JPH0762590A - Aluminum electroplating method - Google Patents
Aluminum electroplating methodInfo
- Publication number
- JPH0762590A JPH0762590A JP21060793A JP21060793A JPH0762590A JP H0762590 A JPH0762590 A JP H0762590A JP 21060793 A JP21060793 A JP 21060793A JP 21060793 A JP21060793 A JP 21060793A JP H0762590 A JPH0762590 A JP H0762590A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- plating
- halide
- mol
- thionyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウムハロゲン
化物とオニウムハロゲン化物とを含有するめっき浴を用
いて効率的にアルミニウム電気めっきを行う方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently electroplating aluminum using a plating bath containing an aluminum halide and an onium halide.
【０００２】[0002]
【従来の技術】電気アルミニウムめっきは、アルミニウ
ムの酸素に対する親和力が大きく、標準電極電位が水素
より卑であるので、水溶液系で行うことは困難である。
このため、従来より電気アルミニウムめっきは、非水溶
液系のめっき浴、特に有機溶媒系のめっき浴を用いて行
われている。この有機溶媒系のめっき浴としては、三塩
化アルミニウムとＬｉＡｌＨ4 又はＬｉＨとをエーテル
に溶解したものや三塩化アルミニウムとＬｉＡｌＨ4 と
をテトラヒドロフランに溶解したものが代表的な例であ
る（例えば、D. E. Couch ら；J. Electrochem., 99
巻,(6),234頁）。しかし、これらめっき浴は、いずれも
浴中に非常に活性なＬｉＡｌＨ4 又は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、電流効率が低下したり、浴の寿命が短くなる問題
があった。また、使用する有機溶媒の沸点が低く、爆発
や燃焼の危険性が高いという問題を有している。2. Description of the Related Art Electrolytic aluminum plating is difficult to perform in an aqueous solution system because aluminum has a large affinity for oxygen and the standard electrode potential is baser than hydrogen.
Therefore, aluminum electroplating has hitherto been performed using a non-aqueous solution type plating bath, particularly an organic solvent type plating bath. Typical examples of the organic solvent-based plating bath include a solution of aluminum trichloride and LiAlH 4 or LiH dissolved in ether, or a solution of aluminum trichloride and LiAlH 4 dissolved in tetrahydrofuran (for example, DE Couch et al .; J. Electrochem., 99
Vol., (6), p. 234). However, since each of these plating baths contains very active LiAlH 4 or LiH in the bath, in the presence of oxygen and moisture, they react with them and decompose, reducing the current efficiency, and There was a problem that the life was shortened. Further, there is a problem that the boiling point of the organic solvent used is low and the risk of explosion and combustion is high.
【０００３】更に、他の例として、トリエチルアルミニ
ウムとフッ化ナトリウムをトルエンに溶解しためっき浴
も提案(R. Suchentrunk, Z. Werkstofftech., 12巻, 19
0 頁）されている。しかしながら、この場合も危険性の
高いトリエチルアルミニウムの取扱いが非常に問題であ
り、実用化は困難であると考えられている。また最近で
は、特開昭６２−７０５９２号、特開平１−２７２７８
８号及び同１−２７２７９０号各公報等に、アルミニウ
ムハロゲン化物とオニウムハロゲン化物とからなる溶融
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
のめっき条件で行っても常に均一な品質のめっき皮膜が
得られるとは限らない。Further, as another example, a plating bath in which triethylaluminum and sodium fluoride are dissolved in toluene is also proposed (R. Suchentrunk, Z. Werkstofftech., 12:19).
0 page). However, also in this case, handling of highly dangerous triethylaluminum is very problematic, and it is considered difficult to put it into practical use. Further, recently, JP-A-62-70592 and JP-A-1-27278.
No. 8 and Nos. 1-272790 and the like propose an electroaluminum plating method using a molten salt composed of an aluminum halide and an onium halide as a plating bath. However, since the plating state of these plating baths greatly changes due to the mixing of water, a plating film of uniform quality is not always obtained even if the plating bath is performed under constant plating conditions.
