JP4986122B2 - Electrolytic aluminum plating solution and aluminum plating film - Google Patents
Electrolytic aluminum plating solution and aluminum plating film Download PDFInfo
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Description
本発明は、電解アルミニウムめっき液およびそれを使用した電気めっき方法と生成しためっき膜に関する。 The present invention relates to an electrolytic aluminum plating solution, an electroplating method using the same, and a generated plating film.
アルミニウムの標準水素電極電位は水のそれよりも卑であるため、水溶液から電解めっきによってアルミニウムを析出させる場合、水の電気分解反応が優先的に起こるので、水溶液からアルミニウムを電析させることはできない。従って、電解アルミニウムめっきには、トルエンなどの非水系溶媒(有機溶媒)を用いためっき液や、イミダゾリウム塩などの常温溶融塩めっき液が用いられ、広く研究がなされてきた。しかしこれらは、安全性や生産性、コスト等の点で課題が多いため未だほとんど実用化されていない。このような中で、安全かつ低コストなめっき液として、特許文献1などにはジメチルスルホンを溶媒とした電解アルミニウムめっき液が報告されている。また、光沢のある緻密なアルミニウムめっき膜を得るためのアルミニウムめっき液として、特許文献2などには有機溶媒にフェナントロリンを添加した常温溶融塩系の電解アルミニウムめっき液が報告されている。
しかし、これらのめっき液は水との親和性が高く、めっき液中に水分を含有しやすい。そのため、このめっき液から得られるアルミニウムめっき膜には、めっき液中に含有されている水分の電気分解の影響によって電流密度の低い部分においてアルミニウムが析出していない未析箇所を生じやすい。さらに、L字型や凹型のような断面形状を有する試料に対しては、電流密度分布の低い折れ曲がった部分へのアルミニウムめっき膜の析出性(付き回り性)が悪いという問題がある。 However, these plating solutions have a high affinity with water and easily contain moisture in the plating solution. Therefore, in the aluminum plating film obtained from this plating solution, an undeposited portion in which aluminum is not precipitated tends to be generated in a portion where the current density is low due to the influence of electrolysis of moisture contained in the plating solution. Furthermore, for a sample having a cross-sectional shape such as an L-shape or a concave shape, there is a problem that the deposition property (attachment property) of the aluminum plating film to a bent portion with a low current density distribution is poor.
したがって本発明の目的は、めっき液に含有されている水分の影響を抑制し、未析箇所のないアルミニウムめっき膜を得ることのできるジメチルスルホンを溶媒とした電解アルミニウムめっき液を提供することにある。また本発明の別の目的は、L字型あるいは凹型断面形状のある試料へのアルミニウムめっき膜の付き回り性を改善することのできるジメチルスルホンを溶媒とした電解アルミニウムめっき液を提供することにある。 Accordingly, an object of the present invention is to provide an electrolytic aluminum plating solution using dimethyl sulfone as a solvent, which can suppress the influence of moisture contained in the plating solution and obtain an aluminum plating film having no undeposited portion. . Another object of the present invention is to provide an electrolytic aluminum plating solution using dimethyl sulfone as a solvent, which can improve the wrapping property of the aluminum plating film to a sample having an L-shaped or concave cross-sectional shape. .
上記の目的は、ジメチルスルホンとアルミニウムハロゲン化物および2,2’-ビピリジル構造を基本骨格に持つ有機化合物またはその誘導体を含有する電解アルミニウムめっき液を用いて電解アルミニウムめっきを行うことで達成することができる。2,2’-ビピリジル構造を基本骨格に持つ有機化合物には例えば構造式(1)〜(7)に示す物質がある。構造式(1)〜(7)に示す物質の窒素部位が、試料の高電流密度部分に吸着して電流密度を抑制するという電気的吸着作用を利用しており、それによって試料の低電流密度部分では電流密度が向上し、試料全体の電流密度分布が均一化される。その結果、試料には電流密度の低い部分がなくなるため、水分の影響による未析箇所は減少し、付き回り性も改善されるのである。 The above object can be achieved by performing electrolytic aluminum plating using an electrolytic aluminum plating solution containing dimethylsulfone, an aluminum halide, and an organic compound having a 2,2′-bipyridyl structure as a basic skeleton or a derivative thereof. it can. Examples of organic compounds having a 2,2′-bipyridyl structure as a basic skeleton include substances represented by structural formulas (1) to (7). The nitrogen portion of the substance represented by the structural formulas (1) to (7) uses an electroadsorption action in which the current density is suppressed by adsorbing to the high current density portion of the sample, thereby reducing the low current density of the sample. In the portion, the current density is improved, and the current density distribution of the entire sample is made uniform. As a result, since the portion having a low current density is eliminated from the sample, the number of unanalyzed portions due to the influence of moisture is reduced, and the throwing power is improved.
