JP4897345B2 - Method for driving polymer actuator element, actuator and method for manufacturing the same - Google Patents

Description

  The present invention relates to a driving method of a polymer actuator element, an actuator, and a manufacturing method thereof.

  A conductive polymer typified by polypyrrole or the like not only has conductivity but also can incorporate ions as a dopant, and can be repeatedly doped and dedoped by applying a voltage. Therefore, the conductive polymer can exhibit electrolytic expansion and contraction, which is a phenomenon that expands or contracts due to electrochemical oxidation and reduction. This electrolytic expansion and contraction of the conductive polymer can be used as a drive for the polymer actuator element.

  An actuator using a conductive polymer can reduce the weight of the entire device incorporated because it is lightweight, and can be used not only as a small drive device such as a micromachine but also as a large drive device. Expected. In particular, application is expected for uses such as artificial muscles, robot arms, artificial hands and actuators. For example, a linear actuator using polypyrrole exhibits an expansion / contraction ratio of 15.1% at maximum per one oxidation-reduction cycle by electrolytic expansion / contraction, and can generate a force of 22 MPa at maximum (for example, see Non-Patent Document 1). .

  However, a polymer actuator element using a conductive polymer has a slow driving speed such as expansion and contraction when a trifluoromethanesulfonate ion, which is a general anion, is used as a dopant. The polymer film could expand and contract only in a direction parallel to the film surface with a small expansion rate per specific time. For this reason, the polymer actuator element using the conductive polymer until now could be used suitably for the use which may be sufficient even if drive speed is slow. On the other hand, when driving a polymer actuator element using the above-described conductive polymer, it is necessary to devise measures such as increasing the size of the polymer actuator element itself in order to achieve a predetermined length of driving within a certain period of time. Met.

Genji, 4 others, “High Stretchable and Powerful Polypyrrole Linear Actuators”, Chemistry Letters, Japan, Vol. 32, 2003 No., p576-577.

  Accordingly, an object of the present invention is to provide a method for driving a polymer actuator element that is excellent in expansion / contraction rate and response speed. Moreover, the objective of this invention is providing the actuator excellent in the expansion-contraction rate and the response speed, and its manufacturing method.

  In order to achieve the above object, the present inventors have intensively studied the driving method of the polymer actuator element. As a result, they have found that the above problem can be solved by using the following method, and have completed the present invention. .

That is, the driving method of the polymer actuator element which is the first invention of the present application is:
A driving method of a polymer actuator element including a conductive polymer that is driven by applying a voltage in a driving electrolyte,
The driving electrolyte is a mixed solution of an organic solvent and an acid, or a mixed solution of an organic solvent, water, and an acid.

The driving method of the polymer actuator element according to the second invention of the present application is as follows.
A driving method of a polymer actuator element including a conductive polymer that is driven by applying a voltage in a driving electrolyte,
The conductive polymer is obtained by contact treatment with an acid, and the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water.

  According to the present invention, as shown in the results of the examples, the driving electrolyte is excellent in stretch rate and response speed when the mixed solution containing acid or the conductive polymer is subjected to contact treatment with acid. The polymer actuator element can be driven. Although the details of the reason for exhibiting such characteristics are not clear, it is presumed that the excellent effect of the present invention can be obtained by rapidly proceeding the doping reaction and the dedoping reaction in the driving electrolyte. Further, in the present invention, even when the same driving performance as that of the prior art is exhibited, the driving voltage can be set lower than that of the prior art.

  In the conventional driving electrolyte, an electrochemically active substance is not added to the driving electrolyte during driving. This is because when such an electrochemically active substance is present in the system, the electrochemically active substance itself usually becomes a reactant of the oxidation-reduction reaction by the application of voltage. As a result, the voltage used for the function as the actuator, the driving performance, etc. are significantly reduced. However, it has been found that the actuator of the present invention can drive a polymer actuator element having an excellent expansion / contraction rate and response speed by using a driving electrolyte containing an acid as described above.

  In the present invention, the organic solvent is preferably a polar organic compound containing at least one bond or functional group among an ester bond, a carbonate bond, and a nitrile group.

  Moreover, in this invention, it is preferable that pH of the said drive electrolyte solution is 0-4. By setting the pH in the above range, it is presumed that the doping reaction and the dedoping reaction in the driving electrolyte solution proceed more reliably and rapidly, and as a result, the above-described excellent effects are exhibited.

  Furthermore, the conductive polymer preferably contains pyrrole and / or a pyrrole derivative in the molecular chain.

Further, the conductive polymer is a film-shaped conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1):
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ]
Or a film-like conductive polymer doped with perfluoroalkylsulfonylmethide ion represented by the following formula (2):
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ]
Is preferred.

On the other hand, the actuator according to the third invention of the present application is an actuator including a conductive polymer and a driving electrolyte,
The driving electrolyte is a mixed solution of an organic solvent and an acid, or a mixed solution of an organic solvent, water, and an acid.

The actuator according to the fourth invention of the present application is an actuator including a conductive polymer and a driving electrolyte,
The conductive polymer is obtained by contact treatment with an acid, and the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water.

On the other hand, the manufacturing method of the actuator which is the fifth invention of the present application,
A method for producing an actuator comprising a conductive polymer and a driving electrolyte, wherein the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water,
The method includes a step of adding an acid to the driving electrolyte.

Moreover, the manufacturing method of the actuator which is the sixth invention of the present application,
A method for producing an actuator comprising a conductive polymer and a driving electrolyte, wherein the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water,
The method includes a step of contacting the conductive polymer with an acid.

  Since the method for manufacturing an actuator of the present invention includes the steps as described above, an actuator excellent in expansion / contraction rate and response speed can be easily manufactured.

  The actuator uses the above-described driving method of the polymer actuator element, and can be easily used for various practical applications as an actuator that causes displacement or bending displacement. In particular, the actuator is suitable for applications that require driving with excellent expansion / contraction rate and response speed. Further, even when the same driving performance as the conventional one is exhibited, the driving voltage can be set lower than the conventional one, so that the side reaction can be easily suppressed, and as a result, the durability is expected to be improved. Furthermore, since the actuator does not require complicated mechanical parts, the apparatus used can be easily reduced in size and weight. Furthermore, by combining the actuator with a device that converts a bending motion into a linear motion, the actuator can be a linear actuator that produces a 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. . Furthermore, the actuator can be used as a pressing portion that performs a linear operation.

  Hereinafter, embodiments of the present invention will be described in detail.

