JP5101798B2 - Surface treatment Al plate - Google Patents
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本発明は、経時後のハンダ濡れ性に優れた表面処理Ａｌ板に関する。 The present invention relates to a surface-treated Al plate having excellent solder wettability after aging.
電子機器等に用いられる端子板やプリント基板用の材料として、従来は真鍮板にハンダめっきを施した材料や銅板などが用いられてきたが、環境に与える影響からＰｂを含まないＰｂフリーのハンダの使用が求められるようになっている。また、電子機器の小型化および軽量化も求められており、それにともなってこれらの電子機器の部品である端子板やプリント基板などの部品についても小型化および軽量化も求められようになってきており、Ｐｂフリーのハンダ付けが可能な材料として、Ａｌ板を母材とした材料が提案されている。
近年、電子機器の小型化および軽量化が求められており、それにともなってこれらの電子機器の部品である端子板やプリント基板などの部品についても小型化および軽量化も求められ、軽量でかつ熱伝導性に優れたＡｌ板にハンダ濡れ性に優れた材料が求められている。また、これらの電子機器の製造および組み立ては東南アジアや中国など、高温多湿の地域で行なわれるようになってきており、組立て前の部品が長期間にわたって高温多湿の雰囲気にさらされるようになり、そのため高温多湿の雰囲気下で長期間経時した後においても良好なハンダ濡れ性を示す材料が求められている。
As materials for terminal boards and printed circuit boards used in electronic devices and the like, conventionally, materials obtained by soldering brass plates or copper plates have been used. However, Pb-free solder that does not contain Pb due to its environmental impact Is required to be used. In addition, there is a demand for downsizing and weight reduction of electronic devices, and accordingly, parts such as terminal boards and printed boards that are components of these electronic devices are also required to be downsized and lightened. As a material capable of Pb-free soldering, a material using an Al plate as a base material has been proposed.
In recent years, there has been a demand for downsizing and weight reduction of electronic devices, and accordingly, parts such as terminal boards and printed circuit boards, which are components of these electronic devices, are also required to be downsized and lightweight. A material having excellent solder wettability is required for an Al plate having excellent conductivity. In addition, these electronic devices are manufactured and assembled in high-temperature and high-humidity areas such as Southeast Asia and China, and parts before assembly are exposed to a high-temperature and high-humidity atmosphere for a long time. There is a need for materials that exhibit good solder wettability even after a long period of time in a hot and humid atmosphere.
軽量のＡｌを用いたハンダ付け用の材料として、以下に示す材料が提案されている。例えば特許文献１は、Ａｌ板またはＡｌ系合金金属材にＮｉめっき層を介してＳｎめっき層が形成されたハンダ付け性およびめっき密着性に優れたＡｌ系合金金属板を提案している。このＡｌ系合金金属板においては、溶融Ａｌめっき鋼板などの基材に真空蒸着法を用いてＮｉめっきを施した後、続いてＳｎめっきを施す。この方法による場合、ＮｉおよびＳｎめっきを施すために真空蒸着法を用いるが、真空装置などの大掛りな装置が必要であり、また製膜速度が小さく生産性に乏しいため、安価に製造することが困難である。 The following materials have been proposed as soldering materials using lightweight Al. For example, Patent Document 1 proposes an Al-based alloy metal plate excellent in solderability and plating adhesion, in which an Sn plate layer is formed on an Al plate or an Al-based alloy metal material via a Ni plating layer. In this Al-based alloy metal plate, Ni plating is performed on a base material such as a hot-dip Al-plated steel plate using a vacuum deposition method, followed by Sn plating. In this method, the vacuum deposition method is used to perform Ni and Sn plating, but a large-scale device such as a vacuum device is necessary, and the film forming speed is low and the productivity is low. Is difficult.
また特許文献２は、アルミニウム基材上に錫または錫合金層が、アルミニウム基材と錫または錫合金層との界面に錫の濃度勾配を形成して被覆されたことを特徴とするハンダ付け性に優れる錫または錫合金層を被覆したアルミニウム材料を提案している。このアルミニウム材料においては、アルミニウム合金板に錫を電気めっきした後に加熱する。または溶融した錫合金中にアルミニウム合金板を通すことにより、アルミニウム基材と錫または錫合金層との界面に錫の濃度勾配を形成して錫めっきするが、アルミニウム基材と錫または錫合金層との密着性が不十分であり、特に曲げ加工を施した場合に、錫めっき皮膜がアルミニウム基材から剥離しやすい欠点を有している。また、これらの材料は、いずれも特に高温多湿の雰囲気下で長期間経時した後のハンダ性を考慮したものではない。 Patent Document 2 discloses solderability, wherein a tin or tin alloy layer is coated on an aluminum substrate by forming a tin concentration gradient at the interface between the aluminum substrate and the tin or tin alloy layer. An aluminum material coated with an excellent tin or tin alloy layer is proposed. In this aluminum material, the aluminum alloy plate is heated after being electroplated with tin. Alternatively, a tin concentration gradient is formed at the interface between the aluminum base and the tin or tin alloy layer by passing an aluminum alloy plate through the molten tin alloy, and the aluminum base and the tin or tin alloy layer are plated. Insufficient adhesion to the aluminum substrate, particularly when subjected to bending, has a drawback that the tin plating film is easily peeled off from the aluminum substrate. In addition, none of these materials take into consideration the solderability after a long period of time in a particularly hot and humid atmosphere.
