JP3200807B2 - Organic thin film manufacturing method - Google Patents
Organic thin film manufacturing methodInfo
- Publication number
- JP3200807B2 JP3200807B2 JP32986592A JP32986592A JP3200807B2 JP 3200807 B2 JP3200807 B2 JP 3200807B2 JP 32986592 A JP32986592 A JP 32986592A JP 32986592 A JP32986592 A JP 32986592A JP 3200807 B2 JP3200807 B2 JP 3200807B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- organic thin
- organic
- anode
- interface
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解重合性有機物の薄
膜を、水銀などの液体金属電極と該有機物の電解液とで
形成した液相界面を利用して製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film of an electropolymerizable organic substance by using a liquid phase interface formed between a liquid metal electrode such as mercury and an electrolytic solution of the organic substance.
【０００２】[0002]
【従来技術とその課題】ポリピロール、ポリチオフェ
ン、ポリフェニレン、ポリアニリン等に代表される高分
子化合物や導電性を有しない有機化合物にドーパントを
含有させて導電性を有するようにした高分子化合物は、
これらの溶液を導電性塩の存在下で陽極重合させること
により導電性のフィルムを得ることができる。従来、上
記導電性高分子化合物フィルムの製造方法として、幾つ
かの方法が知られている。例えば、特開昭５９−２３８
８９号には、上記高分子化合物の電解液中にベルト状の
陽極を連続的に送入して、該陽極上に導電性フィルムを
重合析出させる方法が記載されており、また、特開昭６
０−１３７９２２号および特開昭６０−１３７９２３号
にも同様に高分子化合物の電解液中にベルト状の陽極を
送入する方法または回転体状の陽極を設置する方法が記
載されている。さらに特開平３−１７４４３５号にはベ
ルト状の陽極を用いる際に、該ベルト状陽極を電解槽内
に鉛直方向に移動させる方法が記載されている。2. Description of the Related Art Polymer compounds such as polypyrrole, polythiophene, polyphenylene, and polyaniline, and polymer compounds having conductivity by adding a dopant to a non-conductive organic compound include:
By conducting anodic polymerization of these solutions in the presence of a conductive salt, a conductive film can be obtained. Conventionally, several methods have been known as methods for producing the conductive polymer compound film. For example, JP-A-59-238
No. 89 describes a method in which a belt-shaped anode is continuously fed into an electrolytic solution of the polymer compound to polymerize and deposit a conductive film on the anode. 6
Similarly, JP-A-137922 and JP-A-60-137923 also describe a method of feeding a belt-shaped anode or a method of installing a rotating anode in an electrolyte solution of a polymer compound. Further, Japanese Patent Application Laid-Open No. 3-174435 describes a method in which a belt-shaped anode is vertically moved into an electrolytic cell when a belt-shaped anode is used.
【０００３】これらの製造方法は、上記導電性高分子化
合物フィルムを電解重合によって製造する場合に、陽極
の大きさに制限されずに連続してフィルムを析出させる
ための改良であり、何れの方法も、基本的には陽極上に
高分子化合物フィルムを析出させ、析出したフィルムを
陽極から剥離する点において変わりない。ところが、こ
のような陽極上にフィルムを析出させる方法では、フィ
ルムが陽極の表面状態の影響を受け易く、極薄のフィル
ム製造には適さず、また平滑性が劣る問題がある。さら
に陽極が繰り返し使用されるにつれて陽極表面が荒れ、
フィルムが円滑に剥離できなくなる虞がある。また陽極
の移動手段または回転手段を必要とし装置構成が大型化
する問題がある。とくに電解液中に移動又は回転する陽
極を設置しなければならないので、電解槽の大型化を避
けられない。また電解液中に陽極の移動又は回転機構が
浸漬されるので電解液が汚染され易く、高純度のフィル
ムを製造するには適さない。[0003] These production methods are improvements for continuously depositing the conductive polymer compound film without limitation on the size of the anode when the conductive polymer compound film is produced by electrolytic polymerization. This is basically the same in that a polymer compound film is deposited on the anode and the deposited film is peeled off from the anode. However, such a method of depositing a film on the anode has a problem that the film is easily affected by the surface condition of the anode, is not suitable for producing an extremely thin film, and has poor smoothness. Furthermore, as the anode is used repeatedly, the anode surface becomes rough,
There is a possibility that the film cannot be peeled off smoothly. In addition, there is a problem that an anode moving means or a rotating means is required and the apparatus configuration becomes large. In particular, since an anode that moves or rotates in the electrolyte must be provided, it is unavoidable to increase the size of the electrolytic cell. Further, since the moving or rotating mechanism of the anode is immersed in the electrolyte, the electrolyte is easily contaminated, which is not suitable for producing a high-purity film.
