JP2013007092A - Multilayer-plated aluminum or aluminum alloy foil - Google Patents

Multilayer-plated aluminum or aluminum alloy foil Download PDF

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JP2013007092A
JP2013007092A JP2011139998A JP2011139998A JP2013007092A JP 2013007092 A JP2013007092 A JP 2013007092A JP 2011139998 A JP2011139998 A JP 2011139998A JP 2011139998 A JP2011139998 A JP 2011139998A JP 2013007092 A JP2013007092 A JP 2013007092A
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aluminum
zinc
plating
alloy foil
tin
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JP5977488B2 (en
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Masato Takami
正人 高見
Nobuaki Morioka
伸哲 森岡
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Fukuda Metal Foil and Powder Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To obtain a low-cost, lightweight metal foil that is used as an electromagnetic wave shielding material, a conductive material or a heat conductive material for a radiating substrate, a current collector of an electrode for a secondary battery, an electrode material or an electrical connection material for a printed wiring board, etc., has a high conductivity and a high thermal conductivity and can be mounted and connected by soldering.SOLUTION: The multilayer-plated metal foil comprises an aluminum foil or an aluminum alloy foil of which at least one surface comprises a zinc-immersion plating layer, a nickel-electroplating layer and a tin-electroplating layer that are formed in this order, wherein the zinc-immersion plating layer contains at least one element chosen from Fe, Co, Ni and Cu. The other surface is not subjected to nickel- and tin-electroplating but is roughened by zinc-immersion plating and, if required, is subjected to pickling after the zinc-immersion plating.

Description

本発明は、電気、電子製品に使用される金属材料及びその複合材料に関するものであり、特には電磁波シールド材料や放熱基板用導電材料又は熱伝導材料、二次電池用電極集電体、プリント配線板などの電極材料、電気接続材料として用いられるスズめっき被膜を有するアルミニウム又はアルミニウム合金箔に関するものである。   The present invention relates to a metal material used in electrical and electronic products and a composite material thereof, in particular, an electromagnetic shielding material, a conductive material for heat dissipation substrate or a heat conductive material, an electrode current collector for a secondary battery, and a printed wiring. The present invention relates to an aluminum or aluminum alloy foil having a tin plating film used as an electrode material such as a plate or an electrical connection material.

電磁波シールド材料については通常、銅又は銅合金箔が使われ、これにスズめっきを行うことで耐湿性、耐食性に優れ、さらに、はんだ付け性が良好という特長を持つ材料ができあがる。またこの一方の面に樹脂層又はフィルムを積層した構造が用いられ自動車のワイヤーハーネス等に応用されている（特許文献１）。なお、以前においてはスズめっきではなく、はんだめっきが行われてきた。しかし、2000年頃よりヨーロッパからのELV指令等により、鉛の有害性から鉛を除外し純スズめっきが適用されてきている。   As the electromagnetic shielding material, copper or copper alloy foil is usually used, and by performing tin plating on the foil, a material having excellent moisture resistance and corrosion resistance and good solderability is obtained. Moreover, the structure which laminated | stacked the resin layer or the film on this one surface is used, and it is applied to the wire harness etc. of a motor vehicle (patent document 1). In the past, solder plating has been performed instead of tin plating. However, since around 2000, according to the ELV directive from Europe, etc., pure tin plating has been applied excluding lead from the toxicity of lead.

電磁波シールド材料以外においても放熱基板用導電材料又は熱伝導材料、二次電池用電極集電体、プリント配線板などの電極材料、電気接続材料として銅または銅合金箔が使用されてきた。しかし、貴金属類の価格高騰などが銅にも波及し、価格競争力が無くなってきている。   In addition to the electromagnetic shielding material, copper or copper alloy foil has been used as a conductive material or heat conductive material for a heat radiating substrate, an electrode current collector for a secondary battery, an electrode material such as a printed wiring board, and an electrical connection material. However, the price rise of precious metals has spread to copper, and price competitiveness is disappearing.

本発明は上記銅又は銅合金箔ではなく、その基体の代替材としてアルミニウム又はアルミニウム合金箔を使用してこれにスズめっきをしたことを特徴とする。また、この銅基体部分にアルミニウムを使うことで価格を大幅に低減できるものであり、入手も極めて容易である。さらには、アルミニウムは、銅に対して電気伝導率は約60％とやや劣るものの十分に高く、かつ銅の比重8.96と比較してアルミニウムは2.73と極めて軽量であり、材料部品の軽量化に大いに貢献できる。   The present invention is characterized in that, instead of the above copper or copper alloy foil, aluminum or aluminum alloy foil is used as an alternative material for the substrate and tin is plated thereon. In addition, the use of aluminum for the copper base portion can greatly reduce the price and is extremely easy to obtain. Furthermore, although aluminum has a slightly lower electrical conductivity of about 60% compared to copper, it is sufficiently high, and aluminum is very light at 2.73 compared to the specific gravity of copper of 8.96, greatly reducing the weight of material parts. Can contribute.

