JP2718310B2 - Laminated plating Al plate and method for producing the same - Google Patents
Laminated plating Al plate and method for producing the sameInfo
- Publication number
- JP2718310B2 JP2718310B2 JP3335229A JP33522991A JP2718310B2 JP 2718310 B2 JP2718310 B2 JP 2718310B2 JP 3335229 A JP3335229 A JP 3335229A JP 33522991 A JP33522991 A JP 33522991A JP 2718310 B2 JP2718310 B2 JP 2718310B2
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- JP
- Japan
- Prior art keywords
- zinc
- alloy
- aluminum
- plating
- plate
- 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.)
- Expired - Lifetime
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車の車体等に使用
される表面処理アルミニウム板またはその合金板 (以
下、「Al板」と総称する) に関し、特にプレス成形性、
塗装後塗膜密着性に優れ、リン酸亜鉛処理を施して使用
される用途に好適なAl板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated aluminum plate or an alloy plate thereof (hereinafter, collectively referred to as "Al plate") used for an automobile body and the like, and particularly to press formability,
The present invention relates to an Al plate which has excellent adhesion to a coating film after coating and is suitable for use after being subjected to a zinc phosphate treatment.
【０００２】[0002]
【従来の技術】近年、自動車用鋼板には寒冷地における
凍結防止剤散布による腐食対策および燃費向上のための
軽量化対策の要求がますます強くなってきており、亜
鉛、亜鉛系合金めっき等の表面処理鋼板、高張力鋼板等
の適用が進められてきている。ところでこのような鋼板
を用いた自動車の車体製造ラインにおいては、プレス加
工により所定の形状に成形し、各部品を組み立て、その
後リン酸亜鉛処理、電着塗装、スプレー塗装が施される
のが一般的である。2. Description of the Related Art In recent years, there has been an increasing demand for steel sheets for automobiles to take measures against corrosion by spraying a deicing agent in cold regions and measures to reduce the weight for improving fuel efficiency. Applications of surface-treated steel sheets, high-tensile steel sheets, and the like have been promoted. By the way, in a car body manufacturing line using such a steel sheet, it is common to form into a predetermined shape by press working, assemble each part, and then apply zinc phosphate treatment, electrodeposition coating, spray coating. It is a target.
【０００３】一方、最近では、特に車体軽量化を狙っ
て、Al板を車体に使用することが多くなっている。Al板
を自動車用に使用するといっても鋼板とAl板とを併用す
るのが通常である。この場合、新たに別の製造ラインを
新設せずに済み、また工程の連続性を保つことができる
ことから、同一ラインを用いてリン酸亜鉛処理鋼板とリ
ン酸亜鉛処理Al板とを製造することが要望される。On the other hand, recently, Al plates have been frequently used for vehicle bodies, particularly for the purpose of weight reduction of the vehicle bodies. Although an Al plate is used for an automobile, it is usual to use a steel plate and an Al plate together. In this case, it is not necessary to newly establish a separate production line, and since the continuity of the process can be maintained, the same line should be used to produce the zinc phosphate treated steel sheet and the zinc phosphate treated Al sheet. Is required.
【０００４】しかし、この場合、リン酸亜鉛処理工程に
おいて次のような問題を生じる。すなわち、Al板にリン
酸亜鉛処理を施した場合、Al板表面に良好なリン酸亜鉛
皮膜が形成されないばかりでなく、Al板表面が溶解し
て、リン酸亜鉛処理浴中にAlイオンが溶出してしまう。
その結果、リン酸亜鉛処理浴中のAlイオン濃度がわずか
数ppm になると鋼板表面にも良好なリン酸亜鉛処理皮膜
が形成されなくなる。However, in this case, the following problem occurs in the zinc phosphate treatment step. That is, when a zinc phosphate treatment is applied to an Al plate, not only is a good zinc phosphate film not formed on the surface of the Al plate, but the surface of the Al plate is dissolved, and Al ions are eluted into the zinc phosphate treatment bath. Resulting in.
As a result, when the Al ion concentration in the zinc phosphate treatment bath becomes only a few ppm, a good zinc phosphate treatment film cannot be formed on the steel sheet surface.
