JP5290055B2 - Polymer transducer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer transducer which can be used as a polymer actuator capable of being efficiently driven even at a low voltage and exhibiting excelling performance in the occurrence capability, displacement amount and operating speed or as a deformation sensor excellent in responsiveness and detection capability and fully flexible and excelling in shock resistance, and which is light in weight and flexible and is able to stably work even in a condition where water does not exist. <P>SOLUTION: The polymer transducer 10 has a pair of electrodes, and a polymer solid electrolyte disposed between the pair of electrodes and containing ion liquid and polymer, and in the polymer transducer, a barrier layer for preferentially transmitting cation with respect to anions or transmitting anions to cations is disposed between the polymer solid electrolyte and at least either of the pair of electrodes. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polymer transducer having a barrier layer that preferentially transmits specific ions between a polymer solid electrolyte and an electrode, and a polymer actuator excellent in operation performance and a deformation sensor excellent in signal strength. .

  In recent years, in the fields of medical equipment and micromachines, there is an increasing need for transducers that convert one type of energy into another type of energy, such as small and lightweight actuators and sensors. In addition, in the fields of industrial use and personal robots, there is an increasing need for transducers that are light and flexible.

  From this point of view, polymer actuators are attracting attention as lightweight and flexible actuators. Various types of polymer actuators have been proposed so far. For example, a polymer actuator (for example, refer to Patent Document 1) using a morphological change based on a stimulus such as a temperature change, a pH change, and an electric field applied to the hydrated polymer gel. There has been proposed a polymer actuator (for example, see Patent Document 2), which includes an exchange resin film and electrodes bonded to both surfaces thereof, and causes bending and deformation by applying a potential difference between the electrodes on both surfaces. In particular, in the latter, bending and deformation occur instantaneously after voltage application, and excellent response as an actuator is exhibited. However, since the polymer actuator operates only in a water-containing state, there is a problem that the environment in which it is used is limited and the application range is limited.

  As a means for overcoming the above problems, a polymer actuator including a soft polymer dielectric and a flexible electrode is known (see, for example, Patent Document 3). This type of polymer actuator does not require water for operation, and the operation of the actuator is not a mass transfer phenomenon such as ions, but is due to an electron transfer phenomenon, which is a faster process, so it is very responsive. It is excellent. However, on the other hand, a very high voltage of about several thousand volts is required for the operation, and there is a problem that the application range is limited from the viewpoint of safety.

  In order to overcome this problem, a polymer actuator in which electrodes made of ionic liquid, fluorine polymer and single-walled carbon nanotubes are bonded to both sides of a non-aqueous polymer solid electrolyte made of ionic liquid and fluorine polymer ( For example, see Non-Patent Document 1) and polymer actuators in which electrodes containing activated carbon are bonded to both surfaces of a nonaqueous polymer solid electrolyte made of an ionic liquid and a block copolymer (see, for example, Patent Documents 4 and 5). It has been known. These polymer actuators are characterized by being driven at a low voltage of about several volts even in the absence of water. However, there is room for further improvement in terms of the force that can be generated by the actuator and the operating speed.

  On the other hand, the polymer transducer can also be used as a sensor. Conventionally, piezoelectric elements using piezoelectric ceramics or the like are widely used as sensors that convert mechanical energy into electrical energy. Piezoelectric ceramics represented by barium titanate, lead zirconate titanate (PZT), and the like convert mechanical energy into electrical energy by the piezoelectric effect of generating electric charges when the ceramic is subjected to stress.

  However, sensors using these piezoelectric ceramics often cannot be used in applications that require low weight because they use a high-density inorganic material. In addition, since the impact resistance is inferior, when an external impact is applied, the piezoelectric ceramic is destroyed and the sensor function is likely to be deteriorated. In addition, since it is inferior in flexibility, it is difficult to use it in applications where it is required to be installed on a complex-shaped structure having a spherical surface or unevenness, and it is difficult to detect large deformations or small stresses. It was.

JP-A 63-309252 Japanese Patent Laid-Open No. 4-275078 Special table 2003-505865 gazette International Publication No. 2008/044546 International Publication No. 2008/123064

Future Materials, 2005, Vol. 5, No. 10, p. 14-19

  The present invention is a polymer actuator with excellent performance such as generated force, displacement, and operation speed that can be driven efficiently even at a low voltage, or it has good response, excellent detection performance, and high flexibility. An object of the present invention is to provide a polymer transducer that can be used as a deformation sensor having excellent impact resistance, is lightweight and flexible, and can function stably even in the absence of water.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by providing a barrier layer that preferentially transmits specific ions between the polymer solid electrolyte and the electrode. The present invention was completed through further studies based on the findings.

That is, the present invention
[1] A polymer transducer having a pair of electrodes and a polymer solid electrolyte disposed between the pair of electrodes and containing an ionic liquid and a polymer, the polymer solid electrolyte and the pair of electrodes A polymer transducer in which a barrier layer that preferentially transmits cations to anions is disposed between at least one of them,
[2] The polymer transducer according to [1], wherein the barrier layer contains a cation exchange resin,
[3] A polymer transducer having a pair of electrodes and a polymer solid electrolyte disposed between the pair of electrodes and containing an ionic liquid and a polymer, the polymer solid electrolyte and the pair of electrodes A polymer transducer in which a barrier layer that preferentially transmits anions to cations is disposed between at least one of them,
[4] The polymer transducer according to [3], wherein the barrier layer contains an anion exchange resin.
[5] The above [1], wherein at least one of the electrodes includes at least one carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, carbon nanosheets, polyacene, carbon fiber, carbon black, graphite, and activated carbon. Any one polymer transducer of [4],
[6] The polymer transducer according to any one of [1] to [5], wherein the electrode further includes an ionic liquid,
[7] The polymer transducer according to any one of [1] to [6], wherein the polymer does not substantially contain a dissociable ionic group,
About.

