JP4727193B2 - Actuator element including conductive polymer molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a conductive polymer having an excellent stretching ratio per 1 oxidation reduction cycle, and a method for electrolytically stretching and contracting, excellent in stretching ratio per 1 oxidation reduction cycle. <P>SOLUTION: This method for producing the conductive polymer by using an electrolytic polymerization method is provided by using an electrolytic liquid containing a perfluoroalkylsulfonylimide ion expressed by formula (1): (C<SB>n</SB>F<SB>(2n+1)</SB>SO<SB>2</SB>)(C<SB>m</SB>F<SB>(2m+1)</SB>SO<SB>2</SB>)N<SP>-</SP>[wherein, (n), (m) are each an optional integer], and also the method for electrolytically stretching and contracting by using the conductive polymer-molded article containing the conductive polymer obtained from the production method is provided. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a method for producing a conductive polymer having an excellent stretch rate, a conductive polymer molded article, a laminate, a method for stretching the conductive polymer molded article, and uses of the conductive polymer.

  It is known that a conductive polymer such as polypyrrole exhibits electrolytic stretching, which is a phenomenon that stretches or deforms by electrochemical redox. Electrolytic expansion and contraction of this conductive polymer is expected to be applied to driving for uses such as artificial muscles, robot arms, artificial hands, artificial legs, powered suits and actuators, and has attracted attention in recent years. As a method for producing such a conductive polymer that undergoes electrolytic expansion and contraction, a method of producing by an electropolymerization method is common. As an electropolymerization method, a conductive polymer film is formed on the working electrode by applying a voltage to both electrodes after setting the working electrode and the counter electrode in an electrolytic solution to which a monomer component such as pyrrole is added. The method of making is usually performed.

As for an actuator using a conductive polymer, a configuration of an actuator including an electrolytic solution, a counter electrode, and a polypyrrole film in a cell was reported in 1997 (see Non-Patent Document 1). In this actuator, in a state where the polypyrrole film and the counter electrode are immersed in the electrolytic solution, the polypyrrole film expands and contracts by applying a voltage between the counter electrode and the polypyrrole film, and the polypyrrole film has a load of 14.6 MPa (45 g). It is described that it stretches 1% while receiving. That is, this actuator can generate a force of 14 MPa in the length direction by electrolytic expansion and contraction, but the expansion and contraction is only 1%. In addition, as an actuator using a conductive polymer, it has been reported that a conductive polymer using BF ₄ ^- or the like as a supporting salt at the time of electrolytic polymerization expands and contracts by 10 to 15% (non-patent document). 2).

D. Santa Santa, 2 others, “Performance and work capacity of a polymer conductor polymer synthesizer, S et al. (Elscvier Science), 1997, 90, P93-100. Genji, 4 others, “High Stretchable and Powerful Polypyrrole Linear Actuators”, Chemistry Letters, Japan, Vol. 32, 2003 No., p576-577.

  However, in practical use, artificial muscles, robot arms, prosthetic hands / legs, etc., are usually operated with one extension / contraction as one operation. Therefore, in order for an artificial muscle or the like to perform a sufficient operation, it is required to perform a large expansion / contraction far exceeding 1% expansion / contraction in one expansion / contraction. In the case where a conductive polymer is used as a driving source for such a practical use, a conventional actuator element capable of electrolytic expansion and contraction using a conductive polymer has a cycle of expansion and contraction due to electrolytic expansion and contraction (a redox cycle). ), The amount of expansion / contraction or displacement per one oxidation-reduction cycle is not sufficient. Therefore, in order to use a conductive polymer for artificial muscles, robot arms, artificial hands, etc., which are practical applications, it is necessary that a larger amount of expansion / contraction is obtained in one redox cycle when electrolytic expansion / contraction is performed. is there.

  Also, in order to further enhance the practicality of application to artificial muscles, etc., after a command for causing expansion or contraction such as applying voltage to the conductive polymer was made, the desired amount of expansion or contraction was actually made. It is desirable if the time until displacement occurs is short, that is, if the displacement rate per specific time is large. That is, in order to use a conventional conductive polymer for practical applications, in addition to improving the expansion / contraction rate per one oxidation-reduction cycle of the conductive polymer, a voltage is applied to the conductive polymer. It is practical if it is possible to improve the ratio of stretched length or displaced length to the length of the conductive polymer molded product in the initial state at a specific time, that is, the displacement rate per specific time Desirable to further enhance sex. In addition, large-sized dopant ions, which are organic compound ions, have a wider range of material selection and higher molecular design freedom than inorganic ions, so they can be used as supporting salts during electropolymerization. Is desirable.

The present invention relates to a method for producing a conductive polymer using an electrolytic polymerization method, wherein the electrolytic polymerization method is represented by the chemical formula (1).
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N - (1)
(Here, n and m are arbitrary integers.)
The manufacturing method of the conductive polymer using the electrolyte solution containing perfluoroalkyl sulfonylimide ion represented by these. By using the method for producing a conductive polymer of the present invention, the expansion / contraction rate per one oxidation-reduction cycle can be improved. Moreover, it discovered that the film-like conductive polymer obtained by the said manufacturing method not only was excellent in the expansion-contraction rate per 1 oxidation-reduction cycle, but the displacement rate per specific time was also favorable. In addition, perfluoroalkylsulfonylimide ions, which are anions when the perfluoroalkylsulfonylimide salt is dissociated, are larger in size than conventional dopant ions, and are contained in the bulk of the conductive polymer obtained by the above production method. It is. For example, in a conventional conductive polymer actuator, when an anion having a size larger than that of PF ₆ ⁻ which is an inorganic ion is used as a dopant ion, the conventional conductive polymer can inhale an anion even when a voltage is applied. Does not occur and large expansion and contraction cannot be obtained. However, the conductive polymer obtained by the production method of the present invention can desorb anions, and (C _n F _{(2n + 1)} SO ₂ ) (C _m F _{(2m + 1)} SO ₂ ) N ^- electrolysis stretch in an electrolytic solution containing the conventionally can stretch more than 20% per redox cycle that could not be obtained is excellent in stretchability.

The present invention also relates to a laminate comprising a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer layer contains a conductive polymer obtained by a production method using an electrolytic polymerization method. The electrolytic polymerization method has the chemical formula (1)
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N - (1)
(Here, n and m are arbitrary integers.)
It is also a laminate characterized by being an electrolytic polymerization method using an electrolytic solution containing a perfluoroalkylsulfonylimide ion represented by the formula: The laminate has an excellent stretch rate per one redox cycle.

  Furthermore, this invention is also an actuator element using the said conductive polymer or laminated body. Since the actuator element has an excellent expansion / contraction ratio, and is silent and lightweight, it is excellent as a driving part or a pressing part.

The present invention is a method for producing a conductive polymer using an electrolytic polymerization method, wherein the electrolytic polymerization method is represented by the following formula (C _n F _{(2n + 1)} SO ₂ ) (C _m F _{(2m + 1)} SO ₂ ) N ^−.
(Here, n and m are arbitrary integers.)
The manufacturing method of the conductive polymer using the electrolyte solution containing perfluoroalkyl sulfonylimide ion represented by these.

