WO2011024219A1 - Electroconductive polymer actuator, method for driving the electroconductive polymer actuator, and method for manufacturing the electroconductive polymer actuator - Google Patents
Electroconductive polymer actuator, method for driving the electroconductive polymer actuator, and method for manufacturing the electroconductive polymer actuator Download PDFInfo
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- WO2011024219A1 WO2011024219A1 PCT/JP2009/004131 JP2009004131W WO2011024219A1 WO 2011024219 A1 WO2011024219 A1 WO 2011024219A1 JP 2009004131 W JP2009004131 W JP 2009004131W WO 2011024219 A1 WO2011024219 A1 WO 2011024219A1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
- F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
- F03G7/005—Electro-chemical actuators; Actuators having a material for absorbing or desorbing gas, e.g. a metal hydride; Actuators using the difference in osmotic pressure between fluids; Actuators with elements stretchable when contacted with liquid rich in ions, with UV light, with a salt solution
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- the present invention relates to a conductive polymer actuator that can be applied to household robots and the like, and a method for manufacturing the same.
- the present invention relates to an actuator using an electrochemical reaction and a manufacturing method thereof.
- actuators that are small, light, and flexible in the medical and household robot fields. This is because actuators for operating robots that are expected to play an active role in the immediate vicinity such as housework support and work support at home, office, hospital, etc. This is because such a property (for example, safety that does not cause injury when touched or softness that does not hurt when bumped) is required.
- Electrostatic attractive type, piezoelectric type, ultrasonic type, and shape memory alloy type have already been put to practical use as small and lightweight actuators, but these use inorganic materials and their operating principles. Therefore, it cannot be a flexible actuator. Therefore, in recent years, various attempts have been actively made to realize a lightweight and flexible actuator by using an organic material such as a polymer.
- a gel is bent by an electric field (Patent Document 1), a gel is deformed by applying a strong electric field between dielectric elastomer thin films (Non-Patent Document 1), and a conductive polymer is expanded and contracted by a redox reaction. (Patent Document 2) and the like.
- An actuator that bends the gel by an electric field has a problem that the generated stress is small and the power consumption increases because the bending property cannot be maintained unless the electric field is continuously applied.
- a high voltage of several hundred to several kilovolts is required for deformation, and when used for a home robot, the voltage is too high and there is a risk of electric shock or the like. .
- conductive polymer actuators that use the expansion and contraction associated with oxidation and reduction of conductive polymers have a relatively simple structure, are easy to reduce in size and weight, are flexible, and can be driven at a low voltage of several volts. It has a feature that the generated stress is sufficiently strong.
- a bending type actuator utilizing the expansion and contraction of a conductive polymer has a structure in which a conductive polymer film is laminated on at least one surface of a solid electrolyte film as shown in FIG.
- 201 is an actuator element
- 202a and 202b are conductive polymer films
- 203 is a solid electrolyte film
- 204a and 204b are electrodes.
- a metal electrode thin film (counter electrode) is formed on the other side of the solid electrolyte membrane in order to apply a voltage.
- a metal electrode thin film may be formed on the conductive polymer film in order to apply a voltage. Then, the laminated film is bent by applying a predetermined voltage between the conductive polymer film and the counter electrode or between the conductive polymer films.
- the operating principle of bending is considered as follows. That is, the conductive polymer is oxidized and reduced by voltage application, and ions are taken into or taken out of the conductive polymer film accordingly. The volume of the conductive polymer film changes due to the entry and exit of the ions, and the actuator is bent because it is laminated with the solid electrolyte film that does not change in volume.
- Examples of conductive polymers used for actuators include polyaniline, polypyrrole, polythiophene, and derivatives thereof (Patent Document 2).
- Conductive polymer actuators use ions in and out of the conductive polymer film as a result of the electrical oxidation and reduction of the conductive polymer as the principle of operation.
- An electrolyte is required, and in order to operate in air, a solid electrolyte having sufficient ionic conductivity at a temperature of about room temperature is required.
- a material named ion gel has been created. This is a material in which at least one of polymer or monomer dispersed in an ionic liquid is gelled, and the ionic liquid is retained in the three-dimensional network structure of the gel. It is flexible and has conductivity at room temperature. A value of 10 ⁇ 2 S / cm, which is 100 times or more that of a conventional polyether polymer solid electrolyte, has been achieved (Non-patent Document 2).
- Patent Document 3 is cited as a document that can be related to the present invention.
- Patent Document 3 discloses a polymer actuator device. 9 and its description include a control electrode A (reference numeral 203), an electrolytic displacement part A (reference numeral 201) made of a conductive polymer, an electrolyte part (reference numeral 202), and a high conductivity.
- a polymer actuator device comprising an electrolytic displacement part B (reference symbol: 201 ′) made of molecules and a control electrode B (reference symbol: 203 ′) is disclosed.
- paragraph number 0077 of Patent Document 3 describes that polythiophene is preferable as the conductive polymer.
- Paragraph No. 0078 of Patent Document 3 discloses that a fluorine-based polymer such as polyvinylidene fluoride or a copolymer thereof is used as the polymer solid electrolyte. Furthermore, it is disclosed that sulfonic acid may be introduced into the basic skeleton.
- the solid electrolyte film made of these conductive polymer film and ion gel has low mutual adhesiveness. . Therefore, when a bending type actuator is formed by laminating a solid electrolyte membrane made of a conductive polymer membrane and an ion gel, the solid electrolyte membrane made of the conductive polymer membrane and the ion gel is easy to peel off during the operation.
- Patent Document 4 discloses that at least one selected from an electrolyte layer and an electrode layer is a conductive polymer containing polydioxythiophene and a dopant doped in the polydioxythiophene having a plurality of acid groups, and sulfonic acid It is disclosed that a conductive layer containing a group-containing polymer is effective.
- Patent Documents 5 to 7 can be cited as documents that may be relevant to the present invention.
- a conventional conductive polymer actuator is a conductive polymer in which at least one selected from an electrolyte layer and an electrode layer includes polydioxythiophene and a dopant doped in the polydioxythiophene and having a plurality of acid groups And a polymer having a sulfonic acid group, the mutual adhesiveness between the solid electrolyte membrane made of ion gel is improved. Therefore, compared with the case where a polymer having a sulfonic acid group is not contained, there is a problem that the mechanical strength (Young's modulus) of the conductive polymer film is reduced and the force generated during the bending operation is reduced. .
- the present invention improves the adhesion between a solid electrolyte membrane made of a conductive polymer membrane and an ionic gel, does not lower the mechanical strength (Young's modulus) of the conductive polymer membrane, and does not deteriorate even when it is repeatedly operated.
- An object is to realize a bent conductive polymer actuator. Furthermore, it aims at providing the manufacturing method for implement
- the present invention relates to vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide ( PEO), a solid electrolyte membrane made of a mixture of an organic polymer containing at least one of polyacrylonitrile (PAN) and an ionic liquid, and polyethylene dioxythiophene (PEDOT) and polystyrene formed on at least one surface of the solid electrolyte membrane
- a conductive polymer actuator having a laminated structure with a conductive polymer film made of a mixture of sulfonic acid (PSS), wherein the conductive polymer film contains a perfluorosulfonic acid / PTFE copolymer Conductive polymer actu characterized by It is intended to provide a chromatography data.
- the present invention provides a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), poly
- a solid electrolyte membrane composed of a mixture of an organic polymer containing at least one of ethylene oxide (PEO) and polyacrylonitrile (PAN) and an ionic liquid, and polyethylene dioxythiophene (PEDOT) formed on at least one surface of the solid electrolyte membrane Is a method of manufacturing a conductive polymer actuator having a laminated structure of a conductive polymer film made of a mixture of polystyrene sulfonic acid (PSS), in which both perfluorosulfonic acid / PTFE are contained in the conductive polymer film.
- PSS polystyrene sulfonic acid
- the said conductive polymer film is formed on both surfaces of the said solid electrolyte membrane.
- the adhesion between the solid electrolyte membrane made of the conductive polymer membrane and the ionic gel is improved, and the mechanical strength (Young's modulus) of the conductive polymer membrane is not lowered, and it can be operated repeatedly.
- a bending-type conductive polymer actuator that does not deteriorate is realized.
- FIG. 1 is a schematic cross-sectional view of an actuator according to an embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view of a conventional bending actuator.
- FIG. 1 is a schematic cross-sectional view of an actuator according to an embodiment of the present invention.
- the actuator 101 is composed of a laminate of conductive polymer films 102a and 102b and a solid electrolyte film 103, and electrodes 105a and 105b are installed so as to sandwich one end of the conductive polymer films 102a and 102b.
- the actuator 101 bends with the portion sandwiched between the electrodes 105a and 105b as a fixed portion.
- the conductive polymer used in the present invention has a conjugated double bond, so that ⁇ electrons spread throughout the polymer and contribute to electronic conductivity. Electrical conduction of conducting polymers is thought to occur when polarons and bipolarons generated by the interaction between oxidants doped in polymers and ⁇ electrons in the polymers become charge carriers. .
- polyaniline, polypyrrole, polythiophene, and derivatives thereof can be used as the conductive polymer.
- PEDOT polyethylenedioxythiophene
- PEDOT polyethylenedioxythiophene
- PES polystyrene
- PEDOT Polyethylenedioxythiophene
- polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) of the mixture constituting the conductive polymer are represented by [Chemical Formula 1] and [Chemical Formula 2], respectively.
- Polyethylenedioxythiophene has a feature that the ⁇ -position of a chemically active five-membered ring is preliminarily modified and inactivated by oxygen, and thus is less susceptible to oxidative degradation.
- polystyrene sulfonic acid is strongly bonded to polyethylene dioxythiophene by ionic bond.