  The polymer transducer of the present invention is lightweight and flexible, and can function stably even in the absence of water. When the polymer transducer of the present invention is used as a polymer actuator, it can be driven efficiently even at a low voltage, and the performance such as generated force, displacement, and operation speed is excellent. Further, when the polymer transducer of the present invention is used as a deformation sensor, it has good responsiveness and excellent detection performance, and is rich in flexibility and excellent in impact resistance.

It is the schematic which shows the evaluation method of the performance as a polymer actuator of a polymer transducer. It is the schematic which shows the evaluation method of the performance as a deformation | transformation sensor of a polymer transducer.

Hereinafter, the present invention will be described in detail.
The polymer transducer of the present invention includes a pair of electrodes and a polymer solid electrolyte that is disposed between the pair of electrodes and includes an ionic liquid and a polymer. A barrier layer that preferentially transmits cations or anions is disposed between the solid polymer electrolyte and at least one of the pair of electrodes.

  At least one of the electrodes constituting the polymer transducer of the present invention, preferably both, preferably contains a carbon material. The carbon material can function as a so-called active material in the electrode. The carbon material is not particularly limited. For example, carbon nanotubes (single-walled carbon nanotubes, multi-walled carbon nanotubes, etc.), carbon nanohorns, carbon nanosheets (graphene sheets), polyacene, carbon fibers (PAN-based carbon fibers, pitch-based carbons) Fiber, vapor grown carbon fiber, etc.), carbon black (acetylene black, furnace black, channel black, high specific surface area carbon black (Ketjen black, Vulcan etc.), etc.), graphite, activated carbon and the like.

The electrode may contain a conductive material other than the carbon material described above. Examples of the conductive material include conductive polymers (poly (ethylene-3,4-dioxythiophene) (PEDOT), polyaniline derivatives, polypyrrole derivatives, etc.); gold, platinum, silver, palladium, copper, nickel, Metal materials such as aluminum, titanium, zinc, zirconium, iron, cobalt, tin, lead, indium, chromium, molybdenum, manganese; indium-tin composite oxide (ITO), antimony-tin composite oxide (ATO), ruthenium oxide Examples thereof include metal oxides such as (RuO ₂ ), titanium oxide (TiO ₂ ), and zinc oxide (ZnO); metal sulfides such as zinc sulfide (ZnS) and copper sulfide (CuS).

  Among these, since the electrochemical stability and the oxidation-reduction stability can be improved, the electrode is selected from the group consisting of carbon nanotube, carbon nanohorn, carbon nanosheet, polyacene, carbon fiber, carbon black, graphite and activated carbon. It is preferable to include at least one selected carbon material, and more preferable to include at least one selected from the group consisting of high specific surface area carbon black, carbon nanohorn, and graphite from the viewpoint of industrial economy. From the viewpoint of performance, it is more preferable to include high specific surface area carbon black and / or carbon nanohorn.

The electrode may contain one of the above carbon materials and other conductive materials alone, or may contain two or more. When the electrode contains two or more types of carbon materials and / or other conductive materials, the number of species is preferably about 2 to 5 in order to avoid complication of the manufacturing process. When the electrode contains two or more kinds of carbon materials and / or other conductive materials, at least one of them functions as the active material, and the rest functions as a conductive material for reducing the resistance of the electrode. Can be made.
If the content of the carbon material and / or other conductive material in the electrode is too large, the electrode itself may become hard and the flexibility of the polymer transducer may be impaired. On the other hand, if the content is too small, it may be used as a polymer actuator. In this case, since the displacement tends to be small or the electromotive force tends to be small when used as a deformation sensor, the proportion of the total mass of the carbon material and other conductive materials is the mass of each electrode. It is preferable to be in the range of 1 to 50% by mass, and more preferably in the range of 10 to 40% by mass.

  The electrode constituting the polymer transducer of the present invention may contain a binder. When the electrode contains a binder, the carbon material and / or other conductive material can be fixed on the electrode. As a material constituting the binder, a thermoplastic resin or a thermosetting resin can be used. Specifically, a polyolefin resin such as polyethylene or polypropylene; a polystyrene resin such as polystyrene or poly α-methylstyrene; Poly (meth) acrylic resins such as methacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate; polyvinyl chloride , Vinyl halide resins such as polyvinylidene chloride, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene random copolymer, polytetrafluoroethylene, polytrifluoroethylene; polyethylene glycol terephthalate, polyethylene glycol Polyester resins such as naphthaphthalate and polybutylene glycol terephthalate; Polyamide resins such as nylon-6, nylon-6,6, nylon-9T, nylon-11, nylon-12, nylon-6,12; thermoplastic polyurethane resins ; Polycarbonate resin; Thermosetting resin such as unsaturated polyester, epoxy resin, alkyd resin, phenol resin, thermosetting polyurethane resin; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber (styrene butadiene random copolymer) ), Rubbers such as acrylic rubber, nitrile rubber, norbornene rubber, silicone rubber, urethane rubber (including soft thermosetting polyurethane) or cross-linked products thereof; olefin-based thermoplastic elastomer (TPO), styrene-based thermoplastic Elastomer (TPS), crosslinkable olefin thermoplastic elastomer (TPV), acrylic thermoplastic elastomer (for example, block copolymer of polymethyl methacrylate and polybutyl acrylate, etc.), polyurethane thermoplastic elastomer (TPU), Thermoplastic elastomers such as polyester thermoplastic elastomer (TPEE) and polyamide thermoplastic elastomer (TPAE); fluorine polymers having sulfonic acid groups in the side chain (for example, “Nafion” (manufactured by DuPont), etc.) Can be used. A binder may be used individually by 1 type, or may use 2 or more types together.

