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WO1993011278A1 - Aluminum alloy plate - Google Patents

Aluminum alloy plate Download PDF

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Publication number
WO1993011278A1
WO1993011278A1 PCT/JP1992/001530 JP9201530W WO9311278A1 WO 1993011278 A1 WO1993011278 A1 WO 1993011278A1 JP 9201530 W JP9201530 W JP 9201530W WO 9311278 A1 WO9311278 A1 WO 9311278A1
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WO
WIPO (PCT)
Prior art keywords
aluminum alloy
phosphate
alloy plate
alloy
coating
Prior art date
Application number
PCT/JP1992/001530
Other languages
French (fr)
Japanese (ja)
Inventor
Ltd. Nisshin Steel Co.
Original Assignee
Shimizu, Takeshi
Tatano, Masayoshi
Uchida, Yukio
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shimizu, Takeshi, Tatano, Masayoshi, Uchida, Yukio filed Critical Shimizu, Takeshi
Publication of WO1993011278A1 publication Critical patent/WO1993011278A1/en

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Classifications

    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon

Definitions

  • the present invention relates to an aluminum alloy sheet excellent in phosphatability and post-coating corrosion resistance, particularly as a base for coating, particularly as a base for electrodeposition coating.
  • Such alloy sheets include wrought materials such as Japanese Industrial Standard 5000 series (Al_Mg-Cu series) and 6000 series (A1-Mg-Si series). Is mainly used, but the parts to be used are limited to the parts such as the hood, trunk bridge, front and rear fender, and are used throughout Not yet.
  • the present invention has been made in view of the above problems, and provides an aluminum alloy sheet having the same phosphate treating property as a steel material.
  • the present invention provides an aluminum alloy plate with an A1-Zn alloy plating, thereby improving the phosphate treatment property and after coating. It has improved corrosion resistance, and the aluminum alloy sheet has a Zn content of 3.0 to 5 O mass% on at least one side of the aluminum alloy sheet. 0 g Z m 2
  • the object to be treated is eluted with the free acid in the treatment solution, and the pH rises during the elution, and in the case of zinc-based plated steel sheets, zinc phosphate (Hopeite) is used.
  • Hopeite zinc phosphate
  • crystals of zinc iron phosphate (Phosphophyllite) are precipitated on the surface of the workpiece, but in the case of aluminum alloy sheets, Because a passivation film is formed, it is difficult to etch uniformly.
  • FIG. 1 is a graph showing the relationship between the Zn content of Al-Zn alloy and its phosphate treatment and corrosion resistance after painting on aluminum alloy sheets. is there.
  • Figure 1 shows the plating of A 1 —Zn alloys with different Zn content.
  • the phosphate treatment property is improved. If the Zn content is less than 3 raass%, uniform phosphate crystals do not precipitate due to the phosphate treatment solution.
  • Fig. 1 shows that when the Zn content exceeds 50 mass%, the corrosion resistance after electrodeposition coating sharply decreases. This is because the ⁇ 1-Zn alloy plating layer, which has a high Zn content, exists selectively in this layer. Therefore, in the case of A 1 -Zn alloy, it is necessary to set the Zn content to 3.0 to 50 mass%.
  • the surface cannot be completely covered, resulting in non-uniform phosphate crystals.
  • plating even if the amount The phosphate treatability does not change, but increasing it too much is economically disadvantageous, so at most 10 gm 2 per side is sufficient.
  • the A 1 —Zn alloy preferably has a structure in which Zn does not segregate and is uniformly dispersed microscopically in Zn force.
  • Such A 1 -Zn-alloy plating consists of an electroplating method using a room-temperature molten salt bath, for example, aluminum chloride and organic nitrogen-containing onium chloride. This is possible if a bath in which zinc chloride is added to the molten salt bath is used.
  • An electron beam heating type vapor deposition method in which a pure bath 1 and a pure Zn bath are arranged side by side and vapor deposition of bath 1 and Zn simultaneously from both baths is performed. It may be carried out by vacuuming such as ring or ion sputtering ring. According to these mounting methods, like the melting method
  • A1-Zn alloy plating in which Zn is uniformly dispersed in the plating layer can be performed from the melting plate.
  • the A 1 —Zn alloy on aluminum alloy plate may be applied to only one side if only one side is painted, but it is applied to both sides if both sides are painted.
  • Aluminum alloy plate Japanese Industrial Standard 600,0 material, plate thickness 1.2 mm
  • An aluminum alloy plate with an A 1 -Zn alloy having different Zn content and adhesion was prepared by applying one Zn alloy to one surface.
  • the composition of this industrial standard 6006 is as follows
  • Comparative Example No. 17 is an aluminum alloy plate coated with zinc by a zincate treatment
  • Comparative Example No. 18 is a Zn alloy alloy. Given No aluminum alloy plate.
  • a 1-Zn alloy-coated aluminum base plate was degreased at 40 ° C (the trade name of Nippon Paint Co., Ltd., which is located in Japan, Degreased by immersion for 15 seconds in cold-rolled steel sheets and zinc-based surface-treated steel sheets at 40 ° C (product name SD manufactured by Nippon Paint Co., Ltd.). (A standard concentration solution of 500.000) was used for 2 minutes to perform the phosphate treatment, and the precipitation of phosphate crystals on the phosphate film deposited in Table 2 The morphology was observed with a scanning electron microscope of 100 mm and evaluated on the following three levels.
  • An epoxy resin-based cation-type electrodeposition paint (trade name of Nippon Paint Co., Ltd.) is applied to an aluminum alloy plate that has been treated with phosphate by the above method. (Wattop U80 was coated under standard coating conditions) was subjected to 20 electrodeposition coating, and a cross-corrosion test was carried out after inserting the crosscuts reaching the coating layer on the coating film. did.
  • the combined corrosion test is performed by conducting a salt spray test in accordance with Japanese Industrial Standards Z2371 for 1 hour, and after drying, a wet test (50 ° C, relative humidity 9.8%) for 7 hours. Perform 50 cycles of the cycle test with one cycle of the culm to be dried again, and measure the maximum coating film width from the crosscut.
  • Example 1 (5052, 0 material, thickness 1.2 mm) is heated to 200 ° C in a vacuum, then ion beam activated and deposited under the following conditions. On one side to determine the Zn content and An aluminum alloy plate with an A 1 —Zn alloy having a different coating weight was prepared, and the phosphatability and the post-coating corrosion resistance were investigated in the same manner as in Example 1. Table 2 shows the results. In Comparative Example No. 37, only zinc was vapor-deposited, and the composition of an aluminum alloy plate according to Japanese Industrial Standard 5052 is as follows.
  • the aluminum alloy sheet for the A] -Zn alloy according to the present invention uses, as the phosphate treatment agent, the one used for the pre-coating treatment of the steel material.
  • the phosphate treatment agent since it is excellent in phosphatability and corrosion resistance after painting, it uses steel material and aluminum alloy plate, and the phosphating agent is steel material ⁇ It can be used in applications where it must be used, such as cars, motorcycles, airplanes, and ships.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

