JP2003073853A - Surface treated aluminum material superior in corrosion resistance, and manufacturing method therefor - Google Patents
Surface treated aluminum material superior in corrosion resistance, and manufacturing method thereforInfo
- Publication number
- JP2003073853A JP2003073853A JP2001258089A JP2001258089A JP2003073853A JP 2003073853 A JP2003073853 A JP 2003073853A JP 2001258089 A JP2001258089 A JP 2001258089A JP 2001258089 A JP2001258089 A JP 2001258089A JP 2003073853 A JP2003073853 A JP 2003073853A
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- Prior art keywords
- film
- aluminum
- porous
- coating
- corrosion resistance
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気製品、器物、
装飾品、建材、自動車部品、フィン材等に好適に用いら
れるアルミニウム製品またはアルミニウム合金製品に用
いられて好適な下地処理が施されたアルミニウム材とそ
の製造方法に係わり、耐食性と塗膜密着性を高めること
ができる技術に関するものである。TECHNICAL FIELD The present invention relates to electric appliances, articles,
The aluminum material which is preferably used for decorative products, building materials, automobile parts, fin materials, etc., or aluminum alloy products, which has been subjected to a suitable base treatment and its manufacturing method. It is about technology that can be enhanced.
【０００２】[0002]
【従来の技術】一般に、アルミニウム板やアルミニウム
合金板に塗装を施す場合には、塗膜の密着性を高めるた
めに塗装下地処理が行われている。従来の塗装下地処理
としては、クロメート処理、ベーマイト処理などの化学
皮膜処理や多孔質陽極酸化処理等が挙げられる。これら
の塗装下地処理に要求される特性としては、塗膜密着性
並びに塗装後耐食性に優れていることなどである。とこ
ろが、従来の塗装下地処理においては、以下のような問
題点があった。前記クロメート処理では、塗膜密着性や
耐食性は優れた性能を示すが、クロメート皮膜を塗布す
る際のクロム含有排水が環境汚染につながり、排水処理
にコストがかかってしまうという欠点があり、また、食
品関係の用途には皮膜中のクロムが人体に有害であるこ
とから、脱クロム化の要求がなされている。2. Description of the Related Art Generally, when coating an aluminum plate or an aluminum alloy plate, a coating base treatment is performed in order to enhance the adhesion of the coating film. Examples of conventional coating base treatments include chemical film treatments such as chromate treatment and boehmite treatment, and porous anodizing treatment. The properties required for these coating base treatments are excellent coating film adhesion and corrosion resistance after coating. However, the conventional coating substrate treatment has the following problems. In the chromate treatment, the coating film adhesion and corrosion resistance show excellent performance, but chromium-containing drainage when applying the chromate film leads to environmental pollution, there is a drawback that the wastewater treatment costs high, Since chromium in the film is harmful to the human body for food-related applications, there is a demand for dechromization.
【０００３】前記ベーマイト処理では、皮膜の厚みを薄
くすると耐食性が悪くなるため、通常厚さ１μｍ（１０
０００Å）以上の皮膜を形成するのが一般的であり、ま
た、表面に羽毛状の凹凸を有するためアンカー効果が得
られ、塗膜との密着性が高い傾向にあるとされている
が、ベーマイト皮膜の含水量が通常１５〜３０重量％と
高く、特に焼付け塗装する場合にベーマイト皮膜からの
水分の揮散に起因して塗膜密着性が著しく劣化してしま
うおそれがある。又、皮膜が多孔質であるため、腐食性
物質が容易にアルミニウム基材に達してしまい、耐食性
も充分なものとはならなかった。In the above boehmite treatment, when the thickness of the coating is reduced, the corrosion resistance deteriorates. Therefore, the thickness is usually 1 μm (10
It is common to form a film of 000 Å) or more, and because it has feather-like irregularities on the surface, an anchor effect is obtained, and it is said that the adhesion to the coating film tends to be high, but boehmite The water content of the coating is usually as high as 15 to 30% by weight, and there is a possibility that the adhesion of the coating may be significantly deteriorated due to evaporation of water from the boehmite coating, especially when baking coating is performed. Further, since the film is porous, the corrosive substance easily reaches the aluminum base material, and the corrosion resistance is not sufficient.
【０００４】前記多孔質陽極酸化処理では、焼き付け塗
装する場合に、前述のベーマイト処理と同様に皮膜の多
孔質部分からの水分やイオンの揮散に起因して塗膜密着
性が劣ってしまう問題があり、この対策として多孔質陽
極酸化皮膜に通常施している封孔処理を行わないなどの
対策がとられるが、この場合には耐食性が不十分になる
ことがある。また、多孔質陽極酸化処理では、均一に酸
化皮膜を形成させるために、脱脂、エッチング、デスマ
ット、電解、封孔などの複数の処理が必要となり、コス
ト高となってしまう傾向がある。In the above-mentioned porous anodizing treatment, in the case of baking coating, there is a problem that the adhesion of the coating film is deteriorated due to evaporation of water and ions from the porous portion of the coating film as in the above-mentioned boehmite treatment. As a countermeasure against this, a measure such as not performing the sealing treatment which is usually applied to the porous anodic oxide film is taken, but in this case, the corrosion resistance may be insufficient. Further, in the porous anodizing treatment, a plurality of treatments such as degreasing, etching, desmutting, electrolysis and sealing are required in order to form an oxide film uniformly, which tends to increase the cost.
【０００５】これらの背景から本願出願人においては先
に、特開平８−２８３９９０号公報などに開示されてい
る如き無孔質陽極酸化皮膜を開発し、塗膜密着性並びに
塗装後耐食性に富むアルミニウム材を提供した。この特
許に係るアルミニウム材は、アルミニウム又はアルミニ
ウム合金の表面に、厚さが７０〜２０００Å（０.００
７μｍ〜０.２μｍ）、含水量が１〜５重量％、空孔率
が５％以下の無孔質陽極酸化皮膜を形成したものであ
る。また、このアルミニウム材は、従来の多孔質陽極酸
化皮膜が多孔質に起因する表面部分の凹凸によりアンカ
ー効果を発揮させて塗膜密着性を得ているという塗膜密
着性生成の理論ではなく、多孔質部分を無くすることで
多孔質部分に含まれていた水分やイオンを無くし、塗膜
乾燥時に水分やイオン成分が揮散することに起因する塗
膜密着性の低下現象を生じないという新規な塗膜密着性
の理論から、優れた塗膜密着性を得るというものであっ
た。From these backgrounds, the present applicant has previously developed a non-porous anodic oxide film as disclosed in Japanese Patent Laid-Open No. 8-283990, and has developed aluminum having excellent coating film adhesion and corrosion resistance after coating. Provided the material. The aluminum material according to this patent has a thickness of 70 to 2000Å (0.00) on the surface of aluminum or aluminum alloy.
7 μm to 0.2 μm), the water content is 1 to 5% by weight, and the porosity is 5% or less. Further, this aluminum material is not the theory of generation of coating film adhesion that the conventional porous anodic oxide film obtains the coating film adhesion by exerting the anchor effect due to the unevenness of the surface portion due to the porosity, By eliminating the porous portion, the water and ions contained in the porous portion are eliminated, and a new phenomenon that the coating adhesion is not reduced due to volatilization of water and ionic components during coating drying. From the theory of coating film adhesion, it was to obtain excellent coating film adhesion.
【０００６】[0006]
【発明が解決しようとする課題】ところが、この種の無
孔質陽極酸化皮膜においても塗膜密着性に更に厳しい品
質を要求された場合には、塗膜密着性に不足を来すおそ
れがあった。そこで本願出願人は、特開平９−１８４０
９３号公報などに開示されている如く、アルミニウム又
はアルミニウム合金の表面に、厚さが７００〜３０００
Å（０.０７μｍ〜０.３μｍ）のベーマイト皮膜と、厚
さが７０〜２０００Åの陽極酸化皮膜とからなる複合皮
膜を開発し、更なる塗膜密着性向上をなし得た。ところ
が、この特許に係るアルミニウム材は、塗膜との密着性
を向上するために、ベーマイト皮膜中の水分をベーキン
グ処理で除去し、低水分量とする必要があった。また、
先のアルミニウム材に塗装を施す事なく用いた場合、厳
しい環境下で耐食性が充分とは言えない場合があった。However, even in the case of this kind of non-porous anodic oxide coating, if a further strict quality is required for the coating adhesion, the coating adhesion may be insufficient. It was Therefore, the applicant of the present application has filed Japanese Patent Application Laid-Open No. 9-1840.
As disclosed in Japanese Patent Publication No. 93, etc., a thickness of 700 to 3000 is formed on the surface of aluminum or aluminum alloy.
We have developed a composite coating consisting of Å (0.07 μm-0.3 μm) boehmite coating and an anodized coating with a thickness of 70-2000 Å, and were able to further improve coating adhesion. However, in the aluminum material according to this patent, in order to improve the adhesion to the coating film, it is necessary to remove the water content in the boehmite film by a baking treatment to reduce the water content. Also,
When the above aluminum material was used without coating, the corrosion resistance was not sufficient in a severe environment in some cases.
【０００７】そこで本願発明者は、このような背景の基
でアルミニウム材の表面に形成する下地層としてのベー
マイト皮膜あるいは陽極酸化皮膜の更なる塗膜密着性向
上と耐食性について研究を重ねた結果、本願発明に到達
した。Therefore, the inventors of the present application have conducted research on further improvement of coating adhesion and corrosion resistance of a boehmite film or an anodized film as an underlayer formed on the surface of an aluminum material on the basis of such a background. The present invention has been reached.
【０００８】本願発明は前記の背景に基づき、塗膜密着
性の更なる向上と耐食性の更なる向上をなし得たアルミ
ニウム材とその製造方法の提供を目的とする。更に本願
発明は、塗膜を設けない場合においても耐食性に優れさ
せたアルミニウム材とその製造方法の提供を目的とす
る。Based on the above background, an object of the present invention is to provide an aluminum material capable of further improving coating film adhesion and corrosion resistance, and a method for producing the same. Another object of the present invention is to provide an aluminum material having excellent corrosion resistance even when a coating film is not provided, and a method for producing the aluminum material.