【０００４】[0004]
【発明が解決しようとする課題】本発明者は、上記問題
を解決し、アルミニウムハロゲン化物とオニウムハロゲ
ン化物とからなるめっき浴において、生産性よく常に良
好なめっき状態を有するアルミニウムめっき皮膜を得る
電気めっき方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present inventor has solved the above-mentioned problems, and in an electroplating bath composed of an aluminum halide and an onium halide, obtains an aluminum plating film having good productivity and always having a good plating state. An object is to provide a plating method.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意検討した結果、水分由来の含酸素不純
物を含有するアルミニウムハロゲン化物とオニウムハロ
ゲン化物の溶融塩からなるめっき浴のアルミニウムハロ
ゲン化物濃度を一度低下させた後に、塩化チオニル処理
を行い、再びアルミニウムハロゲン化物濃度を増加させ
て得られた溶融塩をめっき浴として再使用することによ
って安定した状態でめっきできることを見出し本発明を
完成した。Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a plating bath comprising a molten salt of an aluminum halide containing an oxygen-containing impurity derived from water and an onium halide is used. It was found that stable plating can be performed by reusing the molten salt obtained by performing a thionyl chloride treatment after increasing the aluminum halide concentration once again after decreasing the aluminum halide concentration once, and reusing it as a plating bath. Was completed.
【０００６】すなわち、本発明は、水分由来の含酸素不
純物を含有するアルミニウムハロゲン化物３０〜５０モ
ル％とオニウムハロゲン化物７０〜５０モル％との混合
溶融塩に、塩化チオニル処理を行い、アルミニウムハロ
ゲン化物５０〜８０モル％とオニウムハロゲン化物５０
〜２０モル％の組成物に調製して得られた混合溶融塩を
めっき浴として使用して電気アルミニウムめっきをする
ものである。That is, according to the present invention, a mixed molten salt of 30 to 50 mol% of an aluminum halide containing 70 to 50 mol% of an onium halide containing oxygen-containing impurities derived from water is treated with thionyl chloride to obtain an aluminum halogen. 50-80 mol% and onium halide 50
A mixed molten salt obtained by preparing a composition of about 20 mol% is used as a plating bath for electroaluminum plating.
【０００７】本発明で使用するアルミニウムハロゲン化
物の例としては、三塩化アルミニウム、三臭化アルミニ
ウムなどが挙げられる。また、本発明で使用するオニウ
ムハロゲン化物としては、テトラエチルアンモニウムブ
ロミド、トリメチルエチルアンモニウムクロリド等の第
４級アンモニウム塩；ブチルピリジニウムクロリド等の
ピリジニウム塩；１−エチル−３−メチルイミダゾリウ
ムクロリド等のイミダゾリウム塩；エチルトリブチルホ
スホニウムブロミド等のホスホニウム塩などが挙げられ
る。Examples of aluminum halides used in the present invention include aluminum trichloride and aluminum tribromide. The onium halides used in the present invention include quaternary ammonium salts such as tetraethylammonium bromide and trimethylethylammonium chloride; pyridinium salts such as butylpyridinium chloride; and imidazo compounds such as 1-ethyl-3-methylimidazolium chloride. Lithium salt; phosphonium salts such as ethyltributylphosphonium bromide and the like can be mentioned.
【０００８】電気アルミニウムめっき浴としては、アル
ミニウムハロゲン化物５０〜８０モル％とオニウムハロ
ゲン化物５０〜２０モル％の混合溶融塩を用いるが、オ
ニウムハロゲン化物は、吸湿性が高いため、めっき操作
を長時間行うことによって、めっき物及び／またはめっ
き雰囲気中の水を不純物として含有することがある。こ
の水は、めっき条件下でハロゲン化水素及び含酸素不純
物に分解することが知られている。As the electrolytic aluminum plating bath, a mixed molten salt of 50 to 80 mol% of aluminum halide and 50 to 20 mol% of onium halide is used. Since onium halide has high hygroscopicity, the plating operation is prolonged. Water in the plated product and / or the plating atmosphere may be contained as an impurity by performing it for a long time. It is known that this water decomposes into hydrogen halide and oxygen-containing impurities under the plating conditions.
