JPH02133596A - Aluminum electroplating bath ensuring superior sticking power and plating method with same bath - Google Patents
Aluminum electroplating bath ensuring superior sticking power and plating method with same bathInfo
- Publication number
- JPH02133596A JPH02133596A JP28529588A JP28529588A JPH02133596A JP H02133596 A JPH02133596 A JP H02133596A JP 28529588 A JP28529588 A JP 28529588A JP 28529588 A JP28529588 A JP 28529588A JP H02133596 A JPH02133596 A JP H02133596A
- Authority
- JP
- Japan
- Prior art keywords
- bath
- plating
- aluminum
- sticking power
- mol
- 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 5
- 238000009713 electroplating Methods 0.000 title abstract 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 aluminum halide Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 claims abstract description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 abstract description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 abstract 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 abstract 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract 1
- 229940117389 dichlorobenzene Drugs 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、つき回り性（均−電着性）を改８したハロゲ
ン化アルミニウムーブチルビリノニウムクロリドー有機
溶剤からなる電気アルミニウムめっ！浴およびその浴に
よるめっき方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention provides an electrolytic aluminum plating made of an aluminum halide-butylvinonium chloride organic solvent with improved throwing power (uniform electrodeposition). ! This invention relates to a bath and a plating method using the bath.
（従来技術）
本発明者らは、先に低温で安全な電気アルミニウムめっ
き浴として、ハロゲン化アルミニウム（＾１ｘ３、但Ｌ
ＸはＦ％ＣＩ、Ｉ、 Ｂｒ）５０−８０ モル９ｉドブ
チルピリジニウムクロリド（Ｃ６Ｉｔ、Ｎ−Ｃ，ＩＩ、
ＣＩ）２０〜５０モル％からなる溶融塩浴に有機）Ｈ剤
を添加しためっき浴を提案した（特開昭６２−７０５９
３号）。(Prior art) The present inventors previously developed aluminum halide (^1x3, but L
X is F% CI, I, Br) 50-80 mol 9i dobutylpyridinium chloride (C6It, N-C, II,
proposed a plating bath in which an organic H agent was added to a molten salt bath consisting of 20 to 50 mol% CI) (Japanese Patent Laid-Open No. 62-7059).
No. 3).
（発明が解決しようとする問題点）
このめっき浴では、有機溶剤として、ベンゼン、トルエ
ン、キシレンなどの芳香族炭化水素を使用していたが、
このような溶剤を使用した場合、電流密度を平均電流密
度で０．１Ａ／ｄｍ２以上にしないと、均−にめっきで
きず、平均電流密度を０．１＾／ｄｍ”未満ではつき回
り性が劣るものであった。このため、低電流密度で凹凸
のある被めっき材をめっきした場合、陽極より離れた凹
部にめっきが付きにくいという問題があった。(Problems to be Solved by the Invention) This plating bath used aromatic hydrocarbons such as benzene, toluene, and xylene as organic solvents.
When such a solvent is used, uniform plating cannot be achieved unless the average current density is 0.1A/dm2 or higher, and if the average current density is less than 0.1A/dm, the throwing power is poor. For this reason, when plating a material to be plated with unevenness at a low current density, there was a problem that the plating was difficult to adhere to the recessed portions away from the anode.
（問題点を解決するための手段）
本発明は、ハロゲン化アルミニウムとブチルピリノニウ
ムクロリドとの組成が前記比率の溶融塩浴に添加する有
機溶剤に（））エチルベンゼン、クメン、メシチレン、
（）、トリ）クロロベンゼンを用い、これらの１種まｒ
こは２種以上をハロゲン化アルミニウム１モル当たり０
．２〜３モル添加することによりつき回り性を向上させ
た。そして、この浴で浴温Ｏ〜１５０℃、平均電流密度
０．０２〜５０＾／ｄ＋２の直流またはパルス電流でめ
っきできるようにした。(Means for Solving the Problems) The present invention provides that the organic solvent added to the molten salt bath having the composition of aluminum halide and butylpyrinonium chloride in the above-mentioned ratio includes ()) ethylbenzene, cumene, mesitylene,
( ), tri) Using chlorobenzene, one of these or
This is 0 or more types per mole of aluminum halide.
．． By adding 2 to 3 moles, the throwing power was improved. This bath was designed to allow plating with direct current or pulsed current at a bath temperature of 0 to 150°C and an average current density of 0.02 to 50^/d+2.