本発明は、高温多湿の雰囲気下で長期間経時した後においても良好なハンダ濡れ性を示す表面処理Ａｌ板を提供することを目的とする。 An object of the present invention is to provide a surface-treated Al plate that exhibits good solder wettability even after a long period of time in a hot and humid atmosphere.
本発明者は、上記問題点を解決するために、Ａｌ基板へのハンダの濡れ性に優れ高いハンダ強度を得る手段として、Ｎｉ層上に一段とハンダの濡れ性に優れている金属層または合金層を設けることを着想し、さらに高温多湿の雰囲気下で長期間経時した後においても良好なハンダ濡れ性を示す構成について種々研究した結果、ハンダ濡れ性に優れている金属層または合金層を設けたその上に、ハンダ性を阻害せず、耐水性および加工性に優れた水溶性樹脂層を設けることにより、高温多湿の雰囲気下で長期間経時した後においても良好なハンダ濡れ性が得られることを見出し、本発明に到達したものである。
すなわち、上記目的を達成するため本発明の表面処理Ａｌ板は以下の特徴を有する。
（１）Ａｌ基板表面に、基板側から順に、Ｚｎ層、Ｎｉ層、Ｓｎ−Ｂｉ又はＳｎ−ＡｇのＳｎ合金層を形成し、さらにその上に乾燥後の皮膜厚さが０．０５〜１０μｍとなる水溶性樹脂層を形成してなる表面処理Ａｌ板であって、
前記Ｓｎ−Ｂｉ又はＳｎ−ＡｇのＳｎ合金層は、
皮膜量１〜１０ｇ／ｍ ２ のＢｉ又はＡｇをめっきした上に皮膜量０．２〜１０ｇ／ｍ２のＳｎめっきをした後、
Ｓｎの融点以上の温度に加熱することにより形成したものであることを特徴とする。
（２）前記水溶性樹脂層が、水系ウレタン樹脂又は水系アクリル樹脂であることを特徴とする。
In order to solve the above problems, the present inventor is a metal layer or alloy layer that is excellent in solder wettability on an Ni layer as a means for obtaining high solder strength with excellent solder wettability to an Al substrate. In addition, as a result of various studies on a structure showing good solder wettability even after a long period of time in a high temperature and humidity atmosphere, a metal layer or an alloy layer having excellent solder wettability was provided. On top of that, by providing a water-soluble resin layer that does not hinder solderability and is excellent in water resistance and processability, good solder wettability can be obtained even after a long period of time in a hot and humid atmosphere. And the present invention has been achieved.
That is, in order to achieve the above object, the surface-treated Al plate of the present invention has the following characteristics.
(1) A Zn layer, Ni layer, Sn—Bi or Sn—Ag Sn alloy layer is formed on the Al substrate surface in this order from the substrate side, and the film thickness after drying is further 0.05 to 10 μm. A surface-treated Al plate formed by forming a water-soluble resin layer,
The Sn-Bi or Sn-Ag Sn alloy layer is
After the Sn-plated coating amount 0.2 to 10 g / m 2 of Bi or Ag coating amount 1 to 10 g / m 2 on plated,
It is formed by heating to a temperature equal to or higher than the melting point of Sn .
(2) The water-soluble resin layer is a water-based urethane resin or a water-based acrylic resin.
本発明の表面処理Ａｌ板は、Ａｌ基板表面に置換めっきによりＺｎ層を形成させ、その上にＮｉ層とＢｉ層、またはＮｉ層とＩｎ層、またはＮｉ層とＡｇ層、またはＮｉ層とＳｎ層またはＮｉ層とＳｎ合金層を湿式めっき法により形成させているのでＡｌ基板との密着性に優れている。また、これらの金属層の上にハンダ性を阻害せず、耐水性および加工性に優れた水溶性樹脂層を設けているので、８５℃の温度でかつ８５％の湿度のような高温多湿の雰囲気中で長期間経時した後のメニスコグラフ法によるハンダ濡れ性が１０秒以下の優れたハンダ濡れ性が得られる。そのため、東南アジアや中国などの高温多湿の地域で製造および組み立てが行なわれる端子板やプリント基板等の小型で軽量の電子機器用の部品などに好適に適用することができる。 In the surface-treated Al plate of the present invention, a Zn layer is formed on the Al substrate surface by displacement plating, and a Ni layer and a Bi layer, or a Ni layer and an In layer, or a Ni layer and an Ag layer, or a Ni layer and a Sn layer are formed thereon. Since the layer or the Ni layer and the Sn alloy layer are formed by the wet plating method, the adhesion to the Al substrate is excellent. In addition, since a water-soluble resin layer that does not hinder solderability and is excellent in water resistance and workability is provided on these metal layers, it is highly humid at a temperature of 85 ° C. and a humidity of 85%. An excellent solder wettability with a solder wettability of 10 seconds or less after a long period of time in an atmosphere is obtained. Therefore, the present invention can be suitably applied to small and lightweight electronic device parts such as terminal boards and printed boards that are manufactured and assembled in high-temperature and high-humidity regions such as Southeast Asia and China.