【０００５】このような問題を解決する方法としては、
既に特開昭61−157693号公報において、リン酸亜鉛処理
性に優れたAl板を製造する方法が提案されている。すな
わち、Al板表面に亜鉛めっき層、亜鉛系合金めっき層も
しくは鉄系合金めっき層のいずれかを１g/m2以上の付着
量で形成しておくものであり、このように亜鉛めっき層
等を形成しておくことによって、後のリン酸亜鉛処理時
にAl板からAlイオンが処理浴中へ溶出せず、そのため鋼
板とAl板を併用混在処理した場合でも良好なリン酸亜鉛
皮膜を生成することができるとされている。[0005] As a method of solving such a problem,
JP-A-61-157693 has already proposed a method for producing an Al plate having excellent zinc phosphate treatability. That is, a zinc plating layer, a zinc-based alloy plating layer, or an iron-based alloy plating layer is formed on the surface of the Al plate with an adhesion amount of 1 g / m 2 or more. By forming, Al ions do not elute from the Al plate into the treatment bath during the subsequent zinc phosphate treatment, and therefore, a good zinc phosphate film is formed even when the steel plate and the Al plate are used together. It is said that it can be.
【０００６】[0006]
【発明が解決しようとする課題】特開昭61−157693号公
報で提案の方法には、しかしながら、次のような問題が
残されている。すなわち、Al板は通常酸化皮膜で覆われ
ており、前記提案の公報中に示されているような通常の
硫酸酸性浴中で電気めっきを施しただけの場合は、極め
て密着性の劣る皮膜しか生成されない。そのためプレス
成形時に皮膜が剥離してしまい、その後のリン酸亜鉛処
理工程で上述の効果が発揮されなくなる場合がある。However, the method proposed in Japanese Patent Application Laid-Open No. Sho 61-1557693, however, has the following problems. That is, the Al plate is usually covered with an oxide film, and when only electroplating is performed in a normal sulfuric acid bath as shown in the above-mentioned publication, only a film having extremely poor adhesion is obtained. Not generated. Therefore, the film may be peeled off during the press molding, and the above-mentioned effect may not be exhibited in the subsequent zinc phosphate treatment step.
【０００７】このような問題を解決する方法として、特
開平３−146693号公報に次のような方法が提案されてい
る。すなわち、Al板の表面に最下層として、フッ化水素
酸を含む酸性塩化物浴で置換めっきあるいは硫酸酸性浴
で電気めっきによりニッケルめっき層を形成させ、その
上に亜鉛あるいはまた亜鉛系合金めっき層を施すことに
より密着性の良好な表面処理Al板を製造する方法であ
る。As a method for solving such a problem, the following method has been proposed in Japanese Patent Application Laid-Open No. 3-146693. That is, as a lowermost layer on the surface of the Al plate, a nickel plating layer is formed by displacement plating in an acid chloride bath containing hydrofluoric acid or electroplating in a sulfuric acid bath, and a zinc or zinc-based alloy plating layer is formed thereon. This is a method for producing a surface-treated Al plate having good adhesion by performing the following.
【０００８】しかしながら、実際に特開平３−146693号
公報で提案された方法を適用すると次のような大きな２
つの問題を生じることが分かった。すなわち、第１に、
一般に自動車車体用材料はその性能の一つとして塗装後
さらに疵を付与された場合の耐食性が要求される。しか
し、特開平３−146693号公報提案の方法では腐食進行後
塗膜の密着性がなくなり、特に疵部では、大きな膨れ
(ブリスター) を生じてしまう。第２に、プレス成形時
に母材破断を生じてしまう。However, when the method proposed in Japanese Patent Application Laid-Open No. 3-146693 is actually applied, the following large 2
Has been found to cause two problems. That is, first,
In general, a material for an automobile body is required to have corrosion resistance in a case where a flaw is further provided after painting as one of its performances. However, according to the method proposed in JP-A-3-146693, the adhesion of the coating film is lost after the progress of corrosion, and large swelling is particularly caused at the flaw.
(Blister). Secondly, the base material breaks during press forming.
