WO2007069310A1

WO2007069310A1 - Polymer actuator element drivable in air

Info

Publication number: WO2007069310A1
Application number: PCT/JP2005/022946
Authority: WO
Inventors: Kazuo Onishi; Shingo Sewa; Minoru Sugiyama
Original assignee: Eamex Corporation
Priority date: 2005-12-14
Filing date: 2005-12-14
Publication date: 2007-06-21

Abstract

A polymer actuator element having metal electrodes and an electrolyte containing a polymer electrolyte, wherein the metal electrodes are formed in a manner that they can form a pair, the metal electrodes contact with the electrolyte, an organic compound having a boiling point of 180˚C or higher and being liquid under an ordinary pressure and at an ordinary temperature is contained in the electrolyte, and the electrolyte comprises an ion exchange resin being swollen with the organic compound.

Description

Specification

Air-driven polymer actuator element

Technical field

[0001] The present invention relates to a polymer actuator element that functions as an actuator element by applying a voltage to a pair of metal electrodes formed so as to be in contact with an electrolyte containing an ion exchange resin, and thereby functioning as an actuator element. The present invention relates to an air-driven polymer actuator element that can be driven for one day or more even in the environment in air at atmospheric pressure without a cover. Background art

Conventionally, as a polymer actuator element, an ion exchange resin molded article and a metal electrode formed in an insulated state on the surface of the ion exchange resin molded article are provided, and the water content state of the ion exchange resin molded article In US Pat. No. 6,053,086, there is provided a polymer actuator element that functions as an actuator element by applying a potential difference between the metal electrodes to cause displacement and deformation of the ion exchange resin molded product (for example, Patent Document 1).

[0003] Since this polymer actuator element is lightweight and flexible, it can be suitably used as an introduction part of a medical device such as a force tensioner. Furthermore, since the high molecular weight actuator element is light and simple in configuration, it is expected to be applied as various driving devices or pressing devices.

[0004] Patent Document 1: Japanese Patent No. 2961125

Disclosure of the invention

Problems to be solved by the invention

[0005] In the aqueous solution containing ions such as sodium ions and quaternary ammonium ions, the polymer actuator element can drive a large displacement or a displacement for a long time by applying a voltage to a pair of metal electrodes. It is. However, in a state where the polymer actuator element is taken out from the aqueous solution and the polymer actuator element is installed in the air, water evaporates and ions serving as charge carriers do not move. For this reason, the polymer actuator element is water-steamed when exposed to air without coating. As a result, the initial drive (displacement) cannot be maintained for an hour.

[0006] The polymer actuator element can be used for a driving device in various devices in order to bend or displace. However, since the polymer actuator element cannot maintain the initial driving for 1 hour, it is substantially difficult to drive in an environment other than in an aqueous solution due to evaporation of water. is there. Therefore, there is a limit to the use in the case where the high-molecular-weight actuator element is used for a driving device of various devices.

[0007] Even when the polymer actuator element is coated with a flexible polymer to prevent evaporation of water due to the element force, the polymer actuator element is driven to the coating layer. When dripping or the like occurs, water evaporates from the polymer actuator element. For this reason, the polymer actuator element can maintain the initial displacement only for about 20 minutes in the atmosphere when the coating layer is not provided. Therefore, even when the coating layer is provided, the polymer actuator element can be coated. Due to the occurrence of wrinkling of the layer, the initial displacement is greatly reduced within a few hours. In other words, even when the polymer actuator element is coated, it is necessary to drive it while confirming that there is no coating resin cracking. For this reason, the driving device using the polymer actuator element is not suitable for long-term use because of the monitoring burden even when it is coated with a flexible resin. Is limited.

[0008] An object of the present invention is to provide an air-driven polymer actuator element that can be driven for one day or more in an environment in air at atmospheric pressure without a cover. Furthermore, an object of the present invention is also to provide a polymer actuator element that can exhibit almost the same amount of initial bending or displacement even after being left in the atmosphere for 1 hour. Means for solving the problem

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using the polymer actuator element of the present invention. The present invention is a polymer actuator element including a metal electrode and an electrolyte including a polymer electrolyte, wherein the metal electrode is formed so as to form a pair, and the metal electrode is in contact with the electrolyte. The electrolyte has a boiling point or decomposition temperature of 180 ° C or higher and contains a liquid organic compound at normal temperature and pressure. In other words, it is a polymer activator element in which the electrolyte is swollen with the organic compound.

The invention's effect

[0010] The polymer actuator element of the present invention uses a specific polar solvent, and therefore has a high boiling point, and therefore uses a drive that bends or deforms in an environment other than in an aqueous solution such as air. Therefore, it can be easily used for a wide variety of practical applications. In particular, the polymer actuator element is suitable for applications that require long-term driving. In the polymer actuator element, even when a specific voltage higher than 3.0 V is applied to the metal electrode for driving, no electrolysis of the solvent occurs, so that no bubbles are generated.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The present invention provides a polymer activator element including a metal electrode and an electrolyte including a polymer electrolyte, wherein the metal electrode is formed so as to form a pair, and the metal electrode Is a polymer actuator element that is in contact with the electrolyte, has a boiling point or decomposition temperature of 180 ° C or higher in the electrolyte, contains a liquid organic compound at normal temperature and pressure, and the electrolyte is swollen with the organic compound. is there. When the polymer actuator element contains a specific liquid organic compound, the bending amount or the displacement amount of the actuator element is hardly changed. For this reason, the polymer actuator element can be driven outside the solution, that is, in the air, and is suitable for long-term driving because there is almost no evaporation of the solution.

