JPWO2012043129A1 - Electric aluminum plating solution - Google Patents
Electric aluminum plating solution Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
Abstract
本発明の目的は、上記課題を解決し、非水溶媒中の溶解度が高く、電気めっきの通電電気量を大きくすることができ、短時間で効率良くアルミニウムの電気めっきを行うことができる電気アルミニウムめっき液を提供することにある。本発明の電気アルミニウムめっき液は、アルミニウム金属塩と、前記アルミニウム金属塩とイオン対をなす有機化合物がイオン対を形成してなるイオン液体と、誘電率が８以下の有機溶媒とから構成されることを特徴とする。誘電率が８以下の有機溶媒として、ヘキサン，トルエン，ジエチルエーテル，酢酸エチル，シクロヘキサン，キシレン，ベンゼン，ナフタレン，ヘプタン，シクロペンチルメチルエーテル，ジオキサンのうち少なくともひとつを含み、イオン液体と有機溶媒の合計に対して、有機溶媒の体積分率を３０％以上とすることが好ましい。An object of the present invention is to solve the above-mentioned problems, and to achieve high electrosolubility in an aluminum electroplating in a short time with high solubility in a non-aqueous solvent, a large amount of electricity for electroplating. It is to provide a plating solution. The electroaluminum plating solution of the present invention comprises an aluminum metal salt, an ionic liquid formed by forming an ion pair with an organic compound that forms an ion pair with the aluminum metal salt, and an organic solvent having a dielectric constant of 8 or less. It is characterized by that. As an organic solvent having a dielectric constant of 8 or less, it contains at least one of hexane, toluene, diethyl ether, ethyl acetate, cyclohexane, xylene, benzene, naphthalene, heptane, cyclopentyl methyl ether, and dioxane. On the other hand, the volume fraction of the organic solvent is preferably 30% or more.
Description
本発明は、非水溶媒を用いた電気アルミニウムめっき液に関する。 The present invention relates to an electroaluminum plating solution using a non-aqueous solvent.
アルミニウムの電気めっきは、アルミニウムの酸素に対する親和力が大きく、電位が水素より卑であるため、水溶液系のめっき浴で電気めっきを行うことは困難である。このため、アルミニウムの電気めっきでは、非水溶媒めっき液が多く研究されてきた。この有機溶媒系のめっき浴としては、ＡｌＣｌ3とＬｉＡｌＨ4またはＬｉＨとをエーテルに溶解したものやＡｌＣｌ3とＬｉＡｌＨ4とをＴＨＦ（テトラヒドロフラン）に溶解したものが代表的なものである。しかし、これらのめっき浴は、いずれも浴中に非常に活性なＬｉＡｌＨ4やＬｉＨを含んでいるため、酸素や水分が存在すると、それらと反応して分解し、電流効率が低下し、浴寿命も短くなってしまうものであった。このような中で安全且つ低コストなめっき液として、特許文献１，２などにはジメチルスルホンを溶媒とした溶融塩電解めっき液が報告されている。Since electroplating of aluminum has a large affinity for oxygen of aluminum and the potential is lower than that of hydrogen, it is difficult to perform electroplating in an aqueous plating bath. For this reason, many non-aqueous solvent plating solutions have been studied in electroplating aluminum. Typical examples of the organic solvent-based plating bath include those in which AlCl 3 and LiAlH 4 or LiH are dissolved in ether, and those in which AlCl 3 and LiAlH 4 are dissolved in THF (tetrahydrofuran). However, all of these plating baths contain very active LiAlH 4 and LiH in the bath, and therefore, when oxygen and moisture are present, they react with them and decompose, reducing current efficiency and bath life. It would be shorter. Under such circumstances, as a safe and low-cost plating solution, Patent Documents 1 and 2 report a molten salt electrolytic plating solution using dimethyl sulfone as a solvent.
また、近年では、特許文献３，４などに示すような、アルミニウムハロゲン化物と、アルキルピリジニウムハロゲン化物，四級アンモニウム塩，１−アルキルまたは１，３−ジアルキルイミダゾリウムハロゲン化物等とからなる溶融塩をめっき浴として用いる電気アルミニウムめっき法が提案されている。しかしながら、これらめっき浴は、水分の混入によってめっき状態が大きく変化するため、一定のめっき条件で電気めっきを行っても常に均一なめっき被膜が得られるとは限らない。 In recent years, a molten salt comprising an aluminum halide and an alkylpyridinium halide, a quaternary ammonium salt, a 1-alkyl or a 1,3-dialkylimidazolium halide, as shown in Patent Documents 3 and 4, etc. There has been proposed an electroaluminum plating method in which is used as a plating bath. However, since the plating state of these plating baths greatly changes due to the mixing of moisture, a uniform plating film is not always obtained even when electroplating is performed under certain plating conditions.
しかしながら、従来の非水電解液は、一般にアルミニウム塩の溶解度が低く、大電流で短時間でめっき処理することが困難であり、効率よくめっき作業を行うことができない。また、電解液中に酸素や水分が存在すると、それらとアルミニウム塩とが反応して分解し、電流効率が低下したり、めっきの仕上がりが悪くなり、電解液が劣化するという問題があった。 However, conventional non-aqueous electrolytes generally have low solubility of aluminum salts, and it is difficult to perform plating with a large current in a short time, so that the plating operation cannot be performed efficiently. Further, when oxygen or moisture is present in the electrolytic solution, the aluminum salt reacts with the aluminum salt and decomposes, resulting in a problem that current efficiency is lowered, plating finish is deteriorated, and the electrolytic solution is deteriorated.
