WO2011125616A1 - Polymer solid electrolyte and polymer transducer using the same - Google Patents

Abstract

Provided is a polymer solid electrolyte that is lightweight and pliable, functions with stability even in a water-free environment, and has excellent flexibility. Also provided is a polymer transducer that uses the same. The polymer solid electrolyte is a solid at room temperature and the polymer chain thereof has unbonded mobile cations, including an onium cation containing a group 15 element. Moreover, the polymer transducer has at least one pair of electrodes and, disposed between the electrodes, a polymer solid electrolyte that is a solid at room temperature. The cations that are unbonded to the polymer chain forming the polymer solid electrolyte and are capable of moving through the polymer solid electrolyte include an onium cation containing a group 15 element.　

Description

Polymer solid electrolyte and polymer transducer using the same

The present invention relates to a polymer transducer and a manufacturing method thereof, and a polymer solid electrolyte used therein and a manufacturing method thereof.

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 field of industrial use or personal robots, there is an increasing need for transducers that are light and flexible.

In such many fields, polymer actuators are attracting attention as lightweight and flexible actuators. Various types of polymer actuators have been reported so far. Among them, a polymer actuator that uses a solid electrolyte composed of an ionic liquid and a polymer is disclosed as a polymer actuator having a low operating voltage and capable of stable operation in air (for example, Patent Documents 1 to 5). And non-patent documents 1 to 4). These polymer actuators are polymer transducers that also function as sensors when deformed (see, for example, Non-Patent Document 4).

The polymer solid electrolyte used in the polymer transducer described above is a solid electrolyte obtained by holding an ionic liquid that is liquid at room temperature in a polymer. Although these have high ionic conductivity, the ionic liquid may bleed out in some cases. In addition, such a polymer solid electrolyte may be inferior in heat resistance because it is thermoplastic, and in such a case, there is a method in which a polymer holding an ionic liquid is used after crosslinking (for example, Patent Document 6). And 7).

JP 2005-176428 A JP 2006-288040 A International Publication No. 2008/044546 US Patent Application Publication No. 2005/0103706 US Patent Application Publication No. 2006/0266642 JP 2004-98199 A JP 2005-223967 A

Since the above-described solid polymer electrolyte is a solid electrolyte by holding a liquid ionic liquid in a polymer, there is a risk of liquid leakage or performance change due to liquid leakage. Further, in a polymer transducer using such a polymer solid electrolyte, further improvement in responsiveness or the like is desired.

Accordingly, the present invention provides a polymer solid electrolyte that is lightweight and flexible, functions stably even in an environment without water, and is excellent in flexibility, a polymer transducer using the polymer electrolyte, and a method of manufacturing the same. The purpose is to provide.

As a result of repeated studies to achieve the above object, the present inventors have determined that a polymer solid electrolyte composed only of a substance whose mobile ion is only an anion and exhibits a solid property at room temperature is used for a pair of electrodes. It has been found that the polymer transducer disposed between them is excellent in performance, particularly as a deformation sensor, and has reached the present invention.

The polymer solid electrolyte according to claim 1, which has been made to achieve the object, is a solid at room temperature, and a group 15 element is added to a movable cation that is not bonded to a polymer chain. An onium cation is contained.

Similarly, the polymer transducer according to claim 2, which has been made to achieve the object, includes at least a pair of electrodes and a polymer solid electrolyte disposed between the electrodes and having a solid property at room temperature. A polymer transducer, characterized in that an onium cation containing a group 15 element is contained in a cation that is non-bonded to a polymer chain constituting the polymer solid electrolyte and movable in the polymer solid electrolyte. To do.

The polymer transducer according to claim 3 is the polymer transducer according to claim 2, wherein the electrode includes a conductive substance and a binder, and at least one component of the binder contains the cation. It is characterized by being a polymer solid electrolyte.

The polymer transducer described in claim 4 is the polymer transducer described in claim 2, wherein the polymer contained in the polymer solid electrolyte is represented by the following chemical formula (1):

(In the formula (1), each of R ¹ to R ³ is independently a hydrogen atom, a fluorine atom, a linear or branched chain having 1 to 8 carbon atoms, and a part or all of the hydrogen atoms are Represents an alkyl group which may be substituted with a fluorine atom or an aryl group having 6 to 14 carbon atoms, and an anion Y ⁻ with respect to the cation X ⁺ is linked to the polymer main chain forming the polymer directly or via R ^4. R ⁴ has 1 to 10 carbon atoms, and part or all of the hydrogen atoms may be an alkylene group which may be substituted with a fluorine atom, or a carbon which may have 1 to 3 substituents. An arylene group having 6 to 14 carbon atoms, or a (poly) alkylene glycol group having 2 to 50 carbon atoms which may have a substituent and part or all of the hydrogen atoms may be substituted with fluorine atoms And a repeating unit represented by To do.

The polymer transducer according to claim 5 is the polymer transducer according to claim 2, wherein the polymer contained in the polymer solid electrolyte is represented by the following chemical formula (2):

(In the formula (2), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the anion Y ⁻ for the cation X ⁺ is R ⁵ is coupled to the aromatic ring through a, R ⁵ is an alkylene group having 1 to 10 carbon atoms, 1 to 3 substituents the carbon atoms, which may have 6 to 14 arylene group, a substituted group (Poly) alkylene glycol group or a direct bond, which may have a hydrogen atom, R ⁶ represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, n represents a number of 1 to 3, m represents 1 to And a polymer block (A) containing a unit represented by the following formula: m + n is a number satisfying that m + n is 5) and a rubber having substantially no ionic groups at 25 ° C. It is a block copolymer having a polymer block (B) in the form of To.

The polymer transducer described in claim 6 is the polymer transducer described in claim 5, wherein the polymer block (A) has an ionic group at the 4-position of the benzene ring of styrene and / or α-methylstyrene. In the polymer block (B), a part or all of the carbon-carbon double bond may be hydrogenated including a repeating unit in which an anion directly bound to form an ionic group is a sulfonate anion. , 3-butadiene units and / or isoprene units.

The polymer transducer according to claim 7 is the polymer transducer according to claim 4, wherein the cation X ⁺ is an onium cation selected from an imidazolium cation, a pyridinium cation, and an ammonium cation. .