- a conductive polymer film in which perfluorosulfonic acid / PTFE copolymer is mixed is prepared by preparing a liquid in which perfluorosulfonic acid / PTFE copolymer is dispersed in a conductive polymer dispersion or solution, and this is applied to a substrate. It can be prepared by drying the solvent after coating.
- the mixing ratio of the perfluorosulfonic acid / PTFE copolymer to the conductive polymer dispersion or solution is preferably 0.05% by weight to 10% by weight, Preferably they are 0.1 weight% or more and 5 weight% or less. If the amount is less than this range, the adhesion of the solid electrolyte membrane composed of the conductive polymer membrane and the ionic gel cannot be improved, and when the manufactured actuator is operated, the conductive polymer membrane and the solid electrolyte membrane are peeled off and bent. Operation becomes difficult. On the other hand, when it exceeds this range, it becomes difficult to obtain a conductive polymer as a film.
- the solid electrolyte membrane 103 used in the present invention is named an ionic gel in which at least one of a polymer or a monomer dispersed in an ionic liquid is gelled and the ionic liquid is held in the three-dimensional network structure of the gel. It is a material that is flexible and has an electrical conductivity of 10 ⁇ 2 S / cm at room temperature, which is at least 100 times that of conventional polyether polymer solid electrolytes.
- an ionic gel can be used alone as the solid electrolyte membrane, the ionic gel can also be used by impregnating a porous membrane such as paper or a membrane filter.
- the ionic liquid is also called a room temperature molten salt or simply a molten salt, and is a salt that shows a molten state in a wide temperature range including normal temperature (room temperature).
- conventionally known various ionic liquids can be used, and those which show a liquid state and stable at a temperature close to room temperature (room temperature) or room temperature (room temperature) are preferable.
- ionic liquids preferably used in the present invention include those composed of the following cations represented by [Chemical Formula 3] to [Chemical Formula 6] and anions (X ⁇ ).
- R represents an alkyl group having 1 to 12 carbon atoms or an alkyl group having an ether bond and a total number of carbon and oxygen of 3 to 12, and in [Chemical Formula 3], R1 Represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
- R and R1 are preferably different.
- x is an integer of 1 to 4, respectively.
- an imidazolium ion represented by [Chemical Formula 3] is more preferable.
- anion (X ⁇ ) examples include a tetrafluoroborate anion, a hexafluorophosphate anion, a bis (trifluoromethanesulfonyl) imido anion, a perchlorate anion, a tris (trifluoromethanesulfonyl) carbonate anion, and a trifluoromethanesulfonate anion.
- Dicyanamide anion, trifluoroacetate anion, organic carboxylate anion and halogen ion are preferred.
- Organic polymers that can be used to obtain a gel-like composition that becomes an ionic gel include vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), and perfluorosulfonic acid.
- PVDF / HFP vinylidene fluoride / hexafluoropropylene copolymer
- PVDF polyvinylidene fluoride
- perfluorosulfonic acid perfluorosulfonic acid.
- / PTFE copolymer polymethyl methacrylate (PMMA), polyethylene oxide (PEO), and polyacrylonitrile (PAN).
- a monomer for example, methyl methacrylate, MMA
- a crosslinking agent for example, ethylene glycol dimethacrylate, EGDMA
- a polymerization initiator for example, azobisisobutyronitrile, AIBN
- the solid electrolyte is obtained by mixing the ionic liquid and at least one of the polymer or monomer to prepare an ionic gel precursor, heating it, and then cooling it, but from the viewpoint of strength and ionic conductivity.
- the weight ratio is preferably 9: 1 to 6: 4, and more preferably 8: 2 to 7: 3.
- the molar ratio is preferably 3: 7 to 7: 3, and more preferably 4: 6 to 6: 4.
- the electrode may be any material that has electronic conductivity and can easily exchange electrons with the conductive polymer without chemically reacting with the conductive polymer, such as gold, silver, platinum, copper, and chromium, And carbon-containing plates can be used.
- Example 1 [Preparation of conductive polymer film mixed with organic molecules] Water of PEDOT and PSS mixture in which 5% by weight of dimethyl sulfoxide (DMSO) and 1% by weight of perfluorosulfonic acid / PTFE copolymer 10% aqueous dispersion were mixed on a glass slide treated with oxygen plasma after acetone cleaning. A predetermined amount of a dispersion (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped. Then, it was naturally dried at room temperature to evaporate the solvent, and a conductive polymer film was formed on the slide glass. Finally, the conductive polymer film was peeled from the slide glass using a razor. The obtained conductive polymer film had an average thickness of 10 ⁇ m, and the conductivity measured using a four-end needle method was 280 S / cm.
- DMSO dimethyl sulfoxide
- PTFE copolymer 10% aqueous dispersion aqueous dispersion
- a polyethylene terephthalate (PET) sheet having a thickness of 0.1 mm was cut into a size of 76 mm ⁇ 26 mm, and this was closely attached to a slide glass having a size of 76 mm ⁇ 26 mm. Two sets of this were produced. Then, a slide glass produced by sandwiching a capacitor separator paper having a thickness of 40 ⁇ m was adhered so that the two PET sheets face each other with a predetermined gap therebetween. At this time, the capacitor separator paper was impregnated with an ion gel precursor. Thereafter, the mixture was heated at 100 ° C.
- PET polyethylene terephthalate
- electrolyte ion gel the ion gel-impregnated paper obtained here is referred to as electrolyte ion gel.
- Conductive polymer film / electrolyte ion gel / conductive polymer film is formed by superposing conductive polymer films on both sides of the electrolyte ion gel so as to be opposed to each other, heating in a thermostatic bath at 100 ° C. for 30 minutes, and then cooling to room temperature. The three-layer structure was formed.
- This three-layer structure is cut to a width of 2.5 mm and a length of 15 mm, a platinum electrode having a width of 2 mm and a length of 10 mm is attached to a region of 5 mm in the longitudinal direction from one end portion, and a bending type conductive high height having a movable portion length of 10 mm is attached.
- a molecular actuator was fabricated.
- Bending displacement was evaluated by triangulation using a laser displacement meter.
- the measurement point of the triangular measurement was set at a position of 5 mm in the length direction from the electrode mounting portion.
- Table 1 shows the amount of displacement when driven by a 1 Hz rectangular wave.
- the bent type conductive polymer actuator having this configuration has excellent adhesion between the conductive polymer film and the solid electrolyte film, and can be operated for a long time.
- Conductive polymer membranes are laminated on both sides of the electrolyte ion gel produced in the same manner as in Example 1, heated at 100 ° C. for 30 minutes in a thermostatic bath, and then cooled to room temperature, whereby the conductive polymer membrane and the electrolyte ion gel are cooled.
- a three-layer structure was formed by bonding. This three-layer structure is cut to a width of 2.5 mm and a length of 15 mm, a platinum electrode having a width of 2 mm and a length of 10 mm is attached to a region of 5 mm in the longitudinal direction from one end portion, and a bending type conductive high height having a movable portion length of 10 mm is attached.
- a molecular actuator was fabricated.
- This actuator has extremely low adhesiveness between the electrolyte ion gel and the conductive polymer film, and when a voltage of ⁇ 1.0 V is applied, peeling occurs at the interface between the electrolyte ion gel and the conductive polymer film, and the bending responds to the applied voltage. Without operation, the displacement was a 1 Hz rectangular wave and the initial 10-time average displacement was 0.05 mm or less.
- Table 2 shows the mechanical strength (Young's modulus) of the conductive polymer films prepared in Example 1 and Comparative Examples 1 to 4.
- the Young's modulus shown in Table 2 is the Young's modulus (unit GPa) at 1% elongation.
- a highly reliable actuator that is small, light and flexible, and can be suitably used in fields such as medical, industrial, and home robots or micromachines. it can.
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Abstract
Disclosed is an electroconductive polymer actuator. The electroconductive polymer actuator is of a bending operation type and can realize reliable operation by virtue of improved adhesion between an electroconductive polymer membrane and a solid electrolyte membrane.
The electroconductive polymer actuator comprises a laminate structure comprising a solid electrolyte membrane and an electroconductive polymer membrane provided on at least one side of the solid electrolyte membrane. The solid electrolyte membrane comprises a mixture of an organic polymer with an ionic liquid. The organic polymer includes at least one of vinylidene fluoride/hexafluoropropylene copolymers [P(VDF/HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid/PTFE copolymers, polymethylmethacrylate (PMMA), polyethylene oxide (PEO), and polyacrylonitrile (PAN). The electroconductive polymer membrane comprises a mixture of polyethylenedioxythiophene (PEDOT) with polystyrene sulfonic acid (PSS). The electroconductive polymer actuator is characterized in that the electroconductive polymer membrane contains a perfluorosulfonic acid/PTFE copolymer.
Description
本発明は、家庭用のロボットなどに適用することが出来る導電性高分子アクチュエータおよびその製造方法に関する。特に、電気化学反応を利用したアクチュエータとその製造方法に関する。
The present invention relates to a conductive polymer actuator that can be applied to household robots and the like, and a method for manufacturing the same. In particular, the present invention relates to an actuator using an electrochemical reaction and a manufacturing method thereof.
近年、医療、および家庭用のロボット分野において小型かつ軽量で柔軟性に富むアクチュエータの必要性が高まっている。なぜならば、家庭やオフィス、病院などで家事支援や仕事支援、高齢者や障害者の介護支援など人の間近で活躍することが期待されるロボットを動作させるためのアクチュエータには、人間の筋肉のような性質（例えば、触れても怪我をしない安全性やぶつかっても痛くない柔らかさなど）が求められるからである。
In recent years, there is an increasing need for actuators that are small, light, and flexible in the medical and household robot fields. This is because actuators for operating robots that are expected to play an active role in the immediate vicinity such as housework support and work support at home, office, hospital, etc. This is because such a property (for example, safety that does not cause injury when touched or softness that does not hurt when bumped) is required.