【０００９】塩化チオニル処理時の溶融塩の組成は、ア
ルミニウムハロゲン化物３０〜５０モル％であり、オニ
ウムハロゲン化物７０〜５０モル％とする。塩化チオニ
ル処理を行う前のアルミニウムハロゲン化物濃度の調整
は、めっき浴組成物にオニウムハロゲン化物及び／また
は低アルミニウムハロゲン化物組成物を添加することに
よって行うことができる。アルミニウムハロゲン化物の
濃度が、３０モル％未満の場合は、組成物の粘度が高
く、オニウムハロゲン化物の種類によっては固化するこ
とがあるため好ましくない。またアルミニウムハロゲン
化物の濃度が５０モル％を超える場合には、塩化チオニ
ル処理が進行し難いため好ましくない。The composition of the molten salt during the thionyl chloride treatment is 30 to 50 mol% of aluminum halide and 70 to 50 mol% of onium halide. Adjustment of the aluminum halide concentration before performing the thionyl chloride treatment can be performed by adding an onium halide and / or a low aluminum halide composition to the plating bath composition. When the concentration of the aluminum halide is less than 30 mol%, the viscosity of the composition is high and it may be solidified depending on the kind of the onium halide, which is not preferable. When the concentration of the aluminum halide exceeds 50 mol%, the thionyl chloride treatment is difficult to proceed, which is not preferable.
【００１０】塩化チオニル処理は、上記アルミニウムハ
ロゲン化物濃度を調整した溶融塩に塩化チオニルを滴下
し、反応させた後、含酸素不純物を余剰の塩化チオニル
と共に除去することによって行う。添加する塩化チオニ
ルの量は、めっき浴中の含酸素不純物に対し、０．１〜
２倍モルが好ましい。添加量が０．１倍モル未満の場合
には、含酸素不純物の除去が不分でないため好ましくな
い。また添加量が２倍モルを超える場合には、余剰の塩
化チオニルの留去に時間とエネルギーを要し好ましくな
い。反応温度は、室温〜８０℃の範囲が好ましい。８０
℃以上を超える場合には、反応途中で塩化チオニルが留
出するため好ましくない。反応は、塩化チオニルの添加
とともに進行し、添加後５時間以内に終了する。The thionyl chloride treatment is carried out by dropping thionyl chloride into the molten salt having the aluminum halide concentration adjusted to cause a reaction, and then removing oxygen-containing impurities together with excess thionyl chloride. The amount of thionyl chloride added is 0.1 to the oxygen-containing impurities in the plating bath.
A double mole is preferred. If the amount added is less than 0.1 times the molar amount, the removal of oxygen-containing impurities is not inadequate, which is not preferable. On the other hand, if the addition amount exceeds 2 times the molar amount, it takes time and energy to distill off the excess thionyl chloride, which is not preferable. The reaction temperature is preferably in the range of room temperature to 80 ° C. 80
If the temperature exceeds ℃, thionyl chloride is distilled off during the reaction, which is not preferable. The reaction proceeds with the addition of thionyl chloride and is completed within 5 hours after the addition.
【００１１】塩化チオニルの反応終了後、アルミニウム
ハロゲン化物を添加して、めっき浴に用いるアルミニウ
ムハロゲン化物５０〜８０モル％とオニウムハロゲン化
物５０〜２０モル％の組成物として、電気アルミニウム
めっきに供する。含酸素不純物は、余剰の塩化チオニル
と共に、反応終了後又はめっき浴組成物調製後に留去す
る。塩化チオニルの留去は、減圧下、８０℃以下の加熱
によって容易に行える。この時、塩化チオニル残量は、
めっき浴の５重量％以下が好ましい。５重量％を超える
場合には、アルミニウムめっきが正常に行えないため好
ましくない。After completion of the reaction of thionyl chloride, an aluminum halide is added, and a composition of 50 to 80 mol% of aluminum halide and 50 to 20 mol% of onium halide used in a plating bath is subjected to electroaluminum plating. Oxygen-containing impurities are distilled off together with excess thionyl chloride after the reaction is completed or after the plating bath composition is prepared. The thionyl chloride can be easily distilled off by heating at 80 ° C. or lower under reduced pressure. At this time, the remaining amount of thionyl chloride is
It is preferably 5% by weight or less of the plating bath. If it exceeds 5% by weight, aluminum plating cannot be normally performed, which is not preferable.
