JPH0445298A - Aluminum electroplating bath - Google Patents
Aluminum electroplating bathInfo
- Publication number
- JPH0445298A JPH0445298A JP15219090A JP15219090A JPH0445298A JP H0445298 A JPH0445298 A JP H0445298A JP 15219090 A JP15219090 A JP 15219090A JP 15219090 A JP15219090 A JP 15219090A JP H0445298 A JPH0445298 A JP H0445298A
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen
- plating
- halide
- plating bath
- compd
- 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.)
- Pending
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 17
- 238000009713 electroplating Methods 0.000 title abstract description 6
- 238000007747 plating Methods 0.000 claims abstract description 65
- -1 aluminum halide Chemical class 0.000 claims abstract description 33
- 150000004820 halides Chemical class 0.000 claims abstract description 24
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 12
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000004010 onium ions Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- CFPGCCLILKREJU-UHFFFAOYSA-M 1,2-diethylpyridin-1-ium;chloride Chemical compound [Cl-].CCC1=CC=CC=[N+]1CC CFPGCCLILKREJU-UHFFFAOYSA-M 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- WEWUIQHYZXQERU-UHFFFAOYSA-M 1-butyl-2-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1CC WEWUIQHYZXQERU-UHFFFAOYSA-M 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- ABIXGADMNMMARN-UHFFFAOYSA-M 1-cyclohexyl-3-methylpyridin-1-ium;bromide Chemical compound [Br-].CC1=CC=C[N+](C2CCCCC2)=C1 ABIXGADMNMMARN-UHFFFAOYSA-M 0.000 description 1
- SKGNWPJSJGAIPV-UHFFFAOYSA-N 1-ethyl-1h-imidazol-1-ium;bromide Chemical compound [Br-].CCN1C=C[NH+]=C1 SKGNWPJSJGAIPV-UHFFFAOYSA-N 0.000 description 1
- QTXZDFXPUPKBJC-UHFFFAOYSA-M 1-ethyl-2-methylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC=C1C QTXZDFXPUPKBJC-UHFFFAOYSA-M 0.000 description 1
- KNTLRUCYNAFFAH-UHFFFAOYSA-M 1-ethyl-2-methylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1C KNTLRUCYNAFFAH-UHFFFAOYSA-M 0.000 description 1
- PUBHYFMAUADWKI-UHFFFAOYSA-M 1-ethyl-3-methylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC(C)=C1 PUBHYFMAUADWKI-UHFFFAOYSA-M 0.000 description 1
- DVDFUOWAJIWJJN-UHFFFAOYSA-M 1-ethyl-3-methylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC(C)=C1 DVDFUOWAJIWJJN-UHFFFAOYSA-M 0.000 description 1
- YZBRZOWPIBQUEJ-UHFFFAOYSA-M 1-ethyl-4-methylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=C(C)C=C1 YZBRZOWPIBQUEJ-UHFFFAOYSA-M 0.000 description 1
- MZRXHMSIKJRJDJ-UHFFFAOYSA-M 1-ethyl-4-phenylpyridin-1-ium;bromide Chemical compound [Br-].C1=C[N+](CC)=CC=C1C1=CC=CC=C1 MZRXHMSIKJRJDJ-UHFFFAOYSA-M 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- LETVJWLLIMJADE-UHFFFAOYSA-N pyridazin-3-amine Chemical compound NC1=CC=CN=N1 LETVJWLLIMJADE-UHFFFAOYSA-N 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（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含窒素複素環化
合物のオニウムハロゲン化物を混合溶融した電気アルミ
ニウムめっき浴において、厚めつきしても表面の平滑な
めっき屑が得られ、しかも、つき回り性も優れためっき
浴に関する。Detailed Description of the Invention (Industrial Application Field) The present invention is an electrolytic aluminum plating bath in which an aluminum halide and an onium halide, a nitrogen-containing heterocyclic compound, are mixed and melted. The present invention relates to a plating bath that produces plating scraps and also has excellent throwing power.
（従来技術）
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ので、水
溶液系のめっき裕で行うことは困難テアル。このため、
従来よりアルミニウムの電気めっきは、非水溶液系のめ
っき浴、特に有機溶媒系のめっき浴で行なわれている。(Prior Art) Electroplating of aluminum is difficult to perform using an aqueous solution because aluminum has a large affinity for oxygen and its potential is less base than that of hydrogen. For this reason,
Conventionally, aluminum electroplating has been carried out in a non-aqueous plating bath, particularly an organic solvent-based plating bath.