小型で軽量なアクチュエータとしては 静電引力型、圧電型、超音波式、および、形状記憶合金式などがすでに実用化されているが、これらは、無機材料を用いていることと、その動作原理から柔軟性に富むアクチュエータにはなり得ない。そこで、近年、高分子等の有機材料を用いることで、軽量で柔軟性に富むアクチュエータを実現しようとする試みが各方面で盛んに行われている。
Electrostatic attractive type, piezoelectric type, ultrasonic type, and shape memory alloy type have already been put to practical use as small and lightweight actuators, but these use inorganic materials and their operating principles. Therefore, it cannot be a flexible actuator. Therefore, in recent years, various attempts have been actively made to realize a lightweight and flexible actuator by using an organic material such as a polymer.
例えば、ゲルを電界によって屈曲させるもの（特許文献１）、誘電性エラストマー薄膜間に強電界を印加してこれを変形させるもの（非特許文献１）、酸化還元反応によって導電性高分子を伸縮させるもの（特許文献２）等がある。
For example, a gel is bent by an electric field (Patent Document 1), a gel is deformed by applying a strong electric field between dielectric elastomer thin films (Non-Patent Document 1), and a conductive polymer is expanded and contracted by a redox reaction. (Patent Document 2) and the like.
ゲルを電界によって屈曲させる方式のアクチュエータは、発生応力が小さく、電界を印加し続けないと屈曲性が保てないので消費電力が多くなるというという課題を有する。また、誘電性エラストマー薄膜を用いるものは、数百～数キロボルトの高電圧が変形に必要であり、家庭用ロボットに利用する場合には電圧が高過ぎるために感電などの危険性が課題となる。
An actuator that bends the gel by an electric field has a problem that the generated stress is small and the power consumption increases because the bending property cannot be maintained unless the electric field is continuously applied. In addition, when using dielectric elastomer thin film, a high voltage of several hundred to several kilovolts is required for deformation, and when used for a home robot, the voltage is too high and there is a risk of electric shock or the like. .
一方、導電性高分子の酸化還元に伴う伸縮を利用した導電性高分子アクチュエータは比較的単純な構造を持ち、小型化および軽量化が容易で、柔軟性に富み、数ボルトの低電圧で駆動が可能であり、発生応力も十分強いという特徴を有している。
On the other hand, conductive polymer actuators that use the expansion and contraction associated with oxidation and reduction of conductive polymers have a relatively simple structure, are easy to reduce in size and weight, are flexible, and can be driven at a low voltage of several volts. It has a feature that the generated stress is sufficiently strong.
導電性高分子の伸縮を利用した屈曲型アクチュエータは、図２に示すように固体電解質膜の少なくとも片面に導電性高分子膜を積層させた構造をしている。図２において、２０１はアクチュエータ素子、２０２ａ、２０２ｂは導電性高分子膜、２０３は固体電解質膜、２０４ａ、２０４ｂは電極である。固体電解質膜の片面のみに導電性高分子膜を積層させた場合、固体電解質膜のもう片面には電圧を印加するために金属電極薄膜（対極）を形成する。導電性高分子膜には、電圧を印加するために金属電極薄膜が形成される場合もある。そして、導電性高分子膜と対極の間、または導電性高分子膜間に所定の電圧を印加することで積層膜が屈曲する。
2. A bending type actuator utilizing the expansion and contraction of a conductive polymer has a structure in which a conductive polymer film is laminated on at least one surface of a solid electrolyte film as shown in FIG. In FIG. 2, 201 is an actuator element, 202a and 202b are conductive polymer films, 203 is a solid electrolyte film, and 204a and 204b are electrodes. When a conductive polymer film is laminated only on one side of the solid electrolyte membrane, a metal electrode thin film (counter electrode) is formed on the other side of the solid electrolyte membrane in order to apply a voltage. A metal electrode thin film may be formed on the conductive polymer film in order to apply a voltage. Then, the laminated film is bent by applying a predetermined voltage between the conductive polymer film and the counter electrode or between the conductive polymer films.
屈曲の動作原理は、以下のようであると考えられている。すなわち、電圧印加によって導電性高分子が酸化還元し、それに伴い導電性高分子膜中へイオンが取り込まれるか取り出される。このイオンの出入りにより導電性高分子膜の体積が変化し、体積変化しない固体電解質膜と積層させてあることからアクチュエータが屈曲する。
The operating principle of bending is considered as follows. That is, the conductive polymer is oxidized and reduced by voltage application, and ions are taken into or taken out of the conductive polymer film accordingly. The volume of the conductive polymer film changes due to the entry and exit of the ions, and the actuator is bent because it is laminated with the solid electrolyte film that does not change in volume.
例えば、図２の構成において、上側の導電性高分子膜中へイオンが取り込まれた、または下側の導電性高分子膜中からイオンが取り出された場合には下方向に、逆に上側の導電性高分子膜中からイオンが取り出された、または下側の導電性高分子膜中へイオンが取り込まれた場合には上方向に屈曲する。
For example, in the configuration of FIG. 2, when ions are taken into the upper conductive polymer film or ions are taken out from the lower conductive polymer film, the upper side is in the downward direction. When ions are taken out from the conductive polymer film or ions are taken into the lower conductive polymer film, the film bends upward.
アクチュエータに用いる導電性高分子としてはポリアニリン、ポリピロール、ポリチオフェンおよびその誘導体がある（特許文献２）。
Examples of conductive polymers used for actuators include polyaniline, polypyrrole, polythiophene, and derivatives thereof (Patent Document 2).
導電性高分子アクチュエータは、動作原理として導電性高分子が電気的に酸化還元することに伴う導電性高分子膜中へのイオンの出入を利用しているため、動作のためにイオン供給源として電解質が必要であり、空気中動作させるためには室温程度の温度で十分なイオン導電性を持つ固体電解質が必要となるが、近年イオンゲルと名付けられた材料が創製されている。これは、イオン液体中に分散させたポリマーまたはモノマーの少なくともいずれか一方をゲル化させ、ゲルの三次元網目構造中にイオン液体を保持した材料であり、柔軟性を持ち、かつ室温で電導率１０－２Ｓ／ｃｍという、従来のポリエーテル系高分子固体電解質の１００倍以上の値が達成されているものである（非特許文献２）。
Conductive polymer actuators use ions in and out of the conductive polymer film as a result of the electrical oxidation and reduction of the conductive polymer as the principle of operation. An electrolyte is required, and in order to operate in air, a solid electrolyte having sufficient ionic conductivity at a temperature of about room temperature is required. In recent years, a material named ion gel has been created. This is a material in which at least one of polymer or monomer dispersed in an ionic liquid is gelled, and the ionic liquid is retained in the three-dimensional network structure of the gel. It is flexible and has conductivity at room temperature. A value of 10 −2 S / cm, which is 100 times or more that of a conventional polyether polymer solid electrolyte, has been achieved (Non-patent Document 2).
その他、本発明に関連し得る文献として、特許文献３が挙げられる。特許文献３は、高分子アクチュエータデバイスを開示している。そして、その図９およびその説明には、制御電極Ａ（参照符号：２０３）、導電性高分子からなる電解変位部Ａ（参照符号：２０１）、電解質部（参照符号：２０２）、導電性高分子からなる電解変位部Ｂ（参照符号：２０１’）および制御電極Ｂ（参照符号：２０３’）からなる高分子アクチュエータデバイスが開示されている。
In addition, Patent Document 3 is cited as a document that can be related to the present invention. Patent Document 3 discloses a polymer actuator device. 9 and its description include a control electrode A (reference numeral 203), an electrolytic displacement part A (reference numeral 201) made of a conductive polymer, an electrolyte part (reference numeral 202), and a high conductivity. A polymer actuator device comprising an electrolytic displacement part B (reference symbol: 201 ′) made of molecules and a control electrode B (reference symbol: 203 ′) is disclosed.
さらに、特許文献３の段落番号００７７には、導電性高分子としてはポリチオフェンが好ましいと記載されている。特許文献３の段落番号００７８には、高分子固体電解質としては、ポリフッ化ビニリデンなどのフッ素系高分子やその共重合体が用いられることが開示されている。さらに、その基本骨格に、スルホン酸を導入しても良いことが開示されている。
Furthermore, paragraph number 0077 of Patent Document 3 describes that polythiophene is preferable as the conductive polymer. Paragraph No. 0078 of Patent Document 3 discloses that a fluorine-based polymer such as polyvinylidene fluoride or a copolymer thereof is used as the polymer solid electrolyte. Furthermore, it is disclosed that sulfonic acid may be introduced into the basic skeleton.
上記導電性高分子アクチュエータには、導電性高分子としてポリアニリン、ポリピロール、ポリチオフェンおよびその誘導体が用いられているが、これらの導電性高分子膜とイオンゲルからなる固体電解質膜は相互の接着性が低い。そのため、導電性高分子膜とイオンゲルからなる固体電解質膜を積層させ屈曲型アクチュエータを形成した場合、その動作時に導電性高分子膜とイオンゲルからなる固体電解質膜が剥離しやすい。
In the conductive polymer actuator, polyaniline, polypyrrole, polythiophene and derivatives thereof are used as the conductive polymer, but the solid electrolyte film made of these conductive polymer film and ion gel has low mutual adhesiveness. . Therefore, when a bending type actuator is formed by laminating a solid electrolyte membrane made of a conductive polymer membrane and an ion gel, the solid electrolyte membrane made of the conductive polymer membrane and the ion gel is easy to peel off during the operation.