これらの問題に加えて、高温溶融塩系の非水電解液の場合には、作動時に１００℃以上にしなければならず、常温での作動は不可能であるという問題があった。また、常温溶融塩系の非水電解液の場合には、作動可能な範囲が非常に狭く、めっき膜の未析出等の欠陥を低減するためにアルミニウム金属塩の濃度を高くすると、液の粘性が高くなってしまい、めっきの析出速度が低下するとともにめっきのつき周りが悪いという問題があった。 In addition to these problems, in the case of a high-temperature molten salt-based non-aqueous electrolyte, there is a problem that operation at room temperature is impossible because the temperature must be 100 ° C. or higher during operation. Also, in the case of room temperature molten salt-based non-aqueous electrolytes, the operable range is very narrow, and if the concentration of the aluminum metal salt is increased to reduce defects such as undeposited plating film, the viscosity of the solution However, there is a problem that the deposition rate of the plating is lowered and the surrounding area of the plating is poor.
そこで、本発明の目的は、上記課題を解決し、非水溶媒中の溶解度が高く、電気めっきの通電電気量を大きくすることができ、短時間で効率良くアルミニウムの電気めっきを行うことができる電気アルミニウムめっき液を提供することにある。 Therefore, the object of the present invention is to solve the above-mentioned problems, to have a high solubility in a non-aqueous solvent, to increase the amount of electricity applied for electroplating, and to perform electroplating of aluminum efficiently in a short time. It is to provide an electrolytic aluminum plating solution.
本発明の電気アルミニウムめっき液は、アルミニウム金属塩と、前記アルミニウム金属塩とイオン対をなす有機化合物がイオン対を形成してなるイオン液体と、誘電率が８以下の有機溶媒とから構成されることを特徴とする。誘電率が８以下の有機溶媒として、ヘキサン，トルエン，ジエチルエーテル，酢酸エチル，シクロヘキサン，キシレン，ベンゼン，ナフタレン，ヘプタン，シクロペンチルメチルエーテル，ジオキサンのうち少なくともひとつを含み、イオン液体と有機溶媒の合計に対して、有機溶媒の体積分率が３０％以上であることが好ましい。
本発明の他の目的、特徴及び利点は以下の本発明の実施例の記載から明らかになるであろう。The electroaluminum plating solution of the present invention comprises an aluminum metal salt, an ionic liquid formed by forming an ion pair with an organic compound that forms an ion pair with the aluminum metal salt, and an organic solvent having a dielectric constant of 8 or less. It is characterized by that. As an organic solvent having a dielectric constant of 8 or less, it contains at least one of hexane, toluene, diethyl ether, ethyl acetate, cyclohexane, xylene, benzene, naphthalene, heptane, cyclopentyl methyl ether, and dioxane. On the other hand, the volume fraction of the organic solvent is preferably 30% or more.
Other objects, features and advantages of the present invention will become apparent from the following description of embodiments of the present invention.
本発明によれば、めっきの析出効率が向上し、膜厚の均一性を改善することが可能となる。また、上記めっきを適用することで、立体的な形状であっても均一なめっきが施された部品を提供することが可能となる。 According to the present invention, the deposition efficiency of plating is improved, and the film thickness uniformity can be improved. In addition, by applying the above plating, it is possible to provide a component that is evenly plated even in a three-dimensional shape.
本発明の実施の形態について以下に説明する。 Embodiments of the present invention will be described below.
アルミニウム源として使用するアルミニウム金属塩としては、アルミニウムハロゲン化物を使用できる。アルミニウムハロゲン化物としては、塩化アルミニウム，臭化アルミニウム等の無水塩が使用できる。アルミニウム金属塩とイオン対を形成する有機化合物に対して、めっき液中のアルミニウム濃度が等モル以下ではめっきの析出速度が著しく低下するため、濃度が高いほうがめっきの析出均一性が良好となる。めっき液中のアルミニウム濃度は、アルミニウム金属塩とイオン対を形成する有機化合物に対して、等モル以上含有されることがよく、好ましくは１.５倍以上、より好ましくは３倍以上含有されることがよい。 Aluminum halide can be used as the aluminum metal salt used as the aluminum source. As the aluminum halide, anhydrous salts such as aluminum chloride and aluminum bromide can be used. With respect to an organic compound that forms an ion pair with an aluminum metal salt, the deposition rate of the plating is remarkably reduced when the aluminum concentration in the plating solution is equal to or less than the equimolar amount. Therefore, the higher the concentration, the better the deposition uniformity. The aluminum concentration in the plating solution is preferably contained in an equimolar amount or more with respect to the organic compound that forms an ion pair with the aluminum metal salt, preferably 1.5 times or more, more preferably 3 times or more. It is good.
