JPH081857A - Aluminum laminate for drawing - Google Patents
Aluminum laminate for drawingInfo
- Publication number
- JPH081857A JPH081857A JP6144968A JP14496894A JPH081857A JP H081857 A JPH081857 A JP H081857A JP 6144968 A JP6144968 A JP 6144968A JP 14496894 A JP14496894 A JP 14496894A JP H081857 A JPH081857 A JP H081857A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- resin layer
- aluminum
- aluminum laminate
- polyamide resin
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Shaping Metal By Deep-Drawing, Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、絞り加工やかしめ加工
等の二次加工時において、層間剥離や樹脂層のクラック
等の不良が起こりにくい、層間の密着性に優れたアルミ
ニウム板と特定のポリアミド樹脂層からなる絞り加工用
積層体に係り、特にアルミ電解コンデンサを構成するコ
ンデンサ素子を収納するための外装用容器等に好適に使
用できる絞り加工用アルミニウム積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an aluminum plate having excellent adhesion between layers, which is less likely to cause defects such as delamination and cracks in resin layers during secondary processing such as drawing and crimping. The present invention relates to a drawing laminated body including a polyamide resin layer, and particularly relates to a drawing aluminum laminated body that can be suitably used as an outer container or the like for housing a capacitor element that constitutes an aluminum electrolytic capacitor.
【０００２】[0002]
【従来技術とその課題】アルミニウムの防食や電気絶縁
等を目的として、アルミニウム板に接着剤等を介在させ
て、各種の合成樹脂フイルムを設けたアルミニウム積層
体が種々の分野で使用され、合成樹脂フイルムとしては
耐熱性や成形性に優れたナイロン６やナイロン６６等の
ポリアミド系樹脂フイルムの使用が知られている。2. Description of the Related Art Aluminum laminates provided with various synthetic resin films by interposing an adhesive agent on an aluminum plate for the purpose of preventing corrosion of aluminum and electrical insulation are used in various fields. As a film, it is known to use a polyamide resin film such as nylon 6 or nylon 66 having excellent heat resistance and moldability.
【０００３】上記の積層体においては、その最終用途に
応じて所望の形状、例えば有底の円筒容器形状に冷間絞
り加工したり、絞り加工後さらに、かしめ機によりかし
め加工（カーリング）を施すことがなされている。この
ようなアルミニウム積層体の二次加工においては、たと
え絞り加工前の層間の接着強度が良好であっても、深絞
りの程度が大きい冷間加工の場合、樹脂層が破断した
り、クラックが発生する等のトラブルが起こりやすいと
いう問題があった。The above-mentioned laminated body is subjected to cold drawing into a desired shape, for example, a cylindrical container shape having a bottom, or after drawing, further subjected to caulking by a caulking machine (curling). Things have been done. In the secondary processing of such an aluminum laminate, even if the adhesion strength between layers before drawing is good, in the case of cold working with a large degree of deep drawing, the resin layer breaks or cracks occur. There was a problem that troubles such as occurrences were likely to occur.
【０００４】[0004]
【課題を解決するための手段】本発明はアルミニウム板
と特定のポリアミド系樹脂からなる積層体を使用するこ
とにより、上記課題を解消できることを見出したもので
ある。請求項１の発明は、アルミニウム板の少なくとも
片面に球晶の最大径が１０μｍ以下であるポリアミド系
樹脂層を積層したことを特徴とする絞り加工用アルミニ
ウム積層体にある。The present invention has found that the above problems can be solved by using a laminate comprising an aluminum plate and a specific polyamide resin. The invention of claim 1 is the aluminum laminate for drawing, wherein a polyamide resin layer having a maximum spherulite diameter of 10 μm or less is laminated on at least one surface of an aluminum plate.
【０００５】上記発明のアルミニウム積層体では、アル
ミニウム板に特定のポリアミド系樹脂層を積層するとこ
ろに特徴を有するものであり、アルミニウム板として
は、純度９５％以上のアルミニウム単体やアルミニウム
とマグネシウム等との合金系のもので厚みが０．３〜
０．４ｍｍ程度のものが好適に使用でき、さらに表面を
リン酸−クロム酸塩等による化成処理や電解エッチング
等のエッチング処理を施したものも使用できる。The aluminum laminate of the present invention is characterized in that a specific polyamide resin layer is laminated on an aluminum plate. As the aluminum plate, a simple substance of aluminum having a purity of 95% or more, aluminum and magnesium, or the like is used. The alloy-based alloy with a thickness of 0.3-
Those having a thickness of about 0.4 mm can be preferably used, and those having the surface subjected to chemical conversion treatment with phosphoric acid-chromate or the like or etching treatment such as electrolytic etching can also be used.