The method for producing a solid polymer electrolyte according to claim 8 comprises a polymer block (a) comprising at least one of a styrene unit and an α-methylstyrene unit, and a part or all of carbon-carbon double bonds are hydrogen. The block copolymer (c) having a polymer block (b) comprising at least one of 1,3-butadiene unit and isoprene unit which may be added, and at least of the styrene unit and α-methylstyrene unit After sulfonation of a part of the benzene ring, the proton of the cation of the sulfonic acid group bonded to the benzene ring is an imidazolium salt or pyridinium salt having a conjugate anion of an acid having a larger acid dissociation constant than toluenesulfonic acid. By acting at least one selected from ammonium salts, an imidazolium cation, pyridini It is characterized by being converted to an onium cation selected from an um cation and an ammonium cation.

The method for producing a polymer transducer according to claim 9 is a method in which a laminate obtained by laminating an electrode using a polymer having a sulfonic acid group as a binder and an electrolyte layer formed of a polymer having a sulfonic acid group is added to ammonia, amine And immersing in a solution containing at least one selected from imidazolium salts, pyridinium salts, and ammonium salts having a conjugated anion of an acid having a larger acid dissociation constant than sulfonic acid.

The solid polymer electrolyte according to the present invention is useful for a polymer transducer, is lightweight and flexible, functions stably in an environment without water, and is excellent in flexibility. Furthermore, since such a polymer solid electrolyte is composed only of a substance exhibiting a solid property at room temperature, the risk of liquid leakage and liquid leakage can be eliminated. The polymer transducer according to the present invention using such a polymer solid electrolyte has excellent impact resistance, and a large voltage signal can be obtained when used as a deformation sensor. Moreover, it is possible to avoid the risk of liquid leakage from the polymer solid electrolyte and the change in performance due to liquid leakage.

Hereinafter, modes for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these modes.

The solid polymer electrolyte used in the polymer transducer according to the present invention is a solid polymer electrolyte at room temperature (23 ° C.), and the cation of the solid polymer electrolyte is bonded to the polymer chain. It is not a mobile ion that can move in the polymer solid electrolyte. Such a cation is an onium cation containing a Group 15 element. The group 15 element is preferably nitrogen or phosphorus, more preferably nitrogen. In this polymer solid electrolyte, an onium cation is present as a counter cation in the anion bonded to the polymer main chain. Thus, the onium cation is not bonded to the polymer main chain forming the polymer solid electrolyte, and can diffuse in the polymer solid electrolyte. Moreover, it is preferable that this polymer solid electrolyte is a solid at use temperature. The use temperature is usually in the range of −30 to 80 ° C.

As such a polymer solid electrolyte,
The following chemical formula (1)

(In the formula (1), each of R ¹ to R ³ is independently a hydrogen atom, a fluorine atom, a linear or branched chain having 1 to 8 carbon atoms, and a part or all of the hydrogen atoms are Represents an alkyl group which may be substituted with a fluorine atom or an aryl group having 6 to 14 carbon atoms, and an anion Y ⁻ with respect to the cation X ⁺ is linked to the polymer main chain forming the polymer directly or via R ^4. R ⁴ has 1 to 10 carbon atoms, and part or all of the hydrogen atoms may be an alkylene group which may be substituted with a fluorine atom, or a carbon which may have 1 to 3 substituents. An arylene group having 6 to 14 carbon atoms, or a (poly) alkylene glycol group having 2 to 50 carbon atoms which may have a substituent and part or all of the hydrogen atoms may be substituted with fluorine atoms Represents.)
It is preferable that the polymer containing the repeating unit shown by is contained in the polymer solid electrolyte.
Here, these substituents that may have are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group And alkyl groups such as hexyl group, octyl group and 2-ethylhexyl group, alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, methylethoxy group and ethylethoxy group.

The cation X ⁺ which is a mobile ion in the polymer solid electrolyte represented by the chemical formula (1) includes imidazolium cation, 1-methylimidazolium cation, 1,3-dimethylimidazolium cation, 1-ethyl-3- Such as methyl imidazolium cation, 3-ethyl-1-methyl imidazolium cation, 3-butyl-1-methyl imidazolium cation, 3-hexyl-1-methyl imidazolium cation, 3-octyl-1-methyl imidazolium cation, etc. Imidazolium cations; pyridinium cations such as pyridinium cation, N-methylpyridinium cation, N-ethylpyridinium cation, N-butylpyridinium cation; ammonium cation, methylammonium cation, dimethylammonium cation Thion, trimethyl ammonium cation, tetramethyl ammonium cation, ethyl ammonium cation, diethyl ammonium cation, triethyl ammonium cation, tetraethyl ammonium cation, butyl ammonium cation, dibutyl ammonium cation, tributyl ammonium cation, tetrabutyl ammonium cation, methyl tributyl ammonium cation, etc. Mention may be made of ammonium cations. Further, from the viewpoint of further improving the stability and improving the solvent solubility of the polymer solid electrolyte, an imidazolium cation in which the hydrogen atom on the 2-position carbon is substituted with an organic group can be preferably exemplified. Preferable examples include imidazolium cations whose positions are substituted with a methyl group, an ethyl group, or the like. Of these, imidazolium cation, pyridinium cation, and ammonium cation are preferable. These may be used alone or in combination of two or more. By the way, a polymer transducer using a polymer solid electrolyte having a metal cation that is generally used functions to some extent, but for example, in terms of signal intensity when used as a sensor, the above-described onium cation is used. Tend to show better performance.

Furthermore, the anion Y ⁻ for the cation X ⁺ as a mobile ion is bonded to the polymer main chain of the polymer solid electrolyte. Examples of the anion Y 2 ^- include a carboxylic acid anion, a sulfonic acid anion, and a phosphonic acid anion. From the viewpoint of increasing the degree of ion dissociation, a stronger conjugated anion of an acid is preferable, and a sulfonic acid anion and a phosphonic acid anion are preferable, and a sulfonic acid anion is particularly preferable from the viewpoint of easy introduction into a polymer. Thus, in the polymer solid electrolyte represented by the chemical formula (1), only the cation X ⁺ is a mobile ion. On the other hand, in a solid electrolyte in which an ionic liquid is held in a polymer, both cations and anions are diffused to conduct ions. As will be described later, the polymer transducer using the solid polymer electrolyte represented by the chemical formula (1) exhibits superior performance compared to the polymer transducer using the solid electrolyte in which the ionic liquid is held in the polymer. .