【０００４】本発明は従来方法の上記課題を解決した有
機物薄膜の製造方法を提供することを目的とする。金属
塩水溶液の電解については、有機液体／金属塩水溶液界
面に点電極を接触させて電解を行なうと、この界面で木
の葉状に薄く金属が析出することが知られており、その
形態から析出金属は金属葉と称されている（日本金属学
会会報第30巻第12号第985 頁〜第992 頁）。この有機液
体／金属塩水溶液界面に金属を薄く電解析出させる方法
を利用すれば、有機液体／金属塩水溶液界面に金属薄膜
を連続的に析出させることができる（特願平４−９８５
９０号、特願平４−１７００５９号）。本発明はこの方
法を有機物薄膜の製造に応用したしたものであり、本発
明の製造方法によれば、製造設備が簡単で数ミクロン以
下の有機物薄膜を容易に得ることができる。An object of the present invention is to provide a method for producing an organic thin film which has solved the above-mentioned problems of the conventional method. With respect to electrolysis of a metal salt aqueous solution, it is known that when a point electrode is brought into contact with an organic liquid / metal salt aqueous solution interface and electrolysis is performed, a thin metal is deposited like a leaf at this interface. Are referred to as metal leaves (The Japan Institute of Metals, Vol. 30, No. 12, pp. 985-992). By utilizing this method of thinly depositing a metal at the interface between the organic liquid / metal salt aqueous solution, a metal thin film can be continuously deposited at the interface between the organic liquid / metal salt aqueous solution (Japanese Patent Application No. Hei 4-985).
No. 90, Japanese Patent Application No. 4-170059). The present invention is an application of this method to the production of an organic thin film. According to the production method of the present invention, the production equipment is simple and an organic thin film of several microns or less can be easily obtained.
【０００５】[0005]
【課題の解決手段】本発明によれば、(1) 電解重合性有
機物の電解液と液体金属によって液相界面を形成し、該
電解液中に陰極を設けると共に上記液体金属を陽極とし
て電解を行い、該電解液と上記液体金属によって形成さ
れる液相界面に上記有機物の薄膜を重合析出させること
を特徴とする有機物薄膜の製造方法、(2) 上記液相界面
に成長する有機物薄膜を巻き取りながら、該有機物薄膜
の先端を該界面に沿って連続的に成長させることを特徴
とする上記(1) の製造方法、(3) 上記液体金属として水
銀、ガリウム、およびそれらの合金を含む低融点合金を
用いる上記(1) の製造方法、(4) 上記電解重合性有機物
電解液として、ピロール、チオフェン、ベンゼン、アニ
リンの導電性塩を含む溶液を用いる上記(1) の製造方
法、が提供される。According to the present invention, (1) a liquid phase interface is formed by an electrolytic solution of an electropolymerizable organic substance and a liquid metal, a cathode is provided in the electrolytic solution, and electrolysis is performed using the liquid metal as an anode. A method for producing an organic thin film, comprising polymerizing and depositing the organic thin film on a liquid phase interface formed by the electrolytic solution and the liquid metal; (2) winding the organic thin film growing on the liquid phase interface. The method according to the above (1), wherein the tip of the organic thin film is continuously grown along the interface while taking the same, and (3) a liquid containing mercury, gallium, and an alloy thereof as the liquid metal. (4) The method according to the above (1) using a melting point alloy; Is done.
