WO2010018612A1 - 導電性高分子アクチュエータおよびその製造方法 - Google Patents
導電性高分子アクチュエータおよびその製造方法 Download PDFInfo
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- WO2010018612A1 WO2010018612A1 PCT/JP2008/002219 JP2008002219W WO2010018612A1 WO 2010018612 A1 WO2010018612 A1 WO 2010018612A1 JP 2008002219 W JP2008002219 W JP 2008002219W WO 2010018612 A1 WO2010018612 A1 WO 2010018612A1
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- conductive polymer
- solid electrolyte
- film
- organic polymer
- actuator
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S310/00—Electrical generator or motor structure
- Y10S310/80—Piezoelectric polymers, e.g. PVDF
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/42—Piezoelectric device making
Definitions
- 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.
- 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. For example, in the configuration shown in 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 conductive film is turned downward. When ions are extracted from the conductive polymer film or ions are taken into the lower conductive polymer film, the film bends upward.
- 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 at least one of polymers or monomers dispersed in the ionic liquid is gelled, a material holding an ionic liquid into a three-dimensional network structure of the gel has a softness, and at room temperature for 10 - The value of 2 S / cm, which is 100 times or more that of the conventional polyether polymer solid electrolyte, is achieved.
- Patent Document 2 Other documents that may be relevant to the present invention include Patent Document 3 and Patent Document 4.
- Patent Document 3 discloses a polymer actuator device.
- FIG. 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 conductive polymer.
- a polymer actuator device comprising an electrolytic displacement portion B (reference numeral 201 ′) and a control electrode B (reference numeral 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.
- Patent Document 4 discloses a conductive polymer gel and a method for producing the same, an actuator, a patch label for ion introduction, and a bioelectrode.
- paragraph No. 0069 (Example 7) of Patent Document 4 poly (3,4-ethylenedioxythiophene) -poly (ethylenesulfonic acid) colloidal dispersion (abbreviated as PEDOT / PSS) The addition of alcohol is disclosed.
- PEDOT / PSS poly (3,4-ethylenedioxythiophene) -poly (ethylenesulfonic acid) colloidal dispersion
- An object of the present invention is to improve the adhesion between a solid electrolyte membrane made of a conductive polymer membrane and an ionic gel, and to realize a bent type conductive polymer actuator that does not deteriorate even if it is repeatedly operated. Furthermore, it aims at providing the manufacturing method for implement
- the bending type conductive polymer actuator according to the present invention for solving the above-mentioned problems is A pair of electrodes;
- a bending type conductive polymer actuator comprising a laminated structure sandwiched between the pair of electrodes, 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 comprising a mixture of a first organic polymer containing at least one acrylonitrile (PAN) and an ionic liquid; Comprising at least one surface of the solid electrolyte membrane a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and a conductive polymer membrane formed on the solid electrolyte
- the method for driving the bent conductive polymer actuator according to the present invention as described above is as follows. Preparing a bent conductive polymer actuator; and applying a voltage to the pair of electrodes.
- the conductive polymer film is formed on both surfaces of the solid electrolyte film.
- a conductive polymer dispersion or solution is applied onto a substrate, and the dispersion or solution is made of a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] before being dried to form a solid film.
- a second organic polymer composed of a vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] having a specific gravity smaller than that of the conductive polymer dispersion or solution is used as a conductive polymer dispersion or solution.
- a bend-type conductive polymer actuator is realized in which the adhesion between the conductive polymer membrane and the solid electrolyte membrane made of ionic gel is improved, and the characteristics are not deteriorated even when operated repeatedly.
- FIG. 1 is a schematic diagram of an actuator according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram 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 disposed 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.
- a conductive polymer film is laminated on one side of the solid electrolyte membrane, and the other side of the solid electrolyte membrane also bends in the same way, even if it has a structure in which a metal electrode thin film (counter electrode) is formed to apply a voltage.
- a larger bending displacement can be obtained by laminating a conductive polymer film on both surfaces of the solid electrolyte membrane.
- 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) in 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.
- the conductive polymer film in which the second organic polymer made of vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] is dispersed on the surface is the second organic polymer. These particles are embedded in the conductive polymer film, and a part thereof is exposed on the surface of the conductive polymer film.