Among these, from the viewpoint of film forming properties when the electrode is used in the form of a film, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene random copolymer, polytetrafluoroethylene, thermoplastic polyurethane resin, Styrene-butadiene rubber (styrene-butadiene random copolymer), styrene-based thermoplastic elastomer (TPS), and polyurethane-based thermoplastic elastomer (TPU) are preferred. Further, when the electrode contains an ionic liquid described later, it is preferably a polymer species that can be mixed with the ionic liquid.
When the electrode contains a binder, the content is not particularly limited, but in the range of 1 to 20% by mass based on the mass of each electrode, from the viewpoint of electrode resistance and ease of ion diffusion. Is preferable, and it is more preferable that it exists in the range of 3-15 mass%.

  The electrode constituting the polymer transducer of the present invention may contain an ionic liquid. When the electrode contains an ionic liquid, both a cation and an anion can easily move through the electrode, and a polymer transducer having better performance is obtained. The ionic liquid is a salt having a melting point of usually 100 ° C. or lower (preferably 25 ° C. or lower). Although there is no restriction | limiting in particular in the kind of the said ionic liquid used in this invention, For example, what is comprised from an organic cation and an organic type or an inorganic type anion can be used. Examples of the organic cation include those represented by any of the following general formulas (I) to (V).

In the general formula (I), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, or It represents a group selected from the group consisting of a branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an oligoalkenylene oxide group having 2 to 30 carbon atoms.

In the general formula (II), R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, or a carbon number. Represents a group selected from the group consisting of an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and R ′ is linear or branched having 1 to 6 carbon atoms. A chain alkyl group is represented, and n represents an integer of 0 or more and 5 or less.

In the general formula (III), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a straight chain having 2 to 10 carbon atoms. Represents a group selected from the group consisting of a linear or branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and R ⁵ of to R ^8, 2 two groups may form a ring structure together.

In the general formula (IV), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a straight chain having 2 to 10 carbon atoms. Represents a group selected from the group consisting of a linear or branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and R ⁹ of to R ^12, 2 two groups may form a ring structure together.

In the general formula (V), R ¹³ , R ¹⁴ , and R ¹⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, or Represents a group selected from the group consisting of a branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and R ^{13 to} R ^15. Of these, two groups may jointly form a ring structure.

Among these, the organic cation (imidazolium cation) represented by the general formula (I) is preferable from the viewpoint of ionic conductivity and availability of the ionic liquid, and the general formula (I) from the viewpoint of the melting point and viscosity of the ionic liquid. In which R ¹ and R ² are linear or branched alkyl groups having 1 to 6 carbon atoms, and R ¹ and R ² in the general formula (I) are different from each other. Further preferred. Specific examples of such an organic cation include, for example, an ethylmethylimidazolium cation (EMI ⁺ ; ^one in which ^one of R ¹ and R ² in the general formula (I) is a methyl group and the other is an ethyl group), And a butylmethylimidazolium cation (BMI ⁺ ; ^one in which ^one of R ¹ and R ² in the general formula (I) is a methyl group and the other is a butyl group).

Examples of the anion constituting the ionic liquid include a halogen-containing anion, a mineral acid anion, and an organic acid anion. Specific examples of the halogen-containing anion and mineral acid anion include PF ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , ( C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SO ₄ ²⁻ , (CN) ₂ N ⁻ , NO ₃ ^{− and the} like can be mentioned. Specific examples of the organic acid anion include RSO ₃ ⁻ , RCO ₂ ^— (where R is an alkyl group, aryl group, alkenyl group, aralkyl group, aralkenyl group, alkoxyalkyl group, acyloxyalkyl group, sulfoalkyl group, or aromatic complex). Ring residue, which may contain a plurality of cyclic structures or branched structures).
Among these, PF ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , (CF ₃ SO ₂₎ from the viewpoint of the ionic conductivity and availability of the ionic liquid. ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CN) ₂ N ⁻ are preferable, and BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and (C ₂ F ₅ SO ₂ ) ₂ are particularly preferable. N ^- is more preferable.

As the ionic liquid used in the present invention, those composed of a combination of the above organic cation and anion can be used, and these can be used alone or in combination of two or more. Good. As the ionic liquid used in the present invention, since it has excellent ion conductivity, ethylmethylimidazolium tetrafluoroborate (EMIBF ₄ ), ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI), butylmethylimidazolium Tetrafluoroborate (BMIBF ₄ ) and butylmethylimidazolium bis (trifluoromethanesulfonyl) imide (BMITSI) are preferred.

  When the electrode contains an ionic liquid, the content is not particularly limited. However, if it is too much, the ionic liquid oozes out significantly or the mechanical strength of the electrode tends to be inferior. Since the degree of the polymer tends to decrease and the performance as a polymer transducer tends to decrease, it is preferably within the range of 30 to 98% by mass based on the mass of each electrode, and within the range of 45 to 87% by mass. It is more preferable.

  The method for producing the electrode used in the present invention is not particularly limited. For example, a mortar or the like is used as a component constituting the electrode such as the above-described carbon material, conductive material other than the carbon material, binder, ionic liquid, or the like. A method of obtaining a sheet-like electrode by hot press molding after mixing or kneading; dissolving or dispersing the components constituting the electrode in a solvent or dispersion medium, and then molding into a film; It can be manufactured by a method of removing to obtain a sheet-like electrode.

