JP2006200007A - Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property - Google Patents
Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property Download PDFInfo
- Publication number
- JP2006200007A JP2006200007A JP2005013548A JP2005013548A JP2006200007A JP 2006200007 A JP2006200007 A JP 2006200007A JP 2005013548 A JP2005013548 A JP 2005013548A JP 2005013548 A JP2005013548 A JP 2005013548A JP 2006200007 A JP2006200007 A JP 2006200007A
- Authority
- JP
- Japan
- Prior art keywords
- degreasing
- emission intensity
- absorption rate
- aluminum alloy
- maximum emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は防錆潤滑油塗油後成形され、接着剤で接合組み立てされる際の接着性に優れ、その後のアルカリ脱脂処理後の水濡れ性に優れた自動車ボディーシート用アルミニウム合金板(以下アルミニウムを単にAlと言う)に関するものである。 The present invention is an aluminum alloy sheet for automobile body sheets (hereinafter referred to as aluminum) that is formed after application of a rust-preventive lubricating oil and has excellent adhesion when bonded and assembled with an adhesive, and excellent water wettability after subsequent alkaline degreasing treatment. Is simply referred to as Al).
近年、地球温暖化等の環境問題で自動車等の排ガス規制が強化され、軽量化による燃費の向上が避けられない。このため、自動車等に従来より使用されていた鋼鈑に替わり、Ａｌ合金材がフード、フェンダー、ドア等に使用され始めている。特に、自動車用材としてマグネシウム(以下マグネシウムをＭｇと言う)を添加した５０００系合金及び６０００系合金が主に使用されている。
通常、自動車の製造ラインは、潤滑防錆油を塗油して成形その後、組み立て工程で接着剤及びスポット溶接等で接合されて、アルカリ脱脂、化成処理、塗装工程となる。
自動車用材の要求性能として、材料性能の他に表面処理性能(脱脂性、化成処理性、耐糸錆性、塗膜密着性、接着性)が有る。
化成処理性改善としては、たとえば特開２００１−３４８６７０号公報のようにアルミ表面に０．１〜１．５ｇ／ｍ２のジンケート皮膜を生成させる方法が提案されている。
又、特開２０００−２３９７７８号公報では１００オングストローム以下のアルミニウム酸化皮膜を平行偏光使用によるＦＴ−ＩＲ分析の３５００ｃｍ−１のスペクトルピーク高さが０．００７以下となるように水酸基を抑制する方法が提案されている。更に、特開２００３−０１３２５３号公報では厚さが１５００〜１００００オングストロームのアルミニウム水酸化物皮膜で、水接触角≦２０°であることを特徴とするアルミニウム構造材が提案されている。
また更に、脱脂性向上として特公平７−１１６６２９号公報にはＭｇＯリッチな酸化皮膜を化学的に溶解して、酸化皮膜厚さを４５オングストローム以下、表面層のＭｇ／Ａｌ比を０．５以下にする方法が提案されている。
しかし、これらの何れの方法も、漫然と酸化物または水酸化物に着目していたため、接着不良や脱脂後水濡れ不良を引き起こす問題が十分に解決されていなかった。
Usually, an automobile production line is coated with a lubricating rust-preventive oil and then molded and then joined by an adhesive, spot welding, or the like in an assembly process to become an alkali degreasing, chemical conversion treatment, or coating process.
As performance requirements for automotive materials, in addition to material performance, there are surface treatment performance (degreasing, chemical conversion, yarn rust resistance, coating film adhesion, adhesion).
As a chemical conversion treatment improvement, for example, as disclosed in Japanese Patent Application Laid-Open No. 2001-348670, a method of generating a 0.1 to 1.5 g / m 2 zincate film on an aluminum surface has been proposed.
Japanese Patent Application Laid-Open No. 2000-239778 discloses a method for suppressing a hydroxyl group so that a spectral peak height of 3500 cm −1 in an FT-IR analysis using an aluminum oxide film of 100 angstroms or less is parallel polarization, is 0.007 or less. Proposed. Further, Japanese Patent Application Laid-Open No. 2003-013253 proposes an aluminum structural material characterized in that it is an aluminum hydroxide film having a thickness of 1500 to 10000 angstroms and a water contact angle ≦ 20 °.
Furthermore, in order to improve the degreasing property, Japanese Patent Publication No. 7-116629 discloses that an oxide film rich in MgO is chemically dissolved, the oxide film thickness is 45 angstroms or less, and the Mg / Al ratio of the surface layer is 0.5 or less. A method to make it is proposed.
However, since any of these methods has focused attention on oxides or hydroxides, problems that cause poor adhesion or poor wetting after degreasing have not been sufficiently solved.
アルミニウム合金材の表面に生成した酸化皮膜は製造後の保管経時により変質し、自動車ボディシートに組み立てる際にアルミニウム合金板同士あるいはアルミニウム合金板と鋼板との接着性を低下させるという問題があった。
また、アルミニウム合金材の成形、それを組み立てた後にアルカリ脱脂した時、水濡れ性を低下させて、その結果、化成斑を発生させるといった問題も有る。
本発明は、この脱脂した後の水濡れ性を向上させるとともに接着性も良好な自動車ボディシート用のアルミニウム合金板を提供することを目的とする。
また、脱脂後の水濡れ性と接着性に優れたアルミニウム合金板材を製造する方法として低コストで環境への負荷の少ない方法を提供することを目的とする。
The oxide film formed on the surface of the aluminum alloy material has changed in quality after storage after production, and there has been a problem that the adhesiveness between the aluminum alloy plates or between the aluminum alloy plate and the steel plate is lowered when assembling into an automobile body sheet.
In addition, when the aluminum alloy material is molded and alkali degreased after it is assembled, there is a problem that water wettability is lowered, and as a result, chemical spots are generated.
An object of the present invention is to provide an aluminum alloy sheet for an automobile body sheet that improves the water wettability after degreasing and also has good adhesion.
Another object of the present invention is to provide a low-cost and environmentally friendly method as a method for producing an aluminum alloy sheet having excellent water wettability and adhesion after degreasing.
前期目的を解決する為、本発明者は表面処理性能の接着性及び脱脂後水濡れ性を低下させる要因の究明と対応策について研究した。
その結果、通常製造されるＡｌ合金板の軟質化及び溶体化処理工程で生成された表面皮膜のＭｇ量とＯＨ量が接着性及び脱脂後水濡れ性に影響することが判明し、表面ＭｇとＯＨ量は｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５の関係にあり、表面皮膜量を２５０ｍｇ／ｍ２以下となるように表面状態を調整することが重要であることをつきとめ、本発明にいたった。
In order to solve the purpose of the previous term, the present inventor studied the investigation and countermeasures of the factors that reduce the adhesion of the surface treatment performance and the wettability after degreasing.