アルミニウム金属塩とイオン対を形成する有機化合物としては、ジアルキルイミダゾリウム塩，脂肪族ホスホニウム塩，４級アンモニウム塩などの有機化合物カチオンのハロゲン化物が使用できる。ジアルキルイミダゾリウム塩としては、１，３−ジアルキルイミダゾリウムハロゲン化物である１−エチル−３−メチルイミダゾリウムクロリド（［ＥＭＩＭ］・Ｃｌ）、１−エチル−３−メチルイミダゾリウムブロミド（［ＥＭＩＭ］・Ｂｒ）、１−エチル−３−メチルイミダゾリウムヨージド（［ＥＭＩＭ］・Ｉ）、１−ブチル−３−メチルイミダゾリウムクロリド（［ＢＭＩＭ］・Ｃｌ）、１−ブチル−３−メチルイミダゾリウムブロミド（［ＢＭＩＭ］・Ｂｒ）、１−ブチル−３−メチルイミダゾリウムヨージド（［ＢＭＩＭ］・Ｉ）などを好適に用いることができる。また、脂肪族ホスホニウム塩としては、エチルトリブチルホスホニウムクロリド（［ＥＢＰ］・Ｃｌ），エチルトリブチルホスホニウムブロミド（［ＥＢＰ］・Ｂｒ），エチルトリブチルホスホニウムヨージド（［ＥＢＰ］・Ｉ）、などを好適に用いることができる。４級アンモニウム塩として、テトラエチルアンモニウムブロミド（［Ｅ４Ｎ］・Ｂｒ），トリメチルエチルアンモニウムクロリド（［Ｍ３ＥＮ］・Ｃｌ），テトラブチルアンモニウムクロリド（［Ｂｕ４Ｎ］・Ｃｌ）などを好適に用いることができる。 As an organic compound that forms an ion pair with an aluminum metal salt, a halide of an organic compound cation such as a dialkylimidazolium salt, an aliphatic phosphonium salt, or a quaternary ammonium salt can be used. Examples of the dialkylimidazolium salt include 1-ethyl-3-methylimidazolium chloride ([EMIM] · Cl), 1-ethyl-3-methylimidazolium bromide ([EMIM]) which is a 1,3-dialkylimidazolium halide. Br), 1-ethyl-3-methylimidazolium iodide ([EMIM] • I), 1-butyl-3-methylimidazolium chloride ([BMIM] • Cl), 1-butyl-3-methylimidazolium Bromide ([BMIM] · Br), 1-butyl-3-methylimidazolium iodide ([BMIM] · I) and the like can be preferably used. As the aliphatic phosphonium salt, ethyltributylphosphonium chloride ([EBP] · Cl), ethyltributylphosphonium bromide ([EBP] · Br), ethyltributylphosphonium iodide ([EBP] · I), and the like are preferably used. Can be used. As the quaternary ammonium salt, tetraethylammonium bromide ([E4N] · Br), trimethylethylammonium chloride ([M3EN] · Cl), tetrabutylammonium chloride ([Bu4N] · Cl) and the like can be suitably used.
上記したアルミニウム金属塩と、アルミニウム金属塩とイオン対を形成する有機化合物とを混合することにより、以下の反応により、イオン対を形成したイオン液体が形成される。 By mixing the above-described aluminum metal salt and an organic compound that forms an ion pair with the aluminum metal salt, an ionic liquid that forms an ion pair is formed by the following reaction.
Ａｌ・Ｘｎ＋Ｒ・Ｙｍ＝（Ａｌ・Ｒ）（Ｘｎ）（Ｙｍ） …（式１）
（式１において、Ｘ，Ｙはハロゲン化物を示し、Ｒは有機化合物カチオンを示し、ｎ，ｍは価数を示し、１〜４の整数である。）
アルミニウム金属塩に塩化アルミニウム，アルミニウム金属塩とイオン対を形成する有機化合物に１−エチル−３−メチルイミダゾリウムクロリドを用いた場合の反応を例として以下に記載する。Al · Xn + R · Ym = (Al · R) (Xn) (Ym) (Formula 1)
(In Formula 1, X and Y represent a halide, R represents an organic compound cation, n and m represent a valence, and are integers of 1 to 4.)
The reaction when aluminum chloride is used as the aluminum metal salt and 1-ethyl-3-methylimidazolium chloride is used as the organic compound that forms an ion pair with the aluminum metal salt is described below as an example.
このように、アルミニウム塩とジアルキルイミダゾリウム塩などの有機化合物を混合すると、それらはイオン対を形成し、融体（イオン液体）が得られる。このイオン液体は、電気めっき液として機能することが可能である。しかしながら、めっき液としてはアルミニウムの濃度が高いことが望まれるが、例えば、アルミニウム金属塩とイオン対を形成する有機化合物に対してアルミニウム金属塩をモル比で３倍以上とすると、アルミニウムの濃度が高くなるに従い粘性が高く流動性がなくなり、このようなイオン液体からは均一なめっきの析出が得られなくなる。そこで本発明では、粘性が高いイオン液体を有機溶媒に溶解させることによって、モル比が３倍より大きくても粘性を低くでき、めっき液として好適に用いることが可能となる。また、有機溶媒の体積分率が高いほど、相対的にアルミニウムのイオン濃度が低下していくが、粘性が低くなることで見かけの拡散係数が大きくなるために被めっき面での電流を大きく均一にすることが可能となる。従って、基板面への均一なめっきを得ることができる。 Thus, when an organic compound such as an aluminum salt and a dialkylimidazolium salt is mixed, they form an ion pair, and a melt (ionic liquid) is obtained. This ionic liquid can function as an electroplating solution. However, it is desirable for the plating solution to have a high aluminum concentration. For example, if the aluminum metal salt has a molar ratio of 3 times or more with respect to the organic compound that forms an ion pair with the aluminum metal salt, the aluminum concentration is reduced. As it increases, the viscosity becomes high and the fluidity is lost, and uniform plating deposition cannot be obtained from such an ionic liquid. Therefore, in the present invention, by dissolving an ionic liquid having a high viscosity in an organic solvent, the viscosity can be lowered even if the molar ratio is larger than 3 times, and it can be suitably used as a plating solution. In addition, the higher the volume fraction of the organic solvent, the lower the aluminum ion concentration, but the lower the viscosity, the larger the apparent diffusion coefficient, so the current on the surface to be plated becomes larger and more uniform. It becomes possible to. Therefore, uniform plating on the substrate surface can be obtained.