以下、本発明の内容を説明する。
本発明の表面処理Ａｌ板の基板となるＡｌとしては、純Ａｌ板およびＪＩＳ規格の１０００系、２０００系、３０００系、５０００系、６０００系、７０００系のいずれのＡｌ合金板も用いることができる。これらのＡｌ合金板を脱脂し、次いで酸性エッチングし、引き続きスマットを除去した後、Ｚｎを置換めっきする。Ｚｎの置換めっきは、硝酸浸漬処理した後、Ｚｎによる置換めっき処理を行う。Ｚｎ置換めっき処理は第一Ｚｎ置換めっき処理、第二Ｚｎ置換めっき処理の２回の工程に分けて行ってもよい。この場合、各工程の処理後には水洗処理を実施する。この第一Ｚｎ置換めっき処理および第二Ｚｎ置換めっき処理により形成するＺｎめっき層は、この置換めっき処理後にＮｉめっきを施す際にわずかに溶解するので、Ｚｎ層の皮膜量としてはＮｉめっき後の状態で０．００５〜０．５ｇ／ｍ２ であることが好ましく、０．０３〜０．３ｇ／ｍ２ であることがより好ましい。皮膜量は処理液中のＺｎイオン濃度および第二Ｚｎ置換めっき処理において処理液中に浸漬する時間を適宜選択して調整する。皮膜量が０．００５ｇ／ｍ２ 未満であるとＺｎ層の上に形成するＮｉめっき層との密着性に乏しくなり、曲げ加工を施した際にめっき層が剥離しやすくなる。一方、皮膜量が０．５ｇ／ｍ２ を超えるとＮｉめっきが不均一になり、ハンダ強度が低下する。
The contents of the present invention will be described below.
As Al used as the substrate of the surface-treated Al plate of the present invention, a pure Al plate and any JIS standard 1000 series, 2000 series, 3000 series, 5000 series, 6000 series, or 7000 series Al alloy sheet can be used. . These Al alloy plates are degreased and then acid-etched. Subsequently, the smut is removed, and then Zn is replaced by plating. In the displacement plating of Zn, after immersion treatment with nitric acid, displacement plating treatment with Zn is performed. The Zn substitution plating treatment may be performed in two steps, a first Zn substitution plating treatment and a second Zn substitution plating treatment. In this case, the water washing process is implemented after the process of each process. The Zn plating layer formed by the first Zn substitution plating treatment and the second Zn substitution plating treatment is slightly dissolved when Ni plating is performed after the substitution plating treatment. It is preferable that it is 0.005-0.5 g / m < 2 > in a state, and it is more preferable that it is 0.03-0.3 g / m < 2 >. The coating amount is adjusted by appropriately selecting the Zn ion concentration in the treatment liquid and the time of immersion in the treatment liquid in the second Zn displacement plating treatment. When the coating amount is less than 0.005 g / m 2 , the adhesion with the Ni plating layer formed on the Zn layer becomes poor, and the plating layer is easily peeled off when bending is performed. On the other hand, when the coating amount exceeds 0.5 g / m 2 , the Ni plating becomes non-uniform, and the solder strength decreases.