[0012] The organic compound that has a boiling point or a decomposition temperature of 180 ° C or higher and is liquid at normal temperature and pressure is contained in the electrolyte. By including the organic compound in the electrolyte, the actuator element can keep the change in the S-humidity state small even after 1 hour without coating at normal temperature and pressure, and the bending amount or displacement amount. Less is. By containing the organic solvent, the electrolyte is swollen, and the polymer actuator element can be easily bent or displaced. In addition, the boiling point of the present application is, as a matter of course, a boiling point measured under normal pressure.

[0013] The organic compound has a boiling point of 180 ° C or higher or a decomposition temperature, and is liquid at room temperature and normal pressure. If it is a shape, it will not specifically limit. The organic compound preferably has a function as a solvent. The organic compound may be an organic compound that can serve as a salt solvent containing ions that serve as charge carriers, or an organic compound that can serve as charge carriers. The organic compound is preferably a polar organic solvent and / or an ionic liquid.

[0014] The polar organic solvent is not particularly limited as long as it is a polar organic solvent having a boiling point or decomposition temperature of 180 ° C or higher, but a polar organic solvent having a boiling point of 245 ° C or higher. It is more preferable that The polar solvent is particularly preferably diethylene glycol, glycerin, sulfolane or a mixture thereof, more preferably diethylene glycol, glycerin, sulfolane, propylene carbonate, butyrolatatatone or a mixture thereof. Since the solvent component of the solution contained in the polymer actuator element is the polar solvent, bending of 50 ° or more can be performed after one day without sealing the polymer actuator element.

[0015] In addition, a conventional polymer actuator element has a relatively low voltage of 1.2 V. For example, in order to cause bending at an angle of 270 ° or more, an interface with an ion exchange resin is used. In order to increase the surface area of the metal electrode, it is necessary to perform complicated pretreatments during manufacturing. However, in the polymer actuator element of the present invention, even when a specific voltage higher than 3.0 V is applied, there is a case where gas generation due to water electrolysis hardly occurs for a certain period of time. When used under such conditions, the polymer actuator element of the present invention can be easily manufactured because an electrode can be formed more easily. In the present application, the angle (°) representing the degree of bending or displacement is the angle (displacement angle) formed by the tangential direction of the bent or displaced convex surface at the tip of the polymer actuator element and the gravity direction. Is required.

An ionic liquid can be used as the organic compound that is liquid at room temperature and normal pressure and has a boiling point or decomposition temperature of 180 ° C. or higher, which is used in the present invention. The ionic liquid is also called a room temperature molten salt and has almost no vapor pressure at room temperature. Therefore, the polymer actuator element of the present invention, which includes the electrolyte power W on-exchange resin and the ion exchange resin is swollen with an ionic liquid, has a bending resistance substantially equal to the initial value even for a long period of one month. Can be tuned or displaced.

[0017] The ionic liquid is composed of tetraalkyl ammonium ion, dialkyl imidazolium ion, trialkyl imidazolium ion, virazolium ion, pyrrolium ion, pyrrolium ion, pyrrolidinium ion, and piberidinium ion. And at least one selected cation from the group consisting of

PF_, BF_, A1C1_, CIO_, and sulfonimide anion represented by the following formula (1)

6 4 4 4

Anion selected from at least one group

The polymer actuator element according to claim 2, which is a salt comprising a combination of

(C F SO) (C F SO) N— (1)

n (2n + l) 2 m (2m + l) 2

(Where n and m are arbitrary integers.)

[0018] The tetraalkylammonium ion is not particularly limited, and trimethylpropylammonium, trimethylhexylammonium, and tetrapentylammonium ions can be used.

[0019] The imidazolium cation may be a dialkyl imidazolium ion and / or a trialkyl imidazolium ion. For example, the imidazolium cation is not particularly limited, but includes 1-ethyl-3-methyl imidazolium ion, 1 hexyl 3 methyl imidazolium ion, 1-butyl 3-methyl imidazolium ion, 1, 3— Dimethyl imidazolium ion, 1-methyl-3-ethyl imidazolium ion, 1, 2, 3 Trimethyl imidazolium ion, 1, 2 Dimethyl -3-ethyl imidazolium ion, 1, 2 Dimethyl -3 propyl imidazolium ion, 1-butyl 2 , 3 Dimethyl imidazolium ion.

[0020] The alkylpyridinium ion is not particularly limited, but N-butylpyridinium ion, N-methylpyridinium ion, N-ethylpyridinium ion, N-propylpyridinium ion Mion, 1_ethyl_2_methylpyridinium, 1_butyl_4-methylpyridinium, 1_butyl-1,4-dimethylpyridinium can be used.