The polymer chain to which the anion Y 2 ^- is bonded is not particularly limited and may be any of a vinyl polymer, a condensation polymer, a biopolymer, a natural polymer, and the like. Examples of vinyl polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, polyisobutylene, polystyrenes such as polystyrene and poly α-methylstyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, poly 2 -Poly (meth) acrylates such as hydroxyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly 2-hydroxyethyl acrylate, polyvinyl chloride, polytetrafluoroethylene, polyhexafluoropropylene, polyvinylidene fluoride, etc. Halogen-containing polymers, poly (1,3-butadiene), polyisoprene, poly (1,3-cyclohexadiene) and other polyconjugated dienes or hydrogenation thereof Or the like can be mentioned things. Examples of the condensation polymer include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polylactic acid, polyglycolic acid, polyε-caprolactone, and other polyesters, nylon-6, nylon-6,12, nylon- Examples thereof include polyamides such as 6T and nylon-9T, polyurethanes, polysiloxanes, and the like. Among these, polystyrenes and poly (meth) acrylates are preferable from the viewpoints of handleability and availability, and polystyrenes are more preferable from the viewpoint of ease of introduction of a cationic group.

Anion Y ^- and the polymer chains may be bonded directly or may be bonded through a linking group. However, it is predicted that the higher the mobility of the cation X ^+, the better the ionic conductivity of the polymer solid electrolyte, and it is preferable that the cation X ⁺ is via the linking group R ⁴ . No particular limitation on the kind of the linking group R ⁴ is, from the viewpoint of ease of introduction, an alkylene group, an arylene group, and the like (poly) alkylene glycol group. These groups may have a substituent. Further, when the linking group R ⁴ becomes longer or larger, the total ionic group concentration is lowered, and as a result, it is considered that the effect of improving the mobility of the cation X ⁺ is negated. From this viewpoint, when the linking group R ⁴ is an alkylene group which may have a substituent, the number of carbon atoms is preferably 1 to 10. In addition, when the linking group R ⁴ is an arylene group which may have a substituent, it preferably has 6 to 14 carbon atoms. Furthermore, when the linking group R ⁴ is a (poly) alkylene glycol group which may have a substituent, it preferably has 2 to 50 carbon atoms.

Among the polymer solid electrolytes represented by the chemical formula (1) described above, from the viewpoint of ease of introduction of ion groups, flexibility of the polymer solid electrolyte, and flexibility,
The following chemical formula (2)

(In the formula (2), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the anion Y ⁻ for the cation X ⁺ is R ⁵ is coupled to the aromatic ring through a, R ⁵ is an alkylene group having 1 to 10 carbon atoms, 1 to 3 substituents the carbon atoms, which may have 6 to 14 arylene group, a substituted group (Poly) alkylene glycol group or a direct bond, which may have a hydrogen atom, R ⁶ represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, n represents a number of 1 to 3, m represents 1 to 4 is a number satisfying m + n being 5.)
A block copolymer containing a polymer block (A) containing a repeating unit represented by the formula (B) and a polymer block (B) which has substantially no ionic group and is rubbery at 25 ° C. is a polymer. It is preferably contained in the solid electrolyte. In addition, n and m in chemical formula (2) may be integers.

Here, as the polymer block (A), R ¹ is a hydrogen atom or a methyl group, R ⁵ is preferably a direct bond, and n is a number of 1 to 2 from the viewpoint of availability and ease of production. Preferably there is. R ⁶ is preferably a hydrogen atom. As a preferred specific example of such a polymer block (A), a sulfonate anion is bonded to the 4-position of polystyrene and / or poly α-methylstyrene, and the counter cation is a 1,3-disubstituted imidazolium cation, 1 , 2,3-trisubstituted imidazolium cations. One or a plurality of types of cation polymer blocks may be mentioned.

The polymer block (B) is not limited as long as it is rubbery at 25 ° C., but preferred examples include polybutadiene, polyisoprene, poly (butadiene-r-isoprene), poly (styrene-r-butadiene). ), Poly (styrene-r-isoprene), poly (acrylonitrile-r-butadiene) and other polyconjugated dienes, and some or all of the carbon-carbon double bonds contained in these polyconjugated dienes are hydrogenated. Examples thereof include hydrogenated polyconjugated dienes, poly (meth) acrylates such as poly n-butyl acrylate, poly 2-ethylhexyl acrylate, and poly 2-ethylhexyl methacrylate, polyisobutylene, and polysiloxanes. Among these, hydrogenated polybutadiene, water in which all carbon-carbon double bonds are hydrogenated, from the viewpoint of suppressing the side reaction upon introduction of ionic groups into the polymer block (A) as a property of rubber. It is preferably a hydrogenated polyisoprene, a hydrogenated poly (butadiene-r-isoprene) or a polyisobutylene.

There are no particular restrictions on the block sequence of the block copolymer, but AB type diblock polymer, ABA, BAB triblock polymer, and ABAB tetrablock polymer , ABABABA, BABABAB block polymer, (AB) _n -X, (BA) _n -X type star polymer, etc. Can do. Among these, from the viewpoint of ease of production and dynamic toughness of the solid polymer electrolyte, it should be an ABA type triblock copolymer or an ABABA type pentablock copolymer. It is more preferable that it is an ABA type triblock copolymer. The number average molecular weight of the block copolymer is preferably 10,000 to 1,000,000. The total mass ratio of the polymer blocks (A) and (B) is preferably 1: 9 to 9: 1.

Moreover, the block copolymer may have a polymer block different from the polymer block (A) and the polymer block (B) as necessary. The polymer block may be one or plural, and if it is plural, it may have the same chemical structure or may have different chemical structures. Examples of the polymer constituting such a polymer block include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methyl-1-pentene, poly p-methyl styrene, poly p-ethyl styrene, poly Polystyrenes having substituents at the p-position such as p-adamantyl styrene and poly pt-butyl styrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, poly 2-hydroxyethyl methacrylate, polymethyl acrylate, polyethyl acrylate Containing halogens such as poly (meth) acrylates such as polybutyl acrylate and poly 2-hydroxyethyl acrylate, polyvinyl chloride, polytetrafluoroethylene, polyhexafluoropropylene and polyvinylidene fluoride Limers, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polylactic acid, polyglycolic acid, polyesters such as poly-ε-caprolactone, polyamides such as nylon-6, nylon-6,12, nylon-6T, nylon-9T , Polyurethanes, polysiloxanes and the like.