【０００６】このアルミニウム板には、球晶の最大径が
１０μｍ以下であるポリアミド系樹脂層を被覆する必要
がある。ポリアミド系樹脂層で使用するポリアミド系樹
脂としては、通常のナイロン６、ナイロン６６や共重合
樹脂が使用できる。球晶の最大径が１０μｍを超えるも
のでは、深絞り加工により樹脂層が剥離しやすいという
問題がある。球晶の大きさは、偏光顕微鏡，走査型電子
顕微鏡やＸ線回析等により測定すればよい。The aluminum plate must be coated with a polyamide resin layer having a maximum spherulite diameter of 10 μm or less. As the polyamide resin used in the polyamide resin layer, ordinary nylon 6, nylon 66 or copolymer resin can be used. If the maximum diameter of the spherulites exceeds 10 μm, there is a problem that the resin layer is easily peeled off by deep drawing. The size of the spherulites may be measured by a polarization microscope, a scanning electron microscope, X-ray diffraction or the like.
【０００７】このような球晶は、アルミニウム板上にポ
リアミド系樹脂を溶融圧着する際に、冷却速度が遅く徐
冷になると発生し、冷却速度が遅くなる程、その最大径
が大きくなる傾向にある。そこで、球晶の最大径を小さ
くする技術として冷却条件を急冷にする方法がなされ、
急冷の方法とし水冷法があるが、設備が複雑になるとい
う問題やコストがかかるなどの問題がある。また、ポリ
アミド樹脂は吸湿性あるために、水冷は好ましくなかっ
た。Such spherulites are generated when the polyamide resin is melt-pressed onto an aluminum plate and the cooling rate is slow and gradually cooled. The slower the cooling rate, the larger the maximum diameter thereof tends to be. is there. Therefore, as a technique to reduce the maximum diameter of spherulites, a method of rapidly cooling the cooling conditions is made,
Although there is a water cooling method as a rapid cooling method, there are problems such as complicated equipment and high cost. Further, water cooling is not preferable because the polyamide resin has hygroscopicity.
【０００８】そこで、請求項２の発明は請求項１のポリ
アミド系樹脂層に使用するポリアミド系樹脂に特定量の
酸化防止剤を添加することにより、結晶化速度が速くな
り、球晶の成長が抑制されることを見出したものであ
り、上記の水冷用の設備は不必要になる。酸化防止剤と
しては、ハロゲン化銅、芳香族アミン等のアミン系酸化
防止剤、トリエチレングリコールビス［３−（３−ｔ−
ブチル−５メチル−４−ヒドロキシフェニル）プロピオ
ネート］等のフェノール系酸化防止剤等が挙げられる
が、球晶の成長抑制効果の点からフェノール系酸化防止
剤の使用が好ましい。酸化防止剤の添加量としては、
０．５重量％〜２．５重量％の範囲とする必要があり、
０．５重量％未満では球晶の成長抑制効果が少なく、
２．５重量％を越えると製膜加工性に劣るという問題が
ある。Therefore, in the invention of claim 2, by adding a specific amount of the antioxidant to the polyamide resin used in the polyamide resin layer of claim 1, the crystallization rate is increased and the growth of spherulites is increased. It has been found that it is suppressed, and the above-mentioned water cooling equipment is unnecessary. Examples of the antioxidant include copper halides, amine-based antioxidants such as aromatic amines, triethylene glycol bis [3- (3-t-
Examples thereof include phenolic antioxidants such as butyl-5-methyl-4-hydroxyphenyl) propionate, and the use of a phenolic antioxidant is preferable from the viewpoint of the effect of suppressing the growth of spherulites. The amount of antioxidant added is
It must be in the range of 0.5% by weight to 2.5% by weight,
If it is less than 0.5% by weight, the effect of suppressing the growth of spherulites is small,
If it exceeds 2.5% by weight, there is a problem that the film forming processability is poor.
【０００９】上記請求項１及び２のポリアミド系樹脂層
は、単層でも樹脂の種類を変えて２層以上の多層でもよ
く、球晶の最大径が１０μｍ以下としたポリアミド系樹
脂層を全層としてもよいが、最外層のみとしてもよく、
最外層のみに酸化防止剤を添加すればよい。The polyamide-based resin layer of claims 1 and 2 may be a single layer or a multilayer of two or more layers by changing the type of resin, and all the polyamide-based resin layers having a maximum spherulite diameter of 10 μm or less. , But may be only the outermost layer,
The antioxidant may be added only to the outermost layer.