As a result, it was found that the amount of Mg and OH of the surface film produced in the softening and solution treatment process of the Al alloy plate that is normally produced affects the wettability after adhesion and degreasing, and the surface Mg and The amount of OH is {(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5, and it is important to adjust the surface condition so that the surface coating amount is 250 mg / m 2 or less. As a result, the present invention was reached.
すなわち本発明は、Ａｌ−Ｍｇ系及びＡｌ−Ｍｇ−Ｓｉ系アルミニウム合金材表面が、ＧＤＳにより深さ方向のＭｇ発光強度を測定したときの最大発光強度と、ＦＴ−ＩＲで平板の偏光反射法にて測定したときのＯＨ伸縮振動によるＯＨ吸収率が、｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５の関係にあり、且つＭｇ最大発光強度＞０、ＯＨ吸収率＞０の領域に入ることを特徴とする脱脂後水濡れ性及び接着性に優れた自動車ボディーシート用アルミニウム材である。
また、リン酸クロム酸混合液に浸漬した時の重量減少から求められる酸化皮膜、オキシ水酸化皮膜、水酸化皮膜もしくは水和化皮膜の総量が２５０ｍｇ／ｍ２以下であることを特徴とする請求項１に記載の脱脂後水濡れ性及び接着性に優れた自動車ボディーシート用アルミニウム材である。
さらに、Ａｌ−Ｍｇ系及びＡｌ−Ｍｇ−Ｓｉ系アルミニウム合金材を最終焼鈍した後、速やかに温度≧４０℃、電気伝導度≦２００ｍｓ／ｍ、４≦ｐＨ≦９の水と２〜３０ｓｅｃ間接触させた後、乾燥し、室内温度≦４０℃、相対湿度≦７０％の雰囲気で保管して１４日以内に防錆油を０．２〜２ｇ／ｍ２塗油することにより、アルミニウム合金材表面の、ＧＤＳにより深さ方向のＭｇ発光強度を測定したときの最大発光強度と、ＦＴ−ＩＲで平板の偏光反射法にて測定したときのＯＨ伸縮振動によるＯＨ吸収率が、｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５の関係にあり、且つＭｇ最大発光強度＞０、ＯＨ吸収率＞０の領域に入ることを特徴とする、脱脂後水濡れ性及び接着性に優れた自動車ボディーシート用アルミニウム材の製造方法である。
That is, according to the present invention, the Al—Mg-based and Al—Mg—Si-based aluminum alloy material surfaces have the maximum emission intensity when the Mg emission intensity in the depth direction is measured by GDS, and the polarization reflection method of the flat plate by FT-IR. OH absorption rate due to OH stretching vibration when measured by the following relationship: {(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5, and Mg maximum emission intensity> 0, OH It is an aluminum material for automobile body sheets excellent in water wettability and adhesiveness after degreasing, characterized by being in the region of absorption rate> 0.
The total amount of the oxide film, oxyhydroxide film, hydroxide film or hydrated film obtained from the weight reduction when immersed in the chromic acid phosphate mixture is 250 mg / m 2 or less. Item 2. The aluminum material for automobile body sheets according to Item 1, having excellent water wettability and adhesion after degreasing.
Further, after the final annealing of the Al—Mg and Al—Mg—Si aluminum alloy materials, immediately contact with water of temperature ≧ 40 ° C., electrical conductivity ≦ 200 ms / m, 4 ≦ pH ≦ 9 for 2 to 30 seconds. Then, it is dried and stored in an atmosphere of room temperature ≦ 40 ° C. and relative humidity ≦ 70%, and the surface of the aluminum alloy material is applied by applying 0.2 to 2 g / m 2 of rust preventive oil within 14 days. The maximum luminescence intensity when measuring the Mg luminescence intensity in the depth direction by GDS and the OH absorption rate due to OH stretching vibration when measured by the FT-IR flat plate reflection method is {(Mg maximal luminescence). Intensity) + 0.438 × (OH absorption rate)} ≦ 3.5, and is in the range of Mg maximum emission intensity> 0, OH absorption rate> 0, Aluminum for car body sheets with excellent adhesion It is a manufacturing method of chloride material.
本発明によればＡｌ表面に濃化したＭｇ量とＯＨ吸収率との関係を特定の関係とすることで接着性と脱脂後水濡れ性に優れた自動車用ボディーシート材を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the body sheet material for motor vehicles excellent in adhesiveness and water wettability after degreasing | defatting can be provided by making the relationship between Mg amount concentrated on the Al surface and OH absorption rate into a specific relationship.