上記の2,2’-ビピリジル構造を基本骨格に持つ有機化合物は、例えばそれぞれ構造式(1)〜(7)で表される1,10-フェナントロリン,ネオクプロイン,バトフェナントロリン,バトクプロイン,バトクプロイン二スルホン酸二ナトリウム塩,2,2’-ビキノリン,2,2’-ビピリジルの何れか又は2種以上の組み合わせであることが好ましく、構造式(1)で表される1,10-フェナントロリンを用いることが特に好ましい。 The organic compounds having the above 2,2′-bipyridyl structure as the basic skeleton are, for example, 1,10-phenanthroline, neocuproine, batphenanthroline, batocuproin, and batocuproine disulfonic acid represented by structural formulas (1) to (7), respectively. A disodium salt, 2,2′-biquinoline, 2,2′-bipyridyl or a combination of two or more thereof is preferable, and 1,10-phenanthroline represented by the structural formula (1) is used. Particularly preferred.
したがって、本願第1の発明は、ジメチルスルホンとハロゲン化アルミニウム、および2,2’-ビピリジル構造を基本骨格に持つ有機化合物またはその誘導体を含有することを特徴とする電解アルミニウムめっき液である。本発明ではジメチルスルホン10.0molに対してアルミニウムハロゲン化物1.5〜4.0molおよび2,2’-ビピリジル構造を基本骨格に持つ有機化合物またはその誘導体を5×10-4mol〜20×10-4mol含有することが好ましい。 Therefore, the first invention of the present application is an electrolytic aluminum plating solution characterized by containing dimethylsulfone, aluminum halide, and an organic compound or derivative thereof having a 2,2′-bipyridyl structure as a basic skeleton. Organic compounds or 5 × 10 -4 mol~20 × 10 -4 mol containing the derivative with aluminum halides 1.5~4.0mol bipyridyl structures basic skeleton respect dimethylsulfone 10.0mol the present invention It is preferable to do.
また、本願第2の発明は、本願第1の発明の電解アルミニウムめっき液を用いて電気めっきすることにより得られるめっき膜の膜厚比(試料凹部に析出したアルミニウムめっき膜厚/試料凸部に析出したアルミニウムめっき膜厚)が0.1〜0.5のアルミニウムめっき膜である。本発明によって得られるアルミニウムめっき膜は未析がなく、試料全体の膜厚分布が改善される。なお、ここでいう膜厚比とは、被めっき物試料の各部位の中で最も膜厚の薄い凹部のめっき膜厚と最も膜厚の厚い凸部のめっき膜厚との比のことをいい、試料全体の膜厚の均一性を表している。膜厚比が1に近いほど膜厚の均一性が高いことを示す。試料の凹部・凸部の例を図1に示す。 The second invention of the present application is a film thickness ratio obtained by electroplating using the electrolytic aluminum plating solution of the first invention of the present application (the thickness of the aluminum plating deposited on the sample recess / the sample protrusion). This is an aluminum plating film having a deposited aluminum plating film thickness of 0.1 to 0.5. The aluminum plating film obtained by the present invention has no undeposited and the film thickness distribution of the entire sample is improved. In addition, the film thickness ratio here refers to the ratio of the plating film thickness of the concave part with the smallest film thickness to the plating film thickness of the convex part with the largest film thickness in each part of the sample to be plated. Represents the uniformity of the film thickness of the entire sample. The closer the film thickness ratio is to 1, the higher the film thickness uniformity. An example of the concave and convex portions of the sample is shown in FIG.
アルミニウムハロゲン化物には、塩化アルミニウムや臭化アルミニウムの無水塩が使用でき、その濃度はジメチルスルホン10.0molに対してアルミニウムハロゲン化物1.5〜4.0molが好ましく、特に2.0〜3.0molが好ましい。アルミニウム濃度が1.5mol未満ではジメチルスルホンの分解反応が起こり、黒色皮膜を生成する。一方、アルミニウム濃度が4.0molを超えると液抵抗が高くなり、発熱してめっき膜が均一に析出しなくなる。処理温度は105℃〜115℃が好ましい。温度が105℃未満ではめっき液の粘度が高くなると同時に液の電気抵抗が上昇し、めっき膜全体が黒く変色する。一方、115℃を超えるとめっき液中のアルミニウム錯体の構造が変化し、生成する被膜が黄色く変色する。 As the aluminum halide, an anhydrous salt of aluminum chloride or aluminum bromide can be used, and the concentration thereof is preferably 1.5 to 4.0 mol, particularly preferably 2.0 to 3.0 mol, with respect to 10.0 mol of dimethylsulfone. If the aluminum concentration is less than 1.5 mol, the decomposition reaction of dimethylsulfone occurs and a black film is formed. On the other hand, when the aluminum concentration exceeds 4.0 mol, the liquid resistance increases, and heat is generated, so that the plating film does not deposit uniformly. The treatment temperature is preferably 105 ° C to 115 ° C. If the temperature is lower than 105 ° C., the viscosity of the plating solution increases and at the same time, the electrical resistance of the solution increases, and the entire plating film turns black. On the other hand, when the temperature exceeds 115 ° C., the structure of the aluminum complex in the plating solution changes, and the resulting coating turns yellow.