【０００６】本発明において、電解重合性有機物とは、
ピロール、チオフェン、ベンゼン、アニリン等に代表さ
れる有機化合物であって、導電性塩の存在下に電解重合
するものを言う。なお重合体が導電性を有するものに限
らない。上記有機物電解液中に存在する導電性塩として
は、この種の電解に常用されているものであれば良く、
例えばアニオン種として、Ｆ4 - 、ＡｓＦ5 - 、ＳｂＦ
5 - 、ＰＦ5 - 、ＣｌＯ4 - 、ＨＳＯ4 - 、ＳＯ4 2-お
よび芳香族スルホン酸アニオンなどを与えるイオン性ま
たはイオン化性化合物が挙げられ、またカチオン種とし
て、水素イオン、アルカリ金属イオン、ＮＯ+ 、ＮＯ2
+ およびアンモニウムイオンなどを与えるイオン性また
はイオン化性化合物が挙げられる。また上記電解重合性
有機物を溶解する溶媒としては、水、アセトニトリル、
ベンゾニトリル、プロピレンカーボネイト、γ−ブチロ
ラクトン、ジクロルメタン、ジオキサン、ジメチルホル
ムアミド、ニトロメタン、ニトロエタン、ニトロプロパ
ン、ニトロベンゼンなどのニトロ系溶媒が好適に用いら
れるが、これに限らない。上記有機物の単量体と導電性
塩を与える化合物を溶媒に溶解した液を電解液として用
いる。In the present invention, the electropolymerizable organic substance is
Organic compounds typified by pyrrole, thiophene, benzene, aniline, etc., which undergo electrolytic polymerization in the presence of a conductive salt. The polymer is not limited to those having conductivity. As the conductive salt present in the organic electrolyte solution, any one may be used as long as it is commonly used for this type of electrolysis.
For example, as anion species, F 4 − , AsF 5 − , SbF
5 − , PF 5 − , ClO 4 − , HSO 4 − , SO 4 2− and ionic or ionizable compounds which give aromatic sulfonic acid anions, etc., and as the cation species, hydrogen ions, alkali metal ions, NO + , NO 2
And ionic or ionizable compounds which give + and ammonium ions and the like. Further, as the solvent for dissolving the electropolymerizable organic substance, water, acetonitrile,
Nitro solvents such as benzonitrile, propylene carbonate, γ-butyrolactone, dichloromethane, dioxane, dimethylformamide, nitromethane, nitroethane, nitropropane, and nitrobenzene are preferably used, but are not limited thereto. A solution obtained by dissolving the above-mentioned organic monomer and a compound that gives a conductive salt in a solvent is used as an electrolytic solution.
【０００７】本発明は液体金属と上記電解液とによって
液相界面を形成し、該液体金属を陽極として電解を行う
ことにより、該液相界面に上記有機物重合体の薄膜を電
析させる。液体金属としては、常温で液体の金属、例え
ば、水銀、ガリウム、ウッド浴合金（Eu合金）などを用
いることができる。陰極には銅板、白金などの良導電性
材料が用いられる。該陰極は界面に対して平行になるよ
うに設けるのが好ましく、界面に対して網状に広がる状
態のものが好ましい。なお、溶液組成、湿度などの電解
条件は従来の固体電極に電析させる電解条件と同様であ
る。In the present invention, a liquid phase interface is formed by a liquid metal and the above-mentioned electrolytic solution, and electrolysis is performed using the liquid metal as an anode, thereby depositing a thin film of the organic polymer on the liquid phase interface. As the liquid metal, a metal that is liquid at room temperature, for example, mercury, gallium, wood bath alloy (Eu alloy), or the like can be used. A good conductive material such as a copper plate and platinum is used for the cathode. The cathode is preferably provided so as to be parallel to the interface, and is preferably in a state of being spread in a mesh with respect to the interface. The electrolytic conditions such as solution composition and humidity are the same as the conventional electrolytic conditions for electrodeposition on a solid electrode.
