JP2963808B2 - Manufacturing method of electric Al-Zn alloy plated aluminum alloy sheet - Google Patents
Manufacturing method of electric Al-Zn alloy plated aluminum alloy sheetInfo
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- JP2963808B2 JP2963808B2 JP35586591A JP35586591A JP2963808B2 JP 2963808 B2 JP2963808 B2 JP 2963808B2 JP 35586591 A JP35586591 A JP 35586591A JP 35586591 A JP35586591 A JP 35586591A JP 2963808 B2 JP2963808 B2 JP 2963808B2
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- chloride
- alloy
- aluminum alloy
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Description
【001】[0101]
【産業上の利用分野】本発明は、塗装用下地、とくに電
着塗装用下地としてのリン酸塩処理性および塗装後耐食
性に優れたAl−Zn合金をめっき可能にした電気Al
−Zn合金めっきアルミニウム合金板の製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric Al which can be plated with an Al--Zn alloy having excellent phosphatability and post-coating corrosion resistance as a base for coating, especially as a base for electrodeposition coating.
The present invention relates to a method for producing a Zn alloy-plated aluminum alloy plate.
【002】[0092]
【従来技術】近年、大気汚染防止の観点から、自動車の
燃費向上が叫ばれ、その一環として、車体の軽量化が推
進されている。車体の軽量化としては、鉄鋼材料の高張
力化による使用鋼材の薄肉化が従来より行われてきてい
るが、最近ではアルミニウム合金板の使用が注目されて
いる。この合金板としては、JIS5000系(Al−
Mg−Cu系)やJIS6000系(Al−Mg−Si
系)などの展伸材が主に使用されているが、使用部位
は、フ−ド、トランクリッド、フロントおよびリアフェ
ンダ−などの部位に止まっている。2. Description of the Related Art In recent years, from the viewpoint of preventing air pollution, improvement in fuel efficiency of automobiles has been called for, and as a part thereof, weight reduction of vehicle bodies has been promoted. In order to reduce the weight of a vehicle body, steel materials have been conventionally made thinner by increasing the tensile strength of steel materials, but recently, the use of aluminum alloy plates has attracted attention. JIS 5000 series (Al-
Mg-Cu) or JIS6000 (Al-Mg-Si)
Wrought materials such as hoods, trunk lids, front and rear fenders are mainly used.
【003】鋼材を使用した自動車の製造は、通常、部品
を組み立てて車体にした後、脱脂、リン酸塩処理、カチ
オン電着下塗り塗装、中塗り塗装、上塗り塗装の工程で
順次行われているが、アルミニウム合金板の部品を一部
に使用した場合もこの工程で製造されている。従って、
アルミニウム合金板にもリン酸塩処理性が要求される。Manufacturing of automobiles using steel materials is usually performed in the order of degreasing, phosphate treatment, cation electrodeposition undercoating, intermediate coating, and topcoating after assembling parts into a vehicle body. However, even when a part of an aluminum alloy plate is partially used, it is manufactured in this step. Therefore,
Phosphating properties are also required for aluminum alloy sheets.
【004】[0093]
【発明が解決しようとする課題】しかしながら、アルミ
ニウム合金板は、表面が酸化皮膜に覆われているため、
リン酸塩処理性に劣り、緻密で均一な皮膜が得られ難い
という問題があった。この結果、アルミニウム合金板の
組成と相俟って、塗装後塗膜下に著しいふくれ腐食や糸
状腐食が発生する場合があった。However, since the surface of an aluminum alloy plate is covered with an oxide film,
There was a problem that the phosphate treatment was poor and it was difficult to obtain a dense and uniform film. As a result, along with the composition of the aluminum alloy plate, remarkable blister corrosion and thread-like corrosion may occur under the coating film after coating.