Such another polymer block can have a predetermined function. For example, when another polymer block is expected to reinforce shape stability, polyethylene, polypropylene, poly-4-methyl-1-pentene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene Crystalline polymers such as naphthalate, polybutylene terephthalate, polylactic acid, nylon-6, nylon-6,12, nylon 6T, nylon-9T, polyp-methylstyrene, polyp-adamantylstyrene, polypt- It is preferable to use a polymer block made of a polymer having a high glass transition temperature such as butylstyrene. In addition, since the function different from a polymer block (A) is anticipated in this another polymer block, it is common that an ionic group is not included substantially.

As a more specific example of the block copolymer as described above, a sulfonate anion group is directly bonded to the 4-position of the benzene ring of styrene and / or α-methylstyrene, and the counter cation is 1,3. -A polymer block (A) which is one or plural kinds of cations selected from a disubstituted imidazolium cation and a 1,2,3-trisubstituted imidazolium cation, and a 1,3-butadiene unit and / or an isoprene unit. A triblock copolymer comprising a polymer block (B) in which a part or all of carbon-carbon double bonds are hydrogenated and having a block sequence of ABA can be mentioned.

Next, the method for producing a solid polymer electrolyte constituting the present invention comprises a polymer block (a) comprising at least one of a styrene unit and an α-methylstyrene unit, and a part or all of carbon-carbon double bonds. A block copolymer (c) having a polymer block (b) containing a polymer comprising at least one of 1,3-butadiene units and isoprene units, which may be hydrogenated, with respect to the styrene units and α- After sulfonation of at least a part of the benzene ring of the methylstyrene unit, an imidazole having an acid conjugate anion having an acid dissociation constant larger than that of toluenesulfonic acid is used as a cation proton of the sulfonic acid group bonded to the benzene ring. By acting at least one selected from a lithium salt, a pyridinium salt, and an ammonium salt, an imidazolium cutlet is obtained. It can be performed by a method of converting to an onium cation selected from on, pyridinium cation and ammonium cation. In such a method, a styrene thermoplastic elastomer generally produced by a living anion polymerization method is used as a precursor. Examples of the styrenic thermoplastic elastomer include polystyrene-b-poly (1,3-butadiene) -b-polystyrene (SBS) and hydrogenated products thereof (SEBS), polystyrene-b-polyisoprene-b-polystyrene. (SIS), hydrogenated product thereof (SEPS), and polystyrene-b-poly (1,3-butadiene-r-isoprene) -polystyrene hydrogenated product (SEEPS) can be preferably used. These are readily available on the market. Polystyrene-b-polyisobutylene-b-polystyrene (SiBuS) produced by the living cationic polymerization method can also be used. This is also readily available on the market. These can also be easily obtained at the laboratory or bench scale level.

Here, as a more specific example, the production of a hydrogenated product of a block copolymer of poly α-methylstyrene and polyconjugated alkadiene will be described. Examples of the production method include the following methods.
(1) A method of obtaining a triblock copolymer by polymerizing a conjugated alkadiene compound using a dianionic polymerization initiator in a tetrahydrofuran solvent and then polymerizing α-methylstyrene under a temperature condition of −78 ° C. [macromolecule Macromolecules 1969, Vol. 2, No. 5, p. 453-458].
(2) After bulk polymerization of α-methylstyrene using an anionic polymerization initiator, a conjugated alkadiene compound is polymerized, and then a coupling reaction is performed with a coupling agent such as tetrachlorosilane to form a star-type block copolymer. How to get [Cauche. Gummy, Kunstast. (Kautsch. Gummi, Kunstst.) 1984, Vol. 37, No. 5, p. 377-399; Polymer Bulletin, 1984, Vol. 12, p. 71-77].
(3) A concentration of 5 to 50% by mass in a nonpolar solvent using an organolithium compound as an initiator at a temperature of −30 to 30 ° C. in the presence of a polar compound at a concentration of 0.1 to 10% by mass. A method of polymerizing α-methylstyrene of the above, polymerizing a conjugated alkadiene compound to the resulting living polymer, and then adding a coupling agent to obtain a triblock copolymer.
Among these, the method (3) is particularly adopted as a preferable method from the viewpoint of industrial economy. In these methods, a block copolymer having another polymer block can be obtained as a precursor of the solid polymer electrolyte by changing or adding a component to be reacted.

Next, the carbon-carbon double bond derived from the conjugated alkadiene compound can be hydrogenated by reacting the block copolymer obtained by the above-described method with hydrogen in the presence of a hydrogenation catalyst. Examples of the solvent used at this time include hydrocarbon solvents such as cyclohexane, toluene and benzene, and ether solvents such as tetrahydrofuran and 1,4-dioxane. These organic solvents may be used alone or in combination of two or more. However, from the viewpoint of a smooth hydrogenation reaction, the solvent used is preferably cyclohexane. Examples of the hydrogenation catalyst include Ziegler catalysts such as nickel-based Ziegler catalysts and cobalt-based Ziegler catalysts, metallocene catalysts such as titanocene catalysts, and the like. These hydrogenation catalysts may be used alone or in combination of two or more, but one type is usually used when there is no particular purpose. Of these, nickel-based Ziegler catalysts are preferred from the viewpoints of industrial economy and ease of handling. Although there is no restriction | limiting in particular in the preparation method of a nickel-type Ziegler catalyst, For example, it can prepare by making nickel salt of organic acid and a trialkylaluminum react. The temperature during the hydrogenation can be 0 to 100 ° C., the hydrogen pressure can be in the range of 10 to 10000 kPa, and further 20 to 90 ° C. and the hydrogen pressure in the range of 500 to 3000 kPa. It is preferable in view of the progress of the hydrogenation reaction and industrial economy.

By the above-described method, for example, a hydrogenated product of poly α-methylstyrene-b-poly (1,3-butadiene) -b-polyα-methylstyrene (hereinafter sometimes referred to as mSEBmS) can be obtained. . Next, a sulfonic acid group (—SO ₃ H) is introduced into the 4-position of the aromatic ring derived from α-methylstyrene of the polymer (hereinafter, sometimes simply referred to as “sulfonation”). Such sulfonation can be performed by a known method. For example, a method of preparing an organic solvent solution or suspension of mSEBmS, adding a sulfonating agent and mixing, a method of adding a gaseous sulfonating agent directly to mSEBmS, and the like are exemplified. As the sulfonating agent used, sulfuric acid, a mixture of sulfuric acid and an aliphatic acid anhydride (for example, acetyl sulfate), chlorosulfonic acid, a mixture system of chlorosulfonic acid and trimethylsilyl chloride, sulfur trioxide, sulfur trioxide and Examples thereof include a mixture system with triethyl phosphate, and aromatic organic sulfonic acid represented by 2,4,6-trimethylbenzenesulfonic acid. These may be used alone or in combination. Examples of the organic solvent to be used include aliphatic hydrocarbons such as hexane and cyclohexane, and halogenated hydrocarbons such as methylene chloride and ethylene dichloride. These may be used alone or in combination.

