JPWO2011145594A1 - Chromium-free metal surface treatment agent and metal surface treatment method using the same - Google Patents
Chromium-free metal surface treatment agent and metal surface treatment method using the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
Abstract
【課題】クロメート処理に匹敵する優れた塗膜の密着性及び耐食性を達成できるクロムフリー金属表面処理剤を提供する。【解決手段】有機ホスホン酸ポリマーと水溶性錯フッ化物を含むことを特徴とする、アルミニウム、アルミニウム合金、亜鉛、及び亜鉛合金用クロムフリー金属表面処理剤である。有機ホスホン酸ポリマーとしては、アクリル酸とビニルホスホン酸のコポリマーが好ましい。水溶性錯フッ化物としてはフッ化チタン酸が好ましい。【選択図】なしProvided is a chromium-free metal surface treatment agent capable of achieving excellent coating adhesion and corrosion resistance comparable to chromate treatment. A chromium-free metal surface treatment agent for aluminum, aluminum alloy, zinc, and zinc alloy, comprising an organic phosphonic acid polymer and a water-soluble complex fluoride. As the organic phosphonic acid polymer, a copolymer of acrylic acid and vinylphosphonic acid is preferable. The water-soluble complex fluoride is preferably fluorinated titanic acid. [Selection figure] None
Description
本発明は、アルミニウム、アルミニウム合金、亜鉛、及び亜鉛合金に良好な塗膜の密着性と耐食性を付与するクロムフリー金属表面処理剤及びこれを使用する金属表面処理方法に関する。 The present invention relates to aluminum, an aluminum alloy, zinc, a chromium-free metal surface treatment agent that imparts good coating film adhesion and corrosion resistance to a zinc alloy, and a metal surface treatment method using the same.
クロメート処理は、６価のクロム酸によってアルミニウム材表面を不動態化するものであるが、６価クロムが有毒であり、その処理操作を行う作業環境上で問題があると共に、処理後のクロム含有排水やアルミニウム製品廃棄物からの溶出等による環境汚染が懸念されることから、近年においては地球環境保全の観点から厳しい規制が課せられるようになり、既に６価クロムの使用を全廃することが決定されている。このため、代替手段としてのクロムフリー、つまりクロムを使用せずにアルミニウム材の塗膜の密着性と耐食性を高め得る手段が必要になっている。 In the chromate treatment, the surface of the aluminum material is passivated by hexavalent chromic acid. However, hexavalent chromium is toxic and has a problem in the working environment in which the treatment operation is performed, and contains chromium after the treatment. Due to concerns about environmental pollution caused by elution from wastewater and aluminum product waste, in recent years strict regulations have been imposed from the viewpoint of global environmental protection, and it has already been decided to completely abolish the use of hexavalent chromium. Has been. Therefore, there is a need for chromium-free as an alternative means, that is, a means capable of improving the adhesion and corrosion resistance of an aluminum coating without using chromium.
このような代替手段としては、Ｍｏ，Ｗ，Ｔｉ，Ｚｒ，Ｖ，Ｍｎ，Ｃｏ，Ｆｅ等の遷移金属のフッ化物、リン酸塩、硝酸塩、硫酸塩等によって耐食性皮膜を形成する化成処理が代表的である。たとえば、特開２００３−１５５５７８、特開２００４−１８９３０参照。しかしながら、上記のような既存の代替手段では、いずれもアルミニウム材の塗膜の密着性や耐食性はある程度は改善されても、以前のクロメート処理による性能には遠く及ばず、とりわけ塗膜の密着性及び耐食性に関しては甚だ不充分である。そのため、現状では取り敢えず６価クロムを３価クロムに変えた処理方法で対応している事業者が多いが、処理液管理が複雑で手間を要し、ランニングコストが高くつく上、将来的には全てのクロム処理が禁止される方向にあるため、一時凌ぎの手段でしかない。従って、特にアルミニウム材の塗装分野では、更なる性能向上を可能とするクロムフリーの塗装前処理方法の開発が強く要望されている。 As such alternative means, a chemical conversion treatment in which a corrosion-resistant film is formed with fluorides, phosphates, nitrates, sulfates, etc. of transition metals such as Mo, W, Ti, Zr, V, Mn, Co, and Fe is representative. Is. For example, refer to JP2003-155578A and JP2004-18930A. However, with the existing alternatives as described above, even if the adhesion and corrosion resistance of the aluminum coating are improved to some extent, the performance by the previous chromate treatment is not far, especially the adhesion of the coating. And the corrosion resistance is very inadequate. Therefore, at present, there are many businesses that handle the hexavalent chromium instead of the trivalent chromium for the time being, but the treatment liquid management is complicated and time-consuming, and the running cost is high. Since all chrome treatment is in the direction of prohibition, it is only a means of surpassing temporarily. Therefore, especially in the field of coating aluminum materials, there is a strong demand for the development of a chromium-free pretreatment method for painting that enables further performance improvement.
本発明は、アルミニウム、アルミニウム合金、亜鉛、及び亜鉛合金の塗装下地処理における環境負荷の少ないクロムフリー仕様であって、しかもクロメート処理に匹敵する優れた塗膜の密着性及び耐食性を達成できるクロムフリー金属表面処理剤を提供することを目的としている。 The present invention is a chromium-free specification that has a low environmental impact in coating ground treatment of aluminum, aluminum alloy, zinc, and zinc alloy, and can achieve excellent coating adhesion and corrosion resistance comparable to chromate treatment. It aims at providing a metal surface treating agent.