An aluminum alloy plate having a similar phosphatability to that of iron steel material and being plated with an Al-Zn alloy having a zinc content of 3.0-50 % by mass in a coating weight of 0.2-10 g/m<2> on at least one side thereof.

Description

明 細 書  Specification
発明の名称  Title of invention
アル ミ ニウ ム合金板  Aluminum alloy plate
技術分野  Technical field
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 アル ミ ニウ ム 合金板に関する。  The present invention relates to an aluminum alloy sheet excellent in phosphatability and post-coating corrosion resistance, particularly as a base for coating, particularly as a base for electrodeposition coating.
背景技術  Background art
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 ニゥ ム合金板の使用が注目 さ れてい る。 こ の合金板 と し ては、 日本工業規格 5 0 0 0 系 （ A l _ M g — C u 系） や 6 0 0 0 系 （ A 1 — M g— S i 系） な どの展伸材が主に使 用 されているが、 使用部位は、 フ ー ド、 ト ラ ン ク リ ッ ド、 フ ロ ン ト お よ び リ ア フ ェ ンダー な どの部位に止ま り 、 全体 に使用 される ま でには至っ ていない。  In recent years, from the viewpoint of air pollution prevention, it has been called for to improve the fuel efficiency of automobiles, and as part of this, the reduction of body weight has been promoted. To reduce the weight of the car body, the steel used has been made thinner by increasing the tensile strength of the steel, but the use of aluminum alloy sheets has recently attracted attention. ing. Such alloy sheets include wrought materials such as Japanese Industrial Standard 5000 series (Al_Mg-Cu series) and 6000 series (A1-Mg-Si series). Is mainly used, but the parts to be used are limited to the parts such as the hood, trunk bridge, front and rear fender, and are used throughout Not yet.
鉄鋼材料を使用 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 塗装および上塗 り 塗装の工程で順次行 われているが、 アル ミ ニウ ム台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 ニゥ ム合金板に も リ ン酸塩処理性が要求さ れる。  In the manufacture of automobiles using steel materials, usually, after assembling the parts into a car body, the steps of degreasing, phosphate treatment, electrodeposition of cation, undercoating, medium coating and topcoating are sequentially performed. This process is also performed when parts of the aluminum base metal plate are partially used. Therefore, aluminum alloy sheets are also required to have phosphate treatment properties.
しか しなが ら、 アル ミ ニウ ム合金板は、 リ ン酸塩処理件 に劣るため、 緻密で均一な リ ン酸塩皮膜が得られ難いとい う 問題があった。 このため、 塗装した場合、 塗膜下に腐食 が発生 し、 著しい塗膜ふ く れや糸状腐食が発生する場合が ノあった 0 However, aluminum alloy sheets are subject to phosphate treatment. Therefore, there was a problem that it was difficult to obtain a dense and uniform phosphate film. For this reason, when painted, corrosion occurred under the coating film, and there was a case where remarkable film wiping and thread-like corrosion occurred 0