The actuator of the present invention is an actuator containing a conductive polymer and a driving electrolyte,
The driving electrolyte is a mixed solution of an organic solvent and an acid, or a mixed solution of an organic solvent, water, and an acid.

The actuator of the present invention is an actuator including a conductive polymer and a driving electrolyte,
The conductive polymer is obtained by contact treatment with an acid, and the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water.

(Drive electrolyte)
The driving electrolyte used in the present invention includes an electrolyte for driving the polymer actuator element by applying a voltage, and is used as a solvent for dissolving the electrolyte. In the present invention, a mixed solution of an organic solvent and an acid, or a mixed solution of an organic solvent, water, and an acid can be used as a solvent for dissolving the electrolyte. Moreover, when using what the said conductive polymer contact-treated with the acid, an organic solvent or the mixed solution of an organic solvent and water can be used as a solvent which melt | dissolves the said electrolyte. By including these mixed solutions as the driving electrolyte, the polymer actuator element can drive a large amount in the driving electrolyte when the amount of expansion / contraction (driving speed) with respect to time in a state where a constant voltage is applied is measured. Speed can be shown.

  In the present invention, the organic solvent is preferably a polar organic compound containing at least one bond or functional group among an ester bond, a carbonate bond, and a nitrile group.

  The organic solvent is not particularly limited, but is preferably a solvent that can be used as an electrochemical reaction field. Examples of the polar organic compound include γ-butyrolactone, α-methyl-γ-butyrolactone (an organic compound containing an ester bond), propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate (above, carbonate. Organic compounds containing a bond), and acetonitrile, propionitrile, succinonitrile (an organic compound containing a nitrile group). The polar organic compound is preferable because a high expansion rate and a large maximum expansion rate can be obtained, and propylene carbonate is particularly preferable.

  Moreover, when water is contained in the mixed solvent, the mixing ratio of water and the organic solvent is not particularly limited. When a mixed solvent containing water is used as the solvent of the driving electrolyte, the driving speed can be improved twice or more as compared with the case where only the organic solvent is used. Moreover, the said organic solvent may be used independently, and may mix and use 2 or more types.

  It is difficult to specify the mixing ratio of the driving electrolyte according to the type of conductive polymer or organic solvent. The minimum value of the organic solvent for improving the driving speed depends on the kind of the organic solvent due to the ability of the organic solvent to swell the conductive polymer. For example, for propylene carbonate, the water content of the special grade reagent is 0.005%, so the mixing ratio of water and organic solvent can be 0.1: 99.9. The range of the suitable mixing ratio of water and the organic solvent in the mixed solvent is a volume ratio, and the water-containing ratio lower limit is selected from the values selected from 0.5, 1.0, 5.0, 10 or 20. A range in which the upper limit of the ratio is selected from 99.5, 99.0, 95.0, 90.0, or 80.0 can be selected depending on the type of the organic solvent. The mixing ratio can be obtained by analyzing the driving electrolyte by using a measurement method using a gas chromatography method, particularly a measurement method using the Karl Fischer method when the water content is low. it can.

  For example, when the organic solvent is propylene carbonate, the mixing ratio of water and propylene carbonate is 25:75 to 75:25 by volume ratio, so that the driving speed by applying voltage to the conductive polymer is high. It is preferable because it becomes faster. A plurality of the organic solvents may be used as the mixed solvent, and in this case, the mixing ratio is calculated by a ratio between the weight of water and the total weight of all organic solvents.

  The water is not particularly limited, but is preferably distilled water or ion-exchanged water because an inhibitor to electrolytic stretching due to metal ions, chloride ions, or the like is hardly included.

  In addition, a mixed solution containing an acid is used as the driving electrolyte. The acid used in the present invention is not particularly limited, but is preferably a monovalent strong acid.

Examples of the acid include perfluoroalkylsulfonylimide such as (CF ₃ SO ₂ ) ₂ NH, (C ₂ F ₅ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) NH, Perfluoroalkylsulfonylmethides such as (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₃ CH, (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) ₂ CH, and inorganic acids such as nitric acid And the like are preferable.

  The acid may be used alone, or two or more kinds may be mixed and used, but the pH of the driving electrolyte is preferably 0-4, more preferably 1-2. preferable. When the pH is 4 or more, it is difficult to obtain a sufficient addition effect. On the other hand, when the pH is 0 or less, the solvent may be decomposed. In addition, when using what the said conductive polymer contact-treated with the acid, it is not necessary to contain an acid in drive electrolyte solution especially.

Furthermore, the driving electrolyte contains an anion. The anion can use trifluoromethanesulfonic acid ions, BF ₄ ⁻ , PF ₆ ⁻ or perfluoroalkylsulfonylimide ions as dopant ions. Even when these anions are used, the driving speed of the polymer actuator element including the conductive polymer can be improved by using the mixed solvent.

In particular, in order to obtain a higher driving speed in the driving electrolyte solution, a perfluoroalkylsulfonylimide ion represented by the following formula (1) is included in the bulk of the conductive polymer included in the polymer actuator element. In addition, it is more preferable that the driving electrolyte contains a perfluoroalkylsulfonylimide ion represented by the following formula (1).
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ]

Furthermore, in order to obtain a higher driving speed in the driving electrolyte, a perfluoroalkylsulfonylmethide ion represented by the following formula (2) is contained in the bulk of the conductive polymer contained in the polymer actuator element. It is more preferable that the driving electrolyte contains a perfluoroalkylsulfonylmethide ion represented by the following formula (2).
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ]

  By containing these dopant ions, the perfluoroalkylsulfonylimide or perfluoroalkylsulfonylmethide ion is taken into or released from the bulk of the conductive polymer, and the conductive polymer has a large stretching motion. Therefore, the polymer actuator element can exhibit a higher driving speed than the conventional electroconductive polymer electrostretching method.

  In the polymer actuator element of the present invention, the working electrolyte contains the same anion as the anion contained in the conductive polymer tangible material having a specific shape and containing the conductive polymer. It is preferable that The conductive electrolyte used in the polymer actuator element contains the same anion as the anion that can function as a dopant in the working electrolyte solution. Therefore, it is possible to easily obtain a desired amount of electrolytic expansion / contraction. In addition, when the anion contained in the driving electrolyte is perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion, production of a conductive polymer tangible material that causes electrolytic stretching in the driving electrolyte It is preferable that the ionic radius is the same as that of perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion contained in the electrolyte for electrolysis because the electrolytic expansion and contraction can be easily performed.