  The polymer solid electrolyte constituting the polymer transducer of the present invention includes an ionic liquid and a polymer. As the ionic liquid contained in the polymer solid electrolyte, those described above as the ionic liquid that can be contained in the electrode can also be suitably used. When an electrode contains an ionic liquid, it is preferable to use the same kind of ionic liquid as the said ionic liquid which an electrode contains also for a polymer solid electrolyte.

  As the polymer contained in the polymer solid electrolyte, those capable of holding the ionic liquid therein can be preferably used. Examples of the polymer include thermoplastic resins or thermosetting resins. Specifically, polyolefin resins such as polyethylene and polypropylene; polystyrene resins such as polystyrene and poly α-methylstyrene; polymethacrylic acid , Poly (meth) acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate; polyvinyl chloride, poly Vinyl halide resins such as vinylidene chloride, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene random copolymer, polytetrafluoroethylene, polytrifluoroethylene; polyethylene glycol terephthalate, polyethylene glycol naphthalate Polyester resins such as polybutylene glycol terephthalate; polyamide resins such as nylon-6, nylon-6,6, nylon-9T, nylon-11, nylon-12, nylon-6,12; thermoplastic polyurethane resins; polycarbonate Resin: Thermosetting resin such as unsaturated polyester, epoxy resin, alkyd resin, phenol resin, thermosetting polyurethane resin; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber (styrene butadiene random copolymer), Rubbers such as acrylic rubber, nitrile rubber, norbornene rubber, silicone rubber, urethane rubber (including soft thermosetting polyurethane) or cross-linked products thereof; olefin thermoplastic elastomer (TPO), styrene thermoplastic elastomer (TP S), a crosslinkable olefin thermoplastic elastomer (TPV), an acrylic thermoplastic elastomer (for example, a block copolymer of polymethyl methacrylate and polybutyl acrylate, etc.), polystyrene and poly (meth) acrylate Block copolymers, block copolymers of polystyrene and amorphous polyester, thermoplastic elastomers such as polyurethane thermoplastic elastomer (TPU), polyester thermoplastic elastomer (TPEE), polyamide thermoplastic elastomer (TPAE), etc. Fluorine polymers having a sulfonic acid group in the side chain (for example, “Nafion” (manufactured by DuPont)) and the like.

The polymer contained in the polymer solid electrolyte may be a block copolymer in which two or more polymer blocks corresponding to the above-described polymer are bonded, or a graft copolymer. Among these, from the viewpoint of flexibility in selection of the molding method, stability to heat, low corrosiveness to the electrode material, the polymer included in the polymer solid electrolyte is substantially dissociable ionic group (for example, sulfone). Salt of acid group, salt of phosphonic acid group, salt of carboxyl group, ammonium group, etc.) and is incompatible with the ionic liquid used from the viewpoint of ionic conductivity and mechanical strength of the polymer solid electrolyte. It is more preferable that the block copolymer has a polymer block, and the block copolymer has a polymer block compatible with the ionic liquid to be used and a polymer block incompatible with the ionic liquid. Further preferred.
Specific examples of the polymer block incompatible with the ionic liquid described above include polyolefin blocks such as polyethylene blocks and polypropylene blocks; aromatic vinyl heavy polymers such as polystyrene blocks, depending on the type of ionic liquid used. Polymer block etc. which are comprised from (meth) acrylic acid ester of alicyclic alcohol, such as a coalescence block; polymethacrylic acid isobornyl block. On the other hand, as a specific example of the polymer block compatible with the ionic liquid, depending on the type of ionic liquid used, polymethyl methacrylate block, polymethyl acrylate block, polyethyl acrylate block, (Meth) acrylic acid ester polymer block such as polymethoxymethyl block; polyoxyalkylene block such as polyethylene glycol block; polyester block such as polyε-caprolactone.
The polymer solid electrolyte may contain one or two or more kinds of polymers, but in the case of two or more kinds, usually about 2 to 5 kinds are used in order to avoid complication of the manufacturing process. It is preferable that

The mass ratio between the ionic liquid and the polymer in the polymer solid electrolyte is not particularly limited, but from the viewpoint of ionic conductivity and mechanical strength, the ionic liquid is in the range of 1 to 1000 parts by mass with respect to 100 parts by mass of the polymer. It is preferably within the range, more preferably within the range of 10 to 700 parts by mass, even more preferably within the range of 20 to 500 parts by mass, and particularly preferably within the range of 30 to 300 parts by mass. preferable.
The polymer solid electrolyte may be composed of only an ionic liquid and a polymer, but may contain other components than these components as described later. The ratio of the total amount of the ionic liquid and the polymer to the total mass of the solid polymer electrolyte is preferably in the range of 60 to 100% by mass, and more preferably in the range of 70 to 100% by mass. More preferably, it is in the range of 80 to 100% by mass.

  The method for producing the solid polymer electrolyte used in the present invention is not particularly limited. For example, a method of kneading an ionic liquid and a polymer under heating and then forming the polymer into a desired shape (for example, a film shape); A method in which an ionic liquid and a polymer are dissolved or dispersed in a solvent or dispersion medium and then cast, and if necessary, the solvent or dispersion medium is further removed; a molded body containing the polymer is produced in advance and impregnated with the ionic liquid. It can manufacture by the method of making it.

  The barrier layer used in the present invention is a barrier layer that preferentially transmits one of a cation and an anion with respect to the other. The barrier layer is not limited to transmitting only one ion and does not transmit the other ion at all. For example, the barrier layer may be a barrier layer having a larger cation permeability than anion permeability, or an anion. The barrier layer may have a greater permeability than the cation permeability.