本発明は、有機ホスホン酸ポリマーと水溶性錯フッ化物を含むことを特徴とするアルミニウム、アルミニウム合金、亜鉛、及び亜鉛合金用クロムフリー金属表面処理剤である。 The present invention is a chromium-free metal surface treating agent for aluminum, aluminum alloy, zinc, and zinc alloy characterized by containing an organic phosphonic acid polymer and a water-soluble complex fluoride.
本発明のクロムフリー金属表面処理剤により形成された化成皮膜は、後記実験例に示すように、塗膜の密着性及び耐食性に優れていることが示された。 It was shown that the chemical conversion film formed with the chromium-free metal surface treatment agent of the present invention is excellent in the adhesion and corrosion resistance of the coating film as shown in the experimental examples described later.
上記有機ホスホン酸ポリマーを構成する有機ホスホン酸基としては、芳香族、複素環式、脂肪族及び脂環式、低分子量の／及び高分子量のホスホン酸基及びその誘導体があげられる。これらは例えば、ビニルホスホン酸、ポリビニルホスホン酸、２−ホスホノ−エタン−１−スルホン酸、３，３−ジホスホノ−ピメリン酸、ビニルホスホン酸モノメチルエステル、４−クロルフェニルホスホン酸、４−クロル−３−ニトロ−フェニルホスホン酸、これらを有する水溶性コポリマーを含む。より好ましいのは、不飽和結合を持つカルボン酸と不飽和結合を持つ炭化水素のホスホン酸誘導体のコポリマーである。不飽和結合を持つカルボン酸としては、たとえば、アクリル酸（CH2＝CH-COOH）、クロトン酸（CH3−CH=CH−COOH）、メタクリル酸（CH2＝C（CH３）−COOH）があげられる。不飽和結合を持つ炭化水素のホスホン酸誘導体としては、たとえば、ビニルホスホン酸（CH2＝CH−PO3H2）、プロペン−１−ホスホン酸（CH3−CH＝CH−PO3H2）、プロペン−２−ホスホン酸（CH２＝CH（CH３）−PO3H2）があげられる。最も好ましいのは、アクリル酸とビニルホスホン酸のコポリマー（分子量３０ｋＤａ−４０ｋＤａ）である。Examples of the organic phosphonic acid group constituting the organic phosphonic acid polymer include aromatic, heterocyclic, aliphatic and alicyclic, low molecular weight / and high molecular weight phosphonic acid groups and derivatives thereof. These include, for example, vinylphosphonic acid, polyvinylphosphonic acid, 2-phosphono-ethane-1-sulfonic acid, 3,3-diphosphono-pimelic acid, vinylphosphonic acid monomethyl ester, 4-chlorophenylphosphonic acid, 4-chloro-3 -Nitro-phenylphosphonic acids, including water-soluble copolymers with these. More preferred is a copolymer of a carboxylic acid having an unsaturated bond and a phosphonic acid derivative of a hydrocarbon having an unsaturated bond. Examples of the carboxylic acid having an unsaturated bond include acrylic acid (CH 2 ═CH—COOH), crotonic acid (CH 3 —CH═CH—COOH), and methacrylic acid (CH 2 ═C (CH 3 ) —COOH). Is given. Examples of hydrocarbon phosphonic acid derivatives having an unsaturated bond include vinylphosphonic acid (CH 2 ═CH—PO 3 H 2 ) and propene-1-phosphonic acid (CH 3 —CH═CH—PO 3 H 2 ). And propene-2-phosphonic acid (CH 2 ═CH (CH 3 ) —PO 3 H 2 ). Most preferred is a copolymer of acrylic acid and vinyl phosphonic acid (molecular weight 30 kDa-40 kDa).
上記水溶性錯フッ化物としては特に限定されず、例えば、H2ZrF6、(NH4)2ZrF6、K2ZrF6、Na2ZrF6、Li2ZrF6、H2TiF6、(NH4)2TiF6、K2TiF6、Na2TiF6等を挙げることができ、中でもフッ化チタン酸（H2TiF6）が好ましい。これらは、単独で用いてもよく、２種以上を併用してもよい。The water-soluble complex fluoride is not particularly limited. For example, H 2 ZrF 6, (NH 4 ) 2 ZrF 6, K 2 ZrF 6, Na 2 ZrF 6, Li 2 ZrF 6, H 2 TiF 6, (NH 4 ) 2 TiF 6, K 2 TiF 6, Na 2 TiF 6 and the like can be mentioned, among which fluorinated titanic acid (H 2 TiF 6 ) is preferable. These may be used alone or in combination of two or more.
上記有機ホスホン酸ポリマーと水溶性錯フッ化物を溶かすための溶媒は水であり、特にイオン交換水が好ましい。 The solvent for dissolving the organic phosphonic acid polymer and the water-soluble complex fluoride is water, and ion-exchanged water is particularly preferable.
上記有機ホスホン酸ポリマーの含有量は、重量基準で、好ましくは、１０〜５００００ｐｐｍであり、より好ましくは１００〜２００００ｐｐｍであり、最も好ましいのは１０００〜１００００ｐｐｍである。１０ｐｐｍ未満になると塗膜の密着性が低下するおそれがある。５００００ｐｐｍを超えると、化成反応が満足に進行せず、化成皮膜が得られないおそれがある。 The content of the organic phosphonic acid polymer is preferably 10 to 50000 ppm, more preferably 100 to 20000 ppm, and most preferably 1000 to 10000 ppm on a weight basis. If it is less than 10 ppm, the adhesion of the coating film may be reduced. If it exceeds 50000 ppm, the chemical conversion reaction does not proceed satisfactorily, and there is a possibility that a chemical conversion film cannot be obtained.
