JP2576403B2 - Conductive polymer compound - Google Patents
Conductive polymer compoundInfo
- Publication number
- JP2576403B2 JP2576403B2 JP1709094A JP1709094A JP2576403B2 JP 2576403 B2 JP2576403 B2 JP 2576403B2 JP 1709094 A JP1709094 A JP 1709094A JP 1709094 A JP1709094 A JP 1709094A JP 2576403 B2 JP2576403 B2 JP 2576403B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- polyaniline
- acid
- solution
- polymer compound
- 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 - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は各種電子部品、電極等に
広く利用でき、高濃度でも長時間にわたり沈殿を生じな
い安定化された導電性高分子化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized conductive polymer compound which can be widely used for various electronic parts, electrodes and the like and which does not precipitate for a long time even at a high concentration.
【０００２】[0002]
【従来の技術】近年、機能性有機材料の分野においてめ
ざましい技術革新が進み、導電性高分子に限ってもポリ
アセチレン、ポリパラフェニレン、ポリピロール、ポリ
チオフェン、ポリアニリン等の電子共役系高分子に電子
供与性や電子需要性化合物をドーパントとして添加した
導電性高分子が開発され、電極材料や導電性薄膜として
一部実用化されている。2. Description of the Related Art In recent years, remarkable technical innovations have been made in the field of functional organic materials, and even for conductive polymers, electron-donating polymers such as polyacetylene, polyparaphenylene, polypyrrole, polythiophene, and polyaniline have been used. And a conductive polymer to which an electron demand compound is added as a dopant have been developed, and some of them have been put to practical use as an electrode material or a conductive thin film.
【０００３】一般に、導電性高分子は剛直な主鎖構造を
有するため不溶不融であるが、長鎖アルキル置換基を導
入した複素五員環式化合物重合体やポリアニリンが脱ド
ープした中性状態で有機溶媒に溶解することが知られて
いる。また、中性のポリアニリンとカンファスルホン酸
の混合物がｍ−クレゾール等の溶媒に溶解し、溶液から
キャストして形成したフィルムが高い導電率を有するこ
とも報告されている（シンセチックメタルズ（Ｓｙｎｔ
ｈｅｔｉｃ Ｍｅｔａｌｓ）、４８巻、９４頁、１９９
２年）。[0003] In general, conductive polymers are insoluble and infusible because of their rigid main chain structure, but are in a neutral state in which a polymer of a five-membered heterocyclic compound into which a long-chain alkyl substituent is introduced or a polyaniline is undoped. Is known to dissolve in organic solvents. It has also been reported that a film formed by dissolving a mixture of neutral polyaniline and camphorsulfonic acid in a solvent such as m-cresol and casting from the solution has high electrical conductivity (Synthetic Metals (Synt Metals, Inc.)
Hetic Metals), 48, 94, 199
2 years).
【０００４】導電性高分子の中でポリアニリンは優れた
電気化学的性質を示し、安定性にも優れているため注目
されている。その性質はドーパントに依存して変化し、
これまでに種々のドーパントが検討されている。例えば
特開平３−６２４５１号公報にはベンゼンスルホン酸、
ｐ−トルエンスルホン酸、塩化ベンゼンスルホニル、ド
デシルベンゼンスルホン酸、ポリビニルスルホン酸、メ
タンスルホン酸、１−ブタンスルホン酸、改質したナフ
ィオン、２，３，５−トリクロロベンゼンスルホン酸、
ビニルフェニルスルホン酸をドーパントとするポリアニ
リンからなる電極が開示されている。[0004] Among conductive polymers, polyaniline has attracted attention because of its excellent electrochemical properties and excellent stability. Its properties vary depending on the dopant,
Various dopants have been studied so far. For example, JP-A-3-62451 discloses benzenesulfonic acid,
p-toluenesulfonic acid, benzenesulfonyl chloride, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, 1-butanesulfonic acid, modified Nafion, 2,3,5-trichlorobenzenesulfonic acid,
An electrode composed of polyaniline using vinylphenylsulfonic acid as a dopant is disclosed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、中性状
態で溶解する導電性高分子溶液はドーパントを添加する
と直ちに凝集が起こり、溶解度は０．１重量％以下に低
下する。従って、中性の導電性高分子溶液から作製した
高分子膜に導電性を付与するためには、膜形成後何らか
の方法でドーピングする工程が必要であり、また、ドー
パントを添加した低濃度溶液をキャストしても分子量が
小さいために膜形成しないという問題点があった。さら
に、カンファスルホン酸をドーパントとするポリアニリ
ンでは溶媒がｍ−クレゾール等に限定され、成膜する基
板の種類が限定されるという問題点があった。また、ポ
リアニリンとその他の従来公知のドーパントでは、多量
のドーパントを含み高濃度まで安定な溶液を作製できな
かった。However, a conductive polymer solution that dissolves in a neutral state immediately agglomerates as soon as the dopant is added, and the solubility decreases to 0.1% by weight or less. Therefore, in order to impart conductivity to a polymer film prepared from a neutral conductive polymer solution, a step of doping by some method after film formation is necessary, and a low-concentration solution to which a dopant is added is required. Even when cast, there is a problem that a film is not formed due to a small molecular weight. Further, polyaniline using camphorsulfonic acid as a dopant has a problem that the solvent is limited to m-cresol or the like, and the type of a substrate on which a film is formed is limited. Further, with polyaniline and other conventionally known dopants, a solution containing a large amount of dopant and stable up to a high concentration could not be produced.