そこで、 かかる腐食の発生を防止するため、 アルミ ニゥ ム合金板部品を車体に組み込む前にァルミ ニゥム合金板部 品だけに予めク ロメ ー ト系の塗装下地処理を施 し、 その後 車体に組み込んでリ ン酸塩処理を施 して.、 鉄鋼材料部品に も塗装下地処理を施す方法やアルミ ニゥ ム合金板部品を車 体に組み込んだ後、 フ ッ化物のよ う なエツ チング剤の多.量 添加によ り アルミ ニウム合金板との反応性を高めた リ ン酸 塩処理剤で処理する方法な どが一部で試みられている。  Therefore, in order to prevent the occurrence of such corrosion, before the aluminum alloy plate parts are incorporated into the vehicle body, only the aluminum alloy plate parts are subjected to a chromatized paint base treatment in advance, and then incorporated into the vehicle body. After applying phosphate treatment.Steel material parts are also subjected to a paint base treatment, or aluminum alloy sheet parts are incorporated into the vehicle body, and then there are many etching agents such as fluoride. Attempts have been made in some ways, such as by treating with a phosphate treating agent that has increased reactivity with aluminum alloy plates by adding a small amount.
しかし.、 前者の方法は、 作業が繁雑である とと もに、 車 体に組み込んだ後の リ ン酸塩処理の際にク ロメ ー 卜皮膜か ら有害なク ロムが溶出 し、 このク ロムがリ ン酸塩処理液中 に混入する という問題がある。 後者の方法に しても、 .鉄鋼 材料部品でも冷延鋼板や亜鉛系めつき鋼板のよ う な リ ン酸 塩処理性の異なった材料が使用 されているため、 これらの すべてにエ ッ チング剤添加の リ ン酸塩処理剤で良好な リ ン 酸塩皮膜を形成できる ものではなかった。  However, in the former method, not only the work is complicated, but also harmful chromium is eluted from the chromate film during the phosphate treatment after being assembled in the vehicle body, and this There is a problem that rom is mixed into the phosphate treatment solution. Even in the latter method, since all the steel parts are made of different phosphate-treating materials such as cold-rolled steel sheets and galvanized steel sheets, all of them are etched. A good phosphate film could not be formed with the phosphating agent added.
発明の開示  Disclosure of the invention
. 本発明は、 上記の問題に鑑み、 鉄鋼材料と同様の リ ン酸 塩処理性を有するアルミ ニウム合金板を提供する ものであ る。 すなわち、 本発明は、 アルミ ニウム合金板に A 1 一 Z n合金めつ きを施すこ とによ り リ ン酸塩処理性、 塗装後 耐食性を改善 した もので、 アル ミ ニウ ム合金板の少な く と も片面に Z n 含有率が 3 . 0 〜 5 O mass%の A 1 — Z n 合 金め つ きを 0. 2 〜 1 0 g Z m 2施 した こ と を特徴 と してい The present invention has been made in view of the above problems, and provides an aluminum alloy sheet having the same phosphate treating property as a steel material. In other words, the present invention provides an aluminum alloy plate with an A1-Zn alloy plating, thereby improving the phosphate treatment property and after coating. It has improved corrosion resistance, and the aluminum alloy sheet has a Zn content of 3.0 to 5 O mass% on at least one side of the aluminum alloy sheet. 0 g Z m 2
リ ン酸塩処理は、 処理液中の遊離酸で被処理物を溶出 さ せて、 その溶出の際の p H上昇で亜鉛系のめ っ き鋼板の場 合は リ ン酸亜鉛 （ Hopeite) の結晶を、 ま た、 冷延鋼板の 場合は リ ン酸亜鉛鉄 （Phosphophyllite) の結晶を被処理 物の表面に析出 させる方法であ る が、 アル ミ ニ ウ ム合金板 の場合は表面に不動態皮膜が形成さ れている ため、 均一に エ ッ チ ングされ難い。 In the phosphate treatment, the object to be treated is eluted with the free acid in the treatment solution, and the pH rises during the elution, and in the case of zinc-based plated steel sheets, zinc phosphate (Hopeite) is used. In the case of cold-rolled steel sheets, crystals of zinc iron phosphate (Phosphophyllite) are precipitated on the surface of the workpiece, but in the case of aluminum alloy sheets, Because a passivation film is formed, it is difficult to etch uniformly.
アル ミ ニウ ム合金板のエ ッ チ ング性を改善する には、 リ ン酸塩処理液と反応性の高い亜鉛をアル ミ ニ ウ ム合金板中 に含有させる方法、 亜鉛でアル ミ ニウ ム合金板の表面を被 覆する方法な どがあ る が、 前者の方法の場合、 亜鉛が ひ — In order to improve the etching properties of aluminum alloy sheets, a method of incorporating zinc, which is highly reactive with the phosphating solution, into the aluminum alloy sheets, using zinc to remove aluminum There are methods such as coating the surface of the alloy plate. In the case of the former method, zinc is used.