上記クロムフリー金属表面処理剤は、水溶性錯フッ化物の含有量がフッ素原子換算で、好ましくは１０〜５０００ｐｐｍであり、より好ましくは５０〜２０００ｐｐｍであり、最も好ましいのは１００〜１５００ｐｐｍである。１０ｐｐｍ未満になると得られる化成皮膜の性能が不十分である。５０００ｐｐｍを超えると、化成反応が満足に進行せず、化成皮膜が得られないおそれがある。 In the chromium-free metal surface treatment agent, the content of the water-soluble complex fluoride is preferably 10 to 5000 ppm, more preferably 50 to 2000 ppm, and most preferably 100 to 1500 ppm in terms of fluorine atoms. If the concentration is less than 10 ppm, the resulting chemical conversion film has insufficient performance. If it exceeds 5000 ppm, the chemical conversion reaction does not proceed satisfactorily, and a chemical conversion film may not be obtained.
本発明の金属表面処理剤を適用することができるアルミニウム又はその合金の例としては、特に限定されず、アルミニウム、アルミニウム−銅合金、アルミニウム−マンガン合金、アルミニウム−珪素合金、アルミニウム−マグネシウム合金、アルミニウム−マグネシウム−珪素合金、アルミニウム−亜鉛合金、アルミニウム−亜鉛−マグネシウム合金等を挙げることができる。 Examples of aluminum or an alloy thereof to which the metal surface treating agent of the present invention can be applied are not particularly limited, and are aluminum, aluminum-copper alloy, aluminum-manganese alloy, aluminum-silicon alloy, aluminum-magnesium alloy, aluminum. -Magnesium-silicon alloy, aluminum-zinc alloy, aluminum-zinc-magnesium alloy, etc. can be mentioned.
上記アルミニウム又はその合金用のクロムフリー金属表面処理剤は、たとえばイオン交換水で希釈することにより、ｐＨを１．０〜４．０に調整して使用することが好ましい。ｐＨが１．０未満であると、金属表面のエッチングが促進され過ぎるため、皮膜外観が不良となり、また得られる化成皮膜の耐食性も低い。ｐＨが４．０を超えると、化成反応が満足に進行せず、化成皮膜が得られないおそれがある。 The chromium-free metal surface treatment agent for aluminum or an alloy thereof is preferably used by adjusting the pH to 1.0 to 4.0, for example, by diluting with ion exchange water. When the pH is less than 1.0, etching of the metal surface is promoted too much, so that the appearance of the film becomes poor, and the resulting chemical conversion film has low corrosion resistance. If the pH exceeds 4.0, the chemical reaction does not proceed satisfactorily and a chemical conversion film may not be obtained.
本発明を適用することができる亜鉛又はその合金の例としては、特に限定されず、例えば、亜鉛めっき鋼板、亜鉛−ニッケルめっき鋼板、亜鉛−鉄めっき鋼板、亜鉛−クロムめっき鋼板、亜鉛−アルミニウムめっき鋼板、亜鉛−チタンめっき鋼板、亜鉛−マグネシウムめっき鋼板、亜鉛−マンガンめっき鋼板等の亜鉛系の電気めっき、溶融めっき、蒸着めっき鋼板等の亜鉛又は亜鉛系合金めっき鋼板等を挙げることができる。 Examples of zinc or an alloy thereof to which the present invention can be applied are not particularly limited. For example, galvanized steel sheet, zinc-nickel plated steel sheet, zinc-iron plated steel sheet, zinc-chromium plated steel sheet, zinc-aluminum plating Examples thereof include zinc-based electroplating such as steel plates, zinc-titanium-plated steel plates, zinc-magnesium-plated steel plates, and zinc-manganese-plated steel plates, and zinc or zinc-based alloy-plated steel plates such as hot dipped and vapor-deposited steel plates.
上記亜鉛又はその合金用のクロムフリー金属表面処理剤は、たとえばイオン交換水で希釈することにより、ｐＨを１．０〜５．０に調整して使用することが好ましい。ｐＨが１．０未満であると、金属表面のエッチングが促進され過ぎるため、皮膜外観が不良となり、また得られる化成皮膜の耐食性も低い。ｐＨが５．０を超えると、化成反応が満足に進行せず、化成皮膜が得られないおそれがある。 It is preferable to use the chromium-free metal surface treatment agent for zinc or an alloy thereof after adjusting the pH to 1.0 to 5.0, for example, by diluting with ion exchange water. When the pH is less than 1.0, etching of the metal surface is promoted too much, so that the appearance of the film becomes poor, and the resulting chemical conversion film has low corrosion resistance. If the pH exceeds 5.0, the chemical conversion reaction does not proceed satisfactorily, and a chemical conversion film may not be obtained.
上記クロムフリー金属表面処理剤に接触させる方法は特に限定されず、例えば、ロールコート法、スピンコート法、スプレー法、浸漬法等を用いることができる。 The method of contacting the chromium-free metal surface treatment agent is not particularly limited, and for example, a roll coating method, a spin coating method, a spray method, a dipping method, or the like can be used.
上記クロムフリー金属表面処理剤の使用濃度は、好ましくは、１〜２０％、より好ましくは２〜１５％、最も好ましくは３〜１０％である。１％未満であると、反応性が低く、皮膜の形成性が悪くなり、耐食性が低下するおそれがある。２０％を超えると、化成反応が満足に進行しないおそれがある。 The use concentration of the chromium-free metal surface treatment agent is preferably 1 to 20%, more preferably 2 to 15%, and most preferably 3 to 10%. If it is less than 1%, the reactivity is low, the film-forming property is deteriorated, and the corrosion resistance may be lowered. If it exceeds 20%, the chemical conversion reaction may not proceed satisfactorily.