通常自動車用Ａｌ合金板の製造は、Ａｌ合金鋳塊を均質化処理、熱間圧延、冷間圧延して材料性能を満足する為に最終工程で軟質化処理及び溶体化処理の熱処理を施され、その後切断、塗油の工程で製造される。
すなわち、 自動車用Ａｌ材は通常製造工程の最終に高温での軟質化及び溶体化処理が行われるが、一般的にＭｇ含有Ａｌ合金を大気中で熱処理すると、合金中のＭｇが表面に拡散して、酸素と結合して最表面層にリッチなＭｇＯが形成される。したがって、Ａｌ合金表面はＭｇＯとＡｌ２Ｏ３の混在する酸化皮膜が形成される。
この酸化皮膜による表面特性の劣化は、背景技術で説明したように従来でも着目されていたが、従来は漠然と酸化物または水酸化物に着目したため、表面皮膜を除去する方法が一般的に行われており、それでは十分な脱脂後水濡れ性が得られていなかった。
本発明者らは、表面皮膜中に製造工程の最終に高温での軟質化及び溶体化処理を施した際に、Ｍｇが表面に濃化し、酸素と結合してＭｇＯとなり、それが室温に冷却され、製造後の保管経時により大気中の水分を吸収して、水和物ＭｇＯ・（Ｈ２Ｏ）ｎならびに水酸化物Ｍｇ（ＯＨ）２となり、これが接着性を阻害し、また成形・組み立てした後のアルカリ脱脂で防錆油が除去されず、その後の水洗で水濡れ不良となり、その結果、表面調整の化成皮膜生成の核生成となるＴｉコロイドが付着せず化成斑を起こし塗装表面異常を引き起こすことを見出した。
従って、Ｍｇの水和酸化物ならびに水酸化物量を規定することにより、接着性ならびに脱脂後水濡れ性を良好にすることができる。
しかしながら、アルミニウム合金表面にはアルミニウムの水和酸化物、水酸化物も存在し、このためＭｇＯ・（Ｈ２Ｏ）ｎならびにＭｇ（ＯＨ）２を個別に測定することは困難である。そのため、本発明ではＭｇ量をＭｇ最大発光強度で、（ＯＨ）量をＯＨ吸収率で規定することとした。
すなわち、ＭｇＯ・（Ｈ２Ｏ）ｎならびに水酸化物Ｍｇ（ＯＨ）２が多い場合、表面のＭｇ最大発光強度が大きく、またＯＨ吸収率も大きな値となることから、具体的には表面ＭｇとＯＨ量は、｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５の関係になるように表面状態を調整することで接着性と脱脂後水濡れ性の両性能を満足させる良い表面が得られる。
｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝の値が３．５を超える場合は表面に濃化したＭｇは、ＭｇＯ・（Ｈ２Ｏ）ｎならびに水酸化物Ｍｇ（ＯＨ）２の形態となっており、これらが接着性ならびに脱脂後水濡れ性を低下させる。
しかし、Ｍｇ最大発光強度が大きくても、ＯＨ吸収率が小さく上式の範囲内ならば、表面のＭｇはＭｇＯの状態であり、この場合は直接接着力の低下を招かない。
一方、ＯＨ吸収率が大きくても、Ｍｇ最大発光強度が小さく、上式の範囲内ならば、表面は主にアルミニウムの水和酸化物、水酸化物に覆われ、Ｍｇの水和酸化物、水酸化物量は少ないことを意味し、この場合も脱脂後水濡れ性ならびに接着性には悪影響は与えないので、問題無い。
またＭｇ最大発光強度＞０とするのは、素材そのものに含まれるＭｇが板表面に存在し、測定されるためである。
さらに、ＯＨ吸収率＞０とするのは、アルカリ脱脂及び湯洗処理により表面にＯＨ基が生成して測定されるためである。
In general, Al alloy sheets for automobiles are manufactured by homogenizing, hot rolling, and cold rolling Al alloy ingots, and heat treatment of softening and solution treatment is performed in the final process to satisfy material performance. Then, it is manufactured in the process of cutting and oiling.
In other words, automotive Al materials are usually softened and solution treated at high temperatures at the end of the manufacturing process. Generally, when an Mg-containing Al alloy is heat-treated in the atmosphere, Mg in the alloy diffuses to the surface. Thus, rich MgO is formed in the outermost surface layer by combining with oxygen. Therefore, an oxide film in which MgO and Al 2 O 3 are mixed is formed on the Al alloy surface.
As described in the background art, the deterioration of the surface characteristics due to the oxide film has been paid attention to in the past, but conventionally, the method of removing the surface film is generally performed because it has been vaguely focused on oxides or hydroxides. As a result, sufficient wettability after degreasing was not obtained.
When the present inventors performed softening and solution treatment at a high temperature at the end of the manufacturing process in the surface coating, Mg concentrates on the surface and combines with oxygen to become MgO, which cools to room temperature. After the production, the moisture in the atmosphere is absorbed with the passage of time, and it becomes hydrate MgO. (H 2 O) n and hydroxide Mg (OH) 2 , which inhibits adhesion and is also molded and assembled. Rust preventive oil is not removed by alkaline degreasing, and subsequent water washing results in poor water wetting. As a result, Ti colloid that nucleates the formation of the surface-adjusted chemical film does not adhere to the surface and causes abnormal formation of the coating surface. Found to cause.
Therefore, by specifying the amount of hydrated oxide and hydroxide of Mg, the adhesion and water wettability after degreasing can be improved.
However, aluminum hydrated oxides and hydroxides also exist on the surface of the aluminum alloy, and therefore it is difficult to individually measure MgO. (H 2 O) n and Mg (OH) 2 . Therefore, in the present invention, the Mg amount is defined by the Mg maximum emission intensity, and the (OH) amount is defined by the OH absorption rate.
That is, when there are a large amount of MgO. (H 2 O) n and hydroxide Mg (OH) 2 , the surface maximum Mg emission intensity is large and the OH absorption rate is also large. And OH amount: {(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5 by adjusting the surface condition so that both wettability and wettability after degreasing A good surface that satisfies the above can be obtained.
When the value of {(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} exceeds 3.5, Mg concentrated on the surface is MgO. (H 2 O) n and hydroxide Mg (OH ) It becomes the form of 2 , and these reduce adhesiveness and water wettability after degreasing.
However, even if the maximum Mg emission intensity is large, if the OH absorption rate is small and within the range of the above formula, the Mg on the surface is in the state of MgO, and in this case, the adhesive strength is not directly reduced.
On the other hand, even if the OH absorption rate is large, if the Mg maximum emission intensity is small and within the range of the above formula, the surface is mainly covered with aluminum hydrated oxide, hydroxide, Mg hydrated oxide, This means that the amount of hydroxide is small. In this case as well, there is no problem because the wettability and adhesion after degreasing are not adversely affected.
The reason why Mg maximum emission intensity> 0 is that Mg contained in the material itself exists on the plate surface and is measured.
Furthermore, the reason why the OH absorption rate is greater than 0 is that OH groups are generated on the surface and measured by alkali degreasing and hot water washing treatment.
次に酸化皮膜等の総量規制について説明する。
Ｍｇの水和酸化物及び水酸化物以外に存在するＡｌ酸化物及びＡｌ水酸化物は、ある程度以下の量であれば脱脂後水濡れ及び接着性の低下を招かないものの、あまり厚いとＡｌ酸化物及びＡｌ水酸化物の熱膨張率はアルミ材より小さいため、接着剤の焼付け、冷却時に発生する熱膨張、熱収縮のよる残留応力が大きく破壊されやすくなり、接着力の低下を招く。また、脱脂後の水濡れ性は良好となるが成形後のアルカリ脱脂で水和酸化物が除去されず、その後の化成皮膜が生成しないため、塗膜密着不良を招くため好ましくない。
従ってリン酸クロム酸混合液に浸漬した時の重量減少から求められる酸化皮膜、オキシ水酸化皮膜、水酸化皮膜もしくは水和化皮膜の総量が２５０ｍｇ／ｍ２以下であることとした。
Next, the total amount regulation of oxide films and the like will be described.