Λ 1 の結晶粒界に偏析する傾向があ る ため、 微細かつ緻密 な リ ン酸塩結晶が表面に析出 しない こ と が判明 した。 一方、 後者の方法によれば、 均一かつ緻密な結晶が表面に析出す るが、 リ ン酸塩層と下地アル ミ ニ ウ ム台金板 と の間に A 1 よ り耐食性の劣る亜鉛被覆層が存在する ため、 電着塗装後 に塗膜下の腐食が著 し く 発生 し易 く な り 、 耐食性が実用上 非常に不安定であ る こ とが判明 した。 そ こ で、 本発明では、 上記のよ う に、 A 1 — Z n 合金をアル ミ ニウ ム合金板の表 面にめっ き したのであ る。 It was found that fine and dense phosphate crystals did not precipitate on the surface because of the tendency to segregate at the grain boundaries of No. 1. On the other hand, according to the latter method, uniform and dense crystals are precipitated on the surface, but zinc coating, which has lower corrosion resistance than A1, is provided between the phosphate layer and the base aluminum base plate. Since the layer was present, it was found that corrosion under the coating film was liable to occur significantly after the electrodeposition coating, and that the corrosion resistance was extremely unstable in practice. Thus, in the present invention, as described above, the A 1 —Zn alloy is plated on the surface of the aluminum alloy plate.
図面の簡単な説明 W 11 78 BRIEF DESCRIPTION OF THE FIGURES W 11 78
- 4 - 図 1 は、 アル ミ ニウ ム合金板にめ "？ き した A l — Z n合 金の Z n 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。  -4-Fig. 1 is a graph showing the relationship between the Zn content of Al-Zn alloy and its phosphate treatment and corrosion resistance after painting on aluminum alloy sheets. is there.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
図 1 は、 Z n 含有率の異なった A 1 — Z n合金めつきを  Figure 1 shows the plating of A 1 —Zn alloys with different Zn content.
5 g Zm 2施したアル ミ ニウ ム合金板 （日本工業規格 5 0 Aluminum alloy plate with 5 g Zm 2 (Japanese Industrial Standard 50
5 2、 0材、 板厚 1 . 0 m m ) の リ ン酸塩処理性と電着塗 装後の耐食性 （ク ロ スカ ツ 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、 A I 一 Z n 合金の Z n 含有率が  52, 0 material, sheet thickness of 1.0 mm) showed a phosphate treatment property and corrosion resistance after electrodeposition coating (large and small width of the coating film from the cross cut part). But the AI-Zn alloy has a higher Zn content.
3 mass%以上である と、 リ ン酸塩処理性が良好になる こ と を示-している。 Z n 含有率が 3 raass%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  It is shown that when the content is 3 mass% or more, the phosphate treatment property is improved. If the Zn content is less than 3 raass%, uniform phosphate crystals do not precipitate due to the phosphate treatment solution.
応性が良好な Z n量が少ないこ とに起因 している。  This is due to the small amount of Zn that has good responsiveness.
—方、 図 1 は、 Z n含有率が 5 0 mass%を超える と、 電 着塗装後の耐食性が急激に低下する こ とを示しているが、 これは、 リ ン酸塩層の下側に Z n 含有率の高い Λ 1 - Z n 合金めつ 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、 A 1 — Z n合金めつ きは、 Z n含有率を 3 . 0〜 5 0 mass%にする こ とが必要  On the other hand, Fig. 1 shows that when the Zn content exceeds 50 mass%, the corrosion resistance after electrodeposition coating sharply decreases. This is because the Λ1-Zn alloy plating layer, which has a high Zn content, exists selectively in this layer. Therefore, in the case of A 1 -Zn alloy, it is necessary to set the Zn content to 3.0 to 50 mass%.
で、 好ま し く は 5 . 0〜 3 0 mass である といえる。  Therefore, it can be said that it is preferably 5.0 to 30 mass.
