JP4049217B2 - 導電性高分子成形品及び積層体を用いた装置 - Google Patents
導電性高分子成形品及び積層体を用いた装置 Download PDFInfo
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本発明に使用される導電性高分子の製造方法において、電解重合法に用いられる電解液には、電解重合される有機化合物(例えば、ピロール)およびトリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む。この電解液を用いて電解重合を行うことにより、電解伸縮において1酸化還元サイクル当たりの伸縮率が優れた導電性高分子を得ることができる。上記電解重合により、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンが導電性高分子に取り込まれることになる。
本発明に使用される導電性高分子の製造方法は、電解重合時に導電性高分子の重合が行われる作用電極として金属電極を用いる。電解重合において金属電極を用いることにより、ITOガラス電極やネサガラス電極等の非金属製の材料を主とする電極を用いた場合に比べて、得られた導電性高分子を用いたアクチュエータが大きな発生力を発現することができる。前記金属電極は、金属を主とする電極であれば特に限定されるものではなく、Pt、Ti、Ni、Ta、Mo、Cr及びWからなる群より選ばれた金属元素についての金属単体の電極または合金の電極を好適に用いることができる。前記製造方法により得られた導電性高分子の伸縮率及び発生力が大きく、且つ電極を容易に入手できることから、金属電極に含まれる金属種がNi、Tiであることが特に好ましい。なお、前記合金としては、例えば、商品名「INCOLOY alloy 825」、「INCONEL alloy 600」、「INCONEL alloy X−750」(以上、大同スペシャルメタル株式会社製)を用いることができる。
本発明に使用される導電性高分子の製造方法において用いられる電解重合法は、導電性高分子単量体の電解重合として、公知の電解重合法を用いることが可能であり、定電位法、定電流法及び電気掃引法のいずれをも用いることができる。例えば、前記電解重合法は、電流密度0.01〜20mA/cm2、反応温度−70〜80℃で行うことができ、良好な膜質の導電性高分子を得るために、電流密度0.1〜2mA/cm2、反応温度-40〜40℃の条件下で行うことが好ましく、反応温度が−30〜30℃の条件であることがより好ましい。
本発明に使用される導電性高分子の電解重合法は、電解重合時の電解液に含まれる溶媒が特に限定されるものではないが、1酸化還元サイクル当たりの伸縮率が3%以上の導電性高分子を容易に得るために、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む以外に、エーテル結合、エステル結合、カーボネート結合、ヒドロキシル基、ニトロ基、スルホン基及びニトリル基のうち少なくとも1つ以上の結合あるいは官能基を含む有機化合物及び/またはハロゲン化炭化水素を電解液の溶媒として含むことが好ましい。これらの溶媒を2種以上併用することもできる。更に望ましくは、前記電解液の溶媒がエステル基をもつ溶媒であることである。
本発明に使用される導電性高分子の製造方法において、電解重合法に用いられる電解液に含まれる導電性高分子の単量体としては、電解重合による酸化により高分子化して導電性を示す化合物であれば特に限定されるものではなく、例えばピロール、チオフェン、イソチアナフテン等の複素五員環式化合物及びそのアルキル基、オキシアルキル基等の誘導体が挙げられる。その中でもピロール、チオフェン等の複素五員環式化合物及びその誘導体が好ましく、特にピロール及び/またはピロール誘導体を含む導電性高分子であることが、製造が容易であり、導電性高分子として安定であるために好ましい。また、上記モノマーは2種以上併用することができる。
本発明に使用される導電性高分子の製造方法において、電解重合法に用いられる電解液には、前記トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液中に導電性高分子の単量体を含むものであり、さらにポリエチレングリコールやポリアクリルアミドなどの公知のその他の添加剤を含むこともできる。
また、本発明は、上記の製造方法により得られた導電性高分子を所望の形状とした、導電性高分子成形品を使用するものである。つまり、電気化学的酸化還元による伸縮性を有する導電性高分子を、電解重合法により製造する導電性高分子の製造方法であって、前記電解重合法が、電気化学的酸化還元による伸縮性を有する導電性高分子を、電解重合法により製造する導電性高分子の製造方法であって、前記電解重合法が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、導電性高分子が形成される作用電極として金属電極を用いる電解重合法であり、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樹脂成分として含む導電性高分子成形品を使用するものである。前記導電性高分子成形品は、その形状が特に限定されるものではなく、膜状、管状、筒状、角柱及び繊維状等の形状であってもよいが、前記導電性高分子が電解重合時に作用電極に析出することから、膜状であることが好ましい。また、前記成形品が膜状である場合には、本発明の上記の製造方法の導電性高分子により得られた膜状体であってもよい。前記膜状体は、上述の製造方法により得られた導電性高分子が公知の方法により対象となる物品の表面を被覆する形態で形成されても良い。