[0021] The pyrrolium cation is not particularly limited, but 1, 1-dimethylpyrrolium ion, 1_ethyl_1_methylpyrrolium ion, 1_methyl_1_propylpyrrolium ion, 1-Butyl 1-methylpyrrolium ion can be used. [0022] The pyrazolium cation is not particularly limited, however, 1,2-dimethylpyrazolium ion, 1-ethyl-2-methylvirazolium ion, 1-propyl 2-methylvirazolium ion, 1-butyl 2 —Methyl virazolium ion can be used.

[0023] The pyrrolium cation is not particularly limited, but 1,2-dimethylpyrrolium ion, 1_ethyl_2_methylpyrrolonium ion, 1_propyl_2-methylbiphenyl ion, 1 _Butyl _ 2_methylpyrrolium ion can be used.

[0024] The pyrrolidinium cation is not particularly limited, but 1,1-dimethylpyrrolidinium ion, 1_ethyl_1_methylpyrrolidinium ion, 1_methyl_1_propylpyrrolidine 1-butyl-1- 1-methylpyrrolidinium ion can be used.

The piperidinium cation is not particularly limited, but 1, 1_dimethylbiperidinium ion, 1_ethyl_1-methylbiperidinium ion, 1_methyl_1_propyl The ability to use piperidinium ions and 1-butyl-1-methylbiperidinium ions.

[0026] The ionic liquid is not particularly limited to the combination of the anion and the cation. For example, 1-methyl 3-ethylimidazolium trifluoromethane sulfoimide (EMITFSI), 1-methyl-3 —Imidazolium tetrafluoroborate (EM IBF), 1-methyl-3-imidazolium hexafluorophosphate (EMIPF), trimethyl

4 6-neck pyrammonium trifluoromethanesulfoimide, 1 mono-hexyl 3-methyl imidazole tetrafluoroborate, 1 mono-hexyl 3-methyl imidazole hexafluoro fluoro acid, 1 mono-hexyl 3 —Methylimidazolium trifluoromethanesulfonimide can be used.

In the polymer actuator element of the present invention, when the electrolyte includes the ion exchange resin and the ionic liquid, the ion exchange resin becomes a gel electrolyte in a state of being swollen with the ionic liquid. be able to. When the electrolyte contains an ion exchange resin and an ionic liquid, the polymer actuator element can be driven even when left at atmospheric pressure for one month. Furthermore, gel electrolytes containing ion exchange resins and ionic liquids are flexible and can hold a high concentration of electrolyte. Moreover, it is suitable as an electrolyte for an actuator element and a capacitor.

[0028] The production method of the electrolyte containing the ion exchange resin and the ionic liquid is not particularly limited, but the ionic liquid is contained in a known polar solvent having a boiling point of 100 ° C or lower. It can be easily obtained by immersing the ion exchange resin in a mixed solution containing 1 to 90% by weight and leaving it at room temperature until there is no change in size or weight, or leaving it for more than an hour.

[0029] The polymer actuator element of the present invention includes a metal electrode and an ion exchange resin as an electrolyte, and is formed so that the metal electrode can form a pair. The metal electrode is in contact with the electrolyte and has a high height. A molecular actuator element having a structure including a plurality of the metal electrodes. In addition, the actuator element may include one electrode layer on both sides of the ion exchange resin layer, or may include a plurality of electrode layers on both sides or one side. As a specific structure of the actuator element, for example, an actuator element in which a pair of electrode layers form an electrode pair with an ion exchange resin layer sandwiched between them can be used, and an outer surface of a tubular ion exchange resin and / or A plurality of metal electrodes may be provided on the inner surface.

[0030] The polymer actuator element in which the electrode layer forms an electrode pair with an ion exchange resin interposed therebetween can be obtained by a known method. For example, an electroless plating is applied to an ion exchange resin tangent having a membrane shape, a plate shape, or a tubular shape, thereby forming a metal layer on the surface of the ionic exchange resin tangible material or the inner surface of the ion exchange resin tangible surface. Then, by using the metal layer metal as an electrode layer, a metal ion exchange resin joined body which is the polymer actuator element can be obtained.

[0031] As the electroless plating, for example, the following electroless plating method can be preferably used. After the roughening treatment, an adsorption step is performed in which the ion exchange resin is immersed in water and swollen to adsorb a metal complex such as a platinum complex or a gold complex to the ion exchange resin. Next, a reduction process is performed in which the adsorbed metal complex is reduced with a reducing agent to deposit a metal, and a cleaning process is performed after the reduction process to remove the reducing agent as desired.

In this electroless plating, the adsorption process, the reduction process and the cleaning process can be repeated as one cycle in order to make the metal layer as an electrode thick enough to bend or displace when energized. it can. In the thus obtained actuator element, an electrode layer grows in the internal direction of the ion exchange resin to form an electrode, and the electrode layer has a fractal cross section at the interface between the ion exchange resin and the electrode layer. Therefore, a large electric double layer can be provided at the interface between the electrode layer and the ion exchange resin layer. Furthermore, since the electrode layer forms a fractal structure in the inner direction of the ion exchange resin layer, the ion exchange resin joined body is durable even when it is repeatedly bent in order to have an anchor effect. .