本発明のめっき俗でつき回り性が向上するのは、ベンゼ
ン、トルエン、キンレンなどを添加した従来の浴より浴
の粘性が低下するためと考えられる。The reason why the throwing power of the plating according to the present invention is improved is thought to be because the viscosity of the bath is lower than that of conventional baths to which benzene, toluene, quintin, etc. are added.
（））エチルベンゼン、クメンなどの有機溶剤添加量を
ハロビン化アルミニウム１つル当たり０．２〜３モルに
したのは、０．２モル未満ではめっきのつき回り性を改
善できず、３モル超添加しても浴ｌ二溶角イしないため
である。ノエチルベンゼンのエチル基位置は、オルト、
メタ、バラのいずれでもよく、またノまたはトリクロロ
ベンゼンのクロル基位置は１，２．３の位置、１，２．
４の位置または１，３．５の位置でもよい。()) The reason why the amount of organic solvents such as ethylbenzene and cumene added is set to 0.2 to 3 mol per 1 mol of aluminum halobide is that if it is less than 0.2 mol, the coverage of the plating cannot be improved, and if it exceeds 3 mol. This is because even if it is added, the melting angle will not increase in the bath. The ethyl group position of noethylbenzene is ortho,
The chloro group position of chlorobenzene may be either meta or chlorobenzene.
It may be in the 4 position or in the 1,3.5 position.
めっきの際、浴温を０〜１５０℃にするのは、０℃未満
では浴の粘性が著しく高くなり、導電性が低下してつき
回り性が悪くなり、１５０℃超では浴の劣化が著しく速
いため、安定しためっきが得られないためである。During plating, the bath temperature should be between 0 and 150°C because if it is less than 0°C, the viscosity of the bath will be extremely high, the conductivity will be reduced and the throwing power will be poor, and if it exceeds 150°C, the bath will deteriorate significantly. This is because stable plating cannot be obtained because the process is fast.
また、平均電流密度を０．０２〜５０ 八／ｄＬ６２に
したのは、０．０２＾／ｄｒａ２未満ではった回り性に
劣り、５０＾／ｄｍ２超にすると、めっき焼けが発生す
るためである。電流１よ、直流、パルス電流のいずれで
もよいが、高電流密度でめっきする場合は後者の方が好
ましいゆ
本発明によるつき回り性改首は、肢めっき材が冷延鋼板
、ステンレス鋼板などの鋼板であっても、まｒこ、ニッ
ケル板、銅板など非鉄金属板であってもその効果に変化
はない。In addition, the reason why the average current density is set to 0.02 to 50/dL62 is because if it is less than 0.02^/dm2, the maneuverability is poor, and if it is more than 50^/dm2, plating burnout will occur. . For current 1, either direct current or pulsed current may be used, but the latter is preferable when plating with high current density. The effect remains the same whether it is a steel plate or a nonferrous metal plate such as a metal plate, a nickel plate, or a copper plate.
（実施例）
冷延側板（０，１ｍｍ厚）にアルカリ電解脱脂、水洗、
酸洗、水洗の順で前処理を施した後、大気中で乾燥して
、これを陰極、アルミニウム板（純度９９．９９ｕ＋ｔ
％）を陽（歳にし、塩化アルミニウム７０モル％とプチ
ルビリノニウムクロリド３０モル％に本発明の有機溶剤
を添加しためっき浴にて電気めっきした。第１〜５表に
この結果を示す。(Example) Alkaline electrolytic degreasing, water washing,
After performing pretreatment in the order of pickling and water washing, it was dried in the air and used as a cathode, an aluminum plate (purity 99.99u+t).
%) was electroplated using a plating bath containing 70 mol % of aluminum chloride and 30 mol % of butylvinonium chloride to which the organic solvent of the present invention was added. Tables 1 to 5 show the results.
第１表
第
表
第
表
第
表
第
表
（比較例）
実施例と同様の方法で冷延鋼板に電気アルミニウムめっ
きを施した。めっき浴としては、塩化アルミニウムとブ
チルピリジニウムクロリドのモル％比が同じで、有へ溶
剤にベンゼンを添加した浴とベンゼン−トルエンの混合
溶剤を添加した浴を用いた。この結果を第６表に示す。Table 1 Table 1 Table 2 Table 2 Table 2 Table 1 (Comparative example) Cold rolled steel sheets were electrolyzed with aluminum in the same manner as in the examples. The plating baths had the same mole percentage ratio of aluminum chloride and butylpyridinium chloride, and used a bath containing benzene as a solvent and a bath containing a mixed solvent of benzene-toluene. The results are shown in Table 6.