【００１２】電気アルミニウムめっきは、陽極にアルミ
ニウム板、陰極に導電性を有する被めっき物を使用す
る、めっき条件として、直流もしくはパルス電流によ
り、浴温０〜１５０℃、電流密度０．０１〜５０Ａ／ｄ
ｍ2 で行うと電流効率がよく、かつ均一なめっきを得る
ことができる。めっきは、乾燥不活性ガス雰囲気下で行
うことが好ましい。In the aluminum electroplating, an aluminum plate is used for the anode, and an electroplating object is used for the cathode. The plating conditions are direct current or pulsed current, bath temperature 0 to 150 ° C., current density 0.01 to 50 A. / D
If it is performed at m 2 , current efficiency is good and uniform plating can be obtained. The plating is preferably performed in a dry inert gas atmosphere.
【００１３】[0013]
【実施例】以下に、実施例を挙げて、本発明を更に具体
的に説明するが、本発明はこれらに限定されるものでは
ない。 実施例１ 乾燥窒素雰囲気中で合成した、１−エチル−３−メチル
イミダゾリウムクロリド１４７ｇ（１モル）と三塩化ア
ルミニウム２８９ｇ（２モル）とからなる三塩化アルミ
ニウム濃度６７モル％の溶融塩に、水を９ｇ（２重量
％）添加したものを４４５ｇ調製した。この溶融塩は、
含酸素不純物を含有するめっき浴として不適なものであ
るこの溶融塩をガラス製反応器に投入後、１−エチル−
３−メチルイミダゾリウムクロリド１７６ｇ（１．２モ
ル）を加え、三塩化アルミニウムを４８モル％に低下さ
せた。次いで、この溶融塩に、塩化チオニル８９ｇ
（０．７５モル）を徐々に滴下したところ、激しい発泡
が認められた。反応器を７０℃に加熱し、４時間反応さ
せた後、減圧下（１０ｍｍＨｇ）、９０℃で２時間加熱
して余剰の塩化チオニルを留去した。この時、溶融塩中
に残留している塩化チオニルの濃度は、赤外分光分析法
により、０．３重量％（１２３０ｃｍ-1）であった。塩
化チオニル処理した溶融塩に、三塩化アルミニウム３２
０ｇ（２．４モル）を投入し、三塩化アルミニウム６７
モル％、１−エチル−３−メチルイミダゾリウムクロリ
ド３３モル％の溶融塩に調製し直した。このものをめっ
き浴として、陽極にアルミニウム板、陰極に銅板を使用
して、浴温６０℃、直流により電流密度５Ａ／ｄｍ2 の
条件で電解を行ったところ、銅板上には白色のアルミニ
ウム皮膜が得られた。The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Example 1 To a molten salt composed of 147 g (1 mol) of 1-ethyl-3-methylimidazolium chloride and 289 g (2 mol) of aluminum trichloride, which was synthesized in a dry nitrogen atmosphere, and had an aluminum trichloride concentration of 67 mol%, 445 g of a solution prepared by adding 9 g (2 wt%) of water was prepared. This molten salt
This molten salt, which is unsuitable as a plating bath containing oxygen-containing impurities, was charged into a glass reactor, and 1-ethyl-
176 g (1.2 mol) of 3-methylimidazolium chloride was added to reduce aluminum trichloride to 48 mol%. Next, 89 g of thionyl chloride was added to this molten salt.
When (0.75 mol) was gradually added dropwise, vigorous foaming was observed. The reactor was heated to 70 ° C. and reacted for 4 hours, and then heated at 90 ° C. for 2 hours under reduced pressure (10 mmHg) to distill off excess thionyl chloride. At this time, the concentration of thionyl chloride remaining in the molten salt was 0.3% by weight (1230 cm -1 ) by infrared spectroscopy. To thionyl chloride-treated molten salt, aluminum trichloride 32
0 g (2.4 mol) was added, and aluminum trichloride 67 was added.
Molten salt was reconstituted into a molten salt containing 1 mol% of 1-ethyl-3-methylimidazolium chloride and 33 mol%. Using this as a plating bath, an aluminum plate was used as the anode and a copper plate was used as the cathode, and electrolysis was performed under conditions of a bath temperature of 60 ° C. and a current density of 5 A / dm 2 with a direct current. A white aluminum film was formed on the copper plate. was gotten.
【００１４】比較例１ 実施例１において、塩化チオニル処理を行わなかった以
外は、実施例１と同様に行った。電解を行ったところ、
銅板上にアルミニウム皮膜は得られず、黒色の表面とな
った。Comparative Example 1 The procedure of Example 1 was repeated, except that the thionyl chloride treatment was omitted. After electrolysis,
No aluminum film was obtained on the copper plate, and the surface was black.