  The barrier layer is disposed between the solid polymer electrolyte and at least one of the pair of electrodes. Here, in each of the polymer solid electrolyte and the barrier layer, and the electrode and the barrier layer, it is preferable that the members are disposed so as to be in contact with each other. In addition, since it can be driven more efficiently or efficiently in both directions by switching the electrode potential, it is preferable that a barrier layer is provided between the polymer solid electrolyte and both electrodes. In this case, the two barrier layers to be arranged are both those that preferentially permeate cations with respect to anions, or both that preferentially permeate anions with respect to cations. As a specific configuration of such a polymer transducer, for example, a barrier layer that preferentially permeates cations with respect to an electrode / anion / a polymer solid electrolyte / priority with respect to anions. Of barrier layer / electrode to be permeated through, or barrier layer / electrode to preferentially permeate anion with respect to electrode / cation / barrier layer / electrode to preferentially permeate anion with respect to polymer solid electrolyte / cation Etc.

  A cation exchange resin can be used as a material constituting the barrier layer that preferentially permeates cations with respect to the above anions, and specifically, an acid such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group. Examples thereof include a polymer material in which a group is covalently bonded to a polymer molecular chain. More specifically, a polymer of a sulfonic acid derivative having an olefinically polymerizable group such as vinyl sulfonic acid, isopropenyl sulfonic acid, styrene sulfonic acid, α-methyl styrene sulfonic acid, acrylamide-2-methylpropane sulfonic acid; Polymers of carboxylic acid derivatives having olefinic polymerizable groups such as acrylic acid, methacrylic acid, vinyl benzoic acid, isopropenyl benzoic acid; vinyl phosphonic acid, isopropenyl phosphonic acid, styrene phosphonic acid, oxyethyl methacrylate phosphonate, Examples thereof include polymers of phosphoric acid derivatives such as acid polyoxyethylene glycol monomethacrylate, phosphonic acid polyoxypropylene glycol monomethacrylate, and 3-chloro-2-phosphonic acid propyl-1-methacrylate. These polymers may be homopolymers, copolymers of the above-described monomers, or copolymers with other well-known olefinic monomers.

Another example of the cation exchange resin is a resin in which an acid group such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group is introduced into an engineering plastic. Examples of the engineering plastic include, for example, polyether, polysulfide, polyamine, polyester, polyamide, polycarbonate, polyphenylene (poly-p-phenylene, etc.), polyketone, polyetheretherketone, polyetherketone, polysulfone, polyamideimide, and polyimide. And polybenzimidazole. When the engineering plastic contains an aromatic component, an acid group such as a sulfonic acid group can be easily introduced by a known method, which is preferable.
In addition to these, fluoropolymers having sulfonic acid groups in the side chain such as “Nafion” (DuPont), “Flemion” (Asahi Glass Co., Ltd.), “Aciplex” (Asahi Kasei Chemicals Co., Ltd.), etc. It can also be used.

  The cation exchange resin described above may have some or all of its acid groups neutralized. Various neutralized forms are possible, for example, alkali metal salts such as lithium, sodium, potassium, rubidium, cesium, and francium; metal salts such as alkaline earth metal salts such as magnesium, calcium, strontium, and barium. Examples include forms, forms of nitrogen-containing onium salts such as ammonium salts, pyrrolidinium salts, pyridinium salts, and imidazolium salts, and forms of organic onium salts such as phosphonium salts and sulfonium salts.

  On the other hand, an anion exchange resin can be used as a material constituting the barrier layer that preferentially permeates the anion with respect to the above cation, and specifically, an onium such as an amino group, a pyridyl group, and an imidazole group. Polymers having salt-forming groups such as vinylamine, allylamine, 4-vinylbenzylamine, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, vinylimidazole , Allylimidazole, 1- (2- (meth) acryloyloxyethyl) imidazole, 1- (3- (meth) acryloyloxypropyl) imidazole, 1- (4- (meth) acryloyloxybutyl) imidazole, 1- (6 -(Meth) acryloyloxyhexyl) imidazo The polymer obtained by polymerizing a monomer component such as Le, and the like onium obtained by chloride polymer. The polymer may be derived from a homopolymer of the monomer component described above, or may be derived from a copolymer of two or more types of monomer components. Further, it may be derived from a copolymer with a known olefinic monomer.

  The polymer transducer of the present invention may contain other components such as an antioxidant, a UV absorber, a lubricant, a dispersant, a surfactant, a filler, a reinforcing material, and a plasticizer. These other components may be added to the electrode, may be added to the polymer solid electrolyte, or may be added to the barrier layer. The addition amount of these other components is preferably 40 parts by mass or less, and preferably 30 parts by mass or less with respect to 100 parts by mass of each electrode, polymer solid electrolyte, or barrier layer constituting the polymer transducer. More preferably, it is more preferably 20 parts by mass or less.

  The shape of the polymer transducer of the present invention is not particularly limited, but various shapes such as a film shape, a film shape, a sheet shape, a plate shape, a fiber shape, a columnar shape, a columnar shape, and a spherical shape are possible. Among these, when manufacturing a membrane-like, film-like, sheet-like, or plate-like polymer transducer, for example, a barrier layer that is formed into a film is pasted on a polymer solid electrolyte that is formed into a film. And a method of bonding a sheet-like electrode thereon; coating a solution or dispersion containing a component constituting a barrier layer on a polymer solid electrolyte formed into a film; and further comprising a component constituting an electrode A method of applying a solution or dispersion containing a solution; casting a solution or dispersion containing a component constituting an electrode; then casting a solution or dispersion containing a component constituting a barrier layer; and then applying an ionic liquid and a polymer The solution or dispersion liquid containing the component constituting the barrier layer is cast, and then the solution or dispersion liquid containing the component constituting the electrode is further cast. It can be mentioned, such as how to strike. The same method can be adopted in the case of a fiber shape, a columnar shape, a columnar shape, a spherical shape, and the like.

