JP5613088B2 - Functional aluminum material and surface treatment method thereof - Google Patents
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本発明は、抗菌性、耐磨耗等の機能を付与した機能性アルミ材及びその表面処理方法に関する。 The present invention relates to a functional aluminum material provided with functions such as antibacterial properties and abrasion resistance, and a surface treatment method thereof.
陽極酸化皮膜微孔中の析出ヨウ素による抗菌性、耐磨耗性等の機能を付与したアルミ材として、下記特許文献１が知られており、これによれば、アルミ材を、ＰＶＰＩ（ポリビニルピロリドン・アイオダイド）の如きヨウ素化合物を用いた電解浴でヨウ素化合物電解処理（電圧５０Ｖ〜３００Ｖ、時間１〜５ｍｉｎ）を施すものとされ、これによって陽極酸化皮膜に耐磨耗性、抗菌性、殺菌性、抗カビ性、光環境触媒、着色性を付与することができるとして、特に、抗菌性試験、大腸菌に対するハロー試験法による発育阻止試験、殺菌性能試験によって抗菌性、殺菌性に優れた結果が得られたとしており、また、ＰＶＰＩ濃度と着色性について、ＰＶＰＩ濃度を０．０３ｗｔ％〜７ｗｔ％としたときの各実験結果が示され、濃度を０．１ｗｔ％以上としたときに、析出ヨウ素によって陽極酸化皮膜の色調がうぐいす色から赤褐色に変化するとする一方、濃度を上昇すると色調の不均一性が生じる傾向を生じるとし、濃度６ｗｔ％とすると色調の濃淡、即ち、不均一性を招き、７ｗｔ％とすると色調が顕著に不均一になるとしている。 The following Patent Document 1 is known as an aluminum material imparted with functions such as antibacterial properties and abrasion resistance due to precipitated iodine in the micropores of the anodized film. According to this, the aluminum material is PVPI (polyvinylpyrrolidone).・ Iodine compound electrolytic treatment (voltage 50 V to 300 V, time 1 to 5 min) is performed in an electrolytic bath using an iodine compound such as Iodide), whereby the anodized film is resistant to abrasion, antibacterial properties, and bactericidal In particular, antibacterial properties, photoenvironmental catalysts, and coloring properties can be imparted. In addition, regarding the PVPI concentration and colorability, each experimental result when the PVPI concentration is 0.03 wt% to 7 wt% is shown, and the concentration is 0.1 wt% In the case described above, it is assumed that the color tone of the anodized film is changed from light blue to reddish brown by the precipitated iodine, whereas when the concentration is increased, the color tone tends to be non-uniform. In addition, non-uniformity is caused, and if it is 7 wt%, the color tone is markedly non-uniform.
このように耐磨耗性、抗菌性、殺菌性、抗カビ性、光環境触媒等の機能を陽極酸化皮膜に付与したアルミ材は、例えば、その抗菌性、殺菌性、抗カビ性の機能から、手摺、ドアハンドル、壁パネル、カウンター、車椅子のアームレスト等の建材、家具、車両、日用品等、更には耐磨耗性の機能から、各種機械部品等の製品用途に使用することができる優れた材料とし得るが、一方で、ヨウ素化合物の電解処理におけるヨウ素化合物濃度によっては色調に濃淡、即ち、ヨウ素析出の不均一性を招く可能性があるとするように、ヨウ素化合物の電解処理においては必ずしも均一なヨウ素析出をなし得いことがあり、析出ヨウ素が均一でなければ、アルミ材に期待する上記耐磨耗性、抗菌性、殺菌性、抗カビ性、光環境触等の機能がアルミ材に均質に得られない結果となり、更に、陽極酸化皮膜にヨウ素化合物の電解処理を施した場合、該陽極酸化皮膜にピッティングの発生が不可避的に見られるという問題点が残されており、機能性アルミ材の実用化には、これらの問題点を解決する必要がある。 Thus, the aluminum material provided with functions such as abrasion resistance, antibacterial properties, bactericidal properties, antifungal properties, and photo-environmental catalysts on the anodized film is, for example, due to its antibacterial properties, bactericidal properties and antifungal properties , Handrails, door handles, wall panels, counters, building materials such as armrests for wheelchairs, furniture, vehicles, daily necessities, etc. Although it may be a material, on the other hand, in the iodine compound electrolytic treatment, it may cause unevenness in color tone, that is, unevenness of iodine precipitation, depending on the iodine compound concentration in the electrolytic treatment of iodine compound. If the precipitated iodine is not uniform, the aluminum material has the above-mentioned wear resistance, antibacterial properties, bactericidal properties, antifungal properties, light environment touch, etc. Homogeneous In addition, when electrolytic treatment of an iodine compound is performed on the anodized film, there remains a problem that pitting is inevitably seen in the anodized film. It is necessary to solve these problems for practical use.
本発明は、かかる事情に基づいてなされたものであって、その解決課題とするところは、陽極酸化皮膜に対するヨウ素の析出を可及的に均一化することによって析出ヨウ素の上記機能を可及的に均質に確保するとともに上記ヨウ素化合物の電解処理に不可避的に生じるピッティングの発生を可及的に抑止乃至抑制した機能性アルミ材を提供するにあり、また、該機能性アルミ材の表面処理方法を提供するにある。 The present invention has been made based on such circumstances, and the problem to be solved is to make the above function of precipitated iodine as possible by making the precipitation of iodine on the anodized film as uniform as possible. And providing a functional aluminum material that prevents and suppresses the occurrence of pitting inevitably occurring in the electrolytic treatment of the iodine compound as much as possible, and surface treatment of the functional aluminum material Is in providing a way.