この有機溶媒系のめっき浴としては、ＡｌＣｌ、とＬｉ
＾Ｉｔ（、またはＬｉＨとをエーテルに溶解したものや
＾ＩＣ＋、とＬｉＡＩＨ−とをＴＨＦ（テトラヒドロ７
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Ｌｉ
＾ＩＬ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。This organic solvent-based plating bath includes AlCl and Li.
^It (or LiH dissolved in ether, ^IC+, and LiAIH- are dissolved in THF (tetrahydro7
A typical example is a solution dissolved in orchid. but,
All of these plating baths contain highly active Li.
Since it contains IL and LiH, if oxygen or moisture is present, it reacts with them and decomposes, reducing the current efficiency and shortening the bath life.
かかる問題を解決した電気アルミニウムめっき浴として
、アルミニウムハロゲン化物とＮ−フルキルビリシニウ
ムハａデン化物とを混合溶融してなるめっき裕（特開昭
６２−７０５９２号、同６２−７０５９３号〉やアルミ
ニツムハロゲン化物と［フルキルもしくは１１３−７フ
ルキルイミグゾリウムハロゲン化物とを混合溶融してな
るめっき浴（特開平１−２７２７９０号）等のアルミニ
ウムハロゲン化物と含窒素複素環化合物のオニウム塩と
を混合溶融してなるめっき浴が提案されている。As an electrolytic aluminum plating bath that solves this problem, there are plating baths made by mixing and melting aluminum halide and N-furkylbiricinium adenide (Japanese Patent Application Laid-Open Nos. 62-70592 and 62-70593). An onium salt of an aluminum halide and a nitrogen-containing heterocyclic compound, such as a plating bath formed by mixing and melting an aluminum halide and a [fulkyl or 113-7-furkylimigzolium halide (Japanese Patent Application Laid-open No. 1-272790). A plating bath made by mixing and melting has been proposed.
これらのめっき浴は、常温で液体で、発火等の危険性が
なく、しがも、陽極にアルミニウムを用いると、＾１イ
オンが消費量に合わせて自動補給され、浴管理が簡単で
あるため、他のめっき浴より作業性に優れている。These plating baths are liquid at room temperature, so there is no risk of ignition, and if aluminum is used for the anode, ^1 ions are automatically replenished according to the amount consumed, making bath management easy. , it has better workability than other plating baths.
ところで、近年、電気アルミニウムめっき製品は、めっ
き厚が１０〜５０μ−のものが高耐食性材料として注目
を集め、その中で表面を陽極酸化処理したものも望まれ
ている。Incidentally, in recent years, electrolytic aluminum plated products with a plating thickness of 10 to 50 μm have attracted attention as highly corrosion-resistant materials, and among these, products whose surfaces have been anodized are also desired.
（発明が解決しようとする問題点）
しかしながら、前記めっ％浴で１０μ−以上の厚さにめ
っきすると、電析が不均一になって表面粒子が局部的に
成長して、表面が凹凸になり、しかも、摩擦によりその
表面粒子は簡単に脱落してしまう。また、表面が凹凸に
なると、金属光沢が低下するため、反射板などに使用す
るのに難、くががあった。(Problems to be Solved by the Invention) However, when plating with the above plating bath to a thickness of 10μ or more, the electrodeposition becomes uneven and the surface particles grow locally, making the surface uneven. Moreover, the surface particles easily fall off due to friction. In addition, when the surface becomes uneven, the metallic luster decreases, making it difficult to use for reflective plates and the like.
かかる問題が生じないようにするには、ベンゼン、トル
エンなどの有機溶媒をアルミニウムハロゲン化物１モル
に対して１〜２モルの割合で添加すればよいが、このよ
うに多量に有機溶媒を添加すると、溶媒が蒸発し、作業
環境を悪化させるとともに、引火の恐れも生じる。In order to prevent such problems from occurring, organic solvents such as benzene and toluene can be added at a ratio of 1 to 2 moles per mole of aluminum halide, but adding such a large amount of organic solvents , the solvent will evaporate, worsening the working environment and creating the risk of ignition.