[0033] The ion exchange resin contained in the electrolyte of the polymer actuator element of the present invention is not particularly limited. The ion exchange resin is not particularly limited, and a known ion exchange resin can be used. When a cation exchange resin is used, a sulfonic acid group, a carboxyl group, or the like is added to polyethylene, polystyrene, fluororesin, or the like. Those having a hydrophilic functional group introduced therein can be used. Examples of such resins include perfluorosulfonic acid resin (trade name “Nafion”, manufactured by DuPont), perfluorocarbonic resin (trade name “Flemion”, manufactured by Asahi Glass), ACIPLEX (manufactured by Asahi Kasei Kogyo Co., Ltd.). N EOSEPTA (manufactured by Tokuyama Corporation) can be used.

[0034] The metal complex solution used in the electroless plating adsorption process is particularly limited as long as the metal layer formed by reduction contains a metal complex that can function as an electrode layer. It is not a thing. The metal complex is preferably a deposited metal, preferably a metal complex such as a gold complex, a platinum complex, a palladium complex, a rhodium complex, or a ruthenium complex because a metal with a low ionization tendency is electrochemically stable. Is used as an electrode, a metal complex made of a noble metal with good electrical conductivity and high electrochemical stability is preferred, and a gold complex with relatively low electrolysis is preferred. The metal salt solution is not particularly limited, but the metal salt solution preferably contains water as a main component because the metal salt can be easily dissolved and handled easily. Is preferably an aqueous metal salt solution. Therefore, the metal complex solution is preferably an aqueous metal complex solution, particularly preferably an aqueous gold complex solution or an aqueous platinum complex solution, and more preferably an aqueous gold complex solution.

[0035] The reducing agent used in the electroless plating reduction step is appropriately selected according to the type of metal complex used in the metal complex solution adsorbed on the ion exchange resin. For example, sodium sulfite, hydrazine, sodium borohydride, phosphorous acid, sodium hypophosphite and the like can be used.

[0036] The reducing agent may be appropriately selected depending on the metal species to be deposited. When the metal to be precipitated by reduction is Nikkenole or Cobalt, sodium phosphinate, dimethylenoborane, hydrazine, or potassium tetrahydroborate can be used as the reducing agent. When the metal deposited by reduction is palladium, sodium phosphinate, sodium phosphonate, or potassium tetrahydroborate can be used as the reducing agent. When the metal to be deposited by reduction is copper, formalin, sodium phosphonate, or potassium tetrahydroborate can be used as the reducing agent. When the metal deposited by reduction is silver or gold, dimethylaminoborane or potassium tetrahydroborate can be used as the reducing agent. When the metal deposited by reduction is platinum, hydrazine or sodium tetrahydroborate can be used as the reducing agent. When the metal deposited by reduction is tin, trisalt-titanium can be used as the reducing agent. Further, the reducing agent is not limited to the above types, but is used with catalysts such as platinum black, non-metallic acids or ions such as Hg S, HI and I—, Na (H 3 PO 4) and Na 2 SO Lower acid

2 2 2 2 3

Borate, lower oxides such as CO and SO, Li, Na, Cu, Mg, Zn, Fe, Fe (II), Sn (II)

2

, Ti (III), Cr (II) and other highly ionizable metals or their amalgams and low valent metal salts, hydrogen such as A1H [(CH) CHCH] and lithium aluminum hydride

3 2 2 2

Compound, diimide, formic acid, aldehyde, saccharide, L-ascorbic acid and the like can be used as appropriate.

[0037] The reducing agent can be appropriately selected according to the metal species to be reduced. The growth rate of the metal, the particle size of the deposited metal, the contact area between the metal electrode having a fractal structure and the ion exchange resin, In order to change the electrode structure and the flexibility of the resin after plating, it is possible to select and use the optimum type of reducing agent. In addition, the kind of the reducing agent can be appropriately selected so that the reducing bath in the reduction step has a desired pH.

[0038] When reducing the metal complex, an acid or an alkali may be added as necessary.

The concentration of the reducing agent solution is not particularly limited as long as it contains a sufficient amount of reducing agent to obtain the amount of metal to be precipitated by reduction of the metal complex. It is also possible to use a concentration equivalent to that of the metal salt solution used when the electrode is formed by ordinary electroless plating. Further, the reducing agent solution can contain a good solvent for the ion exchange resin.

[0039] The polymer actuator element of the present invention includes a solvent and a salt inside an electrolyte in contact with a metal electrode formed so as to be able to form a pair. The polymer actuator element is preferably flexible so that the polymer actuator element can be bent or displaced. In order to obtain the flexibility, in the polymer activator element, the ion exchange resin is swollen with a liquid organic compound at normal temperature and pressure. The degree of swelling is not particularly limited, but the degree of swelling of the polymer actuator element, that is, the thickness of the polymer electrolyte element with respect to the thickness of the polymer electrolyte in a dry state is swollen. Thickness increase rate power in state 3 ~ 200. / o is preferred. 5 to 60% is more preferred. When the degree of swelling is less than 3%, the displacement bending performance is inferior. When the degree of swelling is greater than 200%, the displacement bending performance is also inferior, and the tensile strength is greatly reduced. turn into. When the force electrode layer contained in the electrolyte is a porous electrode, a part of the solvent may be contained in the pre-metal electrode layer together with the salt.