(Polymer actuator element)
The polymer actuator element of the present invention includes the above-described conductive polymer, and includes a conductive polymer that can be driven by electrolytic expansion and contraction in a driving electrolyte by applying a voltage. If there is, it will not be specifically limited.

  The conductive polymer is not particularly limited in shape as a bulk, but is a film-like body, a cylindrical body, a cylindrical body, a polygonal columnar body such as a prismatic or hexagonal column, a conical body, or a plate-shaped body. Any specific shape such as a rectangular parallelepiped may be used. When the conductive polymer constitutes a part or the whole of the polymer actuator element as a tangible object having a specific shape, the conductive polymer can be easily driven by electrolytic expansion and contraction by applying voltage to the conductive polymer. can do.

  As the shape of the polymer actuator element, besides the above shape, it can be appropriately formed into a shape suitable for the use situation. Moreover, components, such as a protection member, can be added to the shape of the polymer actuator element of this invention, and it can be set as a desired shape. For the polymer actuator element, the conductive polymer film obtained on the working electrode by electrolytic polymerization may be used 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 conductive polymer is not particularly limited as long as the conductive polymer can be doped and dedoped with an anion as a dopant. As the dopant, trifluoromethanesulfonic acid ion, BF ₄ ⁻ , PF ₆ ⁻ , perchloric acid ion or perfluoroalkylsulfonylimide ion can be used according to the required amount of electrolytic expansion and contraction, application, and the like.

In particular, as the conductive polymer, the conductive polymer is a film-shaped conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1):
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ]
Alternatively, as the conductive polymer, a film-shaped conductive polymer doped with perfluoroalkylsulfonylmethide ion represented by the following formula (2) is used. (C _l F _{(2l + 1)} SO ₂ ) (C _{m F (2m + 1) SO} 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ]
However, it is preferable because a higher driving speed can be obtained.

  As described above, the conductive polymer containing perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion in the bulk can also exhibit a large expansion / contraction rate per one oxidation-reduction cycle. These anions have a larger molecular size than conventional dopants such as trifluoromethanesulfonate ions. Therefore, perfluoroalkylsulfonylimide ions or perfluoroalkylsulfonylmethide ions are present inside a tangible material of a conductive polymer having a predetermined shape, but by repeatedly switching the applied voltage between positive and negative. It is speculated that these larger molecular-size anions enter and exit the conductive polymer tangible material, and as a result, can perform large electrolytic expansion and contraction per one redox cycle.

In the perfluoroalkylsulfonylimide ion, a sulfonyl group is bonded to a nitrogen atom that is the center of an anion, and further, there are two perfluoroalkyl groups that are substituents. One of the perfluoroalkylsulfonyl groups is represented by C _n F _{(2n + 1)} SO ₂ , and the other perfluoroalkylsulfonyl group is represented by C _m F _{(2m + 1)} SO ₂ .

  The above m and n are each an arbitrary integer of 1 or more, and m and n 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, etc. it can. Examples of the perfluoroalkylsulfonylimide salt include bis (trifluoromethylsulfonyl) imide salt, bis (pentafluoroethylsulfonyl) imide salt, and bis (heptadecafluorooctylsulfonyl) imide salt.

The perfluoroalkylsulfonylmethide ion has a sulfonyl group bonded to the carbon atom that is the center of the anion, and further has two perfluoroalkyl groups that are substituents. One of the perfluoroalkylsulfonyl groups is represented by C _n F _{2n + 1} SO ₂ , and the other perfluoroalkylsulfonyl group is represented by C _m F _{2m + 1} SO ₂ , and further C _l F _{21 + 1} SO ₂ .

  The above-mentioned l, m, and n are each an arbitrary integer of 1 or more, and l, m, and n may be the same integer, and l, m, and n may be different integers. For example, trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group, heptafluoropropylsulfonyl group, nonafluorobutylsulfonyl group, undecafluoropentylsulfonyl group, tridecafluorohexylsulfonyl group, pentadecafluoroheptylsulfonyl group, heptadecafluoro Examples thereof include an octylsulfonyl group. Examples of the perfluoroalkylsulfonylmethide salt include tris (trifluoromethylsulfonyl) methide salt, tris (pentafluoroethylsulfonyl) methide salt, and tris (heptadecafluorooctylsulfonyl) methide salt. Among them, as an aspect of the present invention, the trimeth (trifluoromethylsulfonyl) methide ion in which the above metide ion is 1 = 1 in the above formula 1, m = 1, n = 1, or n = 1 in the above formula 3 is used. preferable.

In addition, the said conductive polymer can also contain the other anion which can dope and dedope this conductive polymer as an anion as a dopant. For example, trifluoromethanesulfonic acid ions, BF ₄ ⁻ , PF ₆ ⁻ , perchloric acid ions, perfluoroalkylsulfonylimide ions, or the like can be used depending on the required amount of electrolytic expansion and contraction, usage, and the like.

  Further, the perfluoroalkylsulfonylimide ion of the above chemical formula (1) and the perfluoroalkylsulfonylmethide ion of the above chemical formula (2) can form a salt with a cation, and a perfluoroalkylsulfonylimide salt or a perfluoroalkyl A sulfonylmethide ion salt may be added to the electrolytic solution in the electrolytic polymerization method.

The cation that forms a salt with these perfluoroalkylsulfonylimide ions or perfluoroalkylsulfonylmethide ions 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 salt or a perfluoroalkylsulfonylmethide salt as a monovalent cation and dissociating in an electrolyte. Is not to be done.

  The conductive polymer can be easily obtained by an electrolytic polymerization method or the like. The conductive polymer is a conductive polymer obtained by an electrolytic polymerization method, and an electrolytic solution (electrolytic solution for producing a conductive polymer) used for the electrolytic polymerization is an ether bond, an ester bond, a carbonate. It is preferable that an organic compound and / or a halogenated hydrocarbon containing at least one bond or functional group among a bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group be included as a solvent. By including the above-mentioned solvent in the above electrolytic solution and further including perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion, the obtained conductive polymer is larger in one redox cycle. It shows electrolytic expansion and contraction.