  In the film-like, film-like, sheet-like or plate-like polymer transducer described above, the thicknesses of the electrode layer, polymer solid electrolyte layer and barrier layer constituting it are not particularly limited, and the use of the polymer transducer, etc. The thickness of the electrode layer is preferably in the range of 1 μm to 10 mm, more preferably in the range of 5 μm to 1 mm, and in the range of 10 to 500 μm. Further preferred. The thickness of the solid polymer electrolyte layer is preferably in the range of 1 μm to 10 mm, more preferably in the range of 5 μm to 1 mm, and still more preferably in the range of 10 to 500 μm. Furthermore, the thickness of the barrier layer is preferably in the range of 1 nm to 500 μm, more preferably in the range of 10 nm to 300 μm, and still more preferably in the range of 100 nm to 100 μm. A polymer transducer in which the thicknesses of the electrode layer, the polymer solid electrolyte layer, and the barrier layer are within the above-described ranges exhibit the effects of the present invention more remarkably.

  The polymer transducer of the present invention may be provided with a current collector for the purpose of reducing the resistance in the longitudinal direction. Examples of current collectors include metal foils and metal thin films such as gold, silver, copper, platinum, aluminum, and nickel; metal powders such as gold, silver, and nickel; or carbon fine powders such as carbon powder, carbon nanotubes, and carbon fibers. Examples include a film-like molded body composed of a binder resin; a metal thin film formed by a method such as sputtering or plating on a fabric such as woven fabric, paper, or nonwoven fabric, or a polymer film. Among these, from the viewpoint of flexibility, it is preferable that a metal thin film is formed on a film-like molded body, a fabric, a polymer film, or the like made of a metal powder and a binder resin. The current collector can be disposed outside at least one of the pair of electrodes of the polymer transducer of the present invention (on the side opposite to the side on which the polymer solid electrolyte is disposed).

  The polymer transducer of the present invention can operate in air, water, vacuum, and organic solvents. Moreover, you may seal suitably according to a use environment. There is no restriction | limiting in particular as an example of sealing material, Various resin etc. can be mentioned.

  When the polymer transducer of the present invention is used as a polymer actuator (polymer actuator element), it can be driven by applying a potential difference between mutually insulated electrodes, and electric energy can be applied to force, fluctuation, displacement, etc. Can be converted to mechanical energy. On the other hand, when mechanical energy such as displacement and pressure is applied to the polymer transducer of the present invention from the outside, a potential difference (voltage) can be generated as electrical energy between the mutually insulated electrodes. It can also be used as a deformation sensor (deformation sensor element) for detecting pressure or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited at all by these Examples.

The materials used are shown below.
(1) Styrene :
A special grade styrene purchased from Kishida Chemical Co., Ltd. was contacted with alumina to remove the polymerization inhibitor, and then used after thoroughly bubbling with nitrogen to remove dissolved oxygen.
(2) Methyl methacrylate :
The polymerization inhibitor was removed by contacting methyl methacrylate manufactured by Kuraray Co., Ltd. with Zeolam, and dissolved oxygen was removed by sufficient bubbling with nitrogen before use.
(3) Tetrahydrofuran :
A product obtained by purifying a special grade tetrahydrofuran purchased from Kishida Chemical Co., Ltd. by distillation in the presence of sodium-benzophenone ketyl was used.
(4) 1,1-diphenylethylene :
The 1,1-diphenylethylene purchased from Aldrich was purified by distillation under reduced pressure in the presence of calcium hydride.
(5) Lithium chloride :
Lithium chloride (99.998%) purchased from Aldrich was used as it was.
(6) α, α′-Dibromo-p-xylene :
Α, α′-Dibromo-p-xylene purchased from Aldrich was diluted with tetrahydrofuran and used as a 0.095M solution.
(7) Poly (vinylidene fluoride-ran-hexafluoropropylene) [PVDF / HFP] :
“Kayner # 2801” manufactured by Arkema was used as it was.
(8) Ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide [EMITFSI] :
Purchased from Nippon Synthetic Chemical Industry Co., Ltd. and used as it was.
(9) Cation exchange resin :
An aqueous solution of poly (4-styrenesulfonic acid) ammonium salt purchased from Aldrich was used as it was.
(10) Anion exchange resin :
A poly (diallyldimethylammonium chloride) aqueous solution (weight average molecular weight: 100,000-200,000) purchased from Aldrich was used as it was.
(11) Activated carbon :
“YP-50F” manufactured by Kuraray Chemical Co., Ltd. was used as it was.
(12) Acetylene black :
“Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd. was used as it was.
Other materials were used after purification according to the purpose.

Moreover, each evaluation method employ | adopted by the following example and the comparative example is shown below.
Performance Test of Polymer Transducer as Polymer Actuator As shown in FIG. 1, a polymer transducer membrane 10 cut out to a size of 15 mm × 5 mm is sandwiched by 10 mm in the length direction between gold terminals 11 and 12, and the polymer A 5 mm length acting as an actuator was taken out into the air to form a measurement cell. A potential control terminal of a potentiostat 13 (“HAB-151” manufactured by Hokuto Denko Co., Ltd.) and a current control terminal were connected to the gold terminals 11 and 12. The gold terminal 11 is a working electrode, and the gold terminal 12 is a counter electrode and a reference electrode. A target of a laser displacement meter 14 (“LC-2440” manufactured by Keyence Corporation) was set at a position P of 1 mm from the tip of the portion of the surface of the polymer transducer 10 on the gold terminal 11 side exposed to the air. In this state, the measurement cell is fixed, a voltage (potential difference) of +1 V is applied from the potentiostat 13 to the gold terminal 11 with the gold terminal 12 as a reference, and the displacement is measured by the laser displacement meter 14 after 30 seconds. The displacement was used as an index indicating the performance of the polymer transducer as a polymer actuator. The amount of displacement to the side where the laser displacement meter 14 was installed was defined as + (plus), the amount of displacement toward the side opposite to the side where the laser displacement meter 14 was installed was defined as-(minus), and the initial state was defined as displacement 0.