[0040] Further, in the polymer actuator element of the present invention, the degree of swelling of the electrolyte when the organic compound is a polar organic solvent is larger than that when an ionic liquid is used. Therefore, it can be suitably used for applications that require large bending or displacement. On the other hand, when an ionic liquid is used as the organic compound, the degree of swelling is small compared with the case where a polar organic solvent is used, but it is left as an open system at a room temperature and normal pressure for a period of about one month. However, since the volume change due to swelling is small, the polymer actuator element can be driven without a large change in the amount of bending or displacement during a period of about one month without the need for a cover. In order to obtain the electrolyte, it can be obtained by immersing the ion exchange resin layer in a liquid of the organic compound. For example, in the case of an element in which a metal electrode is formed by applying an electroless plating to the high molecular weight element power S ion exchange resin, the high molecular weight element element is placed in a liquid in the organic compound. By immersing for about one night, the ion exchange resin is made of the organic compound. An element in a swollen state can be obtained.

[0041] The electrolyte of the polymer actuator element of the present invention may be in a state in which the ion exchange resin is swollen by the ionic liquid. When the ion exchange resin is swollen by the ionic liquid, the ion exchange resin does not swell even if the ion exchange resin is immersed in the ionic liquid. An electrolyte in which an ion exchange resin is swollen with an ionic liquid can be easily obtained by evaporating the swelling solvent after the ion exchange resin is swollen with the mixed solution. Further, a high boiling polar organic solvent can be used as the swelling solvent and left in the device. The swelling solvent is a solvent that can swell the ion exchange resin and dissolve the ionic liquid. The above-mentioned swelling does not include infinite swelling in the present application.

[0042] In the polymer actuator element of the present invention, the salt contained in the electrolyte in contact with the metal electrode formed so as to form a pair is converted into a liquid organic compound at room temperature and normal pressure. Although it is not particularly limited as long as it can be dissolved, in the case of forming a counter ion with the polyelectrolyte force S cation, a salt of !! to trivalent cation can be used, and Na + Use of monovalent cations such as K +, Li +, etc. allows for large bending or displacement, so using an alkylammonium ion with a large ionic radius is preferable for bending or displacement. It ’s even better because it ’s possible. The alkylammonium ions include CH N ⁺ H, CHN ⁺ H, (CH) N ⁺ H, (CH

) N ⁺ H, (CH) N ⁺ H, (CH) N ⁺ H, (CH) N ⁺ , (CH) N ⁺ , (CH) N ⁺ , (CH) N ⁺ , H

N + (CH) N + H, H C = CHCH N + HCH, H N + (CH) N + H (CH) N + H, HC≡C

CH N + H, CH CH (OH) CH N ⁺ H, H N + (CH) OH, H N + CH (CH OH), (HOC

H) C (CH N ⁺ H), CH OCH CH N ⁺ H, ammonium ions with aliphatic hydrocarbons as substituents, or ammonia with alicyclic cyclic hydrocarbons in addition to hydrocarbons as functional groups Um ion can be used. At this time, the concentration of the salt is 0.01 to 10 mol / l in order to obtain sufficient bending or displacement as long as it is contained in a concentration equal to or higher than the functional group of the ion exchange resin. Preferred 0.1 to: More preferably 1.0 mol / l. When an ionic liquid is used as the liquid organic compound at room temperature and normal pressure, the above-described salt may not be used. [0043] Since the polymer actuator element of the present invention contains the above-mentioned polar solvent, it can be driven for one day or more without being coated with a resin, but is further coated with a flexible resin. Anyway. The resin is not particularly limited, but polyurethane resin and / or silicon resin can be used. The polyurethane resin is not particularly limited, but a flexible thermoplastic polyurethane is particularly preferable because of its high flexibility and good adhesion. As flexible thermoplastic polyurethanes, the product name “Asaflex 825” (flexibility 200%, manufactured by Asahi Kasei), product name “Pelesen 2363—80A” (flexibility 550%), “Pelecene 2363—80AE” (flexibility) 650%), “Pelecene 2 363-90A” (flexibility: 500%), “Pelecene 2363-90AE” (flexibility: 550%), (manufactured by Dow Chemical Co., Ltd.). Further, the silicon resin is not particularly limited, but a resin having a flexibility of 50% or more is particularly preferable because of its high flexibility and good adhesion. As the silicone resin, for example, “SilaSeal 3 FW”, “SilaSeal DC738RTV”, “DC3145”, and “DC3140” (above, manufactured by Dow Corning) can be used. In the present application, the flexibility refers to the tensile elongation at break (Ultimate Elongation%) in accordance with ASTM D412.