【０００９】さらに、特開平２−19488 号公報、同２−
19489 号公報、および同２−19490号公報では、一種の
置換めっきで亜鉛皮膜を形成するジンケート処理後塩基
性浴でZn合金皮膜を電気めっきによって設ける方法が開
示されている。しかし、Znのみの被膜の上に電気めっき
を行う場合、層間のガルバニック電流によりアルミニウ
ムが溶出し、アルミニウムと第一層との間で層間剥離が
発生する。また、塩基性浴では塩基イオンにより孔食や
アルカリ溶解が起こり、アルミニウム表面が再露出し、
できた皮膜の密着性が低下する。Further, Japanese Patent Application Laid-Open Nos.
JP-A-19489 and JP-A-2-19490 disclose a method of forming a zinc film by a kind of displacement plating, and then providing a Zn alloy film by electroplating in a basic bath after a zincate treatment. However, when electroplating is performed on a Zn-only film, aluminum is eluted due to galvanic current between layers, and delamination occurs between aluminum and the first layer. In a basic bath, pitting corrosion or alkali dissolution occurs due to base ions, and the aluminum surface is re-exposed,
The adhesion of the formed film is reduced.
【００１０】そこで本発明は、以上の背景の下に、塗装
後耐食性、プレス成形性ともに満足する、めっき密着性
およびリン酸処理性の双方が良好な表面処理Al板とその
製造法を提供することを目的とするものである。In view of the above, the present invention provides a surface-treated Al plate satisfying both the corrosion resistance after coating and the press formability and having good plating adhesion and phosphating properties, and a method for producing the same. The purpose is to do so.
【００１１】[0011]
【課題を解決するための手段】本発明者らがこれらの課
題解決のため鋭意解析を行った結果、特開平３−146693
号公報で提案の方法において塗装後に大きなブリスター
を生じるのは次のような原因であると分かった。すなわ
ち、アルミニウムは本来電気化学的に卑な金属であり、
イオン化 (溶出) しやすい。これに対してニッケルは電
気化学的に貴な金属であり、イオン化しにくい。この２
つの金属が接触するとアルミニウムが陽極 (アノード)
、ニッケルが陰極 (カソード) となる電気化学セル
(ガルバニックセル) を形成しアルミニウムのみがイオ
ン化して溶出する。すなわち、アルミニウムとニッケル
の間で層間剥離するようになる。その結果、塗膜が浮い
て大きなブリスターを生じる。一方、プレス成形時に母
材破断を生じる原因については次のようであると判明し
た。すなわち、Al板のプレス変形過程の断面を観察した
結果、変形で破壊したニッケル片がAl板に食い込み、生
じたノッチの先から材料内部へ応力集中によりクラック
が伝播している。その結果、母材破断を生じると判断で
きる。Means for Solving the Problems As a result of the present inventors' earnest analysis for solving these problems, Japanese Patent Application Laid-Open No. 3-146693 has been disclosed.
It has been found that the formation of large blisters after painting in the method proposed in Japanese Patent Application Publication No. H11-15093 is as follows. In other words, aluminum is a metal that is inherently electrochemically
Easy ionization (elution). On the other hand, nickel is an electrochemically noble metal and is hardly ionized. This 2
When two metals come in contact, aluminum becomes the anode (anode)
Cell with nickel as cathode (cathode)
(Galvanic cell) and only aluminum is ionized and eluted. That is, delamination occurs between aluminum and nickel. As a result, the coating floats and produces large blisters. On the other hand, it has been found that the cause of the breakage of the base material during press forming is as follows. That is, as a result of observing the cross section of the Al plate during the press deformation process, the nickel pieces broken by the deformation bite into the Al plate, and cracks are propagated from the tip of the generated notch to the inside of the material due to stress concentration. As a result, it can be determined that the base material breaks.