【０００９】[0009]
【課題を解決するための手段】本発明は前記課題を解決
するために、アルミニウム又はアルミニウム合金からな
る金属基材と、該金属基材上に形成された厚さ３００Å
〜２００００Åのアルミニウムの水和酸化物による多孔
質皮膜とを具備してなり、前記多孔質皮膜の表面又は内
部に、Ｓｉ、Ｐの１種以上が付着又は含有されてなるも
のである。多孔質皮膜にＳｉ、Ｐの１種以上が付着又は
含有されていると、耐食性が向上するとともに、塗膜密
着性も向上する。先のＳｉ、Ｐは塗膜中に一般的に含ま
れている顔料との結合性、親和性が高いので、塗膜に対
する密着性も良好なものとなる。In order to solve the above-mentioned problems, the present invention provides a metal base material made of aluminum or an aluminum alloy and a thickness of 300Å formed on the metal base material.
A porous film of hydrated oxide of aluminum up to 20000Å is formed, and one or more kinds of Si and P are attached or contained on the surface or inside of the porous film. When one or more kinds of Si and P are attached or contained in the porous film, the corrosion resistance is improved and the coating film adhesion is also improved. Since the above Si and P have high bondability and affinity with the pigment generally contained in the coating film, the adhesion to the coating film is also good.
【００１０】本発明は前記課題を解決するために、アル
ミニウム又はアルミニウム合金からなる金属基材と、該
金属基材上に形成された厚さ５０Å〜７０００Åの無孔
質皮膜と、該無孔質皮膜上に形成された厚さ３００Å〜
２００００Åのアルミニウムの水和酸化物による多孔質
皮膜とを具備してなり、前記皮膜にＳｉ、Ｐの１種以上
が付着又は含有されてなることを特徴とする。多孔質皮
膜にＳｉ、Ｐの１種以上が付着又は含有されていると、
耐食性が向上するとともに、塗膜密着性も向上する。ま
た、多孔質皮膜の下側に無孔質皮膜が形成されている
と、金属基材側への腐食性物質の侵入を阻止することが
でき、極めて耐食性に優れたアルミニウム材が得られ
る。先のＳｉ、Ｐは塗膜中に一般的に含まれる顔料との
結合性と親和性が高いので、塗膜に対する密着性も良好
なものとなる。In order to solve the above problems, the present invention provides a metal base material made of aluminum or an aluminum alloy, a non-porous coating having a thickness of 50Å to 7,000Å formed on the metal base, and the non-porous material. Thickness of 300 Å formed on the film
And a porous film made of hydrated oxide of aluminum of 20000Å, wherein one or more kinds of Si and P are attached or contained in the film. If at least one of Si and P is attached or contained in the porous film,
Corrosion resistance is improved and coating film adhesion is also improved. In addition, when the non-porous film is formed on the lower side of the porous film, it is possible to prevent the corrosive substance from entering the metal base material side, and an aluminum material having extremely excellent corrosion resistance can be obtained. Since the above Si and P have high bondability and affinity with the pigment generally contained in the coating film, the adhesion to the coating film also becomes good.
【００１１】本発明において、前記Ｓｉ、Ｐの１種以上
が前記皮膜中に２０ｐｐｍ以上、１０００００ｐｐｍ以
下の範囲で含まれてなることが好ましい。この範囲であ
るならば、良好な耐食性を維持したまま塗膜密着性も良
好とすることができる。前記Ｓｉ、Ｐの１種以上が２０
ｐｐｍ未満になると、耐食性の向上効果が得られ難くな
り、逆に１０００００ｐｐｍを越えると耐食性の向上効
果は少なくなり、むしろ塗膜の密着性が低下する傾向に
なる。本発明において、前記アルミニウムの水和酸化物
による多孔質皮膜がベーマイト皮膜であり、前記無孔質
皮膜が陽極酸化皮膜であることが好ましい。なお、ベー
マイト皮膜とは、ベーマイト構造（ＡｌＯＯＨ）を有す
る水和酸化物皮膜と表現することもできるものである。
多孔質皮膜がベーマイト皮膜であるならば、ＳｉとＰが
付着又は含浸されることで、耐食性の向上効果が確実に
発揮される。本発明において、前記無孔質皮膜が、空孔
率３０％以下の無孔質陽極酸化皮膜であることが好まし
い。ベーマイト皮膜の内部側に無孔質陽極酸化皮膜が形
成されていると、腐食性物質が仮に多孔質皮膜を通過し
て無孔質陽極酸化皮膜側に侵入しても、腐食性物質の金
属基材側への侵入を無孔質陽極酸化皮膜が阻止する。In the present invention, it is preferable that at least one of Si and P is contained in the coating in the range of 20 ppm or more and 100000 ppm or less. Within this range, good coating adhesion can be achieved while maintaining good corrosion resistance. One or more of Si and P is 20
If it is less than ppm, it becomes difficult to obtain the effect of improving the corrosion resistance, and conversely, if it exceeds 100,000 ppm, the effect of improving the corrosion resistance becomes small, and the adhesiveness of the coating film tends to decrease. In the present invention, it is preferable that the porous film made of a hydrated oxide of aluminum is a boehmite film and the non-porous film is an anodized film. The boehmite film can be expressed as a hydrated oxide film having a boehmite structure (AlOOH).
When the porous film is a boehmite film, Si and P are adhered or impregnated, so that the effect of improving the corrosion resistance is surely exhibited. In the present invention, the non-porous coating is preferably a non-porous anodic oxide coating having a porosity of 30% or less. If a non-porous anodic oxide film is formed on the inside of the boehmite film, even if the corrosive substance passes through the porous film and enters the non-porous anodic oxide film side, the metal group of the corrosive substance The non-porous anodic oxide film prevents entry into the material side.
【００１２】本発明の製造方法は、アルミニウム又はア
ルミニウム合金からなる金属基材に水和酸化物による多
孔質皮膜を形成した後、前記多孔質皮膜に珪酸塩又はり
ん酸塩の水溶液を接触又は塗布させて該多孔質皮膜に前
記水溶液中のＳｉ又はＰを付着又は含浸させることを特
徴とする。本発明の製造方法は、アルミニウム又はアル
ミニウム合金からなる金属基材に水和酸化物による多孔
質皮膜を形成した後、陽極酸化処理を施して無孔質酸化
皮膜を形成し、前記皮膜に珪酸塩又はりん酸塩の水溶液
を接触又は塗布させて該皮膜に前記水溶液中のＳｉ又は
Ｐを付着又は含浸させることを特徴とする。多孔質皮膜
を有する構造、あるいは多孔質皮膜に加えて下層側に無
孔質皮膜を有する構造においても、皮膜に水溶液中のＳ
ｉ又はＰを付着又は浸透させることで耐食性が向上する
とともに、塗膜密着性が向上する。The manufacturing method of the present invention comprises forming a porous film of hydrated oxide on a metal substrate made of aluminum or an aluminum alloy, and then contacting or applying an aqueous solution of silicate or phosphate to the porous film. Then, the porous film is adhered or impregnated with Si or P in the aqueous solution. The manufacturing method of the present invention comprises forming a porous film of a hydrated oxide on a metal substrate made of aluminum or an aluminum alloy, and then performing anodizing treatment to form a non-porous oxide film, and a silicate on the film. Alternatively, it is characterized in that an aqueous solution of a phosphate is brought into contact with or applied to adhere or impregnate Si or P in the aqueous solution to the film. Even in the structure having a porous film or the structure having a non-porous film on the lower layer side in addition to the porous film, the S in the aqueous solution is added to the film.
By adhering or permeating i or P, corrosion resistance is improved and coating film adhesion is improved.
【００１３】本発明の製造方法は、アルミニウム又はア
ルミニウム合金からなる金属基材に水和酸化物による多
孔質皮膜を形成した後、珪酸塩水溶液又はリン酸塩水溶
液中で陽極酸化処理を施して無孔質酸化皮膜を形成し、
同時に該皮膜に前記陽極酸化処理水溶液中のＳｉ又はＰ
を付着又は含浸させることを特徴とする。更に、珪酸塩
又はリン酸塩以外の処理液で無孔質陽極酸化皮膜を形成
させた前記多孔質皮膜付きの基材を、珪酸塩水溶液又は
リン酸塩水溶液中で陽極酸化処理を施して、該皮膜にＳ
ｉ又はＰを付着又は含浸させることができる。珪酸塩水
溶液又はリン酸塩水溶液で生成させた陽極酸化皮膜であ
るならば、陽極酸化処理中に電解液成分であるＳｉやＰ
が電気的に効率良く皮膜内に付着または含浸されるため
耐食性に優れる。Ｓｉ、Ｐは塗膜中に一般的に含まれる
顔料との結合性が高いので、塗膜に対する密着性を良好
とすることができる。In the production method of the present invention, after forming a porous film of a hydrated oxide on a metal base material made of aluminum or an aluminum alloy, anodizing treatment is performed in an aqueous silicate solution or an aqueous phosphate solution. Form a porous oxide film,
At the same time, the film is coated with Si or P in the anodized aqueous solution.
Is adhered or impregnated. Further, the substrate with a porous film formed a non-porous anodic oxide film with a treatment liquid other than silicate or phosphate, anodized in an aqueous silicate solution or phosphate solution, S on the film
i or P can be attached or impregnated. If it is an anodic oxide film formed with an aqueous solution of silicate or an aqueous solution of phosphate, Si or P which is an electrolyte solution component during anodizing treatment
Has excellent corrosion resistance because it is electrically efficiently attached or impregnated in the film. Since Si and P have high bondability with the pigment generally contained in the coating film, the adhesion to the coating film can be improved.
【００１４】本発明において、前記皮膜付の基材に珪酸
塩又はりん酸塩の水溶液を塗布して珪酸成分またはりん
酸成分を前記皮膜表面部分に付着させることができる。
本発明において、前記多孔質皮膜をベーマイト処理によ
り生成することを特徴とするものでも良い。In the present invention, an aqueous solution of silicate or phosphate can be applied to the above-mentioned base material having a coating to deposit the silicic acid component or the phosphoric acid component on the surface portion of the coating.