さらに、前記めっき裕は、つき回り性が劣るため、形状
物にめっきする場合、電流密度０．０１＾／ｄ謡２以下
の低電部でめっトすると四部にめっきできないものであ
った。Furthermore, since the above-mentioned plating thickness is poor in throwing power, when plating a shaped object, if plating is performed in a low current area with a current density of 0.01^/d2 or less, it is impossible to plate all four parts.
本発明は、かかる、克に鑑み、表面まで緻密で平滑なア
ルミニウムめっ軽を施すことができ、しがも、低電流密
度でめっきしても均一にめっきできる電気アルミニウム
めっき浴を提供するものである。In view of these problems, the present invention provides an electrolytic aluminum plating bath that is capable of applying dense and smooth aluminum plating to the surface, and even plating uniformly even when plating at a low current density. It is.
（問題点を解決するための手段）
本発明者らは、上記問題を解決すべく種々検討した結果
、前記のめっき浴に特定の芳香族化合物とポリマーとを
添加することにより前記問題点を解決した。(Means for Solving the Problems) As a result of various studies to solve the above problems, the present inventors solved the above problems by adding a specific aromatic compound and a polymer to the plating bath. did.
すなわち、アルミニウムハロゲン化物４０〜８０モル％
と含窒素複素環化合物のオニツムハロゲン化物２０〜６
０モル％とを混合溶融してなるめっ％ｍに窒素原子を有
する芳香族化合物を添加すると、厚めつきしてもめっ外
層は金属光沢を示し、かつ、表面も平滑になる。また、
ポリマーを添加すると、つき回り性が向上する。That is, aluminum halide 40-80 mol%
and onitum halides of nitrogen-containing heterocyclic compounds 20-6
When an aromatic compound having a nitrogen atom is added to the plating formed by mixing and melting 0 mol % and 0 mol %, the outer layer of the plating exhibits metallic luster even if it is thick, and the surface becomes smooth. Also,
Adding a polymer improves throwing power.
ここで、本発明のめっき浴に用いられる含窒素複素環化
合物のオニウムハロゲン化物とは、環を形成する原子に
炭素以外に窒素原子を含む含窒素複素環化合物の窒素原
子が陽イオンとなって、その陽イオンにハロゲン原子の
陰イオンが配位したオニウム化合物である。Here, the onium halide of the nitrogen-containing heterocyclic compound used in the plating bath of the present invention refers to the onium halide of the nitrogen-containing heterocyclic compound whose ring-forming atoms include a nitrogen atom in addition to carbon. , is an onium compound whose cation is coordinated with the anion of a halogen atom.
含窒素複素環化合物の環の大きさとしては、殻に５原子
環または６原子環構造のもので、電気めっき浴の作業性
、めっき製品の品質などの点から好ましい化合物を挙げ
れば、イミダゾール、ピリノンである。これらの化合物
のオニウムハロゲン化物としては、イミダゾールの場合
、イミグゾリウムクロライド、イミグゾリウムブロマイ
ド、イミグゾリウムアイオグイド、イミグゾリウムフル
オライドなどがあり、また、ピリノンの場合には、ピリ
ジニウムクロライド、ピリジニウムブロマイド、ピリジ
ニウムアイオグイド、ピリジニウムフルオライドなどが
ある。Regarding the ring size of the nitrogen-containing heterocyclic compound, the shell has a five- or six-atom ring structure, and preferable compounds from the viewpoint of workability of the electroplating bath and quality of the plated product include imidazole, It is pirinone. The onium halides of these compounds include imidazole, imigzolium chloride, imigzolium bromide, imigzolium ioguid, imigzolium fluoride, and in the case of pyrinone, , pyridinium chloride, pyridinium bromide, pyridinium iogide, and pyridinium fluoride.