【００１２】そこで本発明者らは、鋭意実験・検討を行
った結果、最下層のめっきに例えば塩基性亜鉛系合金置
換めっき浴を用いた亜鉛合金層、第２層以降のめっきに
例えば硫酸酸性浴を用いて、Znまたは合金成分あるいは
また合金組成の異なる亜鉛系合金を隣り合った層に用
い、１層あたり0.1 g/m2以上で、形成した２層以上積層
めっきを施すことにより上述の問題を全て解決できるこ
とが分かった。The inventors of the present invention have conducted intensive experiments and studies, and as a result, have found that, for example, a zinc alloy layer using a basic zinc-based alloy substitution plating bath is used for the lowermost layer, and a sulfuric acid acid is used for the second and subsequent layers. Using a bath, Zn or an alloy component or a zinc-based alloy having a different alloy composition is used for adjacent layers, and at least 0.1 g / m2 per layer, and two or more formed layers are subjected to multi-layer plating as described above. It turns out that we can solve all the problems.
【００１３】ここに、本発明の要旨とするところは、ア
ルミニウムまたはアルミニウム合金板の表面に設けた亜
鉛系合金置換めっき層の第１層と、該第１層の上に設け
た各々0.1 g/m2以上の１層または２層以上の亜鉛または
亜鉛合金めっき層とを備えたことを特徴とする積層めっ
きアルミニウムまたはアルミニウム合金板である。Here, the gist of the present invention is that the first layer of the zinc-based alloy-substituted plating layer provided on the surface of the aluminum or aluminum alloy plate and the 0.1 g / a laminated plated aluminum or aluminum alloy plate, characterized in that a m 2 or more one or more layers of zinc or zinc alloy plating layer.
【００１４】また、本発明は、別の面からは、アルミニ
ウムまたはアルミニウム合金板の表面に、塩基性めっき
浴を使って第１層として亜鉛系合金置換めっき層を設
け、次いで第２層目以降として硫酸酸性浴により亜鉛ま
たは亜鉛合金めっき層を各々0.1 g/m2以上設けることを
特徴とする積層めっきアルミニウムまたはアルミニウム
合金板の製造法である。According to another aspect of the present invention, a zinc-based alloy-substituted plating layer is provided as a first layer on a surface of an aluminum or aluminum alloy plate using a basic plating bath, and then the second and subsequent layers are formed. A method for producing a laminated plated aluminum or aluminum alloy plate, wherein a zinc or zinc alloy plated layer is provided in an amount of 0.1 g / m 2 or more in a sulfuric acid acid bath.
【００１５】本発明の好適態様によれば、互いに隣り合
うめっき層は、合金成分および／または合金組成が異な
るように構成してもよい。また、前記第２層以降のめっ
き層を構成する亜鉛合金の合金成分を、Ni−Zn、Fe−Z
n、Co−Zn、Cr−Zn、およびMn−Znから成る群から選ん
でもよい。このように、本発明によれば、従来のジンケ
ート処理による亜鉛皮膜に代えてジンケート処理をアル
ミニウムにより近い電位をもつ亜鉛合金で置換めっきす
ることで行い、層間剥離を防止できる。さらに、硫酸酸
性浴での電気めっきを行うことで、アルミニウムの溶出
も防止でき、密着性に優れた複層めっきアルミニウム板
を得ることができる。According to a preferred embodiment of the present invention, the adjacent plating layers may be configured to have different alloy components and / or alloy compositions. Further, the alloy components of the zinc alloy constituting the second and subsequent plating layers are Ni-Zn, Fe-Z
It may be selected from the group consisting of n, Co-Zn, Cr-Zn, and Mn-Zn. As described above, according to the present invention, zincate treatment is performed by displacement plating with a zinc alloy having a potential closer to that of aluminum instead of the zinc film formed by the conventional zincate treatment, whereby delamination can be prevented. Further, by performing electroplating in a sulfuric acid acid bath, elution of aluminum can be prevented, and a multi-layer plated aluminum plate excellent in adhesion can be obtained.
【００１６】[0016]
【作用】本発明によれば、Al板を一般的な方法で脱脂し
た後、まず第１に塩基性亜鉛系合金置換めっき浴で置換
めっきを施すのであるが、アルミニウムは両性金属であ
り塩基性条件下では酸化皮膜が溶解し、新鮮な純金属ア
ルミニウム表面上で浴中の亜鉛あるいはまた合金金属と
置換反応を起こし金属−金属結合の強固な密着力の亜鉛
合金めっき層が形成される。このときのめっき量は特に
制限ないが、好ましくは 0.1〜５g/m2で十分である。According to the present invention, after the Al plate is degreased by a general method, first, displacement plating is first performed in a basic zinc-based alloy displacement plating bath. Aluminum is an amphoteric metal and basic plating is performed. Under the conditions, the oxide film dissolves and causes a substitution reaction with zinc or alloy metal in the bath on the surface of fresh pure metal aluminum to form a zinc alloy plating layer having a strong metal-metal bond. The plating amount at this time is not particularly limited, but preferably 0.1 to 5 g / m 2 is sufficient.