Al oxides and Al hydroxides present in addition to Mg hydrated oxides and hydroxides will not cause water wetting after degreasing and decrease in adhesion if the amount is below a certain level. Since the thermal expansion coefficient of the product and the Al hydroxide is smaller than that of the aluminum material, the residual stress due to the thermal expansion and thermal shrinkage generated during the baking and cooling of the adhesive is easily broken and the adhesive strength is reduced. In addition, the water wettability after degreasing is good, but the hydrated oxide is not removed by alkali degreasing after molding, and a subsequent chemical conversion film is not formed.
Therefore, the total amount of the oxide film, oxyhydroxide film, hydroxide film or hydrated film determined from the weight reduction when immersed in the phosphoric acid chromic acid mixed solution is 250 mg / m 2 or less.
次に製造方法について説明する。
上記の式の範囲に調整する方法としては、Ｍｇの表面層への析出を最初から抑制する、または表面Ｍｇを取り除く、及び表面皮膜の水和化（水酸基化）を防止するなどが考えられる。
Ｍｇの表面層への析出は合金中のＭｇ含有量が多いほど、熱処理温度が高いほど激しいことから、焼鈍温度を下げる（具体的には５１０℃以下）、または処理時間を短くすることが有効である。また熱延後の冷間圧延の圧下率を大きくすることでＭｇの拡散を抑制できる。しかしながら、材料性能を維持するために圧下率や熱処理温度を下げる等の手段は取り難い場合もある。
表面皮膜の除去方法としては、通常はアルカリ及び酸処理が施されるが、設備が大掛かりとなりコストアップの要因となる。又作業の安全及び、リンス不足等によりアルカリおよび酸成分がアルミ表面に残留すると腐食発生等の原因となり好ましくない。
そこで本発明者は、コストアップとならず、接着性及び脱脂後水濡れ性を低下させない手段を見出すべき検討を行った結果、４０℃以上、電気伝導度≦２００ｍｓ／ｍ、４≦ｐＨ≦９の水に浸漬またはスプレーで２〜３０ｓｅｃ間接触させて洗浄することにより、上式を満たすように表面皮膜のＭｇ量、（ＯＨ）量を低減させることができることを見出した。
洗浄に使用する水温が４０℃未満では十分に表面皮膜のＭｇ量、（ＯＨ）量を低減させることができない。また、電気伝導度は水の純度の指標だが、水の純度は表面Ｍｇ除去性に直接は影響しないが、不純物量が多いと表面に残存するＣｌ、Ｃａ等が腐食発生の起点となるため、電気伝導度≦２００ｍｓ／ｍとする。
またｐＨを、４≦ｐＨ≦９の範囲とするのは、この範囲を超えたもの゛ては、アルミニウム板表面に酸またはアルカリ成分が残存して、これが耐食性を劣化させる等の表面性能を低下されるためである。
水と接触させる方法としては、通常の洗浄方法である浸漬またはスプレーで行う。接触時間は２ｓｅｃ未満では表面皮膜のＭｇ量、（ＯＨ）量を十分に除去できず、一方３０ｓｅｃを超えてもそれ以上の効果は得られないので２〜３０ｓｅｃとする。
この様に表面を調整しても、表面層にＭｇが存在するため、処理後保管されて長時間経時すると、雰囲気の温度、湿度の変化により表面皮膜が変質して、表面にＭｇの水和化・水酸化が進行して、接着性及び脱脂後水濡れ性を低下させる。このため室内温度４０℃以下、相対湿度７０％以下の雰囲気で保管することとし、さらに洗浄による表面調整後１４日以内に防錆油を塗油して表面を保護する必要がある。
保管温度が４０℃超、あるいは相対湿度７０％超では表面の水和化・水酸化が急速に進行してしまい、接着性及び脱脂後水濡れ性が劣化してしまう。従って保管は室内温度４０℃以下、相対湿度７０％以下の雰囲気で行うこととする。
また、この条件で保管したとしても、上記の洗浄後１４日を越えると同様に水和化・水酸化が進行してしまっており、塗油の効果がない。従って１４日以内に防錆油を塗油することとする。なお、塗油量は０．２ｇ／ｍ２未満では効果がなく、上限は性能に影響しないが、塗油量が多いとコストアップとなることから０．２〜２ｇ／ｍ2とする。１４日以内であれば本発明の効果が得られるが、好ましくは表面調整後、ただちに塗油することが望ましい。
Next, a manufacturing method will be described.
As a method of adjusting to the range of the above formula, it is conceivable to suppress precipitation of Mg on the surface layer from the beginning, remove the surface Mg, and prevent hydration (hydroxylation) of the surface film.
Precipitation of Mg on the surface layer increases as the Mg content in the alloy increases and the heat treatment temperature increases, so it is effective to lower the annealing temperature (specifically, 510 ° C. or less) or shorten the treatment time. It is. Moreover, Mg diffusion can be suppressed by increasing the rolling reduction of cold rolling after hot rolling. However, it may be difficult to take measures such as lowering the rolling reduction or heat treatment temperature in order to maintain the material performance.
As a method for removing the surface film, alkali and acid treatments are usually performed, but the equipment is large and increases costs. Further, if alkali and acid components remain on the aluminum surface due to safety of work and lack of rinsing, it is not preferable because it causes corrosion.
Therefore, the present inventor conducted an investigation to find a means that does not increase the cost and does not lower the adhesiveness and the water wettability after degreasing. It was found that the amount of Mg and (OH) in the surface film can be reduced so as to satisfy the above formula by immersing in water or spraying for 2 to 30 seconds by washing.
If the water temperature used for cleaning is less than 40 ° C., the amount of Mg and (OH) in the surface film cannot be reduced sufficiently. In addition, the electrical conductivity is an indicator of the purity of water, but the purity of water does not directly affect the surface Mg removal, but if the amount of impurities is large, Cl, Ca, etc. remaining on the surface is the starting point of corrosion occurrence. Electrical conductivity ≦ 200 ms / m.
In addition, if the pH is in the range of 4 ≦ pH ≦ 9, if it exceeds this range, acid or alkali components remain on the aluminum plate surface, which deteriorates surface performance such as deterioration of corrosion resistance. It is to be done.