[0044] (Driving method)

The present invention is also a method for driving a polymer actuator element. The polymer actuator element is a polymer actuator element having a pair of metal electrodes formed so as to face each other with an ion exchange resin interposed therebetween, and the polymer actuator element having a pair of metal electrodes Since the polymer actuator element includes a polar solvent having a boiling point of 180 ° C. or higher in the ion exchange resin, a voltage higher than 3.0 V is required to cause bending or displacement of 160 ° or higher. Even in the case of applying, it is possible to drive for more than one day without coating with resin since the rusting force that generates bubbles and the evaporation of the solvent hardly occur.

[0045] In the driving method, as described above, a polar solvent having a boiling point of 180 ° C or higher is used for the polymer actuator element as a solvent that swells the element and dissolves ions as charge carriers. If so, it will not be particularly limited. In particular, when the polar solvent is diethylene glycol and / or glycerin, the bend is 160 ° or more. It is preferable because it can be done.

[0046] Examples and comparative examples of the present invention will be described below, but the present invention is not limited thereto.

[Example 1]

Ion exchange resin membrane with a thickness of 0.2 mm when dried (Fluorine resin ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity 1.4 meq / g) Steps (3) to (3) were repeated 6 cycles to obtain an ion exchange resin membrane provided with a pair of metal electrodes formed with an ion exchange resin sandwiched therebetween. (1) Adsorption step: The dichlorophenant phosphine complex was adsorbed in the molded article by immersing it in a dilute phenant phosphonate salt aqueous solution for 12 hours. (2) Reduction step: The adsorbed dichlorophenantine-phosphorus gold complex was reduced in an aqueous solution containing sodium sulfite to form a gold electrode on the membrane polymer electrolyte. At this time, the temperature of the aqueous solution was set to 60 to 80 ° C., and the dichlorophenanthrine gold complex was reduced for 6 hours while gradually adding sodium sulfite. Next, (3) washing step: The membrane-shaped polymer electrolyte with the gold electrode formed on the surface was taken out and washed with 70 ° C. water for 1 hour. The ion exchange resin membrane on which a pair of metal electrodes was formed by the electroless plating was cut into a length of 22 mm and a width of 1.5 mm. Next, the ion exchange resin membrane is dipped in an aqueous solution of 0.5 mol / l tetraethylammonium chloride and dried, and after that, 0.5 mol / l of chloride is added so that the degree of swelling is about 15%. The polymer actuator element of Example 1 was obtained by immersion in a diethylene glycol solution of tetraethylene ammonium for 24 hours.

[0048] (Example 2)

The solvent for immersing the cut ion exchange resin membrane is changed to 0.5 mol / l of tetraethylene ammonium chloride in diethylene glycol solution, and 0.5 mol / l of tetraethylene ammonium chloride in propylene carbonate solution is used. A polymer actuator element of Example 2 was obtained in the same manner as in Example 1 except that it was used.

[0049] (Example 3)

Instead of 0.5 mol / l of tetraethylene ammonium chloride in diethylene glycol solution, the solvent for immersing the cut ion exchange resin membrane is replaced with 0.5 mol / l of tetraethylene ammonium chloride in glycerin solution. The same method as in Example 1 except that Thus, the polymer actuator element of Example 3 was obtained.

[0050] (Example 4)

The solvent for immersing the cut ion exchange resin membrane is changed to 0.5 mol / l tetraethylene ammonium chloride in diethylene glycol solution, and 0.5 mol / l tetraethylene ammonium chloride in sulfolane solution is used. A polymer actuator element of Example 4 was obtained in the same manner as in Example 1 except that the above was obtained.

[0051] (Example 5)

The solvent for immersing the cut ion exchange resin membrane was changed to 0.5 mol / l of tetraethylene ammonium chloride in diethylene glycol solution, and 0.5 mol / l of tetraethylene ammonium chloride in a petit-mouth rataton solution. A polymer actuator element of Example 3 was obtained in the same manner as in Example 1 except that was used.

[0052] (Example 6)

Ion exchange resin membrane with a thickness of 0.2 mm when dried (Fluorine resin ion exchange resin: perfluorocarboxylic acid resin, trade name “Flemion”, manufactured by Asahi Glass Co., Ltd., ion exchange capacity 1.4 meq / g) Steps (3) to (3) were repeated 6 cycles to obtain an ion exchange resin membrane provided with a pair of metal electrodes formed with an ion exchange resin sandwiched therebetween. (1) Adsorption process: The dichlorophenant phosphine complex was adsorbed in the molded article by immersing in a dilute phenant phosphonate salt aqueous solution for 12 hours. (2) Reduction step: The adsorbed dichlorophenantine-phosphorus gold complex was reduced in an aqueous solution containing sodium sulfite to form a gold electrode on the membrane polymer electrolyte. At this time, the temperature of the aqueous solution was set to 60 to 80 ° C., and the dichlorophenanthrine gold complex was reduced for 6 hours while gradually adding sodium sulfite. Next, (3) washing step: The membrane-shaped polymer electrolyte with the gold electrode formed on the surface was taken out and washed with 70 ° C. water for 1 hour. The ion exchange resin membrane on which a pair of metal electrodes was formed by the electroless plating was cut into a length of 22 mm and a width of 1.5 mm. Next, the ion exchange resin membrane was immersed in an aqueous solution of 0.5 mol / l tetraethylammonium chloride and dried, and then 0.2 mol / l ethylmethylimidazolium trifluoromethanesulfonimide salt. A polymer actuator element of Example 6 was obtained by immersing in an aqueous solution of (EMITFSI) at room temperature and air-drying it at room temperature for 2 hours or more to evaporate water. [0053] (Example 7)

Instead of an aqueous solution of 0.2 mol / l ethylmethylimidazolium trifluoromethanesulfonimide salt, an aqueous solution of 0.2 mol / l ethylmethylimidazolium hexafluorophosphate (EMI PF) was used. Except that, the polymer activity of Example 7 was the same as Example 6.