【００１０】また、請求項３の発明はアルミニウム板の
少なくとも片面に、ポリアミド系樹脂層を介してポリア
ミド系ポリマーアロイ層を積層したことを特徴とする絞
り加工用アルミニウム積層体にある。使用するアルミニ
ウム板や、ポリアミド系樹脂層は上述した請求項１の内
容と同一であり、ポリアミド系ポリマーアロイとして
は、ナイロン６６を主体に変成ポリオレフィン等を溶融
ブレンドしたポリマーアロイが挙げられる。ここで変成
ポリオレフィンとしては、エチレン−プロピレン−ジエ
ン共重合体に無水マレイン酸をグラフトした、変成エチ
レン−プロピレン−ジエン共重合体や、エチレン−メタ
アクリル酸共重合体をＮａ、Ｚｎ、Ｍｇ等でイオン化し
たアイオノマー樹脂等が挙げられる。A third aspect of the present invention is an aluminum laminate for drawing, wherein a polyamide polymer alloy layer is laminated on at least one surface of an aluminum plate with a polyamide resin layer interposed therebetween. The aluminum plate and the polyamide resin layer to be used are the same as those in the above-mentioned claim 1, and as the polyamide polymer alloy, a polymer alloy mainly composed of nylon 66 and melt-blended with a modified polyolefin or the like can be mentioned. As the modified polyolefin, ethylene-propylene-diene copolymer is grafted with maleic anhydride, modified ethylene-propylene-diene copolymer or ethylene-methacrylic acid copolymer is Na, Zn, Mg or the like. Examples thereof include ionized ionomer resins.
【００１１】アルミニウム板に上記ポリアミド系樹脂層
とポリアミド系ポリマーアロイ層を被覆する方法として
は、種々の方法が適用できるが、アルミニウム板に各種
接着剤を塗布し焼付けた後、ポリアミド樹脂の溶融温度
以上に加熱し、ポリアミド系樹脂フイルムとポリアミド
系ポリマーアロイフイルムを二層口金を有する押出機に
より溶融押出し積層する方法が生産性が良好で好まし
い。以下、本発明を実施例により説明する。Various methods can be applied to the aluminum plate for coating the above-mentioned polyamide resin layer and polyamide polymer alloy layer. After the aluminum plate is coated with various adhesives and baked, the melting temperature of the polyamide resin is changed. The method of heating and heating and melting and laminating the polyamide resin film and the polyamide polymer alloy film with an extruder having a two-layer die is preferable because of good productivity. Hereinafter, the present invention will be described with reference to examples.
【００１２】[0012]
実施例１ 厚みが０．３ｍｍのアルミニウム板（１１００材）を使
用し、表面をクロメート処理した。当該クロメート処理
層の表面にビスフェノール型エポキシ樹脂（分子量４０
０、エポキシ当量２００）を塗布した後、ナイロン６６
（１０μｍ、透明層）／ナイロン６６（２０μｍ、着色
層）／ナイロン６６（１０μｍ、透明層）からなる多層
のポリアミド樹脂層を溶融ラミネートした。Example 1 An aluminum plate (1100 material) having a thickness of 0.3 mm was used, and the surface was chromated. Bisphenol type epoxy resin (molecular weight 40
Nylon 66 after applying 0, epoxy equivalent 200)
A multilayer polyamide resin layer composed of (10 μm, transparent layer) / nylon 66 (20 μm, colored layer) / nylon 66 (10 μm, transparent layer) was melt-laminated.
【００１３】ここで、最外層のナイロン６６に酸化防止
剤（フェノール系酸化防止剤、イルガノックスＭＤ１０
２４ 日本チバガイギー（株）製）を下記内容で添加し
て各積層体を得た。得られた各試料を用いて、絞り加工
機により直径４ｍｍ、深さが４８ｍｍの有底円筒形の容
器を樹脂層が外側になるように絞り加工した。その際の
樹脂層の状態を目視観察し絞り加工性を評価した。最外
層の球晶最大径は走査型電子顕微鏡により測定した。Here, an antioxidant (phenolic antioxidant, Irganox MD10 is added to the outermost layer of nylon 66.
24 Japan Ciba Geigy Co., Ltd.) was added in the following content to obtain each laminate. Using each of the obtained samples, a bottomed cylindrical container having a diameter of 4 mm and a depth of 48 mm was drawn by a drawing machine so that the resin layer was on the outside. The state of the resin layer at that time was visually observed to evaluate the drawability. The maximum diameter of the spherulites in the outermost layer was measured by a scanning electron microscope.
