JP2004197069A - Method for producing conductive polymer, conductive polymer molded product, electrolytically stretching method, laminated product and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a conductive polymer having an excellent stretching ratio per oxidation-reduction cycle, and to provide an electrolytically stretching method having the excellent stretching ratio per oxidation-reduction cycle. <P>SOLUTION: This method for producing the electrically-conductive polymer comprises producing the conductive polymer having stretchability brought about electrochemical oxidation-reduction through an electrolytic polymerization process, wherein the electrolytic polymerization process uses an electrolyte which contains an organic compound containing at least one linkage or functional group selected from ether linkage, ester linkage, carbonate linkage, hydroxy, nitro, sulfo, and nitrile, and/or a halogenated hydrocarbon as solvents, and the electrolyte contains a trifluoromethanesulfonate ion and/or an anion having two or more fluorine atoms on its center atom. A conductive polymer molded product containing the conductive polymer obtained by the method is used in the electrolytically stretching method. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００９０】
【表２】

【００９１】
【表３】

【００９２】
【表４】

【００９３】
【表５】

【００９４】
【表６】

【００９５】
なお、表１〜６において、ドーパント塩の種類及び溶媒欄の略号は以下のとおりである。
ドーパント塩Ａ：ＴＢＡＣＦ_３ＳＯ_３（トリフルオロメタンスルホン酸テトラブチルアンモニウム）
ドーパント塩Ｂ：ＣＦ_３ＳＯ_３Ｌｉ（トリフルオロメタンスルホン酸リチウム）
ドーパント塩Ｃ：ＴＢＡＢＦ_４（テトラフルオロホウ酸テトラブチルアンモニウム）
ドーパント塩Ｄ：ＴＢＡＰＦ_６（ヘキサフルオロリン酸テトラブチルアンモニウム）
ドーパント塩Ｅ：ｐ−トルエンスルホン酸ナトリウム
溶媒；
ＰＣ：プロピレンカーボネ−ト
ＥＣ：エチレンカーボネート
γ−ＢＬ：γ−ブチロラクトン
ＭＯ：３−メチル−２−オキサゾリジノン
ＤＥＣ：ジエチルカーボネート
ＤＭＣ：ジメチルカーボネート
ＤＭＥ：ジメトキシエタン
ＴＨＦ：テトラヒドロフラン
ＡｃＥｔ：酢酸エチル
Ａｃ−ｎ−Ｂｔ：酢酸ｎ−ブチル
Ａｃ−ｔ−Ｂｔ：酢酸−ｔ−ブチル
ＥＧ：エチレングリコール
ＰＥＧ：ポリエチレングリコール（分子量：２００）
ＳＦ：スルホラン
ＤＯ：１，４−ジオキサン
ＤＡＥ：１，２−ジアセトキシエタン
ＮＭ：ニトロメタン
ＨｘＯＨ：１−ヘキサノール
ＯｔＯＨ：１−オクタノール
ＡＮ：アセトニトリル
ＮＢ：ニトロベンゼン
ＭｅＢ：安息香酸メチル
ＰｈＥｔ：フタル酸ジエチル
ＤＣＭ：ジクロロメタン
【００９６】
また、表１〜５において、混合溶媒を用いている場合には、例えば、ＥＣ／ＰＣ＝１／２とはエチレンカーボネートとプロピレンカーボネートとの重量比が１：２である溶媒を示す。
【００９７】
（評価）
実施例１〜４３並びに比較例１及び２で得られた膜状の導電性高分子成形品を、表１〜５に記載された動作電解質を１ｍｏｌ／ｌとなるように水に溶解した電解液中に保持した。保持された各膜状の導電性高分子成型品について、下記の測定方法により、それぞれ１酸化還元サイクル当たりの伸縮率を測定した。その結果を表１〜５に示す。また、実施例４４及び４５、並びに、比較例３及び４で得られた膜状の導電性高分子成形品について、下記の測定方法により、それぞれ特定時間あたりの変位率を測定した。特定時間あたりの変位率の結果を表６に示す。なお実施例１〜４５及び比較例１〜４の導電性高分子成型品の導電率及び膜厚は、公知の方法により測定した。
【００９８】
〔伸縮率の測定方法〕
実施例１〜４３並びに比較例１及び２で得られた膜状の導電性高分子成形品を長さ１５ｍｍ、幅２ｍｍの動作電極とし、白金プレートを対向電極とし、それぞれ電極の端部に、動作電極を前記電解液中に保持し、リードを介して電源と接続して、電位（−０．９〜＋０．７Ｖ ｖ．ｓ． Ａｇ／Ａｇ^＋）を１サイクル印加して変位量（変位した長さ）を測定した。動作電極が１サイクルの印加（１酸化還元サイクル）で伸長と収縮とをすることにより得られた変位の差を、動作電極の元の長さで割ることにより、１酸化還元サイクル当たりの伸縮率を求めた。なお、動作電解質のＴＥＡＰＦ_６とは、テトラフルオロリン酸テトラエチルアンモニウム塩であり、ＥｔＳＯ_３Ｎａとはエタンスルホン酸ナトリウムを表す。
【００９９】
〔特定時間あたりの変位率〕
実施例４１及び４２、並びに、比較例３及び４で得られた膜状の導電性高分子成形品を長さ１５ｍｍ、幅２ｍｍの動作電極とし、白金プレートを対向電極とし、それぞれ電極の端部に、動作電極を前記電解液中に保持し、リードを介して電源と接続して、電位（＋０．９Ｖ ｖ．ｓ． Ａｇ／Ａｇ^＋または−０．９Ｖ ｖ．ｓ． Ａｇ／Ａｇ^＋）を印加して、印加開始から２０秒後の変位量（変位した長さ）を測定した。印加開始から２０秒後の変位量を、電位を印加する前の動作電極の長さで割ることにより、特定時間当たりの伸縮率を求めた。
【０１００】
（結果）
実施例１５の導電性高分子成形品は、トリフルオロメタンスルホン酸イオンをドーパントアニオンとし、溶媒がエチレンカーボネートとプロピレンカーボネートの混合溶媒（１：２）である電解液を用いた電解重合法による導電性高分子の製造方法により得られた導電性高分子成形品である。比較例１の導電性高分子成形品は、電解液の溶媒が水であり、従来のドーパントであるｐ−トルエンスルホン酸イオンを含む電解液で電解重合された導電性高分子成形品である。実施例１５の導電性高分子成形品を、従来の作動環境である塩化ナトリウムを動作電解質として電解伸縮をさせると、表２に示すとおり、伸縮率３．１％であった。これに対し、比較例１の導電性高分子成形品を、実施例１５と同様に、塩化ナトリウムを動作電解質として電解伸縮をさせると表４に示すように、伸縮率１．３％であった。つまり、実施例１５の導電性高分子成形品は、従来の動作環境である塩化ナトリウム水溶液中であっても、従来のドーパントを含む導電性高分子成形品に比べて、１酸化還元サイクル当たりの伸縮率が約２．４倍である良好な伸縮をすることができた。
【０１０１】
実施例１〜１４及び実施例１６〜４３については、導電性高分子成形品がそれぞれ本願発明の導電性高分子の製造方法により得られた導電性高分子成形品であり、作動環境として、トリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子を複数含むアニオン及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液中で、１酸化還元サイクルの電気化学的酸化還元により導電性高分子成形品を伸縮させた結果、表１〜５に示すように、伸縮率は５％以上であった。これに対し、比較例２については、導電性高分子は、電解液の溶媒が水であり、従来のドーパントであるｐ−トルエンスルホン酸イオンを含む電解液で電解重合された導電性高分子成形品であり、作動環境として、トリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子及び炭素数３以下のスルホン酸塩からなる群より少なくとも１種以上選ばれた化合物を含む電解液中で、１酸化還元サイクルの電気化学的酸化還元により導電性高分子成形品を伸縮させた結果、表４に示すように、伸縮率は１．７％と低かった。即ち、本願発明の導電性高分子成形品は、トリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液中で電気化学的酸化還元により導電性高分子成形品を伸縮させることにより、１酸化還元サイクル当たりの伸縮率が従来の約３倍以上である優れた伸縮をした。
【０１０２】
実施例４４及び４５についての導電性高分子成形品は、それぞれ実施例１５と実施例４の導電性高分子成形品に相当する本願発明の製造方法により得られた導電性高分子成形品である。一方、比較例３及び４の導電性高分子成形品は、それぞれ比較例１及び２に相当する導電性高分子成形品である。従来の作動環境であるＮａＣｌ水溶液中において、比較例３の導電性高分子成形品が特定時間当たりの伸縮率が０．４％であったのに対し、実施例３６の導電性高分子成形品は、特定時間当たりの伸縮率について１．７％という約４倍の向上を図ることができた。つまり、本願発明の導電性高分子成形品を用いることにより、変位の早い電解伸縮を実現することができる。
【０１０３】
また、電解伸縮の作動環境にトリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子を複数含むアニオン及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液とした場合には、比較例４の導電性高分子成形品が特定時間当たりの伸縮率が０．４％であったのに対し、実施例４５の導電性高分子成形品は、特定時間当たりの伸縮率について３．９％という約１０倍の向上を図ることができた。したがって、トリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子を複数含むアニオン及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液中で導電性高分子成形品を電気化学的酸化還元により導電性高分子成形品を伸縮させる電解伸縮方法を用いることにより、さらに変位の早い電解伸縮を実現することができる。
【０１０４】
従って、作動部、対極、及び電解質を含むアクチュエータについて、本発明の製造方法により得られた導電性高分子を含む導電性高分子成形品を作動部とすることにより、伸縮が早く、応答性の良好なアクチュエータとすることができる。また、導電性高分子含有層と固体電解質層とを含む積層体についても、本発明の製造方法により得られた導電性高分子を導電性高分子含有層とに含むことにより、伸縮が早く、応答性の良好なアクチュエータに用いることができる積層体とすることができる。
【０１０５】
【発明の効果】
本発明の導電性高分子の製造方法を用いることにより得られた導電性高分子成形品は、従来の伸縮性を有する導電性高分子成形品に比べて、優れた１酸化還元サイクル当たりの伸縮率を電解伸縮時に発現し、変位の命令に対応して従来より大きな動作をするので実用性に優れ、人工筋肉、ロボットアーム、義手やアクチュエータ等の用途として有用である。本発明の導電性高分子の製造方法により得られた導電性高分子成形品は、電解伸縮の作動環境にトリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子を複数含むアニオン及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液中で電解伸縮させることにより、さらに大きな伸縮率を発現することができるので、さらに大きな伸縮を必要とする用途として有用である。
【０１０６】
さらには、本発明の導電性高分子成形品は、電解伸縮の作動環境にトリフルオロメタンスルホン酸イオン、中心原子に対してフッ素原子を複数含むアニオン及び炭素数３以下のスルホン酸塩からなる群より少なくとも１以上選ばれた化合物を含む電解液中で、電気化学的酸化還元により導電性高分子成形品を伸縮させることにより、従来の伸縮性を有する導電性高分子成形品に比べて約１０倍以上の特定時間当たりの伸縮率を発現するので、変位の命令に対して速い応答が要求される用途の駆動部分として使用することも可能である。
【０１０７】
また、対極と電解質と前記導電性高分子の製造方法により得られた導電性高分子を含む作動部とを含むアクチュエータを用いることにより、伸縮が大きいアクチュエータを得ることができ、しかも静音であるので人工筋肉や、各種駆動装置の駆動部、押圧装置の押圧部に好適に用いることができる。また、作動部が電気化学的酸化還元によって伸縮し、２０秒間の１酸化還元サイクルにおけるアクチュエータの伸縮率が長さ方向に３％以上であるアクチュエータは、変位の応答性が速く、人工筋肉や各種装置における駆動部として用いることができる。
【図面の簡単な説明】
【図１】本発明のアクチュエータにおける一実施態様例の外観についての斜視図。
【図２】図１のアクチュエータについてのＡ−Ａ断面図。
【符号の説明】
１ アクチュエータ
２ 筐体
３ 作動部
４ 導電性接続板
６ 電解質
７、７’ リード線
８ リード線
９ 電源
２１ 先端部
２２ 底部
２３ 作動部嵌合用凹部
２４ 対極嵌合用凹部
２５ 対極嵌合用凹部
５１、５２ 対極[0001]
TECHNICAL FIELD OF THE INVENTION
Method for producing conductive polymer having excellent expansion / contraction ratio per oxidation-reduction cycle, conductive polymer molded article using the conductive polymer, laminate using the conductive polymer, and conductive polymer The present invention relates to an electrolytic expansion and contraction method for a molded article and a laminate having an excellent expansion and contraction rate, and uses thereof.