  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, Ethyl acetate, n-butyl acetate, t-butyl acetate, 1,2-diacetoxyethane, 3-methyl-2-oxazolidinone, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl phthalate ( As mentioned above, organic compound containing ester bond), propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate (organic compound containing carbonate bond), ethylene glycol, butanol, 1-hexanol, cyclohexanol, 1 -Octanol, 1-decanol, 1-dodecanol, 1-octadecanol (above, organic compound containing hydroxyl group), nitromethane, nitrobenzene (above, organic compound containing nitro group), sulfolane, dimethyl sulfone (above, sulfone group) And organic compounds containing nitrile groups), acetonitrile, butyronitrile, and benzonitrile (above, organic compounds containing a nitrile group). The organic compound containing a hydroxyl group is not particularly limited, but is preferably a polyhydric alcohol or a monohydric alcohol having 4 or more carbon atoms because of its high expansion / contraction ratio. In addition to the above 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 for producing a conductive polymer is one in which at least one hydrogen in the hydrocarbon is substituted with a halogen atom, and is stably present as a liquid under electrolytic polymerization conditions. If it can do, it will not specifically limit. 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 electrolytic solution for producing the conductive polymer, two or more kinds can be used in combination. The halogenated hydrocarbon may be used as a mixed solution with the organic compound, or a mixed solvent with the organic solvent may be used as a solvent in the electrolytic solution for producing the conductive polymer.

  In the bulk of the conductive polymer obtained by the electrolytic polymerization method, the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion used in the electrolytic polymerization method is present. The conductive polymer in which the conductive polymer contains the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion has a large expansion / contraction amount per one oxidation-reduction cycle as described above, and the driving speed (% / The value of s) is also large, and it is preferable because it can be easily obtained. For example, in the case of a film-like body of the above-described conductive polymer tangible material, the maximum expansion rate of conventional electroconductive polymer electrostriction can be obtained up to about 10 to 15% per oxidation-reduction cycle in the surface direction. In contrast, the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion is included as a dopant in the bulk of the conductive polymer, so that 16% per oxidation-reduction cycle in the lengthwise direction. As described above, an excellent maximum expansion / contraction rate of 20% or more can be exhibited. The film-like body can be suitably used for applications requiring a large expansion / contraction rate typified by artificial muscle. In addition to the dopant, the conductive polymer tangible material may 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.

  Similarly to the above description, the perfluoroalkylsulfonylimide ion only needs to have a sulfonyl group bonded to the nitrogen atom that is the center of the anion, and further has two perfluoroalkyl groups that are substituents. 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 bis (trifluoromethylsulfonyl) imide salt, bis (pentafluoroethylsulfonyl) imide salt, and bis (heptadecafluorooctylsulfonyl) imide salt.

  In addition, the perfluoroalkylsulfonylmethide ion, as described above, has a sulfonyl group bonded to a carbon atom which is an anion center, and further has three perfluoroalkyl groups which are substituents. Good. For example, trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group, heptafluoropropylsulfonyl group, nonafluorobutylsulfonyl group, undecafluoropentylsulfonyl group, tridecafluorohexylsulfonyl group, pentadecafluoroheptylsulfonyl group, heptadecafluoro Examples thereof include an octylsulfonyl group. Examples of the perfluoroalkylsulfonylmethide salt include tris (trifluoromethylsulfonyl) methide salt, tris (pentafluoroethylsulfonyl) methide salt, and tris (heptadecafluorooctylsulfonyl) methide salt.

The perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion that may be contained in the electrolytic solution of the electrolytic polymerization method can form a salt with a cation, and the perfluoroalkylsulfonylimide salt or perfluoroalkylsulfonyl It may be added as a methide salt in the electrolytic solution in the electrolytic polymerization method. The cation that forms a salt with the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion 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 an electrolyte.

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

  The perfluorosulfonylimide ion that can be used as a dopant for the conductive polymer forms various salts by the combination of the perfluoroalkylsulfonylimide ion that is the base component and the cation that is the acid component as described above. However, since perfluorosulfonylimide salts are easily dissociated in solution and easily available, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, etc. Tetrabutylammonium for lithium bis (perfluoroalkylsulfonyl) imide and bis (perfluoroalkylsulfonyl) imide such as bis (trifluoromethylsulfonyl) imide and bis (pentafluoroethylsulfonyl) imide Umushio, pyridinium salts or imidazolinium indium salts are preferred.

  The perfluoroalkylsulfonylmethide ion, which can be used as a dopant for the conductive polymer, has various salts depending on the combination of the perfluoroalkylsulfonylmethide ion as the base component and the cation as the acid component as described above. However, since perfluorosulfonylmethide salt is easily dissociated in solution and easily available, lithium tris (trifluoromethylsulfonyl) methide, lithium tris (pentafluoroethylsulfonyl) ) For lithium tris (perfluoroalkylsulfonyl) methides such as methide, and tris (perfluoroalkylsulfonyl) methides such as tris (trifluoromethylsulfonyl) methide and tris (pentafluoroethylsulfonyl) methide Tetrabutylammonium salt, pyridinium salt or imidazolium indium salts are preferred.

  The content of the perfluoroalkylsulfonylimide ion or perfluoroalkylsulfonylmethide ion in the electrolytic polymerization method in the electrolytic solution is not particularly limited, but in order to ensure sufficient ionic conductivity of the electrolytic solution. The perfluoroalkylsulfonylimide salt is preferably contained in the electrolytic solution in an amount of 1 to 40% by weight, and more preferably 2.8 to 20% by weight. Moreover, in order to improve the film quality of the conductive polymer film obtained by the electrolytic polymerization method, a composite electrolyte in which 1 to 80% of trifluoromethanesulfonate is added to the electrolytic solution can also be used. Moreover, these ions may be used alone or in combination of two or more.

  In addition, the electrolytic solution (electrolytic solution for producing a conductive polymer) used in the electrolytic polymerization method further contains a monomer of a conductive polymer in addition to the perfluoroalkylsulfonylimide salt. In addition, other known additives such as polyethylene glycol and polyacrylamide may also be included.

As the electropolymerization method, a known electropolymerization method can be used as the electropolymerization of the conductive polymer monomer, and any of the constant potential method, the constant current method, and the electric sweep method can be appropriately used. it can. 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 preferably carried out under the conditions of ˜2 mA cm ⁻² and a reaction temperature of −40 to 40 ° C., more preferably a reaction temperature of −30 to 30 ° C.

  In addition, the working electrode used for the said electrolytic polymerization method 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 suitably. The metal electrode is not particularly limited as long as it is an electrode mainly composed of metal, but a metal for a metal element selected from the group consisting of Pt, Ti, Ni, Au, Ta, Mo, Cr and W. A single electrode or an alloy electrode can be preferably used. Among them, the metal species contained in the metal electrode is particularly preferably Pt or Ti because the obtained conductive polymer has a large expansion / contraction rate and generation force and the electrode can be easily obtained. As the above 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. As the counter electrode, a known electrode such as Pt or Ni can be preferably used.