第 ６ 表
（発明の効果）
以上のように、ハロゲン化アルミニウムとブチルピリジ
ニウムクロリドの溶融塩浴に添加する有機溶剤を（））
エチルベンゼン、クメン、メシチレン、（）、トリ）ク
ロロベンゼンにすると、つき回り性が向上する。Table 6 (Effects of the Invention) As described above, the organic solvent added to the molten salt bath of aluminum halide and butylpyridinium chloride ())
Ethylbenzene, cumene, mesitylene, (), tri)chlorobenzene improves the throwing power.
Claims (3)
Ｆ、Ｃｌ、Ｉ、Ｂｒ）５０〜８０モル％とブチルピリジ
ニウムクロリド（Ｃ＿５Ｈ＿５Ｎ−Ｃ＿４Ｈ＿９Ｃｌ）
２０〜５０モル％からなる溶融塩浴に（ジ）エチルベン
ゼン、クメン、メシチレン、（シ、トリ）クロロベンゼ
ンの１種または２種以上をハロゲン化アルミニウム１モ
ル当たり０．２〜３モル添加したことを特徴とするつき
回り性に優れた電気アルミニウムめっき浴。(1) Aluminum halide (AlX_3, where X is F, Cl, I, Br) 50-80 mol% and butylpyridinium chloride (C_5H_5N-C_4H_9Cl)
0.2 to 3 mol of one or more of (di)ethylbenzene, cumene, mesitylene, and (di,tri)chlorobenzene is added per mol of aluminum halide to a molten salt bath consisting of 20 to 50 mol%. An electrolytic aluminum plating bath with excellent throwing power.
、浴温０〜１５０℃、平均電流密度０．０２〜５０Ａ／
ｄｍ＾２の直流またはパルス電流でめっきすることを特
徴とするつき回り性に優れた電気アルミニウムめっき方
法。(2) Using the plating bath according to claim 1, at a bath temperature of 0 to 150°C and an average current density of 0.02 to 50 A/
An electrolytic aluminum plating method with excellent coverage, characterized by plating with dm^2 direct current or pulsed current.
とを特徴とする特許請求の範囲第２項に記載のつき回り
性に優れた電気アルミニウムめっき方法。(3) The electrolytic aluminum plating method with excellent throwing power according to claim 2, characterized in that plating is performed using an aluminum anode as the anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63285295A JP2623486B2 (en) | 1988-11-11 | 1988-11-11 | Electric aluminum plating bath with excellent throwing power and plating method using the bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63285295A JP2623486B2 (en) | 1988-11-11 | 1988-11-11 | Electric aluminum plating bath with excellent throwing power and plating method using the bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02133596A true JPH02133596A (en) | 1990-05-22 |
| JP2623486B2 JP2623486B2 (en) | 1997-06-25 |
Family
ID=17689675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63285295A Expired - Lifetime JP2623486B2 (en) | 1988-11-11 | 1988-11-11 | Electric aluminum plating bath with excellent throwing power and plating method using the bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2623486B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293991A (en) * | 1992-08-14 | 1994-10-21 | Sony Corp | Aluminum nonaqueous electrolyte, battery using the electrolyte and aluminum electrodepositing method |
| JP2009173977A (en) * | 2008-01-22 | 2009-08-06 | Dipsol Chem Co Ltd | ELECTRIC Al OR Al-ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME |
| US8821707B2 (en) | 2010-08-04 | 2014-09-02 | Dipsol Chemicals Co., Ltd. | Electric Al or Al alloy plating bath using room temperature molten salt bath and plating method using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270593A (en) * | 1985-09-20 | 1987-04-01 | Nisshin Steel Co Ltd | Aluminum electroplating bath and plating method by said plating bath |
-
1988
- 1988-11-11 JP JP63285295A patent/JP2623486B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270593A (en) * | 1985-09-20 | 1987-04-01 | Nisshin Steel Co Ltd | Aluminum electroplating bath and plating method by said plating bath |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293991A (en) * | 1992-08-14 | 1994-10-21 | Sony Corp | Aluminum nonaqueous electrolyte, battery using the electrolyte and aluminum electrodepositing method |
| JP2009173977A (en) * | 2008-01-22 | 2009-08-06 | Dipsol Chem Co Ltd | ELECTRIC Al OR Al-ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME |
| US8821707B2 (en) | 2010-08-04 | 2014-09-02 | Dipsol Chemicals Co., Ltd. | Electric Al or Al alloy plating bath using room temperature molten salt bath and plating method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2623486B2 (en) | 1997-06-25 |
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