2,2’-ビピリジル構造を基本骨格に持つ有機化合物またはその誘導体の濃度はジメチルスルホン10.0molに対して5×10-4mol〜20×10-4molが好ましく、さらには10×10-4mol〜15×10-4が好ましい。濃度が5×10-4mol未満では生成したアルミニウムめっき膜の表面にスジ状の未析箇所が発生し、20×10-4molを超えると生成したアルミニウムめっき膜が黒色に変色する。 Preferably 5 × 10 -4 mol~20 × 10 -4 mol to the organic compound or the concentration of its derivative dimethylsulfone 10.0mol with 2,2'-bipyridyl structures basic skeleton furthermore 10 × 10 -4 mol-15 × 10 −4 is preferred. When the concentration is less than 5 × 10 −4 mol, streaky undeposited portions are generated on the surface of the formed aluminum plating film, and when the concentration exceeds 20 × 10 −4 mol, the generated aluminum plating film turns black.
めっき時の電流密度は1〜10A/dm2が好ましい。特に好ましくは4〜6A/dm2である。電流密度が1A/dm2未満になるとアルミニウム膜が生成しなくなる。一方、10A/dm2を超えるとジメチルスルホンの分解反応が起こり黒色皮膜を生成する。 Current density during plating is preferably from 1 to 10 A / dm 2. Particularly preferred is 4 to 6 A / dm 2 . When the current density is less than 1 A / dm 2 , an aluminum film is not generated. On the other hand, when it exceeds 10 A / dm 2 , the decomposition reaction of dimethyl sulfone occurs and a black film is formed.
本願第3の発明は本願第1の発明の電解アルミニウムめっき液を用いて、素材に電解めっきを施すことを特徴とするアルミニウムめっき膜の形成方法である。 A third invention of the present application is a method for forming an aluminum plating film, wherein the material is subjected to electrolytic plating using the electrolytic aluminum plating solution of the first invention of the present application.
本発明の電解アルミニウムめっき液を用いれば、未析箇所の少ない、結晶粒径の微細なアルミニウム膜を析出させることができる。 By using the electrolytic aluminum plating solution of the present invention, it is possible to deposit an aluminum film having a small crystal grain size with few undeposited portions.
次に本発明を実施例によって具体的に説明するが、これら実施例により本発明が限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.
(実施例1)
ジメチルスルホンと無水塩化アルミニウムをモル比で5:1の割合で混合し、110℃で溶解した後、ジメチルスルホン10.0molに対して1,10-フェナントロリンを5×10-4mol加えて電解アルミニウムめっき液を建浴した。陽極には純度99.99%のAl板を使用し、陰極には図1に示すような銅製L字型試料を使用した。建浴した電解アルミニウムめっき液中で6A/dm2の電流密度で30分間通電した。その結果、試料凹部にもアルミニウムめっき膜は均一に析出した。析出したアルミニウムめっき膜の膜厚は、試料断面を観察することにより測定した。試料各部位のアルミニウムめっき膜厚を表1に示す。試料凹部と凸部のアルミニウムめっき膜厚を比較すると、膜厚比(試料凹部に析出したアルミニウムめっき膜厚/試料凸部に析出したアルミニウムめっき膜厚)は0.23であり、凹部にもアルミニウムめっき膜が析出していることが確認された。
Example 1
Dimethylsulfone and anhydrous aluminum chloride are mixed at a molar ratio of 5: 1 and dissolved at 110 ° C. Then, 5 × 10 -4 mol of 1,10-phenanthroline is added to 10.0 mol of dimethylsulfone, and electrolytic aluminum plating is performed. The solution was erected. An aluminum plate having a purity of 99.99% was used for the anode, and a copper L-shaped sample as shown in FIG. 1 was used for the cathode. It was energized for 30 minutes at a current density of 6 A / dm 2 in the electrolytic aluminum plating solution. As a result, the aluminum plating film was deposited uniformly in the sample recess. The film thickness of the deposited aluminum plating film was measured by observing the sample cross section. Table 1 shows the aluminum plating film thickness of each part of the sample. When comparing the aluminum plating film thickness of the sample recesses and projections, the film thickness ratio (aluminum plating film thickness deposited on the sample recesses / aluminum plating film thickness deposited on the sample projections) is 0.23, and the aluminum plating film also on the recesses It was confirmed that was deposited.