【005】そこで、本発明者らは、かかる腐食の発生を
防止する方法として、Al−Zn合金めっきを施すこと
を案出した。すなわち、リン酸塩処理は、処理液中の遊
離酸で被処理物を溶出させ、その溶出の際のpH上昇に
よりリン酸塩を析出させるのであるが、Al−Zn合金
は、表面に不動態皮膜の形成されたアルミニウムよりエ
ッチング性に優れているので、リン酸塩処理性が向上す
る。また、Al−Zn合金は、Znめっきより耐食性に
優れているため、電着塗装後に塗膜下腐食が発生しにく
い。Therefore, the present inventors have devised to apply Al—Zn alloy plating as a method for preventing the occurrence of such corrosion. That is, in the phosphate treatment, the object to be treated is eluted with the free acid in the treatment solution, and the phosphate is precipitated by an increase in the pH during the elution, but the Al-Zn alloy has a passivation on the surface. Since the etching property is superior to that of the aluminum on which the film is formed, the phosphating property is improved. In addition, since the Al—Zn alloy has better corrosion resistance than Zn plating, corrosion under the coating film is less likely to occur after electrodeposition coating.
【006】しかし、Al−Zn合金をアルミニウム合金
板に工業的にめっきできる適当な方法がまだない。例え
ば、溶融金属めっき法は、アルミニウム合金板とAl−
Zn合金の融点が近似し、困難である。また、電気めっ
き法は、Alの電位が水素より卑であるため、水溶液系
のめっき浴からは不可能である。さらに、真空めっき法
は、基板の加熱とAlイオンの凝縮熱でアルミニウム合
金板はかなり高温になるので、形状が損なわれてしま
う。However, there is no suitable method for industrially plating an Al—Zn alloy on an aluminum alloy plate. For example, the hot metal plating method uses an aluminum alloy plate and an Al-
The melting point of the Zn alloy is close and difficult. In addition, the electroplating method cannot be performed from an aqueous plating bath because the potential of Al is lower than that of hydrogen. Furthermore, in the vacuum plating method, the aluminum alloy plate becomes considerably hot due to the heating of the substrate and the heat of condensation of the Al ions, so that the shape is damaged.
【007】007
【課題を解決するための手段】そこで、本発明は、アル
ミニウム合金板にAl−Zn合金を工業的にめっき可能
な方法によるAl−Zn合金めっきアルミニウム合金板
の製造法を提供するものである。本発明者らは、比較的
低温でAl−Zn合金をアルミニウム合金板にめっきで
きる方法を開発すべく、種々検討した結果、溶融塩浴に
よる電気めっき法を開発し、本発明を完成した。SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for producing an Al-Zn alloy-plated aluminum alloy sheet by a method capable of industrially plating an Al-Zn alloy on an aluminum alloy sheet. The present inventors have conducted various studies in order to develop a method capable of plating an Al-Zn alloy on an aluminum alloy plate at a relatively low temperature. As a result, the present inventors have developed an electroplating method using a molten salt bath and completed the present invention.
【008】すなわち、本発明は、(A)アルカリ金属塩
化物−塩化アルミニウム−塩化亜鉛からなる溶融塩浴ま
たは(B)塩化アルミニウム−有機系窒素含有オニウム
塩化物−塩化亜鉛からなる溶融塩浴で、各浴中のZn/
Alの比率が質量比で0.0015〜0.035である浴
中にアルミニウム合金板を浸漬して、電流密度0.3k
A/m2以上で電解し、アルミニウム合金板にZn含有
率が3.0〜50mass%のAl−Zn合金めっきを少な
くとも片面に0.2〜10g/m2施すことを特徴として
いる。That is, the present invention provides a molten salt bath consisting of (A) an alkali metal chloride-aluminum chloride-zinc chloride or (B) a molten salt bath consisting of (a) aluminum chloride-organic nitrogen-containing onium chloride-zinc chloride. , Zn /
The aluminum alloy plate was immersed in a bath in which the ratio of Al was 0.0015 to 0.035 by mass, and the current density was 0.3 k.
It is characterized in that electrolysis is performed at A / m 2 or more, and an aluminum alloy plate is subjected to Al—Zn alloy plating with a Zn content of 3.0 to 50 mass% on at least one surface in a range of 0.2 to 10 g / m 2 .