【０００８】電解により液体金属の界面に沿って上記有
機物の薄膜が重合して析出する。界面に対して網目状に
広がる陰極を用いた場合には、通電後直ちに界面全体に
薄膜が電析する。析出した薄膜は液体金属の表面張力に
よって液相界面に保持され、次第に成長して膜厚が厚く
なる。なお、上記方法によって製造された有機物重合体
薄膜は、電解条件を制御することにより重合体の配向性
や薄膜の成長方向および薄膜の膜厚を制御することがで
きる。また、電解条件により網膜状の薄膜を成長させる
ことができる。The organic thin film polymerizes and deposits along the interface of the liquid metal by electrolysis. In the case where a cathode that spreads in a mesh pattern with respect to the interface is used, a thin film is deposited on the entire interface immediately after energization. The deposited thin film is held at the liquid phase interface by the surface tension of the liquid metal, and gradually grows to become thick. In the organic polymer thin film produced by the above method, the orientation of the polymer, the growth direction of the thin film, and the thickness of the thin film can be controlled by controlling the electrolysis conditions. Further, a retinal thin film can be grown depending on the electrolysis conditions.
【０００９】[0009]
【実施例】本発明を実施例に基づいて具体的に説明す
る。なお本発明は以下の実施例に限定されない。図１に
示すように、恒温水の流路１１を外周に備えた恒温電解
槽１０を用い、該電解槽１０に水銀１２を入れ、水銀の
液面上に0.1 M 硫酸銅水溶液にピロールを0.02 M 添加
してなる電解液を１４入れて二液相界面を形成した。こ
の電解液に銅製の網を浮かべて陰極１３とし、水銀／水
溶液界面に生じた薄膜を巻取るためのモーター１６を設
けた。一方、水銀には電解槽１０の外側から陽極線１５
を接続し、次表の電解条件に従って電解を行った。この
結果を次表に纏めて示す。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described based on embodiments. The present invention is not limited to the following embodiments. As shown in FIG. 1, a thermostatic electrolytic cell 10 having a constant temperature water flow path 11 on its outer periphery is used. The two-liquid phase interface was formed by adding 14 electrolyte solutions to which M was added. A copper net was floated on the electrolyte to form a cathode 13, and a motor 16 for winding a thin film formed at the mercury / aqueous solution interface was provided. On the other hand, mercury is supplied from the outside of the electrolytic cell 10 to the anode wire 15.
And electrolysis was performed according to the electrolysis conditions shown in the following table. The results are summarized in the following table.
【００１０】[0010]
【表１】 電圧(V) 電流(mA) 液温℃ 膜厚μm 薄膜の状態 (1) １ 50〜100 30 0.1〜１ 平滑な薄膜 (2) ２ 300〜500 30 １〜５ 平滑な薄膜 [Table 1] Voltage (V) Current (mA) Liquid temperature ℃ Thickness μm Thin film condition (1) 1 50-100 30 0.1-1 Smooth thin film (2) 2 300-500 30 1-5 Smooth thin film
【００１１】[0011]
【発明の効果】本発明によれば、数μm 程度の膜厚が均
一で平滑な配向性のある有機物重合体薄膜を容易に製造
することができる。本発明の方法は、従来の電解方法の
ような電極面に析出させた目的金属を剥離するものとは
異なり、液相界面に目的の有機薄膜を析出成長させ、こ
れを順次巻取ることにより連続的に薄膜を製造するの
で、剥離作業の必要がなく、製造が極めて容易である。
また製造される薄膜が電極の表面状態の影響を受けるこ
とがないので高品質の薄膜を得ることができる。さらに
本発明の方法は電解条件を制御することにより網膜状の
薄膜や配向方向を制御した薄膜を製造することができる
利点がある。According to the present invention, it is possible to easily produce an organic polymer thin film having a uniform thickness of about several μm and having a smooth orientation. The method of the present invention is different from a conventional electrolytic method in which a target metal deposited on an electrode surface is separated, and a target organic thin film is deposited and grown on a liquid phase interface, and is successively wound by successively winding it. Since the thin film is manufactured in a specific manner, there is no need for a stripping operation, and the manufacture is extremely easy.