上記課題に沿って本発明は、陽極酸化皮膜微孔中に、事前の金属塩二次電解処理に由来する析出金属と、事後のヨウ素化合物電解処理のＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）に由来する析出ヨウ素を複合的に析出保持したものとすることによって、ヨウ素析出の可及的な均一化とこれによる析出ヨウ素の可及的均質な機能発揮を行い且つヨウ素化合物電解処理に不可避なピッティングの発生を可及的に抑止乃至抑制した機能性アルミ材としたものであって、即ち、請求項１に記載の発明を、陽極酸化皮膜微孔中の析出ヨウ素による機能を付与したアルミ材であって、上記陽極酸化皮膜の微孔中に、事前の二次電解処理の金属塩に由来する析出金属と、事後のヨウ素化合物の電解処理のＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）に由来する析出ヨウ素を複合的に析出保持することによって、ヨウ素析出を均一化し且つピッティングを抑止乃至抑制した陽極酸化皮膜を備えてなることを特徴とする機能性アルミ材としたものである。 In line with the above-mentioned problems, the present invention provides a deposit metal derived from a prior metal salt secondary electrolytic treatment and TMSOI (trimethylsulfoxonium iodide) or iodine compound electrolytic treatment after the metal salt in the micropores of the anodized film. By making the precipitated iodine derived from TMSI (trimethylsulfonium iodide) complex and retained, it is possible to make the iodine precipitation as uniform as possible and to exhibit the homogeneous function of the precipitated iodine. And a functional aluminum material that suppresses or suppresses the occurrence of pitting that is unavoidable in the electrolytic treatment of iodine compounds as much as possible. That is, the invention according to claim 1 is used in the micropores of the anodized film. a aluminum material imparted with by that function in the precipitation of iodine, the microporous in said anodic oxide film, a deposited metal derived in advance of the metal salt of the secondary electrolytic treatment, post By uniformly depositing and retaining precipitated iodine derived from TMSOI (trimethylsulfonium-iodide) or TMSI (trimethylsulfonium-iodide) for electrolytic treatment of urine compounds, the iodine precipitation is made uniform and pitted. It is a functional aluminum material characterized by comprising an anodized film that suppresses or suppresses the above.
請求項２に記載の発明は、陽極酸化処理を施したアルミ材にヨウ素化合物電解処理を施すについて、事前に金属塩の二次電解処理を施し、事後に、ヨウ素化合物としてＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）を用いたヨウ素化合物電解処理を施し、陽極酸化皮膜の微孔中に析出金属と析出ヨウ素を複合的に析出保持することによって、ヨウ素析出の可及的な均一化とこれによる析出ヨウ素の可及的均質な機能発揮を行い且つヨウ素化合物電解処理に不可避なピッティングの発生を可及的に抑止乃至抑制し得るように、これを、陽極酸化皮膜微孔中の析出ヨウ素による機能を付与したアルミ材の表面処理方法であって、陽極酸化処理後のアルミ材に、金属塩の電解浴中における事前の二次電解処理と、事後のヨウ素化合物ＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）の電解浴中における事後のヨウ素化合物電解処理を施すことによって、上記陽極酸化皮膜の微孔中の析出ヨウ素を均一化し且つピッティング発生を抑止乃至抑制することを特徴とする機能性アルミ材の表面処理方法としたものである。 In the invention according to claim 2, regarding the aluminum compound subjected to the anodization treatment, the secondary electrolytic treatment of the metal salt is performed in advance, and after that, TMSOI (trimethylsulfoxo) is used as the iodine compound. Nitrogen / Iodide) or TMSI (Trimethylsulfonium / Iodide) is used to perform an iodine compound electrolysis treatment, and the deposited metal and precipitated iodine are combined and retained in the micropores of the anodized film. In order to perform the uniform homogenization as much as possible and thereby perform the homogeneous function of the precipitated iodine as much as possible, and to suppress or suppress the occurrence of pitting that is unavoidable in the electrolytic treatment of iodine compound as much as possible, a surface treatment method for aluminum materials imparted with by that function in the precipitation of iodine in the oxide film microporous, the aluminum material after the anodic oxidation treatment, electrodeposition of metal salts By applying a secondary secondary electrolytic treatment in the bath and a subsequent iodine compound electrolytic treatment in the electrolytic bath of the iodine compound TMSOI (trimethylsulfonium iodide) or TMSI (trimethylsulfonium iodide) The surface treatment method for a functional aluminum material is characterized in that the precipitated iodine in the micropores of the anodized film is made uniform and the occurrence of pitting is suppressed or suppressed.
請求項３に記載の発明は、上記に加えて、ヨウ素化合物電解処理に際して、ＴＭＳＯＩ又はＴＭＳＩの濃度を規制して、ヨウ素析出による機能性を確保し且つ陽極酸化皮膜のピッティング発生を抑止乃至抑制し得るものとするように、これを、上記ヨウ素化合物電解処理の電解浴におけるＴＭＳＯＩ又はＴＭＳＩの濃度を、０．１ｇ／ｌ〜５０ｇ／ｌとすることを特徴とする請求項２に記載の機能性アルミ材の表面処理方法としたものである。 In addition to the above, the invention described in claim 3 regulates the concentration of TMSOI or TMSI during the electrolytic treatment of iodine compound to ensure functionality by iodine precipitation and to suppress or suppress the occurrence of pitting of the anodic oxide film. The function according to claim 2, wherein the concentration of TMSOI or TMSI in the electrolytic bath of the iodine compound electrolysis treatment is 0.1 g / l to 50 g / l so as to be able to be performed. This is a surface treatment method for a porous aluminum material.
請求項４に発明は、上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量の下限を規制し、上記ヨウ素析出の均一化に可及的有効な金属析出量を確保するとともにピッティングの抑止乃至抑制作用を確保し得るように、これを、上記金属塩二次電解処理の電解浴による金属析出量を１．２ｍｇ／ｍ２以上とすることを特徴とする請求項２又は３に記載の機能性アルミ材の表面処理方法としたものである。 In addition to the above, the invention according to claim 4 regulates the lower limit of the amount of metal deposited in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, and is as effective as possible for uniformizing the iodine precipitation. In order to ensure the amount of metal precipitation and to prevent the suppression or suppression of pitting, the metal precipitation amount in the electrolytic bath of the metal salt secondary electrolysis treatment should be 1.2 mg / m 2 or more. It is set as the surface treatment method of the functional aluminum material of Claim 2 or 3 characterized by the above-mentioned.
請求項５に記載の発明は、同じく上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量の上限を規制し、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保する一方、得られる機能性アルミ材をヨウ素析出の色調とし得るように、これを、上記金属析出量を、５．５ｍｇ／ｍ２以下とすることを特徴とする請求項４に記載の機能性アルミ材の表面処理方法としたものである。 In addition to the above, the invention described in claim 5 regulates the upper limit of the metal precipitation amount in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, and makes the iodine precipitation uniform and pitting. The metal deposition amount is set to 5.5 mg / m 2 or less so that the functional aluminum material obtained can have the color tone of iodine precipitation while ensuring the suppression or suppression action of Item 4. The method for surface treatment of a functional aluminum material according to Item 4.