In the present invention, the porous film may be formed by boehmite treatment.
【００１５】[0015]
【発明の実施の形態】以下、図面を参照して本発明の実
施の形態について説明するが、本発明は以下の実施形態
に限定されるものではない。図１は本発明に係るアルミ
ニウム材の第１の実施の形態を示すもので、この形態の
アルミニウム材Ａは、アルミニウムあるいはアルミニウ
ム合金からなる板状の金属基材１とこの金属基材１の全
外面に形成された厚さ３００Å〜２００００Åのアルミ
ニウムの水和酸化物による多孔質皮膜２とから構成され
ている。なお、この実施の形態の多孔質皮膜２は図１で
は金属基材１の全外面に形成されているが、多孔質皮膜
２は耐食性と塗膜密着性の上で必要な面に形成すれば良
いので、例えば金属基材１の表面のみ、あるいは裏面の
みに形成しても差し支えない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. FIG. 1 shows a first embodiment of an aluminum material according to the present invention. An aluminum material A in this embodiment is a plate-shaped metal base material 1 made of aluminum or an aluminum alloy and the entire metal base material 1. It is composed of a porous film 2 made of a hydrated oxide of aluminum having a thickness of 300Å to 20000Å formed on the outer surface. Although the porous film 2 of this embodiment is formed on the entire outer surface of the metal substrate 1 in FIG. 1, if the porous film 2 is formed on a surface required for corrosion resistance and coating adhesion. Since it is good, for example, it may be formed only on the front surface or the back surface of the metal substrate 1.
【００１６】前記基材１は、アルミニウムあるいはアル
ミニウム合金からなり、ＪＩＳ１０００系等の純アルミ
ニウム系、ＪＩＳ２０００系等のＡｌ-Ｃｕ系、Ａｌ-Ｃ
ｕ-Ｍｇ系、ＪＩＳ３０００系のＡｌ-Ｍｎ系、ＪＩＳ４
０００系のＡｌ-Ｓｉ系、ＪＩＳ５０００系等のＡｌ-Ｍ
ｇ系、ＪＩＳ６０００系等のＡｌ-Ｍｇ-Ｓｉ系、ＪＩＳ
７０００系等のＡｌ-Ｚｎ-Ｍｇ系、Ａｌ-Ｚｎ-Ｍｇ-Ｃ
ｕ系、ＪＩＳ８０００系などのＡｌ-Ｆｅ-Ｍｎ系のいず
れの系のものを用いても良い。また、これらの系の成形
用合金、構造用合金、電気用合金、ＡＣ１Ａ、ＡＣ２
Ａ、ＡＣ３Ａ、ＡＣ４Ｂなどの鋳造合金のいずれの形態
で用いても良い。The base material 1 is made of aluminum or an aluminum alloy, and is made of pure aluminum such as JIS1000 series, Al--Cu series such as JIS2000 series, or Al--C.
u-Mg type, JIS3000 type Al-Mn type, JIS4
000 series Al-Si series, JIS5000 series etc. Al-M
g-based, JIS-6000 based Al-Mg-Si based, JIS
7000 series Al-Zn-Mg series, Al-Zn-Mg-C
Any of Al-Fe-Mn-based materials such as u-based material and JIS8000-based material may be used. Further, molding alloys, structural alloys, electrical alloys, AC1A, AC2 of these systems
It may be used in any form of cast alloy such as A, AC3A, AC4B.
【００１７】前記ＪＩＳ１０００系の純アルミニウム系
のもの、ＪＩＳ２０００系のもの、ＪＩＳ３０００系の
ものは例えば種々の部品などに用いられているので、こ
れらの用途に供する場合に本発明を適用できる。ＪＩＳ
４０００系のものは、例えば建築パネルなどに用いられ
るので、これらの用途に供する場合に本発明を適用する
ことができる。ＪＩＳ５０００系のものは、例えば内外
装板、装飾部品、銘板等に広く使用されるので、これら
の用途に供する場合に本発明を適用することができる。
ＪＩＳ６０００系のものは、例えば建築、装飾品などに
使用されるのでこれらの用途に供する場合に本発明を適
用することができる。ＪＩＳ７０００系のものは例えば
熱交換器用フィン材などに使用されるので、これらの用
途に供する場合に本発明を適用することができる。The JIS1000 series pure aluminum series, the JIS2000 series, and the JIS3000 series are used in various parts, for example, so that the present invention can be applied to these applications. JIS
Since 4000 series products are used, for example, in building panels, the present invention can be applied to these applications. Since JIS 5000 series products are widely used in, for example, interior / exterior plates, decorative parts, name plates, etc., the present invention can be applied to these applications.
Since JIS 6000 series products are used in, for example, construction and ornaments, the present invention can be applied to these applications. Since JIS 7000 series is used for fin materials for heat exchangers, for example, the present invention can be applied to these applications.
【００１８】前記金属基材１上に形成されたアルミニウ
ムの水和酸化物による多孔質皮膜２とは、この実施の形
態ではいわゆるベーマイト皮膜にＳｉ、Ｐの少なくとも
１種が付着又は含浸さまれた皮膜が用いられている。先
のベーマイト皮膜とは、アルミニウムが高温の水と反応
して擬ベーマイト質の水和酸化物皮膜を生成することを
利用して得られるもので、クロメート系の化成皮膜と違
って公害上の問題がなく、ベーマイト皮膜そのものは工
業用途に広く使用されているものである。In the present embodiment, the porous film 2 made of a hydrated oxide of aluminum formed on the metal substrate 1 is a so-called boehmite film in which at least one of Si and P is attached or impregnated. A coating is used. The above boehmite film is obtained by utilizing the fact that aluminum reacts with high-temperature water to form a quasi-boehmite hydrated oxide film. Therefore, the boehmite film itself is widely used for industrial purposes.
【００１９】以下にこのベーマイト皮膜の形成法につい
て説明する。先の用途に合わせた合金系の適切な形状に
加工されたアルミニウム又はアルミニウム合金の金属基
材を用意したならば、この金属基材に対して前処理を施
す。この前処理は、金属基材の表面に付着した油脂分を
除去し、金属基材表面の不均質な酸化物皮膜等を除去で
きるものであればいかなる処理でも良い。例えば、弱ア
ルカリ性の脱脂液による脱脂処理を施した後、水酸化ナ
トリウム水溶液でアルカリエッチングをした後、硝酸水
溶液でデスマット処理を行う方法や、脱脂処理後に酸洗
浄を行う方法などが適宜選択して用いられる。ついで、
この前処理が施された基材を建浴水中でベーマイト処理
を施すことにより、該基材の表面にベーマイト皮膜を形
成する。建浴水としては、高温の水を使用できるが、特
に、電気伝道度が０.１μＳ以下のイオン交換水を用い
るのが、基材表面の黒変の防止とベーマイト皮膜を生成
し易いなどの点で好ましい。The method for forming this boehmite film will be described below. When a metal base material of aluminum or aluminum alloy processed into an appropriate shape of an alloy system suitable for the above-mentioned application is prepared, the metal base material is subjected to pretreatment. This pretreatment may be any treatment as long as it can remove the oil and fat components adhering to the surface of the metal base material and remove the heterogeneous oxide film and the like on the surface of the metal base material. For example, after performing degreasing treatment with a weak alkaline degreasing solution, after performing alkali etching with an aqueous solution of sodium hydroxide, a method of performing desmutting treatment with an aqueous solution of nitric acid, a method of performing acid cleaning after the degreasing treatment, etc. are appropriately selected. Used. Then,
A boehmite film is formed on the surface of the base material by subjecting the pretreated base material to a boehmite treatment in a construction bath water. Although high-temperature water can be used as the bath water, it is particularly preferable to use ion-exchanged water having an electric conductivity of 0.1 μS or less to prevent blackening of the substrate surface and to easily form a boehmite film. It is preferable in terms.
【００２０】建浴水の温度は、９０℃〜沸点（１００
℃）の範囲が望ましい。本発明でのベーマイト処理は、
必要とする多孔質皮膜の厚さに合わせて適宜調節して良
く、厚さ３００Å〜２００００Åの範囲とするので、多
孔質皮膜の膜厚が薄い場合は１０秒〜５分程度で十分で
あり、膜厚が厚い場合は５分を越える時間、〜１２０分
程度処理する。建浴水には、アンモニア、アミン、アル
コールアミン、アミド、トリエタノールアミン等のアル
カリ添加剤を添加して用いるのが、ベーマイト皮膜の生
成速度が速くなるなど点で好ましく、その場合、ベーマ
イト皮膜の膜厚が厚くなり過ぎないようにするため、ベ
ーマイト処理時間はできる限り短時間とすることが好ま
しい。The temperature of the bath water is 90 ° C to the boiling point (100
C) range is desirable. The boehmite treatment in the present invention is
It may be appropriately adjusted according to the required thickness of the porous film, and the thickness is in the range of 300Å to 20000Å. Therefore, when the thickness of the porous film is thin, about 10 seconds to 5 minutes is sufficient, When the film thickness is large, the treatment is performed for more than 5 minutes and for about 120 minutes. To the construction bath water, it is preferable to use an alkaline additive such as ammonia, amine, alcohol amine, amide, triethanol amine, etc. in that the production rate of the boehmite film becomes faster, and in that case, the boehmite film In order to prevent the film thickness from becoming too thick, the boehmite treatment time is preferably as short as possible.
【００２１】このようなベーマイト処理によってアルミ
ニウムまたはアルミニウム合金の金属基材の表面に、羽
毛状の凹凸を有する水和酸化物の多孔質皮膜（ベーマイ
ト皮膜）２が形成される。このベーマイト皮膜の膜厚
は、３００〜２００００Å、好ましくは５００〜１２０
００Å程度である。ベーマイト膜厚が３００Å未満であ
ると、良好な耐食性が得られず、膜厚が２００００Åを
超えると、コイルに巻き上げる段階で皮膜にクラックが
入り易くなり、耐食性が低下する傾向となる。また、こ
のベーマイト皮膜とは、ベーマイト構造（ＡｌＯＯＨ）
を有する水和酸化物皮膜とも表現することができる。By such a boehmite treatment, a porous film (boehmite film) 2 of hydrated oxide having feather-like irregularities is formed on the surface of a metal base material of aluminum or aluminum alloy. The thickness of this boehmite coating is 300 to 20000Å, preferably 500 to 120.