【００１７】続く硫酸酸性浴を用いての第２層以降のめ
っきにおいては、亜鉛あるいはまた亜鉛系合金は、アル
ミニウムに比較して、酸素に対して不活性であるため、
密着性を阻害する酸化皮膜を形成しにくい。さらに好ま
しくは硫酸酸性浴を用いると、塩素イオンによる孔食お
よびアルカリ溶解が起こることなく、アルミニウム表面
が再露出して酸化皮膜が再形成されることもない。その
結果第２層以降のめっき皮膜の密着性も完全なものに維
持できる。In the subsequent plating of the second and subsequent layers using a sulfuric acid acid bath, zinc or a zinc-based alloy is more inert to oxygen than aluminum.
It is difficult to form an oxide film that inhibits adhesion. More preferably, when a sulfuric acid acid bath is used, pitting corrosion and alkali dissolution due to chloride ions do not occur, and the aluminum surface is not re-exposed to form an oxide film. As a result, the adhesion of the second and subsequent plating films can also be kept perfect.
【００１８】ところでこの塩基性亜鉛系合金置換めっき
浴は、操作性、経済性の面から水酸化ナトリウムと酸化
亜鉛ならびに合金成分の酸化塩あるいは水酸化塩からな
ることが望ましい。また、第１層の置換めっきは、一度
置換めっき後、硝酸水溶液あるいは硫酸水溶液中で溶解
除去した後置換めっきを施す操作を２回以上繰り返す
と、より緻密なめっき層が形成されさらに良性能とな
る。The basic zinc-based alloy-substituted plating bath is preferably made of sodium hydroxide and zinc oxide and an oxide or hydroxide of an alloy component from the viewpoint of operability and economy. In addition, the displacement plating of the first layer is performed once more by performing the displacement plating once, dissolving and removing in a nitric acid aqueous solution or a sulfuric acid aqueous solution, and then performing the substitution plating twice or more. Become.
【００１９】一方、塗装後の耐食性、塗膜密着性は前述
のようにガルバニックセルの形成に支配される。ところ
が本発明のように亜鉛または亜鉛系合金めっきを積層さ
せると、アルミニウムならびに亜鉛または亜鉛系合金の
電位が近接しているためにガルバニック電流が分散され
る。すなわち、アルミニウムと第１めっき層間で全て流
れていたガルバニック電流が第２層以降のめっき層間の
ガルバニック電流に置き換えられる。その結果、全体的
に層間のガルバニック電流が減少し、層間剥離がなくな
る。それ故塗装後耐食性、塗膜密着性が大きく改善され
る。On the other hand, the corrosion resistance and coating film adhesion after coating are governed by the formation of galvanic cells as described above. However, when zinc or zinc-based alloy plating is laminated as in the present invention, the galvanic current is dispersed because the potentials of aluminum and zinc or zinc-based alloy are close to each other. That is, the galvanic current flowing between the aluminum and the first plating layer is replaced by the galvanic current between the second and subsequent plating layers. As a result, the galvanic current between the layers is reduced as a whole, and delamination is eliminated. Therefore, corrosion resistance after coating and coating film adhesion are greatly improved.