上記クロムフリー金属表面処理剤の処理温度としては、好ましくは、１５〜７０℃、より好ましくは２０〜５０℃、最も好ましくは２５〜３５℃である。１５℃未満であると、反応性が低く、皮膜の形成性が悪くなり、耐食性が低下するおそれがある。７０℃を超えても、反応性は向上せず、エネルギーのロスが大きくなるおそれがある。 The treatment temperature of the chromium-free metal surface treatment agent is preferably 15 to 70 ° C, more preferably 20 to 50 ° C, and most preferably 25 to 35 ° C. If it is less than 15 ° C., the reactivity is low, the film formability is deteriorated, and the corrosion resistance may be lowered. Even if it exceeds 70 degreeC, the reactivity will not improve and there exists a possibility that the loss of energy may become large.
上記クロムフリー金属表面処理剤の処理時間としては、好ましくは、１0〜６００秒であり、より好ましくは２０〜３００秒であり、最も好ましいのは３０〜１２０秒である。１0秒未満であると、形成される皮膜量が充分でないおそれがあり、密着性、耐食性が低下するおそれがある。６００秒を超えても、反応性は向上せず、エネルギーのロスが大きくなるおそれがある。 The treatment time of the chromium-free metal surface treatment agent is preferably 10 to 600 seconds, more preferably 20 to 300 seconds, and most preferably 30 to 120 seconds. If it is less than 10 seconds, the amount of film formed may be insufficient, and the adhesion and corrosion resistance may be reduced. Even if it exceeds 600 seconds, the reactivity is not improved, and there is a possibility that energy loss becomes large.
上記クロムフリー金属表面処理剤には、防錆成分として、たとえば、トリエタノールアミンを代表とするエタノールアミン類、弗化ジルコン酸アンモニウムを代表とする弗化ジルコン酸塩、メタバナジン酸アンモニウムを代表とするバナジン酸塩、ポリアクリル酸を代表とする有機酸ポリマーとその塩およびコロイダルシリカを添加することができ、反応助剤として、たとえば、エチレンジアミン四酢酸およびその塩を代表とするキレート剤を添加することができる。 In the chromium-free metal surface treatment agent, for example, ethanolamines represented by triethanolamine, zirconate fluoride represented by ammonium zirconate fluoride, and ammonium metavanadate are represented as anticorrosive components. An organic acid polymer represented by vanadate, polyacrylic acid and a salt thereof and colloidal silica can be added. For example, a chelating agent represented by ethylenediaminetetraacetic acid and a salt thereof is added as a reaction aid. Can do.
上記クロムフリー金属表面処理剤による処理に先だって、前記金属材料は、前処理を行うことが好ましい。前処理は、通常は、本処理を行う前に素材に付着した油分、汚れを取り除くためにアルカリ脱脂剤、または酸性脱脂剤で洗浄するか、湯洗、溶剤洗浄等を行う。その後、必要に応じて酸、アルカリ等による表面調整を行う。素材表面の洗浄においては、洗浄剤が素材表面になるべく残留しないように洗浄後に水洗することが好ましい。 Prior to the treatment with the chromium-free metal surface treatment agent, the metal material is preferably pretreated. The pretreatment is usually carried out with an alkaline degreasing agent or an acidic degreasing agent to remove oil and dirt adhering to the raw material before performing this treatment, or with hot water, solvent washing or the like. Thereafter, surface adjustment with acid, alkali or the like is performed as necessary. In cleaning the surface of the material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the material as much as possible.
上記クロムフリー金属表面処理剤は皮膜化成後の水洗が不要である。 The chromium-free metal surface treatment agent does not require water washing after film formation.
皮膜化成後の乾燥は、自然乾燥でもよいが、操業効率を高めるため、８０〜１４０℃で５〜２０分間処理することが好ましい。 Although drying after film | membrane formation may be natural drying, in order to improve operation efficiency, it is preferable to process for 5 to 20 minutes at 80-140 degreeC.
以下本発明について実施例を掲げて更に詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples.
１．クロムフリー金属表面処理剤の調製
下記表１に示す配合比率（残部はイオン交換水）で有機ホスホン酸ポリマーと水溶性錯フッ化物を含有するクロムフリー金属表面処理剤を得た。有機ホスホン酸ポリマーとしてアクリル酸とビニルホスホン酸のコポリマー、水溶性錯フッ化物としてフッ化チタン酸を使用した。1. Preparation of chromium-free metal surface treatment agent A chromium-free metal surface treatment agent containing an organic phosphonic acid polymer and a water-soluble complex fluoride was obtained at a blending ratio shown in Table 1 below (the balance being ion-exchanged water). A copolymer of acrylic acid and vinylphosphonic acid was used as the organic phosphonic acid polymer, and fluorinated titanic acid was used as the water-soluble complex fluoride.
たとえば、アクリル酸とビニルホスホン酸のコポリマー３００ｐｐｍ、フッ化チタン酸中のフッ素３５０ｐｐｍの場合であれば、水９６０質量部にフッ化チタン酸２５質量部、アクリル酸とビニルホスホン酸のコポリマー１５質量部を添加し、得られた水溶液を５％で建浴してクロムフリー金属表面処理剤を得た。 For example, in the case of 300 ppm of acrylic acid and vinylphosphonic acid copolymer and 350 ppm of fluorine in fluorinated titanic acid, 960 parts by mass of water contains 25 parts by mass of fluorinated titanic acid and 15 parts by mass of acrylic acid and vinylphosphonic acid copolymer. Was added and the resulting aqueous solution was bathed at 5% to obtain a chromium-free metal surface treatment agent.
