JPH07116633B2 - Metal plate activation treatment method in electric Al plating - Google Patents
Metal plate activation treatment method in electric Al platingInfo
- Publication number
- JPH07116633B2 JPH07116633B2 JP24457687A JP24457687A JPH07116633B2 JP H07116633 B2 JPH07116633 B2 JP H07116633B2 JP 24457687 A JP24457687 A JP 24457687A JP 24457687 A JP24457687 A JP 24457687A JP H07116633 B2 JPH07116633 B2 JP H07116633B2
- Authority
- JP
- Japan
- Prior art keywords
- bath
- plating
- metal plate
- electric
- molten salt
- 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.)
- Expired - Lifetime
Links
- 238000007747 plating Methods 0.000 title claims description 28
- 229910052751 metal Inorganic materials 0.000 title claims description 18
- 239000002184 metal Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 12
- 230000004913 activation Effects 0.000 title description 12
- 150000003839 salts Chemical class 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- -1 aluminum halide Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- OGGSSJLNGUTKDO-UHFFFAOYSA-N 3-butylpyridin-1-ium chloride Chemical compound [Cl-].CCCCC1=CC=C[NH+]=C1 OGGSSJLNGUTKDO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、金属板に非水溶液系めっき浴により電気Alめ
っきを施す際めっき層の密着性を高める活性化処理法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an activation treatment method for enhancing the adhesion of a plating layer when electroplating a metal plate with a non-aqueous plating bath.
（従来技術） 電気Alめっきは、溶融Alめっきなどに比べて、高純度で
延性に富み、ピンホールの少ないめっきを施すことが可
能である。このため、Alめっきを施した金属板はICリー
ドフレーム等の電子部品分野や外観、耐食性を必要とす
る分野に使用するのに適している。(Prior Art) Electrolytic Al plating can provide plating with high purity, ductility, and few pinholes, as compared with molten Al plating and the like. Therefore, the Al-plated metal plate is suitable for use in the field of electronic components such as IC lead frames and the like, as well as in fields requiring appearance and corrosion resistance.
金属板への電気Alめっきは、水とAlの電位の関係で水溶
液系めっき浴により行うことができないので、従来より
非水溶液めっき浴により行われている。例えばAl電気め
っき法としては、シーメンス社のシーガル法、AlCl3−L
iAlH4−エーテル浴を用いた方法、AlCl3−LiAlH4−THF
浴を用いた方法、及び本発明者らがさきに出願したアル
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
化物からなる溶融塩浴を用いた方法などが知られてい
る。これらの中で、溶融塩浴を用いた方法が浴の安定性
や安全性の面から優れている。しかしこのめっき浴は水
分や酸素と反応し劣化するため、乾燥無酸素雰囲気中に
保っている。Since the electroplating of Al on a metal plate cannot be performed by an aqueous solution plating bath because of the potential of water and Al, it has been conventionally performed by a non-aqueous plating bath. For example, as the Al electroplating method, there is a Sigal method manufactured by Siemens, AlCl 3 -L.
iAlH 4 - method using ether bath, AlCl 3 -LiAlH 4 -THF
A method using a bath, a method using a molten salt bath composed of an aluminum halide and an alkylpyridinium halide, which the present inventors previously applied, are known. Among these, the method using a molten salt bath is excellent in terms of bath stability and safety. However, since this plating bath reacts with moisture and oxygen to deteriorate, it is kept in a dry oxygen-free atmosphere.
従ってめっき浴中に水が混入しないようにする必要があ
るが、めっき前の金属板前処理は、従来水系処理液によ
っていた。これは油分の除去には有機溶剤でも可能であ
るが、酸化物などは無機酸の酸洗によらないと除去でき
ないからである。このため前処理としては電解脱脂、水
洗、無機酸による酸洗、水洗、場合によっては各種スト
ライクめっき等を水系処理液により施して、油分、酸化
物の除去により表面を活性化させていた。Therefore, it is necessary to prevent water from mixing in the plating bath, but the metal plate pretreatment before plating has conventionally been performed with an aqueous treatment solution. This is because the oil can be removed with an organic solvent, but oxides and the like can be removed only by pickling an inorganic acid. Therefore, as the pretreatment, electrolytic degreasing, washing with water, pickling with an inorganic acid, washing with water, and, in some cases, various strike plating and the like are performed with an aqueous treatment liquid to activate the surface by removing oil and oxides.