【００２０】したがって、第１層目の置換めっき層およ
び第２層目以降のめっき層を構成する亜鉛合金の合金元
素としては電位がZnとAlに近いものがよく、Ni−Zn、Fe
−Zn、Co−Zn、Cr−Zn、Mn−Zn等が例示される。また、
プレス成形においても、亜鉛系合金は一般に金属間化合
物を形成しその脆性のために自己潤滑作用を示すため、
本発明の積層めっきAl板ではアルミニウム母材にめっき
片がノッチを加えることなく、母材破断は全く起こさな
い。Therefore, as the alloying element of the zinc alloy constituting the first substitutional plating layer and the second and subsequent plating layers, those having a potential close to Zn and Al are preferable, and Ni-Zn, Fe
-Zn, Co-Zn, Cr-Zn, Mn-Zn and the like are exemplified. Also,
Even in press forming, zinc-based alloys generally form intermetallic compounds and exhibit a self-lubricating action due to their brittleness,
In the laminated plated Al plate of the present invention, the plated piece does not add a notch to the aluminum base material, and the base material does not break at all.
【００２１】[0021]
【実施例】以下実施例にて本発明の効果を説明する。 [塩基性亜鉛系合金置換めっき]水酸化ナトリウム水溶液
（濃度:300〜600 g/l)に酸化亜鉛を10〜200 g/l 溶解
し、合金成分となる金属塩を酸化物あるいはまた水酸化
物の形で０〜100 g/l 添加した。処理液温度を10〜50℃
に設定し、付着量は反応時間により制御した。EXAMPLES The effects of the present invention will be described below with reference to examples. [Basic zinc-based alloy displacement plating] Dissolve 10-200 g / l of zinc oxide in aqueous sodium hydroxide solution (concentration: 300-600 g / l), and convert metal salt as an alloy component to oxide or hydroxide In the form of 0-100 g / l. Processing solution temperature 10 ~ 50 ℃
And the amount of adhesion was controlled by the reaction time.
【００２２】[硫酸酸性めっき]公知の硫酸塩を用いる一
般的な電気めっきによった。めっき付着量は通電時間を
変えて制御した。[Sulfuric acid acid plating] General electroplating using a known sulfate was used. The coating weight was controlled by changing the energization time.
【００２３】[めっき皮膜密着性]表面処理Al板を曲げ戻
し、曲げ部を粘着テープで剥離し、剥離しためっき皮膜
の金属片量によって次のように評価した。 ○ : 剥離片がほとんど見られない △ : 剥離片がテープに10〜50％の面積率で付着 × : 剥離片がテープに50％以上の面積率で付着。[Adhesion of plating film] The surface-treated Al plate was bent back, the bent portion was peeled off with an adhesive tape, and the amount of metal pieces of the peeled plating film was evaluated as follows. :: Almost no peeled pieces are observed. Δ: Peeled pieces are adhered to the tape at an area ratio of 10 to 50%.
【００２４】[リン酸亜鉛処理性]市販のリン酸亜鉛処理
用薬剤を用いて、標準条件下でリン酸亜鉛処理を処理液
１リットルあたり供試材0.5 m2の割合で連続して行いそ
の後の処理液中のAlイオン濃度で次のように評価した。 ○ : Alイオン濃度が１ppm 未満 △ : Alイオン濃度が１ppm 以上10ppm 未満 × : Alイオン濃度が10ppm 以上。[Zinc phosphate treatment property] Using a commercially available zinc phosphate treatment agent, zinc phosphate treatment was carried out continuously under standard conditions at a rate of 0.5 m 2 of the test material per liter of treatment liquid. Was evaluated as follows by the Al ion concentration in the processing solution of :: Al ion concentration of less than 1 ppm Δ: Al ion concentration of 1 ppm or more and less than 10 ppm ×: Al ion concentration of 10 ppm or more.
【００２５】[塗装後耐食性]供試材を電着塗装、スプレ
ー塗装した後、クロスカットを付与し、図１に示す24時
間／サイクルの複合腐食試験を30サイクル実施し、その
後のカット部のブリスター幅により次のように評価し
た。 ○ : 最大ブリスター幅が１mm未満 △ : 最大ブリスター幅が１mm以上、５mm未満 × : 最大ブリスター幅が５mm以上。[Corrosion resistance after coating] After the test material was subjected to electrodeposition coating and spray coating, a cross cut was applied, and a composite corrosion test of 24 hours / cycle shown in FIG. 1 was carried out for 30 cycles. The blister width was evaluated as follows. :: Maximum blister width is less than 1 mm △: Maximum blister width is 1 mm or more and less than 5 mm ×: Maximum blister width is 5 mm or more.