次いでこのようにして形成されたＺｎ層の上にＮｉ層をめっきにより形成する。Ｎｉめっきは電気めっき法または無電解めっき法のいずれを用いて形成してもよい。無電解めっき法を用いる場合は、還元剤としてＰ化合物やＢ化合物を用いるので、Ｎｉめっき皮膜はＮｉ−Ｐ合金やＮｉ−Ｂ合金からなる皮膜として形成するが、電気めっき法による純Ｎｉからなる皮膜と同様に、めっき皮膜のＡｌ基板に対する密着性や、優れたハンダ濡れ性およびハンダ強度が得られる。このようにして得られるＮｉ層は、皮膜量として０．２〜５０ｇ／ｍ２ であることが好ましく、１〜１０ｇ／ｍ２ であることがより好ましい。皮膜量が０．２ｇ／ｍ２ 未満であるとＮｉ層がＺｎ層の全面を均一に被覆することができないので十分なハンダ強度が得られない。一方、皮膜量が５０ｇ／ｍ２ を超えるとハンダ濡れ性およびハンダ強度の向上効果が飽和し、コスト的に有利でなくなる。 Next, a Ni layer is formed on the Zn layer thus formed by plating. Ni plating may be formed using either electroplating or electroless plating. When the electroless plating method is used, since a P compound or a B compound is used as a reducing agent, the Ni plating film is formed as a film made of a Ni-P alloy or a Ni-B alloy, but is made of pure Ni by electroplating. Similar to the coating, adhesion of the plating coating to the Al substrate, and excellent solder wettability and solder strength can be obtained. Thus Ni layer obtained is preferably 0.2 to 50 g / m 2 as a film weight, and more preferably 1 to 10 g / m 2. If the coating amount is less than 0.2 g / m 2 , the Ni layer cannot uniformly cover the entire surface of the Zn layer, and thus sufficient solder strength cannot be obtained. On the other hand, if the coating amount exceeds 50 g / m 2 , the effect of improving the solder wettability and the solder strength is saturated, which is not advantageous in terms of cost.
次いで、湿式めっき法を用いてＮｉ層上にＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかのＳｎ合金めっきを形成させる。これらのＳｎ系合金は、Ｎｉ上に直接Ｓｎをめっきするか、またはＮｉ上にＢｉ、Ｚｎ、Ａｇ、Ｃｕのいずれかの金属をめっきした後それぞれの金属上にＳｎをめっきした後、もしくはＳｎめっき後その上にＢｉ、Ｚｎ、Ａｇ、Ｃｕのいずれかの金属をめっきした後、Ｓｎの融点以上の温度に加熱することにより、形成してもよい。これらの金属めっきおよび合金めっきの皮膜量は、それぞれ０．２〜２０ｇ／ｍ２ であることが好ましく、１〜１０ｇ／ｍ２ であることがより好ましい。皮膜量が０．２ｇ／ｍ２ 未満であると非活性のフラックスを用いた場合にハンダが濡れにくくなる。一方、皮膜量が２０ｇ／ｍ２ を超えるとハンダ濡れ性およびハンダ強度の向上効果が飽和し、コスト的に有利でなくなる。 Next, a metal plating layer of Bi, In, Ag, or Sn, or Sn—Bi alloy, Sn—Ni alloy, Sn—Zn alloy, Sn—Ag alloy, Sn— Either Sn alloy plating of Cu alloy is formed. These Sn-based alloys are obtained by directly plating Sn on Ni, or after plating any of Bi, Zn, Ag, and Cu on Ni and then plating Sn on each metal, or Sn After plating, any of Bi, Zn, Ag, and Cu may be plated thereon, and then heated to a temperature equal to or higher than the melting point of Sn. The coating amounts of these metal plating and alloy plating are each preferably 0.2 to 20 g / m 2 , and more preferably 1 to 10 g / m 2 . When the coating amount is less than 0.2 g / m 2 , solder becomes difficult to wet when an inactive flux is used. On the other hand, when the coating amount exceeds 20 g / m 2 , the effect of improving the solder wettability and the solder strength is saturated, which is not advantageous in terms of cost.
Ｎｉ、Ｂｉ、Ｚｎ、Ａｇ、Ｃｕのいずれかの金属上にＳｎをめっきした後に加熱して合金層を形成させる場合は、Ｎｉ以外のＢｉ、Ｚｎ、Ａｇ、Ｃｕのいずれかの金属については１〜１０ｇ／ｍ２ の皮膜量でめっきした後、Ｎｉについては上記のようにめっき層を形成させたその上にＳｎを０．２〜１０ｇ／ｍ２ の皮膜量でめっきし、次いでＳｎの融点以上の温度に加熱することにより、合金層を形成させる。 When an alloy layer is formed by plating Sn on a metal of Ni, Bi, Zn, Ag, or Cu and heating to form an alloy layer, 1 for any metal of Bi, Zn, Ag, or Cu other than Ni After plating with a coating amount of -10 g / m 2 , with respect to Ni, Sn was plated with a coating amount of 0.2 to 10 g / m 2 on the plating layer formed as described above, and then the melting point of Sn An alloy layer is formed by heating to the above temperature.
また、Ｎｉ上にＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかのＳｎ合金めっきを形成させて得られる表面処理Ａｌ板を、Ａｌの融点以下の温度に加熱して、Ａｌ基板およびＡｌ基板上に形成した各めっき層とをそれぞれ相互拡散させることにより、Ａｌ基板とめっき層、および各めっき層同士の密着強度を向上させることもできる。 Further, a metal plating layer of Bi, In, Ag, or Sn on Ni, or Sn of any of Sn—Bi alloy, Sn—Ni alloy, Sn—Zn alloy, Sn—Ag alloy, and Sn—Cu alloy. The surface-treated Al plate obtained by forming the alloy plating is heated to a temperature not higher than the melting point of Al, and the Al substrate and each plating layer formed on the Al substrate are mutually diffused, whereby the Al substrate and the plating are plated. The adhesion strength between the layers and the plating layers can also be improved.