しかしながら上記のような優れた特長を持ちながら、アルミニウムは表面に生成する酸化皮膜により、そのままの状態では、はんだ実装、接続が困難な材料であり、このことは、電気、電子製品に使用される金属材料としては致命的な問題であった。このため、その表面に所望の金属めっきを施すことが種々検討されてきたが、アルミニウム材料は金属の一般的な前処理では短時間に生成する酸化被膜によりめっき膜の密着性を確保することが難しく、密着性の良い電気めっきを施すことが困難であるという課題があった。   However, while having excellent features as described above, aluminum is a material that is difficult to solder and connect as it is due to the oxide film formed on the surface, which is used for electrical and electronic products. It was a fatal problem as a metal material. For this reason, various studies have been made to apply a desired metal plating to the surface, but aluminum materials can ensure the adhesion of the plating film by an oxide film generated in a short time in a general pretreatment of metal. There was a problem that it was difficult to apply electroplating with good adhesion.

通常、従来においてはアルミニウムに対してはその表面を2回の亜鉛置換めっき、いわゆるダブルジンケートを行い、Ni−Pの無電解めっきを行い、所望の金属めっきを行うのが普通である（特許文献２）。   Normally, conventionally, aluminum is subjected to zinc substitution plating twice, so-called double zincate, electroless plating of Ni-P, and desired metal plating is usually performed (patent document) 2).

本発明においてはダブルジンケートの後、無電解めっきを行わず直接電気めっきを行う。無電解めっきは通常処理温度が60〜90℃と非常に高く、箔体を処理しようとする場合には急な温度変化によるしわの発生など大きな問題があり、現実的ではない。
また、アルミニウムに蒸着やスパッタ法でＮｉおよびＳｎを形成する方法もあるが、設備的にもコスト的にも非常に問題があり、大量生産に不向きである（特許文献３）。
なお、一般にアルミニウム箔は２枚を一度に圧延されて製造される。このため、表裏で外観が異なる。圧延ロールに接触する面側の光沢が高く通常、光沢面（艶面）と呼ばれ、アルミ同士が接触する面はケシ面(艶消し面)と呼ばれる。 In the present invention, after double zincate, direct electroplating is performed without electroless plating. Electroless plating usually has a very high processing temperature of 60 to 90 ° C., and when processing a foil body, there are serious problems such as generation of wrinkles due to a sudden temperature change, which is not realistic.
In addition, there is a method of forming Ni and Sn on aluminum by vapor deposition or sputtering, but it is very problematic in terms of equipment and cost, and is unsuitable for mass production (Patent Document 3).
In general, aluminum foil is manufactured by rolling two sheets at a time. For this reason, the appearance differs on the front and back. The surface that contacts the rolling roll has high gloss and is usually called a glossy surface (glossy surface), and the surface that contacts aluminum is called a poppy surface (matte surface).

特開２００９−２８７０９５号公報JP 2009-287095 A 特開平８−１５８０６０号公報JP-A-8-158060 特開平５−３４５９６９号公報JP-A-5-345969

電磁波シールド材料や放熱基板用導電材料又は熱伝導材料、二次電池用電極集電体、プリント配線板などの電極材料、電気接続材料として用いられる、電気、電子製品に使用される金属材料及びその複合材料に関するものであり、電気伝導性、熱伝導性に優れ、かつ低価格、軽量で、はんだ実装、接続が可能な金属箔であって、樹脂との接着性の高い材料を提供することを課題とする。   Electromagnetic shielding materials, conductive materials for heat dissipation substrates or heat conduction materials, electrode materials for secondary battery electrodes, printed wiring boards, and other metal materials used for electrical and electronic products, It relates to composite materials, and is a metal foil that has excellent electrical and thermal conductivity, is inexpensive, lightweight, and can be soldered and connected, and provides a material with high adhesion to resin. Let it be an issue.