２．クロムフリー金属表面処理材の作成
Ａ１０５０（アルミニウム板材）を、貴和化学薬品社製「アルキレンＦ５００Ｋ」（商標）の３％希釈液を用いて洗浄し（５５℃×９０秒）、水洗し、続いて貴和化学薬品社製「シルミナイズ３２００−２」（商標）の１０％希釈液を用いて洗浄し（３０℃×１２０秒）、水洗した。得られたアルミニウム板材を上記方法により調製され、表１に示した成分を有するクロムフリー金属表面処理剤を浸漬法により化成処理した（３０℃×１２０秒）。その後、１２０℃にて１０分間乾燥させ、クロムフリー金属表面処理材を得た。2. Preparation of chromium-free metal surface treatment material A1050 (aluminum plate) was washed with a 3% dilution of “Alkylene F500K” (trademark) manufactured by Kiwa Chemicals Co., Ltd. (55 ° C. × 90 seconds), followed by washing with water. Washed with a 10% diluted solution of “Silminize 3200-2” (trademark) manufactured by Takawa Chemicals Co., Ltd. (30 ° C. × 120 seconds) and washed with water. The obtained aluminum plate was prepared by the above method, and a chromium-free metal surface treatment agent having the components shown in Table 1 was subjected to chemical conversion treatment by immersion (30 ° C. × 120 seconds). Then, it was made to dry at 120 degreeC for 10 minute (s), and the chromium free metal surface treatment material was obtained.
３．アルミニウム塗装材の作成
得られたクロムフリー金属表面処理材に、下塗りとしてエースペイント社製「カプロン２５００ ホワイト Ａ，Ｂ １８ＡＳ−１」（商標）を塗布し、上塗りとして関西ペイント社製アクリル樹脂塗料「建材用 マジクロン ＡＷ−１０」（商標）を塗布し、１９０℃で２０分間焼付けを行い、塗膜厚が２４〜３０μｍであるアルミニウム塗装材を得た。3. Preparation of aluminum coating material To the obtained chromium-free metal surface treatment material, “Kapron 2500 White A, B 18AS-1” (trademark) manufactured by Ace Paint Co., Ltd. was applied as an undercoat, and an acrylic resin paint manufactured by Kansai Paint Co., Ltd. “Magiclon AW-10” (trademark) for building materials was applied and baked at 190 ° C. for 20 minutes to obtain an aluminum coating material having a coating thickness of 24 to 30 μm.
４．評価方法
得られたアルミニウム塗装材に対して、下記評価を行い、結果を表１に示した。
各種試験の内容は次のとおりである。表２及び表３においても同様である。
１．付着性（一次密着性）
アルミニウム塗装材を１ｍｍ幅で１００個のクロスカットを施し、粘着テープ剥離を行い、塗膜の剥離個数を測定した。
２．耐沸騰水性（二次密着性）
アルミニウム塗装材を１００℃の沸騰水に5時間浸漬後、１ｍｍ幅で１００個のクロスカットを施し、粘着テープ剥離を行い、塗膜の剥離個数を測定した。
３．キャス試験
アルミニウム塗装材の中央付近にカッターにてクロスカットを付け、ＪＩＳ−Ｚ−２３７１記載のキャス試験を行った。試験は塗膜の膨れ幅が3mmに達するまで行った。
４．中性塩水噴霧試験
アルミニウム塗装材の中央付近にカッターにてクロスカットを付け、ＪＩＳ−Ｚ−２３７１記載の中性塩水噴霧試験を行った。試験は塗膜の膨れ幅が3mmに達するまで行った。The contents of the various tests are as follows. The same applies to Tables 2 and 3.
1. Adhesion (primary adhesion)
The aluminum coating material was cut into 100 pieces with a width of 1 mm, peeled off the adhesive tape, and the number of peeled coating films was measured.
2. Boiling water resistance (secondary adhesion)
The aluminum coating material was immersed in boiling water at 100 ° C. for 5 hours, then 100 crosscuts with a width of 1 mm were performed, the adhesive tape was peeled off, and the number of peeled coatings was measured.
3. Cast test A cross cut was made in the vicinity of the center of the aluminum coating material with a cutter, and the cast test described in JIS-Z-2371 was performed. The test was conducted until the swollen width of the coating reached 3 mm.
4). Neutral salt spray test A cross cut was made with a cutter near the center of the aluminum coating material, and a neutral salt spray test described in JIS-Z-2371 was performed. The test was conducted until the swollen width of the coating reached 3 mm.
本発明の金属処理剤を使用したアルミニウム塗装材は、従来のクロメート処理に匹敵する優れた塗膜の密着性及び耐食性を達成している。 The aluminum coating material using the metal treating agent of the present invention achieves excellent coating adhesion and corrosion resistance comparable to conventional chromate treatment.
１．クロムフリー金属表面処理剤の調製
表２に示す配合比率（残部はイオン交換水）で有機ホスホン酸ポリマーと水溶性錯フッ化物を含有するクロムフリー金属表面処理剤を得た。有機ホスホン酸ポリマーとしてアクリル酸とビニルホスホン酸のコポリマー、水溶性錯フッ化物としてフッ化チタン酸を使用した。1. Preparation of chromium-free metal surface treatment agent A chromium-free metal surface treatment agent containing an organic phosphonic acid polymer and a water-soluble complex fluoride was obtained at the blending ratio shown in Table 2 (the balance being ion-exchanged water). A copolymer of acrylic acid and vinylphosphonic acid was used as the organic phosphonic acid polymer, and fluorinated titanic acid was used as the water-soluble complex fluoride.