次いで、これらのＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかの合金めっき層の上に水溶性樹脂層を形成させる。水溶性樹脂としては、ハンダ濡れ性に優れた上記の金属めっき層や合金めっき層の上に形成してもその優れたハンダ濡れ性を阻害せず、かつ耐水性を有し、外気中に含まれる水蒸気とこれらの金属めっき層や合金めっき層を遮断できる皮膜が形成可能な樹脂であり、さらに曲げ加工などの加工を施しても剥離したりすることのないものが好ましい。このような水溶性樹脂として水系ウレタン樹脂や水系アクリル樹脂を用いることができる。これらの樹脂の濃度としては１００〜９００ｇ／Ｌであることが好ましい。１００ｇ／Ｌ未満では耐水性に乏しい皮膜になり、９００ｇ／Ｌを超えるとハンダ濡れ性が低下する。水系アクリル樹脂を用いる場合はフラックス性を付与する水溶性ロジンを５０〜６００ｇ／Ｌ添加することが好ましい。これらの水溶性樹脂を浸漬法、ロールコート法、カーテンフローコート法、スプレーコート法などの被覆法を用いて上記の金属めっき層や合金めっき層上に塗布し、乾燥して皮膜とする。塗布量は乾燥後の皮膜厚さが０．０５〜１０μｍとなるように塗布する。皮膜厚さが０．０５μｍ未満では高温多湿の雰囲気中で長期間経時した後の十分なハンダ濡れ性が得られない。１０μｍを超えると特性向上効果が飽和し、コストメリットがなくなる。 Next, a metal plating layer of any of these Bi, In, Ag, and Sn, or an alloy plating of any of Sn—Bi alloy, Sn—Ni alloy, Sn—Zn alloy, Sn—Ag alloy, and Sn—Cu alloy A water-soluble resin layer is formed on the layer. As a water-soluble resin, even if it is formed on the above metal plating layer or alloy plating layer with excellent solder wettability, it does not hinder the excellent solder wettability, has water resistance, and is contained in the outside air It is preferable to use a resin that can form a film capable of blocking water vapor from these metal plating layers and alloy plating layers, and that does not peel even when subjected to processing such as bending. A water-based urethane resin or a water-based acrylic resin can be used as such a water-soluble resin. The concentration of these resins is preferably 100 to 900 g / L. If it is less than 100 g / L, it will become a film | membrane with poor water resistance, and if it exceeds 900 g / L, solder wettability will fall. When a water-based acrylic resin is used, it is preferable to add 50 to 600 g / L of water-soluble rosin that imparts flux properties. These water-soluble resins are applied onto the metal plating layer or alloy plating layer using a coating method such as a dipping method, a roll coating method, a curtain flow coating method, or a spray coating method, and dried to form a film. The coating amount is applied so that the film thickness after drying is 0.05 to 10 μm. When the film thickness is less than 0.05 μm, sufficient solder wettability after a long period of time in a hot and humid atmosphere cannot be obtained. If it exceeds 10 μm, the effect of improving the characteristics is saturated and the cost merit is lost.
以下、実施例を示して本発明をさらに詳細に説明する。
[供試板の作成］
Ａｌ合金板（ＪＩＳ ５０５２ Ｈ１９、板厚０．５ｍｍ）をめっき基板として、アルカリ液中で脱脂し、次いで硫酸中に浸漬するエッチング処理を施し、引き続いて硝酸中で脱スマット処理を施した後、水酸化ナトリウム：１５０ｇ／Ｌ、ロッシェル塩：５０ｇ／Ｌ、酸化亜鉛：２５ｇ／Ｌ、塩化第一鉄：１．５ｇ／Ｌを含む処理液中に浸漬する第一Ｚｎ置換めっき処理を行い、次いで４００ｇ／Ｌの硝酸水溶液中に浸漬して置換析出したＺｎを除去した後、第一Ｚｎ置換めっき処理で用いたのと同一の処理液中に浸漬して第二Ｚｎ置換めっき処理を行った。この第二Ｚｎ置換めっき処理において、浸漬時間を種々変化させて、表１〜２に示す皮膜量のＺｎ層を形成したＺｎめっきＡｌ板を得た。
Hereinafter, the present invention will be described in more detail with reference to examples.