As a method of contacting with water, it is performed by dipping or spraying, which is a normal cleaning method. If the contact time is less than 2 seconds, the amount of Mg and (OH) in the surface film cannot be sufficiently removed, and if the contact time exceeds 30 seconds, no further effect can be obtained.
Even if the surface is adjusted in this way, since Mg exists in the surface layer, when it is stored after treatment and after a long time, the surface film changes due to changes in the temperature and humidity of the atmosphere, and the surface hydrates Mg. Progression of water and hydroxylation reduces the wettability after adhesion and degreasing. For this reason, it is necessary to store in an atmosphere having an indoor temperature of 40 ° C. or less and a relative humidity of 70% or less, and to protect the surface by applying rust preventive oil within 14 days after the surface adjustment by washing.
If the storage temperature exceeds 40 ° C. or the relative humidity exceeds 70%, surface hydration and hydroxylation proceed rapidly, and the adhesiveness and water wettability after degreasing deteriorate. Therefore, storage is performed in an atmosphere having a room temperature of 40 ° C. or less and a relative humidity of 70% or less.
Even if stored under these conditions, hydration / hydroxylation proceeds in the same manner after 14 days from the above washing, and there is no oil coating effect. Therefore, rust preventive oil should be applied within 14 days. Incidentally, the coating amount of oil has no effect is less than 0.2 g / m 2, the upper limit does not affect the performance, and 0.2 to 2 g / m 2 since it increases the cost and the coating amount of oil is large. The effect of the present invention can be obtained within 14 days, but it is desirable to apply oil immediately after the surface adjustment.
自動車用ボディーシートに使用されている、５１８２合金（Ｍｇ４．５質量％含有）及び６０２２（Ｍｇ０．６質量％含有）からなる最終熱処理板を４０℃温水（ｐＨ＝７．３、電導度５０ｍｓ／ｍ）、スプレー圧１．５ｋｇ／ｃｍ2で６ｓｅｃ洗浄して表面Ｍｇ量を調整後、恒温恒湿槽（４０℃ＲＨ４０〜８０％×１〜１４日）に曝露させ、表面酸化皮膜中のＯＨ量を変化させた供試材を作製した。
その後、自動車のヘミング用構造接着剤（サンスター技研製）を用いて、接着剤厚さ０．１５ｍｍで接着した後１７５℃×２０ｍｉｎ保持の焼付けを施し、剪断引張り試験での剪断強度、凝集破壊率で評価した。
接着性評価
８０％≦凝集破壊率..................◎ ⇒合格
７０％≦凝集破壊率＜８０％......○ ⇒合格
凝集破壊率＜７０％..................× ⇒不合格
また、脱脂後水濡れ性の評価試験としては、Ａｌ板表面に市販の防錆潤滑油を浸漬塗油して１〜１５日室内に放置後、市販のアルカリ脱脂剤（日本パーカライジング製）の劣化液（ＣＯ２ガスにてｐＨ＝１１調整、防錆油３０００ｐｐｍ添加）にて４０℃×２ｍｉｎ浸漬後水道水で３０ｓｅｃ水洗した後、垂直に３０ｓｅｃ保持した時の水濡れ面積を目視で評価した。
脱脂後水濡れ性評価
８０％＜水濡れ面積............◎ ⇒合格
６０≦水濡れ面積≦８０％...○ ⇒合格
水濡れ面積＜６０％............× ⇒不合格
なお、表面のＯＨ量測定はＦＴ-ＩＲ（パーキキンエルマ社製）の偏光反射法での３５００ｃｍ−１のＯＨ吸収率を求めた。
また、表面Ｍｇ量はＧＤＯＥＳ(グロー放電発光分光分析：堀場製作所製ＪＹ５０００ＲＦ)で圧力７７５Ｐａ、出力４０ＷでのＭｇ感度＝９００Ｖで測定し、Ｍｇの最大ピーク高さを求めた。
A final heat-treated plate made of 5182 alloy (contains 4.5% by mass of Mg) and 6022 (contains 0.6% by mass of Mg) used for automobile body sheets is heated at 40 ° C. (pH = 7.3, conductivity 50 ms / m) After cleaning for 6 sec at a spray pressure of 1.5 kg / cm 2 to adjust the amount of surface Mg, it was exposed to a constant temperature and humidity chamber (40 ° C. RH 40-80% × 1 to 14 days), and OH in the surface oxide film Specimens with varying amounts were prepared.
Then, using a structural adhesive for automotive hemming (manufactured by Sunstar Giken), after bonding at an adhesive thickness of 0.15 mm, baking was performed at 175 ° C. for 20 minutes, and shear strength and cohesive failure in a shear tensile test were performed. The rate was evaluated.
Adhesiveness evaluation 80% ≤ cohesive failure rate ... ◎ ⇒ pass 70% ≤ cohesive failure rate <80% ... ○ ⇒ pass
Cohesive failure rate <70% .................. ⇒ Fail
In addition, as an evaluation test of water wettability after degreasing, a commercially available alkaline degreasing agent (manufactured by Nihon Parkerizing Co., Ltd.) is deteriorated after immersing and applying a commercially available rust-preventive lubricating oil to the surface of the Al plate and leaving it in the room for 1 to 15 days. After being immersed in a liquid (pH 2 adjustment with CO 2 gas, addition of 3000 ppm of rust preventive oil) at 40 ° C. for 2 min, washed with tap water for 30 sec, the water wetted area when vertically held for 30 sec was visually evaluated.
Evaluation of water wettability after degreasing 80% <Water wetted area ............ ◎ ⇒Pass 60 ≦ Wet wet area ≦ 80% ... ○ ⇒Pass water wetted area <60% ... ...... x ⇒ rejected The surface OH amount was measured by measuring the OH absorption rate of 3500 cm −1 in the polarization reflection method of FT-IR (manufactured by Perkikin Elma).
Further, the surface Mg amount was measured by GDOES (Glow Discharge Emission Spectroscopy: JY5000RF manufactured by HORIBA, Ltd.) at a pressure of 775 Pa and an output of 40 W with Mg sensitivity = 900 V, and the maximum peak height of Mg was obtained.