本発明は少なくとも一方の面が順に亜鉛置換めっき層、電気ニッケルめっき層、電気スズめっき層からなるアルミニウム又はアルミニウム合金箔であり、亜鉛置換めっき層が0.05〜0.5μｍ、電気ニッケルめっき層が0.3〜3μｍ、電気スズめっき層が0.5〜15μｍであり、また、必要に応じ亜鉛置換めっき層中にFe,Co,Ni,Cuのうちの1種以上の元素を0.1〜1.0 g/m2含むことを特徴とするアルミニウム又はアルミニウム合金箔である。 The present invention is an aluminum or aluminum alloy foil in which at least one surface is composed of a zinc substitution plating layer, an electric nickel plating layer, and an electric tin plating layer in this order, the zinc substitution plating layer is 0.05 to 0.5 μm, and the electric nickel plating layer is 0.3 to 3 μm, electrotin plating layer is 0.5 to 15 μm, and if necessary, one or more elements of Fe, Co, Ni and Cu are contained in the zinc replacement plating layer in an amount of 0.1 to 1.0 g / m 2 It is the characteristic aluminum or aluminum alloy foil.

さらに片方にスズめっきが施されない場合において、スズめっきと反対の面が、亜鉛置換めっきにより粗化されることを特徴とし、さらに必要に応じて亜鉛置換めっきにより粗化後酸洗されることを特徴とするものであって、亜鉛置換めっき又は酸洗後の粗化面の表面粗さRzjisが0.5〜5.0μｍであることを特徴とするアルミニウム又はアルミニウム合金箔である。   Furthermore, when tin plating is not applied to one side, the surface opposite to tin plating is roughened by zinc substitution plating, and further, if necessary, it is pickled after roughening by zinc substitution plating. An aluminum or aluminum alloy foil characterized in that the surface roughness Rzjis of the roughened surface after zinc substitution plating or pickling is 0.5 to 5.0 μm.

本発明のスズめっき被膜を有するアルミニウム又はアルミニウム合金箔は、材料として高い導電性および熱伝導性を有し、低価格、軽量で、はんだ実装、接続が可能である。
また、片面を粗化した場合においては、樹脂などへも接着でき複合材として有効であってその接着性が高く、すなわち信頼性の高い材料を提供することができる。
そして本発明の材料は箔の形態であるためロールトゥロールのような連続的な製造が可能であって、大量生産に極めて対応しやすい、という利点を持っている。 The aluminum or aluminum alloy foil having the tin plating film of the present invention has high electrical conductivity and thermal conductivity as a material, and can be soldered and connected at low cost and light weight.
In addition, when one side is roughened, it is possible to provide a material that can be bonded to a resin or the like and is effective as a composite material and has high adhesiveness, that is, high reliability.
Since the material of the present invention is in the form of a foil, it can be continuously manufactured like a roll-to-roll, and has the advantage that it is extremely easy to cope with mass production.

本発明の方法で製造された本発明の多層めっきアルミニウム又はアルミニウム合金箔の断面図の一例を示した図である。It is the figure which showed an example of sectional drawing of the multilayer plating aluminum or aluminum alloy foil of this invention manufactured by the method of this invention.

アルミニウム又はアルミニウム合金箔基体の厚さは例えば10〜100μmのものを用いる。まず最初に、その表面を脱脂する。脱脂はアルカリ性水溶液に浸漬、あるいは電気分解を行い、表面に付着している油脂類を除去する。脱脂液は水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、リン酸ナトリウムなどの水溶液やアルミニウム用の市販の脱脂液でもよい。   The thickness of the aluminum or aluminum alloy foil substrate is, for example, 10 to 100 μm. First, the surface is degreased. Degreasing is performed by immersing or electrolyzing in an alkaline aqueous solution to remove oils and fats adhering to the surface. The degreasing solution may be an aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, or a commercially available degreasing solution for aluminum.

次いで水洗し、必要に応じて硝酸または硫酸-過酸化水素水などの酸化性酸性水溶液に浸漬し、スマット除去する。この硝酸濃度は10〜50%程度が好ましい。次いで水洗し、亜鉛置換液に浸漬して置換めっきにより亜鉛を析出させる。   Next, it is washed with water, and if necessary, immersed in an oxidizing acidic aqueous solution such as nitric acid or sulfuric acid-hydrogen peroxide solution to remove smut. The nitric acid concentration is preferably about 10 to 50%. Next, it is washed with water and immersed in a zinc replacement solution to deposit zinc by replacement plating.

次いで水洗し、硝酸または硫酸-過酸化水素水などの酸化性酸性水溶液に浸漬し、水洗後、もう1度亜鉛置換液に浸漬する。これはいわゆるダブルジンケートである。一般的に1回の亜鉛置換だけでは次のめっきがうまく行えない。2回行うことで均一なめっきが可能となる。1回では粗雑な亜鉛析出粒子となるが2回行うことにより緻密で微細な析出状態となる。   Next, it is washed with water, immersed in an oxidizing acidic aqueous solution such as nitric acid or sulfuric acid-hydrogen peroxide solution, washed with water, and then immersed in a zinc replacement solution again. This is a so-called double zincate. In general, the next plating cannot be performed well with only one zinc replacement. Performing plating twice enables uniform plating. Once, it becomes coarse zinc precipitate particles, but when it is performed twice, it becomes a fine and fine precipitate state.