[0002]
[Prior art]
It is known that conductive polymers such as polypyrrole exhibit electrolytic stretching, which is a phenomenon of stretching or deforming due to electrochemical redox. Electrolytic expansion and contraction of the conductive polymer is expected to be applied to driving of artificial muscles, robot arms, artificial arms, artificial legs, powered suits, actuators, and the like, and has attracted attention in recent years. As a method for producing such a conductive polymer which undergoes electrolytic expansion and contraction, a method for producing the polymer by an electrolytic polymerization method is generally used. In the electropolymerization method, after a working electrode and a counter electrode are installed in an electrolytic solution containing a monomer component such as pyrrole, a voltage is applied to both electrodes to form a conductive polymer film on the working electrode. The method of making it perform is usually performed.
[0003]
The conductive polymer film obtained by the electrolytic polymerization method can be expanded or contracted or displaced by applying a voltage to the film. Such a conductive polymer that expands and contracts can be used as a conductive polymer alone film for applications such as artificial muscles.For example, JP-A-11-169393 and JP-A-11-169394 describe: It is described that it is also possible to use an artificial muscle having a polyaniline film formed on both sides of a solid electrolyte former.
[0004]
In addition, regarding an actuator using a conductive polymer, a configuration of an actuator including an electrolyte, a counter electrode, and a polypyrrole film in a cell was reported in 1997 (for example, see Non-Patent Document 1). This actuator expands and contracts the polypyrrole film by applying a voltage between the polypyrrole film and the counter electrode while the counter electrode and the counter electrode are immersed in the electrolytic solution, and the polypyrrole film receives a load of 14.6 MPa (45 g). Also expand and contract by 1%. In other words, this actuator can generate a force of 14 MPa in the length direction by electrolytic expansion and contraction.
[0005]
[Patent Document 1]
JP-A-11-169393 (pages 2-5)
[Patent Document 2]
JP-A-11-169394 (pages 2-4)
[Non-patent document 1]
A. Della Santa and two others, "Performance and workcapacity of a polypyrrole conducting conductor polymeric et al. Science (Elscvier Science), 1997, Vol. 90, P93-100
[0006]
[Problems to be solved by the invention]
However, when the artificial muscle, the robot arm, the artificial arm, the artificial leg, and the like, which are practical applications, are operated, one expansion and contraction or displacement is usually one operation. Therefore, in order for an artificial muscle or the like to perform a sufficient operation, it is required that one expansion / contraction or displacement causes a large expansion / contraction or displacement. In the case where a conductive polymer is used as a driving source for such a practical application, a conventional actuator element capable of electrolytic expansion and contraction using a conductive polymer uses a cycle of expansion and contraction due to electrolytic expansion and contraction (an oxidation-reduction cycle). ), The amount of expansion or contraction or displacement per oxidation-reduction cycle is not sufficient. Therefore, in order to use conductive polymers for artificial muscles, robot arms, artificial hands, etc., which are practical applications, a larger amount of expansion or displacement can be obtained in one oxidation-reduction cycle when electrolytic expansion and contraction is performed. is necessary. For example, a conventional conductive polymer such as a conductive polymer containing sodium p-toluenesulfonate as a dopant has a small expansion / contraction rate per one oxidation-reduction cycle, and an actuator for an application in which the amount of expansion / contraction or displacement is small. Etc. can be used. However, when the conductive polymer is used for artificial muscles and the like, which have a large amount of expansion / contraction or displacement per oxidation-reduction cycle, the expansion / contraction rate of the oxidation-reduction cycle of the conductive polymer per cycle is further improved. Need to be done.
[0007]
Further, in order to further enhance the practicality of application to artificial muscles and the like, a command for causing expansion or contraction or displacement such as applying a voltage to the conductive polymer is issued, and then a desired amount of the polymer is actually applied. It is desirable if it is possible that the time required for the expansion or contraction or displacement to occur is short, that is, the displacement rate per specific time is large. That is, in order to use the conventional conductive polymer for practical use, in addition to improving the expansion / contraction ratio per one oxidation-reduction cycle of the conductive polymer, a voltage is applied to the conductive polymer. If it is possible to improve the ratio of the stretched or displaced length to the length of the conductive polymer molded article in the initial state at a specific time, that is, the rate of displacement per specific time, if possible Desirable to further enhance practicality.
[0008]
An object of the present invention is a method for producing a conductive polymer having an excellent expansion / contraction ratio per oxidation-reduction cycle, a conductive polymer molded article using the conductive polymer, and a laminate using the conductive polymer. Another object of the present invention is to provide a method for electrolytically expanding and contracting a conductive polymer molded article and a laminate, an actuator using the conductive polymer, and uses thereof.
[0009]
[Means for Solving the Problems]
The present inventors are a method for producing a conductive polymer, which is a method for producing a conductive polymer having elasticity by electrochemical oxidation-reduction by an electrolytic polymerization method, wherein the electrolytic polymerization method comprises an ether bond, an ester bond, An electrolytic solution containing, as a solvent, an organic compound containing at least one bond or a functional group of at least one of a carbonate bond, a hydroxyl group, a nitro group, a sulfone group and a nitrile group, and / or a halogenated hydrocarbon is used as the solvent. A method for producing a conductive polymer containing a trifluoromethanesulfonate ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom, and a conductive polymer molded article obtained by this production method are used to reduce monooxidation. The present inventors have found that the expansion and contraction rate per cycle can be improved, and have reached the present invention. In addition, it has been found that the conductive polymer molded article obtained by the above-described production method has not only an excellent expansion / contraction rate per oxidation-reduction cycle, but also an excellent displacement rate per specific time. The conductive polymer molded article can be suitably used for an actuator element which is a driving source for practical use.
[0010]
In addition, the present inventors prepared the conductive polymer molded article obtained by the above production method from trifluoromethanesulfonic acid ion, an anion containing a plurality of fluorine atoms with respect to the central atom, and a sulfonate having 3 or less carbon atoms. In an electrolytic solution containing at least one compound selected from the group consisting of: a conductive polymer molded article is expanded and contracted by electrochemical oxidation and reduction to improve the expansion and contraction rate per oxidation-reduction cycle. I found out that it can be done.
[0011]
Further, the present inventors are a laminate comprising a conductive polymer-containing layer and a solid electrolyte layer, wherein the conductive polymer contained in the conductive polymer-containing layer is a conductive polymer produced by an electrolytic polymerization method. The method for producing a conductive polymer, wherein the electrolytic polymerization method comprises an organic bond containing at least one bond or a functional group among ether bonds, ester bonds, carbonate bonds, hydroxyl groups, nitro groups, sulfone groups and nitrile groups. An electrolytic solution containing a compound as a solvent is used, and the high conductivity obtained by the method for producing a conductive polymer containing trifluoromethanesulfonic acid ions and / or anions containing a plurality of fluorine atoms with respect to the central atom in the electrolytic solution is used. It has also been found that the use of a molecular laminate can improve the expansion and contraction rate per oxidation-reduction cycle of the laminate. The laminate can be suitably used for an actuator element that is a driving source for practical use.
[0012]
Further, the present inventors are an actuator including an operating portion, a counter electrode, and an electrolyte, wherein the operating portion is a method for manufacturing a conductive polymer manufactured by an electrolytic polymerization method, wherein the electrolytic polymerization method includes an ether bond. Using an electrolytic solution containing, as a solvent, an organic compound containing at least one bond or a functional group among at least one of a bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group and a nitrile group. By using an actuator using an operating part containing a conductive polymer obtained by a method for producing a conductive polymer containing an acid ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom, a counter electrode and an operating part are obtained. It has been found that the expansion and contraction ratio of the actuator is improved in the expansion and contraction due to the application of a voltage between.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is a method for producing a conductive polymer, which comprises producing a conductive polymer having elasticity by electrochemical oxidation-reduction by an electrolytic polymerization method, wherein the electrolytic polymerization method comprises an ether bond, an ester bond, and a carbonate bond. Using an electrolyte containing, as a solvent, an organic compound containing at least one bond or a functional group of at least one of a hydroxyl group, a nitro group, a sulfone group and a nitrile group and / or a halogenated hydrocarbon; This is a method for producing a conductive polymer containing a sulfonate ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom.