しかし、活性化を水系処理液で行った場合、金属板に付
着した処理液をスクイズロールなどで強く絞っても、水
分を完全には除去できず、めっき浴中に水分が持ち込ま
れてしまう。このため、前処理工程とめっき工程との間
に大気中で乾燥させる乾燥工程を設けて、金属板を完全
に乾燥させていた。However, when the activation is performed with an aqueous treatment liquid, even if the treatment liquid adhering to the metal plate is strongly squeezed with a squeeze roll or the like, the water cannot be completely removed and the water is brought into the plating bath. Therefore, a drying step for drying in the atmosphere is provided between the pretreatment step and the plating step to completely dry the metal plate.
（発明が解決しようとする問題点） しかしながら、この様に前処理工程とめっき工程の間に
大気乾燥の工程を設けると、金属板は活性化されている
ため、大気により再び酸化被膜が形成され、めっきして
もめっき層の密着性は劣り、曲げ加工後のセロテープ剥
離試験で容易に剥離してしまうほどであった。(Problems to be solved by the invention) However, when an air drying step is provided between the pretreatment step and the plating step as described above, since the metal plate is activated, an oxide film is formed again by the air. However, the adhesion of the plated layer was poor even after plating, and it was easily peeled off in the cellotape peeling test after bending.
このため大気乾燥後水分をめっき浴に持ち込まない方法
で酸化被膜を除去する必要があった。Therefore, it is necessary to remove the oxide film by a method that does not bring water into the plating bath after air drying.
（問題点を解決するための手段） 本発明は金属板を大気中で乾燥した後、乾燥無酸素雰囲
気中で、塩化アルミニウムとブチルピリジニウムクロリ
ドとの溶融塩またはそれに有機溶媒を添加した浴中で、
Alめっきすべき金属板を陽極とし、電解活性を施すこと
によって、酸化物被膜を除去し、再び金属板を活性化す
るようにした。(Means for Solving Problems) The present invention is to dry a metal plate in the air, and then in a dry oxygen-free atmosphere, in a molten salt of aluminum chloride and butylpyridinium chloride or in a bath to which an organic solvent is added. ,
The metal plate to be plated with Al was used as an anode, and the electrolytic coating was applied to remove the oxide film and activate the metal plate again.
ここで、溶融塩のAlCl3濃度としては、50〜75モル％の
範囲にする。AlCl3濃度が50モル％より小さい場合、浴
中のブチルピリジニウムカチオンの濃度が高いため、陰
極板上でブチルピリジニウムカチオンの還元により浴が
分解し、浴のバランスが崩れると共に、陰極板上へ有機
物が付着し、カソードの機能を果たせなくなる。また、
AlCl3濃度が75モル％より大きい場合、浴の導電率が低
くなり、蒸気圧も高くなる。Here, the AlCl 3 concentration of the molten salt is in the range of 50 to 75 mol%. When the concentration of AlCl 3 is less than 50 mol%, the concentration of butylpyridinium cations in the bath is high, so the bath is decomposed by the reduction of butylpyridinium cations on the cathode plate, the balance of the bath is disturbed, and the organic substances are transferred onto the cathode plate. Adhere to the cathode, and the cathode cannot function. Also,
If the AlCl 3 concentration is higher than 75 mol%, the conductivity of the bath will be low and the vapor pressure will be high.
塩化アルミニウムの濃度をこの様にした場合、ブチルピ
リジニウムクロリドはその残部であるので濃度は25〜50
モル％となる。また、有機溶媒をvol％で25〜75％添加
すると、導電率は向上し、更に高速で活性化処理が可能
となる。この有機溶媒としては芳香族系有機溶媒のもの
が望ましい。When the concentration of aluminum chloride is set in this way, the concentration of butylpyridinium chloride is 25 to 50 because it is the balance.
It becomes mol%. In addition, when the organic solvent is added in an amount of 25 to 75% by vol%, the conductivity is improved and the activation treatment can be performed at a higher speed. The organic solvent is preferably an aromatic organic solvent.