【００１５】比較例２ 実施例１において、１−エチル−３−メチルイミダゾリ
ウムクロリド１７６ｇの添加を行わず、また塩化チオニ
ル処理した溶融塩への三塩化アルミニウム３２０ｇ
（２．４モル）の添加を行わなかった以外は、実施例１
と同様に行った。電解を行ったことろ、銅板上にアルミ
ニウム皮膜は得られず、黒色の表面となった。Comparative Example 2 In Example 1, 176 g of 1-ethyl-3-methylimidazolium chloride was not added, and 320 g of aluminum trichloride was added to the thionyl chloride-treated molten salt.
Example 1 except that (2.4 mol) was not added.
I went the same way. As a result of the electrolysis, no aluminum film was obtained on the copper plate and the surface became black.
【００１６】[0016]
【発明の効果】本発明によれば、含酸素不純物を含有す
るアルミニウムハロゲン化物とオニウムハロゲン化物と
からなるめっき浴を再生し、これを用いて、生産性よ
く、常に良好なめっき状態を有するアルミニウムめっき
皮膜を得ることができる。According to the present invention, a plating bath composed of an aluminum halide containing an oxygen-containing impurity and an onium halide is regenerated, and using this, aluminum having good productivity and always having a good plating state is obtained. A plating film can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小湊 あさを 茨城県稲敷郡阿見町中央８丁目３番１号 三菱油化株式会社筑波総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Asao Kominato 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute
Claims (2)
ミニウムハロゲン化物３０〜５０モル％とオニウムハロ
ゲン化物７０〜５０モル％との混合溶融塩に、塩化チオ
ニル処理を行い、アルミニウムハロゲン化物５０〜８０
モル％とオニウムハロゲン化物５０〜２０モル％の組成
物に調製して得られた混合溶融塩をめっき浴として使用
することを特徴とする電気アルミニウムめっき方法。1. A mixed molten salt of 30 to 50 mol% of an aluminum halide containing oxygen-containing impurities derived from water and 70 to 50 mol% of an onium halide is subjected to thionyl chloride treatment to obtain an aluminum halide of 50 to 80.
A method for electro-aluminum plating, which comprises using a mixed molten salt obtained by preparing a composition of mol% and onium halide of 50 to 20 mol% as a plating bath.
不純物に対し、０．１〜２倍モルの塩化チオニルを添加
し、室温〜８０℃で反応させた後、含酸素不純物を余剰
の塩化チオニルと共に留去する請求項１に記載のめっき
方法。2. The thionyl chloride treatment is carried out by adding 0.1 to 2 moles of thionyl chloride to the oxygen-containing impurities derived from water and reacting at room temperature to 80 ° C., and then removing the excess oxygen-containing impurities. The plating method according to claim 1, wherein the plating is carried out together with thionyl.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21060793A JPH0762590A (en) | 1993-08-25 | 1993-08-25 | Aluminum electroplating method |
| US08/295,422 US5543522A (en) | 1993-08-25 | 1994-08-25 | Process for preparing an ambient temperature molten salt using thionyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21060793A JPH0762590A (en) | 1993-08-25 | 1993-08-25 | Aluminum electroplating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0762590A true JPH0762590A (en) | 1995-03-07 |
Family
ID=16592130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21060793A Withdrawn JPH0762590A (en) | 1993-08-25 | 1993-08-25 | Aluminum electroplating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0762590A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999053123A1 (en) * | 1997-04-10 | 1999-10-21 | Helios Inc. | Metal tube armored linear body, metal tube armoring linear body, method and apparatus for manufacturing metal tube armored linear body |
| EP3204534A1 (en) * | 2014-10-10 | 2017-08-16 | Solvay Specialty Polymers Italy S.p.A. | Compositions for electrodeposition of metals, electrodeposition process and product obtained |
-
1993
- 1993-08-25 JP JP21060793A patent/JPH0762590A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999053123A1 (en) * | 1997-04-10 | 1999-10-21 | Helios Inc. | Metal tube armored linear body, metal tube armoring linear body, method and apparatus for manufacturing metal tube armored linear body |
| EP3204534A1 (en) * | 2014-10-10 | 2017-08-16 | Solvay Specialty Polymers Italy S.p.A. | Compositions for electrodeposition of metals, electrodeposition process and product obtained |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20001031 |