Next, a phosphonation method for introducing a phosphonic acid group into the obtained copolymer will be described. For this phosphonation, a known phosphonation method can be employed. For example, an organic solvent solution or suspension of a copolymer is prepared, and chloromethyl ether is added to the copolymer in the presence of anhydrous aluminum chloride. And the like, after introducing a halomethyl group into an aromatic ring, phosphorus trichloride and anhydrous aluminum chloride are added and reacted, and a hydrolysis reaction is further introduced to introduce a phosphonic acid group. Alternatively, a method may be exemplified in which phosphorus trichloride and anhydrous aluminum chloride are added to the copolymer and reacted to introduce a phosphinic acid group into the aromatic ring, and then the phosphinic acid group is oxidized with nitric acid to form a phosphonic acid group.

Next, a method for converting a counter cation into an onium cation will be described by taking a polymer having a sulfonic acid group introduced as a precursor as a specific example. A sulfonic acid is usually a sufficiently strong acid, and an acid-base reaction easily proceeds between an imidazole derivative, a pyridine derivative, and an amine derivative. as a result,
The following chemical formulas (3) to (5)

(In the formulas (3) to (5), R represents an organic group)
A salt having the structure shown in FIG.

Here, the present inventors selected from imidazolium salts, pyridinium salts, and ammonium salts having a conjugated anion of an acid (weak acid) having a pKa larger than the acid dissociation constant (pKa) of the acid group with respect to the sulfonic acid group. It was found that the cation of the sulfonic acid group can be directly and easily converted into an onium cation containing a Group 15 element such as an imidazolium cation, a pyridinium cation, or an ammonium cation by acting at least one salt. For example, when the sulfonic acid group is benzenesulfonic acid (pKa = 2.1), a method of treating with a salt composed of the above-described onium cation containing a Group 15 element and the following anion can be mentioned. Examples of the anions include conjugated anions of carboxylic acids such as formic acid (pKa = 3.77) and acetic acid (pKa = 4.76), carbonate anions (pKa of carbonate = 6.35), and hydroxyl anions (water as an acid). Conjugated anions of water, pKa of water = 15.7), hydrogen sulfide (pKa = 7.0), hydrocyanic acid (pKa = 9.4), thiocyanic acid (pKa = 4.0) and the like. be able to. Among these, acetate anion, carbonate anion, and hydroxyl anion are preferable from the viewpoint of ease of cation exchange and availability. From the viewpoint of safety during preparation and handling of salts having these anions, acetate anion is preferable. More preferably. As such a salt, 3-ethyl-1-methylimidazolium acetate and 3-ethyl-1,2-dimethylimidazolium hydroxide are preferable.

Solvents used in the reaction include hydrocarbon solvents such as cyclohexane, toluene, and benzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, nitrile solvents such as acetonitrile, carbonate solvents such as propylene carbonate, chloroform, and dichloromethane. Further, halogen solvents such as tetrachloroethane, alcohol solvents such as methanol, ethanol, propanol, and ethylene glycol, water, and the like can be used. These may be used alone or in combination of two or more. Further, the reaction may proceed in a homogeneous system or may proceed in a heterogeneous system.

The solid polymer electrolyte thus obtained is composed only of a substance that exhibits solid properties at room temperature. Here, the room temperature is in the range of 1 to 30 ° C., preferably 23 ° C. For polymer solid electrolytes containing substances that exhibit liquid properties at room temperature, the performance of the polymer transducer, for example, the strength of the voltage signal when used as a deformation sensor, when used as a polymer transducer, as will be described later. Decreases. Moreover, the polymer solid electrolyte according to the present invention may contain other resins, polymers, and additives shown below as long as the effects thereof are not impaired. Examples of additives include phenolic stabilizers, sulfur stabilizers, phosphorus stabilizers, light stabilizers, antistatic agents, mold release agents, flame retardants, foaming agents, pigments, dyes, and whitening agents. Or two or more types may be used in combination. As the resin and polymers, those described above can be used. Furthermore, the polymer solid electrolyte according to the present invention may contain an inorganic filler as long as the effect thereof is not impaired. Specific examples of such inorganic fillers include talc, calcium carbonate, silica, glass fiber, mica, kaolin, titanium oxide, montmorillonite, and alumina.

The polymer solid electrolyte thus obtained can be sandwiched between a pair of electrodes to form a polymer transducer according to the present invention. As such a pair of electrodes, a metal thin film, a metal foil, a molded body of a resin in which a conductive substance such as a metal or a metal compound, conductive carbon, or a conductive polymer is dispersed can be used. More preferable examples include those in which these conductive substances are dispersed in a polymer solid electrolyte. Examples of metals used here include gold, silver, copper, platinum, aluminum, nickel, etc .; examples of metal compounds include ruthenium oxide (RuO ₂ ), titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), Examples of conductive carbon include iridium dioxide (IrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), indium-tin composite oxide (ITO), and zinc sulfide (ZnS); carbon black, single-walled carbon nanotubes ( SWCNT), double-walled carbon nanotubes (DWCNT), carbon nanotubes such as multi-walled carbon nanotubes (MWCNT), vapor-grown carbon fibers (VGCF), etc .; Examples of conductive polymers include polyacetylene, polypyrrole, polythiophene, Derivatives and the like can be mentioned. These may be used alone or in combination of two or more. From the viewpoint of easy handling and electrochemical stability, conductive carbon is preferable, and from the viewpoint of the performance of the polymer transducer, carbon black and carbon nanotube are more preferable. In addition, it is preferable that the substance serving as a matrix (matrix) for dispersion of these conductive substances is a polymer solid electrolyte, and in particular, the polymer solid electrolyte described so far is the performance of the polymer transducer. More preferable from the viewpoint.