請求項６に記載の発明は、同じく上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量を増加し、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保する一方、得られる機能性アルミ材を該金属塩の二次電解色を表出した色調とし得るように、これを、上記金属析出量を、５．５ｍｇ／ｍ２を上回るようにすることを特徴とする請求項２、３又は４に記載の機能性アルミ材の表面処理方法としたものである。 In addition to the above, the invention described in claim 6 increases the amount of metal deposited in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, thereby making the iodine precipitation uniform and suppressing pitting. While ensuring the suppression effect, the above-mentioned metal deposition amount exceeds 5.5 mg / m 2 so that the functional aluminum material obtained can have a color tone expressing the secondary electrolytic color of the metal salt. The method for surface treatment of a functional aluminum material according to claim 2, 3 or 4, characterized in that:
請求項７に記載の発明は、同じく上記に加えて、電解処理後に陽極酸化皮膜の封孔処理を行うことによって、微孔中の金属及びヨウ素の析出状態を維持して、析出ヨウ素の機能の耐久性を確保し得るものとするように、これを、 上記ヨウ素化合物電解処理後に、陽極酸化皮膜に封孔処理を施すことを特徴とする請求項２、３、４、５又は６に記載の機能性アルミ材の表面処理方法としたものである。 In addition to the above, the invention described in claim 7 performs the sealing treatment of the anodized film after the electrolytic treatment, thereby maintaining the deposited state of the metal and iodine in the micropores, and the function of the precipitated iodine. 7. The method according to claim 2, wherein the anodized film is subjected to a sealing treatment after the iodine compound electrolytic treatment so as to ensure durability. This is a surface treatment method for functional aluminum materials.
本発明は、これらをそれぞれ発明の要旨として上記課題解決の手段としたものである。 The present invention uses each of these as the gist of the invention as means for solving the above problems.
本発明は以上のとおりに構成したから、請求項１に記載の発明は、事前の金属塩二次電解処理に由来する析出金属と、事後のヨウ素化合物電解処理のＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）に由来する析出ヨウ素を複合的に析出保持したものとすることによって、ヨウ素析出の可及的な均一化とこれによる析出ヨウ素の可及的均質な機能発揮を行い且つヨウ素化合物電解処理に不可避なピッティングの発生を可及的に抑止乃至抑制した機能性アルミ材を提供することができる。 Since the present invention is configured as described above, the invention described in claim 1 includes a deposited metal derived from a prior metal salt secondary electrolytic treatment and a TMSOI (trimethylsulfoxonium. Iodide) or TMSI (Trimethylsulfonium Iodide), which is a composite of precipitated iodine, keeps the iodine precipitated as uniform as possible and makes the precipitated iodine as homogeneous as possible. It is possible to provide a functional aluminum material that performs its function and suppresses or suppresses the occurrence of pitting that is unavoidable in the electrolytic treatment of iodine compounds as much as possible.
請求項２に記載の発明は、陽極酸化処理を施したアルミ材にヨウ素化合物電解処理を施すについて、事前に金属塩の二次電解処理を施し、事後に、ヨウ素化合物としてＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）を用いたヨウ素化合物電解処理を施し、陽極酸化皮膜の微孔中に析出金属と析出ヨウ素を複合的に析出保持することによって、ヨウ素析出の可及的な均一化とこれによる析出ヨウ素の可及的均質な機能発揮を行い且つヨウ素化合物電解処理に不可避なピッティングの発生を可及的に抑止乃至抑制し得る機能性アルミ材の表面処理方法を提供することができる。 In the invention according to claim 2, regarding the aluminum compound subjected to the anodization treatment, the secondary electrolytic treatment of the metal salt is performed in advance, and after that, TMSOI (trimethylsulfoxo) is used as the iodine compound. Nitrogen / Iodide) or TMSI (Trimethylsulfonium / Iodide) is used to perform an iodine compound electrolysis treatment, and the deposited metal and precipitated iodine are combined and retained in the micropores of the anodized film. Surface treatment of a functional aluminum material that can achieve uniform homogeneity as much as possible and thereby perform as homogeneous a function as possible of precipitated iodine and suppress or suppress the occurrence of pitting that is unavoidable in the electrolytic treatment of iodine compounds. A method can be provided.
請求項３に記載の発明は、上記に加えて、ヨウ素化合物電解処理に際して、ＴＭＳＯＩ又はＴＭＳＩの濃度を規制して、ヨウ素析出による機能性を確保し且つ陽極酸化皮膜のピッティング発生を抑止乃至抑制し得るものとすることができる。 In addition to the above, the invention described in claim 3 regulates the concentration of TMSOI or TMSI during the electrolytic treatment of iodine compound to ensure functionality by iodine precipitation and to suppress or suppress the occurrence of pitting of the anodic oxide film. Can be.
請求項４に発明は、上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量の下限を規制し、上記ヨウ素析出の均一化に可及的有効な金属析出量を確保するとともにピッティングの抑止乃至抑制作用を確保し得るものとすることができる。 In addition to the above, the invention according to claim 4 regulates the lower limit of the amount of metal deposited in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, and is as effective as possible for uniformizing the iodine precipitation. It is possible to secure the amount of deposited metal and ensure the suppression or suppression action of pitting.
請求項５に記載の発明は、同じく上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量の上限を規制し、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保する一方、得られる機能性アルミ材をヨウ素析出の色調とし得るものとすることができる。 In addition to the above, the invention described in claim 5 regulates the upper limit of the metal precipitation amount in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, and makes the iodine precipitation uniform and pitting. The functional aluminum material obtained can be made into the color tone of iodine precipitation, while ensuring the suppression thru | or the suppression effect of this.
請求項６に記載の発明は、同じく上記に加えて、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量を増加し、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保する一方、得られる機能性アルミ材を該金属塩の二次電解色を表出した色調とし得るものとすることができる。 In addition to the above, the invention described in claim 6 increases the amount of metal deposited in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt, thereby making the iodine precipitation uniform and suppressing pitting. While ensuring the suppression effect, the functional aluminum material obtained can be made to have a color tone expressing the secondary electrolytic color of the metal salt.
請求項７に記載の発明は、同じく上記に加えて、電解処理後に陽極酸化皮膜の封孔処理を行うことによって、微孔中の金属及びヨウ素の析出状態を維持して、析出ヨウ素の機能の耐久性を確保し得るものとすることができる。 In addition to the above, the invention described in claim 7 performs the sealing treatment of the anodized film after the electrolytic treatment, thereby maintaining the deposited state of the metal and iodine in the micropores, and the function of the precipitated iodine. The durability can be ensured.