  The monomer of the conductive polymer contained in the electrolytic solution used in the above electrolytic polymerization method is not particularly limited as long as it is a compound that is polymerized by oxidation by electrolytic polymerization and exhibits conductivity. For example, pyrrole , Hetero five-membered cyclic compounds such as thiophene and isothianaphthene, and derivatives such as alkyl groups and oxyalkyl groups thereof. Of these, hetero five-membered cyclic compounds such as pyrrole and thiophene, and derivatives thereof are preferable, and in particular, a conductive polymer containing pyrrole and / or a pyrrole derivative is easy to produce, and as a conductive polymer. It is preferable because it is stable. These compounds may be used alone or in combination of two or more.

  Moreover, when using what the said conductive polymer contact-treated with the acid, an organic solvent or the mixed solution of an organic solvent and water can be used as a solvent which melt | dissolves the said electrolyte.

  Examples of the contact treatment include a method of immersing in an acid (acid solution) and a method of standing in an acid atmosphere, but are not particularly limited as long as the conductive polymer is brought into contact with an acid.

  Although it does not specifically limit as an acid used for the said contact process, It is preferable that it is a monovalent | monohydric strong acid.

Examples of the acid include perfluoroalkylsulfonylimide such as (CF ₃ SO ₂ ) ₂ NH, (C ₂ F ₅ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) NH, Perfluoroalkylsulfonylmethides such as (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₃ CH, (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) ₂ CH, and inorganic acids such as nitric acid And the like are preferable.

  Moreover, in this invention, it is preferable that pH of the said acid (acid solution) is 0-4, and it is more preferable that it is 1-2. When the pH is 4 or more, a sufficient contact effect may not be obtained. On the other hand, when the pH is 0 or less, the conductive polymer may be decomposed.

  The polymer actuator element in the present invention has the above-described configuration. A tangible object having a desired shape is constituted by the conductive polymer, the tangible object constitutes all or part of the polymer actuator element, and the tangible object drives to drive the polymer actuator element. To do. The shape of the conductive polymer tangible material is not particularly limited, and may be formed or molded into a film shape, a tubular shape, a tubular shape, a prismatic shape, a fibrous shape, or the like. Since the conductive polymer is obtained in the form of a film on the working electrode during the electropolymerization, it is preferable that the conductive polymer is in the form of a film or can be formed into a film. Further, the conductive polymer polymerized on the working electrode is separated from the working electrode using a solvent capable of swelling the conductive polymer such as acetone. Can be easily obtained.

(Driving condition)
In the driving method of the polymer actuator element of the present invention, the temperature of the driving electrolyte is not particularly limited, but is 10 to 100 ° C. in order to cause the conductive polymer to be electrostretched at a higher speed. It is preferable and it is more preferable that it is 20-60 degreeC.

Further, the concentration of the anion in the driving electrolyte is not particularly limited, but it is preferably 0.1 to 5.0 mol dm ⁻³ , and a large expansion / contraction ratio is obtained, so that the driving can be stably performed. Can do.

  In the driving method, a polymer actuator element containing the conductive polymer is placed in the driving electrolyte, and a counter electrode is installed in the driving electrolyte, so that the conductive polymer and the counter electrode are provided. The polymer actuator element can be driven by applying a voltage.

  The voltage for driving the polymer actuator element is not particularly limited, but when the thickness is about 0.01 mm to 1 mm, the absolute value of the normal applied voltage (V) is 0.2. Although it can be -5V, it is preferable that it is 0.5-3V, and it is more preferable that it is 0.5-1.5V. By using the polymer actuator element of the present invention, even when the same driving performance as the conventional one is exhibited, it can be driven with the driving voltage set lower than the conventional one.

  In addition, when the polymer actuator element is continuously displaced, for example, reciprocating left and right, it is preferable that an opposite voltage is applied to each electrode at a period of 0.001 to 100 Hz. More preferably, the cycle is 1 to 10 Hz, and more preferably 1 to 5 Hz.

(Actuator)
The actuator of the present invention is an actuator including the conductive polymer and the driving electrolyte.

  The actuator is not particularly limited as long as it includes an operating part, an electrolyte (driving electrolyte), and a counter electrode as a device configuration, but a shaft attached to the operating part is a housing so that liquid leakage does not occur during operation. It is preferable to use an actuator packed in the case or an actuator provided with a casing that can be expanded and contracted according to the operation of the operating portion, because no leakage of electrolyte or the like occurs.

  The operating part is not particularly limited as long as it includes 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 part, 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 shape of the actuator of the present invention is not particularly limited. The actuator can be formed in a shape corresponding to the use situation such as a cylindrical shape, 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 molding such as lamination. Furthermore, the counter electrode is not limited to a columnar shape, and may be a plate shape or the like.

  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 has the above-described configuration in the internal working portion, it can obtain an excellent expansion / contraction rate and response speed, so that the displacement is large except for applications such as switches and sensors that can be used even if the displacement is small. It can also be suitably used as an artificial muscle that is used. The actuator can be used as a linear actuator, a driving device, or a pressing device. Since the actuator of the present invention is an actuator that is driven by a conductive polymer by application of a voltage, and is silent or low sound when driven, it is suitable as a driving part or a pressing part in an indoor application device. 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 actuator of the present invention can be suitably used for artificial muscles, robot arms, powered suits, artificial hands and artificial legs. Further, the actuator of the present invention is a medical instrument such as tweezers, scissors, forceps, snare, laser knife, spatula, clip, etc. in microsurgery technology, various instruments or inspection tools for performing inspections and repairs, health instruments, hygrometers, etc. Suitable for articles used underwater such as industrial equipment such as hygrometer control device, soft manipulator, submersible valve, soft transport device, underwater mobile such as goldfish, or hobby equipment such as moving fishing bait and propeller fin Can be used.