[Create test plate]
An Al alloy plate (JIS 5052 H19, plate thickness 0.5 mm) was used as a plating substrate, degreased in an alkaline solution, then etched in sulfuric acid, and subsequently desmutted in nitric acid. A first Zn displacement plating treatment is performed by immersing in a treatment solution containing sodium hydroxide: 150 g / L, Rochelle salt: 50 g / L, zinc oxide: 25 g / L, ferrous chloride: 1.5 g / L, and then After removing Zn deposited by substitution by immersion in a 400 g / L nitric acid aqueous solution, it was immersed in the same treatment solution used in the first Zn substitution plating treatment to perform a second Zn substitution plating treatment. In this second Zn displacement plating treatment, the immersion time was variously changed to obtain a Zn-plated Al plate on which a Zn layer having a coating amount shown in Tables 1 and 2 was formed.
次いで、ＺｎめっきＡｌ板に無電解めっき法を用いて、Ｚｎ層上にＮｉ−１２重量％Ｐ合金めっき皮膜を、表１〜２に示す皮膜量で形成し、引き続いてＺｎ層とＮｉ層を形成したＡｌ板に電気めっき法を用いてＮｉ層上にＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかのめっき皮膜、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかの合金めっき皮膜を、表１〜２に示す皮膜量で形成して供試板とした。さらに、上記のようにしてＺｎ層とＮｉ層を形成したＡｌ板に電気めっき法を用いてＮｉ層上に電気めっき法を用いてＳｎ皮膜を表１に示す皮膜量で形成させた後、３５０℃に加熱して表面にＳｎ−Ｎｉ合金皮膜を形成させて供試板とした。またさらに、上記のようにしてＺｎ層とＮｉ層を形成したＡｌ板に電気めっき法を用いてＮｉ層上にＢｉ、Ｚｎ、Ａｇ、Ｃｕのいずれかのめっき皮膜を表１〜２に示す皮膜量で形成させた後、その上に電気めっき法を用いてＳｎ皮膜を表１〜２に示す皮膜量で形成させた後、３５０℃に加熱して表面にＳｎ−Ｂｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金皮膜を形成させてめっきＡｌ板とした。 Next, using an electroless plating method on the Zn-plated Al plate, a Ni-12 wt% P alloy plating film is formed on the Zn layer with the film amounts shown in Tables 1-2, and subsequently the Zn layer and the Ni layer are formed. A plated film of Bi, In, Ag, or Sn on the Ni layer using an electroplating method on the formed Al plate, or Sn—Bi alloy, Sn—Ni alloy, Sn—Zn alloy, Sn—Ag alloy, An alloy plating film of any of the Sn—Cu alloys was formed with the film amounts shown in Tables 1 and 2 to obtain test plates. Furthermore, after forming the Sn film with the coating amount shown in Table 1 on the Ni layer by using the electroplating method on the Al plate on which the Zn layer and the Ni layer were formed as described above, 350 A test plate was prepared by heating to ° C. to form a Sn—Ni alloy film on the surface. Furthermore, the plating film of any one of Bi, Zn, Ag, and Cu is formed on the Ni layer by electroplating on the Al plate on which the Zn layer and the Ni layer are formed as described above. After forming the Sn film on the surface by using an electroplating method, the Sn film is formed with the film amount shown in Tables 1 and 2, and then heated to 350 ° C. to form Sn—Bi alloy or Sn—Zn alloy on the surface. A Sn—Ag alloy and a Sn—Cu alloy film were formed to form a plated Al plate.
次いで、めっきＡｌ板に表３に示す濃度の水系ウレタン樹脂を、ロールコート法を用いて表３に示す乾燥後の皮膜厚さとなるように塗布した後、９０℃の温度で乾燥して供試板とした。また、比較用として、上記のめっきＡｌ板に水溶性樹脂層を設けない供試板を作成した。 Next, a water-based urethane resin having a concentration shown in Table 3 was applied to the plated Al plate so as to have the film thickness after drying shown in Table 3 using a roll coating method, and then dried at a temperature of 90 ° C. A board was used. Moreover, the test plate which does not provide a water-soluble resin layer on said plating Al plate was produced for comparison.
[供試板の特性評価］
上記のようにして得られた供試板を、下記の特性について評価した。
[経時後のハンダ濡れ性]
供試板を８５℃、８５％湿度の恒温恒湿槽中で1週間経時した後、メニスコグラフ法（ＭＩＬ−ＳＴＤ−８８３Ｂ）により、ＳＯＬＤＥＲＣＨＥＣＫＥＲ（ＭＯＤＥＬ ＳＡＴ−５０００、ＲＨＥＳＣＡ製）を使用し、上記の各供試板から切り出した幅７ｍｍの試片をフラックス（ＥＣ−１９Ｓ−８、タムラ化研製）に浸漬し、その後２２５℃に保持したＳｎ（４２％）−Ｂｉ（５７％）−Ａｇ（１％）の組成を有するハンダ浴（タルチンケスター(株)製）に前記のフラックスを塗布した試片を、浸漬速度２ｍｍ／秒で２ｍｍ浸漬し、ハンダが濡れるまでの時間（ゼロクロスタイム）を測定し、下記に示す基準で経時後のハンダ濡れ性を評価した。短時間であるほどハンダ濡れ性が良好であることを示す。
◎：５秒未満
○：５〜１０秒
×：＞１０秒
[Characteristic evaluation of test plate]
The test plates obtained as described above were evaluated for the following characteristics.