以下、本発明を更に具体的に説明すれば、本発明の機能性アルミ材は、陽極酸化皮膜微孔中の析出ヨウ素による抗菌性、耐磨耗性等の機能を付与したものとして、上記陽極酸化皮膜の微孔中に、事前の二次電解処理の金属塩に由来する析出金属と、事後のヨウ素化合物の電解処理のＴＭＳＯＩ（トリメチルスルフォキソニウム・アイオダイド）又はＴＭＳＩ（トリメチルスルフォニウム・アイオダイド）に由来する析出ヨウ素を複合的に析出保持することによって、ヨウ素析出を均一化し且つピッティングを抑止乃至抑制した陽極酸化皮膜を備えたものとしてある。 Hereinafter, the present invention will be described in more detail. The functional aluminum material of the present invention has the above-mentioned anode, assuming that it has functions such as antibacterial properties and abrasion resistance due to iodine deposited in the pores of the anodized film. In the pores of the oxide film, the deposited metal derived from the metal salt of the secondary secondary electrolytic treatment and the TMSOI (trimethylsulfoxonium iodide) or TMSI (trimethylsulfonium. By precipitating and retaining the precipitated iodine derived from (iodide) in a composite manner, it is provided with an anodized film that makes iodine precipitation uniform and suppresses or suppresses pitting.
これによって、該アルミ材は、上記耐磨耗性、抗菌性、殺菌性、抗カビ性、光環境触媒等の他、陽極酸化皮膜に耐食性、強毒性のものを含めた抗ウイルス性、更には潤滑性等の各種機能を付与して、建材、家具、車両、日用品、滑動部品を含む機械部品等の多用途の用途に使用可能な機能性を有するものとすることができる。 As a result, the aluminum material has the above-mentioned wear resistance, antibacterial property, bactericidal property, antifungal property, photo-environmental catalyst, etc., as well as anti-viral properties including corrosion resistance and strong toxicity in the anodized film, Various functions such as lubricity can be imparted to provide functionality that can be used for various purposes such as building materials, furniture, vehicles, daily necessities, and machine parts including sliding parts.
陽極酸化皮膜の微孔中に析出した金属は、事前の二次電解処理の電解浴における金属塩に由来し、また、析出したヨウ素は、事後のヨウ素化合物の電解処理の電解浴におけるヨウ素化合物の上記ＴＭＳＯＩ又はＴＭＳＩに由来するものであるところ、陽極酸化皮膜の微孔中に該金属とヨウ素を複合的、例えば複層的に析出保持することによって、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制をなし得るのは、事前の金属塩の二次電解処理の金属析出によって、析出金属が微孔内に該微孔壁を被覆するように吸着するために、陽極酸化皮膜の全体、即ちアルミ材の全体に亘って微孔内の電気抵抗が均一となり、該二次電解処理後に施した事後のヨウ素化合物の電解処理は、該陽極酸化皮膜の全体に亘って微孔の電気抵抗が均一化した状態で通電析出を行うために、そのヨウ素析出効率を向上することにより、該ヨウ素析出の均一化を確保し得るようになるとともに同じく電気抵抗の均一化が、該ヨウ素化合物の電解処理時に生じる傾向の強い局部的な電流集中を可及的に解消し、該電流集中に起因すると見られる陽極酸化皮膜のピッティングの発生を有効に抑止乃至抑制するからであると認められる。 The metal deposited in the micropores of the anodic oxide film is derived from the metal salt in the electrolytic bath of the previous secondary electrolytic treatment, and the deposited iodine is the iodine compound in the electrolytic bath of the electrolytic treatment of the iodine compound afterwards. It is derived from the above TMSOI or TMSI, and the metal and iodine are deposited and retained in the micropores of the anodized film in a composite manner, for example, in a multi-layered manner, thereby making the iodine precipitation uniform and suppressing pitting. It is possible to suppress the entire anodic oxide film because the deposited metal is adsorbed so as to cover the microporous walls in the micropores by the metal deposition of the secondary electrolytic treatment of the metal salt in advance. The electrical resistance in the micropores becomes uniform over the entire aluminum material, and the subsequent electrolysis treatment of the iodine compound performed after the secondary electrolysis treatment makes the electrical resistance of the micropores uniform over the entire anodic oxide film. Turned into In order to conduct the current deposition in a state, by improving the iodine deposition efficiency, it becomes possible to ensure the uniformity of the iodine deposition, and also the uniformity of the electrical resistance tends to occur during the electrolytic treatment of the iodine compound This is because it is possible to eliminate the strong local current concentration as much as possible and to effectively suppress or suppress the occurrence of pitting of the anodic oxide film, which seems to be caused by the current concentration.
該機能性アルミ材は、これをこのまま又は必要に応じて常法に従って追加的に耐食性向上措置として、例えば、封孔処理を施して、機能性アルミ形材としての上記機能の耐久性を確保し得るようにして、これを製品使用するものとしてある。該機能性アルミ材は、一般に塗膜層を備えないものとして用いることが好ましく、これは、陽極酸化皮膜に塗膜層を形成すると、ヨウ素析出の機能低下乃至機能損傷の可能性を招くからであり、また、特に、該塗膜層を熱硬化性のものとすると、該熱硬化時の加熱によって析出したヨウ素が昇華して、ヨウ素析出の機能損傷の可能性があるためである。 The functional aluminum material is used as it is or if necessary, according to a conventional method, as a measure for improving corrosion resistance, for example, by performing sealing treatment to ensure the durability of the above function as a functional aluminum shape. It is intended to be used as a product. In general, the functional aluminum material is preferably used as a material that does not have a coating film layer. This is because, when a coating film layer is formed on the anodized film, the function of iodine precipitation or the possibility of functional damage is caused. In particular, if the coating layer is thermosetting, iodine deposited by heating during the thermosetting sublimates, and there is a possibility of functional damage of iodine precipitation.
該機能性アルミ材を、その表面処理方法との関係で説明すると、該表面処理方法は、上記の如くに、陽極酸化皮膜微孔中の析出ヨウ素による抗菌性、耐磨耗性等の機能を付与したアルミ材の表面処理方法として、陽極酸化処理後のアルミ材に、金属塩の電解浴中における事前の二次電解処理と、ヨウ素化合物ＴＭＳＯＩ又はＴＭＳＩの電解浴中における事後のヨウ素化合物電解処理を施すことによって、上記陽極酸化皮膜の微孔中の析出ヨウ素を均一化し且つピッティング発生を抑止乃至抑制するものとしてあり、該表面処理方法は、例えば、図１に示す如くに脱脂処理、エッチング処理、中和処理、陽極酸化処理、金属塩二次電解処理、ヨウ素化合物電解処理、封孔処理の工程によるものとし、これら工程の各処理の間に、それぞれ水洗処理を施すものとしてあり、下記に詳述する金属塩二次電解処理及びヨウ素化合物電解処理以外の各処理は、陽極酸化処理、封孔処理を含めて、常法によるか、常法に準じてこれを行うものとしてある。 The functional aluminum material will be described in relation to the surface treatment method. As described above, the surface treatment method has functions such as antibacterial properties and abrasion resistance due to precipitated iodine in the pores of the anodized film. As the surface treatment method for the applied aluminum material, the anodized aluminum material is subjected to a secondary secondary electrolytic treatment in a metal salt electrolytic bath and a subsequent iodine compound electrolytic treatment in an electrolytic bath of an iodine compound TMSOI or TMSI. Is applied to make the precipitated iodine in the micropores of the anodic oxide film uniform and to suppress or suppress the occurrence of pitting. The surface treatment method is, for example, as shown in FIG. Treatment, neutralization treatment, anodizing treatment, metal salt secondary electrolysis treatment, iodine compound electrolysis treatment, sealing treatment process, and water washing treatment between each of these processes. Each treatment other than the metal salt secondary electrolytic treatment and iodine compound electrolytic treatment, which will be described in detail below, may be carried out in accordance with conventional methods, including anodizing treatment and sealing treatment. Is to do.