浸漬時間は脱脂液、硝酸液、亜鉛置換液それぞれ15秒〜60秒程度が好ましい。浸漬温度は室温〜40℃が好ましい。なお、亜鉛置換液組成は亜鉛イオン3〜25g/l、水酸化ナトリウム40〜250g/l、塩化第二鉄（六水塩）0.5〜7.0g/l、錯塩たとえばロッセル塩20〜100g/lが好ましい。さらにNi,Co,Cuイオンなどを添加するのも次のニッケルめっきに対する密着性向上によい。Feイオンを含むこれらの金属イオン合計量は0.3〜5g/l程度が好ましい。0.3g/l未満では2回亜鉛置換をしても密着性の高いニッケルめっき層を得ることができない。5g/lを超えると沈殿生成などの問題が発生する。   The immersion time is preferably about 15 to 60 seconds for each of the degreasing solution, the nitric acid solution, and the zinc replacement solution. The immersion temperature is preferably room temperature to 40 ° C. The composition of the zinc replacement solution is 3 to 25 g / l of zinc ions, 40 to 250 g / l of sodium hydroxide, 0.5 to 7.0 g / l of ferric chloride (hexahydrate), and complex salts such as 20 to 100 g / l of Rossel salt. preferable. Furthermore, addition of Ni, Co, Cu ions, etc. is also good for improving adhesion to the next nickel plating. The total amount of these metal ions including Fe ions is preferably about 0.3 to 5 g / l. If it is less than 0.3 g / l, a nickel plating layer with high adhesion cannot be obtained even if zinc substitution is performed twice. If it exceeds 5 g / l, problems such as precipitation occur.

この2回亜鉛置換めっき処理において得られる亜鉛置換めっき層の厚さはおよそ0.05〜0.5μｍであり、Fe,Ni,Co,Cuのうちの1種以上の含有量は0.1〜1.0g/m2となる。0.05μｍ未満の厚さでは次のニッケルめっきの密着力が弱く、0.5μｍを超える厚さも粗雑な面となりやはり密着力が低下し、よくない。 The thickness of the zinc substitution plating layer obtained in this twice zinc substitution plating treatment is approximately 0.05 to 0.5 μm, and the content of one or more of Fe, Ni, Co, and Cu is 0.1 to 1.0 g / m 2. It becomes. If the thickness is less than 0.05 μm, the adhesion strength of the next nickel plating is weak, and if the thickness exceeds 0.5 μm, the surface becomes rough and the adhesion strength is lowered.

次に水洗後、電気ニッケルめっきを行う。ニッケルめっき液はワット浴やピロリン酸浴などジンケート被膜の溶解を抑えるために中性に近いものが良い。   Next, after washing with water, electro nickel plating is performed. A nickel plating solution such as a watt bath or a pyrophosphoric acid bath is preferably near neutral in order to suppress dissolution of the zincate film.

電流密度は2〜15A/dm2、液温度は20〜60℃が好ましい。めっき厚みは0.3〜3μｍが好ましい。ニッケルめっき厚さは0.3μｍ以上が好ましく、0.3μｍ未満であると次のスズめっきの密着性が低下する、また3μｍを超えると不経済である。 The current density is preferably 2 to 15 A / dm 2 and the liquid temperature is preferably 20 to 60 ° C. The plating thickness is preferably 0.3 to 3 μm. The nickel plating thickness is preferably 0.3 μm or more, and if it is less than 0.3 μm, the adhesion of the next tin plating is lowered, and if it exceeds 3 μm, it is uneconomical.

なお、必要に応じてニッケル合金めっきとすることも可能である。合金元素としてはリン、鉄、銅、コバルト、亜鉛などが上げられる。   In addition, it is also possible to set it as nickel alloy plating as needed. Examples of alloy elements include phosphorus, iron, copper, cobalt, and zinc.

次いで水洗後、スズめっきを行う。スズめっき浴としては、公知のスズめっき液を使うことができる。たとえばアルカノールスルホン酸、アルカンスルフォン酸、ピロリン酸、硫酸等を挙げることができる。めっき条件では、例えば電流密度2〜25A/dm2 、スズ濃度20〜100g/ｌ、浴温20〜60℃ とする。 Next, tin plating is performed after washing with water. As the tin plating bath, a known tin plating solution can be used. Examples include alkanol sulfonic acid, alkane sulfonic acid, pyrophosphoric acid, sulfuric acid and the like. The plating conditions are, for example, a current density of 2 to 25 A / dm 2 , a tin concentration of 20 to 100 g / l, and a bath temperature of 20 to 60 ° C.