(Electrolyte)
The electrolytic polymerization method used in the method for producing a conductive polymer according to the present invention includes a chemical formula (1) in an electrolytic solution.
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N - (1)
(Here, n and m are arbitrary integers.)
Perfluoroalkylsulfonylimide ions represented by the formula: For this reason, the anion is present in the bulk of the conductive polymer obtained by the electrolytic polymerization method. The anion has a larger molecular size than a conventional dopant such as trifluoromethanesulfonate ion. Therefore, in a conductive polymer molded product in which perfluoroalkylsulfonylimide ions are present, a large molecular size anion enters and exits the conductive polymer molded product by repeatedly switching the applied voltage between positive and negative. Therefore, a large electrolytic expansion / contraction per one redox cycle can be achieved.

In the perfluoroalkylsulfonylimide ion, a sulfonyl group is bonded to a nitrogen atom that is an anion center, and further, two perfluoroalkyl groups that are substituents are included. The perfluoroalkyl sulfonyl is represented by _{C n F (2n + 1)} SO 2, other perfluoroalkyl sulfonyl group _is represented by _{C m F (2m + 1)} SO 2. The n and m are each an arbitrary integer of 1 or more, and n and m may be the same integer, or n and m may be different integers. For example, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group and the like can be mentioned. . Examples of the perfluoroalkylsulfonylimide salt include bistrifluoromethylsulfonylimide salt, bis (pentafluoroethylsulfonyl) imide salt, and bis (heptadecafluorooctylsulfonyl) imide salt.

The perfluoroalkylsulfonylimide ion of the above chemical formula (1) can form a salt with a cation, and may be added as a perfluoroalkylsulfonylimide salt to the electrolytic solution in the electrolytic polymerization method. The cation that forms a salt with the perfluoroalkylsulfonylimide may be composed of one element, such as Li ⁺ , or may be composed of a plurality of elements. The cation is not particularly limited as long as it is a Lewis acid capable of forming a perfluoroalkylsulfonylimide ion as a monovalent cation and dissociating in the electrolyte.

  When the cation is a metal element, for example, an element selected from alkali metals such as lithium can be used. When the cation is a molecule, for example, tetrabutylammonium, alkylammonium typified by tetraethylammonium, pyridinium, imidazolium, or the like can be used.

  As described above, the perfluorosulfonylimide ion contained in the electrolytic solution of the electrolytic polymerization method in the production method of the present invention varies depending on the combination of the perfluoroalkylsulfonylimide ion that is the base component and the cation that is the acid component. Although a salt can be formed, perfluorosulfonylimide salt is easily dissociated in solution and easily available, so bis (trifluoromethyl) sulfonylimide lithium, bis (pentafluoroethylsulfonyl) Tetrabutylammonium for bis (perfluoroalkylsulfonyl) imide lithium such as imide lithium and bis (perfluoroalkylsulfonyl) imide such as bis (trifluoromethyl) sulfonylimide and bis (pentafluoroethylsulfonyl) imide Umushio, pyridinium salts or imidazolinium indium salts are preferred.

  The content of the perfluoroalkylsulfonylimide ion in the electrolytic solution in the electrolytic polymerization method is not particularly limited. However, in order to ensure sufficient ionic conductivity of the electrolytic solution, a perfluoroalkylsulfonylimide salt is used. The electrolyte solution preferably contains 1 to 40% by weight, and more preferably 2.8 to 20% by weight.

  In the method for producing a conductive polymer of the present invention, the solvent of the electrolytic solution used for the electrolytic polymerization method is particularly a solvent that can dissolve the perfluoroalkylsulfonylimide salt and can perform electrolytic polymerization. It is not limited. In order to further increase the electrolytic expansion / contraction per one oxidation-reduction cycle for the molded product of the conductive polymer obtained by electrolytic polymerization, the solvent used in the electrolytic polymerization method includes an ether bond, an ester bond, a carbonate bond, It is preferable to use a solvent of an organic compound and / or a halogenated hydrocarbon containing at least one bond or functional group among a hydroxyl group, a nitro group, a sulfone group and a nitrile group. Two or more of these solvents can be used in combination.

  Examples of the organic compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane (an organic compound containing an ether bond), γ-butyrolactone, and ethyl acetate. , N-butyl acetate, t-butyl acetate, 1,2-diacetoxyethane, 3-methyl-2-oxazolidinone, methyl benzoate, ethyl benzoate, butyl benzoate, diethyl phthalate (including ester bond) Organic compounds), propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate (organic compounds including carbonate bonds), ethylene glycol, butanol, 1-hexanol, cyclohexanol, 1-octanol, 1-decano 1-dodecanol, 1-octadecanol (above, organic compound containing a hydroxyl group), nitromethane, nitrobenzene (above, organic compound containing a nitro group), sulfolane, dimethylsulfone (above, organic compound containing a sulfone group) And acetonitrile, butyronitrile, and benzonitrile (an organic compound containing a nitrile group). Note that the organic compound containing a hydroxyl group is not particularly limited, but is preferably a polyhydric alcohol or a monohydric alcohol having 4 or more carbon atoms because the stretching ratio is good. In addition to the above-mentioned examples, the organic compound may have any two or more bonds or functional groups among the ether bond, ester bond, carbonate bond, hydroxyl group, nitro group, sulfone group and nitrile group in the molecule. The organic compound contained in the combination may be sufficient.

  In addition, the halogenated hydrocarbon contained as a solvent in the electrolytic solution in the method for producing a conductive polymer of the present invention is one in which at least one hydrogen in the hydrocarbon is substituted with a halogen atom, and is liquid under electrolytic polymerization conditions. As long as it can exist stably, it is not particularly limited. Examples of the halogenated hydrocarbon include dichloromethane and dichloroethane. Although only one kind of the halogenated hydrocarbon can be used as a solvent in the electrolyte solution, two or more kinds can be used in combination. The halogenated hydrocarbon may be used in a mixture with the above organic compound, or a mixed solvent with the organic solvent may be used as a solvent in the electrolytic solution.

  In the method for producing a conductive polymer of the present invention, an electrolytic solution used in the electrolytic polymerization method includes an organic compound (for example, pyrrole) to be electropolymerized and a perfluoroalkylsulfonylimide ion represented by the chemical formula (1). including. By conducting electrolytic polymerization using this electrolytic solution, it is possible to obtain a conductive polymer excellent in the expansion / contraction rate per one oxidation-reduction cycle and / or the displacement rate per specific time in electrolytic expansion / contraction. The perfluoroalkylsulfonylimide ion represented by the chemical formula (1) is taken into the conductive polymer by the electrolytic polymerization. Moreover, in order to improve the film quality of the conductive polymer film obtained by the electrolytic polymerization method, a composite electrolyte obtained by adding 1 to 80% by weight of trifluoromethanesulfonate to the electrolytic solution can be used.

  In the method for producing a conductive polymer of the present invention, the electrolytic solution used in the electropolymerization method contains a monomer of a conductive polymer in addition to a perfluorosulfonylimide salt, and further includes polyethylene glycol or polyacrylamide. Other known additives such as can also be included.