本発明において使用される積層体は、導電性高分子層と固体電解質層とを含む積層体であり、前記導電性高分子層に上記の導電性高分子を含む積層体でもある。つまり、本発明において使用される積層体は、導電性高分子層と固体電解質層とを含む積層体であって、前記導電性高分子層に、電気化学的酸化還元による伸縮性を有する導電性高分子を、電解重合法により製造する導電性高分子の製造方法であって、前記電解重合法が、電気化学的酸化還元による伸縮性を有する導電性高分子を、電解重合法により製造する導電性高分子の製造方法であって、前記電解重合法が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、導電性高分子が形成される作用電極として金属電極を用いる電解重合法であり、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積層体である。積層体に前記導電性高分子層と前記固体電解質層を含むことにより、前記固体電解質層中の電解質が前記導電性高分子層に供給されることにより、電解伸縮時に大きな1酸化還元サイクル当たりの伸縮率を発現することができ、しかも大きな発生力を得ることができる。前記積層体中の前記導電性高分子層と固体電解質層とは、直接接していることが好ましいが、前記固体電解質中の電解質を前記導電性高分子に移動させることができるのであれば、他の層を間に介していても良い。
また、上記の導電性高分子成形品を電解液中で、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電解伸縮方法により駆動することができる。上記の導電性高分子成形品を電解伸縮させることにより、1酸化還元サイクル当たりにおいて優れた伸縮率を得ることができる。更に、上記の導電性高分子成形品を伸縮させる電解伸縮方法は、優れた特定時間あたりの変位率をも得ることができる。前記導電性高分子成形品の電解伸縮が行われる電解液である動作電解液は、特に限定されるものではないが、主溶媒である水に電解質を含む液体であることが、濃度調製が容易であるために好ましい。
また、本願発明の装置は、作動部、電解質及び対極を含むアクチュエータを使用するものであって、前記作動部が上記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を含むアクチュエータを用いた装置に関するものである。前記アクチュエータは、装置構成として作動部、電解質及び対極を含めば特に限定されるものではないが、作動の際に液漏れがしないように作動部へ取付けられたシャフトが筐体にパッキングされたアクチュエータ、または作動部の作動に従う伸縮が可能な筐体を備えたアクチュエータであることが、電解液等の液漏れを生じないので好ましい。
上記製造方法により得られた導電性高分子は、伸縮率が大きく、しかも発生力が大きいために、マイクロマシンや人工筋肉などのアクチュエータに好適に使用することができる。さらに、本発明に使用される導電性高分子は、従来の導電性高分子に比べて発生力の最大値が大きいために、前記導電性高分子を用いたアクチュエータのサイズを小型化しても従来の導電性高分子を用いたアクチュエータと同等の発生力を得ることができるので、マイクロマシンやマイクロサージェリー技術におけるピンセット、ハサミ、鉗子、スネア、レーザメス、スパチュラ、クリップなどの医療器具に特に有用である。また、検査や補修等を行う各種センサー若しくは補修用工具など、健康器具、湿度計、湿度計コントロール装置、ソフトマニュピュレーター、水中バルブ、ソフト運搬装置などの工業用機器、金魚などの水中モービル、または動く釣り餌や推進ヒレなどのホビー用品などの水中で用いられる物品についても、本発明に使用される導電性高分子成形品及び積層体を好適に使用することができる。
表1に記載されたモノマー及びドーパントイオンの塩を表1に記載の溶媒に公知の撹拌方法により溶解し、モノマーであるピロールの濃度を0.25mol/lとして含み、かつドーパント塩を表1の濃度として含む電解液を調製した。この電解液に作用電極として表1に記載の金属種である市販の金属電極を用い、対向電極としてPt電極を用いて、表1に記載の重合電流密度の定電流法により電解重合を行い、表1に記載の導電率及び膜厚を有する実施例1の膜状の導電性高分子成形品を得た。
表1、2及び4の電解重合条件で行ったこと以外は実施例1と同様の方法により、各実施例の膜状の導電性高分子成形品を得た。
表3及び4の電解重合条件で行い、電極にITOガラス電極を用いたこと以外は実施例1と同様の方法により、比較例1〜12の膜状の導電性高分子成形品を得た。
ドーパント塩B:TBACF3SO3(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C:ベンゼンスルホン酸ナトリウム
ドーパント塩D:p−トルエンスルホン酸ナトリウム
PC:プロピレンカーボネ−ト
DME:ジメトキシエタン
MeB:安息香酸メチル
BuB:安息香酸ブチル
EtPh:フタル酸ジエチル