It is about 00Å. If the boehmite film thickness is less than 300Å, good corrosion resistance cannot be obtained, and if the boehmite film thickness exceeds 20000Å, cracks are likely to occur in the film at the stage of winding into a coil, and the corrosion resistance tends to decrease. The boehmite film has a boehmite structure (AlOOH).
It can also be expressed as a hydrated oxide film having.
【００２２】ベーマイト皮膜を形成したならば、このベ
ーマイト皮膜に珪酸塩とりん酸塩の少なくとも１種を直
接塗布するか、珪酸塩とりん酸塩の水溶液中で通電する
処理を施してベーマイト皮膜表面あるいはその内部に珪
酸塩とりん酸塩の少なくとも１種以上を付着させるか含
ませる処理を行う。ベーマイト皮膜に珪酸塩とりん酸塩
を通電処理により付着させるか含ませるためには、珪酸
塩あるいはりん酸塩の水溶液を用意し、ベーマイト皮膜
付の金属基材１を前記水溶液に浸漬して正極側とし、水
溶液を負極側として通電し、電気的にベーマイト皮膜の
表面層部分に付着させることが好ましい。After the boehmite film is formed, at least one of silicate and phosphate is directly applied to the boehmite film, or the boehmite film surface is treated by energizing in an aqueous solution of silicate and phosphate. Alternatively, a treatment is performed in which at least one of silicate and phosphate is attached or contained therein. In order to deposit or include the silicate and the phosphate in the boehmite film by an electric current treatment, an aqueous solution of the silicate or the phosphate is prepared, and the metal substrate 1 with the boehmite film is immersed in the aqueous solution to form the positive electrode. It is preferable to apply electricity to the surface layer portion of the boehmite film by electrically conducting the aqueous solution with the aqueous solution as the negative electrode side.
【００２３】ベーマイト皮膜の表面に珪酸塩とりん酸塩
の少なくとも１種以上を塗布して物理的にＳｉ、Ｐを付
着した形態とは、ベーマイト皮膜表面の羽毛状の多孔質
部分に珪酸塩とりん酸塩のどちらか一方あるいは両方が
吸着された状態であると推定できる。ベーマイト皮膜の
内部にＳｉ、Ｐの少なくとも一方を含浸させた状態と
は、珪酸塩とりん酸塩のどちらか一方あるいは両方をイ
オンの形でベーマイト皮膜の羽毛状の多孔質部分に含浸
結合させた状態を呈していると推定できる。珪酸塩であ
れば、ＳｉＯ2 2-の式で示される珪酸イオン、りん酸塩
であれば、ＰＯ4 3-で示されるりん酸イオンの形で陽極
酸化皮膜成分として結合しているものと推定できる。以
上説明の如く製造されたアルミニウム材Ａは、多孔質皮
膜（ベーマイト皮膜）中あるいはその表面部分にＳｉ、
Ｐの少なくとも１種を含んでいるので、耐食性に優れる
効果がある。The form in which at least one kind of silicate and phosphate is applied to the surface of the boehmite film and the Si and P are physically adhered to the boehmite film is the silicate on the feather-like porous portion of the boehmite film surface. It can be presumed that one or both of the phosphates are adsorbed. The state in which at least one of Si and P is impregnated inside the boehmite film means that either or both of silicate and phosphate are impregnated and bonded to the feather-like porous portion of the boehmite film in the form of ions. It can be presumed that the state is exhibited. If it is a silicate, it is presumed that it is bonded as an anodized film component in the form of a silicate ion represented by the formula SiO 2 2− , and if it is a phosphate, it is the phosphate ion represented by PO 4 3−. it can. The aluminum material A produced as described above has Si in the porous film (boehmite film) or on its surface.
Since it contains at least one kind of P, it has an effect of excellent corrosion resistance.
【００２４】前述のような多孔質皮膜２が形成されたア
ルミニウム材の表面には必要に応じて塗装が施される。
ここでの塗装に用いられる塗料として特に制限はない
が、特に焼き付けタイプのものを用いる場合に最も有効
に効果が得られる。このような塗料としては、熱可塑性
アクリル樹脂系塗料、熱硬化性アクリル樹脂系塗料、エ
ポキシ樹脂系塗料、ポリウレタン樹脂系塗料、ポリエス
テル樹脂系塗料、ポリアミド樹脂系塗料などが用いられ
る。塗装方法としては、特に制限はないが、吹き付け塗
装、ロールコータ法、グラビアロール法、静電塗装法、
カチオン電着塗装法等が用いられる。また、必要に応じ
て下塗り、中塗り、上塗りなどの多層塗装を施すことも
できる。このようにすると塗装アルミニウム材が得られ
る。また、塗膜を形成したものにおいて、Ｓｉ、Ｐは多
孔質皮膜２上に塗膜を被覆する場合に塗膜中に含まれる
顔料との結合性を有するので、塗膜を被覆した場合に塗
膜との密着性も良好なものとなる。If necessary, the surface of the aluminum material on which the porous film 2 is formed is coated.
There is no particular limitation on the paint used for coating here, but the effect is most effectively obtained when a baking type is used. As such paints, thermoplastic acrylic resin-based paints, thermosetting acrylic resin-based paints, epoxy resin-based paints, polyurethane resin-based paints, polyester resin-based paints, polyamide resin-based paints and the like are used. The coating method is not particularly limited, but spray coating, roll coater method, gravure roll method, electrostatic coating method,
A cationic electrodeposition coating method or the like is used. In addition, a multi-layer coating such as an undercoat, an intermediate coat, and a top coat can be applied if necessary. In this way, a coated aluminum material is obtained. Further, in the case where the coating film is formed, Si and P have a binding property with the pigment contained in the coating film when the coating film is coated on the porous coating film 2, so that it is applied when the coating film is coated. Adhesion with the film is also good.
【００２５】前述のような多孔質皮膜２にＳｉ、Ｐを含
ませるには先の電解処理の他に、ＳｉあるいはＰを含む
水溶液をロールコーターなどの塗布装置で塗布し、１２
０℃程度の温度で乾燥させることで行うこともできる。
この場合に多孔質皮膜２の内部に深くまでＳｉあるいは
Ｐが侵入するわけではないが、多孔質皮膜２の表面部分
にＳｉ、Ｐを存在させることでも本発明の効果を得るこ
とができる。従って、多孔質皮膜２に対して電解により
Ｓｉ、Ｐの少なくとも１種を含ませた後、更にＳｉある
いはＰを含む水溶液をロールコーターなどの塗布装置で
塗布しても良く、逆に塗布してから電解しても良い。In order to contain Si and P in the porous film 2 as described above, in addition to the above electrolytic treatment, an aqueous solution containing Si or P is applied by a coating device such as a roll coater,
It can also be performed by drying at a temperature of about 0 ° C.
In this case, Si or P does not penetrate deep into the porous film 2, but the effect of the present invention can be obtained by allowing Si or P to exist on the surface of the porous film 2. Therefore, the porous film 2 may be electrolyzed to contain at least one of Si and P, and then an aqueous solution containing Si or P may be further applied with a coating device such as a roll coater, or vice versa. You may electrolyze from.
【００２６】「第２の実施の形態」次に、図２は本発明
に係るアルミニウム材の第２の実施の形態を示すもの
で、この形態のアルミニウム材Ｂは、先の実施の形態で
用いたものと同等の金属基材１と、その全外面上に形成
された無孔質の陽極酸化皮膜３と、該陽極酸化皮膜３上
に形成された水和酸化物の多孔質皮膜５とから構成され
ている。なお、この実施の形態の陽極酸化皮膜３と多孔
質皮膜５は図２では金属基材１の全外面に形成されてい
るが、陽極酸化皮膜３と多孔質皮膜５は耐食性と塗膜密
着性の上で必要な面に形成すれば良いので、例えば金属
基材１の表面のみ、あるいは裏面のみに形成しても差し
支えない。[Second Embodiment] Next, FIG. 2 shows a second embodiment of the aluminum material according to the present invention. The aluminum material B of this embodiment is used in the previous embodiment. From a metal base material 1 equivalent to the conventional one, a non-porous anodic oxide film 3 formed on the entire outer surface thereof, and a hydrated oxide porous film 5 formed on the anodic oxide film 3. It is configured. Although the anodic oxide coating 3 and the porous coating 5 of this embodiment are formed on the entire outer surface of the metal substrate 1 in FIG. 2, the anodic oxide coating 3 and the porous coating 5 have corrosion resistance and coating adhesion. Since it may be formed on a necessary surface above, it may be formed on only the front surface or the back surface of the metal substrate 1.
【００２７】この形態において多孔質皮膜５は先の実施
の形態の構造と同様にＳｉ、Ｐの少なくとも１種以上を
付着させたものか、あるいはこれらを含有するものであ
る。この形態において無孔質陽極酸化皮膜３とは、従来
一般の多孔質陽極酸化皮膜とは異なり、空孔率が３０％
以下、好ましくは５％以下と低く、好ましくは含水量１
〜５重量％、好ましくはアニオン含有量０.１〜７重量
％の無孔質あるいは微孔質のものである。In this embodiment, the porous film 5 has at least one of Si and P adhered thereto, or contains these, as in the structure of the previous embodiment. In this form, the non-porous anodic oxide coating 3 has a porosity of 30%, unlike the conventional general porous anodic oxide coating.
Below, preferably as low as 5% or less, preferably with a water content of 1
.About.5% by weight, preferably 0.1 to 7% by weight of anion, non-porous or microporous.