[0014]
(Electropolymerization method)
The electropolymerization method used in the method for producing a conductive polymer according to the present invention includes a bond or a functional group of at least one of an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group. This is an electrolytic polymerization method using an electrolytic solution containing an organic compound as a solvent and further containing trifluoromethanesulfonic acid ions and / or anions containing a plurality of fluorine atoms with respect to a central atom.
[0015]
(Electrolyte)
In the method for producing a conductive polymer of the present invention, the electrolytic solution used in the electrolytic polymerization method includes at least one or more of an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group. Organic compounds and / or halogenated hydrocarbons containing bonds or functional groups are included as solvents. Two or more of these solvents can be used in combination.
[0016]
Examples of the organic compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane (the organic compound containing an ether bond), γ-butyrolactone, and ethyl acetate. , N-butyl acetate, t-butyl acetate, 1,2-diacetoxyethane, 3-methyl-2-oxazolidinone, methyl benzoate, ethyl benzoate, butyl benzoate, diethyl phthalate (including ester bond) Organic compounds), propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate (the organic compounds containing a carbonate bond), ethylene glycol, butanol, 1-hexanol, cyclohexanol, 1-octanol, 1- Cananol, 1-dodecanol, 1-octadecanol (above, an organic compound containing a hydroxyl group), nitromethane, nitrobenzene (above, an organic compound containing a nitro group), sulfolane, dimethyl sulfone (above, an organic compound containing a sulfone group) And acetonitrile, butyronitrile, and benzonitrile (the above are organic compounds containing a nitrile group). The organic compound containing a hydroxyl group is not particularly limited, but is preferably a polyhydric alcohol or a monohydric alcohol having 4 or more carbon atoms because of its good elasticity. In addition, in addition to the above-mentioned examples, the organic compound may have any two or more bonds or functional groups selected from ether bonds, ester bonds, carbonate bonds, hydroxyl groups, nitro groups, sulfone groups, and nitrile groups in the molecule. May be included. The organic compound is preferably an organic compound containing an ester bond, since the obtained conductive polymer has a large expansion and contraction rate.
[0017]
When the organic compound is used as a solvent for an electrolytic solution by mixing two or more of the organic compounds, the organic compound includes an organic compound having an ether bond, an organic compound having an ester bond, an organic compound having a carbonate bond, and a hydroxyl group. Among organic compounds, organic compounds containing a nitro group, organic compounds containing a sulfone group, and organic compounds containing a nitrile group, a combination of an organic compound having excellent extension and an organic compound having excellent contraction is obtained by electrolytic polymerization. The expansion / contraction ratio of the obtained conductive polymer per oxidation-reduction cycle can also be improved.
[0018]
In the method for producing a conductive polymer according to the present invention, the halogenated hydrocarbon contained as a solvent in the electrolytic solution is one in which hydrogen in the hydrocarbon is replaced by at least one halogen atom. There is no particular limitation as long as it can be stably present.
[0019]
Examples of the halogenated hydrocarbon include dichloromethane and dichloroethane. As the halogenated hydrocarbon, only one kind can be used as a solvent in the electrolytic solution, but two or more kinds can be used in combination. The halogenated hydrocarbon may be used as a mixture with the above organic compound, and a mixed solvent with the organic solvent may be used as a solvent in the electrolytic solution.
[0020]
In the method for producing a conductive polymer according to the present invention, the electrolytic solution used in the electrolytic polymerization method includes an organic compound to be electrolytically polymerized (for example, pyrrole) and trifluoromethanesulfonic acid ion and / or a fluorine atom with respect to a central atom. Anion containing a plurality of. By performing electrolytic polymerization using this electrolytic solution, it is possible to obtain a conductive polymer having an excellent expansion / contraction ratio per oxidation-reduction cycle and / or a displacement ratio per specific time in electrolytic expansion / contraction. By the above-mentioned electrolytic polymerization, trifluoromethanesulfonic acid ions and / or anions containing a plurality of fluorine atoms with respect to the central atom are incorporated into the conductive polymer.
[0021]
The content of the trifluoromethanesulfonic acid ion and / or the anion containing a plurality of fluorine atoms with respect to the central atom in the electrolytic solution is not particularly limited, but is contained in the electrolytic solution by 0.1 to 30% by weight. And more preferably 1 to 15% by weight.
[0022]
The trifluoromethanesulfonate ion has the chemical formula CF₃SO₃ ⁻It is a compound represented by these. Further, an anion containing a plurality of fluorine atoms with respect to the central atom has a structure in which a plurality of fluorine atoms are bonded to a central atom such as boron, phosphorus, antimony, and arsenic. Contains a plurality of bonding fluorine atoms. The anion containing a plurality of fluorine atoms with respect to the central atom is not particularly limited, but tetrafluoroborate ion (BF₄ ⁻), Hexafluorophosphate ion (PF₆ ⁻), Hexafluoroantimonate ion (SbF₆ ⁻) And hexafluoroarsenate ion (AsF₆ ⁻) Can be exemplified. Above all, CF₃SO₃ ⁻, BF₄ ⁻And PF₆ ⁻Is preferable in consideration of safety against the human body, etc.₃SO₃ ⁻And BF₄ ⁻Is more preferred. As the anion containing a plurality of fluorine atoms with respect to the central atom, one kind of anion may be used, or a plurality of kinds of anions may be used in the electrolytic solution at the same time. An anion containing a plurality of fluorine atoms with respect to the central atom of the seed may be simultaneously used in the electrolytic solution.
[0023]
In the method for producing a conductive polymer according to the present invention, the electrolytic solution used in the electrolytic polymerization method includes the organic compound solvent and the trifluoromethanesulfonic acid ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom. The solution contains a monomer of a conductive polymer, and may further contain other known additives such as polyethylene glycol and polyacrylamide.
[0024]
The electrolytic polymerization method used in the method for producing a conductive polymer according to the present invention can use a known electrolytic polymerization method as the electrolytic polymerization of the conductive polymer monomer, and includes a constant potential method and a constant current method. And the electric sweep method can be used. For example, the electrolytic polymerization method has a current density of 0.01 to 20 mA / cm.²At a reaction temperature of −70 to 80 ° C. and a current density of 0.1 to 2 mA / cm to obtain a conductive polymer having good film quality.²The reaction is preferably performed at a temperature of -40 to 40 ° C, more preferably at a temperature of -30 to 30 ° C.
[0025]
In the method for producing a conductive polymer according to the present invention, the working electrode is not particularly limited as long as it can be used for electrolytic polymerization, and an ITO glass electrode or a metal electrode can be used. The metal electrode is not particularly limited as long as it is an electrode mainly composed of a metal, but a metal of a metal element selected from the group consisting of Pt, Ti, Ni, Au, Ta, Mo, Cr and W A single electrode or an alloy electrode can be suitably used. It is particularly preferable that the metal species contained in the metal electrode is Ni or Ti, since the conductive polymer obtained by the above-mentioned manufacturing method has a large expansion and contraction rate and a large generating force, and the electrode can be easily obtained. As the alloy, for example, trade names “INCOLOY alloy 825”, “INCONEL alloy 600”, and “INCONEL alloy X-750” (all manufactured by Daido Special Metal Co., Ltd.) can be used.
[0026]
In the method for producing a conductive polymer according to the present invention, the conductive polymer monomer contained in the electrolytic solution used in the electrolytic polymerization method may be a compound which is polymerized by oxidation by electrolytic polymerization and exhibits conductivity. No particular limitation is imposed thereon, and examples thereof include a 5-membered heterocyclic compound such as pyrrole, thiophene, and isothianaphthene, and derivatives thereof such as an alkyl group and an oxyalkyl group. Among them, a five-membered heterocyclic compound such as pyrrole and thiophene and a derivative thereof are preferable, and a conductive polymer containing pyrrole and / or a pyrrole derivative is particularly easy to produce, and is stable as a conductive polymer. It is preferable because there is. Further, two or more of the above monomers can be used in combination.
[0027]
The conductive polymer produced by the method for producing a conductive polymer of the present invention is not particularly limited as long as it has elasticity, and polypyrrole, polythiophene, polyaniline, polyphenylene film, and the like can be used. However, a conductive polymer containing pyrrole and / or a pyrrole derivative in the molecular chain is preferable because it is easy to produce, is not only stable as a conductive polymer, but also has excellent electrolytic stretching properties. . Since the conductive polymer contains, as a dopant, a trifluoromethanesulfonic acid ion and / or an anion containing a plurality of fluorine atoms with respect to the central atom contained in the electrolytic solution, a one-oxidation-reduction cycle excellent in electrolytic stretching. It is considered to indicate the contraction rate per unit, and also indicate the displacement rate per specific time.
[0028]
The method for producing a conductive polymer according to the present invention is a method for producing a conductive polymer by an electrolytic polymerization method, wherein the conductive polymer has elasticity due to electrochemical oxidation-reduction, The polymerization method is a polymerization method using an electrolytic solution containing an organic compound as a solvent, and the organic compound is (1) at least one selected from the group consisting of an ether bond, an ester bond, a carbon-halogen bond, and a carbonate bond. The above-mentioned electrolytic solution contains in the molecule at least one or more functional groups selected from the chemical bond species selected above and / or (2) a functional group consisting of a hydroxyl group, a nitro group, a sulfone group and a nitrile group. A method for producing a conductive polymer, comprising a trifluoromethanesulfonic acid ion and / or an anion containing a plurality of fluorine atoms bonded to a central atom. Kill.
[0029]
(Molding)
Further, the present invention is also a conductive polymer molded article having a desired shape of the conductive polymer obtained by the above production method. That is, a conductive polymer having elasticity due to electrochemical oxidation-reduction, a method for producing a conductive polymer produced by an electrolytic polymerization method, wherein the electrolytic polymerization method comprises an ether bond, an ester bond, a carbonate bond, An electrolytic solution containing, as a solvent, an organic compound containing at least one bond or a functional group of a hydroxyl group, a nitro group, a sulfone group and a nitrile group and / or a halogenated hydrocarbon as a solvent is used. A conductive polymer molded article containing, as a resin component, a conductive polymer obtained by a method for producing a conductive polymer containing an acid ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom. The shape of the conductive polymer molded article is not particularly limited, and may be in the form of a film, a tube, a tube, a prism, a fiber, or the like. It is preferably in the form of a film because it sometimes precipitates on the working electrode. The working electrode is not particularly limited as long as it can be used for electrolytic polymerization, and an ITO glass electrode, a metal electrode, or the like can be used.