本発明の１〜５と比較例の１１はＡｌ−Ｍｇ系、６〜１０と比較例１２はＡｌ−Ｍｇ−Ｓｉ系のＯＨ量を変化させた時の接着性、脱脂後水濡れ性を示す。
Ｎｏ.１〜１０の本発明例は｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５の範囲を満たしており、接着性、脱脂後水濡れ性ともに良好な結果である。
これに対して比較例のＡｌ−Ｍｇ、Ａｌ−Ｍｇ−Ｓｉ系合金はＯＨ量が増加して、式の範囲から逸脱するにつれて、接着性能と脱脂後水濡れ性は低下している。
1 to 5 of the present invention and 11 of the comparative example are Al-Mg-based, and 6 to 10 and Comparative Example 12 are the adhesiveness when changing the OH amount of the Al-Mg-Si-based, and water wettability after degreasing. .
The present invention examples No. 1 to 10 satisfy the range of {(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5, and have good results in both adhesiveness and water wettability after degreasing. It is.
On the other hand, the Al—Mg and Al—Mg—Si based alloys of the comparative examples increase in the amount of OH and deviate from the range of the formula, and the adhesion performance and the water wettability after degreasing decrease.
５１８２合金（Ｍｇ４．５質量％含有）及び６０２２（Ｍｇ０．６質量％含有）からなる最終熱処理板を用いて湯洗処理条件(電導度、温度)を変えて、スプレー圧１．５Ｋｇ／ｃｍ２で供試材を作製し、実施例１の接着性、脱脂後水濡れ性試験により評価した。
湯洗水の電導度は純水に工業用水を添加し調整、ｐH調整の酸性側は希硫酸、アルカリ側は炭酸ナトリウムを添加し調整した。
表面皮膜量は脱皮膜前後の重量差より求めた。脱皮膜液は２０ｇ／ＬＣｒＯ３と５０ｇ／Ｌ燐酸を純水に溶解し８０℃で５ｍｉｎ浸漬後、水洗乾燥した。
The final heat treatment plate made of 5182 alloy (contains 4.5% by weight Mg) and 6022 (contains 0.6% by weight Mg) is used to change the hot water treatment conditions (conductivity, temperature) and spray pressure 1.5 kg / cm 2. Sample materials were prepared and evaluated by the wettability test of Example 1 after adhesion and degreasing.
The electric conductivity of hot water was adjusted by adding industrial water to pure water, and the pH was adjusted by adding dilute sulfuric acid on the acidic side and sodium carbonate on the alkaline side.
The surface coating amount was determined from the weight difference before and after film removal. The film removal solution was prepared by dissolving 20 g / LCrO 3 and 50 g / L phosphoric acid in pure water, immersing them at 80 ° C. for 5 minutes, washing and drying.
本発明１〜９は湯洗水の電導度、ｐＨ、表面皮膜量、Ｍｇ＋０．４３８×ＯＨ≦３．５を満たしていると接着性、水濡れ性とも良好である。
比較例１０、１１は製造ままの状態であるが比較例１０は接着性、脱脂後水濡れ性とも不良、比較例１１はＯＨ量が少ないため、接着性は良好であるが、脱脂後水濡れ性が劣る。
比較例１２は湯洗時間が短く接着性、脱脂後水濡れ性とも不良、比較例１３は湯洗時間が長すぎてベーマイト皮膜を生成し脱脂後水濡れ性は良好であるが、接着性が劣る。
比較例１４、１５は湯洗ｐＨが高い（アルカリ性）ため表面層のＭｇ成分を除去できないため接着性、脱脂後水濡れ性が不良となる。
In the present inventions 1 to 9, when the electric conductivity, pH, surface coating amount, and Mg + 0.438 × OH ≦ 3.5 are satisfied, both the adhesiveness and water wettability are good.
Comparative Examples 10 and 11 are as manufactured, but Comparative Example 10 is poor in adhesion and water wettability after degreasing, and Comparative Example 11 has low OH content, so that the adhesiveness is good, but the water wettability after degreasing. Inferior.
Comparative Example 12 has a short hot water washing time and poor adhesion and water wettability after degreasing. Comparative Example 13 has a long hot water washing time to form a boehmite film and has good water wettability after degreasing. Inferior.
In Comparative Examples 14 and 15, since the hot water pH is high (alkaline), the Mg component of the surface layer cannot be removed, so that the adhesiveness and water wettability after degreasing are poor.
５１８２合金（Ｍｇ４．５質量％含有）及び６０２２（Ｍｇ０．６質量％含有）からなる最終熱処理板を６０℃（ｐＨ＝６．１、電導度＝２０ｍｓ／ｍ）で６ｓｅｃの湯洗処理して表面Ｍｇ量を調整した材料に防錆油の塗油無と塗油量を変え、恒温恒湿槽の温度と湿度を変えた雰囲気に１４日暴露した後に脱脂後水濡れ性を評価した。 A final heat-treated plate made of 5182 alloy (containing 4.5% by weight of Mg) and 6022 (containing 0.6% by weight of Mg) is subjected to a hot water washing treatment at 60 ° C. (pH = 6.1, conductivity = 20 ms / m) for 6 seconds. The material with the surface Mg amount adjusted was changed in the amount of rust-preventive oil and the amount of oil applied, and after exposure for 14 days to an atmosphere in which the temperature and humidity of the constant temperature and humidity chamber were changed, the wettability after degreasing was evaluated.
実施例１〜３は５１８２合金、実施例７、8は６０２２材の無塗油での温度湿度雰囲気での保管条件の発明例、実施例１２，１３は５１８２合金の無塗油保管条件での比較例、実施例１５，１６は６０２２合金の無塗油保管条件の比較例を示す。実施例４〜６は５１８２合金、実施例１０，１１は６０２２合金の塗油量保管条件での発明例、実施例１４は５１８２合金、実施例１７は６０２２合金の塗油量保管での比較例を示す。
防錆潤滑油の塗油なし保管では温度が高いほど、低い湿度で出し後の水濡れ性低下する。４０℃ＲＨ７０％雰囲気で１４日が性能維持限界である。湿度７０％以上で保管すると脱脂後水濡れ性能を維持できない。
防錆潤滑油を塗油後に高湿度環境で保管すると塗油量が０．２ｇ／ｍ２以上であると、表面変質が起きないため脱脂後水濡れ性は維持される。塗油量が２ｇ／ｍ２以下であると高湿度環境下では表面変質のため脱脂後の水濡れ性が低下する。
Examples 1 to 3 are 5182 alloy, Examples 7 and 8 are invention examples of storage conditions in a temperature and humidity atmosphere with 6022 non-oiled oil, and Examples 12 and 13 are 5182 alloy under oil-free storage conditions. Comparative examples, Examples 15 and 16 show comparative examples of the 6022 alloy oil-free storage conditions. Examples 4 to 6 are 5182 alloy, Examples 10 and 11 are invention examples of oil storage amount storage conditions of 6022 alloy, Example 14 is 5182 alloy, Example 17 is a comparative example of oil storage amount storage of 6022 alloy Indicates.