含窒素複素環化合物の複素環は、置換基を有していても
よく、むしろ置換基を有している方が電気めっき浴とし
ての安定性に優れている。この置換基の好ましいものは
、炭素数１〜１５のアルキル基、アルキルアミ／基で、
置換基を２＠以上有する場合は置換基が各Ｎ位に導入さ
れているのが好ましい。前記イミダゾールのオニウムハ
ロゲン化物としてＮ位に置換基が導入されたものには、
１−アルキル、１，３−ジアルキル−（アミ／）イミグ
ゾリウムハロゲン化物があり、ピリノンのオニウムハロ
ゲン化物の場合は、１−フルキル−（アミノ）ピリジニ
ウムハロゲン化物がある。The heterocycle of the nitrogen-containing heterocyclic compound may have a substituent, and if it has a substituent, it has better stability as an electroplating bath. Preferred substituents are alkyl groups and alkylamino groups having 1 to 15 carbon atoms,
When having 2 or more substituents, it is preferable that the substituents be introduced at each N position. The onium halide of imidazole in which a substituent is introduced at the N position includes:
These include 1-alkyl, 1,3-dialkyl-(ami/)imigzolium halides, and in the case of onium halides of pyrinone, 1-furkyl-(amino)pyridinium halides.
一般に、置換基として、アルキル基を有するイミグゾリ
ウムハロゲン化物の場合、好ましいものは、１−アルキ
ル、１，３−ジアルキル、１，２．３−）リアルキルイ
ミグゾリウムハロゲン化物で、これらを具体的に示せば
、１−エチルイミダゾリウムブロマイド、１−エチルイ
ミグゾリウムクロライド、１−プチルイミグゾリウムク
ロライド、゛１，３−ノメチルイミグゾリウムプロマイ
ド、１−メチル−３−エチルイミグゾリウムクロライド
、１−メチル−３−エチルイミグゾリウムア、イオグイ
ド、１−メチル−３−ｎ−プチルイミグゾリウムクロラ
イド、１−メチル−３−ベンノルイミダゾリウムクロラ
イド、１−メチル−３−エチルベンシイミグゾリウムク
ロライド、１．２，３−）リメチルイミグゾリウムブロ
マイド、１，２．３−）リメチルイミグゾリウムアイオ
グイド、１，２−ツメチル−３−エチルイミダゾリウム
ブロマイド、１．２−ジメチル−３−エチルイミグゾリ
ウムクロライド、１，２−ジメチル−３−プチルイミグ
ゾリウムフルオライドなどを挙げることができる。Generally, in the case of imigzolium halides having an alkyl group as a substituent, preferred are 1-alkyl, 1,3-dialkyl, 1,2.3-)realkylimigzolium halides; Specifically, 1-ethylimidazolium bromide, 1-ethylimigzolium chloride, 1-butylimigzolium chloride, 1,3-nomethylimigzolium bromide, 1-methyl-3 -ethylimigzolium chloride, 1-methyl-3-ethylimigzolium a, ioguide, 1-methyl-3-n-butylimigzolium chloride, 1-methyl-3-bennolimidazolium chloride, 1-Methyl-3-ethylbencyimigzolium chloride, 1.2,3-)limethylimigzolium bromide, 1,2.3-)limethylimigzolium ioguide, 1,2-tumethyl Examples include -3-ethylimidazolium bromide, 1,2-dimethyl-3-ethylimigzolium chloride, and 1,2-dimethyl-3-butylimigzolium fluoride.
また、アルキルビリノニウムハロゲン（ｌの場合の好ま
しいものも、モノアルキル置換体、ジアルキル置換体、
トリアルキル置換体で、具体的に示せば、ブチルピリジ
ニウムクロライド、１．２−ノメチルビリノニウムクロ
ライド、■−エチルー２−メチルビリノニウムクロライ
ド、１−エチル−２−メチルピリジニウムブロマイド、
１−エチル−２−メチルビリノニウムアイオグイド、１
−エチル−２−メチルピリジニウムクロライド、１−〇
−ブチルー２−メチルピリジニウムクロライド、１−イ
ンブチル−２−エチルピリジニウムクロライド、ｉｎ−
オクチル−２−エチルピリジニウムクロライド、１−ベ
ンジル−２メチルビリノニウムクロライド、１−エチル
−３−メチルピリジニウムクロライド、１−エチル−３
−メチルピリジニウムブロマイド、１−シクロヘキシル
−３−メチルピリジニウムブロマイド、１−エチル−２
−エチルピリジニウムクロライド、１−ブチル−２−エ
チルピリジニウムクロライド、１−エチル−４−メチル
ピリジニウムブロマイド、１−エチル−４−フェニルピ
リジニウムブロマイド、１−エチル−２，４−ノメチル
ピリノニウムクロライド、１−エチル−２，６−ノメチ
ルビリノニウムクロライド、１−ｎ−ブチル−２，４ノ
メチルビリノニウムクロライドなどを挙げることができ
る。In addition, preferable alkylbilinonium halogens (l) include monoalkyl substituted products, dialkyl substituted products,