6

A ueta element was obtained.

[Example 8]

Instead of 0.2 molZl ethylmethylimidazoletrifluoromethanesulfonimideimide salt solution, 0.2 mol / l ethylmethylimidazole tetrafluoroborate (EM IBF) was used. Except that, the polymer activity of Example 8 was the same as Example 6.

Four

A ueta element was obtained.

[Example 9]

0. Instead of 2 molZl aqueous solution of ethylmethylimidazolium trifluoromethanesulfonimide, 0.2 mol / l trimethylpropylammonium trifluoromethanesulfonimide salt TMPATFSITMPATFSI (TMPATFSI) TMPATFSI

TMPATFSI TMPATFSI TMPATFSI TMPATFSI TMPATFSI A polymer actuator element of Example 9 was obtained in the same manner as Example 6, except that an aqueous solution of TMPATFSI was used.

[Example 10]

Instead of 0.2 mol / l ethylmethylimidazolium trifluoromethanesulfonimide salt aqueous solution, 0.2 mol / l 1-butyl 3-methylimidazolium tetrafluoroborate (BMIBF) aqueous solution was used. The polymer of Example 10 was the same as Example 6 except that it was used.

Four

An actuator element was obtained.

[0057] (Example 11)

Instead of 0.2 molZl aqueous solution of ethylmethylimidazolium trifluoromethanesulfonimide salt, 0.2 mol / l 1_hexyl 3-methylimidazolium hexaoxalate (H MIPF) was used. Except for the polymer polymer of Example 11 in the same manner as Example 6.

6

A cutout element was obtained.

[0058] (Comparative example)

A solvent for immersing the cut ion exchange resin membrane was changed to 0.5 mol / l tetrachloride chloride. The polymer activator element of the comparative example was prepared in the same manner as in Example 1 except that a 0.5 mol / l aqueous solution of tetraethylene ammonium chloride was used instead of the diethylene glycol solution of tylene ammonium. Obtained.

[0059] [Evaluation]

For the polymer actuator elements of Examples 1 to 5 and Comparative Example, the displacement angle in air and the element properties when a 3.0 V voltage was applied were evaluated by the following methods. The results are shown in Table 1.

[0060] (Displacement angle in air)

For each of the polymer actuator elements of Examples 1 to 5 and the comparative example, a polymer terminal is used at the platinum terminal so that each of the pair of metal electrodes can be energized at a position 2 mm inside from one end. The film was sandwiched in the thickness direction of the actuator element so that the film surface was parallel to the gravity direction. Using a potentiostat (DC mode, trade name “Potentio Galvanostat HA-501”, manufactured by Hokuto Denko Co., Ltd.) so that one of the pair of metal electrodes is a positive electrode and the other is a negative electrode. · A voltage of 5 V was applied, and a voltage was applied so that the opposite voltage was applied to each metal electrode at a period of 0.1 Hz, causing displacement movement to reciprocate left and right. The angle formed by the tangential direction of the displacement convex surface at the tip of the polymer actuator element and the gravity direction in the bent or displaced state at the third reciprocation of the reciprocating displacement movement is measured for the right displacement and the left displacement, and averaged. The displacement angle was determined. This measurement was carried out for each high molecular weight actuator element at 1 minute, 1 hour, and 24 hours after being held by the platinum terminal.

[0061] [Table 1]

Example

Comparative example

1 2 3 4 5

Liquid Species Inert Solvent Polar Solvent Polar Solvent Polar Solvent Polar Solvent Inert Solvent

Titanium Diethylene Propylene coupling

«Name Glycerin Sulfolane Contained in molecule Glycol-ponton

Liquid

Body

Boiling

245 242 290 287 204 100

170 90 150 1 10 160 180 After 1 minute in air

Strange in

(Position 1 hour later 170 80 150 1 10 150 10)

24 hours later 100 50 100 90 80 No displacement

[Table 2]

(Result)

In the polymer actuator element of Example 1, diethylene glycol, which is a polar solvent having a boiling point of 245 ° C., is contained in the element as a solvent. Therefore, even after 24 hours, that is, after 1 day, an applied voltage of 1.2 V is 100 A displacement angle of more than ° was shown. On the other hand, since the high molecular weight actuator element of the comparative example contained water as a polar solvent having a boiling point of 100 ° C., no displacement occurred after 24 hours. [0064] Since the polymer actuator elements of Examples 2 to 5 contain polar solvents having a boiling point of 204 to 290 ° C as the solvents, the applied voltage 1. The displacement angle was more than 50 ° at 2V. In particular, in Example 4, the displacement angle after 24 hours was 80% of the displacement angle after 1 minute, which was good with little decrease in displacement.