有機溶媒としては、誘電率が８以下の非極性の溶媒を用いることが好ましい。誘電率の高い極性有機溶媒を用いた場合には、アルミニウムとイオン対を形成している有機化合物とが解離し、めっきの析出効率が低下してしまう。これは、イオン液体中の正負イオン間のクーロン力が媒体の誘電率に反比例し、溶媒の比誘電率が高いほどクーロン力は小さくなり、金属塩の解離が容易になり、アルミニウム金属塩と有機化合物とのイオン対の解離が容易となってしまうためである。したがって、有機溶媒の誘電率は８以下のものが好ましく、より好ましくは５以下とすることが望ましい。このような有機溶媒としては、ヘキサン（誘電率２.０），トルエン（誘電率２.４），ジエチルエーテル（誘電率４.３），酢酸エチル（誘電率６.０），シクロヘキサン（誘電率２.０），キシレン（誘電率２.５），ベンゼン（誘電率２.３），ナフタレン（誘電率２.５），ヘプタン（誘電率１.９），シクロペンチルメチルエーテル（誘電率４.８），ジオキサン（誘電率２.１）が挙げられ、これらのうちいずれか一種、あるいは複数を用いても良い。また、有機溶剤の沸点は、４０℃以上のものが好ましく、沸点が低過ぎると、密閉，冷却等の有機溶剤の発散，引火等への対策が過重となるので好ましくない。また、イオン液体と有機溶媒の合計に対して、有機溶媒の体積分率を３０vol％以上とすることが好ましく、５０vol％以上が更に好ましく、７５vol％以上が望ましい。しかしながら、有機溶媒の体積分率が高くなりすぎると、アルミニウムのイオン濃度が低下しすぎてしまい、９０vol％よりも高くなるとめっきの電流効率低下の原因となってしまう。そのため、有機溶媒の体積分率は９０vol％が好ましい。 As the organic solvent, it is preferable to use a nonpolar solvent having a dielectric constant of 8 or less. When a polar organic solvent having a high dielectric constant is used, aluminum and an organic compound forming an ion pair are dissociated, resulting in a decrease in plating deposition efficiency. This is because the Coulomb force between positive and negative ions in the ionic liquid is inversely proportional to the dielectric constant of the medium. The higher the relative dielectric constant of the solvent, the smaller the Coulomb force, the easier the metal salt dissociates, and the aluminum metal salt and organic This is because dissociation of the ion pair with the compound becomes easy. Therefore, the dielectric constant of the organic solvent is preferably 8 or less, more preferably 5 or less. Such organic solvents include hexane (dielectric constant 2.0), toluene (dielectric constant 2.4), diethyl ether (dielectric constant 4.3), ethyl acetate (dielectric constant 6.0), cyclohexane (dielectric constant). 2.0), xylene (dielectric constant 2.5), benzene (dielectric constant 2.3), naphthalene (dielectric constant 2.5), heptane (dielectric constant 1.9), cyclopentyl methyl ether (dielectric constant 4.8) ), Dioxane (dielectric constant 2.1), and any one or more of these may be used. The boiling point of the organic solvent is preferably 40 ° C. or higher. If the boiling point is too low, countermeasures against organic solvent divergence, ignition, and the like such as sealing and cooling become excessive, which is not preferable. Moreover, it is preferable that the volume fraction of an organic solvent shall be 30 vol% or more with respect to the sum total of an ionic liquid and an organic solvent, 50 vol% or more is further more preferable, and 75 vol% or more is desirable. However, if the volume fraction of the organic solvent is too high, the ion concentration of aluminum is too low, and if it is higher than 90 vol%, the current efficiency of the plating is reduced. Therefore, the volume fraction of the organic solvent is preferably 90 vol%.
アルミニウム塩に加えて、卑金属塩としてＮｉやＣｏ，Ｃｕ、などの遷移金属塩やＴｉ，ＷやＭｏなどの高融点金属塩を加えると、得られるめっき膜にこれらの元素が含まれ、熱的安定性を向上させることができる。例えばニッケルの場合は、塩化ニッケル，硫酸ニッケルなどを０.０１から２０mol％の濃度となるように添加することができ、その場合ニッケル塩とアルミニウム塩を加えた金属塩濃度は一定となるようにアルミニウム塩の添加量を調整すると良い。同様に他の卑金属塩の場合も、塩化物との金属塩などを添加することができる。 In addition to aluminum salts, transition metal salts such as Ni, Co, and Cu, and refractory metal salts such as Ti, W, and Mo are added as base metal salts. Stability can be improved. For example, in the case of nickel, nickel chloride, nickel sulfate, etc. can be added so as to have a concentration of 0.01 to 20 mol%, and in that case, the metal salt concentration with the addition of nickel salt and aluminum salt is made constant. The amount of aluminum salt added should be adjusted. Similarly, in the case of other base metal salts, metal salts with chlorides can be added.