２．クロムフリー金属表面処理材の作成（１）
上記クロムフリー金属表面処理材の作成において、Ａ６０６３（アルミニウム型材）を表２に示す処理工程で処理した以外は実施例１と同様の方法で処理し、クロムフリー金属表面処理材を得た。2. Creation of chromium-free metal surface treatment material (1)
In preparation of the said chromium free metal surface treatment material, it processed by the method similar to Example 1 except having processed A6063 (aluminum mold material) at the process shown in Table 2, and obtained the chromium free metal surface treatment material.
３．クロムフリー金属表面処理材の作成（２）
上記クロムフリー金属表面処理材の作成において、ＡＤＣ１２（アルミニウムダイキャスト）を表２に示す処理工程で処理し、貴和化学薬品社製「シルミナイズ３２００−２」（商標）の処理時間を６０秒にした以外は実施例１と同様の方法で処理し、クロムフリー金属表面処理材を得た。3. Creation of chromium-free metal surface treatment material (2)
In the preparation of the chromium-free metal surface treatment material, ADC12 (aluminum die-cast) is treated in the treatment process shown in Table 2, and the treatment time of “Silminize 3200-2” (trademark) manufactured by Kiwa Chemicals Co., Ltd. is set to 60 seconds. A chromium-free metal surface treatment material was obtained in the same manner as in Example 1 except that.
１．クロメート金属表面処理剤の調製
貴和化学薬品社製「シルミナイズ１５０Ｐ」（商標）を用い、表２に示すクロム酸（残部はイオン交換水）を含有するクロメート金属表面処理剤を得た。1. Preparation of Chromate Metal Surface Treatment Agent A chromate metal surface treatment agent containing chromic acid (the balance is ion-exchanged water) shown in Table 2 was obtained using “Silminize 150P” (trademark) manufactured by Kiwa Chemicals.
２．クロメート金属表面処理材の作成（１）
Ａ１０５０（アルミニウム板材）を、貴和化学薬品社製「アルキレンＦ５００Ｋ」（商標）の３％希釈液を用いて洗浄し（５５℃×９０秒）、水洗し、続いて貴和化学薬品社製「シルミナイズ３２００−２」（商標）の１０％希釈液を用いて洗浄し（３０℃×１２０秒）、水洗した。得られたアルミニウム板材を上記方法により調製され、表２に示した成分を有するクロメート金属表面処理剤を浸漬法により化成処理し（５０℃×１５０秒）、水洗した。その後、１２０℃にて１０分間乾燥させ、クロメート金属表面処理材を得た。2. Preparation of chromate metal surface treatment material (1)
A1050 (aluminum plate material) was washed with a 3% dilution of “Alkylene F500K” (trademark) manufactured by Kiwa Chemicals Co., Ltd. (55 ° C. × 90 seconds), washed with water, and subsequently manufactured by Kiwa Chemicals Co., Ltd. It was washed with a 10% diluted solution of Silminize 3200-2 ”(trademark) (30 ° C. × 120 seconds) and washed with water. The obtained aluminum plate was prepared by the above method, and a chromate metal surface treatment agent having the components shown in Table 2 was subjected to chemical conversion treatment by a dipping method (50 ° C. × 150 seconds) and washed with water. Then, it was made to dry at 120 degreeC for 10 minute (s), and the chromate metal surface treatment material was obtained.
３．クロメート金属表面処理材の作成（２）
上記クロメート金属表面処理材の作成において、Ａ６０６３（アルミニウム型材）を表２に示す処理工程で処理した以外は上記２と同様の方法で処理し、クロメート金属表面処理材を得た。3. Creation of chromate metal surface treatment material (2)
In preparation of the chromate metal surface treatment material, A6063 (aluminum mold material) was treated in the same manner as 2 except that it was treated in the treatment step shown in Table 2 to obtain a chromate metal surface treatment material.
４．クロメート金属表面処理材の作成（３）
上記クロメート金属表面処理材の作成において、ＡＤＣ１２（アルミニウムダイキャスト）を表２に示す処理工程で処理した以外は上記２と同様の方法で処理し、クロメート金属表面処理材を得た。4). Preparation of chromate metal surface treatment material (3)
In preparation of the said chromate metal surface treatment material, it processed by the method similar to said 2 except having processed ADC12 (aluminum die-casting) by the process shown in Table 2, and obtained the chromate metal surface treatment material.
比較評価
得られたアルミニウム塗装材に対して、下記評価を行い、結果を表２に示した。本発明の金属処理剤を使用したアルミニウム塗装材は、従来のクロメート処理に匹敵する優れた塗膜の密着性及び耐食性を達成している。
１．クロムフリー金属表面処理剤の調製
表３に示す配合比率（残部はイオン交換水）で有機ホスホン酸ポリマーと水溶性錯フッ化物を含有するクロムフリー金属表面処理剤を得た。有機ホスホン酸ポリマーとしてアクリル酸とビニルホスホン酸のコポリマー、水溶性錯フッ化物としてフッ化チタン酸を使用した。1. Preparation of chromium-free metal surface treatment agent A chromium-free metal surface treatment agent containing an organic phosphonic acid polymer and a water-soluble complex fluoride was obtained at the blending ratio shown in Table 3 (the balance being ion-exchanged water). A copolymer of acrylic acid and vinylphosphonic acid was used as the organic phosphonic acid polymer, and fluorinated titanic acid was used as the water-soluble complex fluoride.