As the electropolymerization of the conductive polymer monomer, a known electropolymerization method can be used, and any of a constant potential method, a constant current method, and an electric sweep method can be used. For example, the electrolytic polymerization method can be performed at a current density of 0.01 to 20 mA / cm ² and a reaction temperature of −70 to 80 ° C. In order to obtain a conductive polymer having a good film quality, a current density of 0.1 It is preferable to carry out under the conditions of ˜2 mA / cm ² and the reaction temperature of −40 to 40 ° C., more preferably the reaction temperature is −30 to 30 ° C.

  In addition, in the manufacturing method of the conductive polymer of this invention, a working electrode will not be specifically limited if it can be used for electrolytic polymerization, An ITO glass electrode, a carbon electrode, a metal electrode, etc. can be used. The metal electrode is not particularly limited as long as it is an electrode mainly composed of metal, but a metal element selected from the group consisting of Pt, Ti, Ni, Au, Ta, Mo, Cr, C, and W. A single metal electrode or an alloy electrode can be preferably used. It is particularly preferable that the metal species contained in the metal electrode is Ni or Ti because the conductive polymer obtained by the above production method has a large expansion and contraction rate and generation force and the electrode can be easily obtained. As the alloy, for example, trade names “INCOLOY alloy 825”, “INCONEL alloy 600”, “INCONEL alloy X-750” (manufactured by Daido Special Metal Co., Ltd.) can be used.

  In the method for producing a conductive polymer of the present invention, the monomer of the conductive polymer contained in the electrolytic solution used in the electrolytic polymerization method may be a compound that is polymerized by oxidation by electrolytic polymerization and exhibits conductivity. Examples thereof include, but are not particularly limited to, for example, heterocyclic 5-membered cyclic compounds such as pyrrole, thiophene, and isothianaphthene, and derivatives such as alkyl groups and oxyalkyl groups thereof. Among them, hetero five-membered cyclic compounds such as pyrrole and thiophene and derivatives thereof are preferable. Particularly, a conductive polymer containing pyrrole and / or a pyrrole derivative is easy to produce and stable as a conductive polymer. It is preferable because there is. Moreover, the said monomer can be used together 2 or more types.

(Molded product)
The present invention is also a conductive polymer molded product in which the conductive polymer obtained by the above production method has a desired shape. That is, a method for producing a conductive polymer using an electrolytic polymerization method, wherein the electrolytic polymerization method uses an electrolytic solution containing a perfluoroalkylsulfonylimide ion represented by the following formula (2): the method of manufacturing _{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) n - (2)
(Here, n and m are arbitrary integers.) A conductive polymer molded product containing the conductive polymer obtained as a resin component. The shape of the conductive polymer molded product is not particularly limited, and may be a film shape, a tubular shape, a cylindrical shape, a prismatic shape, a fiber shape, or the like. It is preferably in the form of a film because it sometimes precipitates on the working electrode. The working electrode is not particularly limited as long as it can be used for electrolytic polymerization, and a known electrode such as an ITO glass electrode or a metal electrode can be used.

  In particular, by including the perfluoroalkylsulfonylimide ion as a dopant in the bulk of the conductive polymer, when the conductive polymer molded product of the present invention is made into a film, The maximum expansion / contraction ratio was obtained only up to about 10 to 15% per oxidation-reduction cycle in the plane direction, whereas in the length direction, 16% or more, especially 20%, per oxidation-reduction cycle. It became possible to show the above excellent maximum expansion / contraction ratio. While conventional low-stretch conductive polymer molded products could only be used for applications that do not require large displacements such as switches and sensors, the stretch ratio per oxidation-reduction cycle is in the length direction. A conductive polymer molded product of 16% or more can be suitably used for applications that require a large expansion / contraction rate typified by artificial muscle. In addition, in order to reduce the resistance value as an operation electrode, the said conductive polymer molded product can contain suitably conductive materials, such as a metal wire and a conductive oxide, in addition to a dopant.

(Laminate)
The present invention is a laminate including a conductive polymer layer and a solid electrolyte layer, and is also a laminate including the conductive polymer in the conductive polymer layer. That is, the present invention is a laminate comprising a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer layer is a method for producing a conductive polymer using an electrolytic polymerization method, The electrolytic polymerization method is represented by the formula (C _n F _{(2n + 1)} SO ₂ ) (C _m F _{(2m + 1)} SO ₂ ) N ⁻ (2)
(Here, n and m are arbitrary integers.)
It is the laminated body containing the conductive polymer obtained by the manufacturing method of the conductive polymer using the electrolyte solution containing perfluoroalkyl sulfonylimide ion represented by these. By including the conductive polymer layer and the solid electrolyte layer in the laminate, the electrolyte in the solid electrolyte layer is supplied to the conductive polymer layer, so that a large per redox cycle during electrolytic expansion and contraction. The expansion / contraction rate can be expressed. The conductive polymer layer and the solid electrolyte layer in the laminate are preferably in direct contact with each other as long as the electrolyte in the solid electrolyte can be moved to the conductive polymer. The layers may be interposed between them.

  Although the solid electrolyte is not particularly limited, the solid electrolyte is preferably an ion exchange resin by being driven largely as an actuator by displacing the laminate. As the ion exchange resin, a known ion exchange resin can be used. For example, a trade name “Nafion” (perfluorosulfonic acid resin, manufactured by DuPont) can be used.

(Electrolytic stretching method)
The present invention is also an electrolytic expansion / contraction method in which the conductive polymer molded product is expanded and contracted in an electrolytic solution by electrochemical oxidation and reduction. An excellent expansion / contraction rate per one oxidation-reduction cycle can be obtained by electrolytic expansion / contraction of the conductive polymer molded product. Furthermore, the electrolytic expansion / contraction method for expanding / contracting the above-mentioned conductive polymer molded product can also obtain an excellent displacement rate per specific time. The working electrolytic solution that is an electrolytic solution in which the electroconductive polymer molded product is subjected to electrolytic expansion / contraction is not particularly limited, but it is preferable to use a good solvent such as water or propylene carbonate (PC), For those having n of 2 or more, it is preferable to use a good solvent such as propylene carbonate because a larger expansion and contraction can be obtained. In addition, in order to obtain the target expansion / contraction rate, electrolytic solvent may be selected and used as the working electrolyte. The good solvent is not particularly limited, but is preferably a solvent that can be used in a reaction field of an electrochemical reaction because there is no need to adjust conditions and the like.

For the electrolytic expansion and contraction method of the present invention, an electrolytic solution for operating a conductive polymer is
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N -
(Where n and m are arbitrary integers) can be used as an operating electrolyte. That is, the present invention is a method for producing a conductive polymer using an electrolytic polymerization method, and the electrolytic polymerization method is represented by the chemical formula (C _n F _{(2n + 1)} SO ₂ ) (C _m F _{(2m + 1)} SO ₂ ) N. ⁻
(Here, n and m are arbitrary integers.)
A method for producing a conductive polymer using an electrolyte solution containing a perfluoroalkylsulfonylimide ion represented by:
Conductive polymer molded product containing the conductive polymer obtained by the above as a resin component,
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N -
(Where n and m are arbitrary integers) is an electrolytic expansion / contraction method in which electrolytic expansion / contraction is performed with an electrolytic solution containing an operating electrolyte. In the electrolytic expansion / contraction method of the present invention, since the perfluoroalkylsulfonylimide is also contained in the operating electrolyte, it is easily taken in during the expansion / contraction of the electroconductive polymer molded product. Compared to an electrolytic expansion / contraction method using an electrolytic solution containing an acid ion or the like, it exhibits an excellent expansion / contraction rate per one oxidation-reduction cycle, and further exhibits an excellent displacement rate per specific time.