Performance test of polymer transducer as deformation sensor (1) Silver paste (manufactured by Nippon Graphite Industry Co., Ltd.) at the center of each side of two insulating films (made of thermoplastic elastomer, thickness of about 150 μm) of 30 mm x 20 mm “Bunny Height M-15A”) was applied by screen printing to form a current collector layer having a size of 20 mm × 10 mm.
(2) As shown in FIG. 2, the two insulating films 21 and 22 are superposed on both sides of the polymer transducer film 20 cut to a size of 20 mm × 10 mm so that the current collector layers match each other. A measurement sample 23 was obtained by hot pressing at 130 ° C. for 5 minutes and bonding. At this time, the lead wire 24 is provided between the current collector layer (not shown) of the insulating film 21 and the polymer transducer film 20, and the current collector layer (not shown) of the insulating film 22 and the polymer transducer film 20. Each of the lead wires 25 was sandwiched between them.
(3) The measurement sample 23 is sandwiched between fixing jigs 26 and 27 so that 10 mm, which is a half of the length of the polymer transducer membrane, 20 mm, is left, and the lead wires 24 and 25 are connected to the data logger 28 ("NR-" manufactured by Keyence Corporation). ST04 "). In addition, in order to measure the amount of displacement given, a laser displacement meter 29 ("LK-G155" manufactured by Keyence Corporation) is installed on the insulating film 21 side of the measurement sample 23, and at the insulating film 21 side of the measurement sample 23 The target of the laser displacement meter 29 was set at a position P of 5 mm from the fixed end of the outer surface. In this state, the data logger 28 measured the peak voltage generated when a displacement of +2 mm was given to the laser displacement meter 29 side. A value (sensor performance, unit: μV / mm) obtained by dividing the peak voltage (the potential on the lead wire 24 side with respect to the lead wire 25 side) by the displacement amount is an index indicating the performance of the polymer transducer as a deformation sensor. did.

[Production Example 1]
Production of Polystyrene-b-Polymethylmethacrylate-b-Polystyrene (1) A magnetic stirring bar was placed in a 1 L eggplant-shaped flask from which the water inside was completely removed, and a three-way cock was attached. In an eggplant flask in an argon atmosphere, 370 mg (8.73 mmol) of lithium chloride was charged. The eggplant flask was taken out from the glove box, and 560 mL of tetrahydrofuran was charged into the eggplant flask. The eggplant flask was immersed in a dry ice / methanol bath and cooled to −78 ° C., and then 2 mL of a sec-butyllithium solution (2.6 mmol as sec-butyllithium) was added dropwise. To this solution, 33.9 mL (297 mmol) of styrene was slowly added dropwise, and polymerization was performed at −78 ° C. for 1 hour.
(2) 1,1-Diphenylethylene 1.54 mL (8.72 mmol) was added dropwise thereto. When a very small amount of the polymerization solution was extracted with a syringe and GPC measurement was performed, Mn = 18,800 and Mw / Mn = 1.15. The initiator efficiency determined by calculation was 63.3 mol%.
(3) 26.9 mL (252 mmol) of methyl methacrylate was slowly added thereto while maintaining the polymerization solution in the eggplant flask at -78 ° C. By adding methyl methacrylate, the inside of the system changed from dark red to light yellow. The polymerization was continued for 1 hour. When a very small amount of the polymerization solution was extracted by a syringe and GPC measurement was performed, Mn = 31,200 and Mw / Mn = 1.08, and it was confirmed that polystyrene-b-polymethyl methacrylate was produced.

(4) While maintaining the polymerization solution in the eggplant flask at -78 ° C, 8.66 mL of α, α'-dibromo-p-xylene tetrahydrofuran solution (0.823 mmol as α, α'-dibromo-p-xylene) ) Was added dropwise and stirring was continued for 2 days at -78 ° C. A small amount of methanol was added thereto to stop the reaction. When a part was sampled and GPC measurement was performed, the main peak was Mn = 56,400 and Mw / Mn = 1.07, and the triblock ratio determined from the GPC curve area ratio was 88% (that is, 12% Was a diblock form of polystyrene-b-polymethylmethacrylate).
(5) The obtained polymerization solution was added to a large excess of n-hexane to reprecipitate the polymer, thereby removing residual 1,1-diphenylethylene and collecting the polymer by filtration. The obtained white powdery polymer was redissolved in toluene, this solution was washed with water to remove the remaining lithium salt, reprecipitated with a large excess of methanol, and the polymer was recovered by filtration. The polymer was vacuum-dried at 50 ° C. for 24 hours to remove the remaining solvent and water.
(6) When the polymer obtained as described above was measured by ¹ H-NMR, the content of polystyrene block in the polymer was 58% by mass, and the content of polymethyl methacrylate block was 42% by mass. .

[Production Example 2]
Production of Electrode Film (1) 0.1 g of activated carbon, 0.06 g of acetylene black, 0.04 g of PVDF / HFP, and 0.3 g of EMITFSI were taken in a mortar and ground well with a pestle to obtain a massive electrode material.
(2) The obtained bulk electrode material was hot pressed at 130 ° C. using a spacer having a thickness of 100 μm and a mold to obtain an electrode film.