[0030]
In particular, by containing a trifluoromethanesulfonic acid ion and / or an anion containing a plurality of fluorine atoms relative to the central atom in the conductive polymer as a dopant, the conductive polymer molded article of the present invention was formed into a film. In this case, the conventional electroconductive polymer has an electrostriction rate of only about 1% per one oxidation-reduction cycle in the plane direction, whereas the expansion and contraction rate of the electroconductive polymer is 3% per oxidation-reduction cycle in the length direction. %, Especially 5% or more. Whereas conventional low-stretch conductive polymer molded products could only be used for applications that do not require large displacement, such as switches and sensors, the stretch ratio per oxidation-reduction cycle in the length direction The conductive polymer molded product having a content of 3% or more can be suitably used for applications requiring a large expansion and contraction ratio, as represented by artificial muscle. In addition, the conductive polymer molded article may appropriately contain a conductive material such as a metal wire or a conductive oxide in order to reduce the resistance value as an operating electrode, in addition to the dopant.
[0031]
The present invention also relates to a conductive polymer molded article which expands and contracts by electrochemical oxidation and reduction, wherein the expansion and contraction rate in one oxidation-reduction cycle for 20 seconds is 3% or more in the length direction. The conductive polymer molded article is a method for manufacturing a conductive polymer manufactured by an electrolytic polymerization method, wherein the electrolytic polymerization method includes an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, and An organic solution containing at least one bond or a functional group among nitrile groups and / or an electrolytic solution containing a halogenated hydrocarbon as a solvent is used, and a plurality of fluorine atoms with respect to trifluoromethanesulfonic acid ion and / or a central atom are used. By including a conductive polymer obtained by the method for producing a conductive polymer containing an anion in the electrolytic solution, compared to a conventional conductive polymer, starting application of a voltage at one point Therefore, a large displacement of the leading end of the conductive polymer molded article can be obtained within a certain period of time.
[0032]
When the conductive polymer molded product is used as an actuator, the conductive polymer molded product, an actuator including a counter electrode and an electrolyte, wherein the counter electrode and the conductive polymer molded product are interposed via the electrolyte. The actuator may be provided with a counter electrode and an electrolyte so that a voltage can be applied therebetween. By applying a voltage from one end of the conductive polymer molded article to the conductive polymer molded article, the stretch ratio in one oxidation-reduction cycle for 20 seconds is 3% or more in the length direction. The present invention can be suitably used for actuators for applications requiring faster response, such as drive units of various devices.
[0033]
(Laminate)
The present invention is a laminate including a conductive polymer-containing layer and a solid electrolyte layer, and also a laminate including the conductive polymer obtained in the above-described production method in the conductive polymer-containing layer. That is, the present invention is a laminate including a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer contained in the conductive polymer-containing layer is a conductive polymer produced by an electrolytic polymerization method. A conductive polymer obtained by a production method, wherein the electrolytic polymerization method in the production method is at least one of an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group. An organic solution containing a bond or a functional group and / or a halogenated hydrocarbon as a solvent is used as the solvent, and trifluoromethanesulfonic acid ions and / or anions containing a plurality of fluorine atoms with respect to the central atom are contained in the electrolytic solution. It is a laminate characterized by including. By including the conductive polymer-containing layer and the solid electrolyte layer in the laminate, the electrolyte in the solid electrolyte layer is supplied to the conductive polymer layer, and the conductive polymer contained in the conductive polymer-containing layer Since the polymer expands and contracts greatly by electrochemical oxidation and reduction, a large expansion and contraction rate per one oxidation-reduction cycle can be exhibited during electrolytic expansion and contraction. It is preferable that the conductive polymer layer and the solid electrolyte layer in the laminate are in direct contact with each other. However, if the electrolyte in the solid electrolyte can be transferred to the conductive polymer, other Layer may be interposed. In addition, the conductive polymer-containing layer may include a substrate or the like that does not significantly impede electrolytic expansion and contraction, and may also include a conductive oxide or a metal wire.
[0034]
Although the solid electrolyte is not particularly limited, it is preferable that the solid electrolyte be an ion-exchange resin by being largely driven as an actuator by displacing the laminate. As the ion exchange resin, a known ion exchange resin can be used, and for example, a trade name “Nafion” (perfluorosulfonic acid resin, manufactured by DuPont) can be used.
[0035]
When the laminate is used as an actuator, an actuator including a counter electrode and the laminate, wherein the counter electrode and the conductive polymer-containing layer in the laminate are interposed via a solid electrolyte in the laminate. The actuator may be provided with a counter electrode so that a voltage can be applied between the electrodes.
[0036]
(Electrolytic stretching method)
The present invention is also an electrolytic expansion / contraction method for expanding / contracting the conductive polymer molded article by electrochemical oxidation / reduction of the conductive polymer molded article in an electrolytic solution. By subjecting the conductive polymer molded article to electrolytic expansion and contraction, an excellent expansion and contraction rate per one oxidation-reduction cycle can be obtained. Further, the above-mentioned electrolytic expansion / contraction method for expanding / contracting the conductive polymer molded article can also obtain an excellent displacement ratio per specific time. The working electrolyte, which is an electrolyte in which the conductive polymer molded article is subjected to electrolytic expansion and contraction, is not particularly limited. However, it is easy to adjust the concentration by using a solvent whose main solvent is water and contains an electrolyte. Is preferred.
[0037]
In the electrolytic stretching method of the present invention, the electrolytic solution is a compound selected from at least one selected from the group consisting of a trifluoromethanesulfonic acid ion, an anion containing a plurality of fluorine atoms relative to a central atom, and a sulfonate having 3 or less carbon atoms. It can be an electrolytic solution containing as a working electrolyte. That is, the present invention relates to a method for producing a conductive polymer, wherein the conductive polymer molded article is a conductive polymer having elasticity by electrochemical oxidation-reduction produced by an electrolytic polymerization method. Electrolysis in which an organic compound containing at least one bond or a functional group of at least one of an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group and a nitrile group and / or a halogenated hydrocarbon is used as a solvent. A conductive polymer obtained by a method for producing a conductive polymer containing a trifluoromethanesulfonic acid ion and / or an anion containing a plurality of fluorine atoms with respect to a central atom in the electrolytic solution using a liquid as a resin component By using the method for electrolytically expanding and contracting conductive polymer molded products, it exhibits excellent expansion and contraction rate per oxidation-reduction cycle during electrolytic expansion and contraction. Further is indicate displacement rate per specified time excellent. Further, in an electrolytic solution containing at least one compound selected from the group consisting of a trifluoromethanesulfonic acid ion, an anion containing a plurality of fluorine atoms with respect to a central atom and a sulfonate having 3 or less carbon atoms as a working electrolyte, By subjecting the conductive polymer molded article to electrolytic expansion and contraction, the conductive polymer molded article can exhibit a larger expansion and contraction rate per oxidation-reduction cycle. It is clear that the salt used in the electrolyte can be used as a salt contained in the electrolyte of the solid electrolyte in the laminate of the present invention, and the solid electrolyte exhibits an excellent expansion / contraction ratio per oxidation-reduction cycle. Can be obtained.
[0038]
In order to expand and contract the conductive polymer molded article, the trifluoromethanesulfonic acid ion and / or the anion containing a plurality of fluorine atoms with respect to the central atom contained as the working electrolyte in the electrolytic solution as the external environment is the above-mentioned conductive material. This is the same as the trifluoromethanesulfonic acid ion and / or the anion containing a plurality of fluorine atoms with respect to the central atom in the description of the method for producing a polymer. The trifluoromethanesulfonate ion has the chemical formula CF₃SO₃ ⁻It is a compound represented by these. The anion containing a plurality of fluorine atoms with respect to the central atom is an ion having a structure in which a plurality of fluorine atoms of the central atom are bonded to atoms such as boron, phosphorus, antimony, and arsenic. The sulfonate having 3 or less carbon atoms is not particularly limited as long as it is a salt of a sulfonic acid having 3 or less carbon atoms, and for example, sodium methanesulfonate and sodium ethanesulfonate can be used.
[0039]
Further, the present invention is also an electrolytic stretching method for expanding and contracting the conductive polymer molded article by electrochemical oxidation-reduction of the conductive polymer molded article in an electrolytic solution, wherein the electrolytic solution mainly comprises sodium chloride. An electrolytic expansion / contraction method that is an aqueous solution containing an electrolyte may be used. Since the electrolytic solution mainly contains sodium chloride, which is an electrolyte contained in a biological component, it is possible to operate in a state in which a body fluid in a living body is easily interchangeable with the electrolytic solution.
[0040]
The temperature of the electrolytic solution or the solid electrolyte that undergoes electrolytic expansion and contraction in the present invention is not particularly limited, but in order to electrolytically expand and contract the above-described conductive polymer at a higher speed, 20 to 100 ° C., more preferably It is preferably 50 to 80 ° C.
[0041]
(Actuator)
Further, the present invention is an actuator including an operating portion, an electrolyte, and a counter electrode, wherein the operating portion includes a conductive polymer obtained by the manufacturing method. The actuator is not particularly limited as long as it includes an operating portion, an electrolyte, and a counter electrode as a device configuration, but an actuator in which a shaft attached to the operating portion is packed in a housing so as not to leak liquid during operation. Alternatively, an actuator having a housing that can expand and contract in accordance with the operation of the operation unit is preferable because leakage of an electrolyte or the like does not occur.
[0042]
FIG. 1 is a perspective view showing the appearance of the actuator of the present invention. The actuator 1 is a columnar actuator, and has an outermost layer formed of a housing made of a flexible material such as urethane rubber. At the bottom portion 22 of the actuator 1, there are provided a lead 8 for applying a potential to the operating portion 3 inside the actuator and leads 7, 7 'for applying a potential to the counter electrode. The power is supplied from the power supply 9 and a voltage is applied to the operating section and the counter electrode, whereby the operating section electrolytically expands and contracts. Due to this electrolytic expansion and contraction, the distal end of the actuator 1 is displaced by expansion and contraction in the length direction. When the actuator 1 is extended, the actuator 1 can generate a pressing force F.
