank,
The temperature of the regeneration tank is set higher than the trivalent chromium plating temperature,
The apparatus for regenerating a trivalent chromium plating solution, wherein the temperature of the cooling tank is set to be equal to or higher than the temperature of the trivalent chromium plating and lower than the temperature of the regeneration tank.
３価クロムめっきを施すための本槽と、前記本槽との間で３価クロムめっき液を循環して前記本槽に３価クロムめっき液を供給するためのサブ槽とを備え、
前記サブ槽内の３価クロムめっき液を前記再生装置に循環することを特徴とする３価クロムめっきシステム。 A trivalent chromium plating system comprising the trivalent chromium plating solution regeneration device according to claim 1 or 2,
A main tank for performing trivalent chromium plating, and a sub tank for circulating the trivalent chromium plating solution between the main tank and supplying the trivalent chromium plating solution to the main tank;
A trivalent chromium plating system, wherein the trivalent chromium plating solution in the sub-tank is circulated to the regenerator.
加熱された前記３価クロムめっき液を前記３価クロムめっき温度まで冷却して前記本槽に戻す冷却工程と、
を含むことを特徴とする３価クロムめっき液の再生方法。 A heating step of heating the trivalent chromium plating solution taken out from the main tank for performing the trivalent chromium plating to a temperature higher than the trivalent chromium plating temperature;
A cooling step of cooling the heated trivalent chromium plating solution to the trivalent chromium plating temperature and returning it to the main tank;
A method for regenerating a trivalent chromium plating solution, comprising:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013201768A JP5880510B2 (en) | 2013-09-27 | 2013-09-27 | Regeneration apparatus for trivalent chromium plating solution, trivalent chromium plating system equipped with the regeneration apparatus, and method for regenerating trivalent chromium plating solution |
| RU2014139021/02A RU2583563C2 (en) | 2013-09-27 | 2014-09-26 | METHOD OF PRODUCING CHROME-PLATED PRODUCT, Cr(III) SOLUTION REGENERATION DEVICE FOR CHROMIUM PLATING, APPARATUS FOR CHROME PLATING WITH Cr(III) AND METHOD OF REGENERATING Cr(III) SOLUTION FOR CHROME PLATING |
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Citations (6)
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|---|---|---|---|---|
| JPS5235133A (en) * | 1975-09-13 | 1977-03-17 | Matsushita Electric Works Ltd | Means for regenerating chromate treating bath |
| JPH06173100A (en) * | 1992-12-08 | 1994-06-21 | Nippon Steel Corp | Chromium sulfate for chromium based electroplating |
| JPH06306698A (en) * | 1993-04-26 | 1994-11-01 | Kawasaki Steel Corp | Method for controlling zn based electroplating bath containing trivalent chromium ion |
| JPH07118899A (en) * | 1993-10-22 | 1995-05-09 | Nkk Corp | Reducing method of fe3+ ion and/or cr6+ in electroplasting solution |
| JPH07150377A (en) * | 1993-12-01 | 1995-06-13 | Nkk Corp | Method for reducing fe3+ ion and/or cr6+ ion in electroplating solution |
| JP2002322599A (en) * | 2001-04-23 | 2002-11-08 | Shigeo Hoshino | Method for plating with trivalent chromium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1201352A1 (en) * | 1983-12-23 | 1985-12-30 | Казанский инженерно-строительный институт | Method of reclaiming chromium-containing solutions |
| RU2231581C1 (en) * | 2002-12-25 | 2004-06-27 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Electrolyte of chromium plating and a method of chromium coatings plating on steel parts |
| JP4142616B2 (en) * | 2004-07-13 | 2008-09-03 | 株式会社三原産業 | Preparation method of surface treatment liquid |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5235133A (en) * | 1975-09-13 | 1977-03-17 | Matsushita Electric Works Ltd | Means for regenerating chromate treating bath |
| JPH06173100A (en) * | 1992-12-08 | 1994-06-21 | Nippon Steel Corp | Chromium sulfate for chromium based electroplating |
| JPH06306698A (en) * | 1993-04-26 | 1994-11-01 | Kawasaki Steel Corp | Method for controlling zn based electroplating bath containing trivalent chromium ion |
| JPH07118899A (en) * | 1993-10-22 | 1995-05-09 | Nkk Corp | Reducing method of fe3+ ion and/or cr6+ in electroplasting solution |
| JPH07150377A (en) * | 1993-12-01 | 1995-06-13 | Nkk Corp | Method for reducing fe3+ ion and/or cr6+ ion in electroplating solution |
| JP2002322599A (en) * | 2001-04-23 | 2002-11-08 | Shigeo Hoshino | Method for plating with trivalent chromium |
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| RU2014139021A (en) | 2016-04-20 |
| JP5880510B2 (en) | 2016-03-09 |
| RU2583563C2 (en) | 2016-05-10 |
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