【009】[0099]
【作用】Al−Zn合金を電気めっき法で施すと、Zn
が偏析せず、Al中にZnがミクロ的に均一に分散す
る。また、アルカリ金属塩化物−塩化アルミニウム−塩
化亜鉛からなる溶融塩浴の場合、融点が90〜200
℃、塩化アルミニウム−有機系窒素含有オニウム塩化物
−塩化亜鉛からなる溶融塩浴の場合は、融点が60℃以
下であるので、めっきによりアルミニウム合金板の形状
が損なわれることがない。When the Al-Zn alloy is applied by electroplating, Zn
Are not segregated, and Zn is uniformly and microscopically dispersed in Al. In the case of a molten salt bath composed of alkali metal chloride-aluminum chloride-zinc chloride, the melting point is 90 to 200.
In the case of a molten salt bath composed of aluminum chloride-organic nitrogen-containing onium chloride-zinc chloride at a melting point of 60 ° C. or less, the shape of the aluminum alloy plate is not impaired by plating.
【010】溶融塩浴のアルカリ金属塩化物としては、L
iCl、KCl、NaClなどの1種または2種以上を
使用すればよく、また、有機系窒素含有オニウム塩化物
としては、アルキルイミダゾリウムクロライド、アルキ
ルピリジニウムクロライドなどの1種または2種以上を
使用すればよい。As the alkali metal chloride in the molten salt bath, L
One or more of iCl, KCl, NaCl and the like may be used, and as the organic nitrogen-containing onium chloride, one or more of alkyl imidazolium chloride and alkyl pyridinium chloride may be used. I just need.
【011】前記溶融塩浴で亜鉛を析出させるには、いず
れの浴の場合も浴中Zn/Alの比率を質量比で0.0
015〜0.035の範囲に、また、電流密度を0.3k
A/m2以上にして電解する必要がある。これらの範囲
は、亜鉛電析が拡散律速となる範囲で、Zn/Alの比
率および電流密度が前記範囲より外れると、めっき層中
のZn含有率が3.0〜50mass%のAl−Zn合金を
工業的に安定してめっきできない。In order to precipitate zinc in the molten salt bath, the ratio of Zn / Al in the bath is set to 0.0 by mass in any of the baths.
015-0.035, and the current density is 0.3 k.
It is necessary to conduct electrolysis at A / m 2 or more. These ranges are ranges in which zinc deposition is diffusion-controlled. If the Zn / Al ratio and the current density deviate from the above ranges, the Zn-content in the plating layer is 3.0 to 50 mass% in an Al-Zn alloy. Cannot be plated industrially stably.
【012】図1は、Zn含有率の異なったAl−Zn合
金めっきを施したアルミニウム合金板(JIS606
1、O材、板厚1.2mm)のリン酸塩処理性と電着塗
装後の耐食性(クロスカット部からの塗膜ふくれ幅の大
小)を示したグラフであるが、Al−Zn合金のZn含
有率が3mass%以上でリン酸塩処理性が良好になること
がわかる。Zn含有率が3mass%未満であると、均一な
リン酸塩結晶が析出しないのは、リン酸塩処理液との反
応性が良好なZn量が少ないことに起因している。FIG. 1 shows an aluminum alloy plate (JIS 606) plated with Al—Zn alloys having different Zn contents.
1, O material, plate thickness of 1.2 mm) is a graph showing the phosphatability and the corrosion resistance after electrodeposition coating (the size of the coating blister width from the cross-cut portion). It can be seen that when the Zn content is 3 mass% or more, the phosphatability is improved. If the Zn content is less than 3 mass%, uniform phosphate crystals do not precipitate due to a small amount of Zn having good reactivity with the phosphating solution.