  In the electrolytic expansion / contraction method, the perfluoroalkylsulfonylimide ion contained in the working electrolyte contains perfluoroalkylsulfonylimide ions contained in the electrolytic solution used in the production of a conductive polymer molded product that undergoes electrolytic stretching in the working electrolyte. It is preferable that the ionic radius is approximately the same as that of the alkylsulfonylimide ion since electrolytic expansion and contraction can be easily performed.

  In addition, it is clear that the salt used for the above-mentioned operating electrolyte solution can be used as a salt contained in the electrolyte solution of the solid electrolyte in the laminate of the present invention, and exhibits an excellent stretch rate per one oxidation-reduction cycle. A laminate with a solid electrolyte can be obtained.

  The present invention is also an electrolytic expansion / contraction method in which the conductive polymer molded product is expanded and contracted by electrochemical oxidation-reduction in the electrolytic solution, and the electrolytic solution mainly contains sodium chloride. An electrolytic expansion / contraction method which is an aqueous solution containing an electrolyte may be used. The electrolytic solution mainly contains sodium chloride, which is an electrolyte contained in a biological component, so that it can be operated in a state where the body fluid in the living body is easily compatible with the electrolytic solution.

  The temperature of the electrolyte solution or solid electrolyte that performs electrolytic expansion and contraction in the present invention is not particularly limited, but in order to perform electrolytic expansion and contraction of the conductive polymer at a faster rate, it is preferably 10 to 100 ° C., more preferably It is preferable that it is 40-80 degreeC. Further, the concentration of the perfluoroalkylsulfonylimide salt in the working electrolyte is not particularly limited.

(Use)
The conductive polymer molded article and laminate of the present invention can be suitably used as an actuator element for artificial muscles, robot arms and artificial hands. Also, medical instruments such as tweezers, scissors, forceps, snare, laser knife, pertula, and clips in microsurgery technology, various sensors or repair tools for inspection and repair, etc., health instruments, hygrometers, hygrometer control devices, The electrical conductivity of the present invention is also applicable to articles used underwater such as industrial equipment such as soft manipulators, underwater valves, and soft transport devices, underwater mobiles such as goldfish, or hobby equipment such as moving fishing baits and propeller fins. Molecular molded products and laminates can be suitably used. Since the actuator element is lighter than conventional linear actuator elements due to fewer metal parts, the positioning device, posture control device, lifting device, transport device, moving device, adjusting device, adjusting device, guiding device, and joint It can be suitably used as a drive unit of the apparatus.

(Actuator)
Moreover, this invention is an actuator containing an operation part, an electrolyte, and a counter electrode, Comprising: The said operation part contains the conductive polymer obtained by the said manufacturing method, It is an actuator characterized by the above-mentioned. The actuator is not particularly limited as long as it includes an operating part, an electrolyte, and a counter electrode as a device configuration, but an actuator in which a shaft attached to the operating part is packed in a casing so as not to leak during operation. Alternatively, it is preferable that the actuator includes a housing that can be expanded and contracted according to the operation of the operation unit, because a liquid leak such as an electrolyte does not occur.

  FIG. 1 is a perspective view of the appearance of the actuator of the present invention. The actuator 1 is a columnar actuator, and the outermost layer is formed of a casing made of a flexible material such as urethane rubber. At the bottom 22 of the actuator 1, a lead 8 for applying a potential to the operating unit 3 inside the actuator and leads 7 and 7 ′ for applying a potential to the counter electrode are provided. When the power source 9 supplies electric power and a voltage is applied to the operating unit and the counter electrode, the operating unit expands and contracts electrolytically. Due to this electrolytic expansion / contraction, the distal end portion of the actuator 1 is displaced due to expansion / contraction in the length direction. When the actuator 1 expands, it can generate F, which is a pressing force.

  FIG. 2 is a cross-sectional view taken along the line AA of the actuator 1 of FIG. The actuator 1 includes a columnar operating portion 3 in an internal space of a housing 2 formed of a flexible material. A recess 23 is formed on the inner surface of the bottom 22 of the housing 2. One end of the operating portion 3 is fitted into the recess 23 via the conductive connecting plate 4, and the operating portion is attached to the housing 2. The operating portion 3 is fixed to the housing 2 by joining the other end of the operating portion 3 on the inner surface of the distal end portion 21 of the housing 2. Further, in the internal space of the housing 2, the columnar counter electrodes 51 and 52 are fitted in the vicinity of the inner surface of the side wall of the housing 2 by fitting into the counter electrode fitting recesses 24 and 25 provided on the bottom portion 22, respectively. It has been. In the internal space of the housing 2, the remaining internal space excluding the counter electrodes 51 and 52 and the operating portion 3 is filled with the electrolyte 6. The power source 9 is connected to the counter electrodes 51 and 52 via the leads 7 and 7 ′, and is connected to the conductive connection plate 4 in contact with the operating portion 3 via the lead 8. By supplying electric power from the power source 9, a voltage can be applied between the counter electrodes 51, 52 and the operating unit 3, and the operating unit 3 can be subjected to electrolytic expansion and contraction. When the actuator 1 expands and contracts, a force F can be generated at the distal end portion 21 and can be suitably used as an artificial muscle.

  The distal end portion 21 of the actuator 1 may or may not be joined to the distal end of the operating portion 3 on the inner surface. In the case where the tip 21 and the tip of the operating portion 3 are not joined, the actuator is configured such that the casing 2 formed of a flexible material is subjected to a force that contracts into the actuator due to contraction stress. When the operating part 3 is electrolytically expanded and contracted, the distal end part 21 can be expanded and contracted following the electrolytic expansion and contraction of the operating part 3.

  The operating part is not particularly limited as long as it contains the above-described conductive polymer and undergoes electrolytic expansion and contraction by voltage application. In particular, it is preferable that the operating portion exhibits a stretchability of 16% or more when a voltage is applied. An actuator that expands and contracts by 16% or more can be obtained by expanding and contracting by 16% or more when a voltage is applied to the operating portion, and this actuator is used for applications that require a large expansion and contraction rate typified by artificial muscles. Can be suitably used. In addition to the dopant, the operating unit can appropriately include a conductive material such as a metal wire or a conductive oxide in order to reduce the resistance value as the working electrode.

  The flexible material forming the housing 2 is not particularly limited. The flexible material can be appropriately selected according to the elongation rate of the actuator, and a synthetic resin having an elongation rate of 16% or more is preferably used, and a synthetic resin having an elongation rate of 20% or more is more preferably used. As the flexible material, for example, a silicone resin, a urethane resin, a silicone rubber, a urethane rubber, or the like can be used. The flexible material preferably has a solvent resistance because it also has a function of preventing the electrolyte from leaking to the outside of the actuator, and is preferably a silicon-based resin, a urethane-based resin, a silicon-based rubber, or a urethane-based material. Rubber can be preferably used. In addition, since the actuator 1 has a structure in which the operation part is sealed by the housing 2, the means for transmitting a force like a rod-like body is used over a long period of time compared to a structure in which the housing penetrates the housing. Since there is no leakage of electrolyte, it is excellent for use as mechanical parts such as artificial muscles.