【００１４】[0014]
【表１】 表１から最外層への酸化防止剤がなく、球晶最大径が１
０μｍを越えている試料１については絞り加工性が劣る
ことが判る。これに対して酸化防止剤を添加し、球晶最
大径が１０μｍ以下の試料２、３については絞り加工性
に優れていることが判る。[Table 1] From Table 1, there is no antioxidant in the outermost layer and the maximum spherulite diameter is 1
It can be seen that Sample 1 having a diameter of more than 0 μm has poor drawability. On the other hand, it is understood that Samples 2 and 3 in which an antioxidant is added and the maximum spherulite diameter is 10 μm or less are excellent in drawability.
【００１５】実施例２ 実施例１に使用した樹脂層の構成をポリアミド系ポリマ
ーアロイ（１０μｍ、ザイテルＳＴ−８０１ デュポン
・ジャパン（株）製）／ナイロン６６（２０μｍ）とし
た以外は実施例１と同一内容で、絞り加工性を評価した
が、クラックの発生等がなく良好であった。Example 2 Example 1 except that the composition of the resin layer used in Example 1 was polyamide polymer alloy (10 μm, Zytel ST-801 DuPont Japan KK) / nylon 66 (20 μm). The drawability was evaluated with the same content, and it was good with no occurrence of cracks.
【００１６】[0016]
【発明の効果】以上説明したように、本発明のアルミニ
ウム積層体によれば、絞り加工性等の二次加工性に優れ
ているため生産し易いという利点を有し、コンデンサ外
装容器類等の絞り加工品に好適に使用できる。As described above, according to the aluminum laminate of the present invention, it is easy to produce because it is excellent in the secondary workability such as the drawability, and the aluminum laminated body such as the capacitor outer container is manufactured. It can be suitably used for drawn products.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 5/00 ＫＫＵ Ｃ０８Ｌ 77/00 ＬＲＣ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08K 5/00 KKU C08L 77/00 LRC
Claims (3)
晶の最大径が１０μｍ以下であるポリアミド系樹脂層を
積層したことを特徴とする絞り加工用アルミニウム積層
体。1. An aluminum laminate for drawing, wherein a polyamide resin layer having a maximum spherulite diameter of 10 μm or less is laminated on at least one surface of an aluminum plate.
化防止剤を０．５重量％〜２．５重量％の範囲で添加し
てなることを特徴とする請求項１記載の絞り加工用アル
ミニウム積層体。2. The aluminum laminate for drawing according to claim 1, wherein the polyamide-based resin is obtained by adding an antioxidant to the polyamide resin in the range of 0.5% by weight to 2.5% by weight. .
リアミド系樹脂層を介してポリアミド系ポリマーアロイ
層を積層したことを特徴とする絞り加工用アルミニウム
積層体。3. An aluminum laminate for drawing, wherein a polyamide polymer alloy layer is laminated on at least one side of an aluminum plate with a polyamide resin layer interposed therebetween.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14496894A JP3382014B2 (en) | 1994-06-27 | 1994-06-27 | Aluminum laminate for drawing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14496894A JP3382014B2 (en) | 1994-06-27 | 1994-06-27 | Aluminum laminate for drawing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH081857A true JPH081857A (en) | 1996-01-09 |
| JP3382014B2 JP3382014B2 (en) | 2003-03-04 |
Family
ID=15374388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14496894A Expired - Lifetime JP3382014B2 (en) | 1994-06-27 | 1994-06-27 | Aluminum laminate for drawing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3382014B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11245330A (en) * | 1998-03-02 | 1999-09-14 | Toyo Kohan Co Ltd | Manufacture of polyamide resin-coated metal plate with excellent processing adhesion, polyamide resin-coated metal plate and container using it |
| JP2001129923A (en) * | 1999-11-09 | 2001-05-15 | Mitsubishi Plastics Ind Ltd | Polyamide resin laminated metal panel and manufacturing method of exterior container for electrolytic capacitor |
| US7022391B2 (en) | 2000-10-13 | 2006-04-04 | Showa Denko Packaging Co. | Packaging material for electronic-part case, and others |
-
1994
- 1994-06-27 JP JP14496894A patent/JP3382014B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11245330A (en) * | 1998-03-02 | 1999-09-14 | Toyo Kohan Co Ltd | Manufacture of polyamide resin-coated metal plate with excellent processing adhesion, polyamide resin-coated metal plate and container using it |
| JP2001129923A (en) * | 1999-11-09 | 2001-05-15 | Mitsubishi Plastics Ind Ltd | Polyamide resin laminated metal panel and manufacturing method of exterior container for electrolytic capacitor |
| US7022391B2 (en) | 2000-10-13 | 2006-04-04 | Showa Denko Packaging Co. | Packaging material for electronic-part case, and others |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3382014B2 (en) | 2003-03-04 |
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