【００２８】前記構造の無孔質陽極酸化皮膜３と多孔質
皮膜５とを備えたアルミニウム材Ｂを製造するために
は、先の実施の形態で形成した多孔質皮膜（ベーマイト
皮膜）２と同等の構造の多孔質皮膜（ベーマイト皮膜）
５をまず形成する。この多孔質皮膜５を形成する方法は
先の実施の形態において説明した方法と同等で良い。金
属基材１上に多孔質皮膜５を形成したならば、次に、こ
の金属基材１を電解浴中で電解する陽極酸化処理を施す
ことにより、金属基材１と多孔質皮膜５との境界部分に
陽極酸化皮膜３を形成することができる。電解浴として
は、生成する無孔質陽極酸化皮膜を溶解しにくく、かつ
無孔質の陽極酸化皮膜を生成可能な電解質であり、Ｓ
ｉ、Ｐを添加可能な電解浴として、珪酸ナトリウム、又
はりん酸アンモニウムの単独電解浴を例示することがで
きる。電解質水溶液中の電解質濃度は２重量％からその
電解質の飽和濃度の範囲で選ばれる。電解浴の浴温は２
０℃〜９０℃の範囲である。In order to manufacture the aluminum material B having the non-porous anodic oxide coating 3 and the porous coating 5 having the above-mentioned structure, it is equivalent to the porous coating (boehmite coating) 2 formed in the previous embodiment. Porous film (boehmite film)
5 is first formed. The method of forming this porous film 5 may be the same as the method described in the previous embodiment. After the porous film 5 is formed on the metal substrate 1, the metal substrate 1 and the porous film 5 are then subjected to anodic oxidation treatment in which the metal substrate 1 is electrolyzed in an electrolytic bath. The anodic oxide film 3 can be formed on the boundary portion. The electrolytic bath is an electrolyte that is difficult to dissolve the non-porous anodic oxide film to be formed and is capable of forming a non-porous anodic oxide film, and S
As an electrolytic bath to which i and P can be added, a single electrolytic bath of sodium silicate or ammonium phosphate can be exemplified. The electrolyte concentration in the aqueous electrolyte solution is selected from the range of 2% by weight to the saturation concentration of the electrolyte. Bath temperature of electrolysis bath is 2
It is in the range of 0 ° C to 90 ° C.
【００２９】この電解浴中で、アルミニウムまたはアル
ミニウム合金素材は、連続あるいは断続であっても陽極
となるように電源に接続されて電解される。陰極には不
溶性の導電材料が用いられる。電解電流は、直流電流が
用いられ、直流電解では直流密度１〜３０Ａ／ｄｍ2程
度、電解時間数秒〜３分程度で電解が行われる。In this electrolytic bath, the aluminum or aluminum alloy material is electrolyzed by being connected to a power source so as to become an anode even if it is continuous or intermittent. An insoluble conductive material is used for the cathode. A direct current is used as the electrolysis current, and in the direct current electrolysis, electrolysis is performed with a direct current density of about 1 to 30 A / dm 2 and an electrolysis time of about several seconds to about 3 minutes.
【００３０】印加電圧は、直流電流では、電圧１Ｖに対
して形成される酸化皮膜厚さが約１４Åとなる関係があ
ることから約５〜５００Ｖ、好ましくは約３０〜３００
Ｖの範囲とされることが好ましい。電源装置などの点か
らは２００Ｖ以下とすることが好ましく、このような低
電圧の電解でも優れた塗膜密着性と塗装後耐食性が得ら
れる。このような陽極酸化処理によって多孔質皮膜（ベ
ーマイト皮膜）５の下地層として厚さの均一な無孔質陽
極酸化皮膜３が形成される。無孔質陽極酸化皮膜３の膜
厚は、５０〜７０００Åであることが好ましく、より好
ましくは４００〜４０００Å程度である。膜厚が５０Å
未満であると、厚さが薄すぎて耐食性の更なる向上効果
が得られ難いからである。一方、膜厚の上限としては、
７０００Åまで可能であるが、４０００Åを超えて厚く
しても、もはや効果の増大は期待できず、電解時間の増
加や電解設備等にコストがかかり経済的にも不利とな
り、また、成形性が低下し、皮膜の割れなどが発生する
傾向があるため、４０００Å以下とすることが好まし
い。The applied voltage is about 5 to 500 V, and preferably about 30 to 300 V, since the thickness of the oxide film formed is about 14 Å for a voltage of 1 V under direct current.
It is preferably in the range of V. From the viewpoint of a power supply device, it is preferably 200 V or less, and excellent coating adhesion and corrosion resistance after coating can be obtained even with such low voltage electrolysis. By such anodizing treatment, the non-porous anodized film 3 having a uniform thickness is formed as an underlayer of the porous film (boehmite film) 5. The thickness of the non-porous anodic oxide coating 3 is preferably 50 to 7,000 Å, more preferably about 400 to 4,000 Å. Film thickness is 50Å
If it is less than the above range, the thickness is too thin and it is difficult to obtain a further effect of improving the corrosion resistance. On the other hand, as the upper limit of the film thickness,
It is possible up to 7,000 Å, but even if it exceeds 4000 Å, the effect cannot be expected to increase anymore, and it becomes economically disadvantageous because the electrolysis time increases and the cost of electrolytic equipment increases, and the formability decreases. However, it is preferable that the thickness is 4000 Å or less, since the coating film tends to crack.
【００３１】このようにして得られた陽極酸化皮膜３は
無孔質であり、その空孔率は最大でも３０％程度以下、
好ましくは５％以下であり、通常は２％程度以下となっ
ている。また、陽極酸化皮膜の含水量は１〜５重量％程
度、通常は１〜３重量％程度と極めて低い値を示す。さ
らに酸化皮膜のアニオン含有量は０.１〜７重量％程
度、通常は１〜５重量％程度と低い値となっている。一
方、通常の硫酸浴、シュウ酸浴で得られた多孔質の陽極
酸化皮膜は、空孔率が３０〜７０％と非常に高く、含水
量は封孔処理後で１５重量％程度、アニオン含有量は１
２〜１５重量％程度である。但し、硫酸やシュウ酸浴で
も多孔質化する前の無孔質から多孔質の間で電解を停止
することで空孔率３０％以下として用いることができ
る。The anodic oxide coating 3 thus obtained is non-porous and its porosity is about 30% or less at the maximum.
It is preferably 5% or less, and usually about 2% or less. The water content of the anodic oxide coating is about 1 to 5% by weight, usually about 1 to 3% by weight, which is a very low value. Further, the anion content of the oxide film is about 0.1 to 7% by weight, usually about 1 to 5% by weight, which is a low value. On the other hand, the porous anodic oxide film obtained by a normal sulfuric acid bath or oxalic acid bath has a very high porosity of 30 to 70%, the water content is about 15% by weight after the sealing treatment, and the anion content is included. Quantity is 1
It is about 2 to 15% by weight. However, even in a sulfuric acid or oxalic acid bath, porosity of 30% or less can be used by stopping the electrolysis between the non-porous state and the porous state before being made porous.
【００３２】このため本発明での陽極酸化皮膜は、腐食
性物質の侵入を抑制して優れた耐食性を有するものとな
る。また、皮膜から揮散する水分、アニオンが格段に微
かなものとなり、焼付塗装時において、水分、アニオン
の放出による塗膜の剥離が小さくなる。また、本発明で
の無孔質の陽極酸化皮膜３の形成においては、電解浴の
浴温が２０℃〜９０℃と温度範囲が広いから、浴管理が
容易となる。さらに、酸化皮膜溶解性の低い電解質を用
いているので、電解中の皮膜の溶解が少なく、電流効率
もよくなる。以上の陽極酸化処理は、コイル状などの未
加工の状態のアルミニウムまたはアルミニウム合金に対
して行うこともでき、またプレス加工などの加工を施し
た後のものに対しても行うことができる。Therefore, the anodic oxide film of the present invention has excellent corrosion resistance by suppressing the penetration of corrosive substances. In addition, the water and anions that volatilize from the film become remarkably fine, and the peeling of the film due to the release of water and anions during baking coating becomes small. Further, in the formation of the non-porous anodic oxide coating 3 in the present invention, the bath temperature of the electrolytic bath is wide, ranging from 20 ° C. to 90 ° C., so that bath management becomes easy. Furthermore, since the electrolyte having low oxide film solubility is used, the film is less likely to be dissolved during electrolysis and the current efficiency is improved. The above anodic oxidation treatment can be performed on unprocessed aluminum or aluminum alloy such as a coil, or can be performed on the aluminum or aluminum alloy after being subjected to processing such as pressing.
【００３３】以上説明の如く製造されたアルミニウム材
Ｂは、Ｓｉ、Ｐを含む多孔質皮膜（ベーマイト皮膜）５
と無孔質の陽極酸化皮膜３とを両方有するので、先の実
施の形態の多孔質皮膜５のみを備えたアルミニウム材Ａ
よりも耐食性の面でより優れている特徴を有する。即
ち、多孔質皮膜５に加えてＳｉ、Ｐを含む陽極酸化皮膜
３自体が耐食性を発揮するので、より優れた耐食性が得
られる。The aluminum material B manufactured as described above has a porous film (boehmite film) 5 containing Si and P.
Since it has both the non-porous anodic oxide film 3 and the porous film 5 of the previous embodiment, the aluminum material A
It has the feature that it is superior in terms of corrosion resistance. That is, since the anodic oxide coating 3 itself containing Si and P exhibits corrosion resistance in addition to the porous coating 5, more excellent corrosion resistance can be obtained.
【００３４】これらの皮膜を備えたアルミニウム材Ｂに
は、更に必要に応じて樹脂製の塗膜が形成される。この
塗膜については、アクリル系樹脂膜などの樹脂製の塗膜
が選択される。ここでの塗膜には、商品の表示などのた
めに顔料が含まれたものが適用されるが、先の皮膜に含
ませた顔料はＳｉ、Ｐとの親和性に優れるので、塗膜の
密着性も良好なものとなる。If necessary, a resin coating film is further formed on the aluminum material B provided with these coating films. For this coating film, a resin coating film such as an acrylic resin film is selected. As the coating film here, one containing a pigment is used for displaying products, etc., but since the pigment contained in the above coating has excellent affinity with Si and P, Adhesion is also good.