このとき、上記ピッティング発生を抑止乃至抑制し、必要に応じて析出金属の色調とする上記金属塩二次電解処理は、陽極酸化皮膜の着色に用いる各種金属塩の電解浴を用いて、金属析出量をコントロールすることによって、これを行うものとしてある。このとき、上記金属塩の二次電解処理における陽極酸化皮膜の微孔中の金属析出量を、１．２ｍｇ／ｍ２以上（例えば通電時間２秒程度で該金属析出量とすることができる）とすることによって、上記ヨウ素析出の均一化に可及的有効な金属析出量を確保するとともにピッティングの抑止乃至抑制作用を確保することができる。該金属析出量を１．８ｍｇ／ｍ２（通電時間３秒程度）以上とすれば、１．２ｍｇ／ｍ２のときのピッティング抑制効果を更に高めて、ピッティング抑止効果を得ることができるから、ピッティングのない機能性のアルミ材とする上で、金属析出量は、これを１．８ｍｇ／ｍ２以上とするのが好ましい。 At this time, the above-mentioned metal salt secondary electrolysis treatment, which suppresses or suppresses the occurrence of pitting and makes the color of the deposited metal as necessary, is performed using an electrolytic bath of various metal salts used for coloring the anodized film. This is done by controlling the amount of precipitation. At this time, the amount of metal deposited in the micropores of the anodized film in the secondary electrolytic treatment of the metal salt is 1.2 mg / m 2 or more (for example, the amount of deposited metal can be obtained in about 2 seconds of energization time). As a result, it is possible to secure the amount of metal precipitation as effective as possible for the uniform precipitation of iodine and to prevent or suppress the pitting. When the amount of deposited metal is 1.8 mg / m 2 (energization time of about 3 seconds) or more, the pitting suppression effect at 1.2 mg / m 2 can be further enhanced and the pitting suppression effect can be obtained. Therefore, in order to obtain a functional aluminum material without pitting, the amount of metal deposition is preferably 1.8 mg / m 2 or more.
また、金属析出量を５．５ｍｇ／ｍ２（通電時間１０秒程度）以下とすることによって、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保する一方、得られる機能性アルミ材をヨウ素析出の色調とすることができるから、機能性アルミ材を所望の析出ヨウ素の色調とするには、金属析出量は、これを５．５ｍｇ／ｍ２以下とすることが好ましい。因みに金属析出量を４ｍｇ／ｍ２程度とすると、二次電解色が幾分現れ、ヨウ素析出の色調との混合色とすることができる。 Further, by making the amount of metal precipitation 5.5 mg / m 2 (energization time of about 10 seconds) or less, the above-described functional aluminum material is obtained while ensuring uniform iodine precipitation and suppressing or suppressing the pitting. Therefore, in order to make the functional aluminum material have a desired color tone of precipitated iodine, the amount of deposited metal is preferably set to 5.5 mg / m 2 or less. Incidentally, when the amount of metal deposition is about 4 mg / m 2 , the secondary electrolytic color appears somewhat, and a mixed color with the color tone of iodine deposition can be obtained.
一方、事前の金属塩の二次電解処理によって金属析出量を増加すると、機能性アルミ材は、上記ヨウ素析出の均一化とピッティングの抑止乃至抑制作用を確保し且つ析出ヨウ素の色調に勝り、該金属塩の二次電解色の色調とすることができるから、該二次電解色を呈する機能性アルミ材とするには、上記金属析出量を、５．５ｍｇ／ｍ２を上回るようにすればよく、例えば該析出量を１０ｍｇ／ｍ２程度以上とすれば、相当程度の二次電解色の機能性アルミ材とすることができる。 On the other hand, when the amount of deposited metal is increased by the secondary electrolytic treatment of the metal salt in advance, the functional aluminum material ensures the above-described uniform precipitation of iodine and suppresses or suppresses the effect of pitting and is superior to the color of the precipitated iodine. Since the color tone of the secondary electrolytic color of the metal salt can be obtained, in order to obtain a functional aluminum material exhibiting the secondary electrolytic color, the metal deposition amount should be made to exceed 5.5 mg / m 2. For example, if the amount of precipitation is about 10 mg / m 2 or more, a functional aluminum material having a considerable secondary electrolytic color can be obtained.
金属塩の二次電解処理は、例えば、Ｎｉ、Ｆｅ、Ｃｕ、Ｚｎ、Ｓｎ等の金属塩を用いた電解浴によって、上記処理時間をコントロールする以外、常法によって行うことができ、析出金属を上記１０ｍｇ／ｍ２程度以上とすれば、それぞれに二次電解色の色調とすることができる。 The secondary electrolytic treatment of the metal salt can be performed by a conventional method except that the treatment time is controlled by an electrolytic bath using a metal salt such as Ni, Fe, Cu, Zn, Sn, etc. If it is about 10 mg / m 2 or more, the color tone of the secondary electrolytic color can be obtained.
上記ヨウ素化合物電解処理は、該金属塩二次電解処理後のアルミ材をヨウ素化合物ＴＭＳＯＩ又はＴＭＳＩの電解浴中で事後的に電解処理を施すことによって、これを行うものとしてあり、陽極酸化皮膜の微孔に事前の二次電解処理による金属析出状態で、該事後のヨウ素化合物の電解処理を施すことにより、陽極酸化皮膜の電気抵抗が均一となり、該ヨウ素化合物の電解処理におけるヨウ素析出効率向上と局所的な電流集中を解消して、ヨウ素析出の均一化を確保し且つ陽極酸化皮膜のピッティング発生を抑止乃至抑制することができ、極酸化皮膜の微孔中に、事前の二次電解処理の金属塩に由来する析出金属と、事後のヨウ素化合物の電解処理のＴＭＳＯＩ又はＴＭＳＩに由来する析出ヨウ素を複合的に析出保持したものとすることができる。 The above-mentioned iodine compound electrolytic treatment is performed by subjecting the aluminum material after the metal salt secondary electrolytic treatment to an electrolytic treatment afterwards in an electrolytic bath of iodine compound TMSOI or TMSI. By applying the subsequent electrolytic treatment of the iodine compound in the metal deposition state by the prior secondary electrolytic treatment to the micropores, the electrical resistance of the anodized film becomes uniform, and the iodine deposition efficiency in the electrolytic treatment of the iodine compound is improved. Eliminate local current concentration, ensure uniform iodine precipitation and suppress or suppress pitting of anodic oxide film. Pre-secondary electrolytic treatment in micropores of polar oxide film It is possible to deposit and hold the deposited metal derived from the metal salt and the deposited iodine derived from TMSOI or TMSI in the subsequent electrolytic treatment of the iodine compound in combination. That.