【０００６】本発明の課題は前期問題点を解決すること
により、多量のドーパントを含み、高濃度まで安定に保
持できる導電性高分子化合物を提供することにある。An object of the present invention is to provide a conductive polymer compound which contains a large amount of dopant and can be stably maintained at a high concentration by solving the above problems.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために種々の検討を行った。その結果、メン
タン骨格を有するアニオンを含有することにより高いド
ーパント濃度においても有機溶媒に溶解する導電性高分
子を見い出し、本発明に至った。Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems. As a result, a conductive polymer that is soluble in an organic solvent even at a high dopant concentration by containing an anion having a menthane skeleton was found, and the present invention was achieved.
【０００８】すなわち本発明は、メンタン骨格を有する
アニオンを含有する導電性高分子化合物である。That is, the present invention is a conductive polymer compound containing an anion having a menthol skeleton.
【０００９】本発明において導電性高分子の種類は特に
限定されず、ポリアニリン、ポリピロール、ポリアセチ
レン、ポリチオフェン、ポリパラフェニレン、ポリパラ
フェニレンビニレン、ポリチェニレンビニレン、ポリア
ズレン、ポリフラン等が用いられるが、高導電性の面か
ら特にポリアニリンおよびポリピロールが好ましい。本
発明においてポリアニリン、およびポリピロールとはそ
れぞれアニリン、およびピロールもしくはその誘導体を
主な繰り返し単位とする重合体である。In the present invention, the kind of the conductive polymer is not particularly limited, and polyaniline, polypyrrole, polyacetylene, polythiophene, polyparaphenylene, polyparaphenylenevinylene, polychenylenevinylene, polyazulene, polyfuran and the like are used. Particularly, polyaniline and polypyrrole are preferable from the viewpoint of conductivity. In the present invention, polyaniline and polypyrrole are polymers containing aniline and pyrrole or a derivative thereof as main repeating units, respectively.
【００１０】本発明においてメンタン骨格を有するアニ
オンとは分子内にメンタン骨格を有し、スルホン酸基、
カルボン酸基、リン酸基等のアニオン性基を含むもので
あれば特に限定されない。このような化合物として、例
えば３−ｐ−メントキシ酢酸等が挙げられる。メンタン
骨格を有するアニオンは嵩高いため、これを含有する導
電性高分子の溶解性が高いと考えられる。In the present invention, the term "anion having a menthol skeleton" refers to an anion having a menthol skeleton in a molecule, a sulfonic acid group,
There is no particular limitation as long as it contains an anionic group such as a carboxylic acid group or a phosphoric acid group. Examples of such a compound include 3-p-menthoxyacetic acid. Since an anion having a menthane skeleton is bulky, it is considered that a conductive polymer containing the anion has high solubility.