【００３５】[0035]
【実施例】ＪＩＳ規定純アルミニウム系合金（ＪＩＳ１
０５０）からなる厚さ０.３ｍｍのアルミニウム製の板
状の金属基材を複数用意した。これらの金属基材をアル
カリ脱脂（日本ペイント製サーフクリーナ３３０の３％
溶液、６０℃に３０秒浸漬）した後、常温にて１０秒水
洗し、１０％硝酸で３０秒中和処理し、処理後に常温で
１０秒水洗した。次に、これら金属基材に９８℃のｐＨ
９に調整したイオン交換水中に浸漬してベーマイト処理
を施した。なお、このベーマイト処理の際の浸漬時間を
適宜調節し、ベーマイト皮膜の厚さを調整した。[Example] JIS standard pure aluminum alloy (JIS1
050) and a plurality of plate-shaped metal base materials made of aluminum and having a thickness of 0.3 mm were prepared. Alkali degreasing of these metal base materials (3% of Nippon Paint Surf Cleaner 330)
The solution was immersed in 60 ° C. for 30 seconds), washed with water at room temperature for 10 seconds, neutralized with 10% nitric acid for 30 seconds, and after the treatment, washed with water at room temperature for 10 seconds. Next, the pH of these metal substrates is 98 ° C.
It was immersed in ion-exchanged water adjusted to 9 and subjected to boehmite treatment. The thickness of the boehmite film was adjusted by appropriately adjusting the immersion time during the boehmite treatment.
【００３６】先のベーマイト処理した複数の金属基材の
一部をイオン交換水で１０秒水洗した後、試料を陽極に
接続し、１０％硼酸水溶液に浸漬し、負極を水溶液中に
浸漬して、水溶液温度を６０℃として１.０Ａ／ｄｍ2の
電流密度で５分間電解処理し、以下の表１に示す種々の
膜厚の無孔質陽極酸化皮膜を形成した。この無孔質陽極
酸化皮膜の膜厚は電解時間で調整した。電解処理後、各
試料を１０秒間水洗し、１２０℃で乾燥させて以下の表
１に示す試料を得た。得られた無孔質陽極酸化皮膜はベ
ーマイト皮膜と金属基材の境界部分に形成されていた。
先のベーマイト処理した複数の金属基材の残りのものに
１％珪酸塩水溶液あるいは１％りん酸塩水溶液を塗布
し、塗布後に１２０℃で乾燥させて以下の表１に示す試
料を得た。A part of the plurality of boehmite-treated metal substrates was washed with ion-exchanged water for 10 seconds, the sample was connected to an anode, immersed in a 10% aqueous solution of boric acid, and the negative electrode was immersed in the aqueous solution. Electrolytic treatment was performed for 5 minutes at a current density of 1.0 A / dm 2 at an aqueous solution temperature of 60 ° C. to form non-porous anodic oxide coatings of various thicknesses shown in Table 1 below. The thickness of this non-porous anodic oxide film was adjusted by the electrolysis time. After the electrolytic treatment, each sample was washed with water for 10 seconds and dried at 120 ° C. to obtain the samples shown in Table 1 below. The obtained non-porous anodic oxide film was formed at the boundary between the boehmite film and the metal substrate.
A 1% silicate aqueous solution or a 1% phosphate aqueous solution was applied to the rest of the plurality of boehmite-treated metal base materials and dried at 120 ° C. after application to obtain the samples shown in Table 1 below.
【００３７】空孔率は皮膜断面をミクロトームで切断し
て１０万倍で１０カ所透過電子顕微鏡（ＴＥＭ）観察
し、ベーマイト皮膜と無孔質皮膜の境界部の孔の面積率
を求め、空孔率とした。なお、ここでの孔とはアルミニ
ウム基板からベーマイト層に向かう５０〜１０００Å程
度の孔のことである。但し、金属間化合物が存在し、皮
膜が不連続な部位を除いた。図３にその概要を示すが、
アルミニウム基板６上に無孔質皮膜７とベーマイト層８
とが順次積層されている構造の場合、無孔質皮膜７の途
中部分からベーマイト層８へ向かう孔が複数形成されて
いる場合、孔の面積をＣとし、断面から見た無孔質皮膜
の面積をＤとした時、有孔度（空孔率）＝（Ｃの面積の
総和／Ｄ）×１００の関係式で示される。The porosity was obtained by cutting the cross section of the coating with a microtome and observing it at 100,000 times at 10 locations with a transmission electron microscope (TEM) to determine the area ratio of the pores at the boundary between the boehmite coating and the non-porous coating. And rate. The holes here are holes of about 50 to 1000 Å from the aluminum substrate to the boehmite layer. However, a portion where the intermetallic compound was present and the film was discontinuous was removed. The outline is shown in Fig. 3.
Non-porous film 7 and boehmite layer 8 on aluminum substrate 6
In the case of a structure in which and are sequentially laminated, when a plurality of holes extending from the middle part of the non-porous film 7 to the boehmite layer 8 are formed, the area of the holes is defined as C and When the area is D, the porosity (porosity) = (total area of C / D) × 100.
【００３８】次に、Ｓｉ、Ｐの濃度は、グロー放電質量
分析（ＧＤＭＳ）で皮膜表面からエッチングしながら、
Ｓｉ又はＰの質量分析を行い、ＡｌとＯの濃度がクロス
する点までを膜厚とみなし、得られたＳｉ又はＰの濃度
値を平均して求めた。即ち、図４に示すように横軸にエ
ッチング時間をとり、縦軸に濃度（ｐｐｍ）を取る線図
を作成し、ＡｌとＯとＳｉの濃度を測定し、Ｓｉ濃度に
ついては、図４に示した（ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇ
＋ｈ＋ｊ＋ｋ＋ｌ＋ｍ）／βの計算式から求めた。Next, the concentrations of Si and P were determined by glow discharge mass spectrometry (GDMS) while etching from the film surface.
The mass analysis of Si or P was performed, the thickness up to the point where the concentrations of Al and O crossed was regarded as the film thickness, and the obtained concentration values of Si or P were averaged to obtain. That is, as shown in FIG. 4, a diagram in which the horizontal axis represents the etching time and the vertical axis represents the concentration (ppm) was prepared, and the concentrations of Al, O, and Si were measured. Shown (a + b + c + d + e + f + g
+ H + j + k + l + m) / β was calculated.
【００３９】[0039]
【表１】 [Table 1]
【００４０】以上の製造方法により得られた各試料に対
し、耐食性試験と密着性試験を行った。耐食性試験は５
０℃で相対湿度９５％以上の湿潤環境に２４０時間暴露
し、表面の腐食状態を比較観察することで行った。その
結果を以下の表２に示すが、表２において◎印で示す試
料は腐食が全く見られなかった試料、〇印で示す試料は
腐食面積が表面積に対して５％以下の試料、△印で示す
試料は腐食面積が表面積に対して１５％以下の試料、×
印で示した試料は腐食面積が表面積に対して３０％以上
の試料である。密着性試験は、先の耐食性試験を行った
試料を取り出して直ちに碁盤目試験（カッターで１ｍｍ
角の升目を１００個形成し、粘着テープで剥離する試
験）を行った。その結果を表２に示すが、表２において
〇印で示す試料は剥離部分が５％以下の試料、×印で示
す試料は剥離部分が５％を越える試料である。A corrosion resistance test and an adhesion test were performed on each sample obtained by the above manufacturing method. Corrosion resistance test is 5
It was performed by exposing it to a humid environment having a relative humidity of 95% or more at 0 ° C. for 240 hours and comparatively observing the corrosion state of the surface. The results are shown in Table 2 below. In Table 2, the samples marked with ⊚ have no corrosion, the samples marked with ∘ have a corroded area of 5% or less of the surface area, and the marks marked Δ. The sample indicated by is a sample whose corroded area is 15% or less of the surface area, ×
The sample indicated by the mark is a sample having a corroded area of 30% or more of the surface area. For the adhesion test, take out the sample that has been subjected to the above corrosion resistance test and immediately perform a cross-cut test (1 mm with a cutter.
A test of forming 100 square cells and peeling them off with an adhesive tape was performed. The results are shown in Table 2. In Table 2, the sample marked with a circle is a sample having a peeled portion of 5% or less, and the sample marked with a cross is a sample having a peeled portion of more than 5%.
【００４１】[0041]
【表２】 [Table 2]
【００４２】表１と表２に示す結果から、本願発明に係
る試料においてはいずれも優れた耐食性と塗膜密着性を
示すことが明らかとなった。まず、表１のＮｏ.１〜３
の試料はアルミニウム基材の表面に厚さ３００Å、８０
００Å、２００００Åの水和酸化物の多孔質皮膜（ベー
マイト皮膜）のみを形成し、珪酸ナトリウム溶液（Ｓｉ
濃度１００００ｐｐｍ）に浸漬してから乾燥することで
得られた試料であるが、多孔質皮膜の厚さが３００Åで
は耐食性が若干低下するがそれよりも厚い試料（８００
０Å、２００００Å）ではいずれも耐食性は優れてい
た。Ｎｏ.２２の試料は水和酸化物の多孔質皮膜を２０
０Å形成した試料であるが、耐食性に劣る結果となっ
た。Ｎｏ.２３の試料は水和酸化物の多孔質皮膜を２２
０００Å形成した試料であるが、この試料は膜にクラッ
クが多数入り、これが原因となって耐食性に劣る結果と
なった。従って水和酸化物の多孔質皮膜は少なくとも３
００Åは必要であるものと思われ、逆に２００００Åを
超えるとクラックが生成して耐食性に劣るものとなるこ
とが判明した。従って水和酸化物の多孔質皮膜は３００
Å以上、２００００Å以下の厚さの範囲に形成されるこ
とが好ましいと判明した。From the results shown in Tables 1 and 2, it became clear that the samples according to the present invention both show excellent corrosion resistance and coating adhesion. First, Table 1 Nos. 1-3
The sample of the thickness of the aluminum substrate is 300Å, 80
Only a porous film (boehmite film) of hydrated oxide of 00Å and 20000Å is formed, and a sodium silicate solution (Si
It is a sample obtained by immersing it in a concentration of 10000 ppm) and then drying it. When the porous film has a thickness of 300 Å, the corrosion resistance is slightly reduced, but a thicker sample (800
At 0Å and 20000Å), the corrosion resistance was excellent. The sample of No. 22 has a porous film of hydrated oxide 20
Although the sample was formed with 0Å, the result was inferior in corrosion resistance. The sample of No. 23 has a porous film of hydrated oxide 22
Although the sample was 000Å formed, many cracks were formed in the film, which resulted in poor corrosion resistance. Therefore, the porous film of hydrated oxide should be at least 3
It seems that 00Å is necessary, and conversely, when it exceeds 20000Å, cracks are generated and the corrosion resistance is inferior. Therefore, the porous film of hydrated oxide is 300
It has been found that it is preferable to form in a thickness range of Å or more and 20000 Å or less.