めっき処理温度は作業性を勘案すると１０〜６０℃以下が好ましく、さらには４０℃以下が望ましい。温度が１０℃未満となると、粘度が高くなりめっき膜全体が黒くなる傾向を示す。 In consideration of workability, the plating temperature is preferably 10 to 60 ° C. or lower, more preferably 40 ° C. or lower. When the temperature is less than 10 ° C., the viscosity increases and the entire plating film tends to be black.
電気アルミニウムめっきは、めっき条件として、直流もしくはパルス電流により、電流密度０.０１〜１０Ａ／ｄｍ2で行うと電流効率がよくかつ均一なめっきをすることができる。電流密度が高すぎると、有機化合物の分解，めっき層の不均一化、さらには電流効率の低下が起り好ましくない。また、めっき液が酸素，水分に対して不安定なため、めっきは乾燥不活性ガス雰囲気下で行うことが望ましい。When the electroaluminum plating is carried out at a current density of 0.01 to 10 A / dm 2 by direct current or pulse current as plating conditions, it is possible to perform uniform plating with good current efficiency. If the current density is too high, decomposition of the organic compound, non-uniformity of the plating layer, and further decrease in current efficiency are undesirable. Further, since the plating solution is unstable with respect to oxygen and moisture, the plating is preferably performed in a dry inert gas atmosphere.
連続めっきを行う場合には、めっき浴にＡｌイオンを補給して、浴中のＡｌイオン濃度を一定の範囲に保つ必要があるが、この場合、陽極をアルミニウム製可溶性陽極にすると、通電量に応じてＡｌイオンが自動補給され、アルミニウムハロゲン化物の補給によらなくてもＡｌイオン濃度を一定の範囲に保つことができ、しかも、浴組成を崩すことがない。 When performing continuous plating, it is necessary to replenish the plating bath with Al ions and keep the Al ion concentration in the bath within a certain range. Accordingly, Al ions are automatically replenished, and the Al ion concentration can be kept within a certain range without depending on the replenishment of aluminum halide, and the bath composition is not destroyed.
めっき後の洗浄に用いる有機溶剤は、ヘキサン，ドデカン等の飽和脂肪族炭化水素類、および、ベンゼン，トルエン，ヘキシルベンゼン，ドデシルベンゼン等の芳香族炭化水素類である。これらは、めっき液中に混入しても悪影響を及ぼさず、中でも、アルキル置換基を有する芳香族炭化水素、特に炭素数８以下のアルキル置換基を有するアルキルベンゼンは、めっき液中に混入してもめっきに悪影響を及ぼさないので、特に好ましい。有機溶剤の沸点は、４０℃以上のものが好ましく、沸点が低過ぎると、密閉，冷却等の有機溶剤の発散，引火等への対策が過重となるので好ましくない。 Organic solvents used for cleaning after plating are saturated aliphatic hydrocarbons such as hexane and dodecane, and aromatic hydrocarbons such as benzene, toluene, hexylbenzene, and dodecylbenzene. These have no adverse effect even when mixed in the plating solution. Among them, aromatic hydrocarbons having an alkyl substituent, particularly alkylbenzenes having an alkyl substituent of 8 or less carbon atoms may be mixed in the plating solution. This is particularly preferable because it does not adversely affect the plating. The boiling point of the organic solvent is preferably 40 ° C. or higher. If the boiling point is too low, measures against divergence of the organic solvent such as sealing and cooling, ignition, etc. are excessively undesirable.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの記載に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these descriptions.
〔実施例１〕
１−エチル−３−メチルイミダゾリウムクロリド（関東化学製；［ＥＭＩＭ］Ｃｌ）と無水塩化アルミニウム（和光純薬，ＡｌＣｌ3）を用いた。湿度５％，温度２５℃としたグローブボックス内で秤量し、［ＥＭＩＭ］Ｃｌ：ＡｌＣｌ3＝１：３のモル比となるようにＡｌＣｌ3を加え、１００ｍｌの融体を得た。３００ｍｌのトルエン（和光純薬工業）に前述の融体を溶解させ、総量で４００ｍｌとなるようにめっき液を作製した。得られた電解液４００ｍｌを、縦×横×深さが１００mm×５０mm×１００mmのポリプロピレン製の電解槽に入れた。[Example 1]
1-ethyl-3-methylimidazolium chloride (manufactured by Kanto Chemical; [EMIM] Cl) and anhydrous aluminum chloride (Wako Pure Chemicals, AlCl 3 ) were used. Weighing was carried out in a glove box with a humidity of 5% and a temperature of 25 ° C., and AlCl 3 was added so that the molar ratio of [EMIM] Cl: AlCl 3 = 1: 3 was obtained, thereby obtaining 100 ml of a melt. The aforementioned melt was dissolved in 300 ml of toluene (Wako Pure Chemical Industries), and a plating solution was prepared so that the total amount was 400 ml. 400 ml of the obtained electrolytic solution was placed in an electrolytic cell made of polypropylene having a length × width × depth of 100 mm × 50 mm × 100 mm.