A 1 一 Z n合金めつ 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 き付着量を片面当た り  In order to improve the phosphate treatment of aluminum alloy sheets by A1-Zn alloy plating, the amount of plating must be applied to one side.
0. 2 gZ m 2以上にする必要がある。 0 . 2 g Z m 2未満で It must be 0.2 gZ m 2 or more. Less than 0.2 g Z m 2
ある と、 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, 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 も片面当た り 1 0 g m 2 で十分であ る。 In some cases, the surface cannot be completely covered, resulting in non-uniform phosphate crystals. On the other hand, with plating, even if the amount The phosphate treatability does not change, but increasing it too much is economically disadvantageous, so at most 10 gm 2 per side is sufficient.
A 1 — Z n合金め つ き は、 Z nが偏析せず、 Λ 1 中 に Z n力 ミ ク ロ的に均一に分散 した ものにする のが好ま しい。 かかる A 1 — Z n -合金め つ き は、 常温型溶融塩浴を用 いる 電気め つ き方法、 例えば、 塩化アル ミ ニ ウ ム と有機系窒素 含有ォニ ゥ ム塩化物 とか らな る溶融塩浴に塩化亜鉛を添加 した浴を甩いれば可能であ る。 ま た、 純 Λ 1 浴 と純 Z n浴 とを並べて配置 して、 両浴か ら Λ 1 と Z n と を同時に蒸着 する電子線加熱型蒸着め つ き 、 イ オ ンプ レ ー テ ィ ン グ、 ィ オ ンスパ ッ タ リ ング等の真空め つ き で行 っ て も よ い。 こ れ らのめつ き方法に よれば、 溶融め つ き の よ う に  The A 1 —Zn alloy preferably has a structure in which Zn does not segregate and is uniformly dispersed microscopically in Zn force. Such A 1 -Zn-alloy plating consists of an electroplating method using a room-temperature molten salt bath, for example, aluminum chloride and organic nitrogen-containing onium chloride. This is possible if a bath in which zinc chloride is added to the molten salt bath is used. An electron beam heating type vapor deposition method in which a pure bath 1 and a pure Zn bath are arranged side by side and vapor deposition of bath 1 and Zn simultaneously from both baths is performed. It may be carried out by vacuuming such as ring or ion sputtering ring. According to these mounting methods, like the melting method
Z nの偏析が起 こ らず、 溶融め つ き の場台 よ り Z nがめ つ き層中に均一に分散 した A 1 — Z n合金め つ き を施す こ と . ができ る。  The segregation of Zn does not occur, and A1-Zn alloy plating in which Zn is uniformly dispersed in the plating layer can be performed from the melting plate.
アル ミ ニウ ム合金板への A 1 — Z n合金め つ き は、 片面 だけに塗装を施すのであれば、 片面だけでよ いが、 両面に 塗装を施す場合は両面に施す。  The A 1 —Zn alloy on aluminum alloy plate may be applied to only one side if only one side is painted, but it is applied to both sides if both sides are painted.
実施例 1  Example 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 (日本工業規格 6 0 6 1、 0材、 板厚 1. 2 mm) に次の 条件で電解活性化処理、 電気 A 1 一 Z n合金め つ き を片面 に施 して、 Z n含有率およ びめ つ き 付着量の異な る A 1 —Z n合金め つ き アル ミ ニウ ム合金板を作製 した。 なお、 曰 本工業規格 6 0 6 1 の組成は次の通り である Aluminum alloy plate (Japanese Industrial Standard 600,0 material, plate thickness 1.2 mm), which has been subjected to electrolytic degreasing and pickling by a conventional method, is subjected to electrolytic activation treatment under the following conditions. An aluminum alloy plate with an A 1 -Zn alloy having different Zn content and adhesion was prepared by applying one Zn alloy to one surface. In addition, The composition of this industrial standard 6006 is as follows
成 分 S i F e C u M n M g C r 残部 raass% 0.65 0.48 0.30 0.06 0.93 0.18 A 1 Ingredient S i Fe C u M n M g C r Residual raass% 0.65 0.48 0.30 0.06 0.93 0.18 A 1