Specific examples of trialkyl substituents include butylpyridinium chloride, 1,2-nomethylvinonium chloride, ■-ethyl-2-methylvinonium chloride, 1-ethyl-2-methylpyridinium bromide,
1-Ethyl-2-methylbilinonium ioguido, 1
-Ethyl-2-methylpyridinium chloride, 1-〇-butyl-2-methylpyridinium chloride, 1-inbutyl-2-ethylpyridinium chloride, in-
Octyl-2-ethylpyridinium chloride, 1-benzyl-2methylvinonium chloride, 1-ethyl-3-methylpyridinium chloride, 1-ethyl-3
-Methylpyridinium bromide, 1-cyclohexyl-3-methylpyridinium bromide, 1-ethyl-2
-ethylpyridinium chloride, 1-butyl-2-ethylpyridinium chloride, 1-ethyl-4-methylpyridinium bromide, 1-ethyl-4-phenylpyridinium bromide, 1-ethyl-2,4-nomethylpyridinium chloride, Examples include 1-ethyl-2,6-nomethylvinonium chloride and 1-n-butyl-2,4nomethylvinonium chloride.
さらに、１−フルキル−アミノビリノニウムハロゲン化
物については、１−メチル−４−ジメチルアミノビリン
ニウムアイオグイド、１−エチル＋ツメチルアミノビリ
ジニウムブロマイド、１−エチル−４ツメチルアミノビ
リノニウムクロライド、１−エチル−４−（Ｎ−エチル
、Ｎ−メチル）アミ／ビリンニウムクロライド、１−エ
チル−４−アミ／ビリジニウムアイオダイド、１−ｎ−
ブチル−４−ツメチルアミノピリジニウムフルオライド
、■−ベンツルー４−ツメチルアミノビリノニウムクロ
ライド、１−ｎ−オクチル−４−ノメチルアミノビリノ
ニウムクロライド、１−エチル−４−ピペリジ７ビリジ
ニウムブロマイト、１−エチル−４−ビロリン／ピリジ
ニウムクロライド、１−エチル−４−ビロリン／ピリジ
ニウムブロマイドなどを挙げることができる
また、含窒素複素環化合物の複素環は、縮合環を形成し
ていてもよい。この縮合複素環化合物の代表的なものは
、ノアルキルベンズイミグゾリウムハロゲン化物で、具
体例としては、１，３−ノメチルベンズイミグゾリウム
クロライド、１−メチル−３−エチルベンズイミグゾリ
ウムブロマイドなどを挙げることができる。Furthermore, regarding 1-furkyl-aminobilinonium halides, 1-methyl-4-dimethylaminobilinium ioguide, 1-ethyl + trimethylaminobilinium bromide, 1-ethyl-4-trimethylaminobilinium bromide, Nium chloride, 1-ethyl-4-(N-ethyl, N-methyl)ami/virinium chloride, 1-ethyl-4-ami/viridinium iodide, 1-n-
Butyl-4-trimethylaminopyridinium fluoride, ■-bentrue-4-trimethylaminopyridinium chloride, 1-n-octyl-4-nomethylaminopyridinium chloride, 1-ethyl-4-piperidi7pyridinium In addition, the heterocycle of the nitrogen-containing heterocyclic compound forms a fused ring. Good too. A typical example of this fused heterocyclic compound is noalkylbenzimigzolium halide, and specific examples include 1,3-nomethylbenzimigzolium chloride, 1-methyl-3-ethylbenzimigzolium chloride, Examples include migsolium bromide.
以上帯げた含窒素複素環化合物は、アルキル置換体や綜
合状態に関係なくアルキルイミダゾリウムハロゲン化物
同志またアルキルビリジニウムノ）ロゲン化物同志であ
れば、単独でも混合状態でも使用できる。しかし、ジア
ルキルイミグゾリウムハロゲン化物とアルキルピリジニ
ウム７１０デン化物がめつき浴にした場合に電導度が高
くなるので、特に好ましい。The above-mentioned nitrogen-containing heterocyclic compounds can be used alone or in a mixed state as long as they are alkylimidazolium halides or alkylpyridinium halides, regardless of the alkyl substituents or the state of synthesis. However, dialkylimigzolium halides and alkylpyridinium 710 denides are particularly preferred because they provide high conductivity when used in a plating bath.