[0043]
FIG. 2 is a sectional view of the actuator 1 shown in FIG. The actuator 1 includes a column-shaped operating portion 3 in an internal space of a housing 2 formed of a flexible material. A concave portion 23 is formed on the inner surface of the bottom portion 22 of the housing 2. One end of the operation section 3 is fitted into the recess 23 via the conductive connection plate 4, and the operation section is attached to the housing 2. The operating portion 3 is fixed to the housing 2 by being joined to the other end of the operating portion 3 on the inner surface of the distal end portion 21 of the housing 2. Further, in the internal space of the housing 2, the columnar counter electrodes 51, 52 are fitted near the inner surfaces of the side walls of the housing 2 into the counter electrode fitting recesses 24, 25 provided on the bottom 22, respectively, so that the mounting is performed. Have been. In the internal space of the housing 2, the remaining internal space excluding the counter electrodes 51 and 52 and the operating part 3 is filled with the electrolyte 6. The power supply 9 is connected to the counter electrodes 51 and 52 via the leads 7 and 7 ′, and is connected to the conductive connection plate 4 in contact with the operating section 3 via the leads 8. By supplying power from the power supply 9, a voltage can be applied between the counter electrodes 51 and 52 and the operating section 3, and the operating section 3 can be expanded and contracted electrolytically. When the actuator 1 expands and contracts, a force F can be generated at the distal end portion 21 and can be suitably used as an artificial muscle.
[0044]
The tip 21 of the actuator 1 may or may not be joined to the tip of the operating section 3 on the inner side. When the distal end portion 21 and the distal end portion of the operating section 3 are not joined, the actuator sets the housing 2 formed of a flexible material in a state in which a contraction stress acts on the inside of the actuator due to contraction stress. The distal end portion 21 can expand and contract following the electrolytic expansion and contraction of the operating portion 3 by the electrolytic expansion and contraction of the operating portion 3.
[0045]
The operating portion is not particularly limited as long as it includes the above-described conductive polymer and undergoes electrolytic expansion and contraction by voltage application. It is preferable that the operating portion exhibits an elasticity of 5% or more when applied with a voltage. An actuator that expands and contracts by 5% or more when the operating section expands or contracts by 5% or more when a voltage is applied can be obtained. This actuator is required to have a large expansion and contraction rate represented by artificial muscle. Can be suitably used. The operating portion may appropriately include a conductive material such as a metal wire or a conductive oxide in order to reduce a resistance value as an operating electrode in addition to the dopant.
[0046]
The flexible material forming the housing 2 is not particularly limited. The flexible material can be appropriately selected according to the elongation percentage of the actuator, and it is preferable to use a synthetic resin having an elongation percentage of 5% or more, and it is more preferable to use a synthetic resin having an elongation percentage of 20% or more. As the flexible material, for example, silicon-based resin, urethane-based resin, silicon-based rubber, urethane-based rubber, or the like can be used. Further, since the flexible material also has a function of preventing the electrolyte from leaking to the outside of the actuator, the flexible material preferably has solvent resistance, and is preferably a silicone resin, a urethane resin, a silicone rubber or a urethane resin. Rubber can be suitably used. In addition, since the actuator 1 has a structure in which the operating portion is sealed by the housing 2, it has a longer use than a structure in which a means for transmitting a force such as a rod penetrates the housing. Since there is no electrolyte leakage, it is excellent for use as a mechanical part such as an artificial muscle.
[0047]
The shape of the actuator of the present invention is not particularly limited. Although the actuator is formed in a cylindrical shape in FIG. 1, the actuator can be formed in a shape most suitable for the application. As the shape of the actuator, other than the cylindrical shape, the actuator can be formed into a shape corresponding to the usage conditions, such as a polygonal prism, such as a prism or a hexagon, a cone, a plate, or a rectangular parallelepiped. Further, the operating portion installed inside the actuator of the present invention is not limited to a columnar shape, but may be a polygonal column such as a prismatic or hexagonal column, a conical shape, a rectangular parallelepiped shape, or the like. Shape. The operating portion may be a conductive polymer film obtained on the working electrode by electrolytic polymerization as it is, or may be formed into a desired shape by performing molding such as lamination. Further, the counter electrode is not limited to a columnar shape, but may be a plate-like shape or the like.
[0048]
The electrolyte contained in the actuator of the present invention may be a liquid or a solid electrolyte. When the electrolyte is in a liquid state, the solvent may be water, or may be an organic solvent, but since the rate of volatilization is relatively slow, handling is easy, and large expansion and contraction can be obtained. Preferably, it is an aqueous solvent. When the electrolytic solution is a solid electrolyte, it may be a polymer electrolyte or a solid electrolyte that is completely solid, but a gel polymer electrolyte is preferable because of high ionic conductivity in the electrolyte. . As the gel used for the gel polymer electrolyte, it is preferable to use polyacrylamide, polyethylene glycol, or agar since the gel polymer electrolyte can be easily adjusted by being combined with an aqueous solution electrolyte. The actuator may be an electrolyte containing at least one compound selected from the group consisting of a trifluoromethanesulfonic acid ion, an anion containing a plurality of fluorine atoms with respect to a central atom, and a sulfonate having 3 or less carbon atoms. Is preferable because it can cause a larger expansion and contraction per oxidation-reduction cycle.
[0049]
In the actuator, a laminate of a conductive polymer-containing layer and a solid electrolyte may be used as the operating portion and the electrolyte. The laminate, the conductive polymer-containing layer, by using a layer containing a conductive polymer obtained by the above-described method for producing a conductive polymer, the conductive polymer in the layer greatly expanded and contracted , Can be used for larger expansion and contraction applications. The counter electrode may be installed so that a voltage can be applied between the counter electrode and the conductive polymer-containing layer via the solid electrolyte, and the place where the counter electrode is installed is not particularly limited.
[0050]
The actuator can obtain a large expansion and contraction rate by including the above-described conductive polymer in the internal operation portion, and therefore can be used even when the displacement is small. Can also be suitably used as an artificial muscle. In other words, the actuator of the present invention can be used only for applications having a small displacement, and can be applied to an actuator containing a conductive polymer to an application having a large displacement such as an artificial muscle. The actuator can be used as a linear actuator. For example, by attaching a force transmitting member such as a metal wire to a distal end portion 21 of the actuator 1 of FIG. It can be used as a pressing device by pressing the distal end portion 21 against an object to be controlled. Since the actuator of the present invention is an actuator in which the conductive polymer is driven by electricity, it has no sound or low sound when driven, and thus is suitable as a driving unit or a pressing unit in an indoor use device. Further, since the actuator is lighter than a conventional linear actuator due to a small number of metal parts, a positioning device, a posture control device, an elevating device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, and a joint are used. It can be suitably used as a drive unit of the device.
[0051]
(Application)
The conductive polymer molded article, laminate and actuator of the present invention of the present invention can be suitably used for artificial muscles, robot arms, powered suits, artificial hands and artificial legs. In addition, medical instruments such as tweezers, scissors, forceps, snares, laser scalpels, spatulas, clips in microsurgery technology, various sensors or repair tools for inspection and repair, health instruments, hygrometer, hygrometer control device, Industrial equipment such as soft manipulators, underwater valves, and soft transporters, underwater mobils such as goldfish, and articles used in water such as hobbies such as moving fishing baits and propulsion fins, also have the high conductivity of the present invention. A molecular molded product, a laminate, and an actuator can be suitably used.
[0052]
That is, when the conductive polymer molded article, laminate, and actuator of the present invention are used for the artificial muscle, robot arm, or artificial hand, the conductive polymer obtained by the above-described method for manufacturing a conductive polymer is used. The conductive polymer molded article or the conductive polymer layer containing as a base resin can be used as an artificial muscle, a robot arm, and an artificial hand used for the drive unit.
[0053]
When the conductive polymer molded article, laminate, and actuator of the present invention are used for the medical device, a conductive polymer containing the conductive polymer obtained by the above-described method for producing a conductive polymer as a base resin is used. The polymer molded article or the conductive polymer layer can be used as a medical device including tweezers, scissors, forceps, a snare, a laser scalpel, a spatula, and a clip used for a drive unit.
[0054]
When the conductive polymer molded article and the laminate of the present invention are used for the above-described sensor or repair tool, the conductive polymer obtained by the above-described method for producing a conductive polymer is used as a base resin. A conductive polymer molded article or a conductive polymer layer containing the same can be used as a sensor and a repair tool including inspection and repair used for a drive unit.
[0055]
When the conductive polymer molded article and the laminate of the present invention are used in the above-mentioned industrial equipment, the conductive polymer containing the conductive polymer obtained by the above-described method for producing a conductive polymer as a base resin has a high conductivity. The molecular molded article or the conductive polymer layer can be used as an industrial device including a health appliance, a hygrometer, a hygrometer control device, a soft manipulator, a submersible valve, and a soft transport device that are used in a driving unit.
[0056]
When the conductive polymer molded article and the laminate of the present invention are used in the above-mentioned article used in water, the conductive polymer obtained by the above-described method for producing a conductive polymer is used as a base resin. The conductive polymer molded article or the conductive polymer layer containing the same can be an underwater mobil used for the drive unit, or an article used in water including a hobby article including a moving fishing bait or a propulsion fin.
[0057]
As described above, the conductive polymer molded article and the laminate of the present invention can generate displacement, and thus can be used as an actuator. In the conductive polymer molded article of the present invention, for example, those not coated with a resin or the like can be used as an actuator capable of linear displacement in an electrolytic solution. In addition, as described above, the actuator including the operating portion, the counter electrode, and the electrolyte may be an actuator including the conductive polymer obtained by the manufacturing method of the present invention.
[0058]
As described above, the conductive polymer molded article and the laminate of the present invention can generate displacement, and thus can be used as an actuator. In the conductive polymer molded article of the present invention, for example, those not coated with a resin or the like can be used as an actuator capable of linear displacement in an electrolytic solution. In the laminate of the present invention, for example, one or both of the upper and lower layers when the conductive polymer layer is an intermediate layer, the stretch ratio of the conductive polymer layer at the time of electrolytic expansion or contraction or higher. When the solid electrolyte layer has elasticity, it can be used as an actuator that performs linear displacement. Further, in the laminate of the present invention, for example, one of the upper and lower layers when the conductive polymer layer is used as the intermediate layer has a lower elasticity than the elastic expansion and contraction of the conductive polymer layer during electrolytic expansion and contraction. In the case where the solid electrolyte layer or the resin layer has a solid electrolyte layer or a resin layer, the solid electrolyte layer or the resin layer does not expand and contract as compared with the conductive polymer layer, and thus can be used as an actuator that performs bending displacement. An actuator that generates a linear displacement or a bending displacement can be used as a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type orbit formed by an arc portion. . Further, the actuator can be used as a pressing portion that performs a linear operation.