  More specifically, the actuator is an OA device, an antenna, a device on which a person such as a bed or a chair is placed, a medical device, an engine, an optical device, a fixture, a side trimmer, a vehicle, a lifting device, a food processing device, or a cleaning device. , Measuring equipment, inspection equipment, control equipment, machine tools, processing machines, electronic equipment, electron microscopes, electric razors, electric toothbrushes, manipulators, masts, amusement equipment, amusement equipment, riding simulation equipment, vehicle occupant restraining devices and aircraft A track-type track consisting of a drive part or a circular arc part that generates a linear drive force in valves, brakes, and lock devices used in all machines including the above equipments such as attached equipment extension devices, OA equipment and measuring equipment Drive unit that generates driving force to move the unit, or linear or curvilinear operation It can be suitably used as a pressure part. In addition to the above-described 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 devices. 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 or 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. In addition, the actuator can be suitably used as a drive unit in a joint device, such as a joint unit that can be directly driven, such as a joint intermediate member, or a drive unit that 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 focal point, 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 includes, for example, a driving unit for a massage unit of a chair-shaped massage machine, a driving unit for a nursing care or medical bed, a driving unit for a posture 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 a drive unit used for driving a turn of the bed, and a drive unit for posture control of a 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, forceps, or the like, and an ultrasonic wave. Drive unit for cataract surgery device, drive unit for exercise device such as jaw motion device, drive unit for means for relatively expanding and contracting chassis member of sick hoist, 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 drive unit for a vibration isolator that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, a drive unit for a valve operating device for intake and exhaust valves 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 for a calibration device of an imaging apparatus with a camera shake correction function, a driving unit for a lens driving mechanism such as a home video camera lens, and a mechanism for driving a moving lens group of an optical device such as a still camera or a video camera. 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 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 example, for a pressing portion of a fixture such as caulking and fixing a hose fitting to a hose body.

  The actuator includes, for example, a driving unit such as a winding spring of an automobile suspension, a driving unit of a fuel filler lid opener that unlocks a fuel filler lid of a vehicle, a driving unit of a bulldozer blade extending and retracting, 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 for a lifting device for a wheelchair with a seat plate lifting device, a driving unit for a lift for removing a step, a driving unit for a lifting / lowering transfer device, a medical bed, an electric bed, an electric table, an electric chair, and 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 or the like, a lifting drive unit for various lifting machines, and a drive 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 discharge nozzle device of a food processing apparatus.

  The said actuator can be used suitably for drive parts, such as raising / lowering of the trolley | bogie of a cleaning apparatus, a cleaning part, etc., for example.

  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 tire operating characteristics, 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., etc., measuring device support device or detection unit drive unit in flatness measuring instrument, as well as assembly of fine devices, semiconductor exposure devices and semiconductors It can be suitably used for a driving unit of a precision positioning device such as an inspection device or 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 above-mentioned actuator is desired, for example, by changing the shape of a driving target surface 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 that drives and controls the focusing lens group in the optical axis direction Driving unit for disc exposure apparatus, driving unit for head driving means for driving optical head, driving unit for 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 drive unit of a rubber composition press molding vulcanizing device, a driving unit of a component aligning device that aligns a component to be transferred 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 Drive units such as drive systems, looper drive systems, and knife drive systems, drive units for polishing devices that polish parts such as cam grinders and ultra-precision machined parts, and drive for brake devices for hook frames in looms , An opening device driving unit for forming a warp opening for weft insertion in a loom, a driving unit for a protective sheet peeling device such as a semiconductor substrate, a driving unit for a threading device, and a driving unit for an assembly device for an electron gun for CRT , A drive unit of a shifter fork drive selection linear control device in a torsion race machine for manufacturing a torsion race having application to a garment for clothing, a table cloth, a seat cover, etc., a drive unit of a horizontal movement mechanism of an annealing window drive device, Driving unit for glass melting furnace for hearth, driving unit for advancing and retreating the rack of exposure device such as fluorescent screen forming method of color picture tube, driving unit for torch arm of ball bonding device, driving of bonding head in XY direction Parts mounting process and measurement / inspection process drive unit for mounting, chip component mounting and measurement using probes, etc. In the fields of up / down drive unit for cleaning tool support of substrate cleaning device, drive unit for moving back and forth detection head that scans glass substrate, drive unit for exposure device positioning device that transfers pattern onto substrate, precision processing, etc. The exposure used when manufacturing circuit devices such as conductor parts and liquid crystal display elements, etc., in the sub-micron order, micropositioning device drive unit, chemical mechanical polishing tool measurement device positioning unit drive unit A drive unit for positioning a stage device suitable for an apparatus and a scanning exposure apparatus, a drive unit for transporting or positioning a workpiece, a drive unit for positioning and transporting a reticle stage, a wafer stage, etc. Precision positioning stage drive, workpiece in chemical mechanical polishing system or Represented by semiconductor wafer positioning device drive unit, semiconductor stepper device drive unit, drive unit for precise positioning in the processing machine introduction station, machine tools such as NC machines and machining centers, etc. or IC industry steppers The reference grating plate of the light beam scanning device is used 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 for 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 driving unit for a probe positioning device of a scanning probe microscope such as an electron microscope and a driving unit for positioning a sample micro-movement device for an electron microscope.

  The actuator includes, for example, an automatic welding robot, a robot including an industrial robot and 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 openable / closable fingers, a drive unit of a handling robot, a drive unit of a prosthesis, and a drive unit of a power suit.

  The said actuator can be used suitably for the press part of the apparatus which presses the upper rotary blade of a side trimmer, a lower rotary blade, etc., for example.

  The actuator can be suitably used for, for example, a driving unit for an accessory in a game device such as a pachinko machine, a driving unit for an amusement device such as a doll or a pet robot, and a driving unit for a simulation device of 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, the valve drive unit of an evaporative helium gas reliquefaction device, the 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 can be suitably used as a valve drive section, a suck back valve drive section, and a pressure regulating valve section drive section.

  The actuator can be used, for example, as a brake pressing unit used in all machines including the equipment and the like. For example, a braking device suitable for use in an emergency brake, a safety brake, a stop brake, or an elevator brake. And 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 equipment and the like. For example, a pressing portion of a mechanical locking device, a pressing portion of a vehicle steering lock device, and a load limiter It can be suitably used for a pressing portion of a power transmission device having both a mechanism and a coupling release mechanism.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below. In addition, the evaluation item in an Example etc. measured as follows.

<Measurement of stretch rate>
The expansion / contraction rate (%) per oxidation-reduction cycle of the polymer actuator element produced by the following method was measured.

Each polymer actuator element has a strip shape with a length of 15 mm and a width of 2 mm, the polymer actuator element as an operating electrode, a platinum plate as a counter electrode, a lead connected to the end of each electrode, and each electrode as the above electrolyte solution While being held in, it is connected to a power source through a lead, and a potential (−0.7 to +0.7 V vs. Ag / Ag ⁺ ) at each frequency (Hz) is applied for one cycle to apply a displacement amount ( 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. (%) Was calculated.

<Measurement of displacement angle>
The displacement angle (°) of the polymer actuator element produced by the following method was measured.