【００１１】本発明に用いられるポリアニリンの重合方
法は特に限定されず、例えばプロトン酸を含む溶媒にモ
ノマーとしてアニリンまたはその誘導体を溶解させた
後、酸化剤を加えて酸化重合させる方法や、プロトン酸
と酸化剤を含む溶液にモノマーを加えるか、あるいはモ
ノマー蒸気を接触させる方法等が挙げられる。ここで用
いられる酸化剤は特に限定されず、アニリンの酸化剤と
して従来公知のものが使用できる。例えば、過硫酸アン
モニウム、過硫酸カリウム等の過硫酸塩、重クロム酸カ
リウム、重クロム酸アンモニウム等の重クロム酸塩、過
酸化水素、二酸化マンガン、ベンゾキノン等が挙げられ
る。これらの酸化剤を用いてポリアニリンを重合し、ア
ンモニア水などで脱ドープ処理を行うことにより、中性
状態のポリアニリンとなる。このポリアニリンをメンタ
ン骨格を有するドーパントでドーピングすることによ
り、本発明の導電性高分子が得られる。The polymerization method of the polyaniline used in the present invention is not particularly limited. For example, a method of dissolving aniline or a derivative thereof as a monomer in a solvent containing a protonic acid and then adding an oxidizing agent to carry out oxidative polymerization, And a method in which a monomer is added to a solution containing a solvent and an oxidizing agent, or a monomer vapor is brought into contact. The oxidizing agent used here is not particularly limited, and a conventionally known oxidizing agent for aniline can be used. Examples include persulfates such as ammonium persulfate and potassium persulfate, dichromates such as potassium dichromate and ammonium dichromate, hydrogen peroxide, manganese dioxide, benzoquinone and the like. Polyaniline is polymerized using these oxidizing agents, and is dedoped with ammonia water or the like, whereby polyaniline in a neutral state is obtained. By doping this polyaniline with a dopant having a menthane skeleton, the conductive polymer of the present invention can be obtained.
【００１２】本発明に用いられるポリピロールの重合方
法は特に限定されず、例えばモノマーとしてピロールま
たはその誘導体を含む溶液に酸化剤を加えて重合する方
法や、電気化学的に陽極酸化する電解重合法等が挙げら
れる。これらの方法で重合したポリピロールを脱ドーピ
ングし、メンタン骨格を有するドーパントで再ドープす
ることにより、本発明の導電性高分子が得られる。The method for polymerizing polypyrrole used in the present invention is not particularly limited. Examples thereof include a method of adding an oxidizing agent to a solution containing pyrrole or a derivative thereof as a monomer, and a method of electrochemically anodizing electrochemically. Is mentioned. The conductive polymer of the present invention can be obtained by undoping polypyrrole polymerized by these methods and re-doping with a dopant having a menthane skeleton.
【００１３】また、本発明の導電性高分子を溶解する溶
媒としては導電性高分子化合物を溶解するものであれば
特に限定されず、クロロホルム、ジクロロメタン、ジク
ロロベンゼン等の塩素系溶媒、ベンゼン、トルエン、キ
シレン、ｍ−クレゾール、ニトロベンゼン等の芳香族系
炭化水素溶媒、メタノール、エタノール、アセトン、イ
ソプロピルアルコール、メチルエチルケトン、テトラヒ
ドロフラン、ヘキサン、アセトニトリル、ニトロメタ
ン、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミ
ド、ジメチルスルホキシド等が挙げられる。これら溶媒
に導電性高分子を溶解した溶液は、導電性高分子薄膜を
形成するときに非常に有用である。The solvent for dissolving the conductive polymer of the present invention is not particularly limited as long as it dissolves the conductive polymer compound. Chlorine-based solvents such as chloroform, dichloromethane, dichlorobenzene, benzene, toluene , Xylene, m-cresol, aromatic hydrocarbon solvents such as nitrobenzene, methanol, ethanol, acetone, isopropyl alcohol, methyl ethyl ketone, tetrahydrofuran, hexane, acetonitrile, nitromethane, N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, etc. Is mentioned. A solution in which a conductive polymer is dissolved in these solvents is very useful when forming a conductive polymer thin film.
【００１４】本発明の導電性高分子は導電性薄膜材料と
して、電極や電磁波シールド、帯電防止膜等の様々な用
途に使用可能である。The conductive polymer of the present invention can be used as a conductive thin film material in various applications such as electrodes, electromagnetic wave shields, and antistatic films.