即ち、事後の電解処理のヨウ素化合物は、これを、上記ヨウ素化合物を下記分子式のＴＭＳＯＩ又はＴＭＳＩとすることによって、析出ヨウ素を該ＴＭＳＯＩ又はＴＭＳＩに由来するものとすることができる。 In other words, the iodine compound in the subsequent electrolytic treatment can be derived from TMSOI or TMSI by using the iodine compound as TMSOI or TMSI of the following molecular formula.
ＴＭＳＯＩは白色又は微黄色結晶性の粉末であり、これと同様の性状を示すＴＭＳＩは白色の粉末であり、いずれも医薬用途のものとされるが、該電解処理にヨウ素化合物としてＴＭＳＯＩ又はＴＭＳＩを使用するのは、ＰＶＰＩに比してヨウ素析出効率が低いから、該電解処理に際して析出反応を鈍化することができ、このとき析出金属塩による電流抵抗の均一化と相俟って、陽極酸化皮膜の微孔中への析出を好ましい形態として、該ヨウ素析出の均一性を確保できるためである。 TMSOI is a white or slightly yellow crystalline powder, and TMSI showing the same properties as this is a white powder, both of which are for pharmaceutical use, but TMSOI or TMSI is used as an iodine compound for the electrolytic treatment. Since the iodine deposition efficiency is lower than that of PVPI, the precipitation reaction can be slowed down during the electrolytic treatment. At this time, combined with the uniform current resistance by the deposited metal salt, an anodic oxide film is used. This is because it is possible to ensure the uniformity of the iodine precipitation by making the precipitation into the micropores a preferable form.
ＴＭＳＯＩ又はＴＭＳＩの濃度は、これを、例えば１ｇ／ｌ、５ｇ／ｌとし、電気量を２Ｃ／ｄｍ２、４．５Ｃ／ｄｍ２、９Ｃ／ｄｍ２、１８Ｃ／ｄｍ２として電解処理を行うと、当初からアルミ材に析出ヨウ素の着色が見られるも、いずれもヨウ素析出の改善効果が認められ、ヨウ素析出の均一性を確保し得るとともにピッティング発生の抑止乃至抑制効果が認められる。従って、事後のヨウ素化合物の電解処理に、該ＴＭＳＯＩ又はＴＭＳＩを用いた電解液を用いることによって、電気量の増減変化にも拘らず、析出ヨウ素の均一性の確保とピッティング抑止乃至抑制をなし得るから、該電解処理に際して電流管理範囲を拡大することができ、従って、電流管理の煩雑さを解消するとともに工場生産に際して機能性アルミ材の高い歩留りを確保して、生産効率を良好に確保することができる。 Concentration of TMSOI or TMSI does this, for example, 1 g / l, and 5 g / l, the quantity of electricity to 2C / dm 2, when performing electrolytic treatment as 4.5C / dm 2, 9C / dm 2, 18C / dm 2 From the beginning, although coloring of precipitated iodine is observed in the aluminum material, all have an effect of improving iodine precipitation, and it is possible to ensure the uniformity of iodine precipitation and to suppress or suppress the occurrence of pitting. Therefore, by using the electrolytic solution using TMSOI or TMSI for the subsequent electrolytic treatment of iodine compounds, it is possible to ensure uniformity of precipitated iodine and prevent or suppress pitting despite the change in the amount of electricity. Therefore, it is possible to expand the current management range during the electrolytic treatment, thus eliminating the complexity of current management and ensuring a high yield of functional aluminum material during factory production, thereby ensuring good production efficiency. be able to.
電解浴のＴＭＳＯＩ又はＴＭＳＩの濃度は、これを、０．１ｇ／ｌ〜５０ｇ／ｌとするのが好ましく、１ｇ／ｌ〜１０ｇ／ｌとすることが特に好ましい。即ち、ＴＭＳＯＩの濃度が０．１ｇ／ｌを下回ると、陽極酸化皮膜に抗菌性等の機能を付与することが困難になり、５０ｇ／ｌを上回ると、抗菌性等の機能の付与に変化がなく、ヨウ素化合物の使用量が過剰となって濃度上昇の技術的意味がなく、経済的ロスを招くからである。また、１ｇ／ｌを下回ると、抗菌性等の機能の付与が必ずしも充分ではなくなる傾向を招き易く、１０ｇ／ｌを上回ると、ヨウ素化合物の過剰使用の傾向を招き易いからである。 The concentration of TMSOI or TMSI in the electrolytic bath is preferably 0.1 g / l to 50 g / l, and particularly preferably 1 g / l to 10 g / l. That is, when the concentration of TMSOI is less than 0.1 g / l, it becomes difficult to impart functions such as antibacterial properties to the anodized film, and when it exceeds 50 g / l, there is a change in imparting functions such as antibacterial properties. This is because the amount of iodine compound used becomes excessive and there is no technical meaning of increasing the concentration, resulting in an economic loss. Moreover, if it is less than 1 g / l, it tends to cause the tendency to impart functions such as antibacterial properties to be insufficient, and if it exceeds 10 g / l, it tends to cause excessive use of iodine compounds.
このようにヨウ素化合物としてＴＭＳＯＩ又はＴＭＳＩを用いた電解処理を行うことによって、析出ヨウ素の均一性を確保、即ち、機能性アルミ材の析出ヨウ素の機能を均質化するとともにピッティングの発生を抑止乃至抑制することができるが、電解処理時の電気量が、例えば１Ｃ／ｄｍ２を下回ると、ヨウ素析出が量的に不足して、該ヨウ素析出による機能を有効に確保し得ない傾向を招くことがあるから、該電気量は、これを、１Ｃ／ｄｍ２以上とすることが好ましい。 Thus, by performing electrolytic treatment using TMSOI or TMSI as the iodine compound, the uniformity of the precipitated iodine is ensured, that is, the function of the precipitated iodine of the functional aluminum material is homogenized and the occurrence of pitting is suppressed. Although it can be suppressed, when the amount of electricity during the electrolytic treatment is less than 1 C / dm 2 , for example, iodine precipitation is quantitatively insufficient, and the function due to the iodine precipitation cannot be effectively secured. Therefore, the amount of electricity is preferably 1 C / dm 2 or more.