[Production Example 3]
Production of Polymer Solid Electrolyte Membrane (1) 10 g of the polymer containing polystyrene-b-polymethylmethacrylate-b-polystyrene obtained in Production Example 1 was completely dissolved in 50 mL of tetrahydrofuran. EMITFSI 8.4g was added to this solution, and the uniform solution was obtained. This solution was spread on a PET film and dried. The obtained transparent and flexible solid was vacuum-dried at 50 ° C. overnight to obtain a polymer solid electrolyte.
(2) The obtained solid polymer electrolyte was subjected to hot press molding at 200 ° C. using a spacer and a mold having a thickness of 100 μm to obtain a solid polymer electrolyte membrane.

[Comparative Example 1]
Production of Polymer Transducer Membrane (1) With two electrode membranes obtained in Production Example 2, sandwiching both sides of the polymer solid electrolyte membrane obtained in Production Example 3, using a spacer and a mold having a thickness of 300 μm, The polymer transducer film laminated | stacked by the structure of an electrode film / polymer solid electrolyte membrane / electrode film was obtained by heat-pressing at 150 degreeC.
(2) From this polymer transducer membrane, a vertical cutter (“PF-20” manufactured by Nishiwaki Seisakusho Co., Ltd.) was used to cut out a predetermined size from the center of the membrane to obtain a test element. The tester confirmed that the electrodes on both sides of the test element were insulated. Using the obtained test element, the performance of the polymer transducer as a polymer actuator and deformation sensor was evaluated by the method described above. The results are shown in Table 1 below.

[Example 1]
Preparation of polymer transducer film having barrier layer (I)
(1) A poly (4-styrenesulfonic acid) ammonium salt aqueous solution was sprayed on one side of the electrode film obtained in Production Example 2 using an air brush (“HP-CH” manufactured by Anest Iwata Corporation) and dried. . This operation was repeated 10 times to form a barrier layer that preferentially permeates cations with respect to anions.
(2) On the other hand, on both surfaces of the polymer solid electrolyte membrane obtained in Production Example 3, an aqueous solution of poly (4-styrenesulfonic acid) ammonium salt using an air brush (“HP-CH” manufactured by Anest Iwata Co., Ltd.) Sprayed to dry. This operation was repeated 10 times to form a barrier layer that preferentially permeates cations with respect to anions.
(3) An electrode film in which the barrier layer obtained in (1) is formed on the polymer solid electrolyte film in which the barrier layer is formed on both surfaces obtained in (2) is provided on the polymer solid electrolyte side. Electrode film / barrier layer / polymer solid electrolyte membrane / barrier layer / electrode film, and heat-pressed at 150 ° C. using a 300 μm thick spacer and mold. A polymer transducer membrane having a barrier layer that preferentially permeates cations with respect to anions was obtained between the polymer electrolyte membrane and the polymer solid electrolyte membrane.
(4) A test element was obtained from this polymer transducer membrane in the same manner as (2) of Comparative Example 1. Using the obtained test element, the performance of the polymer transducer as a polymer actuator and deformation sensor was evaluated by the method described above. The results are shown in Table 1 below.

[Example 2]
Fabrication of polymer transducer membrane with barrier layer (II)
Barrier layer that performs the same operation as in Example 1 except that an aqueous poly (diallyldimethylammonium chloride) solution is used instead of an aqueous solution of poly (4-styrenesulfonic acid) ammonium salt, and allows anions to preferentially permeate cations. A test element composed of a polymer transducer film having Using the obtained test element, the performance of the polymer transducer as a polymer actuator and deformation sensor was evaluated by the method described above. The results are shown in Table 1 below.

  According to the present invention, it can be driven efficiently even at a low voltage as a polymer actuator having excellent performance such as generated force, displacement, and operating speed, or it has excellent responsiveness, excellent detection performance, and flexibility. There is provided a polymer transducer that can be used as a deformation sensor that is rich in impact resistance and is lightweight and flexible and that can function stably even in the absence of water. The polymer transducer can be suitably used for applications such as small actuators, flexible sensors, and artificial muscles.

10, 20 Polymer transducer film 11, 12 Gold terminal 13 Potentiostat 14, 29 Laser displacement meter 21, 22 Insulating film 23 Measurement sample 24, 25 Lead wire 26, 27 Fixing jig 28 Data logger

Claims (7)

  A polymer transducer having a pair of electrodes and a solid polymer electrolyte disposed between the pair of electrodes and containing an ionic liquid and a polymer, wherein the polymer solid electrolyte and at least one of the pair of electrodes A polymer transducer in which a barrier layer that preferentially permeates cations with respect to anions is disposed between them.   The polymer transducer according to claim 1, wherein the barrier layer contains a cation exchange resin.   A polymer transducer having a pair of electrodes and a solid polymer electrolyte disposed between the pair of electrodes and containing an ionic liquid and a polymer, wherein the polymer solid electrolyte and at least one of the pair of electrodes A polymer transducer in which a barrier layer that preferentially transmits anions to cations is disposed between them.   The polymer transducer according to claim 3, wherein the barrier layer contains an anion exchange resin.   5. The method according to claim 1, wherein at least one of the electrodes includes at least one carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, carbon nanosheets, polyacene, carbon fiber, carbon black, graphite, and activated carbon. 2. The polymer transducer according to claim 1.   The polymer transducer according to claim 1, wherein the electrode further contains an ionic liquid.   The polymer transducer according to claim 1, wherein the polymer does not substantially contain a dissociable ionic group.

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