  About each produced polymer actuator element, it sandwiched in the thickness direction of the polymer actuator element with a platinum terminal so that each of a pair of metal electrodes can be energized at a position 2 mm inside from one end, and the film surface is It was held so as to be parallel to the direction of gravity.

  Next, using a potentiostat (Bottensio Galvanostat HA-151, manufactured by Hokuto Denko Co., Ltd.) and a multifunction generator (manufactured by NF Circuit Design Block Co., Ltd., Wave Factory WF 1946), one of the pair of metal electrodes is the positive electrode and the other is the positive electrode. A sine wave voltage of ± 0.5 V was applied so as to be a negative electrode, and then a voltage was applied so that an opposite voltage was applied to each metal electrode in a cycle of 3.0 Hz, and a displacement motion reciprocating left and right was performed. .

  The angle between the tangential direction of the displacement convex surface at the tip of the polymer actuator element in the reciprocating displacement movement and the state of gravity and the direction of gravity are measured at room temperature for both the right side displacement and the left side displacement, and this is averaged. The displacement angle.

[Example 1]
Mixed solvent (volume ratio 1: 5) of methyl benzoate and dimethyl phthalate containing pyrrole (0.1 mol dm ⁻³ ), tetrabutylammonium bis (trifluoromethylsulfonyl) imide (TBATFSI) (0.2 mol dm ⁻³ ) ) As an electrolytic solution, a stainless steel plate (SUS310S plate) sputtered with platinum as a working electrode, a nickel plate as a counter electrode, and electropolymerization at 0 ° C. for 4 hours by a constant current method with a current density of 0.2 mA cm ^−2. Then, a polypyrrole film (a) doped with bis (trifluoromethylsulfonyl) imide ion (TFSI) was obtained on the working electrode. The polypyrrole film (a) was peeled off in acetone, washed, and air-dried to prepare a self-supporting polypyrrole film (a) as a polymer actuator element.

The obtained polypyrrole film (a) was cut into strips (length 2 mm × width 10 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (1.0 mol dm ⁻³ ) was used as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution (volume ratio 2: 3) of a propylene carbonate (PC) solution and a 0.05 mol dm ⁻³ nitric acid aqueous solution.

[Comparative Example 1]
The obtained polypyrrole film (a) was cut into strips (length 10 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (1.0 mol dm ⁻³ ) was used as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution of propylene carbonate solution and water (volume ratio 2: 3) and a platinum plate as a counter electrode.

  The expansion / contraction rate (%) of the polymer actuator element obtained in Example 1 and Comparative Example 1 was measured. The obtained results are shown in Table 1.

  From the results of Table 1 above, when the frequency is high (0.25 to 2.0 Hz), when the aqueous nitric acid solution is added to the driving electrolyte (Example 1), when the aqueous nitric acid solution is not added (Comparative Example 1) It was found that a larger expansion / contraction rate was exhibited. By adding an aqueous nitric acid solution, the polypyrrole film can be driven at a higher speed.

[Example 2]
An electrolytic polymerization solution similar to that in Example 1 was prepared, and a base plate on which gold was sputtered on both sides of an expanded porous polytetrafluoroethylene (ePTFE) film as a working electrode, a nickel plate was disposed on the counter electrode, and current density Electropolymerization was performed at 0 ° C. for 4 hours by a constant current method of 0.2 mA cm ⁻² to obtain a polypyrrole ePTFE composite film doped with bis (trifluoromethylsulfonyl) imide ion (TFSI). This composite film is a bimorph type polymer actuator element in which ePTFE is an insulating film and polypyrrole doped with TFSI is disposed on both sides thereof.

The obtained polypyrrole ePTFE composite membrane was cut into a strip shape (length 15 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (0.5 mol dm ⁻³ ) was contained as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution (volume ratio 1: 1) of a propylene carbonate solution and a 0.1 mol dm ⁻³ nitric acid aqueous solution.

[Comparative Example 2]
The obtained polypyrrole ePTFE composite membrane was cut into a strip shape (length 15 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (0.5 mol dm ⁻³ ) was contained as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution (volume ratio 1: 1) of a propylene carbonate (PC) solution and water.

  The displacement angle (°) of the polymer actuator element obtained in Example 2 and Comparative Example 2 was measured. The obtained results are shown in Table 2.

  From the results shown in Table 2 above, when the nitric acid aqueous solution is added to the driving electrolyte at the same frequency and the same voltage (Example 2), it can shake more greatly than when the nitric acid aqueous solution is not added (Comparative Example 2). all right. By adding an aqueous nitric acid solution, the displacement performance of the polypyrrole ePTFE composite membrane can be greatly improved.

Example 3
Mixed solvent (volume ratio 1: 5) of methyl benzoate and dimethyl phthalate containing pyrrole (0.1 mol dm ⁻³ ), tetrabutylammonium bis (trifluoromethylsulfonyl) imide (TBATFSI) (0.2 mol dm ⁻³ ) ) As an electrolyte, platinum as a working electrode, a nickel plate as a counter electrode, and + 1.4V v. s. Electropolymerization was performed at −10 ° C. for 6 hours by a constant potential method of Ag / AgCl to obtain a polypyrrole film (b) doped with bis (trifluoromethylsulfonyl) imide ion (TFSI) on the working electrode. The polypyrrole film (b) was peeled off in acetone, washed, and air-dried to prepare a self-supporting polypyrrole film (b) as a polymer actuator element.

The obtained polypyrrole film (b) was cut into strips (length 2 mm × width 10 mm), and mixed with propylene carbonate and 0.1 mol dm ⁻³ nitric acid aqueous solution (volume ratio 9: 1) to 5 After impregnating for minutes, it was again washed with acetone and air dried. The polypyrrole film (b) subjected to contact treatment with an acid was mixed with a propylene carbonate solution containing lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (1.0 mol dm ⁻³ ) as a driving electrolyte and water ( Polymer actuator elements were evaluated using a volume ratio of 2: 3).

[Comparative Example 3]
The obtained polypyrrole film (b) was cut into strips (length 10 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) was used as the driving electrolyte without performing the contact treatment with the acid of Example 3. ) Polymer actuator elements were evaluated using a mixed solution of propylene carbonate solution containing imide (LiTFSI) (1.0 mol dm ⁻³ ) and water (volume ratio 2: 3) and a platinum plate as a counter electrode.

  The expansion / contraction rate (%) of the polymer actuator elements obtained in Example 3 and Comparative Example 3 was measured. The obtained results are shown in Table 3.