DCM:ジクロロメタン
MMP:3−メトキシプロピオン酸メチル
MeSa:サリチル酸メチル
〔発生力〕
実施例1〜17並びに比較例1〜12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、導電性高分子成形品それぞれの端部に重りを吊るし、それぞれの他の端部を動作電解液中に保持し、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)で収縮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、表1〜4に記載した伸縮率となる時の重りの重さを発生力とした。なお、動作電解液は、ヘキサフルオロリン酸ナトリウムの15wt%の水溶液を用いた。その結果を表1〜4に示す。なお、上記重りの重量を変えることにより、負荷重量に対する伸縮率を測定し、その測定値を単位断面積当たりに換算することにより、発生力を測定した。
実施例1〜13において、電極として非金属電極であるITOガラス電極を使用したこと以外は同様の電解重合条件で製造した導電性高分子成形品に対応する比較例について、同じ伸縮率を示す際の発生力比(〔実施例の発生力〕/〔比較例の発生力〕)を算出した。結果を表1〜2に示す。
実施例1〜13の導電性高分子成形品は、従来の導電性高分子を用いたアクチュエータでは得られなかった1酸化還元サイクル当たりの収縮である3〜5%の伸縮率を示し、しかも発生力は、3.9〜15.6MPaという大きな値を示し、伸縮率と発生力とのバランスに優れた導電性高分子成形品であった。しかも、実施例1〜13の導電性高分子成形品は、金属電極を用いているために、非金属電極を用いた対応する実施例に比べて2.0〜10.5倍という優れた発生力の向上が認められた。さらに、実施例14〜17については、13.4〜18.4MPaという優れた最大発生力を得ることができたが、比較例11および12については、それぞれの発生力0.7MPa及び3.5MPaが最大発生力であった。なお、最大発生力とは、重りの重量を変化させながら伸縮率を測定し、収縮する範囲内で膜状の導電性高分子成形品が重りの重みで切断される直前の発生力をいう。なお、上記実施例及び比較例において、重りを重力方向に負荷させた状態での伸縮を測定したために、伸縮率として導電性高分子成形品の収縮する割合(収縮率)を測定し、伸縮率とした。
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
Claims (6)
- 電解重合法により得られる電気化学的酸化還元により伸縮性を有する導電性高分子が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、
前記導電性高分子が形成される作用電極に金属電極を用いて製造されるものであり、
前記導電性高分子を樹脂成分として含む導電性高分子成形品を駆動部に用いた位置決め装置、姿勢制御装置、昇降装置、搬送装置、移動装置、調節装置、調整装置、誘導装置、または関節装置。 - 電解重合法により得られる電気化学的酸化還元により伸縮性を有する導電性高分子が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、
前記導電性高分子が形成される作用電極に金属電極を用いて製造されるものであり、
前記導電性高分子を樹脂成分として含む導電性高分子成形品を押圧部に用いた押圧装置。 - 電解重合法により得られる電気化学的酸化還元により伸縮性を有する導電性高分子が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、前記導電性高分子が形成される作用電極に金属電極を用いて製造されるものであり、
前記導電性高分子を樹脂成分として含む導電性高分子層と、固体電解質層とを含む積層体を駆動部に用いた位置決め装置、姿勢制御装置、昇降装置、搬送装置、移動装置、調節装置、調整装置、誘導装置、または関節装置。 - 電解重合法により得られる電気化学的酸化還元により伸縮性を有する導電性高分子が、トリフルオロメタンスルホン酸イオン及び/または中心原子に対してフッ素原子を複数含むアニオンを含む電解液を用い、前記導電性高分子が形成される作用電極に金属電極を用いて製造されるものであり、
前記導電性高分子を樹脂成分として含む導電性高分子層と、固体電解質層とを含む積層体を押圧部に用いた押圧装置。 - 前記導電性高分子が分子鎖にピロール及び/またはピロール誘導体を含む請求項1又は3に記載の位置決め装置、姿勢制御装置、昇降装置、搬送装置、移動装置、調節装置、調整装置、誘導装置、または関節装置。
- 前記導電性高分子が分子鎖にピロール及び/またはピロール誘導体を含む請求項2又は4に記載の押圧装置。
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JP2003343075A Expired - Fee Related JP4049217B2 (ja) | 2002-10-02 | 2003-10-01 | 導電性高分子成形品及び積層体を用いた装置 |
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2003
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