電解活性化浴は酸素や水分に触れても安全であるが、ア
ルミニウム錯イオンの酸化を防ぐために、めっきは乾燥
無酸素雰囲気中（例えば乾燥N2やAr中）で行うのが好ま
しい。また電解条件は溶融塩中の場合、０〜150℃で直
流またはパルス電流を用いて、1x10-3〜1A/dm2にすると
効率よく活性化できる。浴温が０℃より低い場合、粘度
も高く、均一に活性化することが困難となり、逆に浴温
を150℃より高くして電流密度をより高くすること、副
反応が起こりやすくなり、金属表面の活性化は行われ
ず、有機物が付着する場合がある。パルス電流を用いた
場合も、平均電流密度は1x10-3〜1A/dm2の範囲で均一に
活性化が可能である。The electrolytic activation bath is safe even if it is exposed to oxygen and moisture, but in order to prevent the oxidation of aluminum complex ions, it is preferable to perform plating in a dry oxygen-free atmosphere (for example, in dry N 2 or Ar). In the case of molten salt, the electrolysis condition can be efficiently activated by using direct current or pulsed current at 0 to 150 ° C. and 1 × 10 −3 to 1 A / dm 2 . If the bath temperature is lower than 0 ° C, the viscosity will be high and it will be difficult to activate it uniformly. Conversely, if the bath temperature is higher than 150 ° C and the current density will be higher, side reactions will easily occur and The surface is not activated and organic substances may adhere. Even when the pulse current is used, the average current density can be uniformly activated within the range of 1 × 10 −3 to 1 A / dm 2 .
電解活性化浴に有機触媒を添加した場合、10〜80℃で直
流またはパルス電流をもちいて1x10-3〜1A/dm2にすると
効率よく活性化できる。浴温が10℃より低い場合、液の
凝固が起こる場合もあり、80℃より高くすると、溶媒の
蒸発が激しくなり、扱いにくくなる。When an organic catalyst is added to the electrolytic activation bath, it can be efficiently activated by using direct current or pulse current at 10 to 80 ° C. to 1 × 10 −3 to 1 A / dm 2 . When the bath temperature is lower than 10 ° C, solidification of the liquid may occur, and when it is higher than 80 ° C, the evaporation of the solvent becomes violent and it becomes difficult to handle.
処理時間は５秒〜１時間の範囲とする。５秒より短い場
合、金属表面の活性化が充分に行われず、Alめっきの密
着性は悪く、テープにより簡単に剥離する。また、処理
時間が１時間を越えると、時間がかかり過ぎ、生産性が
悪い。The processing time is in the range of 5 seconds to 1 hour. If it is shorter than 5 seconds, the metal surface is not sufficiently activated, the adhesion of Al plating is poor, and the tape is easily peeled off. Further, if the processing time exceeds 1 hour, it takes too much time, resulting in poor productivity.
なお、電解の際、陰極をAl板にすると、金属板から浴中
に溶出した不純物が電位差により陰極に置換析出して、
浴中に蓄積されず、浴を常に清浄な状態に保つことがで
きる。During the electrolysis, if the cathode is an Al plate, impurities eluted from the metal plate into the bath are substituted and deposited on the cathode due to the potential difference,
It does not accumulate in the bath and can keep it clean at all times.
また、めっき浴に前記電流活性化浴と同一組成の浴を用
いると、活性化処理液が持ち込まれても浴組成が変動せ
ず、浴管理が簡単になる。When a bath having the same composition as the current activation bath is used as the plating bath, the bath composition does not change even when the activation treatment liquid is brought in, and bath management is simplified.
（実施例） 実施例.1 板厚がともに0.1mmである冷延鋼板、SUS430、SUS316を
水系処理液により電解脱脂、水洗、無機酸による酸洗及
び水洗したのち、大気中で乾燥し、N2雰囲気にしてAlCl
3−ブチルピリジニウムクロリド（BPC）系電解活性浴
（混合モル比2:1）をもちい、直流で電解活性を行い、
直ちに前記電解活性化浴と同じ組成のめっき浴で電気Al
めっきを施した。そしてめっき後に2t折り曲げ試験を施
してめっき密着性を調査した。第１表にこの結果を示
す。(Example) Example.1 Cold-rolled steel sheet having a thickness of 0.1 mm, SUS430, SUS316, electrolytic degreasing with an aqueous treatment solution, washing with water, pickling with an inorganic acid and washing with water, and then drying in air, N 2 Atmosphere and AlCl
Using 3 -butylpyridinium chloride (BPC) -based electrolytic activation bath (mixing molar ratio 2: 1), electrolytic activation is performed at direct current,
Immediately using a plating bath with the same composition as the electrolytic activation bath,
It was plated. After the plating, a 2t bending test was performed to investigate the plating adhesion. The results are shown in Table 1.