[Solder wettability after aging]
After aging the test plate in a constant temperature and humidity chamber at 85 ° C. and 85% humidity for 1 week, by using a SOLDERCHECKER (MODEL SAT-5000, manufactured by RHESCA) according to the meniscograph method (MIL-STD-883B), the above-mentioned A specimen having a width of 7 mm cut out from each test plate was immersed in a flux (EC-19S-8, manufactured by Tamura Kaken), and then maintained at 225 ° C. Sn (42%)-Bi (57%)-Ag (1 %) Is immersed in a solder bath (made by Tarchin Kester Co., Ltd.) with the above-mentioned flux for 2 mm at an immersion speed of 2 mm / second, and the time until the solder gets wet (zero cross time) is measured. The solder wettability after aging was evaluated according to the following criteria. The shorter the time, the better the solder wettability.
◎: Less than 5 seconds ○: 5 to 10 seconds ×:> 10 seconds
[経時後のハンダ強度］
上記の８５℃、８５％湿度の恒温恒湿槽中で1週間経時した後の各供試板から切り出した幅７ｍｍ、長さ５０ｍｍの試片をＬ字型に折り曲げた２つの切り出し片を、評価面を向かい合わせてＴ字状になるように重ね、Ｔ字の縦棒の部分に厚さ０．５ｍｍの鋼板を挟み、Ｔ字の縦棒の下部に０．５ｍｍの空隙部を形成した試片を作成した。この試片の空隙部に上記のハンダ濡れ性の評価に用いたのと同様のフラックスを塗布した後、ソルダーチェッカー（ＳＡＴ−５０００、レスカ製）を用い、２５０℃に保持した上記の鉛フリーハンダ浴に試片の空隙部を１０ｍｍの深さまで浸漬し５秒間保持して空隙部にハンダを充填した後取り出し、Ｔピール試験片とした。次いでテンシロンを用い、Ｔピール試験片のＴ字の横棒の部分をチャックで挟んで引っ張ってＴ字の縦棒の部分のハンダ充填部を引き剥がし、このときの引張強度をハンダ強度として測定し、下記の基準で経時後のハンダ強度の優劣を評価した。
◎：４ｋｇｆ／７ｍｍ以上
○：３〜４ｋｇｆ／７ｍｍ未満
△：１〜３ｋｇｆ／７ｍｍ未満
×：１ｋｇｆ／７ｍｍ未満
[Solder strength after aging]
Two cut pieces obtained by bending a test piece having a width of 7 mm and a length of 50 mm cut out from each test plate after aging for one week in the above-described 85 ° C. and 85% humidity constant temperature and humidity chamber into an L-shape, The evaluation surfaces were face-to-face and overlapped to form a T shape, a 0.5 mm thick steel plate was sandwiched between the T-shaped vertical bars, and a 0.5 mm gap was formed below the T-shaped vertical bars. A specimen was created. The above-mentioned lead-free solder held at 250 ° C. using a solder checker (SAT-5000, manufactured by Resca) after applying the same flux as that used for the evaluation of the solder wettability to the void portion of the specimen. The test sample was immersed in the void of the specimen to a depth of 10 mm, held for 5 seconds, filled with solder in the void, and then taken out to obtain a T peel test piece. Next, using Tensilon, the portion of the T-shaped horizontal bar of the T-peel test piece is pulled with a chuck, and the solder filling portion of the T-shaped vertical bar is peeled off. The tensile strength at this time is measured as the solder strength. The superiority or inferiority of the solder strength after aging was evaluated according to the following criteria.
◎: 4 kgf / 7 mm or more ○: 3-4 kgf / 7 mm or less △: 1-3 kgf / 7 mm or less X: 1 kgf / 7 mm or less
その結果、表４に示すように、Ａｌ板にＺｎ層、Ｎｉ層を形成し、さらにその上にＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかのＳｎ合金めっき層を形成し、さらにその上に水系ウレタン樹脂層を設けた本発明の表面処理Ａｌ板は、８５℃、８５％湿度の恒温恒湿槽中で1週間経時した後のハンダの濡れ性に優れ、ハンダ強度も大きい。 As a result, as shown in Table 4, a Zn layer and a Ni layer were formed on the Al plate, and a metal plating layer of Bi, In, Ag, or Sn, or a Sn—Bi alloy, Sn—Ni was formed thereon. The surface-treated Al plate of the present invention in which an Sn alloy plating layer of any one of an alloy, a Sn—Zn alloy, a Sn—Ag alloy, and a Sn—Cu alloy is formed and a water-based urethane resin layer is further provided thereon is 85 ° C. Excellent solder wettability after aging for 1 week in a constant temperature and humidity chamber of 85% humidity and high solder strength.