In such a polymer transducer, a current collector may be provided on the outer side of the electrode layer in order to reduce the resistance in the longitudinal direction. Examples of current collectors include metal foils and metal thin films such as gold, silver, copper, platinum, and aluminum; metal powders such as gold, silver, and nickel; carbon powders such as carbon powder, carbon nanotubes, and carbon fibers; and a binder resin. A molded body comprising: 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 constituting the polymer transducer (on the side opposite to the side on which the polymer solid electrolyte is disposed).

The shape of such a polymer transducer is not particularly limited, and 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, in the case of manufacturing a membrane-like, film-like, sheet-like, or plate-like polymer transducer, for example, sheet-like electrode layers are formed on both sides of a polymer solid electrolyte formed into a membrane shape. A method in which insulation is secured and a current collecting layer is formed by a coating method if necessary; a solution or dispersion containing the components constituting the electrode is applied to both sides of the polymer solid electrolyte formed into a film shape. A method of forming electrodes insulated from each other and forming a current collecting layer by a coating method or the like as necessary; forming a current collecting layer on a film substrate as necessary, and then forming an electrode Coating / drying in the order of a solution or dispersion containing the components, a solution or dispersion containing the components constituting the polymer solid electrolyte, and a solution or dispersion containing the components constituting the electrode to form an electrode layer-polymer solid A laminated structure of electrolyte layer-electrode layer is formed Then, a current collecting layer is formed if necessary, and a film base material is pasted as a cover if necessary; a current collecting layer is optionally formed on the film base material, and then an electrode is formed. A layered structure of electrode layer-polymer solid electrolyte layer was formed by coating / drying in the order of solution or dispersion liquid containing component and solution or dispersion liquid containing component constituting polymer solid electrolyte Examples thereof include a method in which the film-like precursors are bonded to each other by heat pressing or laminating the surfaces of the polymer solid electrolyte layers. As such a film substrate, a polymer film generally used, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyolefin film, a polyurethane film, a polyvinyl chloride film, an elastomer film or the like can be appropriately used depending on the application. . The film substrate may be removed when using the polymer transducer or may be integrated as it is. When used as it is, the film substrate acts as a protective layer.

In the membrane-like, film-like, sheet-like or plate-like polymer transducer, the thicknesses of the electrode layer, the polymer solid electrolyte layer, the current collecting layer arranged as necessary, and the film substrate are particularly It is not limited and can be adjusted as appropriate depending on the use of the polymer transducer. However, 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 still more preferably in the range of 10 to 500 μm. The thickness of the solid polymer electrolyte 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. When the current collecting layer is provided, the thickness thereof is preferably in the range of 1 nm to 1 mm, more preferably in the range of 5 nm to 100 μm, and still more preferably in the range of 10 nm to 50 μm. The thickness of the film base material is preferably in the range of 1 μm to 10 mm from the viewpoint of ease of handling during production and the strength as the protective layer, regardless of whether or not it is used as it is as a protective layer. The thickness is preferably in the range of 10 μm to 1 mm, and more preferably in the range of 30 μm to 500 μm.

The polymer transducer according to the present invention can operate in air, water, vacuum, and organic solvent. Furthermore, sealing may be appropriately performed according to the use environment. There is no restriction | limiting in particular as a sealing material, Various resin etc. can be mentioned.

When mechanical energy such as displacement and pressure is applied to the polymer transducer according to the present invention from the outside, a potential difference (voltage) can be generated as electrical energy between the mutually insulated electrodes. For this reason, the polymer transducer according to the present invention can also be used as a deformation sensor (deformation sensor element) for detecting fluctuation, displacement, or pressure.

Examples 1 to 4 show a polymer solid electrolyte to which the present invention is applied, a production method thereof, and a polymer transducer. Compositions that are not applicable to the present invention are shown in Comparative Examples 1 and 2.

(material)
The materials used in the examples and comparative examples are shown below.

(1) Polystyrene-b-poly (1,3-butadiene) -b-polystyrene hydrogenated product (SEBS): “Septon 8007” manufactured by Kuraray Co., Ltd. was dissolved in toluene and then washed three times with water. Subsequently, the product purified by reprecipitation in a large excess of acetone was used.
(2) Polystyrene-b-polyisoprene-b-polystyrene hydrogenated product (SEPS): “Septon 2002” manufactured by Kuraray Co., Ltd. was dissolved in toluene, washed three times with water, and then washed with a large excess of acetone. What was purified by reprecipitation was used.
(3) Poly α-methylstyrene-b-poly (1,3-butadiene) -poly α-methylstyrene hydrogenated product (mSEBmS): in the same manner as a known method (International Publication No. WO02 / 40611) A poly α-methylstyrene-b-poly (1,3-butadiene) -b-polyα-methylstyrene type triblock copolymer was synthesized. The number average molecular weight [measured by gel permeation chromatography (GPC), converted to polystyrene] of the obtained triblock copolymer was 76,000, and 1,3-butadiene determined from ¹ H-NMR (nuclear magnetic resonance) The amount of 1,4-bond derived from was 55%, and the content of α-methylstyrene units was 30% by mass. A cyclohexane solution of the synthesized triblock copolymer was prepared and charged into a pressure-resistant vessel that had been sufficiently purged with nitrogen. Then, the Ni / Al Ziegler-type hydrogenation catalyst was used for 5 hours at 80 ° C. in a hydrogen atmosphere. The hydrogenation reaction was carried out to obtain mSEBmS. The hydrogenation rate of the obtained mSEBmS was 99.6 mol% from ¹ H-NMR.

(3) Acetic anhydride: purchased from Wako Pure Chemical Industries, Ltd. and used as it is.
(4) Concentrated sulfuric acid: purchased from Wako Pure Chemical Industries, Ltd. and used as it is.
(5) Dichloromethane: A product purchased from Kishida Chemical Co., Ltd. and contacted with molecular sieve (4A) was used.
(6) 3-ethyl-1-methylimidazolium acetate: purchased from Aldrich and used as it is.
(7) 3-ethyl-1,2-dimethylimidazolium bromide: purchased from Kanto Chemical Co., Inc. and used as it was.
(8) 3-Ethyl-1-imidazolium bromide: Purchased from Aldrich and used as is.
(9) 3-Ethyl-1-imidazolium tetrafluoroborate: purchased from Aldrich and used as is.
(10) Anion exchange resin: “Amberlite IRA400 OH AG” purchased from Organo Corporation was used after being wetted with water.
(11) Tetramethylammonium hydroxide aqueous solution (10 w / v%): purchased from Tokyo Chemical Industry Co., Ltd. and used as it is.