In storage without rust-preventive lubricant, the higher the temperature, the lower the wettability after taking out at lower humidity. The performance maintenance limit is 14 days in an atmosphere of 40 ° C. and RH 70%. If it is stored at a humidity of 70% or more, the water-wetting performance cannot be maintained after degreasing.
If the rust preventive lubricating oil is stored in a high humidity environment after coating, if the amount of coating is 0.2 g / m 2 or more, surface alteration does not occur and water wettability after degreasing is maintained. When the oil coating amount is 2 g / m 2 or less, the wettability after degreasing decreases due to surface alteration in a high humidity environment.
Claims (3)
｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５
の関係にあり、且つ
Ｍｇ最大発光強度＞０
ＯＨ吸収率＞０
の領域に入ることを特徴とする脱脂後水濡れ性及び接着性に優れた自動車ボディーシート用アルミニウム材。 When the surface of Al-Mg and Al-Mg-Si-based aluminum alloy materials is measured by GDS and the maximum emission intensity when measuring the Mg emission intensity in the depth direction, and by FT-IR with a flat plate polarization reflection method OH absorption rate due to OH stretching vibration of
{(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5
And the maximum emission intensity of Mg> 0
OH absorption rate> 0
An aluminum material for automobile body sheets excellent in water wettability and adhesion after degreasing, characterized in that it falls within the range of
｛（Ｍｇ最大発光強度）＋０．４３８×（ＯＨ吸収率）｝≦３．５
の関係にあり、且つ
Ｍｇ最大発光強度＞０
ＯＨ吸収率＞０
の領域に入ることを特徴とする、脱脂後水濡れ性及び接着性に優れた自動車ボディーシート用アルミニウム材の製造方法。 After the final annealing of the Al—Mg-based and Al—Mg—Si-based aluminum alloy materials, they were immediately brought into contact with water of temperature ≧ 40 ° C., electrical conductivity ≦ 200 ms / m, 4 ≦ pH ≦ 9 for 2 to 30 seconds. After drying, storing in an atmosphere of room temperature ≦ 40 ° C. and relative humidity ≦ 70%, and applying 0.2 to 2 g / m 2 of rust preventive oil within 14 days, the surface of the aluminum alloy material The maximum emission intensity when measuring the Mg emission intensity in the depth direction by GDS, and the OH absorption rate due to the OH stretching vibration when measured by FT-IR using a flat plate polarization reflection method,
{(Mg maximum emission intensity) + 0.438 × (OH absorption rate)} ≦ 3.5
And the maximum emission intensity of Mg> 0
OH absorption rate> 0
A method for producing an aluminum material for an automobile body sheet, which is excellent in water wettability and adhesion after degreasing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005013548A JP2006200007A (en) | 2005-01-21 | 2005-01-21 | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005013548A JP2006200007A (en) | 2005-01-21 | 2005-01-21 | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006200007A true JP2006200007A (en) | 2006-08-03 |
Family
ID=36958265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005013548A Pending JP2006200007A (en) | 2005-01-21 | 2005-01-21 | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006200007A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101016915B1 (en) | 2007-11-28 | 2011-02-22 | 가부시키가이샤 고베 세이코쇼 | Aluminium alloy material with excellent surface stability and production method thereof |
| CN102312233A (en) * | 2010-06-29 | 2012-01-11 | 株式会社神户制钢所 | Surface treated aluminium alloy plate and method of manufacture thereof |
| JP2014198911A (en) * | 2010-10-18 | 2014-10-23 | 株式会社神戸製鋼所 | Aluminum alloy sheet, joined body using the same, and automotive member |
| CN104619880A (en) * | 2012-09-20 | 2015-05-13 | 株式会社神户制钢所 | Aluminum-alloy plate, and joined body and vehicle member using same |
| JP2015206117A (en) * | 2015-05-07 | 2015-11-19 | 株式会社神戸製鋼所 | Surface-treated aluminum alloy sheet |
| KR20160111449A (en) | 2014-02-21 | 2016-09-26 | 가부시키가이샤 고베 세이코쇼 | Aluminum alloy plate, joined body, and automotive member |
| US10357944B2 (en) | 2013-05-23 | 2019-07-23 | Kobe Steel, Ltd. | Aluminum alloy sheet, bonded object, and member for motor vehicle |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01319692A (en) * | 1988-06-17 | 1989-12-25 | Kobe Steel Ltd | Production of mg-containing aluminum alloy sheet having excellent degreasing property |
| JPH02115385A (en) * | 1988-10-24 | 1990-04-27 | Kobe Steel Ltd | Oil-coated aluminum alloy sheet having excellent degreasing property |
| JPH0892773A (en) * | 1994-09-20 | 1996-04-09 | Sumitomo Light Metal Ind Ltd | Production of alloy material excellent in zinc phosphate processability and formability |
| JPH091734A (en) * | 1995-06-16 | 1997-01-07 | Sky Alum Co Ltd | Plate material such as resin-coated aluminum and manufacture thereof |
| JPH11323577A (en) * | 1998-05-11 | 1999-11-26 | Sky Alum Co Ltd | Treatment of alloy surface and alloy excellent in resistance against surface deterioration with time |
| JP2000239778A (en) * | 1999-02-25 | 2000-09-05 | Kobe Steel Ltd | Aluminum alloy material excellent in chemical convertibility |
| JP2003013253A (en) * | 2001-07-04 | 2003-01-15 | Kobe Steel Ltd | Aluminum-alloy structural material superior in adhesiveness to coating and method for evaluating adhesiveness to coating of aluminum-alloy structural material |
| JP2003119570A (en) * | 2001-10-15 | 2003-04-23 | Sky Alum Co Ltd | Pretreated aluminum material superior in coating adhesiveness and corrosion resistance |
| JP2003160879A (en) * | 2001-11-22 | 2003-06-06 | Sky Alum Co Ltd | Method for manufacturing pretreated aluminum material superior in long-term storability and scratch resistance |
| WO2004001096A2 (en) * | 2002-06-20 | 2003-12-31 | Pechiney Rhenalu | Method for surface treatment of sheets and strips of aluminium alloy |
-
2005
- 2005-01-21 JP JP2005013548A patent/JP2006200007A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01319692A (en) * | 1988-06-17 | 1989-12-25 | Kobe Steel Ltd | Production of mg-containing aluminum alloy sheet having excellent degreasing property |