アルミニウムハロゲン化物は、一般式＾ＩＸ、（Ｘはハ
ロゲン原子）で示される化合物で、具体的には＾ＩＦｚ
、＾ＩＣ１７、＾ＩＢｒｚ、＾１１．を挙げることがで
かる。Aluminum halide is a compound represented by the general formula ^IX, (X is a halogen atom), specifically ^IFz
, ^IC17, ^IBrz, ^11. It is possible to list the following.
アルミニウムハロゲン化物と含窒素複素環化合物のオニ
ラムノ１０デン化物とを混合溶融してなるめっき裕は、
アルミニラムノ１０デン化物４０〜８０モル％と含窒素
複素環化合物のオニウム／’％ロデン化物２０〜６０モ
ル％とを不活性〃スの雰囲気下で加熱するか、適当な溶
媒に両者を懸濁させた状態で加熱混合した後、溶媒を除
去することにより得られる。The plating layer obtained by mixing and melting an aluminum halide and a nitrogen-containing heterocyclic compound, onyramnodecadenide, is
40 to 80 mol% of aluminum rhamno-10denide and 20 to 60 mol% of onium/'% rodenide of a nitrogen-containing heterocyclic compound are heated in an inert gas atmosphere, or both are suspended in an appropriate solvent. It can be obtained by heating and mixing in a heated state and then removing the solvent.
このめっき俗に添加する窒素原子を有する芳香族化合物
としては、環内に窒素原子を２＠以上有する不飽和複素
環化合物、アミノ基を有する芳香族化合物が挙げられる
。これらの化合物は、単環化合物、縮合環化合物であっ
てもよいが、後者のアミノ基を有する芳香族化合物を使
用すると、つ外回り性が前者の不飽和複素環化合物を用
（また場合より向上するという利点がある。環内にＮを
２個以上有する不飽和複素環化合物としては、ピリミジ
ンやバルビッル酸などのジアジン、ナフチリジン、７エ
ナジン、７エナントロリン、ビリグジン、ピラジンなど
が、また、アミノ基を有する芳香族化合物としては、ノ
フェニルアミン、７ミ／ピリミジンのようなアミノジア
ジンなどを挙げることができ、これらは２種以上併用す
ることも可能である。Examples of the aromatic compound having a nitrogen atom that is commonly added to this plating include an unsaturated heterocyclic compound having 2 or more nitrogen atoms in the ring, and an aromatic compound having an amino group. These compounds may be monocyclic compounds or condensed ring compounds, but when the latter aromatic compound having an amino group is used, the roundness is improved compared to the former unsaturated heterocyclic compound. Examples of unsaturated heterocyclic compounds having two or more N atoms in the ring include diazines such as pyrimidine and barbylic acid, naphthyridine, 7-enazine, 7-enanthroline, biligine, and pyrazine. Examples of the aromatic compound having the above include nophenylamine and aminodiazine such as 7mi/pyrimidine, and two or more of these can be used in combination.
これらの窒素原子を有する芳香族化合物の添加量は、め
っき浴に対して、通常０．００１〜０．１モル／ｌであ
る。添加量がＯ８ｏ Ｏ１モル／ｌヨ＋）少ないと添加
効果がなく、０．１モル／ｌより多くなると高電流密度
でめっきした場合、めっき焼けが発生する。The amount of these nitrogen atom-containing aromatic compounds added to the plating bath is usually 0.001 to 0.1 mol/l. If the addition amount is too small (O8o O1 mol/l), there will be no effect of addition, and if it is more than 0.1 mol/l, plating burn will occur when plating is performed at a high current density.
他の添加成分であるポリマーとしては、溶融塩浴に溶解
し、かつ、めっき操作条件下で安定なものであれば種類
を問わず使用できる。溶融塩浴は、非常に溶解力が大き
いので、はとんどの有機ポリマーを溶解し、溶解困難な
ものは７７素樹脂のように耐食性が極めて大きいものだ
けである。As the other additive component, any polymer can be used as long as it is soluble in the molten salt bath and stable under the plating operating conditions. Since the molten salt bath has a very high dissolving power, it can dissolve most organic polymers, and the only things that are difficult to dissolve are those that have extremely high corrosion resistance, such as 77 base resin.