(12) Tetraethylammonium hydroxide aqueous solution (10 w / v%): purchased from Tokyo Chemical Industry Co., Ltd. and used as it is.
(13) Tetrapropylammonium hydroxide aqueous solution (10 w / v%): purchased from Tokyo Chemical Industry Co., Ltd. and used as it is.
(14) Tetra n-butylammonium hydroxide aqueous solution (10 w / v%): Purchased from Tokyo Chemical Industry Co., Ltd. and used as it was.
(15) Tri-n-butylmethylammonium hydroxide aqueous solution (20 w / v%): Purchased from Aldrich and used as it was.
(16) Ammonia water (10%): purchased from Wako Pure Chemical Industries, Ltd. and used as it was.
(17) Imidazole aqueous solution (10%): Imidazole purchased from Wako Pure Chemical Industries, Ltd. was dissolved in distilled water to a concentration of 10% (w / v) and used as an aqueous solution.
(18) Conductive carbon black: “Ketjen Black EC600JD” purchased from Lion Co., Ltd., vacuum-dried at 150 ° C. for 12 hours was used.
(19) 0.01N standard aqueous sodium hydroxide solution: purchased from Wako Pure Chemical Industries, Ltd. and used as is.
(20) 1% phenolphthalein ethanol solution: purchased from Wako Pure Chemical Industries, Ltd. and used as it is.
Other solvents and reagents used were commercially available products that were purified by general methods as needed.

(Reference Production Example 1)
Sulfonation of mSEBmS 355 g of mSEBmS was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, and after replacing the system with nitrogen, 3 L of methylene chloride was added and stirred at 35 ° C. for 2 hours. Dissolved. After dissolution, a sulfonating agent (acetyl sulfate) obtained by reacting 34.7 mL of acetic anhydride and 77.5 mL of concentrated sulfuric acid at 0 ° C. in 155 mL of methylene chloride was gradually added dropwise over 5 minutes. After stirring at 35 ° C. for 7 hours, the reaction solution was poured into 10 L of distilled water while stirring to coagulate and precipitate sulfonated mSEBmS. The precipitated solid was washed with distilled water at 90 ° C. for 30 minutes and further filtered. This washing and filtering operation was repeated until there was no change in the pH of the washing water. Finally, the polymer collected by filtration was vacuum-dried to obtain sulfonated mSEBmS. The sulfonation rate of the benzene ring of the α-methylstyrene unit of the obtained sulfonated mSEBmS was 49.8 mol% from ¹ H-NMR (nuclear magnetic resonance) spectrum measurement, and the proton exchange capacity was 1.08 mmol / g.

(Reference Production Example 2)
Sulfonation of SEBS In Reference Production Example 1, SEBS was used in place of mSEBmS, and the same operation was performed except that the reaction time and the amount of the sulfonating agent used were changed to obtain sulfonated SEBS. The resulting sulfonated SEBS had a styrene unit benzene ring sulfonation rate of 48.5 mol% and a proton exchange capacity of 1.21 mmol / g.

(Reference Production Example 3)
Synthesis of 3-ethyl-1,2-dimethylimidazolium hydroxide aqueous solution 10 g of 3-ethyl-1,2-dimethylimidazolium bromide was dissolved in 50 mL of distilled water. This solution was then contacted with a large excess of anion exchange resin (Amberlite IRA400 OH AG) at room temperature for 24 hours to convert bromide ions to hydroxyl ions. Further, the anion exchange resin was removed from the aqueous solution by filtration to obtain an aqueous 3-ethyl-1,2-dimethylimidazolium hydroxide solution.

(Production Example 1)
Production of Polymer Solid Electrolyte (I) The sulfonated mSEBmS obtained in Reference Production Example 1 was cast from a tetrahydrofuran (THF) / methanol mixed solvent (weight ratio 8/2) to form a film. A 10 g portion of the membrane was immersed in an aqueous solution in which 5.5 g of 3-ethyl-1-methylimidazolium acetate was dissolved in 100 mL of water. Immersion was performed for 24 hours. Further, the membrane was recovered from the aqueous solution, washed 5 times with water, and then once with methanol. The obtained membrane was vacuum-dried all day and night to obtain a polymer solid electrolyte (I). A portion of the obtained polymer solid electrolyte (I) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N aqueous sodium hydroxide solution to obtain a polymer solid electrolyte. The proton exchange capacity of (I) is zero, and all the protons of sulfonic acid are polymer solid electrolytes substituted with 3-ethyl-1-methylimidazolium cation, which is an onium cation containing a Group 15 element I understood.

(Production Example 2)
Polymer solid electrolyte (II)
A solid polymer electrolyte (II) was obtained in the same manner as in Production Example 1 except that the sulfonated SEBS obtained in Reference Production Example 2 was used in place of the sulfonated mSEBmS. A portion of the obtained polymer solid electrolyte (II) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N aqueous sodium hydroxide solution. (II) has a proton exchange capacity of zero, and is a polymer solid electrolyte in which all protons of sulfonic acid are replaced with 3-ethyl-1-methylimidazolium cation, which is an onium cation containing a Group 15 element. I understood.

(Production Example 3)
Polymer solid electrolyte (III)
Instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate in Production Example 1, the aqueous 3-ethyl-1,2-dimethylimidazolium hydroxide produced in Reference Production Example 3 (3-ethyl-1,2, A solid polymer electrolyte (III) was obtained in the same manner as above except that 4.6 g of dimethylimidazolium hydroxide was used. A portion of the obtained polymer solid electrolyte (III) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N aqueous sodium hydroxide solution. In the solid polymer electrolyte in which the proton exchange capacity of (III) is zero and all protons of sulfonic acid are replaced with 3-ethyl-1,2-dimethylimidazolium cation, which is an onium cation containing a Group 15 element I found out.

(Production Example 4)
Polymer solid electrolyte (IV)
In Production Example 3, a polymer solid electrolyte (IV) was obtained by performing the same operation except that sulfonated SEBS was used instead of sulfonated mSEBmS. A portion of the obtained polymer solid electrolyte (IV) was immersed in saline overnight, and after removing the electrolyte, the sodium chloride aqueous solution was regulated with a 0.01 N aqueous sodium hydroxide solution. The proton exchange capacity of (IV) is zero, and a solid polymer electrolyte in which all protons of sulfonic acid are replaced with 3-ethyl-1,2-dimethylimidazolium cation, which is an onium cation containing a Group 15 element. I found out.