【００１５】[0015]
【実施例】以下、本発明を実施例に従って説明するが、
本発明はその要旨を越えない限り以下の実施例に限定さ
れるものではない。Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
【００１６】（実施例１）ガラス製容器に水／エチルア
ルコール（体積比３０：７０）の混合溶液５０ｇを入
れ、パラトルエンスルホン酸６．８８ｇ（０．０４モ
ル）とアニリン０．９３ｇ（０．０１モル）を添加し、
攪拌してモノマー溶液を作成した。また、別のガラス製
容器に水／エチルアルコール（体積比３０：７０）の混
合溶液５０ｇを入れ、パラトルエンスルホン酸８．６ｇ
（０．０５モル）を溶解し、さらに２クロム酸アンモニ
ウム１２．６ｇ（０．０５モル）を添加して酸化剤溶液
を作成した。上記酸化剤溶液とモノマー溶液を０℃で３
時間重合し、その後アンモニア水で脱ドープし、洗浄、
減圧してポリアニリンを得た。このポリアニリン２ｇを
３−ｐ−メントキシ酢酸１ｇと共にメタノール１００ｇ
に添加し、６時間攪拌したところ３−ｐ−メントキシ酢
酸をドーパントとするポリアニリンのメタノール溶液が
得られた。この溶液をガラス基板上に展開し、溶媒を蒸
発させて得たフィルムの室温での導電率を測定したとこ
ろ、１５Ｓ／ｃｍであった。(Example 1) A glass container was charged with 50 g of a mixed solution of water / ethyl alcohol (volume ratio: 30:70), and 6.88 g (0.04 mol) of paratoluenesulfonic acid and 0.93 g (0. .01 mol),
The mixture was stirred to prepare a monomer solution. In another glass container, 50 g of a mixed solution of water / ethyl alcohol (volume ratio: 30:70) was added, and 8.6 g of paratoluenesulfonic acid was added.
(0.05 mol) was dissolved, and 12.6 g (0.05 mol) of ammonium dichromate was further added to prepare an oxidizing agent solution. The oxidizing agent solution and the monomer solution are mixed at 0 ° C for 3 hours.
Polymerized for hours, then dedoped with aqueous ammonia, washed,
The pressure was reduced to obtain polyaniline. 2 g of this polyaniline and 100 g of methanol together with 1 g of 3-p-menthoxyacetic acid
And stirred for 6 hours to obtain a methanol solution of polyaniline using 3-p-menthoxyacetic acid as a dopant. This solution was spread on a glass substrate, and the conductivity of the film obtained by evaporating the solvent at room temperature was 15 S / cm.
【００１７】（実施例２）ガラス製容器に水１００ｇを
入れ、ピロール０．６６ｇ（０．０１モル）と３−ｐ−
メントキシ酢酸２．１４ｇ（０．０１モル）を添加し攪
拌した。この溶液に２枚の白金製電極を浸漬し、２．８
Ｖの電圧を加えたところ、直ちに陽極表面上に青色の析
出物が生成した。３０分反応後陽極を取り出しメタノー
ルに浸漬したところ、析出物は溶解し、３−ｐ−メント
キシ酢酸をドーパントとするポリピロールのメタノール
溶液が得られた。この溶液をガラス基板上に展開し、溶
媒を蒸発させて得たフィルムの室温での導電率を測定し
たところ、２５Ｓ／ｃｍであった。Example 2 100 g of water was put in a glass container, and 0.66 g (0.01 mol) of pyrrole and 3-p-
2.14 g (0.01 mol) of menthoxyacetic acid was added and stirred. Two platinum electrodes were immersed in this solution, and 2.8
Upon application of a voltage of V, a blue precipitate was immediately formed on the anode surface. After the reaction for 30 minutes, the anode was taken out and immersed in methanol, and the precipitate was dissolved to obtain a methanol solution of polypyrrole using 3-p-menthoxyacetic acid as a dopant. This solution was spread on a glass substrate, and the conductivity of the film obtained by evaporating the solvent at room temperature was 25 S / cm.
【００１８】[0018]
【発明の効果】以上説明したように、本発明によれば各
種電子部品、電極等に広く利用でき、高濃度でも長時間
にわたり沈殿を生じない安定化された導電性高分子化合
物およびその溶液を提供することができ、その効果は大
である。As described above, according to the present invention, a stabilized conductive polymer compound which can be widely used for various electronic parts and electrodes and which does not cause precipitation for a long time even at a high concentration, and a solution thereof are provided. Can be provided, the effect is great.