特許文献４は、電解質層及び電極層から選ばれる少なくとも１つが、ポリジオキシチオフェンと該ポリジオキシチオフェンにドープされたドーパントであって複数の酸基を有するドーパントとを含む導電性ポリマーと、スルホン酸基を有するポリマーと、を含有する導電層であることが有効であることを開示している。
Patent Document 4 discloses that at least one selected from an electrolyte layer and an electrode layer is a conductive polymer containing polydioxythiophene and a dopant doped in the polydioxythiophene having a plurality of acid groups, and sulfonic acid It is disclosed that a conductive layer containing a group-containing polymer is effective.
特許文献１～４の他、本発明に関連し得る文献として、特許文献５～７を挙げることができる。
In addition to Patent Documents 1 to 4, Patent Documents 5 to 7 can be cited as documents that may be relevant to the present invention.
従来の導電性高分子アクチュエータは、電解質層及び電極層から選ばれる少なくとも１つが、ポリジオキシチオフェンと該ポリジオキシチオフェンにドープされたドーパントであって複数の酸基を有するドーパントとを含む導電性ポリマーと、スルホン酸基を有するポリマーと、を含有する導電層であることによりイオンゲルからなる固体電解質膜との相互の接着性を向上させている。そのため、スルホン酸基を有するポリマーを含有しない場合と比較して、導電性高分子膜の機械的強度（ヤング率）が低下し、屈曲動作時に発生する力が小さくなってしまうといった課題があった。
A conventional conductive polymer actuator is a conductive polymer in which at least one selected from an electrolyte layer and an electrode layer includes polydioxythiophene and a dopant doped in the polydioxythiophene and having a plurality of acid groups And a polymer having a sulfonic acid group, the mutual adhesiveness between the solid electrolyte membrane made of ion gel is improved. Therefore, compared with the case where a polymer having a sulfonic acid group is not contained, there is a problem that the mechanical strength (Young's modulus) of the conductive polymer film is reduced and the force generated during the bending operation is reduced. .
本発明は、導電性高分子膜とイオンゲルからなる固体電解質膜相互の接着性が向上し、かつ導電性高分子膜の機械的強度（ヤング率）を低下させず、繰り返し動作させても劣化しない屈曲型導電性高分子アクチュエータを実現することを目的とする。さらに、このアクチュエータを実現するための製造方法を提供することを目的とする。
The present invention improves the adhesion between a solid electrolyte membrane made of a conductive polymer membrane and an ionic gel, does not lower the mechanical strength (Young's modulus) of the conductive polymer membrane, and does not deteriorate even when it is repeatedly operated. An object is to realize a bent conductive polymer actuator. Furthermore, it aims at providing the manufacturing method for implement | achieving this actuator.
本発明は、フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）の少なくとも一種以上を含む有機ポリマーとイオン液体との混合物からなる固体電解質膜と、前記固体電解質膜の少なくとも片面に形成された、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）の混合体からなる導電性高分子膜との積層構造を有する導電性高分子アクチュエータであって、前記導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体が含まれることを特徴とする導電性高分子アクチュエータを提供するものである。
The present invention relates to vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide ( PEO), a solid electrolyte membrane made of a mixture of an organic polymer containing at least one of polyacrylonitrile (PAN) and an ionic liquid, and polyethylene dioxythiophene (PEDOT) and polystyrene formed on at least one surface of the solid electrolyte membrane A conductive polymer actuator having a laminated structure with a conductive polymer film made of a mixture of sulfonic acid (PSS), wherein the conductive polymer film contains a perfluorosulfonic acid / PTFE copolymer Conductive polymer actu characterized by It is intended to provide a chromatography data.
また、本発明は、フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）の少なくとも一種以上を含む有機ポリマーとイオン液体との混合物からなる固体電解質膜と、前記固体電解質膜の少なくとも片面に形成された、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）の混合体からなる導電性高分子膜との積層構造を有する導電性高分子アクチュエータの製造方法であって、前記導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体を混合する工程と、前記固体電解質膜の少なくとも片面に前記導電性高分子膜を積層させる工程からなることを特徴とする導電性高分子アクチュエータの製造方法を提供するものである。
In addition, the present invention provides a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), poly A solid electrolyte membrane composed of a mixture of an organic polymer containing at least one of ethylene oxide (PEO) and polyacrylonitrile (PAN) and an ionic liquid, and polyethylene dioxythiophene (PEDOT) formed on at least one surface of the solid electrolyte membrane Is a method of manufacturing a conductive polymer actuator having a laminated structure of a conductive polymer film made of a mixture of polystyrene sulfonic acid (PSS), in which both perfluorosulfonic acid / PTFE are contained in the conductive polymer film. Mixing the polymer, and the solid electrolysis There is provided a method for producing a conductive polymer actuator characterized by comprising the step of laminating the conductive polymer film on at least one side of the membrane.
なお、前記固体電解質膜の両面に前記導電性高分子膜が形成されていることが好ましい。
In addition, it is preferable that the said conductive polymer film is formed on both surfaces of the said solid electrolyte membrane.
本発明の上記目的、他の目的、特徴および利点は、添付図面参照の下、以下の好適な実施態様の詳細な説明から明らかにされる。
The above object, other objects, features, and advantages of the present invention will become apparent from the following detailed description of preferred embodiments with reference to the accompanying drawings.
本発明によれば、導電性高分子膜とイオンゲルからなる固体電解質膜相互の接着性が向上し、かつ導電性高分子膜の機械的強度（ヤング率）を低下させず、繰り返し動作させても劣化しない屈曲型導電性高分子アクチュエータが実現する。
According to the present invention, the adhesion between the solid electrolyte membrane made of the conductive polymer membrane and the ionic gel is improved, and the mechanical strength (Young's modulus) of the conductive polymer membrane is not lowered, and it can be operated repeatedly. A bending-type conductive polymer actuator that does not deteriorate is realized.
以下に、本発明の実施の形態について、図面を参照しながら説明する。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、本発明による実施形態のアクチュエータの模式断面図である。アクチュエータ１０１は、導電性高分子膜１０２ａおよび１０２ｂ、固体電解質膜１０３の積層体から成り、導電性高分子膜１０２ａおよび１０２ｂの一端を挟むように電極１０５ａおよび１０５ｂが設置されている。電極１０５ａと電極１０５ｂ間に数ボルトの電圧を印加することによりアクチュエータ１０１は電極１０５ａおよび１０５ｂで挟持された部分を固定部として屈曲動作する。
FIG. 1 is a schematic cross-sectional view of an actuator according to an embodiment of the present invention. The actuator 101 is composed of a laminate of conductive polymer films 102a and 102b and a solid electrolyte film 103, and electrodes 105a and 105b are installed so as to sandwich one end of the conductive polymer films 102a and 102b. By applying a voltage of several volts between the electrodes 105a and 105b, the actuator 101 bends with the portion sandwiched between the electrodes 105a and 105b as a fixed portion.
本発明に用いられる導電性高分子は、共役二重結合を有し、これによりπ電子が高分子全体に広がり電子導電性に寄与する。導電性高分子の電気伝導は、高分子中にドープされた酸化剤と高分子中のπ電子との相互作用により生成したポーラロンおよびバイポーラロンが荷電キャリアとなることにより起こるものと考えられている。本発明では導電性高分子に、ポリアニリン、ポリピロール、ポリチオフェンおよびその誘導体を用いることができるが、特に、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）を含むことが好ましく、さらに、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）の混合体を用いることが好ましい。
The conductive polymer used in the present invention has a conjugated double bond, so that π electrons spread throughout the polymer and contribute to electronic conductivity. Electrical conduction of conducting polymers is thought to occur when polarons and bipolarons generated by the interaction between oxidants doped in polymers and π electrons in the polymers become charge carriers. . In the present invention, polyaniline, polypyrrole, polythiophene, and derivatives thereof can be used as the conductive polymer. In particular, polyethylenedioxythiophene (PEDOT) is preferably included, and further, polyethylenedioxythiophene (PEDOT) and polystyrene are included. It is preferable to use a mixture of sulfonic acid (PSS).
ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）は、このモノマーを予め化学重合することが可能であるので、この高分子が分散した液を基板に塗布するだけで導電性高分子膜が形成可能である。このため、スピンコートやスリットコート、バーコート、ディップ、キャスト法を用いることで大面積基板に均一な厚みの高分子膜を容易に実現することができ、また、作製方法も簡単で量産化に適している。
Polyethylenedioxythiophene (PEDOT) can chemically polymerize this monomer in advance, so that a conductive polymer film can be formed simply by applying a liquid in which this polymer is dispersed to a substrate. For this reason, a polymer film with a uniform thickness can be easily realized on a large-area substrate by using spin coating, slit coating, bar coating, dip, and casting methods, and the manufacturing method is simple and mass production is possible. Is suitable.
前記導電性高分子を構成する混合体のポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）は、それぞれ［化１］および［化２］で表される。ポリエチレンジオキシチオフェンは、化学的に活性な五員環のβ位が予め酸素によって修飾され不活性化されているために酸化劣化を受けにくいという特徴を持っている。また、混合体において、ポリスチレンスルホン酸はポリエチレンジオキシチオフェンとイオン結合で強く結合している。
The polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) of the mixture constituting the conductive polymer are represented by [Chemical Formula 1] and [Chemical Formula 2], respectively. Polyethylenedioxythiophene has a feature that the β-position of a chemically active five-membered ring is preliminarily modified and inactivated by oxygen, and thus is less susceptible to oxidative degradation. In the mixture, polystyrene sulfonic acid is strongly bonded to polyethylene dioxythiophene by ionic bond.