(比較例1)
ジメチルスルホンと無水塩化アルミニウムをモル比で5:1の割合で混合し、110℃で溶解して電解アルミニウムめっき液を建浴した。その他は実施例1と同様にして試料にアルミニウムめっき膜を形成した。その結果、試料凹部にはアルミニウムめっき膜がほとんど析出せず未析に近い状態であった。試料凹部と凸部のアルミニウムめっき膜厚を比較すると、膜厚比(凹部/凸部)は0.04であり、凸部に比べて凹部にはアルミニウムめっき膜がほとんど析出していないことが確認された。
(Comparative Example 1)
Dimethylsulfone and anhydrous aluminum chloride were mixed at a molar ratio of 5: 1 and dissolved at 110 ° C. to form an electrolytic aluminum plating solution. Otherwise, an aluminum plating film was formed on the sample in the same manner as in Example 1. As a result, almost no aluminum plating film was deposited in the sample recess, and the sample was almost undeposited. When the aluminum plating film thickness of the sample concave part and the convex part was compared, the film thickness ratio (concave part / convex part) was 0.04, and it was confirmed that the aluminum plating film was hardly deposited in the concave part compared to the convex part. .
(実施例2)
ジメチルスルホンと無水塩化アルミニウムをモル比で5:1の割合で混合し、110℃で溶解した後、さらにジメチルスルホン10.0molに対して1,10-フェナントロリンを5×10-4mol加えて電解アルミニウムめっき液を建浴した。その後、めっき液に純水5wt%を添加した。その他は実施例1と同様にして試料にアルミニウムめっき膜を形成した。
(Example 2)
Dimethylsulfone and anhydrous aluminum chloride are mixed in a molar ratio of 5: 1 and dissolved at 110 ° C. Then, 5 × 10 -4 mol of 1,10-phenanthroline is added to 10.0 mol of dimethylsulfone, and electrolytic aluminum is added. The plating solution was erected. Thereafter, 5 wt% of pure water was added to the plating solution. Otherwise, an aluminum plating film was formed on the sample in the same manner as in Example 1.
生成したアルミニウムめっき膜の外観の様子を図2に示す。生成したアルミニウムめっき膜は、添加した純水の電気分解の影響を受けることなく平滑で未析のない膜であった。
(比較例2)
The appearance of the produced aluminum plating film is shown in FIG. The produced aluminum plating film was a smooth and undeposited film without being affected by the electrolysis of the added pure water.
(Comparative Example 2)
ジメチルスルホンと無水塩化アルミニウムをモル比で5:1の割合で混合し、110℃で溶解することにより電解アルミニウムめっき液を建浴した。その後、めっき液に純水5wt%を添加した。その他は実施例1と同様にして試料にアルミニウムめっき膜を形成した。 Dimethylsulfone and anhydrous aluminum chloride were mixed at a molar ratio of 5: 1 and dissolved at 110 ° C. to form an electrolytic aluminum plating solution. Thereafter, 5 wt% of pure water was added to the plating solution. Otherwise, an aluminum plating film was formed on the sample in the same manner as in Example 1.
生成したアルミニウムめっき膜の外観と断面の様子を図3に示す。生成したアルミニウムめっき膜には添加した純水の電気分解の影響により未析(スジ状の未析箇所)が発生した。 The appearance and cross-sectional appearance of the produced aluminum plating film are shown in FIG. In the formed aluminum plating film, undeposited (streaky undeposited portions) occurred due to the electrolysis of the added pure water.
本発明によれば、生成するアルミニウムめっき膜への水分の影響を抑制し、未析のないアルミニウムめっき膜を得ることのできるジメチルスルホンを溶媒とした電解アルミニウムめっき液を提供することができる。本発明によれば、L字型あるいは凹型断面形状のある試料へのアルミニウムめっき膜の付き回り性を改善することのできるジメチルスルホンを溶媒とした電解アルミニウムめっき液を提供することができる。 According to the present invention, it is possible to provide an electrolytic aluminum plating solution using dimethyl sulfone as a solvent, which can suppress the influence of moisture on the produced aluminum plating film and obtain an aluminum plating film free from undeposited. According to the present invention, it is possible to provide an electrolytic aluminum plating solution using dimethyl sulfone as a solvent, which can improve the coverage of an aluminum plating film on a sample having an L-shaped or concave cross-sectional shape.
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