Examples 6 to 11: The polymer actuator elements of 11 had a swelling degree of 14.0-22.1% and a large displacement angle, but there was almost no decrease in displacement. In addition, the polymer actuator elements of Examples 6 to 11 were good with little decrease in displacement even when left for one month in an open system at room temperature without covering. A polymer actuator element using an ionic liquid is not very suitable for applications requiring a large amount of displacement, but is preferably used for applications requiring a small amount of displacement, such as a switching device.

[0066] Examples: As shown in the polymer actuator elements of! To 11, sufficient performance with time is possible with one-day driving in a room temperature release system and almost no decrease in displacement after 1 hour. For applications requiring a large amount of displacement, a polar organic solvent can be suitably used as the organic compound that is liquid at normal pressure and room temperature with a boiling point of 180 ° C. or higher. On the other hand, although a large amount of displacement is not required, the boiling point is 180% for applications that can be displaced even after one month in a room temperature release system where the amount of displacement is negligible even if left for one day. An ionic liquid can be suitably used as the organic compound that is liquid at normal temperature and room temperature, which is not lower than ° C. In addition, in order to control the displacement amount and the change of the displacement amount over time, the polar organic solvent and the ionic liquid may be mixed at an arbitrary ratio.

[0067] Examples 1 to 11: Even when the polymer actuator elements of 11 were coated and scratched, they were damaged by scratches compared to the polymer actuator elements using an aqueous solvent as in Comparative Example 1. Even in a released state, it can be driven for a long time. Further, when the polymer actuator elements of Examples:! To 11 are not coated, the coating layer does not hinder the bending, and therefore the bending inherent in the element can be performed.

Industrial applicability

The polymer actuator element of the present invention can be used as an actuator element that generates displacement or bending displacement. In addition, the laminate is combined with a device that converts the bending motion into a linear motion, thereby forming an actuator that produces a linear displacement. You can also. 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 track composed of an arcuate portion. . Furthermore, the actuator can also be used as a pressing portion that performs a linear operation.

That is, the actuator is an office equipment, an antenna, a device 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 measurement device. 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, vehicular occupant restraints, and aircraft In the accessory equipment extension device, a drive unit that generates a linear drive force or a drive unit that generates a drive force for moving a track-type orbit made of a circular arc, or a linear or curved operation It can use suitably as a press part to do. The actuator is, for example, a track-type track including a drive unit or a circular arc unit that generates a linear drive force in a valve, a brake, and a lock device used in all machines including the above-described devices such as OA devices and measurement devices. It can be used as a driving unit that generates a driving force for moving the oscillating member or a pressing unit that performs a linear operation. In addition to the above-described devices, equipment, instruments, etc., in general mechanical equipment, a positioning device drive unit, a posture control device drive unit, a lifting device drive unit, a transport device drive unit, and a movement device drive unit. It can be suitably used as a drive unit for an adjustment device such as an amount and a direction, a drive unit for an adjustment device such as a shaft, a drive unit for a guidance device, and a pressing unit for a pressing device. Further, since the actuator can make a rotational movement, the drive unit of the switching device, the drive unit of the reversing device such as a transported object, the drive unit of the scraping device such as a wire, and the drive of the traction device It can also be used as a drive unit for a right and left swiveling device such as a swinging part.

Claims

The scope of the claims

[1] A polymer actuator element comprising a metal electrode and an electrolyte containing a polymer electrolyte,

The metal electrodes are formed to form a pair;

The metal electrode is in contact with the electrolyte;

The electrolyte has a boiling point or decomposition temperature of 180 ° C or higher and contains an organic compound that is liquid at normal temperature and pressure.

A polymer actuator element, wherein the electrolyte is in a state where an ion exchange resin is swollen by the organic compound.

[2] The polymer actuator element according to claim 1, wherein the organic compound is a polar organic solvent and / or an ionic liquid.

[3] The ionic liquid is

A cation selected from the group consisting of tetraalkylammonium ion, dialkylimidazolium ion, trianorequinoleum ion, dazolyumin, virazolium, pyrrolium, pyrrolinium, pyrrolidin, and piberidinium ions. When,

6 4 4 4

Anion selected from at least one group

The polymer actuator element according to claim 2, wherein the polymer actuator element is a salt comprising a combination thereof.

(C F SO) (C F SO) N— (1)

n (2n + l) 2 m (2m + l) 2

(Where n and m are arbitrary integers.)

4. The polymer actuator element according to claim 1, wherein the electrolyte is a polymer gel electrolyte containing an ion exchange resin and an ionic liquid.

5. The polymer actuator element according to claim 1, wherein the polymer actuator element is in a state swollen by the organic compound and has a swelling degree of 3 to 200%.

6. The polymer actuator element according to claim 1, wherein the polymer actuator element is coated with a flexible resin.

[7] A polymer gel electrolyte containing an ion exchange resin and an ionic liquid. The method for driving a polymer actuator element according to claim 1, wherein the polymer actuator element according to claim 1 is driven under an atmospheric environment under atmospheric pressure.