このポリマーの好ましいものとしては、芳香族系の置換
基を有するエチレンの重合体、もしくはポリエーテルで
ある。芳香族系の置換基を有するエチレンの重合体の具
体例として、ポリスチレン、ポリビニルカルバゾールな
どが挙げられる。また、ポリエーテルの具体例として、
エチレンオキサイド−プロピレンオキサイド共重合体が
挙げられる。Preferred examples of this polymer are ethylene polymers or polyethers having aromatic substituents. Specific examples of ethylene polymers having aromatic substituents include polystyrene, polyvinylcarbazole, and the like. In addition, as a specific example of polyether,
Examples include ethylene oxide-propylene oxide copolymers.
上記ポリマーの好ましい分子量としては、例えばポリス
チレンでは、２７００〜４０万である。The preferable molecular weight of the above polymer is, for example, 2700 to 400,000 for polystyrene.
このポリマーの添加量は、めっき俗に対して、３０ＩＩ
＋９７Ｃ〜１９／ｌである。添加量が３０ＩＩ９／ｌよ
り少ないと、低電部でのつき回り性が向上せず、１９７
ｅより多くなると、高電流密度でめっきした場合にめっ
き焼けが発生す−る。The amount of this polymer added is 30II for general plating.
+97C to 19/l. If the amount added is less than 30II9/l, the throwing power in the low current area will not improve, and 197
If it exceeds e, plating burn will occur when plating is performed at high current density.
本発明のめっき浴によりめっきする場合も従来のめっき
裕の場合と同様に乾燥無酸素雰囲気中でめっきする。電
解条件は、直流もしくはパルス電流で浴温０〜１５０℃
、電流密度０．０１〜５０＾／ｄ＋ａ２で行うと、電流
効率がよ（、均一にめっきできる。浴温が０℃より低い
と、均一にめっきできず、１５０℃より高くすると、電
流密度を５０＾／ｄ＋ｎ２より高くした場合に含窒素複
素環化合物のオニウムイオンの還元が起こり、めっき層
が灰色になるとともに、結晶も相いデンドライト結晶と
なり、外観、加工性が低下してしまう。When plating with the plating bath of the present invention, plating is carried out in a dry oxygen-free atmosphere as in the case of conventional plating baths. Electrolysis conditions are direct current or pulsed current, bath temperature 0 to 150°C.
When the current density is 0.01 to 50^/d+a2, the current efficiency is good (and uniform plating is possible. If the bath temperature is lower than 0°C, uniform plating is not possible, and if the bath temperature is higher than 150°C, the current density is When the value is higher than 50^/d+n2, the onium ions of the nitrogen-containing heterocyclic compound are reduced, the plating layer becomes gray, and the crystals also become dendrite crystals, deteriorating the appearance and workability.
（実施例）
アルミニウムハロゲン化物と含窒素複素環化合物のオニ
ウムハロゲン化物との溶融塩浴に窒素原子を有する芳香
族化合物と有機ポリマーとを添加して、１１４１表に示
すような組成のめっき裕を調製し、このめっき浴を用い
て板厚が０．５１の冷延鋼板に電気アルミニウムめっト
を施した。めっきは、冷延鋼板を常法により溶剤蒸気洗
浄、アルカリ脱脂および酸洗を施した後、乾燥して、直
ちに予め窒素雰囲気に保っておいためっき浴に浸漬し、
冷延鋼板を陰極、アルミニウム板（純度９９．９９％、
板厚ＩＩ）を陽極にし、直流で電解した。第２表に電解
条件と得られたアルミニウムめっき鋼板の性能を示す。(Example) An aromatic compound having a nitrogen atom and an organic polymer were added to a molten salt bath of an aluminum halide and an onium halide of a nitrogen-containing heterocyclic compound to obtain a plating thickness having a composition as shown in Table 1141. A cold rolled steel plate having a thickness of 0.51 mm was electrolytically aluminum plated using this plating bath. For plating, cold-rolled steel sheets are subjected to solvent vapor cleaning, alkaline degreasing, and pickling using conventional methods, then dried, and immediately immersed in a plating bath that has been kept in a nitrogen atmosphere in advance.