次に、アノード電極として縦×横が７５mm×７５mm、厚さが２mmの純度９９.９％のアルミニウム板を、またカソード電極として縦×横が５０mm×５０mm、厚さが０.１mmの銅箔を、互いに３０mmの間隔を置いて電解槽内に対向させて配置し、電解液内に浸漬した。電極と接続用のリード線を電解槽の蓋を気密状態で貫通させ、電源に接続した。 Next, an aluminum plate with a vertical length of 75 mm × 75 mm and a thickness of 2 mm as the anode electrode and a purity of 99.9%, and a cathode electrode with a vertical length of 50 mm × 50 mm and a thickness of 0.1 mm copper foil Were placed opposite to each other in the electrolytic cell at an interval of 30 mm and immersed in the electrolytic solution. The electrode and connection lead wires were passed through the electrolytic cell lid in an airtight state and connected to a power source.
以上の作業をグローブボックス中で行った後、外に取り出した。 After performing the above operation in the glove box, it was taken out.
電気アルミニウムめっきは定電流源を用いて、電流密度−１０ｍＡ／cm2で２０分間または電流密度−２０ｍＡ／cm2で１０分間行い、銅箔の表面にアルミニウムめっき膜を形成した。めっき時の電圧は３Ｖ以下として行った。その後、電流効率の評価と、めっき膜の表面状態の観察を行った。電流効率は、アルミニウムの析出量を実測して求め、これをクーロンメータの電流値を基に予め算出される析出量と比較し、後者の計算上の析出量に対する割合を百分率として求めた。Electro-aluminum plating was performed using a constant current source at a current density of −10 mA / cm 2 for 20 minutes or at a current density of −20 mA / cm 2 for 10 minutes to form an aluminum plating film on the surface of the copper foil. The voltage during plating was 3 V or less. Thereafter, the current efficiency was evaluated and the surface state of the plating film was observed. The current efficiency was obtained by actually measuring the amount of deposited aluminum, comparing this with the amount of precipitation calculated in advance based on the current value of the coulometer, and determining the percentage of the latter calculated amount as a percentage.
上記のようにして行った結果、めっき状態が良好であった。また、銅箔面内の５か所について膜厚測定を行った結果、めっき膜厚は４μｍであり、分布は５％以内と、良好な結果が得られた。また、電流効率は９７％と良好であった。 As a result of the above, the plating state was good. Moreover, as a result of measuring the film thickness at five locations in the copper foil surface, the plating film thickness was 4 μm, and the distribution was within 5%, and good results were obtained. The current efficiency was as good as 97%.
この結果から明らかなように、本実施例の溶媒および溶質を用いると、電気めっきの通電電流を大きく取ることができ、短時間で効率良くアルミニウムのめっきができると共に、電流効率が良く、電解液の劣化によるトラブルも回避され、均一性良く良好なめっき状態を得ることができることがわかった。 As is clear from this result, when the solvent and the solute of this example are used, it is possible to increase the energization current of electroplating, to perform aluminum plating efficiently in a short time, and to improve the current efficiency. It has been found that troubles due to deterioration of the resin can be avoided and a good plating state can be obtained with good uniformity.
〔実施例２〜１２〕
塩化アルミニウム塩ＡｌＣｌ3を、表１に示した有機化合物，有機溶媒を用いて、種々の塩濃度Ａ（モル／１）の１つとなるように溶解させて、実施例２〜１２のめっき液を実施例１と同様に作成した。[Examples 2 to 12]
The aluminum chloride salt AlCl 3 was dissolved in one of various salt concentrations A (mol / 1) using the organic compounds and organic solvents shown in Table 1 to prepare the plating solutions of Examples 2 to 12. Prepared in the same manner as in Example 1.
電気アルミニウムめっきは定電流源を用いて、電流密度−１０ｍＡ／cm2で２０分間または電流密度−２０ｍＡ／cm2で１０分間行った。その後、電流効率，めっき表面状態の観察を行った。めっき時の電圧は３Ｖ以下として行った。電流効率は、アルミニウムの析出量を実測して求め、これをクーロンメータの電流値を基に予め算出される析出量と比較し、後者の計算上の析出量に対する割合を百分率として求めた。その結果を表１に示す。The electroaluminum plating was performed using a constant current source at a current density of −10 mA / cm 2 for 20 minutes or at a current density of −20 mA / cm 2 for 10 minutes. Thereafter, the current efficiency and the plating surface state were observed. The voltage during plating was 3 V or less. The current efficiency was obtained by actually measuring the amount of deposited aluminum, comparing this with the amount of precipitation calculated in advance based on the current value of the coulometer, and determining the percentage of the latter calculated amount as a percentage. The results are shown in Table 1.
この結果から明らかなように、実施例１〜１２の溶媒および溶質を用いると、電気めっきの通電電流を大きく取ることができ、短時間で効率良くアルミニウムのめっきができると共に、電流効率が良く、電解液の劣化によるトラブルも回避され、良好なめっき状態を得ることができる。アルミニウム塩の濃度が高くなるとめっきの際の電流効率を向上可能であった。また、有機溶媒の濃度は高い方が粘性を低下させることができ、膜厚ばらつきを低減できた。また、実施例４，５のようにアルミニウム塩以外の卑金属を加えた場合、電流効率が低下する場合もあったがめっき膜の膜厚のばらつきが低減できた。 As is clear from this result, when the solvents and solutes of Examples 1 to 12 are used, the energization current of electroplating can be increased, aluminum can be efficiently plated in a short time, and the current efficiency is good. Troubles due to deterioration of the electrolytic solution can be avoided, and a good plating state can be obtained. When the concentration of the aluminum salt was increased, the current efficiency during plating could be improved. In addition, the higher the concentration of the organic solvent, the lower the viscosity and the film thickness variation. In addition, when a base metal other than an aluminum salt was added as in Examples 4 and 5, the current efficiency was sometimes reduced, but variations in the thickness of the plating film could be reduced.