[0059]
That is, the actuator is an OA device, an antenna, a device for mounting a person such as a bed or a chair, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting device, a food processing device, a cleaning device, a measuring device, Inspection equipment, control equipment, machine tools, processing machines, electronic equipment, electron microscopes, electric razors, electric toothbrushes, manipulators, masts, play equipment, amusement equipment, riding simulation equipment, vehicle occupant holding equipment and aircraft accessory equipment In the device, as a drive unit that generates a linear drive force or a drive unit that generates a drive force for moving a track-type trajectory composed of an arc part, or as a pressing unit that performs a linear operation or a curved operation It can be suitably used. The actuator is, for example, a track-type trajectory including a driving unit or an arc portion that generates a linear driving force in a valve, a brake, and a lock device used in a general machine including the above-described devices such as an OA device and a measuring device. Can be used as a driving unit that generates a driving force for moving the motor, or as a pressing unit that operates linearly. In addition to the above-described devices, devices, instruments, and the like, in general, mechanical devices, a driving unit of a positioning device, a driving unit of an attitude control device, a driving unit of a lifting device, a driving unit of a transport device, a driving unit of a moving device. It can be suitably used as a driving unit of an adjusting device for adjusting the amount or direction, a driving unit of an adjusting device such as a shaft, a driving unit of a guiding device, and a pressing unit of a pressing device. In addition, the actuator can be suitably used as a drive unit in a joint device, such as a joint unit that can be directly driven, such as a joint intermediate member, or a drive unit that applies rotational motion to a joint.
[0060]
The actuator is, for example, a driving unit of an ink jet part in an ink jet printer such as a CAD printer, a driving unit that displaces the optical axis direction of the light beam of the printer, a head driving unit of a disk drive device such as an external storage device, and It can be suitably used as a drive unit of a paper pressing contact force adjusting means in a paper feeding device of an image forming apparatus including a printer, a copying machine, and a facsimile.
[0061]
The actuator includes, for example, a driving unit of a driving mechanism that moves and installs a measuring unit and a feeding unit such as moving a high-frequency feeding unit such as a frequency-sharing antenna for radio astronomy to a second focal point, and a pneumatic operation that is mounted on a vehicle. It can be suitably used for a mast such as a mast (telescopic coping mast) or a driving unit of a lift mechanism in an antenna.
[0062]
The actuator is, for example, a driving unit of a massage unit of a chair-shaped massage machine, a driving unit of a nursing or medical bed, a driving unit of a posture control device of an electric reclining chair, a reclining chair used for a massage machine, a comfortable chair, and the like. The backrest of the ottoman can be moved up and down, the drive unit of the telescopic rod, the backrest of the chair or the bed for the nursing care, the legrest, etc. It can be suitably used as a drive unit used for turning drive of a bed and a drive unit for controlling the posture of an upright chair.
[0063]
The actuator uses, for example, a driving unit of an examination device, a driving unit of a pressure measuring device such as a blood pressure used in an extracorporeal blood treatment device, a catheter, a driving unit of an endoscope device or forceps, or an ultrasonic wave. A drive unit for a cataract surgery device, a drive unit for an exercise device such as a jaw exercise device, a drive unit for relatively expanding / contracting a member of a chassis of a hoist for the disabled, and ascent / descent, movement and / or posture control of a nursing bed. It can be suitably used for a drive unit for
[0064]
The actuator is, for example, a driving unit of a vibration isolator that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, a driving unit of a valve operating device for an intake and exhaust valve of an internal combustion engine, It can be suitably used as a drive unit of a fuel control device of an engine and a drive unit of a fuel supply device of an engine such as a diesel engine.
[0065]
The actuator includes, for example, a driving unit of a calibration device of an imaging device with a camera shake correction function, a driving unit of a lens driving mechanism such as a home video camera lens, and a mechanism for driving a moving lens group of an optical device such as a still camera or a video camera. , A drive unit for an autofocus unit of a camera, a drive unit for a lens barrel used in an imaging device such as a camera or a video camera, a drive unit for an auto guider that captures light from an optical telescope, and a stereoscopic camera and binoculars. A lens driving mechanism or a lens barrel driving unit of an optical device having an optical system, a driving unit or a pressing unit that applies a compressive force to a fiber for wavelength conversion of a fiber type tunable filter used for optical communication, optical information processing, optical measurement, and the like. , The drive unit of the optical axis alignment device, and the drive unit of the shutter mechanism of the camera.
[0066]
The actuator can be suitably used for, for example, a pressing portion of a fixing tool such as caulking and fixing a hose fitting to a hose body.
[0067]
The actuator includes, for example, a driving unit such as a winding spring of a suspension of an automobile, a driving unit of a fuel filler lid opener for unlocking a fuel filler lid of a vehicle, a driving unit for driving extension and retraction of a bulldozer blade, and a vehicle transmission. The present invention can be suitably applied to a drive unit of a drive device for automatically switching the gear ratio of the drive unit and for automatically connecting and disconnecting the clutch.
[0068]
The actuator may be, for example, a driving unit of a lifting device of a wheelchair with a seat plate lifting device, a driving unit of a lifting device for removing a step, a driving unit of a lifting and lowering device, a medical bed, an electric bed, an electric table, an electric chair, and nursing care. The present invention can be suitably used for a bed, a lifting table, a CT scanner, a cabin tilt device of a truck, a lift driving unit of a lifter and various lifting machinery, and a driving unit of a loading / unloading device of a special vehicle for transporting heavy goods.
[0069]
The actuator can be suitably used, for example, as a drive unit of a discharge amount adjusting mechanism such as a food discharge nozzle device of a food processing device.
[0070]
The actuator can be suitably used for, for example, a drive unit for raising and lowering a truck or a cleaning unit of a cleaning device.
[0071]
The actuator includes, for example, a driving unit of a measuring unit of a three-dimensional measuring device that measures the shape of a surface, a driving unit of a stage device, a driving unit of a sensor unit such as a system for detecting a tire operating characteristic, and a shock sensor of a force sensor. The drive unit of the device that gives the initial speed of the evaluation device, the drive unit of the piston drive device of the piston cylinder of the device including the borehole permeability test device, the drive unit for moving in the elevation direction in the concentrating and tracking type power generation device, the gas concentration measurement Alignment is required for the sapphire laser oscillation wavelength switching mechanism tuning device of the measuring device including the device, the driving unit of the oscillating device of the mirror, the inspection device of the printed circuit board and the inspection device of the flat panel display such as the liquid crystal and the PDP when the XYθ table is required. Drive, electron beam (E-beam) system or focused ion beam (FIB) system Drive unit of an adjustable aperture device used in a charged particle beam system, etc., drive unit of a support device or detection unit of a measurement object in a flatness measuring device, as well as assembly of fine devices, semiconductor exposure apparatus and semiconductor inspection It can be suitably used for a drive unit of a precision positioning device such as a device and a three-dimensional shape measuring device.
[0072]
The actuator can be suitably used for, for example, a driving unit of an electric razor and a driving unit of an electric toothbrush.
[0073]
The actuator is, for example, an imaging device for a three-dimensional object or a drive unit of a device for adjusting the depth of focus of a readout optical system for both CD and DVD. A drive unit for a variable mirror that can easily change the focal point position by approximately forming a curved surface of the disk drive; a drive unit for a disk device that can linearly move a moving unit having at least one of a magnetic head such as an optical pickup; A drive unit of a head feed mechanism of a magnetic tape head actuator assembly such as a tape storage system, a drive unit of an image forming apparatus applied to an electrophotographic copying machine, a printer, a facsimile, etc., and a drive unit of a mounting member such as a magnetic head member. Optical disc drive that controls the focusing lens group in the optical axis direction A driving unit of an exposure device, a driving unit of a head driving unit that drives an optical head, a driving unit of an information recording / reproducing device that records information on a recording medium or reproduces information recorded on the recording medium, and a circuit breaker ( It can be suitably used for a drive unit for opening / closing operation of a power distribution circuit breaker.
[0074]
The actuator is, for example, a driving unit of a rubber composition press-molding vulcanizing device, a driving unit of a component aligning device that aligns the transferred components in a single row / single layer or a predetermined posture, and a compression molding device. Driving unit, driving unit for holding mechanism of welding device, driving unit for bag making and filling machine, driving unit for machine tool such as machining center, molding machine such as injection molding machine and press machine, printing device, coating device and spraying lacquer Driving unit of fluid application device such as device, driving unit of manufacturing device that manufactures camshaft, etc., driving unit of lifting device for lining material, driving device of tufting restrictor in shuttleless loom, needle of tufting machine Drive unit such as drive system, looper drive system, knife drive system, etc., drive unit of polishing device that grinds parts such as cam grinders and ultra-precision parts, drive unit of heald frame braking device in loom. A driving unit of an opening device that forms an opening of a warp for inserting a weft in a loom, a driving unit of a protective sheet peeling device such as a semiconductor substrate, a driving unit of a threading device, a driving unit of an assembling device of a CRT electron gun, A drive unit of a shifter fork drive selection linear control device in a torsion lace machine for manufacturing a torsion lace for use as a decoration for clothing, a table cloth, a seat cover, etc., a drive unit of a horizontal movement mechanism of an annealing window drive device, glass A drive unit for a support arm of a forge hearth of a melting furnace, a drive unit for moving a rack of an exposure apparatus such as a method for forming a fluorescent screen of a color picture tube, a drive unit for a torch arm of a ball bonding apparatus, and a drive unit for an XY direction of a bonding head. , Driving of component mounting process and measurement inspection process in mounting of chip components and measurement using probe In the fields of lifting and lowering drive of the cleaning tool support of the substrate cleaning device, drive for moving the detection head that scans the glass substrate forward and backward, drive for the positioning device of the exposure device that transfers the pattern onto the substrate, precision machining, etc. Exposure used in manufacturing lithography process for driving parts of micro positioning equipment, driving parts of positioning equipment for measuring devices of chemical mechanical polishing tools, and circuit devices such as conductive circuit elements and liquid crystal display elements on the order of submicrons. Driving unit for positioning the stage apparatus suitable for the apparatus and scanning exposure apparatus, driving unit for transporting or positioning the work, etc., driving unit for positioning and transporting the reticle stage, wafer stage, etc., inside the chamber Of precision positioning stage equipment, work piece in chemical mechanical polishing system Or a drive unit of a semiconductor wafer positioning device, a drive unit of a semiconductor stepper device, a drive unit of a device that accurately positions a workpiece in an introduction station of a processing machine, a machine tool such as an NC machine or a machining center, or a stepper in the IC industry. The drive unit of the passive vibration isolation device and the active vibration isolation device for various devices to be used, the reference grating plate of the light beam scanning device in the exposure device used in the lithography process of manufacturing semiconductor devices and liquid crystal display devices, and the like. The present invention can be suitably used for a drive unit for displacing in the optical axis direction of a light beam, and a drive unit for a transfer device for transferring the light beam into the article processing unit in a transverse direction of the conveyor.