上記ヨウ素電解処理を施した後に封孔処理を行うには、封孔剤を用い又は用いることなく、８０℃以上、所定時間の熱水処理を施すようにすればよい。 In order to perform the sealing treatment after the iodine electrolytic treatment, the hot water treatment may be performed at 80 ° C. or more for a predetermined time with or without a sealing agent.
以上の如くに、陽極酸化処理後のアルミ材に、事前に金属塩の二次電解処理を施し、ヨウ素化合物ＴＭＳＯＩ又はＴＭＳＩの電解浴中で事後のヨウ素化合物電解処理を施すことによって、析出ヨウ素による上記耐磨耗性、抗菌性、殺菌性、抗カビ性、光環境触媒、更に陽極酸化皮膜の耐食性、強毒性のものを含めた抗ウイルス性、潤滑性等の各種機能を有効且つ均質に有するとともにピッティングの発生を抑止乃至抑制して、皮膜欠陥がなく、必要に応じて析出ヨウ素の色調乃至二次電解色の色調を呈する機能性アルミ材を得ることができる。 As described above, by subjecting the aluminum material after the anodizing treatment to the secondary electrolytic treatment of the metal salt in advance and performing the subsequent iodine compound electrolytic treatment in the electrolytic bath of the iodine compound TMSOI or TMSI, Effective and homogeneous with various functions such as abrasion resistance, antibacterial properties, bactericidal properties, antifungal properties, photocatalytic catalysts, corrosion resistance of anodized films, antiviral properties including highly toxic materials, and lubricity. At the same time, it is possible to obtain a functional aluminum material that suppresses or suppresses the occurrence of pitting, has no film defects, and exhibits the color tone of precipitated iodine or the color of secondary electrolytic color as required.
アルミ材を、形材とし、パネル材とし、鋳造品とすることを含めて、本発明の実施に当って、アルミ材、陽極酸化皮膜、析出金属、析出ヨウ素、その表面処理方法、これに用いる金属塩、ヨウ素化合物のＴＭＳＯＩ又はＴＭＳＩ、事前及び事後の電解処理等の、各具体的構造、材質、形状、条件、用途、これらの関係、これらに対する付加等は、上記発明の要旨に反しない限り様々な形態のものとすることができる。 In carrying out the present invention, including aluminum material as a shape material, panel material, and cast product, aluminum material, anodized film, precipitated metal, precipitated iodine, surface treatment method thereof, and the like are used. Each specific structure, material, shape, condition, use, relationship between these, addition to these, etc., such as metal salt, TMSOI or TMSI of iodine compound, pre- and post-electrolytic treatment, etc. are not contrary to the gist of the above invention. It can be of various forms.
脱脂、エッチング及び中和の各処理を経たアルミ材（サンプル数９）を、硫酸１７０ｇ／ｌの硫酸浴中で、１２０Ａ／ｍ２×８１５秒通電して陽極酸化処理を施して、皮膜厚５μｍの陽極酸化皮膜を形成し、硫酸Ｎｉ浴中で、０．５Ａ／ｄｍ２のＮｉ塩二次電解処理を施して、Ｎｉ析出量を０．６ｍｇ／ｍ２（通電１秒）、１．２ｍｇ／ｍ２（通電２秒）、１．８ｍｇ／ｍ２（通電３秒）、２．４ｍｇ／ｍ２（通電４秒）、２．９ｍｇ／ｍ２（通電５秒）、４．１ｍｇ／ｍ２（通電７秒）、５．３ｍｇ／ｍ２（通電９秒）、１０．６ｍｇ／ｍ２（通電１８秒）と変化し、比較のために該二次電解処理を省略してＮｉ析出量を０．０ｍｇ／ｍ２（通電０秒）とし、その後、ＴＭＳＯＩ１ｇ／ｌ、定電圧５５Ｖ（ソフトスタート１０秒）、１８Ｃ／ｄｍ２、２５℃でヨウ素化合物電解処理を施し、ヨウ素析出効率の変化、ピッティングの有無及びＮｉによる二次電解色の着色の有無を肉視によって判定評価した。結果を表１に示す。 An aluminum material (number of samples: 9) that has been subjected to degreasing, etching, and neutralization treatment was subjected to an anodizing treatment by applying electricity at 120 A / m 2 × 815 seconds in a sulfuric acid bath of 170 g / l of sulfuric acid, and a film thickness of 5 μm And an Ni salt secondary electrolytic treatment of 0.5 A / dm 2 in a sulfuric acid Ni bath, and the Ni precipitation amount is 0.6 mg / m 2 (energization 1 second), 1.2 mg / M 2 (energization 2 seconds), 1.8 mg / m 2 (energization 3 seconds), 2.4 mg / m 2 (energization 4 seconds), 2.9 mg / m 2 (energization 5 seconds), 4.1 mg / m 2 (energized for 7 seconds), 5.3 mg / m 2 (energized for 9 seconds), 10.6 mg / m 2 (energized for 18 seconds), and the secondary electrolytic treatment was omitted for comparison, and the amount of Ni deposited 0.0 mg / m 2 (energization 0 sec), then TMSOI 1 g / l, constant voltage 55 V (soft start 10 Second), an iodine compound electrolysis treatment was performed at 18 C / dm 2 , 25 ° C., and changes in iodine precipitation efficiency, presence or absence of pitting, and presence or absence of coloring of the secondary electrolysis color by Ni were evaluated by visual inspection. The results are shown in Table 1.