〔実施例１３〕
実施例１と同様のめっき方法に従い、被めっき物は中央でＬ字型に９０度折った銅箔へのめっきを実施した。銅箔面の５か所について膜厚測定を行った結果、めっき膜厚は４μｍであり、分布は８％以内と、良好な結果が得られた。電流効率は９７％と良好であった。Example 13
In accordance with the same plating method as in Example 1, the object to be plated was plated on a copper foil which was folded 90 degrees into an L shape at the center. As a result of measuring the film thickness at five locations on the copper foil surface, the plating film thickness was 4 μm, and the distribution was within 8%, and good results were obtained. The current efficiency was as good as 97%.
この結果から明らかなように、本実施例の溶媒および溶質を用いると、電気めっきの通電電流を大きく取ることができ、短時間で効率良くアルミニウムのめっきができると共に、立体的な形状であっても均一なめっきが施された部品を提供することが可能とわかった。 As is clear from this result, when the solvent and solute of this example are used, it is possible to increase the energization current of electroplating, to efficiently plate aluminum in a short time, and to have a three-dimensional shape. It has also been found that it is possible to provide parts with uniform plating.
（比較例１）
実施例１と同様に１−エチル−３−メチルイミダゾリウムクロリド（２０モル％）と三塩化アルミニウム（８０モル％）とからなるイオン液体をめっき液として用いてめっきを施した。この場合は、電流密度が２０ｍＡ／cm2で実施したが、良好なめっきができずアルミニウムめっきの表面が黒く焼けためっき膜となった。また、めっき液の粘性が高いため、膜厚の分布が大きくなってしまった。(Comparative Example 1)
In the same manner as in Example 1, plating was performed using an ionic liquid composed of 1-ethyl-3-methylimidazolium chloride (20 mol%) and aluminum trichloride (80 mol%) as a plating solution. In this case, the current density was 20 mA / cm 2 , but good plating could not be performed, and the surface of the aluminum plating was burnt black. Moreover, since the viscosity of the plating solution is high, the film thickness distribution has become large.
（比較例２）
実施例１と同様に１−エチル−３−メチルイミダゾリウムクロリド（２０モル％）と三塩化アルミニウム（８０モル％）とからなるイオン液体を極性溶媒であるプロピレンカーボネート（誘電率６５）に溶解しめっき液として用いてめっきを施した。この場合は、電流密度が２０ｍＡ／cm2で実施したが、良好なめっきができずほとんどアルミニウムの析出が起きなかった。このような極性を有する溶媒にイオン液体を溶解させると、アルミニウム塩とイオン対を形成している有機化合物とが解離してしまい、めっき反応を阻害したと考えられる。(Comparative Example 2)
Similarly to Example 1, an ionic liquid composed of 1-ethyl-3-methylimidazolium chloride (20 mol%) and aluminum trichloride (80 mol%) was dissolved in propylene carbonate (dielectric constant 65) as a polar solvent. Plating was performed using it as a plating solution. In this case, although the current density was 20 mA / cm 2 , satisfactory plating could not be performed and aluminum deposition hardly occurred. When the ionic liquid is dissolved in a solvent having such a polarity, it is considered that the aluminum salt and the organic compound forming the ion pair are dissociated to inhibit the plating reaction.
（比較例３）
実施例１と同様に１−エチル−３−メチルイミダゾリウムクロリド（２０モル％）と三塩化アルミニウム（８０モル％）とからなるイオン液体を極性溶媒であるアセトニトリル（誘電率３８）に溶解しめっき液として用いてめっきを施した。この場合は、電流密度が２０ｍＡ／cm2で実施したが、良好なめっきができずほとんどアルミニウムの析出が起きなかった。
上記記載は実施例についてなされたが、本発明はそれに限らず、本発明の精神と添付の請求の範囲の範囲内で種々の変更および修正をすることができることは当業者には明らかである。(Comparative Example 3)
In the same manner as in Example 1, an ionic liquid composed of 1-ethyl-3-methylimidazolium chloride (20 mol%) and aluminum trichloride (80 mol%) was dissolved in acetonitrile (dielectric constant 38) as a polar solvent and plated. Plating was performed using the solution. In this case, although the current density was 20 mA / cm 2 , satisfactory plating could not be performed and aluminum deposition hardly occurred.
While the above description has been made with reference to exemplary embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention and the scope of the appended claims.