| JPH07116629B2 (en) * | 1988-06-17 | 1995-12-13 | 株式会社神戸製鋼所 | Method for producing Mg-containing aluminum alloy sheet excellent in degreasing property |
| JPH02115385A (en) * | 1988-10-24 | 1990-04-27 | Kobe Steel Ltd | Oil-coated aluminum alloy sheet having excellent degreasing property |
| JP2528698B2 (en) * | 1988-10-24 | 1996-08-28 | 株式会社神戸製鋼所 | Method for producing oil-coated aluminum alloy sheet having excellent degreasing property |
| JPH0892773A (en) * | 1994-09-20 | 1996-04-09 | Sumitomo Light Metal Ind Ltd | Production of alloy material excellent in zinc phosphate processability and formability |
| JPH091734A (en) * | 1995-06-16 | 1997-01-07 | Sky Alum Co Ltd | Plate material such as resin-coated aluminum and manufacture thereof |
| JPH11323577A (en) * | 1998-05-11 | 1999-11-26 | Sky Alum Co Ltd | Treatment of alloy surface and alloy excellent in resistance against surface deterioration with time |
| JP2000239778A (en) * | 1999-02-25 | 2000-09-05 | Kobe Steel Ltd | Aluminum alloy material excellent in chemical convertibility |
| JP2003013253A (en) * | 2001-07-04 | 2003-01-15 | Kobe Steel Ltd | Aluminum-alloy structural material superior in adhesiveness to coating and method for evaluating adhesiveness to coating of aluminum-alloy structural material |
| JP2003119570A (en) * | 2001-10-15 | 2003-04-23 | Sky Alum Co Ltd | Pretreated aluminum material superior in coating adhesiveness and corrosion resistance |
| JP2003160879A (en) * | 2001-11-22 | 2003-06-06 | Sky Alum Co Ltd | Method for manufacturing pretreated aluminum material superior in long-term storability and scratch resistance |
| WO2004001096A2 (en) * | 2002-06-20 | 2003-12-31 | Pechiney Rhenalu | Method for surface treatment of sheets and strips of aluminium alloy |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101016915B1 (en) | 2007-11-28 | 2011-02-22 | 가부시키가이샤 고베 세이코쇼 | Aluminium alloy material with excellent surface stability and production method thereof |
| CN102312233A (en) * | 2010-06-29 | 2012-01-11 | 株式会社神户制钢所 | Surface treated aluminium alloy plate and method of manufacture thereof |
| JP2014198911A (en) * | 2010-10-18 | 2014-10-23 | 株式会社神戸製鋼所 | Aluminum alloy sheet, joined body using the same, and automotive member |
| CN104619880A (en) * | 2012-09-20 | 2015-05-13 | 株式会社神户制钢所 | Aluminum-alloy plate, and joined body and vehicle member using same |
| CN104619880B (en) * | 2012-09-20 | 2016-08-31 | 株式会社神户制钢所 | Aluminium alloy plate, the conjugant using it and member for automobile |
| US9669604B2 (en) | 2012-09-20 | 2017-06-06 | Kobe Steel, Ltd. | Aluminum-alloy plate and joined body as well as automobile member using the same |
| US10357944B2 (en) | 2013-05-23 | 2019-07-23 | Kobe Steel, Ltd. | Aluminum alloy sheet, bonded object, and member for motor vehicle |
| KR20160111449A (en) | 2014-02-21 | 2016-09-26 | 가부시키가이샤 고베 세이코쇼 | Aluminum alloy plate, joined body, and automotive member |
| JP2015206117A (en) * | 2015-05-07 | 2015-11-19 | 株式会社神戸製鋼所 | Surface-treated aluminum alloy sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2006200007A (en) | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property | |
| JP5968637B2 (en) | Surface-treated aluminum alloy plate and manufacturing method thereof | |
| JP5745788B2 (en) | Surface-treated aluminum alloy plate and manufacturing method thereof | |
| KR20150038677A (en) | Aluminum-alloy plate, and joined body and vehicle member using same | |
| JP4909178B2 (en) | Continuous processing method for aluminum alloy sheet | |
| WO2015125897A1 (en) | Aluminum alloy plate, joined body, and automotive member | |
| JP5745791B2 (en) | Surface-treated aluminum alloy plate | |
| JP4819520B2 (en) | Aluminum material and manufacturing method thereof | |
| JP2010222659A (en) | Aluminum alloy material and method of manufacturing the same | |
| JP3932823B2 (en) | Lubricated steel sheet with excellent chemical conversion and adhesion | |
| JP5968956B2 (en) | Aluminum alloy plate, joined body and automobile member using the same | |
| JP5969087B2 (en) | Surface-treated aluminum alloy plate | |
| KR960004783B1 (en) | Aluminium alloy sheet for automotive body and method of manufacturing the same | |
| JP2014173123A (en) | Surface-treated aluminum alloy sheet and method of manufacturing the same | |
| JP5451965B2 (en) | Surface treatment agent for aluminum alloy | |
| WO2017195811A1 (en) | Aluminum alloy material, aluminum alloy material provided with adhesive resin layer, production method for aluminum alloy material, and production method for aluminum alloy material provided with adhesive resin layer | |
| JP5192986B2 (en) | Aluminum alloy material with excellent surface stability | |
| JP2017155289A (en) | Method for manufacturing surface treated aluminum alloy plate | |
| JP2005530047A (en) | Surface treatment method for aluminum alloy plates and strips | |
| JP5661602B2 (en) | Aluminum alloy plate for automobile, joined body and automobile member using the same | |
| JP6278882B2 (en) | Surface-treated aluminum alloy plate and manufacturing method thereof | |
| JP2003013253A (en) | Aluminum-alloy structural material superior in adhesiveness to coating and method for evaluating adhesiveness to coating of aluminum-alloy structural material | |
| JP5969086B2 (en) | Surface-treated aluminum alloy plate and manufacturing method thereof | |
| JP2017203212A (en) | Aluminum alloy material, aluminum alloy material with adhesive resin layer, method for producing aluminum alloy material and method for producing aluminum alloy material with adhesive resin layer | |
| JP3214835B2 (en) | Al alloy material for transport equipment with excellent water resistance and yarn rust resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071226 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101026 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101109 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110322 |