- a conductive polymer dispersion or solution is applied onto a substrate, and a second organic polymer is sprayed and applied before the dispersion or solution is dried to form a solid film. It can be performed by the procedure of embedding in a distributed state using the attached means.
- the second organic polymer made of vinylidene fluoride / hexafluoropropylene copolymer has a specific gravity smaller than that of the conductive polymer dispersion or solution.
- the second organic polymer can be embedded in a dispersed state on the surface of the conductive polymer film by dispersing the polymer in the conductive polymer dispersion or solution.
- the second organic polymer needs to be insoluble in the conductive polymer dispersion or the solvent of the solution.
- the second organic polymer When the second organic polymer is dispersed on the surface of the conductive polymer film after the conductive polymer film becomes a solid film, the second organic polymer is not embedded in the conductive polymer film. The effect of improving the adhesion between the polymer membrane and the solid electrolyte is not exhibited.
- the second organic polymer made of vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] is formed as a continuous film on the surface of the conductive polymer film, the principle of operation of the conductive polymer actuator This is not preferable because it inhibits the entry and exit of ions from the electrolyte.
- the amount of dispersion of the second organic polymer made of vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] is the conductive polymer dispersion or solution of the second organic polymer (conductive polymer).
- the mixing ratio with respect to the solid content (1 weight percent) is preferably 0.1 weight percent to 10 weight percent. When the amount is less than this range, the adhesion between the conductive polymer and the ion gel cannot be obtained, and the bending operation becomes difficult when the actuator is manufactured.
- 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.
- the material is flexible and has a value of 10 ⁇ 2 S / cm at room temperature, which is 100 times or more that of a conventional polyether-based polymer solid electrolyte.
- 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, but those which show a liquid state at a room temperature (room temperature) or a temperature close to room temperature (room temperature) and are stable are preferable.
- Examples of the ionic liquid preferably used in the present invention include those composed of the following cations represented by (Chemical Formula 3) to (Chemical Formula 6) and an anion (X ⁇ ).
- R represents an alkyl group having 1 to 12 carbon atoms or an alkyl group containing an ether bond and having 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 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 embedded with second organic polymer dispersed] PEDOT in which 5% by weight of dimethyl sulfoxide (DMSO) and 0.1% by weight of vinylidene fluoride-hexafluoropropylene copolymer [P (VDF / HFP)] were mixed on a glass slide treated with oxygen and treated with oxygen plasma A predetermined amount of an aqueous dispersion of PSS mixture (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped. Since the specific gravity of P (VDF / HFP) is smaller than that of the aqueous dispersion of PEDOT and PSS mixture, P (VDF / HFP) floats on top of the mixture.
- DMSO dimethyl sulfoxide
- PVDF / HFP vinylidene fluoride-hexafluoropropylene copolymer
- the film was naturally dried at room temperature to volatilize the solvent, and a conductive polymer film embedded with PVP dispersed on the slide glass was formed. Finally, the conductive polymer film was peeled from the slide glass using a razor.
- the obtained conductive polymer film had an average thickness of 20 ⁇ m and an electrical conductivity of 230 S / cm measured using a four-end needle method.
- 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 adhered 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
- an electrolyte ion gel obtained here is referred to as an electrolyte ion gel.
- 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.
- Example 2 Preparation of conductive polymer film embedded with second organic polymer dispersed
- a predetermined amount of an aqueous dispersion of PEDOT mixed with 5% by weight of N-methylpyrrolidone (NMP) and a PSS mixture (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped onto a silicon substrate that had been cleaned with acetone and treated with oxygen plasma.
- NMP N-methylpyrrolidone
- PSS mixture trade name Vitron PH500, manufactured by Starck Co., Ltd.
- P (VDF / HFP) a vinylidene fluoride / hexafluoropropylene copolymer
- the silicon substrate was immersed in a 50% by volume aqueous potassium hydroxide solution, and the conductive polymer film was peeled from the substrate.
- the obtained conductive polymer film had an average thickness of 13 ⁇ m, and the conductivity measured using a four-end needle method was 238 S / cm.