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| US9771661B2 (en) | 2012-02-06 | 2017-09-26 | Honeywell International Inc. | Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates |
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| US20150101935A1 (en) * | 2013-10-14 | 2015-04-16 | United Technologies Corporation | Apparatus and method for ionic liquid electroplating |
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| US10087540B2 (en) | 2015-02-17 | 2018-10-02 | Honeywell International Inc. | Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same |
| WO2017023743A1 (en) * | 2015-07-31 | 2017-02-09 | University Of South Florida | ELECTRODEPOSITION OF Al-Ni ALLOYS AND AI/Ni MULTILAYER STRUCTURES |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134193A (en) * | 1989-10-18 | 1991-06-07 | Mitsubishi Petrochem Co Ltd | Low-melting point composition and electric aluminum plating method |
| JPH0421794A (en) * | 1990-05-16 | 1992-01-24 | Mitsubishi Petrochem Co Ltd | Composition having low melting point and aluminum electroplating method |
| JPH06101088A (en) * | 1992-09-21 | 1994-04-12 | Mitsubishi Petrochem Co Ltd | Electric aluminum plating method |
| JP2008195988A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | ELECTRIC Al-Zr ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME |
| JP2009197318A (en) * | 2008-01-22 | 2009-09-03 | Dipsol Chem Co Ltd | ELECTRIC Al-Zr-Mn ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME ELECTROPLATED FILM |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2446349A (en) * | 1944-02-29 | 1948-08-03 | William Marsh Rice Inst For Th | Electrodeposition of aluminum |
| JPH0613758B2 (en) | 1985-09-20 | 1994-02-23 | 日新製鋼株式会社 | Electro aluminum plating method |
| JP2678984B2 (en) * | 1988-04-26 | 1997-11-19 | 日新製鋼株式会社 | Electric aluminum plating bath and plating method using the bath |
| JP2657991B2 (en) | 1988-04-26 | 1997-09-30 | 日新製鋼株式会社 | Electric aluminum plating bath and plating method using the bath |
| JP2662635B2 (en) * | 1988-04-26 | 1997-10-15 | 日新製鋼株式会社 | Electric aluminum plating bath and plating method using the bath |
| US5336378A (en) * | 1989-02-15 | 1994-08-09 | Japan Energy Corporation | Method and apparatus for producing a high-purity titanium |
| JPH0361392A (en) * | 1989-07-28 | 1991-03-18 | Mitsubishi Petrochem Co Ltd | Composition having low melting point and aluminum electroplating method using the same as bath |
| US5041194A (en) * | 1989-05-18 | 1991-08-20 | Mitsubishi Petrochemical Co., Ltd. | Aluminum electroplating method |
| JP3324101B2 (en) * | 1992-08-14 | 2002-09-17 | ソニー株式会社 | Aluminum non-aqueous electrolyte, battery using the same, and aluminum electrodeposition method |
| JP4693010B2 (en) * | 1995-06-30 | 2011-06-01 | コバレント アソシェーツ，インコーポレイテッド | Hydrophobic ionic liquid |
| JP2004076031A (en) | 2002-08-09 | 2004-03-11 | Ishikawajima Harima Heavy Ind Co Ltd | Plating bath for electroplating and plating bath for composite plating, and their production method |
| JP4756462B2 (en) | 2004-11-09 | 2011-08-24 | 日立金属株式会社 | Electrolytic aluminum plating solution |
| JP5080097B2 (en) * | 2007-02-09 | 2012-11-21 | ディップソール株式会社 | Molten salt electroplating bath and plating method using the same |
| EP1983079A1 (en) * | 2007-04-17 | 2008-10-22 | Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO | Barrier layer and method for making the same |
| EP1983592A1 (en) * | 2007-04-17 | 2008-10-22 | Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO | Method for manufacturing an electrode |
| JP5581523B2 (en) * | 2009-10-19 | 2014-09-03 | ディップソール株式会社 | Aluminum or aluminum alloy barrel electroplating method |
-
2011
- 2011-09-01 JP JP2012536292A patent/JPWO2012043129A1/en active Pending
- 2011-09-01 EP EP20110828690 patent/EP2623643A4/en not_active Withdrawn
- 2011-09-01 US US13/820,701 patent/US20130168258A1/en not_active Abandoned
- 2011-09-01 WO PCT/JP2011/069895 patent/WO2012043129A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134193A (en) * | 1989-10-18 | 1991-06-07 | Mitsubishi Petrochem Co Ltd | Low-melting point composition and electric aluminum plating method |
| JPH0421794A (en) * | 1990-05-16 | 1992-01-24 | Mitsubishi Petrochem Co Ltd | Composition having low melting point and aluminum electroplating method |
| JPH06101088A (en) * | 1992-09-21 | 1994-04-12 | Mitsubishi Petrochem Co Ltd | Electric aluminum plating method |
| JP2008195988A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | ELECTRIC Al-Zr ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME |
| JP2009197318A (en) * | 2008-01-22 | 2009-09-03 | Dipsol Chem Co Ltd | ELECTRIC Al-Zr-Mn ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME ELECTROPLATED FILM |
Non-Patent Citations (1)
| Title |
|---|
| JPN6015038617; Ｆｒａｎｋ Ｅｎｄｒｅｓ， Ｄｏｕｇｌａｓ ＭａｃＦａｒｌａｎｅ， Ａｎｄｒｅｗ Ａｂｂｏｔｔ: Ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ ｆｒｏｍ Ｉｏｎｉｃ Ｌｉｑｕｉｄｓ , 20080422, １６-１８，８８-９０，１２６-１３２，３５６，３５７, Ｗｉｌｅｙ-ＶＣＨ * |
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| Publication number | Publication date |
|---|---|
| US20130168258A1 (en) | 2013-07-04 |
| EP2623643A1 (en) | 2013-08-07 |
| EP2623643A4 (en) | 2015-03-04 |
| WO2012043129A1 (en) | 2012-04-05 |
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