  The shape of the actuator of the present invention is not particularly limited. Although the actuator is formed in a cylindrical shape in FIG. 1, the actuator can be formed in an optimum shape for the application. As the shape of the actuator, in addition to the cylindrical shape, it can be formed in a shape corresponding to the use situation such as a polygonal column shape such as a prismatic shape or a hexagonal column shape, a conical shape, a plate shape, or a rectangular parallelepiped shape. In addition, the operating portion installed inside the actuator of the present invention is not limited to a cylindrical shape, and is appropriate according to the outer shape of the actuator, such as a polygonal column shape such as a prismatic shape or a hexagonal column shape, a conical shape, a rectangular parallelepiped shape, etc. It can be made into a simple shape. The working part may use the conductive polymer film obtained on the working electrode by electrolytic polymerization as it is, or may be formed into a desired shape by forming such as lamination. Furthermore, the counter electrode is not limited to a columnar shape, and may be a plate shape or the like.

  The electrolyte contained in the actuator of the present invention may be a liquid or a solid electrolyte. When the electrolyte is in a liquid state, the solvent may be water or an organic solvent, but since the rate of volatilization is relatively slow, handling is easy, and large expansion and contraction can be obtained. In addition, an aqueous solvent is preferable. When the electrolytic solution is a solid electrolyte, it may be a polymer electrolyte or a solid electrolyte that is completely solid, but a gel polymer electrolyte is preferred because of its high ionic conductivity in the electrolyte. . The gel used for the gel polymer electrolyte is preferably polyacrylamide, polyethylene glycol, or agar because the gel polymer electrolyte can be easily adjusted by combining with an aqueous electrolyte. It is preferable that the electrolyte is an electrolyte containing at least one compound selected from the group consisting of trifluoromethanesulfonate ions, anions containing a plurality of fluorine atoms with respect to the central atom, and sulfonates having 3 or less carbon atoms. Is preferable because it can cause further expansion and contraction per one oxidation-reduction cycle.

  In the actuator, a laminate of a conductive polymer-containing layer and a solid electrolyte can also be used as the operating part and the electrolyte. In the laminate, the conductive polymer-containing layer is made of a layer containing the conductive polymer obtained by the above-described method for producing a conductive polymer, so that the conductive polymer in the layer expands and contracts greatly. It can be used for larger expansion and contraction applications. In addition, the counter electrode should just be installed so that a voltage can be applied between a counter electrode and a conductive polymer content layer through the said solid electrolyte, and the place to install in particular is not limited.

  Since the actuator can obtain a large expansion / contraction ratio by including the above-described conductive polymer in the internal working part, the actuator has a large displacement other than a switch or a sensor that can be used even if the displacement is small. It can be suitably used as an artificial muscle. That is, the actuator of the present invention can be used only for applications where the displacement is small, and the application including the conductive polymer can be expanded to applications where the displacement of the artificial muscle or the like is large. The actuator can be used as a linear actuator. For example, by attaching a member for force transmission such as a metal wire to the distal end portion 21 of the actuator 1 in FIG. In addition, it can be used as a pressing device by pressing the tip 21 against the object to be controlled. Since the actuator of the present invention is an actuator in which a conductive polymer is driven by electricity, and is silent or driven at the time of driving, it is suitable as a driving unit or a pressing unit in an indoor use apparatus. In addition, the actuator is lighter than conventional linear actuators because there are few metal parts, so a positioning device, a posture control device, a lifting device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, and a joint It can be suitably used as a drive unit of the apparatus.

(Use)
The conductive polymer molded article, laminate and actuator of the present invention of the present invention can be suitably used for artificial muscles, robot arms, powered suits, artificial hands and artificial legs. In addition, the conductive polymer molded article, laminate and actuator of the present invention can be applied to various instruments or medical instruments such as tweezers, scissors, forceps, snare, laser knife, spatula and clip in microsurgery technology, Repair tools and other health equipment, hygrometers, hygrometer control devices, soft manipulators, underwater valves, soft transporters and other industrial equipment, goldfish and other underwater mobiles, and moving fishing baits and propulsion fins It can use suitably for the articles | goods used underwater.

  That is, when the conductive polymer molded article, laminate and actuator of the present invention are used in the above artificial muscle, robot arm and artificial hand, the conductive polymer obtained by the above-described conductive polymer manufacturing method is used. Can be used as an artificial muscle, a robot arm, and a prosthetic hand used in the drive unit.

  When the conductive polymer molded article, laminate and actuator of the present invention are used in the above-described medical device, the conductive polymer containing the conductive polymer obtained by the above-described conductive polymer manufacturing method as a base resin. The polymer molded product or the conductive polymer layer can be a medical instrument including tweezers, scissors, forceps, snare, laser knife, spatula, and clip used for the drive unit.

  In addition, when the conductive polymer molded article and laminate of the present invention are used in the above-mentioned sensor or repair tool, the conductive polymer obtained by the above-described conductive polymer manufacturing method is used as the base resin. The conductive polymer molded article or the conductive polymer layer that is included can be used as a sensor and a repair tool including inspection and repair that are used in the drive unit.

  When the conductive polymer molded article and laminate of the present invention are used in the above industrial equipment, the conductive polymer containing the conductive polymer obtained by the above-described conductive polymer production method as a base resin. The molecular molded product or the conductive polymer layer can be used as industrial equipment including a health device, a hygrometer, a hygrometer control device, a soft manipulator, a submersible valve, and a soft transport device used in the driving unit.

  In addition, when the conductive polymer molded article and laminate of the present invention are used in the above-mentioned articles used in water, the conductive polymer obtained by the above-described method for producing a conductive polymer is used as a base resin. The conductive polymer molded article or the conductive polymer layer that is included can be an article used in water, including an underwater mobile used for a drive unit, or a hobby article including a moving fishing bait or a propeller fin.

  Since the conductive polymer molded article and laminate of the present invention can cause displacement as described above, they can be used as actuators. In the conductive polymer molded product of the present invention, for example, one that is not coated with a resin or the like can be used as an actuator that can be linearly displaced in the electrolytic solution. Moreover, it is an actuator containing an operation part, a counter electrode, and electrolyte as mentioned above, Comprising: It can also be set as the actuator in which an operation part contains the conductive polymer obtained by the manufacturing method of this invention.