導電性高分子膜と固体電解質膜の接着性を向上させるためには、導電性高分子にこの分子とは異なる有機分子を混入することが有効であることを本発明者らは見出した。特に、有機分子として、パーフルオロスルホン酸／ＰＴＦＥ共重合体を用いることでその接着性が際だって向上することを本発明者らは見出した。パーフルオロスルホン酸／ＰＴＦＥ共重合体を混合した導電性高分子膜は、導電性高分子分散液または溶液にパーフルオロスルホン酸／ＰＴＦＥ共重合体を分散させた液体を作製し、これを基板に塗布した後溶媒を乾燥することにより作製することができる。
In order to improve the adhesion between the conductive polymer membrane and the solid electrolyte membrane, the present inventors have found that it is effective to mix an organic molecule different from this molecule into the conductive polymer. In particular, the present inventors have found that by using a perfluorosulfonic acid / PTFE copolymer as an organic molecule, the adhesiveness is remarkably improved. A conductive polymer film in which perfluorosulfonic acid / PTFE copolymer is mixed is prepared by preparing a liquid in which perfluorosulfonic acid / PTFE copolymer is dispersed in a conductive polymer dispersion or solution, and this is applied to a substrate. It can be prepared by drying the solvent after coating.
導電性高分子分散液または溶液（導電性高分子固体含有率１重量％）に対するパーフルオロスルホン酸／ＰＴＦＥ共重合体の混合割合としては、０．０５重量％以上１０重量％以下が好ましく、さらに好ましくは０．１重量％以上５重量％以下である。この範囲よりも少ない場合、導電性高分子膜とイオンゲルからなる固体電解質膜の接着性の向上は得られず、作製したアクチュエータを動作した時に導電性高分子膜と固体電解質膜は剥離し、屈曲動作が困難となる。一方、この範囲よりも多い場合、導電性高分子を膜として得ることが困難になる。
The mixing ratio of the perfluorosulfonic acid / PTFE copolymer to the conductive polymer dispersion or solution (conductive polymer solid content 1% by weight) is preferably 0.05% by weight to 10% by weight, Preferably they are 0.1 weight% or more and 5 weight% or less. If the amount is less than this range, the adhesion of the solid electrolyte membrane composed of the conductive polymer membrane and the ionic gel cannot be improved, and when the manufactured actuator is operated, the conductive polymer membrane and the solid electrolyte membrane are peeled off and bent. Operation becomes difficult. On the other hand, when it exceeds this range, it becomes difficult to obtain a conductive polymer as a film.
本発明に用いられる固体電解質膜１０３は、イオン液体中に分散させたポリマーまたはモノマーの少なくともいずれか一方をゲル化させ、ゲルの三次元網目構造中にイオン液体を保持した、イオンゲルと名付けられた材料であり、柔軟性を持ち、かつ室温で電導率１０－２Ｓ／ｃｍという、従来のポリエーテル系高分子固体電解質の１００倍以上の値が達成されているものである。固体電解質膜としてイオンゲルを単独で用いることも出来るが、イオンゲルを紙やメンブレンフィルター等の多孔質膜に含浸させて用いることも出来る。
The solid electrolyte membrane 103 used in the present invention is named an ionic gel in which at least one of a polymer or a monomer dispersed in an ionic liquid is gelled and the ionic liquid is held in the three-dimensional network structure of the gel. It is a material that is flexible and has an electrical conductivity of 10 −2 S / cm at room temperature, which is at least 100 times that of conventional polyether polymer solid electrolytes. Although an ionic gel can be used alone as the solid electrolyte membrane, the ionic gel can also be used by impregnating a porous membrane such as paper or a membrane filter.
イオン液体は、常温溶融塩または単に溶融塩などとも称されるものであり、常温（室温）を含む幅広い温度域で溶融状態を示す塩である。
The ionic liquid is also called a room temperature molten salt or simply a molten salt, and is a salt that shows a molten state in a wide temperature range including normal temperature (room temperature).
本発明においては、従来から知られた各種のイオン液体を使用することができるが、常温（室温）または常温（室温）に近い温度において液体状態を示し安定なものが好ましい。
In the present invention, conventionally known various ionic liquids can be used, and those which show a liquid state and stable at a temperature close to room temperature (room temperature) or room temperature (room temperature) are preferable.
本発明において好ましく用いられるイオン液体として、下記の［化３］から［化６］で表されるカチオンと、アニオン（Ｘ－）よりなるものを例示する。
Examples of ionic liquids preferably used in the present invention include those composed of the following cations represented by [Chemical Formula 3] to [Chemical Formula 6] and anions (X − ).
上記の［化３］から［化６］において、Ｒは炭素数１～１２のアルキル基またはエーテル結合を含み炭素と酸素の合計数が３～１２のアルキル基を示し、［化３］においてＲ１は炭素数１～４のアルキル基または水素原子を示す。［化３］において、ＲとＲ１は異なることが好ましい。［化５］および［化６］において、ｘはそれぞれ１～４の整数である。本発明においては、［化３］で示されるイミダゾリウムイオンがより好適である。
In the above [Chemical Formula 3] to [Chemical Formula 6], R represents an alkyl group having 1 to 12 carbon atoms or an alkyl group having an ether bond and a total number of carbon and oxygen of 3 to 12, and in [Chemical Formula 3], R1 Represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. In [Chemical Formula 3], R and R1 are preferably different. In [Chemical Formula 5] and [Chemical Formula 6], x is an integer of 1 to 4, respectively. In the present invention, an imidazolium ion represented by [Chemical Formula 3] is more preferable.
アニオン（Ｘ－）としては、テトラフルオロホウ酸アニオン、ヘキサフルオロリン酸アニオン、ビス（トリフルオロメタンスルホニル）イミド酸アニオン、過塩素酸アニオン、トリス（トリフルオロメタンスルホニル）炭素酸アニオン、トリフルオロメタンスルホン酸アニオン、ジシアンアミドアニオン、トリフルオロ酢酸アニオン、有機カルボン酸アニオンおよびハロゲンイオンより選ばれる少なくとも１種が好ましい。
Examples of the anion (X − ) include a tetrafluoroborate anion, a hexafluorophosphate anion, a bis (trifluoromethanesulfonyl) imido anion, a perchlorate anion, a tris (trifluoromethanesulfonyl) carbonate anion, and a trifluoromethanesulfonate anion. , Dicyanamide anion, trifluoroacetate anion, organic carboxylate anion and halogen ion are preferred.
イオンゲルとなるゲル状組成物を得るのに用いることのできる有機ポリマーとしては、フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）が挙げられる。
Organic polymers that can be used to obtain a gel-like composition that becomes an ionic gel include vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), and perfluorosulfonic acid. / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide (PEO), and polyacrylonitrile (PAN).
また、イオン液体中にモノマー（例えばメタクリル酸メチル、ＭＭＡ）、架橋剤（例えばエチレングリコールジメタクリラート、ＥＧＤＭＡ）、重合開始剤（例えばアゾビスイソブチロニトリル、ＡＩＢＮ）を溶解させ、イオン液体中で重合反応を行うことによって有機ポリマーを形成しても、イオンゲルとなるゲル状組成物を得ることができる。
In addition, a monomer (for example, methyl methacrylate, MMA), a crosslinking agent (for example, ethylene glycol dimethacrylate, EGDMA), and a polymerization initiator (for example, azobisisobutyronitrile, AIBN) are dissolved in the ionic liquid. Even if an organic polymer is formed by carrying out a polymerization reaction in step 1, a gel composition that becomes an ionic gel can be obtained.
固体電解質は、上記イオン液体と、上記ポリマーまたはモノマーの少なくとも一方とを混合してイオンゲル前駆体を調製し、これを加熱した後冷却することで得られるが、強度およびイオン導電性の観点から鑑みて、イオン液体と有機ポリマーの場合、重量比は９：１～６：４であることが好ましく、８：２～７：３であることがより好ましい。また、イオン液体とモノマーの場合、モル比は３：７～７：３が好ましく、４：６～６：４であることがより好ましい。
The solid electrolyte is obtained by mixing the ionic liquid and at least one of the polymer or monomer to prepare an ionic gel precursor, heating it, and then cooling it, but from the viewpoint of strength and ionic conductivity. In the case of an ionic liquid and an organic polymer, the weight ratio is preferably 9: 1 to 6: 4, and more preferably 8: 2 to 7: 3. In the case of the ionic liquid and the monomer, the molar ratio is preferably 3: 7 to 7: 3, and more preferably 4: 6 to 6: 4.
電極は、電子伝導性を持ち、導電性高分子と化学反応することなく容易に導電性高分子と電子の授受を行うものであれば良く、金、銀、白金、銅、クロム等の金属、および炭素含有板を用いることができる。
The electrode may be any material that has electronic conductivity and can easily exchange electrons with the conductive polymer without chemically reacting with the conductive polymer, such as gold, silver, platinum, copper, and chromium, And carbon-containing plates can be used.
以下、実施例を挙げて本発明によるアクチュエータをさらに詳細に説明するが、本発明はこれに限定されるものではない。
Hereinafter, the actuator according to the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
（実施例１）
［有機分子が混合された導電性高分子膜作製］
アセトン洗浄後酸素プラズマ処理したスライドグラス上に、５重量％のジメチルスルホキシド（ＤＭＳＯ）、１重量％のパーフルオロスルホン酸／ＰＴＦＥ共重合体１０％水分散液を混合したＰＥＤＯＴとＰＳＳ混合体の水分散液（スタルク社製、商品名バイトロンＰＨ５００）を所定量滴下した。その後、室温で自然乾燥して溶媒を揮発させ、スライドグラス上に導電性高分子膜を形成した。最後に、剃刀を用いて導電性高分子膜をスライドグラスから剥離した。得られた導電性高分子膜は平均厚さ１０μｍ、四端針法を用いて測定した導電率は２８０Ｓ／ｃｍであった。 Example 1
[Preparation of conductive polymer film mixed with organic molecules]
Water of PEDOT and PSS mixture in which 5% by weight of dimethyl sulfoxide (DMSO) and 1% by weight of perfluorosulfonic acid / PTFE copolymer 10% aqueous dispersion were mixed on a glass slide treated with oxygen plasma after acetone cleaning. A predetermined amount of a dispersion (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped. Then, it was naturally dried at room temperature to evaporate the solvent, and a conductive polymer film was formed on the slide glass. Finally, the conductive polymer film was peeled from the slide glass using a razor. The obtained conductive polymer film had an average thickness of 10 μm, and the conductivity measured using a four-end needle method was 280 S / cm.