【００２６】[プレス成形性]供試材を直径90mmのサイズ
の円盤状に切り出し、ポンチ系50mmの円筒深絞りを行っ
て次のように評価した。 ○ : 絞り抜けるまで母材破断なし △ : 絞り高さ20mm以上で母材破断 × : 絞り高さ20mm未満で母材破断。[Press Formability] A test material was cut into a disc having a size of 90 mm in diameter, punched into a cylindrical 50 mm deep cylinder, and evaluated as follows. ○: No break of base material until drawn out △: Break of base material at draw height of 20 mm or more ×: Break of base material at draw height of less than 20 mm
【００２７】表１に比較例とともに結果をまとめて示
す。これらからも分かるように、試験番号１〜11の本発
明例はいずれの特性についても満足のゆく結果を示す
が、置換めっき層を設けなかった試験番号12の場合には
めっき密着性が十分でなく、第２めっき層のめっき付着
量が十分でない試験番号13および置換めっき層だけの試
験番号14の場合にはプレス成形性が十分でない。さら
に、第１層をZnのみの置換めっき層とした試験番号15の
場合にはめっき密着性およびプレス成形性が十分でな
い。試験番号17は特開平３−146693号に対応する従来例
であって、塗装後耐食性およびプレス成形性が十分でな
い。Table 1 shows the results together with comparative examples. As can be seen from the above, the examples of the present invention of Test Nos. 1 to 11 show satisfactory results with respect to any of the properties, but in the case of Test No. 12 having no displacement plating layer, the plating adhesion was sufficient. On the other hand, in the case of Test No. 13 where the coating weight of the second plating layer is not sufficient and Test No. 14 where only the replacement plating layer is used, the press formability is not sufficient. Further, in the case of Test No. 15 in which the first layer was a substitution plating layer of only Zn, the plating adhesion and press formability were not sufficient. Test No. 17 is a conventional example corresponding to JP-A-3-146693, in which the corrosion resistance after press and the press formability are not sufficient.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明により自動車の車体等に使用され
る、プレス成形性、塗装後塗膜密着性に優れ、リン酸亜
鉛処理工程でもAlイオンの溶出問題を生じないAl板を得
ることができる。According to the present invention, it is possible to obtain an Al plate which is excellent in press moldability and coating film adhesion after coating and which does not cause Al ion elution problem even in a zinc phosphate treatment step, which is used for an automobile body or the like. it can.
【図１】複合腐食試験の工程と試験条件の説明図であ
る。FIG. 1 is an explanatory view of steps and test conditions of a composite corrosion test.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 津田 哲明 大阪市中央区北浜４丁目５番33号 住友 金属工業株式会社内 (72)発明者 辻 正規 和歌山市湊1850番地 住友金属工業株式 会社和歌山製鉄所内 (72)発明者 保母 芳彦 和歌山市湊1850番地 住友金属工業株式 会社和歌山製鉄所内 (72)発明者 池田 洋 東京都港区新橋５丁目11番３号 住友軽 金属工業株式会社内 (72)発明者 相武 隆男 東京都港区新橋５丁目11番３号 住友軽 金属工業株式会社内 (72)発明者 宇都 秀之 東京都港区新橋５丁目11番３号 住友軽 金属工業株式会社内 (56)参考文献 特開 平４−311582（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuaki Tsuda 4-5-33 Kitahama, Chuo-ku, Osaka City Inside Sumitomo Metal Industries, Ltd. (72) Inventor Masaru Tsuji 1850 Minato, Wakayama-shi Sumitomo Metal Industries Wakayama Steel In-house (72) Inventor Yoshihiko Hobo 1850 Minato, Wakayama-shi Sumitomo Metal Industries Co., Ltd.Wakayama Works (72) Inventor Hiroshi Ikeda 5-11-3 Shimbashi, Minato-ku, Tokyo Sumitomo Light Metal Industries, Ltd. (72) Invention Person Takao Aitake 5-1-1-3 Shimbashi, Minato-ku, Tokyo Sumitomo Light Metal Industries Co., Ltd. (72) Inventor Hideyuki Utsu 5-1-1-3 Shimbashi, Minato-ku, Tokyo Sumitomo Light Metal Industries Co., Ltd. (56) Reference Document JP-A-4-311582 (JP, A)
Claims (4)
の表面に設けた亜鉛系合金置換めっき層の第１層と、該
第１層の上に設けた各々0.1 g/m2以上の１層または２層
以上の亜鉛または亜鉛合金めっき層とを備えたことを特
徴とする積層めっきアルミニウムまたはアルミニウム合
金板。1. A first layer of a zinc-based alloy-substituted plating layer provided on a surface of an aluminum or aluminum alloy plate, and one or more layers of 0.1 g / m 2 or more each provided on the first layer. And a zinc or zinc alloy plating layer.