- 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 adhered 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.
- the bent type conductive polymer actuator having this configuration is excellent in adhesiveness between the conductive polymer film and the solid electrolyte film and can be operated for a long time.
- Example 3 A bending type conductive polymer actuator was prepared in the same manner as in Example 1 except that 0.5, 1, 5, 10, 20 weight percent of vinylidene fluoride / hexafluoropropylene copolymer [P (VDF / HFP)] was mixed. Produced. When a voltage of ⁇ 1.0 V was applied to these actuators, bending action was made in response to the applied voltage without peeling at the electrolyte ion gel-conductive polymer film interface. Similar to the first and second embodiments, these were able to perform a bending operation stably even in long-term continuous driving.
- Comparative Example 1 A predetermined amount of an aqueous dispersion of PEDOT and PSS mixture (trade name Vitron PH500, manufactured by Starck Co., Ltd.) in which 5 weight percent of dimethyl sulfoxide (DMSO) was dissolved was dropped onto a slide glass that had been cleaned with acetone and treated with oxygen plasma. 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.
- PEDOT and PSS mixture trade name Vitron PH500, manufactured by Starck Co., Ltd.
- DMSO dimethyl sulfoxide
- Conductive polymer membranes are stacked on both sides of an 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 electrolyte ion gel and the conductive polymer membrane 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 3).
- Comparative Example 2 A predetermined amount of an aqueous dispersion of PEDOT and PSS mixture in which 5% by weight of N-methylpyrrolidone (NMP) was dissolved (trade name Vitron PH500, manufactured by Starck Co., Ltd.) was dropped onto a silicon substrate that had been cleaned with acetone and treated with oxygen plasma. Thereafter, the solvent was volatilized by natural drying at room temperature, and a conductive polymer film was formed on the silicon substrate. Finally, the silicon substrate was immersed in a 50% by volume potassium hydroxide aqueous solution, and the conductive polymer film was peeled from the substrate.
- NMP N-methylpyrrolidone
- Conductive polymer membranes are stacked on both sides of the electrolyte ion gel produced in the same manner as in Example 2, 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.
- Conductive polymer membranes are stacked on both sides of an 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 electrolyte ion gel and the conductive polymer membrane 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 an area of 5 mm in the longitudinal direction from one end, and a bending type conductive high electrode having a movable part 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.
- 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.
Abstract
Description
その他、本発明に関連し得る文献として、特許文献3および特許文献4が挙げられる。
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
を具備している屈曲型導電性高分子アクチュエータであって、
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第1の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)の混合体からなり、前記固体電解質膜上に形成された導電性高分子膜と
を具備し、
前記導電性高分子膜表面にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる第2の有機ポリマーが分散された状態で埋め込まれ、かつ
前記固体電解質膜と前記導電性高分子膜表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面とが接している。
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
前記一対の電極に電圧を印加する工程
を有する。
基板上に導電性高分子分散液または溶液を塗付し、前記分散液または溶液が乾燥し固体膜となる前にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる第2の有機ポリマーを散布、塗付の手段を用いて分散された状態で埋め込む工程と、
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表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面を対向させて積層させる工程と
を有する。
予めフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる、比重が前記導電性高分子分散液または溶液よりも小さい第2の有機ポリマーを導電性高分子分散液または溶液中に分散させることによって前記導電性高分子膜表面に前記第2の有機ポリマーを分散された状態で埋め込む工程と、
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表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面を対向させて積層させる工程と
を有する。
102a 導電性高分子膜
102b 導電性高分子膜
103 固体電解質膜
104a 第2の有機ポリマー
104b 第2の有機ポリマー
105a 電極
105b 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
固体電解質膜の片面に導電性高分子膜を積層させ、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)を形成した構造であっても同様に屈曲動作するが、固体電解質膜の両面に導電性高分子膜を積層することでより大きな屈曲変位が得られる。