２．クロムフリー金属表面処理材の作成（浸漬法１）
Ａ１０５０（アルミニウム板材）を、貴和化学薬品社製「アルキレンＦ５００Ｋ」（商標）の３％希釈液を用いて洗浄し（５５℃×９０秒）、水洗し、続いて貴和化学薬品社製「シルミナイズ３２００−２」（商標）の１０％希釈液を用いて洗浄し（３０℃×１２０秒）、水洗した。得られたアルミニウム板材を上記方法により調製され、表１に示した成分を有するクロムフリー金属表面処理剤を浸漬法により化成処理した（３０℃×１２０秒）。その後、１２０℃にて１０分間乾燥させ、クロムフリー金属表面処理材を得た。2. Creation of chromium-free metal surface treatment material (immersion method 1)
A1050 (aluminum plate material) was washed with a 3% dilution of “Alkylene F500K” (trademark) manufactured by Kiwa Chemicals Co., Ltd. (55 ° C. × 90 seconds), washed with water, and subsequently manufactured by Kiwa Chemicals Co., Ltd. It was washed with a 10% diluted solution of Silminize 3200-2 ”(trademark) (30 ° C. × 120 seconds) and washed with water. The obtained aluminum plate was prepared by the above method, and a chromium-free metal surface treatment agent having the components shown in Table 1 was subjected to chemical conversion treatment by immersion (30 ° C. × 120 seconds). Then, it was made to dry at 120 degreeC for 10 minute (s), and the chromium free metal surface treatment material was obtained.
３．クロムフリー金属表面処理材の作成（スプレー法）
Ａ１０５０（アルミニウム板材）を、貴和化学薬品社製「アルキレンＦ５００Ｋ」（商標）の３％希釈液を用いて洗浄し（５５℃×６０秒）、水洗し、続いて貴和化学薬品社製「シルミナイズ３２００−２」（商標）の７％希釈液を用いて洗浄し（３０℃×９０秒）、水洗した。得られたアルミニウム板材を上記方法により調製され、表３に示した成分を有するクロムフリー金属表面処理剤をスプレー法により化成処理した（３０℃×９０秒）。その後、１２０℃にて１０分間乾燥させ、クロムフリー金属表面処理材を得た。3. Preparation of chromium-free metal surface treatment material (spray method)
A1050 (aluminum plate material) was washed with a 3% dilution of “Alkylene F500K” (trademark) manufactured by Kiwa Chemical Co., Ltd. (55 ° C. × 60 seconds), washed with water, and subsequently manufactured by Kiwa Chemical Co., Ltd. It was washed with a 7% dilution of Silminize 3200-2 ”(trademark) (30 ° C. × 90 seconds) and washed with water. The obtained aluminum plate material was prepared by the above method, and a chromium-free metal surface treatment agent having the components shown in Table 3 was subjected to chemical conversion treatment by spraying (30 ° C. × 90 seconds). Then, it was made to dry at 120 degreeC for 10 minute (s), and the chromium free metal surface treatment material was obtained.
４．クロムフリー金属表面処理材の作成（浸漬法２）
上記クロムフリー金属表面処理材の作成において、Ａ６０６３（アルミニウム型材）を使用した以外は同様の方法で処理し、クロムフリー金属表面処理材を得た。4). Preparation of chromium-free metal surface treatment material (immersion method 2)
In preparation of the said chromium free metal surface treatment material, it processed by the same method except having used A6063 (aluminum mold material), and obtained the chromium free metal surface treatment material.
５．クロムフリー金属表面処理材の作成（スプレー法）
上記クロムフリー金属表面処理材の作成において、Ａ６０６３（アルミニウム型材）を使用した以外は同様の方法で処理し、クロムフリー金属表面処理材を得た。5. Preparation of chromium-free metal surface treatment material (spray method)
In preparation of the said chromium free metal surface treatment material, it processed by the same method except having used A6063 (aluminum mold material), and obtained the chromium free metal surface treatment material.
６．アルミニウム塗装材の作成（１）
得られたクロムフリー金属表面処理材に、下塗りとしてエースペイント社製「カプロン２５００ ホワイト Ａ，Ｂ １８ＡＳ−１」（商標）を塗布し、上塗りとして関西ペイント社製アクリル樹脂塗料「建材用 マジクロン ＡＷ−１０」（商標）を塗布し、１９０℃で２０分間焼付けを行い、塗膜厚が２４〜３０μｍであるアルミニウム塗装材を得た。6). Preparation of aluminum paint (1)
“Kapron 2500 White A, B 18AS-1” (trademark) manufactured by Ace Paint was applied as an undercoat to the resulting chromium-free metal surface treatment material, and an acrylic resin paint “Magiclon AW- for building materials” manufactured by Kansai Paint Co., Ltd. was used as an overcoat. 10 ”(trademark) was applied and baked at 190 ° C. for 20 minutes to obtain an aluminum coating material having a coating thickness of 24 to 30 μm.
７．アルミニウム塗装材の作成（２）
得られたクロムフリー金属表面処理材に、下塗りとしてエースペイント社製「カプロン２５００ ホワイト Ａ，Ｂ １８ＡＳ−１」（商標）を塗布し、上塗りとしてトウペ社製フッ素樹脂塗料「構造物用 ニューガメット♯３０００ ３分艶N−９０」（商標）を塗布し、１９０℃で２０分間焼付けを行い、塗膜厚が２０〜２５μｍであるアルミニウム塗装材を得た。7). Preparation of aluminum paint (2)
“Kapron 2500 White A, B 18AS-1” (trademark) manufactured by Ace Paint Co., Ltd. was applied as an undercoat to the obtained chromium-free metal surface treatment material, and a fluororesin paint “Tohpe Co., Ltd. New Gamut # 3000 for structures” was applied as an overcoat. 3 minutes gloss N-90 ”(trademark) was applied and baked at 190 ° C. for 20 minutes to obtain an aluminum coating material having a coating thickness of 20 to 25 μm.