［有機分子が混合された導電性高分子膜作製］
アセトン洗浄後酸素プラズマ処理したスライドグラス上に、５重量％のジメチルスルホキシド（ＤＭＳＯ）、１重量％のパーフルオロスルホン酸／ＰＴＦＥ共重合体１０％水分散液を混合したＰＥＤＯＴとＰＳＳ混合体の水分散液（スタルク社製、商品名バイトロンＰＨ５００）を所定量滴下した。その後、室温で自然乾燥して溶媒を揮発させ、スライドグラス上に導電性高分子膜を形成した。最後に、剃刀を用いて導電性高分子膜をスライドグラスから剥離した。得られた導電性高分子膜は平均厚さ１０μｍ、四端針法を用いて測定した導電率は２８０Ｓ／ｃｍであった。 Example 1
[Preparation of conductive polymer film mixed with organic molecules]
Water of PEDOT and PSS mixture in which 5% by weight of dimethyl sulfoxide (DMSO) and 1% by weight of perfluorosulfonic acid / PTFE copolymer 10% aqueous dispersion were mixed on a glass slide treated with oxygen plasma after acetone cleaning. A predetermined amount of a dispersion (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped. Then, it was naturally dried at room temperature to evaporate the solvent, and a conductive polymer film was formed on the slide glass. Finally, the conductive polymer film was peeled from the slide glass using a razor. The obtained conductive polymer film had an average thickness of 10 μm, and the conductivity measured using a four-end needle method was 280 S / cm.
［イオンゲル原料調製］
イオンゲルを作製するためのイオン液体には、カチオンとして、エチルメチルイミダゾリウム（ＥＭＩ）、アニオンとして、ビス（トリフルオロメタンスルホニル）イミド［（ＣＦ３ＳＯ２）２Ｎ－］（ＴＦＳＩ）を用いた。混合するポリマーとしてはフッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］を用いた。ＥＭＩＴＦＳＩとＰ（ＶＤＦ／ＨＦＰ）混合比は重量比で８：２とし、混合した後マグネチックスターラーを用いて十分攪拌した。以下、この混合液をイオンゲル前駆体と記す。 [Ion gel raw material preparation]
In the ionic liquid for producing the ion gel, ethylmethylimidazolium (EMI) was used as a cation, and bis (trifluoromethanesulfonyl) imide [(CF 3 SO 2 ) 2 N − ] (TFSI) was used as an anion. As the polymer to be mixed, a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] was used. The mixing ratio of EMITFSI and P (VDF / HFP) was 8: 2, and after mixing, the mixture was sufficiently stirred using a magnetic stirrer. Hereinafter, this mixed solution is referred to as an ion gel precursor.
イオンゲルを作製するためのイオン液体には、カチオンとして、エチルメチルイミダゾリウム（ＥＭＩ）、アニオンとして、ビス（トリフルオロメタンスルホニル）イミド［（ＣＦ３ＳＯ２）２Ｎ－］（ＴＦＳＩ）を用いた。混合するポリマーとしてはフッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］を用いた。ＥＭＩＴＦＳＩとＰ（ＶＤＦ／ＨＦＰ）混合比は重量比で８：２とし、混合した後マグネチックスターラーを用いて十分攪拌した。以下、この混合液をイオンゲル前駆体と記す。 [Ion gel raw material preparation]
In the ionic liquid for producing the ion gel, ethylmethylimidazolium (EMI) was used as a cation, and bis (trifluoromethanesulfonyl) imide [(CF 3 SO 2 ) 2 N − ] (TFSI) was used as an anion. As the polymer to be mixed, a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] was used. The mixing ratio of EMITFSI and P (VDF / HFP) was 8: 2, and after mixing, the mixture was sufficiently stirred using a magnetic stirrer. Hereinafter, this mixed solution is referred to as an ion gel precursor.
［電解質イオンゲル作製］
厚み０．１ｍｍのポリエチレンテレフタレート（ＰＥＴ）シートを７６ｍｍ×２６ｍｍの大きさに裁断し、これを大きさ７６ｍｍ×２６ｍｍのスライドグラスに密着させた。これを２組作製した。そして、二つのＰＥＴシートが所定の間隔を空けて対向するように、４０μｍ厚のコンデンサセパレータ紙を挟んで作製したスライドガラスを密着させた。この時、コンデンサセパレータ紙にイオンゲル前駆体を含浸させておいた。その後、恒温槽にて１００℃、３０分間加熱し、その後室温に冷却することで厚さ４０μｍのイオンゲル含浸紙を得た。ＰＥＴシートとイオンゲル含浸紙は相互の接着性が極めて低いため容易に剥離できた。以下、ここで得られたイオンゲル含浸紙を電解質イオンゲルと記す。 [Preparation of electrolyte ion gel]
A polyethylene terephthalate (PET) sheet having a thickness of 0.1 mm was cut into a size of 76 mm × 26 mm, and this was closely attached to a slide glass having a size of 76 mm × 26 mm. Two sets of this were produced. Then, a slide glass produced by sandwiching a capacitor separator paper having a thickness of 40 μm was adhered so that the two PET sheets face each other with a predetermined gap therebetween. At this time, the capacitor separator paper was impregnated with an ion gel precursor. Thereafter, the mixture was heated at 100 ° C. for 30 minutes in a thermostatic bath, and then cooled to room temperature to obtain an ion gel-impregnated paper having a thickness of 40 μm. The PET sheet and the ionic gel-impregnated paper were easily peeled off because of their extremely low adhesiveness to each other. Hereinafter, the ion gel-impregnated paper obtained here is referred to as electrolyte ion gel.
厚み０．１ｍｍのポリエチレンテレフタレート（ＰＥＴ）シートを７６ｍｍ×２６ｍｍの大きさに裁断し、これを大きさ７６ｍｍ×２６ｍｍのスライドグラスに密着させた。これを２組作製した。そして、二つのＰＥＴシートが所定の間隔を空けて対向するように、４０μｍ厚のコンデンサセパレータ紙を挟んで作製したスライドガラスを密着させた。この時、コンデンサセパレータ紙にイオンゲル前駆体を含浸させておいた。その後、恒温槽にて１００℃、３０分間加熱し、その後室温に冷却することで厚さ４０μｍのイオンゲル含浸紙を得た。ＰＥＴシートとイオンゲル含浸紙は相互の接着性が極めて低いため容易に剥離できた。以下、ここで得られたイオンゲル含浸紙を電解質イオンゲルと記す。 [Preparation of electrolyte ion gel]
A polyethylene terephthalate (PET) sheet having a thickness of 0.1 mm was cut into a size of 76 mm × 26 mm, and this was closely attached to a slide glass having a size of 76 mm × 26 mm. Two sets of this were produced. Then, a slide glass produced by sandwiching a capacitor separator paper having a thickness of 40 μm was adhered so that the two PET sheets face each other with a predetermined gap therebetween. At this time, the capacitor separator paper was impregnated with an ion gel precursor. Thereafter, the mixture was heated at 100 ° C. for 30 minutes in a thermostatic bath, and then cooled to room temperature to obtain an ion gel-impregnated paper having a thickness of 40 μm. The PET sheet and the ionic gel-impregnated paper were easily peeled off because of their extremely low adhesiveness to each other. Hereinafter, the ion gel-impregnated paper obtained here is referred to as electrolyte ion gel.
［電解質イオンゲル－導電性高分子膜の積層］
電解質イオンゲルの両面に導電性高分子膜を対向させて重ね、恒温槽にて１００℃、３０分間加熱し、その後室温に冷却することで、導電性高分子膜／電解質イオンゲル／導電性高分子膜の三層構造体を形成した。この三層構造体を幅２．５ｍｍ、長さ１５ｍｍに裁断し、一端部から長手方向に５ｍｍの領域に幅２ｍｍ、長さ１０ｍｍの白金電極を取り付け、可動部長さ１０ｍｍの屈曲型導電性高分子アクチュエータを作製した。 [Lamination of electrolyte ion gel-conductive polymer film]
Conductive polymer film / electrolyte ion gel / conductive polymer film is formed by superposing conductive polymer films on both sides of the electrolyte ion gel so as to be opposed to each other, heating in a thermostatic bath at 100 ° C. for 30 minutes, and then cooling to room temperature. The three-layer structure was formed. This three-layer structure is cut to a width of 2.5 mm and a length of 15 mm, a platinum electrode having a width of 2 mm and a length of 10 mm is attached to a region of 5 mm in the longitudinal direction from one end portion, and a bending type conductive high height having a movable portion length of 10 mm is attached. A molecular actuator was fabricated.