Further, since the manufactured thin film is not affected by the surface condition of the electrode, a high quality thin film can be obtained. Further, the method of the present invention has an advantage that a retinal thin film or a thin film having a controlled orientation can be produced by controlling the electrolysis conditions.
【図１】 本発明の実施例に用いた電解装置の概略断面
図FIG. 1 is a schematic sectional view of an electrolytic apparatus used in an embodiment of the present invention.
１０−電解槽 １１−恒温水水路 １２−水銀 １３−銅製網 １４−電解液 １５−陽極線 １６−モーター DESCRIPTION OF SYMBOLS 10-Electrolysis tank 11-Constant temperature water channel 12-Mercury 13-Copper net 14-Electrolyte 15-Anode wire 16-Motor
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−136101（ＪＰ，Ａ) 特開 平６−158379（ＪＰ，Ａ) 特開 平５−339780（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25B 1/00 - 15/08 C08G 85/00 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-136101 (JP, A) JP-A-6-158379 (JP, A) JP-A-5-339780 (JP, A) (58) Field (Int.Cl. 7 , DB name) C25B 1/00-15/08 C08G 85/00
Claims (4)
よって液相界面を形成し、該電解液中に陰極を設けると
共に上記液体金属を陽極として電解を行い、該電解液と
上記液体金属によって形成される液相界面に上記有機物
の薄膜を重合析出させることを特徴とする有機物薄膜の
製造方法。1. A liquid phase interface is formed by an electrolytic solution of an electrolytic polymerizable organic substance and a liquid metal, a cathode is provided in the electrolytic solution, and electrolysis is performed using the liquid metal as an anode. A method for producing an organic thin film, comprising polymerizing and depositing the organic thin film on a formed liquid phase interface.
き取りながら、該有機物薄膜の先端を該界面に沿って連
続的に成長させることを特徴とする請求項１の製造方
法。2. The method according to claim 1, wherein the tip of the organic thin film is continuously grown along the interface while winding the organic thin film growing on the liquid phase interface.
よびそれらの合金を含む低融点合金を用いる請求項１の
製造方法。3. The method according to claim 1, wherein a low-melting alloy containing mercury, gallium, or an alloy thereof is used as the liquid metal.
ロール、チオフェン、ベンゼン、アニリンの導電性塩を
含む溶液を用いる請求項１の製造方法。4. The method according to claim 1, wherein a solution containing a conductive salt of pyrrole, thiophene, benzene, or aniline is used as the electrolytic polymerizable organic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32986592A JP3200807B2 (en) | 1992-11-17 | 1992-11-17 | Organic thin film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32986592A JP3200807B2 (en) | 1992-11-17 | 1992-11-17 | Organic thin film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06158375A JPH06158375A (en) | 1994-06-07 |
| JP3200807B2 true JP3200807B2 (en) | 2001-08-20 |
Family
ID=18226110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32986592A Expired - Lifetime JP3200807B2 (en) | 1992-11-17 | 1992-11-17 | Organic thin film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3200807B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6787980B2 (en) * | 2000-09-22 | 2004-09-07 | Matsushita Electric Industrial Co., Ltd. | Mercury-containing material, method for producing the same and fluorescent lamp using the same |
| KR101136904B1 (en) * | 2009-12-31 | 2012-04-20 | 한국수력원자력 주식회사 | A metal separation and purification system and the method for the same by using liquid metal electrode |
| JP5350409B2 (en) * | 2011-01-11 | 2013-11-27 | ラサ工業株式会社 | Electrolytic generator |
| CN114724770A (en) * | 2022-03-24 | 2022-07-08 | 西南民族大学 | Preparation method of liquid metal flexible conductor |
-
1992
- 1992-11-17 JP JP32986592A patent/JP3200807B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06158375A (en) | 1994-06-07 |
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