( 1 ) 電解活性化処理 (1) Electrolytic activation treatment
(浴組成》  (Bath composition)
ェチルイ ミ ダゾ リ ゥ ム ク ロライ ド 5 0 7 g / 1 塩化アル ミ ニウ ム 8 6 5 g Ζ 1 (処理条件）  Ethylimidazonium chloride 507 g / 1 Aluminum chloride 865 g Ζ 1 (processing conditions)
浴温 8 0 °C 電流密度 0.5 k A m 2 処理時間 2 0秒Bath temperature 80 ° C Current density 0.5 kA m 2 Processing time 20 seconds
( 2 ) 電気 A l — Z n合金めつ き (2) Electric Al-Zn alloy
(浴組成）  (Bath composition)
ェチノレイ ミ ダゾ リ ウ ム ク ロ ライ ド 5 ひ 7 g 1 塩化アル ミ ニウ ム 8 6 5 g X 1 塩化亚鉛 0. ： -〜 1 5 gノ 1 Etinorei midazomium chloride 5 pcs 7 g 1 aluminum chloride 8 6 5 g X 1 lead chloride 0.:-~ 15 g no 1
(めっ き条件） (Making conditions)
浴温 8 0  Bath temperature 8 0
めっき液流速 1. 0 m Z秒 電流密度 1.0〜 6. 0 k A m 2 次に、 こ の A 】 一 Z n合金めつ きアルミニウム合金板の リ ン酸塩処理性と塗装後耐食性とを次の要領で調査 した。 この結果を第 1表に示す。 なお、 比較例 N o . 1 7はジ ン ケー ト処理によ り アル ミ ニウ ム合金板上に亜鉛を被覆 した もので、 比較例 N o . 1 8は Λ 1 一 Z n合金めつ きを施さ ないアル ミ ニウ ム合金板であ る。 Plating solution flow rate 1. 0 m Z s current density 1.0~ 6. 0 k A m 2 Next, A in this] and re emissions salt treatability and corrosion resistance after coating one Z n alloy dark-out aluminum alloy plate The investigation was conducted as follows. Table 1 shows the results. Comparative Example No. 17 is an aluminum alloy plate coated with zinc by a zincate treatment, and Comparative Example No. 18 is a Zn alloy alloy. Given No aluminum alloy plate.
( 3 ) リ ン酸塩処理性  (3) Phosphate treatment
A 1 一 Z n 合金め つ き アル ミ ニ ウ ム台金扳を 4 0 °Cの脱 脂液 （曰本国に存在の 日本ペイ ン ト株式会社製の商品名 リ ド リ ン 1 0 8 9 を使用 した） に 1 5 秒間浸漬 して脱脂 した 後、 4 0 °Cの冷延鋼板およ び亜鉛系表面処理鋼板用 リ ン酸 塩処理剤 （日本ペイ ン ト株式会社製の商品名 S D 5 0 0 0 の標準濃度液を使用 した） に 2 分間浸漬する こ と に よ り リ ン酸塩処理を施 して、 表 ¾に析出 した リ ン酸塩皮膜の リ ン 酸塩結晶の析出形態を 1 0 0 0 掊の走査型電子顕微鏡で観 察 し、 以下の 3 水準で評価 した。  A 1-Zn alloy-coated aluminum base plate was degreased at 40 ° C (the trade name of Nippon Paint Co., Ltd., which is located in Japan, Degreased by immersion for 15 seconds in cold-rolled steel sheets and zinc-based surface-treated steel sheets at 40 ° C (product name SD manufactured by Nippon Paint Co., Ltd.). (A standard concentration solution of 500.000) was used for 2 minutes to perform the phosphate treatment, and the precipitation of phosphate crystals on the phosphate film deposited in Table 2 The morphology was observed with a scanning electron microscope of 100 mm and evaluated on the following three levels.
〇 緻密で均一な リ ン酸塩結晶が析出  〇 Precise and uniform precipitation of phosphate crystals
Δ 粗 く 、 不均一な リ ン酸塩結晶が析出  Δ Coarse and uneven phosphate crystals precipitate
X リ ン酸塩結晶がほ とん ど析出せず  X Phosphate crystals hardly precipitate
( 4 ) 塗装後耐食性  (4) Corrosion resistance after painting
上記方法で リ ン酸塩処理 した A 1 一 Z n 台金め つ き アル ミ ニゥ ム合金板にエポキ シ系樹脂系カ チオ ン型電着塗料 (日本ペイ ン ト株式会社製の商品名パ ワ ー ト ッ プ U 8 0 を 標準塗装条件で塗装 した） を 2 0 電着塗装 して、 塗膜 にめ つ き層に達する ク ロ スカ ツ ト を入れた後、 複合腐食試 験を実施 した。 