電解質イオンゲルの両面に導電性高分子膜を対向させて重ね、恒温槽にて１００℃、３０分間加熱し、その後室温に冷却することで、導電性高分子膜／電解質イオンゲル／導電性高分子膜の三層構造体を形成した。この三層構造体を幅２．５ｍｍ、長さ１５ｍｍに裁断し、一端部から長手方向に５ｍｍの領域に幅２ｍｍ、長さ１０ｍｍの白金電極を取り付け、可動部長さ１０ｍｍの屈曲型導電性高分子アクチュエータを作製した。 [Lamination of electrolyte ion gel-conductive polymer film]
Conductive polymer film / electrolyte ion gel / conductive polymer film is formed by superposing conductive polymer films on both sides of the electrolyte ion gel so as to be opposed to each other, heating in a thermostatic bath at 100 ° C. for 30 minutes, and then cooling to room temperature. The three-layer structure was formed. This three-layer structure is cut to a width of 2.5 mm and a length of 15 mm, a platinum electrode having a width of 2 mm and a length of 10 mm is attached to a region of 5 mm in the longitudinal direction from one end portion, and a bending type conductive high height having a movable portion length of 10 mm is attached. A molecular actuator was fabricated.
屈曲変位量は、レーザー変位計を用いた三角測定で評価した。三角測定の測定点は、電極取付け部から長さ方向に５ｍｍの位置とした。
Bending displacement was evaluated by triangulation using a laser displacement meter. The measurement point of the triangular measurement was set at a position of 5 mm in the length direction from the electrode mounting portion.
このアクチュエータに±１．０Ｖの電圧を印加したところ、電解質イオンゲル－導電性高分子膜界面で剥離することなく印加電圧に応答した屈曲動作をした。１Ｈｚの矩形波で駆動した際の変位量を表１に示す。
When a voltage of ± 1.0 V was applied to this actuator, the bending action responded to the applied voltage without peeling at the electrolyte ion gel-conductive polymer film interface. Table 1 shows the amount of displacement when driven by a 1 Hz rectangular wave.
表１から、この構成の屈曲型導電性高分子アクチュエータは導電性高分子膜と固体電解質膜の接着性に優れ、長期動作可能であることが示された。
From Table 1, it was shown that the bent type conductive polymer actuator having this configuration has excellent adhesion between the conductive polymer film and the solid electrolyte film, and can be operated for a long time.
（比較例１）
アセトン洗浄後酸素プラズマ処理したスライドグラス上に、５重量％のジメチルスルホキシド（ＤＭＳＯ）を溶解したＰＥＤＯＴとＰＳＳ混合体の水分散液（スタルク社製、商品名バイトロンＰＨ５００）を所定量滴下した。その後、室温で自然乾燥して溶媒を揮発させ、スライドグラス上に導電性高分子膜を形成した。最後に、剃刀を用いて導電性高分子膜をスライドグラスから剥離した。 (Comparative Example 1)
A predetermined amount of an aqueous dispersion of PEDOT and PSS mixture in which 5% by weight of dimethyl sulfoxide (DMSO) was dissolved (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped onto a slide glass treated with oxygen plasma after acetone cleaning. Then, it was naturally dried at room temperature to evaporate the solvent, and a conductive polymer film was formed on the slide glass. Finally, the conductive polymer film was peeled from the slide glass using a razor.
アセトン洗浄後酸素プラズマ処理したスライドグラス上に、５重量％のジメチルスルホキシド（ＤＭＳＯ）を溶解したＰＥＤＯＴとＰＳＳ混合体の水分散液（スタルク社製、商品名バイトロンＰＨ５００）を所定量滴下した。その後、室温で自然乾燥して溶媒を揮発させ、スライドグラス上に導電性高分子膜を形成した。最後に、剃刀を用いて導電性高分子膜をスライドグラスから剥離した。 (Comparative Example 1)
A predetermined amount of an aqueous dispersion of PEDOT and PSS mixture in which 5% by weight of dimethyl sulfoxide (DMSO) was dissolved (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped onto a slide glass treated with oxygen plasma after acetone cleaning. Then, it was naturally dried at room temperature to evaporate the solvent, and a conductive polymer film was formed on the slide glass. Finally, the conductive polymer film was peeled from the slide glass using a razor.
実施例１と同様にして作製した電解質イオンゲルの両面に導電性高分子膜を重ね、恒温槽にて１００℃、３０分間加熱し、その後室温に冷却することで導電性高分子膜と電解質イオンゲルを接着して三層構造体を形成した。この三層構造体を幅２．５ｍｍ、長さ１５ｍｍに裁断し、一端部から長手方向に５ｍｍの領域に幅２ｍｍ、長さ１０ｍｍの白金電極を取り付け、可動部長さ１０ｍｍの屈曲型導電性高分子アクチュエータを作製した。
Conductive polymer membranes are laminated on both sides of the electrolyte ion gel produced in the same manner as in Example 1, heated at 100 ° C. for 30 minutes in a thermostatic bath, and then cooled to room temperature, whereby the conductive polymer membrane and the electrolyte ion gel are cooled. A three-layer structure was formed by bonding. This three-layer structure is cut to a width of 2.5 mm and a length of 15 mm, a platinum electrode having a width of 2 mm and a length of 10 mm is attached to a region of 5 mm in the longitudinal direction from one end portion, and a bending type conductive high height having a movable portion length of 10 mm is attached. A molecular actuator was fabricated.
このアクチュエータは、電解質イオンゲルと導電性高分子膜の接着性が極めて低く、±１．０Ｖの電圧を印加したところ、電解質イオンゲル－導電性高分子膜界面で剥離を起こして印加電圧に応答した屈曲動作をせず、変位量は１Ｈｚの矩形波で初期の１０回平均変位量が０．０５ｍｍ以下であった。
This actuator has extremely low adhesiveness between the electrolyte ion gel and the conductive polymer film, and when a voltage of ± 1.0 V is applied, peeling occurs at the interface between the electrolyte ion gel and the conductive polymer film, and the bending responds to the applied voltage. Without operation, the displacement was a 1 Hz rectangular wave and the initial 10-time average displacement was 0.05 mm or less.
（比較例２）
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：２．２重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 2)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 2.2 parts by weight
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：２．２重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 2)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 2.2 parts by weight
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
（比較例３）
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：４．４重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 3)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 4.4 parts by weight,
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：４．４重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 3)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 4.4 parts by weight,
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
（比較例４）
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：８．８重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 4)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 8.8 parts by weight,
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
ポリ（３，４－エチレンジオキシチオフェン）－ポリ（スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）の水分散液（固形分１．２質量％、スタルク社製、Ｂａｙｔｒｏｎ Ｐ ＨＣ Ｖ４）：１００重量部、
スルホン酸変性水分散型ポリエステル樹脂（固形分２７質量％、東洋紡社製、ＶＹＬＯＮＡＬ ＭＤ－１９８５）：８．８重量部、
Ｎ－メチルピロリドン：５重量部、
をホモジナイザーを用いて混合及び分散して、スルホン酸基を有するポリマーを含む導電層用ペーストを得、これをガラス基板上に展開し、８０℃で３０分の加熱により乾燥及び架橋させて導電性高分子膜を形成した。 (Comparative Example 4)
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) aqueous dispersion (solid content 1.2% by mass, manufactured by Starck, Baytron P HC V4): 100 parts by weight
Sulfonic acid-modified water-dispersed polyester resin (solid content 27% by mass, manufactured by Toyobo Co., Ltd., VYLONAL MD-1985): 8.8 parts by weight,
N-methylpyrrolidone: 5 parts by weight
Are mixed and dispersed using a homogenizer to obtain a conductive layer paste containing a polymer having a sulfonic acid group, which is spread on a glass substrate, dried and crosslinked by heating at 80 ° C. for 30 minutes, and conductive. A polymer film was formed.
［導電性高分子膜の機械的強度］
表２に、実施例１、比較例１～４で作製した導電性高分子膜の機械的強度（ヤング率）を示す。なお、表２に示すヤング率は、１％伸長時におけるヤング率（単位ＧＰａ）である。 [Mechanical strength of conductive polymer film]
Table 2 shows the mechanical strength (Young's modulus) of the conductive polymer films prepared in Example 1 and Comparative Examples 1 to 4. The Young's modulus shown in Table 2 is the Young's modulus (unit GPa) at 1% elongation.
表２に、実施例１、比較例１～４で作製した導電性高分子膜の機械的強度（ヤング率）を示す。なお、表２に示すヤング率は、１％伸長時におけるヤング率（単位ＧＰａ）である。 [Mechanical strength of conductive polymer film]
Table 2 shows the mechanical strength (Young's modulus) of the conductive polymer films prepared in Example 1 and Comparative Examples 1 to 4. The Young's modulus shown in Table 2 is the Young's modulus (unit GPa) at 1% elongation.
表２より、ＰＥＤＯＴとＰＳＳ混合体の水分散液にパーフルオロスルホン酸／ＰＴＦＥ共重合体１０％水分散液を混合することにより、導電性高分子膜とイオンゲルからなる固体電解質膜相互の接着性が向上し、かつ導電性高分子膜の機械的強度（ヤング率）を低下させず、繰り返し動作させても劣化しない屈曲型導電性高分子アクチュエータが実現することが示された。
From Table 2, by mixing a 10% aqueous dispersion of perfluorosulfonic acid / PTFE copolymer with an aqueous dispersion of PEDOT and PSS mixture, the adhesiveness between the conductive polymer membrane and the solid electrolyte membrane made of ion gel It has been shown that a bent type conductive polymer actuator is realized that does not deteriorate even when repeatedly operated without reducing the mechanical strength (Young's modulus) of the conductive polymer film.
上記説明から、当業者にとっては、本発明の多くの改良や他の実施の形態が明らかである。したがって、上記説明は例示としてのみ解釈されるべきであり、本発明を実行する最良の態様を当業者に教示する目的で提供されたものである。本発明の精神を逸脱することなく、その構造および／または機能の詳細を実質的に変更できる。
From the above description, many modifications and other embodiments of the present invention are apparent to persons skilled in the art. Accordingly, the foregoing description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.