【００４３】Ｎｏ.４〜Ｎｏ.２１の試料は、無孔質陽極
酸化皮膜と多孔質皮膜（ベーマイト皮膜）を両方設けた
試料であり、Ｎｏ.４〜６が電解法によりＳｉを付与し
た試料、Ｎｏ.７〜９が塗布法によりＳｉを付与した試
料、Ｎｏ.１０〜１３が電解法によりＰを付与した試
料、Ｎｏ.１４の試料が塗布法によりＰを付与した試
料、Ｎｏ.１５〜１９が電解法によりＰを付与した試
料、Ｎｏ.２１が電解法によりＳｉを付与した試料、Ｎ
ｏ.２２が電解法によりＰを付与した試料である。ま
た、Ｎｏ.１〜Ｎｏ.２１の試料において処理塩として
は、珪酸ナトリウム、りん酸二水素アンモニウム、りん
酸二水素ナトリウム、りん酸二水素カリウム、りん酸二
水素アルミニウム、りん酸二水素マグネシウム、りん酸
二水素のいずれかを用いた。更に、Ｎｏ.２０、２１の
試料には厚さ５μｍの塗装膜を形成して塗膜密着性も評
価した。The samples No. 4 to No. 21 are samples provided with both a non-porous anodic oxide film and a porous film (boehmite film), and Nos. 4 to 6 are samples provided with Si by an electrolytic method. , Nos. 7 to 9 are samples to which Si is applied by the coating method, Nos. 10 to 13 are samples to which P is applied by the electrolytic method, No. 14 samples are samples to which P is applied by the coating method, No. 15 to No. 19 is a sample to which P is added by the electrolytic method, No. 21 is a sample to which Si is added by the electrolytic method, N
No. 22 is a sample to which P is added by the electrolytic method. Further, in the samples of No. 1 to No. 21, as the treated salt, sodium silicate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, aluminum dihydrogen phosphate, magnesium dihydrogen phosphate, Either dihydrogen phosphate was used. Further, a coating film having a thickness of 5 μm was formed on the samples of Nos. 20 and 21, and the coating film adhesion was also evaluated.
【００４４】Ｎｏ.４の試料は水和酸化物皮膜を３００
Å、無孔質の陽極酸化物皮膜を５０Å形成した試料であ
るが、水和酸化物皮膜のみを３００Å厚に形成したＮ
ｏ.１の試料よりも耐食性において更に良好な試験結果
を示した。しかし、Ｎｏ.２５の試料の如く厚さ４０Å
の陽極酸化皮膜では耐食性に劣る結果となった。以上の
ことから無孔質の陽極酸化物皮膜を設けることは耐食性
向上に寄与するものであり、その厚さが最低５０Åは必
要であることがわかる。Ｎｏ.８の試料はＳｉ濃度（４
１０００ｐｐｍ）をＮｏ.６の試料よりも少なくした試
料（２０ｐｐｍ）であるが、耐食性が若干低下してい
る。また、Ｓｉ濃度を１８ｐｐｍとしたＮｏ.２４の試
料については耐食性に劣る結果となったので、Ｓｉ濃度
については２０ｐｐｍ以上必要であると考えられる。The sample No. 4 has a hydrated oxide film of 300.
Å, a sample with 50 Å non-porous anodic oxide film formed, but N with only hydrated oxide film formed to 300 Å thickness
The test result of the corrosion resistance is better than that of the sample of No. However, as with the No. 25 sample, the thickness is 40Å
The result was inferior to the corrosion resistance of the anodic oxide film. From the above, it is understood that the provision of the non-porous anodic oxide film contributes to the improvement of the corrosion resistance, and the thickness thereof needs to be at least 50Å. The sample of No. 8 has a Si concentration (4
It is a sample (20 ppm) in which the amount of 1000 ppm) is smaller than that of the sample of No. 6, but the corrosion resistance is slightly reduced. Further, since the sample No. 24 having the Si concentration of 18 ppm was inferior in corrosion resistance, it is considered that the Si concentration needs to be 20 ppm or more.
【００４５】Ｎｏ.２６の試料は電解に使用するりん酸
塩としてりん酸三ナトリウムを用いた試料であるが、耐
食性は向上しなかった。このことから、処理塩として
は、珪酸ナトリウム、りん酸二水素アンモニウム、りん
酸二水素ナトリウム、りん酸二水素カリウム、りん酸二
水素アルミニウム、りん酸二水素マグネシウム、りん酸
二水素のいずれかを用いることはできるが、りん酸三ナ
トリウムは用いることができないことが判明した。Ｎ
ｏ.２７、２８の試料はＳｉ濃度かＰ濃度が低い（１７
ｐｐｍ、１８ｐｐｍ）ものであるが、ＳｉあるいはＰ濃
度が低いものでは耐食性と塗膜密着性の両方の特性が不
十分であった。Ｎｏ.２９は空孔度３０％の試料である
が先のＮｏ.１の試料と同等の特性となり、Ｎｏ.３０は
空孔度３５％の試料であるが、先の例と異なり、耐食性
が劣化した。The sample of No. 26 was a sample using trisodium phosphate as the phosphate used in electrolysis, but the corrosion resistance was not improved. From this, as the treated salt, any of sodium silicate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, aluminum dihydrogen phosphate, magnesium dihydrogen phosphate, and dihydrogen phosphate is used. It has been found that trisodium phosphate cannot be used, although it can be used. N
The samples of o.27 and 28 have low Si concentration or P concentration (17
ppm, 18 ppm), but those having a low Si or P concentration had insufficient properties of both corrosion resistance and coating adhesion. No. 29 is a sample with a porosity of 30%, but has the same characteristics as the sample of No. 1 above, and No. 30 is a sample with a porosity of 35%, but unlike the previous example, the corrosion resistance is Deteriorated.
【００４６】以上の試験結果から、金属基材上に形成さ
れた厚さ３００Å〜２００００Åのアルミニウムの水和
酸化物による多孔質皮膜を具備してなり、前記多孔質皮
膜の表面又は内部に、Ｓｉ、Ｐの１種以上が付着又は含
有されてなるアルミニウム材であるならば、優れた耐食
性を得られることが判明した。次に、金属基材上に形成
された厚さ５０Å〜７００Åの無孔質皮膜と、該無孔質
皮膜上に形成された厚さ３００Å〜２００００Åのアル
ミニウムの水和酸化物による多孔質皮膜とを具備してな
り、前記皮膜の表面または内部にＳｉ、Ｐの１種以上が
含有されてなるアルミニウム材であるならば、優れた耐
食性と優れた塗膜密着性を有することが判明した。From the above test results, a porous film made of a hydrated oxide of aluminum having a thickness of 300 Å to 20000 Å formed on a metal substrate is provided, and the surface or the inside of the porous film has a Si film. It has been found that excellent corrosion resistance can be obtained if the aluminum material is one in which at least one of P and P is attached or contained. Next, a non-porous film having a thickness of 50Å to 700Å formed on a metal substrate, and a porous film made of hydrated aluminum oxide having a thickness of 300Å to 20000Å formed on the non-porous film. It has been found that an aluminum material comprising the above-mentioned film and containing at least one of Si and P on the surface or inside thereof has excellent corrosion resistance and excellent coating adhesion.
【００４７】[0047]
【発明の効果】以上説明したように本発明は、金属基材
上に形成された厚さ３００Å〜２００００Åのアルミニ
ウムの水和酸化物による多孔質皮膜を具備し、多孔質皮
膜中にＳｉ、Ｐを含んでなるので、優れた耐食性を得る
ことができる。更に本発明は、金属基材上の厚さ５０Å
〜７０００Åの無孔質皮膜と、該無孔質皮膜上に形成さ
れた厚さ３００Å〜２００００Åのアルミニウムの水和
酸化物による多孔質皮膜とを具備してなり、前記皮膜の
表面または内部にＳｉ、Ｐの１種以上が含有されてなる
アルミニウム材であるならば、優れた耐食性と優れた塗
膜密着性を得ることができる。As described above, the present invention comprises a porous film made of a hydrated oxide of aluminum having a thickness of 300Å to 20000Å formed on a metal substrate, and the porous film contains Si and P. Since it contains, it is possible to obtain excellent corrosion resistance. Furthermore, the present invention has a thickness of 50Å on a metal substrate.
To 7,000 Å non-porous film, and a porous film formed on the non-porous film with a hydrated oxide of aluminum having a thickness of 300 Å to 20,000 Å, wherein Si is formed on the surface or inside of the film. If it is an aluminum material containing at least one of P and P, excellent corrosion resistance and excellent coating film adhesion can be obtained.
【００４８】また、先のＰ、Ｓｉを膜中に２０〜１００
０００ｐｐｍ含んでいることにより、優れた耐食性を確
実に得ることができるとともに、優れた塗膜密着性も確
実に得ることができる。これらＳｉ、Ｐについては表面
に塗布しても良いし、電解等の方法によりイオン状態で
含ませるか結合させても良く、いずれの方法によっても
表面の耐食性に優れたアルミニウム材を得ることができ
る。無孔質陽極酸化皮膜として空孔率３０％以下のもの
であれば、内部の水分量が少ないので、加熱時に水分が
揮発することが少なく、塗膜形成時などの加熱によって
塗膜が剥離し易くなることがない。また、腐食性物質の
侵入を抑制できる効果があり、また、多孔質皮膜として
ベーマイト皮膜を適用することができる。In addition, the above P and Si are added to the film in an amount of 20 to 100.