スズめっき被膜の厚みは0.5μｍ以上であることが好ましい。0.5μｍ未満では、はんだ接続の信頼性が低く、ニッケルめっき層が薄い場合耐食性が低下する。また、スズめっき被膜の厚さの上限は15μｍが好ましい。15μｍを超えると、スズを必要以上に付けることとなり、不経済であり、比重7.28のスズが厚くなることは軽量化という観点において問題がある。   The thickness of the tin plating film is preferably 0.5 μm or more. If the thickness is less than 0.5 μm, the reliability of solder connection is low, and the corrosion resistance is reduced when the nickel plating layer is thin. Further, the upper limit of the thickness of the tin plating film is preferably 15 μm. If it exceeds 15 μm, tin will be added more than necessary, which is uneconomical, and the thickening of tin with a specific gravity of 7.28 is problematic in terms of weight reduction.

樹脂や接着剤を介して接着させる側は表面を粗化することにより樹脂や接着剤との密着性が上がり、特に電磁波シールド材料、放熱基板材料、プリント配線板材料に好適となる。たとえば２回亜鉛置換めっきにより、アルミニウム表面に微細な凹凸ができるが、この粗面を利用する。この亜鉛置換めっきの状態のままでもよいが、好ましくは2回亜鉛置換めっき処理後に硝酸または硫酸-過酸化水素水などの酸化性酸性水溶液で酸洗し、余剰、非固着性の析出亜鉛を除去した方がよく、そうすることによって、アルミニウム基体に固着した粗面が得られる。酸洗後も亜鉛及び置換めっき液成分金属元素は微量残留する。さらなる粗面形成を必要とする場合は工程が増加するが2回亜鉛置換めっき凹凸形成後エッチング粗化してもよい。エッチング粗化には薬液に浸漬する、陽極電解する、交流電解するなど各種方法があり、公知の方法で行うことができる。   By roughening the surface of the side to be bonded via a resin or an adhesive, the adhesion to the resin or the adhesive is improved, and is particularly suitable for an electromagnetic shielding material, a heat dissipation board material, and a printed wiring board material. For example, fine unevenness is formed on the aluminum surface by twice zinc substitution plating, but this rough surface is used. This zinc replacement plating state may be left as it is, but preferably after the zinc replacement plating treatment twice, pickling with an oxidizing acidic aqueous solution such as nitric acid or sulfuric acid-hydrogen peroxide solution to remove excess and non-adhering deposited zinc. It is better to do so, so that a rough surface fixed to the aluminum substrate is obtained. Even after pickling, trace amounts of zinc and metal elements of the displacement plating solution remain. When further rough surface formation is required, the number of steps increases, but etching roughening may be performed after forming the zinc-plated plating unevenness twice. Etching roughening includes various methods such as immersion in a chemical solution, anodic electrolysis, and alternating current electrolysis, and can be performed by a known method.

亜鉛置換めっき及びその後の酸洗による粗面粗さは、素地粗さに対してRzjisで0.1μｍから1.0μｍの上昇となり、特にRzjis 0.1μｍ以上の上昇が好ましい。   The roughness of the rough surface by zinc displacement plating and subsequent pickling increases from 0.1 μm to 1.0 μm in Rzjis with respect to the substrate roughness, and in particular, an increase of Rzjis of 0.1 μm or more is preferable.

電磁波シールド材料とする場合はその特性は金属箔体の電気伝導度に主に依存し、本発明アルミニウム又はアルミニウム合金箔は銅の60%となるが、厚みを1.7倍にすれば良い。比重が銅の33%であるので重量では約半分となり、重量及びさらに価格を考慮すると銅と比較して有利となる。また、ニッケル層があるので磁気シールド性もあり総合性能的に高い材料となる。   When an electromagnetic wave shielding material is used, its characteristics mainly depend on the electric conductivity of the metal foil, and the aluminum or aluminum alloy foil of the present invention is 60% of copper, but the thickness may be 1.7 times. Since the specific gravity is 33% of copper, the weight is about half, and considering weight and price, it is advantageous compared to copper. Further, since there is a nickel layer, it has a magnetic shielding property and is a material with high overall performance.