本発明によれば、小型かつ軽量で柔軟性に富む高信頼性のアクチュエータを簡便に製造することが可能となり、医療、産業、および家庭用のロボット、またはマイクロマシンなどの分野において好適に用いることができる。
According to the present invention, it is possible to easily manufacture a highly reliable actuator that is small, light and flexible, and can be suitably used in fields such as medical, industrial, and home robots or micromachines. it can.
１０１ アクチュエータ素子
１０２ａ 導電性高分子膜
１０２ｂ 導電性高分子膜
１０３ 固体電解質膜
１０４ａ 電極
１０４ｂ 電極
２０１ アクチュエータ素子
２０２ａ 導電性高分子膜
２０２ｂ 導電性高分子膜
２０３ 固体電解質膜
２０４ａ 電極
２０４ｂ 電極 DESCRIPTION OFSYMBOLS 101 Actuator element 102a Conductive polymer film 102b Conductive polymer film 103 Solid electrolyte film 104a Electrode 104b Electrode 201 Actuator element 202a Conductive polymer film 202b Conductive polymer film 203 Solid electrolyte film 204a Electrode 204b Electrode
１０２ａ 導電性高分子膜
１０２ｂ 導電性高分子膜
１０３ 固体電解質膜
１０４ａ 電極
１０４ｂ 電極
２０１ アクチュエータ素子
２０２ａ 導電性高分子膜
２０２ｂ 導電性高分子膜
２０３ 固体電解質膜
２０４ａ 電極
２０４ｂ 電極 DESCRIPTION OF
Claims (8)
- 屈曲型導電性高分子アクチュエータの駆動方法であって、
前記駆動方法は、
前記屈曲型導電性高分子アクチュエータを用意する工程、および
ここで、前記屈曲型導電性高分子アクチュエータは、
一対の電極と、
前記一対の電極の間に挟まれる積層構造と、
を具備しており、
前記積層構造は、
フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）の少なくとも一種以上を含む有機ポリマーとイオン液体との混合物からなる固体電解質膜と、
前記固体電解質膜の少なくとも片面に形成された、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合体からなり、さらにパーフルオロスルホン酸／ＰＴＦＥ共重合体を含む導電性高分子膜と、
を具備し、
前記一対の電極に電圧を印加する工程
を有する、屈曲型導電性高分子アクチュエータの駆動方法。 A driving method for a bending type conductive polymer actuator,
The driving method is:
Preparing the bent conductive polymer actuator, and wherein the bent conductive polymer actuator comprises:
A pair of electrodes;
A laminated structure sandwiched between the pair of electrodes;
It has
The laminated structure is
Vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide (PEO), poly A solid electrolyte membrane made of a mixture of an organic polymer containing at least one acrylonitrile (PAN) and an ionic liquid;
A conductive polymer film comprising a mixture of polyethylenedioxythiophene (PEDOT) and polystyrenesulfonic acid (PSS) formed on at least one surface of the solid electrolyte film, and further comprising a perfluorosulfonic acid / PTFE copolymer When,
Comprising
A method for driving a bent conductive polymer actuator, comprising a step of applying a voltage to the pair of electrodes. - 前記固体電解質膜の両面に前記導電性高分子膜が形成されている、請求項２に記載の屈曲型導電性高分子アクチュエータの駆動方法。 The method for driving a bent conductive polymer actuator according to claim 2, wherein the conductive polymer film is formed on both surfaces of the solid electrolyte film.
- 第１電極、固体電解質膜、導電性高分子膜、および第２電極が順に積層された積層体からなる屈曲型導電性高分子アクチュエータであって、
前記固体電解質膜は、有機ポリマーとイオン液体との混合物からなり、
前記有機ポリマーは、フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）の少なくとも一種以上を含み、
前記導電性高分子膜は、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合体からなり、さらに
前記導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体が含まれることを特徴とする、
屈曲型導電性高分子アクチュエータ。 A bending type conductive polymer actuator comprising a laminate in which a first electrode, a solid electrolyte membrane, a conductive polymer membrane, and a second electrode are sequentially laminated,
The solid electrolyte membrane is composed of a mixture of an organic polymer and an ionic liquid,
The organic polymer includes vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide. (PEO), including at least one polyacrylonitrile (PAN),
The conductive polymer film is composed of a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and the conductive polymer film further includes a perfluorosulfonic acid / PTFE copolymer. It is characterized by
Bending type conductive polymer actuator. - 請求項３に記載の屈曲型導電性高分子アクチュエータであって、
前記第１電極と前記固体電解質膜との間に、第２の導電性高分子膜を具備し、
前記第２の導電性高分子膜は、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合体からなり、さらに
前記第２の導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体が含まれることを特徴とする、
屈曲型導電性高分子アクチュエータ。 The bending type conductive polymer actuator according to claim 3,
A second conductive polymer film is provided between the first electrode and the solid electrolyte film,
The second conductive polymer film is composed of a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and the second conductive polymer film includes perfluorosulfonic acid / PTFE. A copolymer is included,
Bending type conductive polymer actuator. - 請求項３に記載の屈曲型導電性高分子アクチュエータであって、
前記有機ポリマーは、前記フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］である、
屈曲型導電性高分子アクチュエータ。 The bending type conductive polymer actuator according to claim 3,
The organic polymer is the vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)].
Bending type conductive polymer actuator. - 屈曲型導電性高分子アクチュエータの製造方法であって、
屈曲型導電性高分子アクチュエータは、第１電極、固体電解質膜、導電性高分子膜、および第２電極が順に積層された積層体からなり、
前記固体電解質膜は、有機ポリマーとイオン液体との混合物からなり、
前記有機ポリマーは、フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］、ポリフッ化ビニリデン（ＰＶＤＦ）、パーフルオロスルホン酸／ＰＴＦＥ共重合体、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンオキシド（ＰＥＯ）、ポリアクリロニトリル（ＰＡＮ）の少なくとも一種以上を含み、
前記導電性高分子膜は、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合体からなり、さらに
前記導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体が含まれ、
前記屈曲型導電性高分子アクチュエータの製造方法は、
前記導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体を混合する工程と、
前記固体電解質膜の少なくとも片面に前記導電性高分子膜を積層する工程と
を有することを特徴とする屈曲型導電性高分子アクチュエータの製造方法。 A method for producing a bent conductive polymer actuator,
The bending type conductive polymer actuator is composed of a laminate in which a first electrode, a solid electrolyte membrane, a conductive polymer membrane, and a second electrode are sequentially laminated,
The solid electrolyte membrane is composed of a mixture of an organic polymer and an ionic liquid,
The organic polymer includes vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)], polyvinylidene fluoride (PVDF), perfluorosulfonic acid / PTFE copolymer, polymethyl methacrylate (PMMA), polyethylene oxide. (PEO), including at least one polyacrylonitrile (PAN),
The conductive polymer film is composed of a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and further includes a perfluorosulfonic acid / PTFE copolymer in the conductive polymer film. ,
The manufacturing method of the bent conductive polymer actuator is as follows:
Mixing a perfluorosulfonic acid / PTFE copolymer in the conductive polymer film;
And a step of laminating the conductive polymer film on at least one surface of the solid electrolyte membrane. - 請求項６記載の屈曲型導電性高分子アクチュエータの製造方法であって、
前記第１電極と前記固体電解質膜との間に、第２の導電性高分子膜を具備し、
前記第２の導電性高分子膜は、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合体からなり、さらに
前記第２の導電性高分子膜中にパーフルオロスルホン酸／ＰＴＦＥ共重合体が含まれ、
前記導電性高分子膜を積層させる工程においては、前記固体電解質膜の両面に前記導電性高分子膜を積層させることによって、前記導電性高分子膜および前記第２の導電性高分子膜が形成される、
屈曲型導電性高分子アクチュエータの製造方法。 It is a manufacturing method of the bending type conductive polymer actuator according to claim 6,
A second conductive polymer film is provided between the first electrode and the solid electrolyte film,
The second conductive polymer film is composed of a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and the second conductive polymer film includes perfluorosulfonic acid / PTFE. A copolymer,
In the step of laminating the conductive polymer film, the conductive polymer film and the second conductive polymer film are formed by laminating the conductive polymer film on both surfaces of the solid electrolyte film. To be
A manufacturing method of a bending type conductive polymer actuator. - 請求項６に記載の屈曲型導電性高分子アクチュエータの製造方法であって、
前記有機ポリマーは、前記フッ化ビニリデン／ヘキサフルオロプロピレン共重合体［Ｐ（ＶＤＦ／ＨＦＰ）］である、
屈曲型導電性高分子アクチュエータの製造方法。 It is a manufacturing method of the bending type conductive polymer actuator according to claim 6,
The organic polymer is the vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)].
A manufacturing method of a bending type conductive polymer actuator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2009/004131 WO2011024219A1 (en) | 2009-08-26 | 2009-08-26 | Electroconductive polymer actuator, method for driving the electroconductive polymer actuator, and method for manufacturing the electroconductive polymer actuator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2009/004131 WO2011024219A1 (en) | 2009-08-26 | 2009-08-26 | Electroconductive polymer actuator, method for driving the electroconductive polymer actuator, and method for manufacturing the electroconductive polymer actuator |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007329334A (en) * | 2006-06-08 | 2007-12-20 | Univ Of Fukui | High molecular actuator and its manufacturing method |
| JP4287504B1 (en) * | 2008-08-15 | 2009-07-01 | パナソニック株式会社 | Conductive polymer actuator and manufacturing method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007329334A (en) * | 2006-06-08 | 2007-12-20 | Univ Of Fukui | High molecular actuator and its manufacturing method |
| JP4287504B1 (en) * | 2008-08-15 | 2009-07-01 | パナソニック株式会社 | Conductive polymer actuator and manufacturing method thereof |
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