From the results of Table 3 above, when the contact treatment with acid was performed (Example 3 ), when the contact treatment with acid was not performed (Comparative Example 3 ), the frequency was higher (0.1 to 2 .0 Hz) at +0.7 Vv. Elongation with constant potential of s.Ag/AgCl applied, -0.7 Vv. It was found that any shrinkage to which a constant potential of s.Ag/AgCl was applied showed a larger stretch rate. By performing the acid pretreatment, the polypyrrole film can be driven at a higher speed.

Example 4
The polypyrrole film (a) doped with TFSI prepared in the same manner as in Example 1 was cut into strips (size of 2 mm length × 10 mm width), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) as a driving electrolyte. ) A mixed solution (volume ratio 2: 3) of a propylene carbonate (PC) solution containing (1.0 mol dm ⁻³ ) and a 0.05 mol dm ⁻³ aqueous bis (trifluoromethylsulfonyl) imidic acid (HTFSI) solution. The polymer actuator element was evaluated using this.

[Comparative Example 4]
The obtained polypyrrole film (a) was cut into strips (length 10 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (1.0 mol dm ⁻³ ) was used as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution of propylene carbonate solution and water (volume ratio 2: 3) and a platinum plate as a counter electrode.

  The expansion / contraction rate (%) of the polymer actuator element obtained in Example 4 and Comparative Example 4 was measured. Table 4 shows the obtained results.

  From the results of Table 4 above, when the aqueous nitric acid solution was added to the driving electrolyte (Example 4), the case where the frequency was higher (0.1 to 2.0 Hz) than when the aqueous nitric acid solution was not added (Comparative Example 4). ) + 0.7V v. s. Elongation with constant potential of Ag / AgCl applied, -0.7 V It was found that any expansion / contraction with a constant potential of s. Ag / AgCl showed a larger expansion / contraction rate. By adding an aqueous nitric acid solution, the polypyrrole film can be driven at a higher speed.

Example 5
Methyl benzoate containing pyrrole (0.25 mol dm ⁻³ ), 1,2-dimethyl-3-propylimidazolium tris (trifluoromethylsulfonyl) methide (DMPIMe) (0.12 mol dm ⁻³ ) is used as an electrolyte. Using a glassy carbon plate as the working electrode and a nickel plate as the counter electrode, + 1.2V v. s. Electropolymerization was performed at −10 ° C. for 15 hours by a constant potential method of Ag / AgCl to obtain a polypyrrole film (c) doped with tris (trifluoromethylsulfonyl) methide ion on the working electrode. The polypyrrole film (c) was peeled off in acetone, washed and air-dried to prepare a self-supporting polypyrrole film (c) as a polymer actuator element.

The obtained polypyrrole membrane (c) was cut into strips (size of 2 mm length × 10 mm width), and 1,2-dimethyl-3-propylimidazolium tris (trifluoromethylsulfonyl) methide (DMPIMe) was used as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution (volume ratio 2: 3) of a propylene carbonate (PC) solution containing (0.10 mol dm ⁻³ ) and a 0.1 mol dm ⁻³ nitric acid aqueous solution.

[Comparative Example 5]
The obtained polypyrrole film (c) was cut into strips (length 10 mm × width 2 mm), and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (1.0 mol dm ⁻³ ) was used as a driving electrolyte. The polymer actuator element was evaluated using a mixed solution of propylene carbonate solution and water (volume ratio 9: 1) and a platinum plate as a counter electrode.

  The expansion / contraction rate (%) of the polymer actuator elements obtained in Example 5 and Comparative Example 5 was measured. The results obtained are shown in Table 5.

  From the results of Table 5 above, when the frequency is high (0.1 to 0.5 Hz), when the aqueous nitric acid solution is added to the drive electrolyte (Example 5), when the aqueous nitric acid solution is not added (Comparative Example 5) It was found that a larger expansion / contraction rate was exhibited. By adding an aqueous nitric acid solution, the polypyrrole film can be driven at a higher speed.

Claims (12)

An actuator including a conductive polymer and a driving electrolyte,
The actuator, wherein the driving electrolyte is a mixed solution of an organic solvent and an acid, or a mixed solution of an organic solvent, water, and an acid. An actuator including a conductive polymer and a driving electrolyte,
An actuator, wherein the conductive polymer is contact-treated with an acid, and the driving electrolyte is an organic solvent or a mixed solution of an organic solvent and water. The actuator according to claim 1 or 2, wherein the acid is at least one selected from the group consisting of perfluoroalkylsulfonylimide, perfluoroalkylsulfonylmethide, and inorganic acid. The actuator according to any one of claims 1 to 3, wherein the organic solvent is a polar organic compound containing at least one bond or a functional group among an ester bond, a carbonate bond, and a nitrile group. The actuator according to any one of claims 1 to 4 , wherein the driving electrolyte has a pH of 0 to 4 . The actuator according to any one of claims 1 to 5 , wherein the conductive polymer includes pyrrole and / or a pyrrole derivative in a molecular chain. The actuator according to claim 1 , wherein the conductive polymer is a film-shaped conductive polymer doped with perfluoroalkylsulfonylimide ions represented by the following formula (1).
_{(C m F (2m + 1} ) SO 2) (C n F (2n + 1) SO 2) N - (1)
[In the above formula (1), m and n are arbitrary integers. ] The actuator according to claim 1 , wherein the conductive polymer is a film-shaped conductive polymer doped with a perfluoroalkylsulfonylmethide ion represented by the following formula (2).
_{(C l F (2l + 1} ) SO 2) (C m F (2m + 1) SO 2) (C n F (2n + 1) SO 2) C - (2)
[In the above formula (2), l, m and n are arbitrary integers. ] It is a manufacturing method of the actuator in any one of Claim 1 and Claim 3-8 ,
The manufacturing method of the actuator characterized by including the process of adding an acid to the said drive electrolyte solution. A method for manufacturing the actuator according to any one of claims 2 to 8 ,
A method for manufacturing an actuator comprising the step of contacting the conductive polymer with an acid. Containing perfluoroalkylsulfonylimide ion and / or perfluoroalkylsulfonylmethide ion in the electrolytic solution for producing the conductive polymer,
The method for manufacturing an actuator according to claim 9 or 10, wherein the conductive polymer is manufactured in the electrolytic solution by an electrolytic polymerization method. A driving method of the actuator according to any one of claims 1 to 8,
By applying a voltage in the drive electrolytic solution, a driving method of the actuator the conductive polymer characterized that you drive.