[0075]
The actuator can be suitably used, for example, as a drive unit for a probe positioning device of a scanning probe microscope such as an electron microscope, and a drive unit for positioning a sample fine movement device for an electron microscope.
[0076]
The actuator is, for example, an automatic welding robot, a driving unit of a joint mechanism represented by a wrist of a robot arm in a robot or a manipulator including an industrial robot or a nursing robot, a driving unit of a joint other than a direct drive type, a robot. A finger itself, a drive unit of a motion conversion mechanism of a slide opening / closing type chuck device used as a hand of a robot, etc., a micro unit for manipulating a minute object to an arbitrary state in cell micro operation or micro component assembling work. The present invention can be suitably used for a drive unit of a manipulator, a drive unit of an artificial limb such as an electric prosthesis having a plurality of fingers that can be opened and closed, a drive unit of a handling robot, a drive unit of a prosthesis, and a drive unit of a power suit.
[0077]
The actuator can be suitably used, for example, as a pressing portion of a device that presses an upper rotary blade or a lower rotary blade of a side trimmer.
[0078]
The actuator can be suitably used, for example, as a drive unit for an accessory in a game machine such as a pachinko machine, a drive unit for an amusement device such as a doll or a pet robot, and a drive unit for a simulation device of a boarding simulation device. .
[0079]
The actuator can be used for, for example, a drive unit of a valve used in a general machine including the above-described devices and the like, for example, a drive unit of a valve of a reliquefaction apparatus for evaporating helium gas, a drive of a bellows-type pressure-sensitive control valve. , Drive unit of the opening device for driving the heald frame, drive unit of the vacuum gate valve, drive unit of the solenoid operated control valve for hydraulic system, valve drive unit incorporating a motion transmission device using a pivot lever, rocket It can be suitably used for the drive unit of the valve of the movable nozzle, the drive unit of the suck back valve, and the drive unit of the pressure regulating valve unit.
[0080]
The actuator can be used, for example, as a pressing portion of a brake used in a general machine including the above-described devices and the like, for example, a braking device suitable for use in an emergency, security, parking etc. brake or an elevator brake. And a pressing portion of a brake structure or a brake system.
[0081]
The actuator can be used, for example, as a pressing portion of a lock device used in general machines including the above-described devices and the like, for example, a pressing portion of a mechanical locking device, a pressing portion of a vehicle steering lock device, and a load limiter. It can be suitably used for a pressing portion of a power transmission device having both a mechanism and a coupling release mechanism.
[0082]
【Example】
Hereinafter, Examples and Comparative Examples of the present invention are shown, but the present invention is not limited to the following.
[0083]
(Example 1)
The monomers and the dopant ion salts shown in Table 1 were dissolved in the solvents shown in Table 1 by a known stirring method, the conductive polymer monomer was set to 0.25 mol / l, and the dopant salts were dissolved in the concentrations shown in Table 1. Was prepared. Using an ITO glass electrode as a working electrode and a Pt electrode as a counter electrode in the electrolytic solution, electrolytic polymerization was performed by a constant current method having a polymerization current density shown in Table 1. By this electrolytic polymerization, a film-shaped conductive polymer molded article of Example 1 having the conductivity and the film thickness shown in Table 1 was obtained.
[0084]
(Examples 2 to 40, and Examples 44 and 45)
Except that the electropolymerization conditions shown in Tables 1 to 6 were used, the film-like conductive polymer molded articles of Examples 2 to 40 and Examples 44 and 45 were obtained in the same manner as in Example 1. In Example 15, the monomer of the conductive polymer had a mixing ratio of pyrrole and 3-methylthiophene of 1/1 (mol / mol).
[0085]
(Example 41)
The film-form conductive polymer of Example 41 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used and that a Ti electrode which was a metal electrode was used as a working electrode. A molded product was obtained. In addition, the metal electrode in this application used the commercially available metal electrode.
[0086]
(Example 42)
A film-like conductive polymer of Example 42 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used and that a Ni electrode serving as a metal electrode was used as a working electrode. A molded product was obtained.
[0087]
(Example 43)
A film-like conductive polymer of Example 43 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used and that a Ni electrode which was a metal electrode was used as a working electrode. A molded product was obtained.
[0088]
(Comparative Examples 1-4)
Except that the electropolymerization conditions in Tables 5 and 6 were used, the same method as in Example 1 was used to obtain film-shaped conductive polymer molded articles of Comparative Examples 1 to 4.
[0089]
[Table 1]

[0090]
[Table 2]

[0091]
[Table 3]

[0092]
[Table 4]

[0093]
[Table 5]

[0094]
[Table 6]

[0095]
In Tables 1 to 6, the abbreviations in the columns of the types of dopant salts and the solvents are as follows.
Dopant salt A: TBACF₃SO₃(Tetrabutylammonium trifluoromethanesulfonate)
Dopant salt B: CF₃SO₃Li (lithium trifluoromethanesulfonate)
Dopant salt C: TBABF₄(Tetrabutylammonium tetrafluoroborate)
Dopant salt D: TBAPF₆(Tetrabutylammonium hexafluorophosphate)
Dopant salt E: sodium p-toluenesulfonate
solvent;
PC: Propylene carbonate
EC: Ethylene carbonate
γ-BL: γ-butyrolactone
MO: 3-methyl-2-oxazolidinone
DEC: diethyl carbonate
DMC: dimethyl carbonate
DME: dimethoxyethane
THF: tetrahydrofuran
AcEt: ethyl acetate
Ac-n-Bt: n-butyl acetate
Ac-t-Bt: t-butyl acetate
EG: ethylene glycol
PEG: polyethylene glycol (molecular weight: 200)
SF: Sulfolane
DO: 1,4-dioxane
DAE: 1,2-diacetoxyethane
NM: Nitromethane
HxOH: 1-hexanol
OtOH: 1-octanol
AN: acetonitrile
NB: Nitrobenzene
MeB: methyl benzoate
PhEt: diethyl phthalate
DCM: dichloromethane
[0096]
In Tables 1 to 5, when a mixed solvent is used, for example, EC / PC = 1/2 indicates a solvent in which the weight ratio of ethylene carbonate to propylene carbonate is 1: 2.
[0097]
(Evaluation)
An electrolytic solution obtained by dissolving the film-shaped conductive polymer molded products obtained in Examples 1 to 43 and Comparative Examples 1 and 2 in water so that the working electrolyte described in Tables 1 to 5 becomes 1 mol / l. Kept inside. With respect to each of the film-shaped conductive polymer molded products held, the expansion ratio per one oxidation-reduction cycle was measured by the following measurement method. The results are shown in Tables 1 to 5. Further, with respect to the film-shaped conductive polymer molded products obtained in Examples 44 and 45 and Comparative Examples 3 and 4, the displacement ratio per specific time was measured by the following measurement method. Table 6 shows the results of the displacement rate per specific time. The conductivity and the film thickness of the conductive polymer molded products of Examples 1 to 45 and Comparative Examples 1 to 4 were measured by a known method.
[0098]
(Measurement method of stretch ratio)
The film-shaped conductive polymer molded articles obtained in Examples 1 to 43 and Comparative Examples 1 and 2 were used as working electrodes having a length of 15 mm and a width of 2 mm, and a platinum plate as a counter electrode. The working electrode is held in the electrolytic solution and connected to a power supply via a lead, and the potential (−0.9 to +0.7 V vs. Ag / Ag) is connected.⁺) Was applied for one cycle, and the displacement (displaced length) was measured. By dividing the difference in displacement obtained by extending and contracting the working electrode by applying one cycle (one oxidation-reduction cycle) by the original length of the working electrode, the expansion / contraction ratio per oxidation-reduction cycle I asked. The working electrolyte TEAPF₆Is tetraethylammonium tetrafluorophosphate, and EtSO₃Na represents sodium ethanesulfonate.
[0099]
[Displacement rate per specific time]
The film-shaped conductive polymer molded products obtained in Examples 41 and 42 and Comparative Examples 3 and 4 were used as working electrodes having a length of 15 mm and a width of 2 mm, and a platinum plate was used as a counter electrode. Then, the working electrode is held in the electrolytic solution, and connected to a power supply via a lead, so that the potential (+0.9 V vs. Ag / Ag)⁺Or -0.9V v. s. Ag / Ag⁺) Was applied, and the displacement (displaced length) 20 seconds after the start of application was measured. The amount of displacement 20 seconds after the start of the application was divided by the length of the working electrode before the application of the potential to obtain the expansion / contraction ratio per specific time.
[0100]
(result)
The conductive polymer molded article of Example 15 was formed by electropolymerization using an electrolytic solution in which trifluoromethanesulfonic acid ion was used as a dopant anion and the solvent was a mixed solvent of ethylene carbonate and propylene carbonate (1: 2). It is a conductive polymer molded article obtained by a method for producing a polymer. The conductive polymer molded article of Comparative Example 1 is a conductive polymer molded article in which the solvent of the electrolytic solution is water and is electrolytically polymerized with an electrolytic solution containing p-toluenesulfonic acid ion which is a conventional dopant. When the conductive polymer molded article of Example 15 was subjected to electrolytic expansion and contraction using sodium chloride as a conventional operating environment as a working electrolyte, the expansion ratio was 3.1% as shown in Table 2. On the other hand, when the conductive polymer molded article of Comparative Example 1 was subjected to electrolytic expansion and contraction using sodium chloride as a working electrolyte in the same manner as in Example 15, the expansion ratio was 1.3% as shown in Table 4. . In other words, the conductive polymer molded product of Example 15 was compared with the conventional conductive polymer molded product containing a dopant even in an aqueous solution of sodium chloride as a conventional operating environment. Good expansion and contraction with an expansion and contraction ratio of about 2.4 times could be obtained.