【013】一方、Zn含有率が50mass%を超えると、
電着塗装後の耐食性が急激に低下しているが、これは、
リン酸塩層の下側にZn含有率の高いAl−Zn合金め
っき層が存在しているため、この層が選択的に腐食され
ることに起因している。従って、Al−Zn合金めっき
は、Zn含有率を3.0〜50mass%にすることが必要
で、好ましくは5.0〜30mass%であるといえる。On the other hand, when the Zn content exceeds 50 mass%,
Corrosion resistance after electrodeposition coating has dropped sharply,
This is because the Al-Zn alloy plating layer having a high Zn content exists under the phosphate layer, and this layer is selectively corroded. Therefore, in the Al—Zn alloy plating, it is necessary to set the Zn content to 3.0 to 50 mass%, and preferably it can be said to be 5.0 to 30 mass%.
【014】Al−Zn合金めっきによりアルミニウム合
金板のリン酸塩処理性を改善するには、めっき付着量を
0.2g/m2以上にする必要がある。0.2g/m2未満
では表面を完全に被覆できないため、リン酸塩結晶が不
均一になってしまう。一方、めっき付着量を多くしても
リン酸塩処理性は変わらないが、あまり多くすることは
経済的に不利になるので、多くとも10g/m2で十分
である。In order to improve the phosphatability of the aluminum alloy sheet by the Al-Zn alloy plating, it is necessary to make the coating weight 0.2 g / m 2 or more. If it is less than 0.2 g / m 2 , the surface cannot be completely covered, and the phosphate crystals become non-uniform. On the other hand, although the phosphatability does not change even if the plating adhesion amount is increased, it is economically disadvantageous to increase it too much, so that at most 10 g / m 2 is sufficient.
【015】[0151]
実施例1 常法による電解脱脂、酸洗を施したアルミニウム合金板
(JIS6061、O材、板厚1.2mm)に次の条件
で電解活性化処理、電気Al−Zn合金めっきを施し
て、Zn含有率およびめっき付着量の異なる電気Al−
Zn合金めっきアルミニウム合金板を製造した。めっき
層中のZn含有率を第1表に示す。Example 1 An aluminum alloy plate (JIS6061, O material, plate thickness: 1.2 mm) subjected to electrolytic degreasing and pickling by a conventional method was subjected to electrolytic activation treatment and electric Al-Zn alloy plating under the following conditions to obtain Zn. Electric Al- with different content and plating weight
A Zn alloy plated aluminum alloy plate was manufactured. Table 1 shows the Zn content in the plating layer.
【016】 (1)電解活性化処理 (浴組成) エチルメチルイミダゾリウムクロライド 507g/l 塩化アルミニウム 865g/l (処理条件) 浴温 80℃ 電流密度 0.3kA/m2 処理時間 15秒(1) Electrolytic activation treatment (bath composition) Ethyl methyl imidazolium chloride 507 g / l Aluminum chloride 865 g / l (treatment conditions) Bath temperature 80 ° C. Current density 0.3 kA / m 2 Treatment time 15 seconds
【017】 (2)電気Al−Zn合金めっき (浴組成) エチルメチルイミダゾリウムクロライド 507g/l 塩化アルミニウム 865g/l 塩化亜鉛 0.1〜15g/l (めっき条件) 浴温 80℃ めっき液流速 1.0m/s 電流密度 0.1〜6.0kA/m2 (2) Electric Al-Zn alloy plating (bath composition) Ethyl methyl imidazolium chloride 507 g / l aluminum chloride 865 g / l zinc chloride 0.1 to 15 g / l (plating conditions) Bath temperature 80 ° C. Plating solution flow rate 1 0.0 m / s Current density 0.1 to 6.0 kA / m 2
【018】[0182]
【第1表】 [Table 1]
【019】実施例2 実施例1と同様に電解脱脂、酸洗を施した同一アルミニ
ウム合金板に次の条件で電解活性化処理、電気Al−Z
n合金めっきを施して、Zn含有率およびめっき付着量
の異なる電気Al−Zn合金めっきアルミニウム合金板
を製造した。めっき層中のZn含有率を第2表に示す。Example 2 The same aluminum alloy plate subjected to electrolytic degreasing and acid washing as in Example 1 was subjected to electrolytic activation treatment under the following conditions,
An n-alloy plating was performed to produce aluminum Al-Zn alloy-plated aluminum alloy sheets having different Zn contents and different amounts of plating. Table 2 shows the Zn content in the plating layer.