本材料を樹脂との複合材料として使用する場合、例えばプリント配線板用としては各種FR-4やポリイミドなどのプリプレグに加熱圧着成型させる。また、フィルムに対してはFPCやシールド材料用として例えばPET(ポリエチレンテレフタレート) 、ポリイミド、液晶ポリマー、PEN（ポリエチレンナフタレート）などが上げられる。フィルムは、接着剤により本アルミニウム又はアルミニウム合金箔に接着してもよいが、フィルムをアルミニウム又はアルミニウム合金箔に熱圧着させる、あるいはキャスティングの方法で成型する。またこれらフィルムの厚さは5〜70μｍのものを用いる。   When this material is used as a composite material with a resin, for example, for printed wiring boards, various prepregs such as FR-4 and polyimide are thermocompression-molded. For the film, for example, PET (polyethylene terephthalate), polyimide, liquid crystal polymer, PEN (polyethylene naphthalate), etc. are used for FPC and shield materials. The film may be adhered to the present aluminum or aluminum alloy foil with an adhesive, but the film is thermocompression bonded to the aluminum or aluminum alloy foil, or formed by a casting method. The thickness of these films is 5 to 70 μm.

本発明者らはアルミニウム又はアルミニウム合金箔のエポキシ樹脂（FR-4）に対する接着性を調査したが、受理状態においてはその表裏のケシ面及び光沢面の形状差のみによる差はほとんど認められなかった。亜鉛置換めっき粗化処理により接着力が高くなることが判明した。さらに亜鉛置換めっき後に酸洗することにより、固着性の高い面となり、熱処理後の接着力が高いことが判明した。   The present inventors investigated the adhesion of aluminum or aluminum alloy foil to epoxy resin (FR-4), but in the accepted state, there was almost no difference due to the shape difference between the front and back poppy surfaces and glossy surfaces. . It was found that the adhesive strength was increased by the zinc substitution plating roughening treatment. Furthermore, it was found that by pickling after zinc substitution plating, a surface having high adhesion was obtained and the adhesive strength after heat treatment was high.

なお、アルミニウム又はアルミニウム合金箔を最初に亜鉛置換処理し、凹凸を形成させた後、その片面と樹脂やフィルムとをラミネート法などで接着させ、この複合材の金属面側にニッケル、スズめっきを施してもよい。もちろんアルミニウム又はアルミニウム合金箔と接着性が極めて良い樹脂、接着剤、フィルムなどを使用する場合は粗化の必要はない。しかし、凹凸があることで汎用性の高い製品となる。   The aluminum or aluminum alloy foil is first subjected to zinc substitution treatment to form irregularities, and then one surface thereof is bonded to a resin or film by a lamination method or the like, and nickel or tin plating is applied to the metal surface side of this composite material. You may give it. Of course, there is no need for roughening when using resin, adhesive, film, or the like that has excellent adhesion to aluminum or aluminum alloy foil. However, the unevenness makes the product highly versatile.

以下に実施例を示す。但し本発明はこれらに限定されるものではない。   Examples are shown below. However, the present invention is not limited to these.

（実施例１〜１０）
30μｍ厚さの1N30アルミニウム箔を用意し、その両面に脱脂、酸洗浄（スマット除去）、第一亜鉛置換処理、酸洗浄（第一亜鉛置換めっきの溶解）、第二亜鉛置換処理を行い、必要に応じ片面に対して酸洗浄（第二亜鉛置換めっきの溶解）、さらに片面（酸洗浄を実施した場合はその反対面）に電解ニッケルめっき、電解スズめっき、乾燥の順に実施した。各工程の間には水洗を設けた。 (Examples 1 to 10)
1N30 aluminum foil with a thickness of 30μm is prepared, and degreasing, acid cleaning (smut removal), first zinc substitution treatment, acid washing (dissolution of first zinc substitution plating), and second zinc substitution treatment are necessary on both sides. Accordingly, acid cleaning (dissolution of the second zinc substitution plating) was performed on one surface, and electrolytic nickel plating, electrolytic tin plating, and drying were performed on one surface (the opposite surface when acid cleaning was performed). Water washing was provided between each process.

（比較例１）
30μｍ厚さの1N30アルミニウム箔を用意した。 (Comparative Example 1)
A 30 μm thick 1N30 aluminum foil was prepared.

（比較例２）
30μｍ厚さの1N30アルミニウム箔を用意し、両面に脱脂、酸洗浄（スマット除去）、乾燥の順に実施した。各工程の間には水洗を設けた。 (Comparative Example 2)
A 30 μm-thick 1N30 aluminum foil was prepared and degreased on both sides, acid washed (smut removed), and dried. Water washing was provided between each process.

以下に用いた処理液の組成等を示す。   The composition of the treatment liquid used is shown below.