複合腐食試験は 日本工業規格 Z 2 3 7 1 に準 じた塩水噴霧試験を 1 時間実施 して、 乾燥 した後湿潤 試験 （ 5 0 °C、 相対湿度 9 8 % ) を 7 時間実施 して、 再度 乾燥するェ稈を 1 サイ ク ルとするサイ ク ル試験を 5 0 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 An epoxy resin-based cation-type electrodeposition paint (trade name of Nippon Paint Co., Ltd.) is applied to an aluminum alloy plate that has been treated with phosphate by the above method. (Wattop U80 was coated under standard coating conditions) was subjected to 20 electrodeposition coating, and a cross-corrosion test was carried out after inserting the crosscuts reaching the coating layer on the coating film. did. The combined corrosion test is performed by conducting a salt spray test in accordance with Japanese Industrial Standards Z2371 for 1 hour, and after drying, a wet test (50 ° C, relative humidity 9.8%) for 7 hours. Perform 50 cycles of the cycle test with one cycle of the culm to be dried again, and measure the maximum coating film width from the crosscut. Set
第 1 表  Table 1
Figure imgf000010_0001
Figure imgf000010_0001
実施例 2  Example 2
常法によ り脱脂 したアルミ ニウム合金板 （日本工業規格 Aluminum alloy plate degreased by standard method (Japanese Industrial Standards)
5 0 5 2、 0材、 板厚 1 . 2 mm) を真空中で 2 0 0 °Cま で加熱 した後、 次の条件でイ オンビーム活性化処理、 蒸着 A 1 — Z n 合金めつ きを片面に施 して、 Z n含有率および め っ き付着量の異な る A 1 — Z n 合金め つ き アル ミ ニ ウ ム 合金板を作製 し、 実施例 1 と同要領で リ ン酸塩処理性、 塗 装後耐食性を調査 した。 第 2表に こ の結果を示す。 なお、 比較例 N o . 3 7 は亜鉛だけを蒸着め つ き した も のであ り 、 ま た、 日本工業規格 5 0 5 2 のアル ミ ニウ ム合金板組成は 次の通 り であ る。 (5052, 0 material, thickness 1.2 mm) is heated to 200 ° C in a vacuum, then ion beam activated and deposited under the following conditions. On one side to determine the Zn content and An aluminum alloy plate with an A 1 —Zn alloy having a different coating weight was prepared, and the phosphatability and the post-coating corrosion resistance were investigated in the same manner as in Example 1. Table 2 shows the results. In Comparative Example No. 37, only zinc was vapor-deposited, and the composition of an aluminum alloy plate according to Japanese Industrial Standard 5052 is as follows.
成 分 S i F e C u M n M g C r 残部 mass% 0.05 0.25 0.03 0.03 2.60 0.21 A 1 ( 1 ) ィ ォ ン ビー ム活性化処理  Ingredient S i Fe C u M n M g C r Residual mass% 0.05 0.25 0.03 0.03 2.60 0.21 A 1 (1) ion beam activation treatment
真空度 1 x 1 0 "ZP a Vacuum 1 x 10 " Z Pa
A r イ オ ン照射量 5 C m  A r Ion irradiation dose 5 C m
( 2 ) 蒸着 A 1 一 Z n 合金め つ き  (2) Evaporation A 1 -Zn alloy
真空度 1 x 1 0 - 2 P a め っ き方式 純 A 1 浴、 純 Z n 浴並置方式 蒸着浴の加熱方式 電子 ビー ム加熱 （スキ ャ ニ ン グ） Vacuum 1 x 1 0 - 2 P a Ki Tsu Me scheme pure A 1 bath, heating system electron beam heating of the pure Z n bath juxtaposed manner deposition bath (liked catcher d in g)
Figure imgf000011_0001
第 2表
Figure imgf000011_0001
Table 2
Figure imgf000012_0001
Figure imgf000012_0001
産業上の利用可能性  Industrial applicability
以上のよ う に、 本発明の A 】 一 Z n合金めつ きアルミ 二 ゥム合金板は、 -リ ン酸塩処理剤と して、 鉄鋼材料の塗装前 処理に使用する ものを使用 しても、 リ ン酸塩処理性、 塗装 後耐食性に優れているので、 鉄鋼材料とアルミ ニウム合金 板とを使用 し、 、つ、 リ ン酸塩処理剤に鉄鋼材料甩の もの を使用 しなければな らない用途、 例えば、 自動車、 オー ト バイ 、 飛行機、 船な どに も使用でき る。 As described above, the aluminum alloy sheet for the A] -Zn alloy according to the present invention uses, as the phosphate treatment agent, the one used for the pre-coating treatment of the steel material. However, since it is excellent in phosphatability and corrosion resistance after painting, it uses steel material and aluminum alloy plate, and the phosphating agent is steel material 甩 It can be used in applications where it must be used, such as cars, motorcycles, airplanes, and ships.