８．アルミニウム塗装材の作成（３）
得られたクロムフリー金属表面処理材に、下塗りとしてエースペイント社製「カプロン２５００ ホワイト Ａ，Ｂ １８ＡＳ−１」を塗布し、上塗りとして関西ペイント社製ウレタン樹脂塗料「建材用 レタン ＰＡＱ ＣＮ−１０」（商標）を塗布し、１３７℃で２０分間焼付けを行い、塗膜厚が２４〜３０μｍであるアルミニウム塗装材を得た。8). Preparation of aluminum paint (3)
The resulting chromium-free metal surface treatment material was coated with “Apron 2500 White A, B 18AS-1” manufactured by Ace Paint as an undercoat, and urethane resin paint “Retan PAQ CN-10 for building materials” manufactured by Kansai Paint as an overcoat. (Trademark) was applied and baked at 137 ° C. for 20 minutes to obtain an aluminum coating material having a coating thickness of 24 to 30 μm.
１．クロメート金属表面処理剤の調製
貴和化学薬品社製「シルミナイズ１５０Ｐ」（商標）を用い表３に示すクロム酸（残部はイオン交換水）を含有するクロメート金属表面処理剤を得た。1. Preparation of Chromate Metal Surface Treatment Agent A chromate metal surface treatment agent containing chromic acid (the balance is ion-exchanged water) shown in Table 3 was obtained using “Silminize 150P” (trademark) manufactured by Kiwa Chemicals.
２．クロメート金属表面処理材の作成（１）
Ａ１０５０（アルミニウム板材）を、貴和化学薬品社製「アルキレンＦ５００Ｋ」（商標）の３％希釈液を用いて洗浄し（５５℃×９０秒）、水洗し、続いて貴和化学薬品社製「シルミナイズ３２００−２」（商標）の１０％希釈液を用いて洗浄し（３０℃×１２０秒）、水洗した。得られたアルミニウム板材を上記方法により調製され、表３に示した成分を有するクロメート金属表面処理剤を浸漬法により化成処理し（５０℃×１５０秒）、水洗した。その後、１２０℃にて１０分間乾燥させ、クロメート金属表面処理材を得た。2. Preparation of chromate metal surface treatment material (1)
A1050 (aluminum plate material) was washed with a 3% dilution of “Alkylene F500K” (trademark) manufactured by Kiwa Chemicals Co., Ltd. (55 ° C. × 90 seconds), washed with water, and subsequently manufactured by Kiwa Chemicals Co., Ltd. It was washed with a 10% diluted solution of Silminize 3200-2 ”(trademark) (30 ° C. × 120 seconds) and washed with water. The obtained aluminum plate was prepared by the above method, and a chromate metal surface treatment agent having the components shown in Table 3 was subjected to chemical conversion treatment by immersion (50 ° C. × 150 seconds) and washed with water. Then, it was made to dry at 120 degreeC for 10 minute (s), and the chromate metal surface treatment material was obtained.
３．クロメート金属表面処理材の作成（２）
上記クロメート金属表面処理材の作成において、Ａ６０６３（アルミニウム型材）を使用した以外は同様の方法で処理し、クロメート金属表面処理材を得た。3. Creation of chromate metal surface treatment material (2)
In preparation of the said chromate metal surface treatment material, it processed by the same method except having used A6063 (aluminum mold material), and obtained the chromate metal surface treatment material.
比較評価
得られたアルミニウム塗装材に対して、下記評価を行い、結果を表３に示した。本発明の金属処理剤を使用したアルミニウム塗装材は、従来のクロメート処理に匹敵する優れた塗膜の密着性及び耐食性を達成している。
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| PCT/JP2011/061265 WO2011145594A1 (en) | 2010-05-21 | 2011-05-17 | Chromium-free metal surface treatment agent, and metal surface treatment method using same |
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| MY169256A (en) | 2012-08-29 | 2019-03-19 | Ppg Ind Ohio Inc | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| KR20150040377A (en) | 2012-08-29 | 2015-04-14 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| CN103074623A (en) * | 2013-01-11 | 2013-05-01 | 大连工业大学 | Energy-saving environmental-friendly zirconium treatment process before coating |
| CN104651821A (en) * | 2015-02-11 | 2015-05-27 | 常州君合科技股份有限公司 | Novel aluminum and high-molecular aluminum alloy chromium-free film forming agent |
| KR102206483B1 (en) * | 2015-05-01 | 2021-01-22 | 노벨리스 인크. | Continuous coil pretreatment method |
| CN105063595A (en) * | 2015-08-18 | 2015-11-18 | 昆明理工大学 | Phytic acid passivation solution and preparing method and application thereof |
| CN105779983B (en) * | 2016-04-19 | 2018-05-25 | 昆明理工大学 | A kind of Chrome-free color passivation solution |
| KR20190043155A (en) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Alkaline compositions for treating metal substrates |
| CN108330475B (en) * | 2017-12-29 | 2020-10-13 | 广东省建筑科学研究院集团股份有限公司 | High-corrosion-resistance marine aluminum alloy surface metal-organic framework film treatment liquid and use method thereof |
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