Claims (2)
ことを特徴とする導電性高分子化合物。1. A conductive polymer compound comprising an anion having a menthol skeleton.
はポリピロールもしくはそれらの誘導体であることを特
徴とする請求項１記載の導電性高分子化合物。2. The conductive polymer compound according to claim 1, wherein the conductive polymer compound is polyaniline, polypyrrole, or a derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1709094A JP2576403B2 (en) | 1994-02-14 | 1994-02-14 | Conductive polymer compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1709094A JP2576403B2 (en) | 1994-02-14 | 1994-02-14 | Conductive polymer compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07224207A JPH07224207A (en) | 1995-08-22 |
| JP2576403B2 true JP2576403B2 (en) | 1997-01-29 |
Family
ID=11934296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1709094A Expired - Fee Related JP2576403B2 (en) | 1994-02-14 | 1994-02-14 | Conductive polymer compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2576403B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4614445B2 (en) * | 2005-09-29 | 2011-01-19 | 日本航空電子工業株式会社 | Conductive thin film, flexible member using the same, transparent electrode member, and electromagnetic shielding coating film |
| JP5206922B2 (en) * | 2007-03-23 | 2013-06-12 | アキレス株式会社 | Polypyrrole fine particle dispersion |
-
1994
- 1994-02-14 JP JP1709094A patent/JP2576403B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07224207A (en) | 1995-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| D'Aprano et al. | Synthesis and characterization of polyaniline derivatives: poly (2-alkoxyanilines) and poly (2, 5-dialkoxyanilines) | |
| KR100733093B1 (en) | Process for the Preparation of Water-Soluble ?-conjugated Polymers | |
| Yano | Electrochemical and structural studies on soluble and conducting polymer from o‐phenylenediamine | |
| Pei et al. | Poly [3-(4-octylphenyl) thiophene], a new processible conducting polymer | |
| Lee et al. | A novel conducting soluble polypyrrole composite with a polymeric co-dopant | |
| JPH0786093A (en) | Solid-state electrolytic capacitor and its manufacture | |
| US4505841A (en) | Fused 6,6,6-membered heterocyclic electroactive polymers | |
| Bıçak et al. | Preparation of organo-soluble polyanilines in ionic liquid | |
| US4548738A (en) | Electrically conducting complexes of poly (3,6-N-alkylcarbazolyl alkenes) and method of making | |
| JPH0632845A (en) | Production of electrically conductive high molecular complex material | |
| JP2601207B2 (en) | Method for producing conductive polymer molded article | |
| JP2605596B2 (en) | Conductive polymer film and method for producing the same, conductive polymer compound solution, and solid electrolytic capacitor and method for producing the same | |
| JP2576403B2 (en) | Conductive polymer compound | |
| JP2008169255A (en) | Highly conductive polyaniline having excellent solubility and method for producing the same | |
| Trivedi | Influence of counter ion on polyaniline and polypyrrole | |
| Udum et al. | Electrochemical synthesis of soluble sulfonated poly (3-methyl thiophene) | |
| EP1361244B1 (en) | Poly(5-aminoquinoxalines); preparation and use thereof | |
| JPH01500835A (en) | Water-soluble self-doped conductive polymer and method for producing the same | |
| KR100318153B1 (en) | Method for Preparation of the Conductive Polypyrrole having a high Solubility in Alcohol and Various Organic Solvents | |
| KR100514643B1 (en) | Preparation Method of Polyanilines | |
| JPH0757802B2 (en) | Method for producing polyaniline derivative | |
| Jen et al. | Low band-gap conjugated polymers: poly (thienylene vinylene) and poly (substituted thienylene vinylenes) | |
| JPH0547211A (en) | High molecular charge-transfer complex | |
| Sivakumar et al. | Electroactive conducting blends of poly (o-toluidine) and poly (vinylidene fluoride) and characterisation | |
| JPH06279584A (en) | Production of polyaniline or thin conductive polyailine film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19960910 |
|
| LAPS | Cancellation because of no payment of annual fees |