Claims

請 求 の 範 囲 The scope of the claims
1. アルミ ニゥム合金板の少な く と も片面に Z n含有率が 1. Zn content on at least one side of aluminum alloy plate
3. 0〜 5 0 mass%の A 1 — Z n合金めつ きを片面当た り 0. 2〜： L 0 g Zm 2施 したアルミ ニウム合金板。 3. 0~ 5 0 mass% of A 1 - Z n alloy dark-out on one side per Ri 0. 2~: L 0 g Zm 2 facilities were aluminum alloy plate.
2. Λ 1 — Z n合金めつ きの Z n含有率力 5. ひ〜 3 0 mass%である請求の範囲 1 に記載のアルミ ニウ ム合金板 〜 2. Λ 1 —Zn content ratio power of Zn alloy 5. Aluminum alloy plate according to claim 1, which has a mass of 30 to 30 mass%.
3. A 1 — Z n合金めつ きが電気めつ きで施 した ものであ る請求の範匪 1 に記載のアル ミ ニゥム合金板。 3. The aluminum alloy sheet according to claim 1, wherein the A 1 -Zn alloy plating is applied by electric plating.
4. A 1 — Z n合金めつ きが真空めつ きで施 した ものであ ひ る請求の範囲 1 に記載のアル ミ ニウム合金板。  4. The aluminum alloy plate according to claim 1, wherein the A 1 —Zn alloy plating is applied by vacuum plating.
PCT/JP1992/001530 1991-11-29 1992-11-24 Aluminum alloy plate WO1993011278A1 (en)

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Cited By (2)

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CN104562098A (en) * 2014-12-30 2015-04-29 沈阳理工大学 Method for synthesizing titanium-nickel alloy layer through electron beam
CN106947983A (en) * 2017-03-31 2017-07-14 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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JP2016000838A (en) * 2012-10-15 2016-01-07 住友電気工業株式会社 Aluminum film, aluminum film formed body and production method of aluminum film

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JPS63153262A (en) * 1986-12-17 1988-06-25 Kobe Steel Ltd Al or al alloy sheet coated with zn-base plating by vapor deposition
JPS63166964A (en) * 1986-12-27 1988-07-11 Kobe Steel Ltd Zinc galvanized aluminum or aluminum alloyed plate
JPS63174748A (en) * 1987-01-14 1988-07-19 Sumitomo Metal Ind Ltd Continuous wire drawing method for Ti and Ti alloy wire for cold forging
JPS63174749A (en) * 1987-01-14 1988-07-19 Sumitomo Metal Ind Ltd Lubrication treatment method for Ti and Ti alloy materials for presses
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JPS61157693A (en) * 1984-12-28 1986-07-17 Sumitomo Metal Ind Ltd Al plate having superior suitability to phosphating
JPS63153262A (en) * 1986-12-17 1988-06-25 Kobe Steel Ltd Al or al alloy sheet coated with zn-base plating by vapor deposition
JPS63166964A (en) * 1986-12-27 1988-07-11 Kobe Steel Ltd Zinc galvanized aluminum or aluminum alloyed plate
JPS63174748A (en) * 1987-01-14 1988-07-19 Sumitomo Metal Ind Ltd Continuous wire drawing method for Ti and Ti alloy wire for cold forging
JPS63174749A (en) * 1987-01-14 1988-07-19 Sumitomo Metal Ind Ltd Lubrication treatment method for Ti and Ti alloy materials for presses
JPH05825B2 (en) * 1988-11-28 1993-01-06 Ee Yuu Ii Kenkyusho Kk

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CN104562098A (en) * 2014-12-30 2015-04-29 沈阳理工大学 Method for synthesizing titanium-nickel alloy layer through electron beam
CN106947983A (en) * 2017-03-31 2017-07-14 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
CN106947983B (en) * 2017-03-31 2019-06-18 湖南金磐新材料科技有限公司 Intercalated zinc-aluminum alloy powder and zinc-aluminum synergistic anti-corrosion coating prepared therefrom and method

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