【020】 (1)電解活性化処理 (浴組成) 塩化ナトリウム 294g/l 塩化カリウム 153g/l 塩化アルミニウム 1154g/l (処理条件) 浴温 230℃ 電流密度 0.3kA/m2 処理時間 15秒(1) Electrolytic activation treatment (bath composition) 294 g / l sodium chloride 153 g / l potassium chloride 1154 g / l aluminum chloride (treatment conditions) bath temperature 230 ° C. current density 0.3 kA / m 2 treatment time 15 seconds
【021】 (2)電気Al−Zn合金めっき (浴組成) 塩化ナトリウム 294g/l 塩化カリウム 153g/l 塩化アルミニウム 1154g/l 塩化亜鉛 0.5〜20g/l (めっき条件) 浴温 230℃ めっき液流速 1.0m/s 電流密度 0.1〜6.0kA/m2 (2) Electric Al-Zn alloy plating (bath composition) Sodium chloride 294 g / l Potassium chloride 153 g / l Aluminum chloride 1154 g / l Zinc chloride 0.5 to 20 g / l (Plating conditions) Bath temperature 230 ° C Plating solution Flow velocity 1.0 m / s Current density 0.1 to 6.0 kA / m 2
【022】[0222]
【第2表】 [Table 2]
【023】実施例3 実施例1および2の製造法により電気Al−Zn合金め
っきアルミニウム合金板を製造し、リン酸塩処理性、塗
装後耐食性を調査した。第3表に実施例1の製造法によ
る場合を、第4表に実施例2による場合を示す。また、
図1にめっき層中のZn含有率がリン酸塩処理性および
塗装後耐食性に及ぼす影響を示す。Example 3 Electric Al—Zn alloy-plated aluminum alloy sheets were manufactured by the manufacturing methods of Examples 1 and 2, and their phosphatability and corrosion resistance after painting were investigated. Table 3 shows the case according to the manufacturing method of Example 1, and Table 4 shows the case according to Example 2. Also,
FIG. 1 shows the effect of the Zn content in the plating layer on phosphatability and corrosion resistance after painting.
【024】(1)リン酸塩処理性 Al−Zn合金めっきアルミニウム合金板を常法により
脱脂した後、40℃のリン酸塩処理液[日本ペイント
(株)製、SD5000]に2分間浸漬してリン酸塩処
理を施し、1000倍のSEM観察によりリン酸塩結晶
の析出形態を観察し、以下の3水準で評価した。 ○ 緻密で均一なリン酸塩結晶が析出 △ 粗く不均一なリン酸塩結晶が析出 × リン酸塩結晶がほとんど析出せず(1) Phosphate treatment property An Al—Zn alloy-plated aluminum alloy plate was degreased by a conventional method, and then immersed in a phosphate treatment solution [SD5000, manufactured by Nippon Paint Co., Ltd.] at 40 ° C. for 2 minutes. The phosphate treatment was performed, and the precipitation form of phosphate crystals was observed by SEM observation at a magnification of 1000 times, and evaluated by the following three levels. ○ Precise and uniform phosphate crystals precipitated △ Coarse and uneven phosphate crystals precipitated × Phosphate crystals hardly precipitated
【025】(2)塗装後耐食性 上記方法でリン酸塩処理した電気Al−Zn合金めっき
アルミニウム合金板にカチオン型電着塗料[日本ペイン
ト(株)製、パワ−トップU80]を20μm塗装し
て、クロスカットを入れた後、JIS Z 2371に準
じた塩水噴霧試験1時間→乾燥→湿潤試験(50℃、相
対湿度98%)7時間→乾燥を1サイクルとする複合腐
食試験を50サイクル実施して、クロスカットからの最
大塗膜ふくれ幅を測定した。(2) Corrosion Resistance after Painting A cationic electrodeposition paint [Power Top U80, manufactured by Nippon Paint Co., Ltd.] was applied to an electric Al—Zn alloy-plated aluminum alloy plate that had been subjected to a phosphate treatment in the above-mentioned manner by 20 μm. After a cross cut, a salt spray test according to JIS Z 2371 for 1 hour → dry → wet test (50 ° C., 98% relative humidity) for 7 hours → combined corrosion test with dry as one cycle was performed for 50 cycles. The maximum coating blister width from the cross cut was measured.