よび／または合金組成が異なることを特徴とする請求項
１記載の積層めっきアルミニウムまたはアルミニウム合
金板。2. The laminated plated aluminum or aluminum alloy sheet according to claim 1, wherein the adjacent plating layers have different alloy components and / or alloy compositions.
を構成する亜鉛合金の合金成分が、Ni−Zn、Fe−Zn、Co
−Zn、Cr−Zn、およびMn−Znから成る群から選ばれたも
のである請求項１または２記載の積層めっきアルミニウ
ムまたはアルミニウム合金板。3. The alloy component of the zinc alloy constituting the first and second and subsequent plating layers is Ni—Zn, Fe—Zn, Co
The laminated plated aluminum or aluminum alloy plate according to claim 1 or 2, which is selected from the group consisting of -Zn, Cr-Zn, and Mn-Zn.
の表面に、第１層として亜鉛系合金置換めっき層を設
け、次いで第２層目以降として硫酸酸性浴での電気めっ
きにより亜鉛または亜鉛合金めっき層を各々0.1 g/m2以
上設けることを特徴とする積層めっきアルミニウムまた
はアルミニウム合金板の製造法。4. A zinc-based alloy-substituted plating layer is provided on a surface of an aluminum or aluminum alloy plate as a first layer, and then a zinc- or zinc-alloy plating layer is formed as a second layer and thereafter by electroplating in a sulfuric acid acid bath. A method for producing a laminated plated aluminum or aluminum alloy plate, comprising providing at least 0.1 g / m 2 .
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3335229A JP2718310B2 (en) | 1991-12-18 | 1991-12-18 | Laminated plating Al plate and method for producing the same |
| EP92121502A EP0547609B1 (en) | 1991-12-18 | 1992-12-17 | Automobile body panel made of multilayer plated aluminum sheet |
| US07/992,111 US5356723A (en) | 1991-12-18 | 1992-12-17 | Multilayer plated aluminum sheets |
| DE69222129T DE69222129T2 (en) | 1991-12-18 | 1992-12-17 | Automotive body panel made of multi-coated aluminum plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3335229A JP2718310B2 (en) | 1991-12-18 | 1991-12-18 | Laminated plating Al plate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05171492A JPH05171492A (en) | 1993-07-09 |
| JP2718310B2 true JP2718310B2 (en) | 1998-02-25 |
Family
ID=18286190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3335229A Expired - Lifetime JP2718310B2 (en) | 1991-12-18 | 1991-12-18 | Laminated plating Al plate and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2718310B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006342369A (en) * | 2005-06-07 | 2006-12-21 | Toyo Kohan Co Ltd | SURFACE TREATED Al SHEET |
| JP2007254866A (en) * | 2006-03-24 | 2007-10-04 | Dowa Holdings Co Ltd | Plating pretreatment method for aluminum or aluminum alloy raw material |
| US11913131B2 (en) * | 2016-05-24 | 2024-02-27 | Macdermid, Incorporated | Ternary zinc-nickel-iron alloys and alkaline electrolytes or plating such alloys |
| KR102656417B1 (en) * | 2022-02-18 | 2024-04-12 | (주)일성도금 | High corrosion resistance surface treatment method of liftgate hinge made of aluminum alloy material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2812571B2 (en) * | 1991-04-09 | 1998-10-22 | 新日本製鐵株式会社 | Multi-layer plated Al alloy sheet with excellent press formability |
-
1991
- 1991-12-18 JP JP3335229A patent/JP2718310B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05171492A (en) | 1993-07-09 |
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