A cold-rolled steel plate was used as the cathode, and an aluminum plate (purity 99.99%,
The plate thickness II) was used as an anode and electrolyzed with direct current. Table 2 shows the electrolytic conditions and the performance of the obtained aluminum-plated steel sheets.
（発明の効果）
以上のように、本発明のめっき浴によれば、厚めつきに
してもめっきＮ表面は平滑となり、また、低電流密度で
めっきして６つき回り性に優れている。(Effects of the Invention) As described above, according to the plating bath of the present invention, the plated N surface becomes smooth even when thick plating is performed, and the plating is performed at a low current density and has excellent 6-turn performance.
Claims (6)
窒素複素環化合物のオニウムハロゲン化物２０〜６０モ
ル％とを混合溶融してなるめっき浴に窒素原子を有する
芳香族化合物とポリマーとを添加したことを特徴とする
電気アルミニウムめっき浴。(1) An aromatic compound having a nitrogen atom and a polymer were added to a plating bath formed by mixing and melting 40 to 80 mol% of an aluminum halide and 20 to 60 mol% of an onium halide, which is a nitrogen-containing heterocyclic compound. An electric aluminum plating bath featuring:
−アルキル、１，３−ジアルキル、トリアルキルイミダ
ゾリウムハロゲン化物から選んだものであることを特徴
とする特許請求の範囲第１項に記載の電気アルミニウム
めっき浴。(2) The onium halide of the nitrogen-containing heterocyclic compound is 1
The electrolytic aluminum plating bath according to claim 1, characterized in that the bath is selected from -alkyl, 1,3-dialkyl and trialkylimidazolium halides.
ノアルキル、ジアルキル、トリアルキルピリジニウムハ
ロゲン化物から選んだものであることを特徴とする特許
請求の範囲第１項に記載の電気アルミニウムめっき浴。(3) The electrolytic aluminum plating bath according to claim 1, wherein the onium halide of the nitrogen-containing heterocyclic compound is selected from monoalkyl, dialkyl, and trialkylpyridinium halides.
以上有する不飽和複素環化合物を０．００１〜０．１モ
ル／ｌ添加したことを特徴とする特許請求の範囲第１項
に記載の電気アルミニウムめっき浴。(4) Claim 1, characterized in that 0.001 to 0.1 mol/l of an unsaturated heterocyclic compound having two or more N atoms is added as the aromatic compound having a nitrogen atom. electroaluminum plating bath.
を有する芳香族化合物を０．００１〜０．１モル／ｌ添
加したことを特徴とする特許請求の範囲第１項に記載の
電気アルミニウムめっき浴。(5) Electroaluminum plating according to claim 1, characterized in that 0.001 to 0.1 mol/l of an aromatic compound having an amino group is added as the aromatic compound having a nitrogen atom. bath.
キサイド−プロピレンオキサイド共重合体から選んだ１
種を３０ｍｇ／ｌ〜１ｇ／ｌ添加したことを特徴とする
特許請求の範囲第１項に記載の電気アルミニウムめっき
浴。(6) Polymer selected from polystyrene and ethylene oxide-propylene oxide copolymer
The electrolytic aluminum plating bath according to claim 1, characterized in that 30 mg/l to 1 g/l of seeds are added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15219090A JPH0445298A (en) | 1990-06-11 | 1990-06-11 | Aluminum electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15219090A JPH0445298A (en) | 1990-06-11 | 1990-06-11 | Aluminum electroplating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0445298A true JPH0445298A (en) | 1992-02-14 |
Family
ID=15535032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15219090A Pending JPH0445298A (en) | 1990-06-11 | 1990-06-11 | Aluminum electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0445298A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029395A1 (en) * | 2005-09-07 | 2007-03-15 | Nissan Motor Co., Ltd. | Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process |
| JP2008195989A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | Molten salt electric aluminum plating bath and plating method using the same |
| JP2008195990A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | Electric aluminum plating bath and plating method using the same |
-
1990
- 1990-06-11 JP JP15219090A patent/JPH0445298A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029395A1 (en) * | 2005-09-07 | 2007-03-15 | Nissan Motor Co., Ltd. | Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process |
| JP2008195989A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | Molten salt electric aluminum plating bath and plating method using the same |
| JP2008195990A (en) * | 2007-02-09 | 2008-08-28 | Dipsol Chem Co Ltd | Electric aluminum plating bath and plating method using the same |
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