  Since the conductive polymer molded article and the laminate of the present invention can cause displacement as described above, they can be used as actuators. The conductive polymer molded product of the present invention can be used as an actuator that can be linearly displaced in the electrolytic solution, for example, those that are not covered with a resin or the like. In the laminate of the present invention, for example, one or both of the upper and lower layers when the conductive polymer layer is an intermediate layer is equal to or higher than the expansion ratio at the time of electrolytic expansion / contraction of the conductive polymer layer. In the case of a solid electrolyte layer having elasticity, it can be used as an actuator that performs linear displacement. Also, in the laminate of the present invention, for example, one of the upper and lower layers when the conductive polymer layer is an intermediate layer has a stretchability smaller than the stretch rate during electrolytic stretching of the conductive polymer layer. In the case of the solid electrolyte layer or the resin layer, the solid electrolyte layer or the resin layer does not expand and contract as compared with the conductive polymer layer, so that it can be used as an actuator for bending displacement. An actuator that generates a linear displacement or a bending displacement can be used as a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type orbit made of an arc portion. . Further, the actuator can be used as a pressing portion that performs a linear operation.

  That is, the actuator is an OA device, an antenna, a device for placing a person such as a bed or a chair, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting device, a food processing device, a cleaning device, a measuring device, Inspection equipment, control equipment, machine tools, processing machines, electronic equipment, electron microscopes, electric razors, electric toothbrushes, manipulators, masts, amusement equipment, amusement equipment, vehicle simulation equipment, vehicle occupant restraints, and aircraft accessories In order to move a track-type track composed of a drive unit or a circular arc part that generates a linear driving force in valves, brakes, and locking devices used in all machines including the above-mentioned devices such as devices, OA devices and measuring devices. Preferred as a drive unit that generates a large driving force, or a pressing unit that performs linear or curvilinear motion It can be used for. In addition to the devices, devices, instruments, etc., the actuator is a positioning device drive unit, a posture control device drive unit, a lifting device drive unit, a transport device drive unit, and a movement in general mechanical equipment. A drive unit that generates a linear driving force in a drive unit of the device, a drive unit of an adjustment device such as an amount and a direction, a drive unit of an adjustment device such as a shaft, a drive unit of a guidance device, and a pressing unit of a pressing device or It can be suitably used as a driving unit that generates a driving force for moving a track-type orbit formed by an arc portion, or a pressing unit that performs a linear operation or a curved operation. The actuator can be suitably used as a drive unit in a joint device, such as a joint unit that can be directly driven, such as a joint intermediate member, or a drive unit that gives a rotational motion to the joint.

  The actuator includes, for example, a drive unit of an inkjet part in an inkjet printer such as a CAD printer, a drive unit that displaces the optical axis direction of the light beam of the printer, a head drive unit of a disk drive device such as an external storage device, and the like. It can be suitably used as a drive unit for paper pressing contact force adjusting means in a paper feeding device of an image forming apparatus including a printer, a copier, and a fax machine.

  The actuator includes, for example, a measurement unit for moving a high-frequency power supply unit such as a frequency sharing antenna for radio astronomy to the second focus, a drive unit for a drive mechanism for moving the power supply unit, and a vehicle-mounted pneumatic operation expansion / contraction It can be suitably used for a mast (telescope coping mast) or other mast or drive unit of a lift mechanism in an antenna.

  The actuator is, for example, a driving unit for a massage unit of a chair-shaped massage machine, a driving unit for a nursing or medical bed, a driving unit for an attitude control device of an electric reclining chair, a reclining chair used for a massage machine, an easy chair, etc. The backrest of the ottoman, the telescopic rod drive that allows the ottoman to move up and down, the backrest of the chair and the bed for nursing, and the backrest of the chair, the legrest and the bed for the nursing It can be suitably used for the drive unit used for turning the bed, etc., and the drive unit for controlling the posture of the standing chair.

  The actuator uses, for example, a driving unit of a testing device, a driving unit of a pressure measuring device such as a blood pressure used in an extracorporeal blood treatment device, a driving unit of a catheter, an endoscope device or forceps, and an ultrasonic wave. Driving unit for cataract surgery device, driving unit for exercise device such as jaw movement device, driving unit for means for relatively expanding and contracting the chassis member of the hoist for the sick, and raising / lowering, moving and posture control of care bed It can use suitably for the drive part for.

  The actuator includes, for example, a vibration isolator driving unit that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, a driving unit driving unit for an intake and exhaust valve of an internal combustion engine, It can be suitably used for a drive unit of an engine fuel control device and a drive unit of an engine fuel supply device such as a diesel engine.

  The actuator includes, for example, a driving unit of a calibration device of an imaging apparatus with a camera shake correction function, a driving unit of a lens driving mechanism such as a home video camera lens, and a mechanism that drives a moving lens group of an optical device such as a still camera or a video camera. 2 such as a camera driving unit, a camera auto-focusing unit driving unit, a lens barrel driving unit used in an imaging apparatus such as a camera or a video camera, an auto-guider driving unit that captures light from an optical telescope, a stereoscopic camera, binoculars, etc. Lens drive mechanism or lens barrel drive unit of an optical device having an optical system, drive unit or pressing unit that applies a compressive force to a wavelength conversion fiber of a fiber-type wavelength tunable filter used for optical communication, optical information processing, optical measurement, etc. It can be suitably used for the drive unit of the optical axis alignment device and the drive unit of the shutter mechanism of the camera.

  The actuator can be suitably used for a pressing portion of a fixture such as a caulking fixing of a hose fitting to a hose body, for example.

  The actuator includes, for example, a drive unit such as a winding spring of an automobile suspension, a drive unit of a fuel filler lid opener that unlocks a fuel filler lid of a vehicle, a drive unit of a bulldozer blade extension and retraction drive, and an automobile transmission. It can be suitably used for a drive unit of a drive device for automatically switching the gear ratio and for automatically connecting and disconnecting the clutch.

  The actuator includes, for example, a driving unit of a lifting device of a wheelchair with a seat plate lifting device, a driving unit of an elevator for level difference, a driving unit of a lifting / lowering transfer device, a medical bed, an electric bed, an electric table, an electric chair, a nursing care The present invention can be suitably used for a bed, a lifting table, a CT scanner, a truck cabin tilt device, a lifter and the like, a driving unit for lifting and lowering various lifting machines, and a driving unit for a heavy vehicle carrying special vehicle loading / unloading device.

  The actuator can be suitably used for, for example, a drive unit of a discharge amount adjusting mechanism such as a food material discharge nozzle device of a food processing apparatus.

  For example, the actuator can be suitably used for a drive unit such as a carriage or a cleaning unit of a cleaning device.

  The actuator includes, for example, a driving unit of a measuring unit of a three-dimensional measuring device that measures the shape of a surface, a driving unit of a stage device, a driving unit of a sensor part such as a detection system for a tire operating characteristic, and an impact response of a force sensor. Drive unit of the device that gives the initial speed of the evaluation device, drive unit of the piston drive device of the piston cylinder of the device including the in-hole water permeability test device, drive unit for moving in the elevation angle direction of the concentrating tracking power generation device, measurement of gas concentration When the alignment is required in the driving unit of the tuning mirror vibration device of the sapphire laser oscillation wavelength switching mechanism of the measuring device, the inspection device of the printed circuit board, and the flat panel display such as a liquid crystal display and a PDP, etc. Drive unit, electron beam (E beam) system or focused ion beam (FIB) system Adjustable aperture device drive unit used in charged particle beam systems, etc., support device or detection unit drive unit to be measured in flatness measuring device, as well as assembly of fine devices, semiconductor exposure apparatus and semiconductor inspection It can be suitably used for a drive unit of a precision positioning device such as a three-dimensional shape measuring device.