Ａｌ基板表面に置換めっきによりＺｎ層を形成し、その上にＮｉ層と、さらにその上にＢｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかの合金めっき層を形成し、さらにその上に水溶性樹脂層を設けた本発明の表面処理Ａｌ板は、Ａｌ板とめっき層の密着性に優れており、Ｂｉ、Ｉｎ、Ａｇ、Ｓｎのいずれかの金属めっき層、またはＳｎ−Ｂｉ合金、Ｓｎ−Ｎｉ合金、Ｓｎ−Ｚｎ合金、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金のいずれかの合金めっき層を設け、さらにその上に耐水性および加工性に優れた水溶性樹脂層を設けているので、８５℃の温度でかつ８５％の湿度のような高温多湿の雰囲気中で長期間経時した後のメニスコグラフ法によるハンダ濡れ性が１０秒以下の優れたハンダ濡れ性が得られる。そのため、東南アジアや中国などの高温多湿の地域で製造および組み立てが行なわれる端子板やプリント基板等の小型で軽量の電子機器用の部品などに好適に適用することができる。
A Zn layer is formed on the Al substrate surface by displacement plating, and a Ni layer is formed thereon, and further a metal plating layer of Bi, In, Ag, or Sn, or a Sn—Bi alloy, a Sn—Ni alloy, The surface-treated Al plate of the present invention in which an alloy plating layer of any one of a Sn—Zn alloy, a Sn—Ag alloy, and a Sn—Cu alloy is formed, and a water-soluble resin layer is further provided thereon, includes an Al plate and a plating layer. Of any one of Bi, In, Ag, and Sn, or any of Sn—Bi alloy, Sn—Ni alloy, Sn—Zn alloy, Sn—Ag alloy, and Sn—Cu alloy. Since an alloy plating layer is provided, and a water-soluble resin layer excellent in water resistance and workability is provided thereon, it is long in a high-temperature and high-humidity atmosphere such as a temperature of 85 ° C. and a humidity of 85%. Meniscograph after a period of time Excellent solderability solder wettability is less than 10 seconds due to obtain. Therefore, the present invention can be suitably applied to small and lightweight electronic device parts such as terminal boards and printed boards that are manufactured and assembled in high-temperature and high-humidity regions such as Southeast Asia and China.
Claims (2)
前記Ｓｎ−Ｂｉ又はＳｎ−ＡｇのＳｎ合金層は、
皮膜量１〜１０ｇ／ｍ ２ のＢｉ又はＡｇをめっきした上に皮膜量０．２〜１０ｇ／ｍ２のＳｎめっきをした後、
Ｓｎの融点以上の温度に加熱することにより形成したものであることを特徴とする表面処理Ａｌ板。 A Zn layer, Ni layer, Sn—Bi or Sn—Ag Sn alloy layer is formed on the Al substrate surface in this order from the substrate side, and the film thickness after drying is 0.05 to 10 μm. A surface-treated Al plate formed by forming a conductive resin layer,
The Sn-Bi or Sn-Ag Sn alloy layer is
After the Sn-plated coating amount 0.2 to 10 g / m 2 of Bi or Ag coating amount 1 to 10 g / m 2 on plated,
A surface-treated Al plate formed by heating to a temperature equal to or higher than the melting point of Sn .
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| JPS5429555A (en) * | 1977-08-09 | 1979-03-05 | Toshiba Corp | Heat sink constituent |
| JPH0198252A (en) * | 1987-10-12 | 1989-04-17 | Oki Electric Ind Co Ltd | Package for semiconductor |
| JP2966079B2 (en) * | 1990-10-11 | 1999-10-25 | 新光電気工業株式会社 | Lead frame, semiconductor device using the same, and method of mounting semiconductor device |
| JP2002511187A (en) * | 1997-01-30 | 2002-04-09 | ジィ・シィ・ビィ・テクノロジーズ・リミテッド・ライアビリティ・カンパニー | Improved lead frame structure with pre-plated leads and method of making same |
| JP2003126987A (en) * | 2001-10-16 | 2003-05-08 | Denki Kagaku Kogyo Kk | Lead-free solder for circuit board and circuit board |
| JP2004204244A (en) * | 2002-12-20 | 2004-07-22 | Toyo Kohan Co Ltd | Post-treatment liquid for plated steel sheet, post-treated plated steel sheet with the use of it, and manufacturing method therefor |
| JP4159897B2 (en) * | 2003-02-26 | 2008-10-01 | 東洋鋼鈑株式会社 | Surface-treated Al plate excellent in solderability, heat sink using the same, and method for producing surface-treated Al plate excellent in solderability |
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2005
- 2005-02-14 JP JP2005035516A patent/JP5101798B2/en not_active Expired - Fee Related
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