[0101]
In Examples 1 to 14 and Examples 16 to 43, the conductive polymer molded articles were the conductive polymer molded articles obtained by the method for producing a conductive polymer of the present invention, respectively. Electrochemical oxidation in one oxidation-reduction cycle in an electrolyte containing at least one compound selected from the group consisting of methanesulfonate ion, an anion containing a plurality of fluorine atoms with respect to the central atom, and a sulfonate having 3 or less carbon atoms As a result of expanding and contracting the conductive polymer molded article by selective oxidation and reduction, as shown in Tables 1 to 5, the expansion ratio was 5% or more. On the other hand, in Comparative Example 2, the conductive polymer was a conductive polymer formed by electrolytically polymerizing with an electrolytic solution containing p-toluenesulfonic acid ion, which is a conventional dopant, in which the solvent of the electrolytic solution was water. In an electrolyte containing at least one compound selected from the group consisting of trifluoromethanesulfonic acid ions, a fluorine atom with respect to the central atom and a sulfonate having 3 or less carbon atoms as a working environment. As a result of expanding and contracting the conductive polymer molded article by electrochemical oxidation and reduction in the oxidation-reduction cycle, as shown in Table 4, the expansion and contraction ratio was as low as 1.7%. That is, the conductive polymer molded article of the present invention is an electrolytic solution containing at least one compound selected from the group consisting of trifluoromethanesulfonic acid ions, a fluorine atom with respect to the central atom, and a sulfonate having 3 or less carbon atoms. By expanding and contracting the conductive polymer molded article by electrochemical oxidation and reduction, excellent expansion and contraction in which the expansion and contraction rate per oxidation-reduction cycle is about three times or more as compared with the conventional case.
[0102]
The conductive polymer molded articles of Examples 44 and 45 are conductive polymer molded articles obtained by the production method of the present invention corresponding to the conductive polymer molded articles of Examples 15 and 4, respectively. . On the other hand, the conductive polymer molded articles of Comparative Examples 3 and 4 are conductive polymer molded articles corresponding to Comparative Examples 1 and 2, respectively. In a NaCl aqueous solution which is a conventional operating environment, the conductive polymer molded product of Comparative Example 3 had an expansion / contraction ratio of 0.4% per specific time, whereas the conductive polymer molded product of Example 36 As a result, the expansion / contraction ratio per specific time was 1.7%, which was about a four-fold improvement. That is, by using the conductive polymer molded article of the present invention, electrolytic expansion and contraction with a rapid displacement can be realized.
[0103]
An electrolytic solution containing at least one compound selected from the group consisting of a trifluoromethanesulfonic acid ion, an anion containing a plurality of fluorine atoms relative to a central atom, and a sulfonate having 3 or less carbon atoms in a working environment of electrolytic expansion and contraction. In this case, the conductive polymer molded product of Comparative Example 4 had an expansion / contraction ratio of 0.4% per specific time, whereas the conductive polymer molded product of Example 45 had The expansion and contraction ratio was improved to about 3.9%, about 10 times. Therefore, conductive polymer molding in an electrolyte containing at least one compound selected from the group consisting of trifluoromethanesulfonic acid ions, anions containing a plurality of fluorine atoms with respect to the central atom, and sulfonates having 3 or less carbon atoms. By using the electrolytic expansion and contraction method of expanding and contracting the conductive polymer molded article by electrochemical oxidation-reduction of the article, it is possible to realize electrolytic expansion and contraction with even faster displacement.
[0104]
Therefore, for the actuator including the operating portion, the counter electrode, and the electrolyte, by using the conductive polymer molded article including the conductive polymer obtained by the manufacturing method of the present invention as the operating portion, the expansion and contraction is fast, and the responsiveness is high. A good actuator can be obtained. Further, also for a laminate including a conductive polymer-containing layer and a solid electrolyte layer, by including the conductive polymer obtained by the production method of the present invention in the conductive polymer-containing layer, the expansion and contraction quickly, A laminate that can be used for an actuator having good responsiveness can be obtained.
[0105]
【The invention's effect】
The conductive polymer molded article obtained by using the method for producing a conductive polymer of the present invention has a superior expansion / contraction per oxidation-reduction cycle as compared with a conventional conductive polymer molded article having elasticity. The ratio is expressed during electrolytic expansion and contraction, and performs a larger operation than before in response to a displacement command, so that it has excellent practicability and is useful as an artificial muscle, a robot arm, an artificial hand, an actuator, and the like. The conductive polymer molded article obtained by the method for producing a conductive polymer according to the present invention has a trifluoromethanesulfonic acid ion in an operating environment of electrolytic expansion and contraction, an anion containing a plurality of fluorine atoms with respect to a central atom, and 3 or less carbon atoms. Electrolytic expansion and contraction in an electrolytic solution containing at least one compound selected from the group consisting of sulfonates of the formula (1) can exhibit a higher expansion and contraction rate, and is therefore useful as an application requiring further expansion and contraction. is there.
[0106]
Further, the conductive polymer molded article of the present invention is preferably formed by a group consisting of a trifluoromethanesulfonic acid ion in a working environment of electrolytic expansion and contraction, an anion containing a plurality of fluorine atoms relative to a central atom, and a sulfonate having 3 or less carbon atoms. By expanding and contracting a conductive polymer molded article by electrochemical oxidation-reduction in an electrolytic solution containing at least one or more selected compounds, it is about 10 times as large as a conventional conductive polymer molded article having elasticity. Since the above-described expansion / contraction ratio per specific time is exhibited, it can be used as a drive part for applications that require a quick response to a displacement command.
[0107]
In addition, by using an actuator including a counter electrode, an electrolyte, and an operating portion including the conductive polymer obtained by the method for manufacturing a conductive polymer, an actuator having large expansion and contraction can be obtained, and furthermore, the sound is silent. It can be suitably used for artificial muscles, driving units of various driving devices, and pressing units of a pressing device. In addition, an actuator in which the operating portion expands and contracts due to electrochemical oxidation and reduction, and the expansion and contraction rate of the actuator in one oxidation-reduction cycle of 20 seconds is 3% or more in the length direction, has a quick response to displacement, and has a high response rate to artificial muscles and various types. It can be used as a drive unit in the device.
[Brief description of the drawings]
FIG. 1 is a perspective view showing the appearance of an embodiment of an actuator according to the present invention.
FIG. 2 is an AA cross-sectional view of the actuator of FIG.
[Explanation of symbols]
1 Actuator
2 Case
3 Working part
4 Conductive connection plate
6 electrolyte
7, 7 'lead wire
8 Lead wire
9 Power supply
21 Tip
22 bottom
23 Actuator fitting recess
24 recess for mating electrode
25 recess for counter electrode fitting
51, 52 Counter electrode

Claims (24)

A conductive polymer having elasticity by electrochemical oxidation-reduction, a method for producing a conductive polymer by an electrolytic polymerization method,
The electrolytic polymerization method comprises the steps of using an organic compound and / or a halogenated hydrocarbon containing at least one bond or a functional group of at least one of an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group and a nitrile group as a solvent. Using an electrolyte solution containing
A method for producing a conductive polymer comprising trifluoromethanesulfonic acid ions and / or anions containing a plurality of fluorine atoms with respect to a central atom in the electrolytic solution. The method for producing a conductive polymer according to claim 1, wherein the conductive polymer includes pyrrole and / or a pyrrole derivative in a molecular chain. A conductive polymer molded article containing the conductive polymer obtained by the method of claim 1 as a resin component. A positioning device, a posture control device, a lifting device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, or a joint device using the conductive polymer molded product according to claim 3 as a driving portion. A pressing device using the conductive polymer molded product according to claim 3 for a pressing portion. An electrolytic stretching method for expanding and contracting the conductive polymer molded article by electrochemical oxidation-reduction of the conductive polymer molded article according to claim 3 in an electrolytic solution. 7. The electrolytic stretching method according to claim 6, wherein the electrolytic stretching is performed in a temperature environment of room temperature or higher. 7. The electrolyte according to claim 6, wherein the electrolyte contains at least one compound selected from the group consisting of trifluoromethanesulfonic acid ions, anions containing a plurality of fluorine atoms relative to the central atom, and sulfonates having 3 or less carbon atoms. Electrolytic stretching method. The electrolytic stretching method according to claim 6, wherein the electrolytic solution contains sodium chloride. A laminate comprising a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer layer comprises the conductive polymer according to claim 3. A positioning device, a posture control device, an elevating device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, or a joint device using the laminate according to claim 10 as a driving unit. A pressing device using the laminate according to claim 10 for a pressing portion. A film-shaped conductive polymer molded product that expands and contracts by electrochemical oxidation-reduction, wherein the conductive polymer has a stretch ratio of 5% or more in the film surface direction. A laminate comprising a conductive polymer-containing layer and a solid electrolyte layer, wherein the conductive polymer contained in the conductive polymer-containing layer is a conductive polymer obtained by the method for producing a conductive polymer according to claim 1. A laminate that is a conductive polymer. A positioning device, a posture control device, an elevating device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, or a joint device using the laminate according to claim 14 as a driving unit. A pressing device using the laminate of claim 14 for a pressing portion. A conductive polymer molded article that expands and contracts by electrochemical oxidation-reduction, wherein the conductive polymer has a stretch ratio of 3% or more in the length direction. A conductive polymer molded article that expands and contracts by electrochemical oxidation and reduction, wherein the expansion and contraction rate in one oxidation-reduction cycle for 20 seconds is 3% or more in the length direction. An actuator including an operating portion, a counter electrode, and an electrolyte, wherein the operating portion includes a conductive polymer obtained by the manufacturing method according to claim 1. An actuator including an operating part, a counter electrode, and an electrolyte, wherein the operating part expands and contracts by electrochemical redox, and the actuator expands and contracts by 3% or more in a length direction. An actuator including an operating part, a counter electrode, and an electrolyte, wherein the operating part expands and contracts by electrochemical oxidation and reduction, and the expansion and contraction rate of the actuator in one oxidation-reduction cycle for 20 seconds is 3% or more in a length direction. An artificial muscle using the actuator according to claim 19. 20. A positioning device, a posture control device, a lifting device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, or a joint device using the actuator according to claim 19 as a driving unit. A pressing device using the actuator according to claim 19 for a pressing portion.

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