水溶液A：脱脂液
水酸化ナトリウム 10g/l

水溶液B：酸洗浄液
硝酸 20容量%

水溶液C：亜鉛置換液
酸化亜鉛 9g/l
水酸化ナトリウム 70g/l
ロッセル塩 25g/l
塩化第二鉄(六水塩) 2g/l

水溶液D：電気ニッケルめっき液
硫酸ニッケル(六水塩) 250ｇ/ｌ
塩化ニッケル (六水塩) 50ｇ/ｌ
ホウ酸 20ｇ/ｌ
ｐH4.0

水溶液E：電気スズめっき液
アルカノールスルホン酸めっき液
（上村工業株式会社製 ティナデス(登録商標) GHS-51）

水溶液F：亜鉛置換液
酸化亜鉛 14g/l
水酸化ナトリウム 110g/l
ロッセル塩 40g/l
塩化第二鉄(六水塩) 4g/l

水溶液G：亜鉛置換液
酸化亜鉛 16g/l
水酸化ナトリウム 120g/l
ロッセル塩 50g/l
塩化第二鉄（六水塩） 4g/l
硫酸銅（五水塩） 1g/l Aqueous solution A: Degreasing solution Sodium hydroxide 10g / l

Aqueous solution B: Acid cleaning solution Nitric acid 20% by volume

Aqueous solution C: Zinc replacement solution Zinc oxide 9g / l
Sodium hydroxide 70g / l
Roselle salt 25g / l
Ferric chloride (hexahydrate) 2g / l

Aqueous solution D: Electro nickel plating solution Nickel sulfate (hexahydrate) 250g / l
Nickel chloride (hexahydrate) 50g / l
Boric acid 20g / l
pH 4.0

Aqueous solution E: Electrotin plating solution Alkanol sulfonic acid plating solution (Tinades (registered trademark) GHS-51, manufactured by Uemura Kogyo Co., Ltd.)

Aqueous solution F: Zinc replacement solution Zinc oxide 14g / l
Sodium hydroxide 110g / l
Roselle salt 40g / l
Ferric chloride (hexahydrate) 4g / l

Aqueous solution G: Zinc replacement solution Zinc oxide 16g / l
Sodium hydroxide 120g / l
Roselle salt 50g / l
Ferric chloride (hexahydrate) 4g / l
Copper sulfate (pentahydrate) 1g / l

実施例1〜10では、得られたスズめっきアルミニウム箔に対して、スズめっきされている面の亜鉛置換めっき厚さおよび亜鉛置換めっき中に含まれる鉄および銅の含有量、ニッケルめっき厚さ、スズめっき厚さを蛍光エックス線膜厚さ計により測定した。
また、実施例1〜10では、スズめっきされていない面の表面粗さ、樹脂接着性を調べた。比較例1では、光沢面側の、比較例2ではケシ面側の表面粗さ、樹脂接着性を調べた。
表面粗さは、JIS-B-0601:2001に記載の、RaおよびRzjisにて評価した。樹脂接着性は、FR-4グレード相当のガラスエポキシ樹脂含浸基材に成型温度170℃、圧力4MPaでプレス成型した。これをJIS-C-6481:1996に従って、90°剥離試験により接着強度（受理）を評価した。また、接着強度測定用試片を熱風循環式オーブン中に入れ180℃、48時間の熱処理を行った後、接着強度（熱処理後）を評価した。 In Examples 1 to 10, for the obtained tin-plated aluminum foil, the zinc-substituted plating thickness of the surface plated with tin and the iron and copper contents contained in the zinc-substituted plating, the nickel-plated thickness, The tin plating thickness was measured with a fluorescent X-ray film thickness meter.
In Examples 1 to 10, the surface roughness and the resin adhesion of the surface not tin-plated were examined. In Comparative Example 1, the surface roughness and resin adhesion on the glossy surface side and in Comparative Example 2 on the poppy surface side were examined.
The surface roughness was evaluated by Ra and Rzjis described in JIS-B-0601: 2001. The resin adhesion was press-molded on a glass epoxy resin-impregnated base material equivalent to FR-4 grade at a molding temperature of 170 ° C. and a pressure of 4 MPa. This was evaluated for adhesive strength (acceptance) by a 90 ° peel test in accordance with JIS-C-6481: 1996. Moreover, after putting the test piece for adhesive strength measurement into hot-air circulation type oven, and heat-processing for 48 hours at 180 degreeC, adhesive strength (after heat processing) was evaluated.