【026】[0262]
【第3表】 [Table 3]
【027】[0279]
【第4表】 [Table 4]
【028】[0285]
【発明の効果】以上のように、本発明法は、低温でAl
−Zn合金を施すことができるので、形状の良好な電気
Al−Zn合金めっきアルミニウム合金板を製造でき
る。As described above, according to the method of the present invention, Al
Since the -Zn alloy can be applied, an electric Al-Zn alloy-plated aluminum alloy plate having a good shape can be manufactured.
【図1】アルミニウム合金板にめっきしたAl−Zn合
金のZn含有率とリン酸塩処理性および塗装後耐食性と
の関係を示すグラフである。FIG. 1 is a graph showing the relationship between the Zn content of an Al—Zn alloy plated on an aluminum alloy plate, phosphatability, and corrosion resistance after painting.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−89493(JP,A) 特開 平4−72089(JP,A) 特表 昭62−500249(JP,A) (58)調査した分野(Int.Cl.6,DB名) C25D 1/00 - 3/66 C25D 5/30 C25D 13/00 C25D 13/20 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-89493 (JP, A) JP-A-4-72089 (JP, A) JP-T-62-500249 (JP, A) (58) Investigation Field (Int.Cl. 6 , DB name) C25D 1/00-3/66 C25D 5/30 C25D 13/00 C25D 13/20
Claims (1)
ニウム−塩化亜鉛からなる溶融塩浴、または(B)塩化
アルミニウム−有機系窒素含有オニウム塩化物−塩化亜
鉛からなる溶融塩浴で、各浴中のZn/Alの比率が質
量比で0.0015〜0.035である浴中にアルミニウ
ム合金板を浸漬して、電流密度0.3kA/m2以上で電
解し、アルミニウム合金板にZn含有率が3.0〜50m
ass%のAl−Zn合金めっきを少なくとも片面に0.2
〜10g/m2施すことを特徴とする電気Al−Zn合
金めっきアルミニウム合金板の製造法。1. A molten salt bath composed of (A) an alkali metal chloride-aluminum chloride-zinc chloride, or a molten salt bath composed of (B) an aluminum chloride-organic nitrogen-containing onium chloride-zinc chloride. The aluminum alloy plate was immersed in a bath having a Zn / Al ratio of 0.0015 to 0.035 by mass, and was electrolyzed at a current density of 0.3 kA / m 2 or more. Rate is 3.0-50m
ass% Al-Zn alloy plating on at least one side 0.2
To 10 g / m 2 preparation of electric Al-Zn alloy-plated aluminum alloy sheet, wherein the subjecting.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP35586591A JP2963808B2 (en) | 1991-12-21 | 1991-12-21 | Manufacturing method of electric Al-Zn alloy plated aluminum alloy sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP35586591A JP2963808B2 (en) | 1991-12-21 | 1991-12-21 | Manufacturing method of electric Al-Zn alloy plated aluminum alloy sheet |
Publications (2)
Publication Number | Publication Date |
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JPH05171490A JPH05171490A (en) | 1993-07-09 |
JP2963808B2 true JP2963808B2 (en) | 1999-10-18 |
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JP35586591A Expired - Lifetime JP2963808B2 (en) | 1991-12-21 | 1991-12-21 | Manufacturing method of electric Al-Zn alloy plated aluminum alloy sheet |
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CN106947983B (en) * | 2017-03-31 | 2019-06-18 | 湖南金磐新材料科技有限公司 | Intercalation Zn-Al alloy powder and its zinc-aluminium of preparation collaboration anticorrosive paint and method |
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1991
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JPH05171490A (en) | 1993-07-09 |
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