By including 000 ppm, excellent corrosion resistance can be surely obtained, and also excellent coating film adhesion can be surely obtained. These Si and P may be applied to the surface, or may be contained or bonded in an ionic state by a method such as electrolysis, and any method can provide an aluminum material having excellent surface corrosion resistance. . If the non-porous anodic oxide film has a porosity of 30% or less, the amount of water in the inside is small, so the water is less likely to volatilize during heating, and the film is peeled off by heating during film formation. It never gets easier. Further, it has an effect of suppressing the invasion of corrosive substances, and a boehmite film can be applied as the porous film.
【００４９】本発明方法は、金属基材に対して水和酸化
物による多孔質皮膜を形成し、これに珪酸塩あるいはり
ん酸塩を塗布するか、電解することによりＳｉ、Ｐを含
ませることができ、これにより耐食性に優れたアルミニ
ウム材を得ることができる。また、この方法に加えて、
多孔質皮膜を形成した後、陽極酸化処理を施して陽極酸
化皮膜を形成し、その後に珪酸塩あるいはりん酸塩を塗
布するか、電解することによりＳｉ、Ｐを含ませること
ができ、これにより耐食性と塗膜密着性の両方に優れた
アルミニウム材を得ることができる。In the method of the present invention, a porous film of hydrated oxide is formed on a metal substrate, and silicate or phosphate is applied to this or electrolysis is performed to contain Si and P. Therefore, an aluminum material having excellent corrosion resistance can be obtained. In addition to this method,
After forming a porous film, an anodizing treatment is applied to form an anodizing film, and then Si or P can be contained by applying a silicate or a phosphate or electrolyzing. An aluminum material excellent in both corrosion resistance and coating adhesion can be obtained.
【図１】 図１は本発明に係るアルミニウム材の第１の
実施の形態の構造を示す断面図。FIG. 1 is a sectional view showing a structure of a first embodiment of an aluminum material according to the present invention.
【図２】 図２は本発明に係るアルミニウム材の第２の
実施の形態の構造を示す断面図。FIG. 2 is a sectional view showing a structure of a second embodiment of an aluminum material according to the present invention.
【図３】 図３は本発明に係るアルミニウム材の第２の
実施の形態の積層構造を模式的に示す断面図。FIG. 3 is a sectional view schematically showing a laminated structure of a second embodiment of an aluminum material according to the present invention.
【図４】 図４は実施例のアルミニウム材のＳｉ濃度の
特定法の一例であるＧＤＭＳ法を説明するための線図で
ある。FIG. 4 is a diagram for explaining a GDMS method, which is an example of a method for specifying the Si concentration of an aluminum material according to an embodiment.
Ａ、Ｂ…アルミニウム材、１…金属基材、２…多孔質皮
膜、３…陽極酸化皮膜。A, B ... Aluminum material, 1 ... Metal substrate, 2 ... Porous film, 3 ... Anodized film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２５Ｄ 11/18 Ｃ２５Ｄ 11/18 Ａ ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI Theme Coat (Reference) C25D 11/18 C25D 11/18 A
Claims (8)
なる金属基材と、該金属基材上に形成された厚さ３００
Å〜２００００Åのアルミニウムの水和酸化物による多
孔質皮膜とを具備してなり、前記多孔質皮膜の表面又は
内部に、Ｓｉ、Ｐの１種以上が付着又は含有されてなる
ことを特徴とする耐食性に優れる表面処理アルミニウム
材。1. A metal base material made of aluminum or an aluminum alloy, and a thickness 300 formed on the metal base material.
A porous film made of hydrated oxide of aluminum having a thickness of Å to 20000Å, wherein at least one of Si and P is attached or contained on the surface or inside of the porous film. Surface-treated aluminum material with excellent corrosion resistance.
なる金属基材と、該金属基材上に形成された厚さ５０Å
〜７０００Åの無孔質皮膜と、該無孔質皮膜上に形成さ
れた厚さ３００Å〜２００００Åのアルミニウムの水和
酸化物による多孔質皮膜とを具備してなり、前記皮膜の
表面または内部にＳｉ、Ｐの１種以上が付着又は含有さ
れてなることを特徴とする耐食性に優れる表面処理アル
ミニウム材。2. A metal base material made of aluminum or an aluminum alloy, and a thickness of 50Å formed on the metal base material.
To 7,000 Å non-porous film, and a porous film formed on the non-porous film with a hydrated oxide of aluminum having a thickness of 300 Å to 20,000 Å, wherein Si is formed on the surface or inside of the film. A surface-treated aluminum material having excellent corrosion resistance, characterized in that at least one of P and P is attached or contained.
０ｐｐｍ以上、１０００００ｐｐｍ以下の範囲で含まれ
てなることを特徴とする請求項１又は２に記載の表面処
理アルミニウム材。3. The coating contains 2 or more of at least one of Si and P.
The surface-treated aluminum material according to claim 1 or 2, which is contained in a range of 0 ppm or more and 100000 ppm or less.
孔質皮膜がベーマイト皮膜であり、前記無孔質皮膜が陽
極酸化皮膜であり、該陽極酸化皮膜が空孔率３０％以下
の無孔質陽極酸化皮膜であることを特徴とする請求項１
〜３のいずれかに記載の表面処理アルミニウム材。4. A non-porous anode in which the porous film made of a hydrated oxide of aluminum is a boehmite film, the non-porous film is an anodized film, and the anodized film has a porosity of 30% or less. It is an oxide film, It is characterized by the above-mentioned.
The surface-treated aluminum material according to any one of to 3.
なる金属基材に水和酸化物による多孔質皮膜を形成した
後、前記多孔質皮膜に珪酸塩又はりん酸塩の水溶液を接
触又は塗布させて該多孔質皮膜に前記水溶液中のＳｉ又
はＰを付着又は含浸させることを特徴とする耐食性に優
れる表面処理アルミニウム材の製造方法。5. A porous film made of a hydrated oxide is formed on a metal substrate made of aluminum or an aluminum alloy, and the porous film is brought into contact with or coated with an aqueous solution of silicate or phosphate to form the porous film. A method for producing a surface-treated aluminum material having excellent corrosion resistance, which comprises depositing or impregnating a coating with Si or P in the aqueous solution.
なる金属基材に水和酸化物による多孔質皮膜を形成した
後、陽極酸化処理を施して無孔質酸化皮膜を形成し、前
記皮膜に珪酸塩又はりん酸塩の水溶液を接触又は塗布さ
せて該皮膜に前記水溶液中のＳｉ又はＰを付着又は含浸
させることを特徴とする耐食性に優れる表面処理アルミ
ニウム材の製造方法。6. After forming a porous film of hydrated oxide on a metal substrate made of aluminum or aluminum alloy, anodizing treatment is applied to form a non-porous oxide film, and the film is made of silicate or phosphorus. A method for producing a surface-treated aluminum material having excellent corrosion resistance, which comprises contacting or coating an aqueous solution of an acid salt to adhere or impregnate Si or P in the aqueous solution to the coating.
なる金属基材に水和酸化物による多孔質皮膜を形成した
後、珪酸塩水溶液又はリン酸塩水溶液中で陽極酸化処理
を施して無孔質酸化皮膜を形成し、同時に該皮膜に前記
陽極酸化処理水溶液中のＳｉ又はＰを付着又は含浸させ
ることを特徴とする耐食性に優れる表面処理アルミニウ
ム材の製造方法。7. A non-porous oxide film is formed by forming a porous film of a hydrated oxide on a metal substrate made of aluminum or an aluminum alloy and then subjecting it to anodic oxidation treatment in an aqueous silicate solution or an aqueous phosphate solution. A method for producing a surface-treated aluminum material having excellent corrosion resistance, which comprises forming and simultaneously depositing or impregnating Si or P in the aqueous solution of anodizing treatment on the coating.
生成することを特徴とする請求項６又は７に記載の表面
処理アルミニウム材の製造方法。8. The method for producing a surface-treated aluminum material according to claim 6, wherein the porous film is formed by boehmite treatment.
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| JP2001258089A JP3816363B2 (en) | 2001-08-28 | 2001-08-28 | Surface-treated aluminum material excellent in corrosion resistance and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001258089A JP3816363B2 (en) | 2001-08-28 | 2001-08-28 | Surface-treated aluminum material excellent in corrosion resistance and method for producing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063600A (en) * | 2005-08-30 | 2007-03-15 | Sumitomo Light Metal Ind Ltd | Aluminum alloy plate for hot blow molding |
| JP2007126693A (en) * | 2005-11-02 | 2007-05-24 | Denka Himaku Kogyo Kk | Aluminum material of hardly eluting impurity and manufacturing method therefor |
| JP2008163379A (en) * | 2006-12-27 | 2008-07-17 | Mitsubishi Alum Co Ltd | Method for manufacturing surface-treated aluminum material |
| JP2019186123A (en) * | 2018-04-13 | 2019-10-24 | トヨタ自動車株式会社 | Positive electrode, nonaqueous electrolyte secondary battery and method for manufacturing positive electrode |
| JP2022100314A (en) * | 2020-05-22 | 2022-07-05 | ダイキン工業株式会社 | Method for producing heat exchanger |
-
2001
- 2001-08-28 JP JP2001258089A patent/JP3816363B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063600A (en) * | 2005-08-30 | 2007-03-15 | Sumitomo Light Metal Ind Ltd | Aluminum alloy plate for hot blow molding |
| JP2007126693A (en) * | 2005-11-02 | 2007-05-24 | Denka Himaku Kogyo Kk | Aluminum material of hardly eluting impurity and manufacturing method therefor |
| JP2008163379A (en) * | 2006-12-27 | 2008-07-17 | Mitsubishi Alum Co Ltd | Method for manufacturing surface-treated aluminum material |
| JP2019186123A (en) * | 2018-04-13 | 2019-10-24 | トヨタ自動車株式会社 | Positive electrode, nonaqueous electrolyte secondary battery and method for manufacturing positive electrode |
| JP2022100314A (en) * | 2020-05-22 | 2022-07-05 | ダイキン工業株式会社 | Method for producing heat exchanger |
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| Publication number | Publication date |
|---|---|
| JP3816363B2 (en) | 2006-08-30 |
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