[第2の有機ポリマーが分散された状態で埋め込まれている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重量パーセントのジメチルスルホキシド(DMSO)、0.1重量パーセントのフッ化ビニリデン-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。P(VDF/HFP)の比重はPEDOTとPSS混合体の水分散液よりも小さいためにP(VDF/HFP)は混合液の上部に浮上する。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PVPが分散された状態で埋め込まれている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20μm、四端針法を用いて測定した導電率は230S/cmであった。
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。
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を電解質イオンゲルと記す。
電解質イオンゲルの両面に、導電性高分子膜の[P(VDF/HFP)]が分散された状態で埋め込まれている面を対向させて重ね、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。
[第2の有機ポリマーが分散された状態で埋め込まれている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シリコン基板上に、5重量パーセントのNメチルピロリドン(NMP)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。この膜が乾燥する前にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]をPEDOTとPSS混合体の水分散液に対して1重量パーセント表面に散布し、その後、室温で自然乾燥して溶媒を揮発させ、シリコン基板上にP(VDF/HFP)が分散された状態で埋め込まれている導電性高分子膜を形成した。
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、ブチルメチルイミダゾリウム(BMI)、アニオンとしてヘキサフルオロリン酸アニオン(PF6 -)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。
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。
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。
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0.5、1、5、10、20重量パーセント混合した以外実施例1と同様にして屈曲型導電性高分子アクチュエータを作製した。これら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。これらは実施例1および2と同様に長期連続駆動においても安定して屈曲動作することが可能であった。一方 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20重量パーセント溶解させた分散液は膜質が非常に脆く実施例1と同様にして屈曲型導電性高分子アクチュエータを作製することが出来なかった(表3)。
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重量パーセント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。
アセトン洗浄後酸素プラズマ処理したシリコン基板上に、5重量%のNメチルピロリドン(NMP)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、シリコン基板上に導電性高分子膜を形成した。最後に、シリコン基板を50体積%の水酸化カリウム水溶液に浸漬し、導電性高分子膜を基板から剥離した。
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重量パーセント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。導電性高分子膜を形成した後に、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)]を表面に散布した。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。
Claims (6)
- 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
を具備している屈曲型導電性高分子アクチュエータであって、
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第1の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)の混合体からなり、前記固体電解質膜上に形成された導電性高分子膜と
を具備し、
前記導電性高分子膜表面にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる第2の有機ポリマーが分散された状態で埋め込まれ、かつ
前記固体電解質膜と前記導電性高分子膜表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面とが接している
ことを特徴とする屈曲型導電性高分子アクチュエータ。 - 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1に記載の屈曲型導電性高分子アクチュエータ。
- 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第1の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)の混合体からなり、前記固体電解質膜上に形成された導電性高分子膜と
を具備し、
前記導電性高分子膜表面にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる第2の有機ポリマーが分散された状態で埋め込まれ、かつ
前記固体電解質膜と前記導電性高分子膜表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面とが接しており、
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。 - 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3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。
- 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、
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第1の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)の混合体からなり、前記固体電解質膜上に形成された導電性高分子膜と
を具備している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、
基板上に導電性高分子分散液または溶液を塗付し、前記分散液または溶液が乾燥し固体膜となる前にフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる第2の有機ポリマーを散布、塗付の手段を用いて分散された状態で埋め込む工程と、
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表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面を対向させて積層させる工程と
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。 - 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、
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第1の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)の混合体からなり、前記固体電解質膜上に形成された導電性高分子膜と
を具備している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、
予めフッ化ビニリデン/ヘキサフルオロプロピレン共重合体[P(VDF/HFP)]からなる、比重が前記導電性高分子分散液または溶液よりも小さい第2の有機ポリマーを導電性高分子分散液または溶液中に分散させることによって前記導電性高分子膜表面に前記第2の有機ポリマーを分散された状態で埋め込む工程と、
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表面の前記第2の有機ポリマーが分散された状態で埋め込まれている面を対向させて積層させる工程と
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。
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Also Published As
Publication number | Publication date |
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US7733000B2 (en) | 2010-06-08 |
CN101828330B (zh) | 2012-05-30 |
US20100039001A1 (en) | 2010-02-18 |
CN101828330A (zh) | 2010-09-08 |
JP4287504B1 (ja) | 2009-07-01 |
JPWO2010018612A1 (ja) | 2012-01-26 |
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