  The actuator can be suitably used for, for example, an electric razor drive unit and an electric toothbrush drive unit.

  The actuator is desired, for example, by changing the shape of the surface to be driven as an active curved surface by a driving unit of an imaging device for a three-dimensional object or a device for adjusting the depth of focus of a reading optical system shared by CDs and DVDs, and a plurality of actuators. The drive unit of the variable mirror that can form the curved surface approximately and easily change the focal position, the drive unit of the disk device that can linearly move the moving unit having at least one of the magnetic heads such as an optical pickup, and the linear Drive unit of head feeding mechanism of magnetic tape head actuator assembly such as tape storage system, drive unit of image forming apparatus applied to electrophotographic copying machine, printer, facsimile, etc., drive unit of mounting member such as magnetic head member , An optical disc original that controls the focusing lens group in the optical axis direction. Driving unit of exposure apparatus, driving unit of head driving means for driving optical head, driving unit of information recording / reproducing apparatus for recording information on recording medium or reproducing information recorded on recording medium, and circuit breaker ( It can be suitably used for a drive unit for opening / closing operation of a distribution circuit breaker).

  The actuator includes, for example, a driving unit of a rubber composition press molding vulcanizing device, a driving unit of a component aligning device that aligns a transferred component into a single row / single layer and a predetermined posture, and a compression molding device Drive unit, drive unit for welding device holding mechanism, drive unit for bag making filling and packaging machine, drive unit for machine tool such as machining center, molding machine such as injection molding machine and press machine, printing device, coating device and lacquer spraying Drive unit of fluid application device such as device, drive unit of manufacturing device that manufactures camshaft, etc., drive unit of lifting device of lining material, drive device such as tuft ear regulating body in non-woven loom, needle of tufting machine Driving unit for driving system, looper driving system, knife driving system, etc., driving unit for polishing device that polishes parts such as cam grinder and ultra-precision machined parts, driving unit for brake device for hook frame in loom A driving unit of an opening device for forming an opening of a warp for inserting a weft in a loom, a driving unit of a protective sheet peeling device such as a semiconductor substrate, a driving unit of a threading device, a driving unit of an assembly device for an electron gun for CRT, Drive unit of shifter fork drive selection linear control device, drive unit of horizontal movement mechanism of annealing window drive device, glass for torsion race machine for manufacturing torsion races with application to clothing trim, table cloth, seat cover, etc., glass Support unit for melting furnace for hearth, drive unit for moving back and forth the rack of exposure device such as phosphor screen forming method of color picture tube, drive unit for torch arm of ball bonding device, drive unit for bonding head in XY direction , Component mounting process and measurement / inspection process drive unit for chip component mounting and measurement using probes, etc. In a field such as a drive unit for raising and lowering a cleaning tool support of a substrate cleaning device, a drive unit for moving a detection head that scans a glass substrate forward and backward, a drive unit for a positioning device of an exposure apparatus that transfers a pattern onto a substrate, and precision processing Submicron-order micro-positioning device drive unit, chemical mechanical polishing tool measurement device drive unit drive unit, exposure equipment used when manufacturing circuit devices such as conductor circuit elements and liquid crystal display elements in the lithography process And a drive unit for positioning a stage device suitable for a scanning exposure apparatus, a drive unit for conveying or positioning a workpiece, a drive unit for positioning and transporting a reticle stage, a wafer stage, etc., and a precision in the chamber Positioning stage drive, workpiece in chemical mechanical polishing system or Representative of drive units for conductor wafer positioning devices, drive units for semiconductor stepper devices, drive units for devices that accurately position in the processing machine introduction station, machine tools such as NC machines and machining centers, etc. or steppers in the IC industry The reference grating plate of the light beam scanning device in the drive unit of the passive vibration isolation device for various devices and the vibration isolation device for active vibration isolation, the exposure device used in the lithography process of manufacturing semiconductor elements and liquid crystal display elements, etc. It can be suitably used for a drive unit that is displaced in the direction of the optical axis and a drive unit of a transfer device that transfers the product into the article processing unit in the transverse direction of the conveyor.

  The actuator can be suitably used for, for example, a drive unit for a probe positioning device of a scanning probe microscope such as an electron microscope, and a drive unit for positioning an electron microscope sample fine movement device.

  The actuator is, for example, an automatic welding robot, a robot including an industrial robot or a nursing robot, or a joint mechanism represented by a wrist of a robot arm in a manipulator, a joint drive other than a direct drive type, a robot drive Micro for operating a minute object in an arbitrary state in a finger itself, a drive unit of a motion conversion mechanism of a slide opening / closing chuck device used as a hand of a robot or the like, a micro operation of a cell or an assembly of a micro part, etc. It can be suitably used for a drive unit of a manipulator, a drive unit of a prosthesis such as an electric prosthesis having a plurality of fingers that can be opened and closed, a drive unit of a handling robot, a drive unit of a prosthesis, and a drive unit of a power suit.

  The actuator can be suitably used for, for example, a pressing portion of a device that presses the upper rotary blade or the lower rotary blade of the side trimmer.

  The actuator can be suitably used for, for example, a driving unit for an accessory in a game machine such as a pachinko machine, a driving unit for an amusement device such as a doll or a pet robot, and a driving unit of a simulation device for a boarding simulation device. .

  The actuator can be used, for example, in a valve drive unit used in general machines including the above-described devices. For example, a valve drive unit of an evaporative helium gas reliquefaction device, a drive of a bellows pressure-sensitive control valve , Opening device drive unit for driving the frame, vacuum gate valve drive unit, solenoid operated control valve drive unit for hydraulic system, valve drive unit incorporating a motion transmission device using a pivot lever, rocket The movable nozzle valve drive unit, the suck back valve drive unit, and the pressure regulating valve unit drive unit can be suitably used.

  The actuator can be used, for example, as a brake pressing unit used in all machines including the above-described devices. For example, the braking device is suitable for use in an emergency brake, a safety brake, a stop brake, or an elevator brake. Can be suitably used for the pressing portion of the brake structure or the pressing portion of the brake structure or brake system.

  The actuator can be used, for example, as a pressing portion of a locking device used in all machines including the above-described devices. For example, a pressing portion of a mechanical locking device, a pressing portion of a steering lock device for a vehicle, and a load limiter It can be suitably used for a pressing portion of a power transmission device having both a mechanism and a coupling release mechanism.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Example 1)
Polypyrrole which is a monomer of the conductive polymer and the salt described in Table 1 are dissolved in the solvent described in Table 1 by a known stirring method, the monomer concentration is 0.25 mol / l, and the dopant salt of Table 1 An electrolyte solution having a concentration of 0.2 mol% was prepared. Using a commercially available electrode, which is a metal species listed in Table 1, as the working electrode, and a commercially available Pt electrode as the counter electrode, this electrolytic solution was electrolyzed by a constant current method having a polymerization current density of the value described in Table 1. Polymerization was performed. By this electrolytic polymerization, a film-like conductive polymer molded product of Example 1 having the conductivity and film thickness shown in Table 1 was obtained.