二次電解処理のないＮｉ析出量０ｍｇ／ｍ２、二次電解処理を行ってもＮｉ析出量０．６ｍｇ／ｍ２（通電時間１秒）のものは、ヨウ素による赤褐色系の着色が見られず、陽極酸化皮膜の全面にピッティングが見られ、二次電解処理のヨウ素析出の改善効果とピッティング抑制効果は認められなかった。Ｎｉ析出量１．２ｍｇ／ｍ２（通電時間２秒）のものは赤褐色系の色調が僅かに見られるとともにピッティングが減少して、二次電解処理のヨウ素析出効率の改善効果とピッティング抑制効果が幾分認められたが、Ｎｉ析出量１．８ｍｇ／ｍ２（通電時間３秒）乃至それ以上のものは、ヨウ素による赤褐色系色調の着色が見られるもピッティングは見られず、二次電解処理のヨウ素析出効率の改善効果とピッティング抑止効果が認められた。また、Ｎｉ析出量２．９ｍｇ／ｍ２（通電時間５秒）以下においては、Ｎｉの二次電解色は認められず、Ｎｉ析出量４．１ｍｇ／ｍ２（通電時間７秒）、Ｎｉ析出量５．３ｍｇ／ｍ２（通電時間９秒）においては、Ｎｉの二次電解色が僅かに認められたが、Ｎｉ析出量１０．６ｍｇ／ｍ２（通電時間１８秒）では、二次電解色の着色が顕著に認められた。 Ni precipitation amount of 0 mg / m 2 without secondary electrolysis treatment, even if secondary electrolysis treatment is performed, Ni precipitation amount of 0.6 mg / m 2 (energization time 1 second) shows reddish brown coloration by iodine In addition, pitting was observed on the entire surface of the anodic oxide film, and the effect of improving iodine precipitation and the effect of suppressing pitting by the secondary electrolytic treatment were not recognized. Ni precipitation amount 1.2mg / m 2 (energization time 2 seconds) shows a slight reddish brown color tone and decreases pitting, improving the iodine precipitation efficiency of secondary electrolytic treatment and suppressing pitting Although some effects were recognized, Ni precipitation amount of 1.8 mg / m 2 (energization time 3 seconds) or more showed red-brown coloration due to iodine, but no pitting was observed. The effect of improving the efficiency of iodine precipitation and the effect of deterring pitting by secondary electrolytic treatment were observed. In addition, at a Ni precipitation amount of 2.9 mg / m 2 (energization time 5 seconds) or less, no secondary electrolytic color of Ni was observed, and the Ni precipitation amount 4.1 mg / m 2 (energization time 7 seconds), Ni precipitation At an amount of 5.3 mg / m 2 (energization time 9 seconds), a slight secondary electrolytic color of Ni was observed, but at an Ni deposition amount of 10.6 mg / m 2 (energization time 18 seconds), secondary electrolysis was observed. Remarkable coloration was observed.
析出ヨウ素の着色が見られるのは、該ヨウ素析出の均一性が確保されたことを意味するとともにピッティングが見られず又は減少したのは、該ピッティング発生の抑止乃至抑制がなされたことを意味するところ、これらは、Ｎｉ析出量１．２ｍｇ／ｍ２（通電時間２秒）から幾分認められる、Ｎｉ析出量１．８ｍｇ／ｍ２（通電時間３秒）乃至それ以上とすることによってヨウ素析出の均一性とピッティング抑止効果が認められる、また、該ヨウ素析出の均一性とピッティング抑止効果を確保した上、Ｎｉ析出量を５．３ｍｇ／ｍ２程度以下（通電時間１０秒以下）とし、また、これを超え、１０．６ｍｇ／ｍ２（通電時間２０秒程度）乃至これ以上とすることによってアルミ材の色調を所望のものとすることができる。従って、これらに応じて事前の金属塩二次電解処理及びＴＭＳＯＩ又はＴＭＳＩを用いた事後のヨウ素化合物電解処理の条件設定を行って、好ましい機能性アルミ材を得ることができる。 The coloration of the precipitated iodine means that the uniformity of the iodine precipitation is ensured, and the fact that the pitting is not observed or decreased is that the occurrence of the pitting is suppressed or suppressed. In a sense, these are somewhat recognized from a Ni precipitation amount of 1.2 mg / m 2 (energization time 2 seconds), and by a Ni precipitation amount of 1.8 mg / m 2 (energization time 3 seconds) or more. The uniformity of iodine precipitation and the effect of inhibiting pitting are recognized. Further, the uniformity of iodine precipitation and the effect of inhibiting pitting are ensured, and the amount of deposited Ni is about 5.3 mg / m 2 or less (the energization time is 10 seconds or less). In addition, by exceeding this and 10.6 mg / m 2 (energization time of about 20 seconds) or more, the desired color tone of the aluminum material can be obtained. Therefore, according to these, the preferable functional aluminum material can be obtained by setting the conditions of prior metal salt secondary electrolytic treatment and subsequent iodine compound electrolytic treatment using TMSOI or TMSI.
脱脂、エッチング及び中和の各処理を経たアルミ材（サンプル数２）を、硫酸１７０ｇ／ｌの硫酸浴中で、１２０Ａ／ｍ２×１６３０秒通電して陽極酸化処理を施して、皮膜厚１０μｍの陽極酸化皮膜を形成した。一方のサンプルに、硫酸Ｎｉ浴中で、０．５Ａ／ｄｍ２のＮｉ塩二次電解処理を９秒間施した後、他方のサンプルは二次電解処理を省略して、いずれもＴＭＳＯＩ１ｇ／ｌ、定電圧３０Ｖ（ソフトスタート１０秒）、４．５Ｃ／ｄｍ２、２５℃でヨウ素化合物電解処理を施し、それぞれＥＰＭＡによる面分析を行って元素分析を行った。二次電解処理を行った場合の結果を図２に、二次電解処理を行わなかった場合の結果を図３にそれぞれ図示する。 The aluminum material (number of samples 2) that has been subjected to degreasing, etching, and neutralization treatment is subjected to an anodizing treatment by applying 120 A / m 2 × 1630 seconds in a sulfuric acid bath of 170 g / l of sulfuric acid, and the film thickness is 10 μm. An anodic oxide film was formed. One sample was subjected to a 0.5 A / dm 2 Ni salt secondary electrolytic treatment for 9 seconds in a Ni sulfate sulfuric acid bath, and the other sample was omitted from the secondary electrolytic treatment, both of which were TMSOI 1 g / l, An iodine compound electrolytic treatment was performed at a constant voltage of 30 V (soft start 10 seconds), 4.5 C / dm 2 , and 25 ° C., and an elemental analysis was performed by performing a surface analysis using EPMA. FIG. 2 shows the results when the secondary electrolysis is performed, and FIG. 3 shows the results when the secondary electrolysis is not performed.
図２の二次電解処理を施したものは、陽極酸化皮膜中に析出ヨウ素が多く検出されるのに対して、図３の二次電解処理を省略したものは析出ヨウ素の検出は少ない。従って、二次電解処理を施すことが、ヨウ素析出を促進するヨウ素析出効率向上作用を有するものと認められる。 In the case where the secondary electrolytic treatment of FIG. 2 is applied, a large amount of precipitated iodine is detected in the anodic oxide film, whereas in the case where the secondary electrolytic treatment of FIG. Therefore, it is recognized that the secondary electrolytic treatment has an effect of improving iodine precipitation efficiency that promotes iodine precipitation.
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