実施例.2 実施例１のAlCl3−BPC系溶融塩電解活性化浴にベンゼ
ン、トルエンまたはベンゼン−トルエン混合溶媒をvol
％で50％添加した浴をもちい、実施例１と同要領で前処
理、電気めっきを施し、めっき密着性を調査した。この
結果を第２表に示す。 Example 2 In the AlCl 3 —BPC-based molten salt electrolytic activation bath of Example 1, benzene, toluene or a benzene-toluene mixed solvent was vol.
%, 50% was added to the bath, pretreatment and electroplating were performed in the same manner as in Example 1, and the plating adhesion was investigated. The results are shown in Table 2.
（発明の効果） 以上のように、本発明法により電気Alめっき前に金属板
を活性化すれば、めっき密着性は向上する。 (Effects of the Invention) As described above, if the metal plate is activated before the electric Al plating by the method of the present invention, the plating adhesion is improved.
Claims (2)
た後、大気中で乾燥し、しかる後に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との溶融塩
浴またはこの浴に有機溶媒を添加した浴で電気めっきを
施す際、乾燥後電気めっき前に、塩化アルミニウム50〜
75モル％とブチルピリジニウムクロリド25〜50モル％と
からなる溶融塩浴またはこの浴に有機溶媒25〜75vol％
を添加した浴にて金属板を陽極して、浴温０〜150℃、
平均電流密度１×10-3〜1A/dm2で５秒間〜１時間電解
し、活性化することを特徴とする電気Alめっきにおける
金属板活性化処理法。1. A metal plate is treated with an aqueous treatment liquid to be activated and then dried in the air, and then a molten salt bath of an aluminum halide and an alkylpyridinium halide or an organic solvent is added to this bath. When applying electroplating in a dry bath, after drying, before electroplating, aluminum chloride 50 ~
A molten salt bath consisting of 75 mol% and butylpyridinium chloride 25 to 50 mol% or an organic solvent in this bath 25 to 75 vol%
Anode the metal plate in a bath containing
A method for activating a metal plate in electric Al plating, which comprises activating by electrolyzing at an average current density of 1 × 10 −3 to 1 A / dm 2 for 5 seconds to 1 hour.
求の範囲第１項に記載の電気Alめっきにおける金属板活
性化処理法。2. The method for activating a metal plate in electric Al plating according to claim 1, wherein the cathode is an Al plate.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24457687A JPH07116633B2 (en) | 1987-09-29 | 1987-09-29 | Metal plate activation treatment method in electric Al plating |
| DE8888906056T DE3875943T2 (en) | 1987-07-13 | 1988-06-30 | METHOD FOR ELECTROPLATING A METAL LAYER WITH ALUMINUM. |
| US07/269,142 US4966660A (en) | 1987-07-13 | 1988-06-30 | Process for electrodeposition of aluminum on metal sheet |
| EP88906056A EP0323520B1 (en) | 1987-07-13 | 1988-06-30 | Process for electroplating metal plate with aluminum |
| PCT/JP1988/000658 WO1989000616A1 (en) | 1987-07-13 | 1988-06-30 | Process for electroplating metal plate with aluminum |
| CA 575270 CA1324105C (en) | 1987-09-29 | 1988-08-19 | Process for electrodeposition of aluminum on metal sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24457687A JPH07116633B2 (en) | 1987-09-29 | 1987-09-29 | Metal plate activation treatment method in electric Al plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6487799A JPS6487799A (en) | 1989-03-31 |
| JPH07116633B2 true JPH07116633B2 (en) | 1995-12-13 |
Family
ID=17120774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24457687A Expired - Lifetime JPH07116633B2 (en) | 1987-07-13 | 1987-09-29 | Metal plate activation treatment method in electric Al plating |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07116633B2 (en) |
| CA (1) | CA1324105C (en) |
-
1987
- 1987-09-29 JP JP24457687A patent/JPH07116633B2/en not_active Expired - Lifetime
-
1988
- 1988-08-19 CA CA 575270 patent/CA1324105C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA1324105C (en) | 1993-11-09 |
| JPS6487799A (en) | 1989-03-31 |
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