(Examples 2-8 and Examples 13-17)
The membrane-shaped conductive polymer molded articles of Examples 2 to 6 were obtained in the same manner as in Example 1 except that the electropolymerization was performed using the salt, solvent, electrode and current density described in Table 1 or Table 3. It was. However, in Example 6, the bis (trifluoromethane) sulfonylimide lithium salt was 0.13 mol%, the trifluoromethanesulfonic acid tetrabutylammonium salt was 0.07 mol%, and the total salt concentration was 0.2 mol%. TBA represents tetrabutylammonium.

(Examples 9 to 12)
Membrane-like conductive polymers of Examples 2 to 6 were obtained in the same manner as in Example 1 except that the electropolymerization was performed using the salt, solvent, electrode and current density shown in Table 2. PC represents propylene carbonate.

(Comparative example)
A film-like conductive polymer molded product of Comparative Example 1 was obtained in the same manner as in Example 1 except that the electropolymerization was performed using the salt, solvent, electrode and current density shown in Table 1.

(Evaluation)
Each of the film-like conductive polymer molded products obtained in Examples 1 to 8 and Examples 13 to 17 and Comparative Example 1 was dissolved in water so that (CF ₃ SO ₂ ) ₂ NLi was 1 mol / l. The film-like conductive polymer of Examples 1 to 8 was retained in a dissolved operating electrolyte solution and subjected to the following method. The expansion / contraction rate per oxidation-reduction cycle and the displacement rate after 10 seconds, Examples 13 to About 17 film-like electroconductive polymer molded products, the expansion / contraction rate per one oxidation-reduction cycle was measured. The results are shown in Tables 1 and 3.

  Further, each of the film-like conductive polymers obtained in Examples 9 to 12 was dissolved in the solvent of Table 2 so that the salt of the dopant anion and lithium shown in Table 2 had the concentration shown in Table 2. The expansion / contraction rate per one oxidation-reduction cycle was measured by the following method while being held in the operating electrolyte solution. The results are shown in Table 2.

[Elasticity]
The film-like conductive polymer moldings obtained in Examples 1 to 8, Example 13 and Example 14 and Comparative Example 1 are 15 mm long and 2 mm wide working electrodes, and the platinum plate is the counter electrode, At the end of the electrode, the working electrode is held in the electrolytic solution and connected to a power source via a lead, and a potential (−0.9 to +0.7 V v at 2 mV / s and / or 0.2 mV / s). .S. Ag / Ag ⁺ ) was applied for 1 cycle, and the amount of displacement (displaced length) was measured. The expansion / contraction rate per oxidation-reduction cycle is obtained by dividing the displacement obtained by extending and contracting the working electrode by applying one cycle (one redox cycle) by the original length of the working electrode. Asked. However, for the film-like conductive polymer molded products obtained in Examples 9 to 12 and Examples 15 to 17, the potential (−0.6 to +1.5 V vs. Ag / Ag) at 2 mV / s. ⁺ ) Was applied for 1 cycle, and the amount of displacement (displaced length) was measured.

[Displacement rate after 10 seconds]
The film-like conductive polymer molded product obtained in Examples 1, 3, 4 and 6 and Comparative Example 1 was used as a working electrode having a length of 15 mm and a width of 2 mm, and a platinum plate was used as a counter electrode. In addition, the working electrode is held in the electrolytic solution and connected to a power source through a lead. s. Ag / Ag ⁺ was applied, and the displacement amount (displaced length) 10 seconds after the start of application was measured. The expansion / contraction rate after 10 seconds was obtained by dividing the displacement amount after 10 seconds from the start of application by the length of the working electrode before applying the potential.

(result)
The conductive polymer molded product of Examples 1 to 8 which is a conductive polymer molded product obtained by the method for producing a conductive polymer of the present invention has an expansion / contraction rate per oxidation-reduction cycle of 16% or more, Moreover, since the conductive polymer molded products of Examples 1, 3, 4 and 6 also had a displacement rate after 10 seconds of 5% or more, they exhibited an excellent stretch rate and a displacement rate after 10 seconds. In particular, in Examples 1, 2, and 5, the expansion / contraction rate per oxidation-reduction cycle is 20% or more, and shows an expansion / contraction rate superior to that of a conductive polymer molded product using a conventional conductive polymer. It was.

  Moreover, although the conductive polymer molded products of Examples 13 to 17 were electrolytically polymerized using a salt of tetrabutylammonium ion and sulfonylimide ion, the sulfonylimide ion was doped as in Examples 1 to 8. The obtained conductive polymer is obtained, and the expansion / contraction rate per oxidation-reduction cycle is 20% or more, and Examples 13 to 16 can have a high expansion / contraction rate of 25% or more.

  The conductive polymer films of Examples 1 to 17 obtained by the method for producing a conductive polymer of the present invention have an expansion / contraction rate of 20% or more per one redox cycle that is the first redox cycle. In particular, when propylene carbonate, which is a good solvent for the conductive polymer film, is used as a solvent, it is possible to perform excellent expansion / contraction exceeding 30% as in Examples 10 to 12. .

  The conductive polymer molded product obtained by using the method for producing a conductive polymer of the present invention is superior in stretch per one redox cycle as compared with a conventional conductive polymer molded product having stretchability. The rate is expressed during electrolytic expansion and contraction, and is more practical than conventional methods in response to displacement commands. Therefore, it is highly practical and useful for applications such as artificial muscles, robot arms, artificial hands and actuators. The conductive polymer molded product obtained by the method for producing a conductive polymer of the present invention has a larger expansion / contraction rate by electrolytic expansion / contraction in an electrolytic solution containing a perfluorosulfonimide salt in an electrolytic expansion / contraction working environment. Since it can be expressed, it is useful as an application that requires even greater expansion and contraction.

The perspective view about the external appearance of the example of 1 embodiment of the actuator of this invention. FIG. 2 is a cross-sectional view of the actuator of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Actuator 2 Housing | casing 3 Actuation part 4 Connection board 51,52 Counter electrode 6 Electrolyte 7 Lead 8 Lead 9 Power supply 21 Tip 22 Bottom 23 Recess 24, 25 Counter electrode fitting recessed

Claims (4)

An actuator element including a conductive polymer molded article containing a conductive polymer and an operating electrolyte,
The conductive polymer is obtained by an electrolytic polymerization method,
The conductive polymer is a conductive polymer doped with a perfluoroalkylsulfonylimide ion represented by the following formula (1):
The conductivity of the conductive polymer is 20.97 S / cm or more,
The working electrolyte comprises the perfluoroalkylsulfonylimide ion;
An actuator element characterized in that the expansion / contraction rate of one oxidation-reduction cycle is 16% or more.
_{(C n F (2n + 1} ) SO 2) (C m F (2m + 1) SO 2) N - (1)
(Here, n and m are integers of 8 or less.) The conductive polymer according to claim 1 Symbol mounting of the actuator element, characterized in that it comprises at least one selected from the group consisting of five-membered heterocyclic compounds and derivatives thereof. The conductive polymer actuator element according to claim 1 or 2, characterized in that it comprises a pyrrole the molecular chain and / or a pyrrole derivative. The actuator device according to any one of claims 1 to 3, characterized in that it comprises an actuating portion and a counter electrode including the conductive polymer.

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