実施例および比較例の手順の一覧を表1に、各箔のめっき厚さ及び特性結果を表２に示す。なお、実施例１においては亜鉛置換めっき厚さは0.37μｍ、この層中Fe含有量は0.35 g/m2、実施例10においては亜鉛置換めっき厚さは0.41μｍ、この層中Fe含有量は0.35 g/m2、Cuは0.03g/m2であった。 Table 1 shows a list of procedures of Examples and Comparative Examples, and Table 2 shows plating thicknesses and characteristic results of each foil. In Example 1, the zinc displacement plating thickness is 0.37 μm, and the Fe content in this layer is 0.35 g / m 2. In Example 10, the zinc displacement plating thickness is 0.41 μm, and the Fe content in this layer is 0.35 g / m 2 and Cu were 0.03 g / m 2 .

この結果から比較例に対し、本実施例の片面は樹脂との接着において、受理ばかりでなく、熱処理後においても高い十分な接着性を示した。さらにもう一方の面は外層がスズ表面となっており、はんだ接続が容易な複合箔体であって、各種導電性、熱伝導性、電磁波シールド性に有効な材料となっている。   From this result, compared with the comparative example, one side of this example showed not only acceptance but also high sufficient adhesion even after heat treatment. Further, the other surface has a tin surface as an outer layer, and is a composite foil body that can be easily connected by solder, and is an effective material for various conductivity, thermal conductivity, and electromagnetic wave shielding properties.

本発明材料は電気伝導性、熱伝導性に優れ、かつ低価格、軽量で、はんだ実装、接続が容易であることから、電磁波シールド材料や放熱基板用導電材料又は熱伝導材料、二次電池用電極集電体、プリント配線板などの電極材料、電気接続材料として広範囲に応用できる。   The material of the present invention is excellent in electrical conductivity and thermal conductivity, low in price, lightweight, and easy to solder and connect. Therefore, the electromagnetic shielding material, the conductive material for heat dissipation board, the thermal conductive material, and the secondary battery. It can be used in a wide range of electrode materials such as electrode current collectors and printed wiring boards, and electrical connection materials.

１ アルミニウム箔（又はアルミニウム合金箔）
２ 亜鉛置換めっき層
２ａ 亜鉛置換めっき処理凹凸層
３ 電気ニッケルめっき層
４ 電気スズめっき層 1 Aluminum foil (or aluminum alloy foil)
2 Zinc replacement plating layer 2a Zinc replacement plating treatment uneven layer 3 Electro nickel plating layer 4 Electro tin plating layer

Claims (6)

少なくとも一方の面が順に亜鉛置換めっき層、電気ニッケルめっき層、電気スズめっき層からなる総厚さ130μｍ以下のアルミニウム又はアルミニウム合金箔。   An aluminum or aluminum alloy foil having a total thickness of 130 μm or less, wherein at least one surface is composed of a zinc-substituted plating layer, an electric nickel plating layer, and an electric tin plating layer in this order. 亜鉛置換めっき層が0.05〜0.5μｍ、電気ニッケルめっき層が0.3〜3μｍ、電気スズめっき層が0.5〜15μｍであることを特徴とする請求項１記載のアルミニウム又はアルミニウム合金箔。   2. The aluminum or aluminum alloy foil according to claim 1, wherein the zinc displacement plating layer is 0.05 to 0.5 μm, the electro nickel plating layer is 0.3 to 3 μm, and the electro tin plating layer is 0.5 to 15 μm. 亜鉛置換めっき層中にFe,Co,Ni,Cuのうちの1種以上の元素を0.1〜1.0g/m2含むことを特徴とする請求項１又は２記載のアルミニウム又はアルミニウム合金箔。 Fe in zincate plating layer, Co, Ni, aluminum or aluminum alloy foil according to claim 1 or 2, wherein one or more elements, characterized in that it comprises 0.1 to 1.0 g / m 2 of Cu. 片方の面がニッケル、スズめっきされず、亜鉛置換めっきにより粗化されることを特徴とする請求項１乃至３のいずれか１項に記載のアルミニウム又はアルミニウム合金箔。   4. The aluminum or aluminum alloy foil according to claim 1, wherein one surface is not plated with nickel or tin but is roughened by zinc substitution plating. 5. 片方の面がニッケル、スズめっきされず、亜鉛置換めっきにより粗化後酸洗されることを特徴とする請求項１乃至３のいずれか１項に記載のアルミニウム又はアルミニウム合金箔。   4. The aluminum or aluminum alloy foil according to claim 1, wherein one surface is not plated with nickel or tin but is pickled after being roughened by zinc substitution plating. 5. 粗化面の表面粗さRzjisが0.5〜5.0μｍであることを特徴とする請求項４又は５記載のアルミニウム又はアルミニウム合金箔。   The aluminum or aluminum alloy foil according to claim 4 or 5, wherein the roughened surface has a surface roughness Rzjis of 0.5 to 5.0 µm.
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