(Production Examples 5 to 9)
Polymer solid electrolyte (V) to (IX)
In Production Example 1, instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of tetraethylammonium hydroxide, an aqueous solution of tetrapropylammonium hydroxide, an aqueous solution of tetra-n-butylammonium hydroxide, Polymer solid electrolytes (V) to (IX) were obtained in the same manner except that an aqueous solution of tri-n-butylmethylammonium hydroxide was used. A portion of each of the polymer solid electrolytes (V) to (IX) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N aqueous sodium hydroxide solution. The proton exchange capacities of the molecular solid electrolytes (V) to (IX) are zero, and all protons of the sulfonic acid are onium cations containing a group 15 element such as tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, It was found that the polymer solid electrolyte was a tetra n-butylammonium cation and a tri-n-butylmethylammonium cation.

(Comparative Production Example 1)
A polymer solid electrolyte (XII) was prepared in the same manner as in Production Example 1, except that an aqueous solution of 3-ethyl-1-methylimidazolium bromide was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. Got. A portion of the obtained polymer solid electrolyte (XII) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N sodium hydroxide solution to obtain a polymer solid electrolyte. The proton exchange capacity was 1.05 mmol / g, indicating a proton exchange capacity equivalent to that of the raw material sulfonated mSEBmS. This indicates that the proton of sulfonic acid is not substituted with an onium cation containing a Group 15 element.

(Comparative Production Example 2)
In the same manner as in Comparative Production Example 1, except that an aqueous solution of 3-ethyl-1-methylimidazolium tetrafluoroborate was used, a polymer solid electrolyte (XIII) was obtained. A portion of the obtained polymer solid electrolyte (XIII) was immersed in saline overnight, and after removing the electrolyte, the saline was adjusted with a 0.01 N sodium hydroxide solution to obtain a polymer solid electrolyte. The proton exchange capacity was 1.04 mmol / g, indicating a proton exchange capacity equivalent to that of the sulfonated mSEBmS as a raw material. This indicates that the proton of sulfonic acid is not substituted with an onium cation containing a Group 15 element.

A summary of the above Reference Production Examples, Production Examples and Comparative Production Examples is shown in [Table 1] below.

As can be seen from Table 1, according to the method for producing a solid polymer electrolyte of the present invention, the proton of sulfonic acid can be easily converted to an onium cation containing a Group 15 element.

(Production Example 1)
Production of Polymer Transducer (1) 50 g of the sulfonated mSEBmS obtained in Reference Production Example 1 was dissolved in 200 g of diisopropylbenzene / 1-hexanol mixed solvent (weight ratio 8/2) (referred to as electrolyte solution A).
(2) 4.4 g of ketjen black was added to the solution A prepared in (1) and mixed, and then uniformly mixed using a homogenizer (electrode dispersion B). Moreover, the electrode dispersion liquid B was applied on a polypropylene film (thickness 50 μm) provided with a distribution line with a commercially available silver paste using a screen printer, and then dried at 80 ° C. This process was performed until the dry film thickness of the electrode reached 100 μm (laminate A). This step of applying the electrolyte solution A to the obtained laminate A using a screen printer and then drying at 80 ° C. was performed until the dry film thickness of the sulfonated mSEBmS was 15 μm (laminate B). . Further, the obtained laminate B was immersed in a 3-ethyl-1-methylimidazolium acetate aqueous solution prepared to 0.2 M for 1 hour. The laminate B after the immersion was sufficiently washed with distilled water and then sufficiently dried. The layered product B after washing was measured for proton exchange capacity. As a result, the proton exchange capacity was 0 mmol / l. All protons of the sulfonic acid groups present in the electrode and the electrolyte were all of 3-ethyl-1 -It was confirmed that it was converted to methylimidazolium cation. Next, two layers of the laminated body B subjected to washing and drying were overlapped so that the electrolyte surfaces were bonded to each other, and in this state, the polymer transducer (1) was obtained by pressing at 100 ° C. for 5 minutes. At this time, lead wires were provided for evaluation as transducers.

(Production Examples 2 to 4)
Production of Polymer Transducer Same as in Production Example 1, except that 3-ethyl-1,2-dimethylimidazolium hydroxide aqueous solution and tetramethylammonium aqueous solution were used instead of 3-ethyl-1-methylimidazolium acetate aqueous solution Thus, polymer transducers (2) to (3) were obtained.

(Comparative Production Example 3)
Production of Polymer Transducer A polymer transducer (4) was obtained in the same manner as in Production Example 1 except that the ion exchange step was not performed.

(Comparative Production Example 4)
Production of Polymer Transducer In Production Example 1, the washed and dried laminate B was brought into contact with ethyl lactate for 10 minutes. The ethyl lactate remaining on the surface was wiped off. Thereafter, the same operation as in Production Example 1 was performed to obtain a polymer transducer (5).

(Examples 1 to 3 and Comparative Examples 1 to 2)
The sensor performance of each of the polymer transducers obtained in Production Examples 1 to 3 and Comparative Production Examples 1 and 2 is shown in [Table 2] below.

As is clear from Table 2, the polymer transducers of Production Examples 1 to 4 showed higher signal strength when used as sensors than the polymer transducers of Production Comparative Examples 1 and 2, It can be suitably used as a sensor.

The solid polymer electrolyte used in the present invention can be easily produced and exhibits excellent performance as a solid polymer electrolyte, particularly as an electrolyte for a polymer transducer. The polymer transducer according to the present invention exhibits high performance as a deformation sensor and can be suitably used as a flexible sensor for measuring various deformations and displacements.

Claims (9)

1. A solid polymer electrolyte characterized in that an onium cation containing a Group 15 element is contained in a movable cation that is solid at room temperature and is not bonded to a polymer chain.
2. A polymer transducer comprising at least a pair of electrodes and a solid polymer electrolyte that is disposed between the electrodes and is solid at room temperature,
   A polymer transducer characterized in that an onium cation containing a Group 15 element is contained in a cation that is non-bonded to a polymer chain constituting the polymer solid electrolyte and moves in the polymer solid electrolyte.
3. 3. The polymer transducer according to claim 2, wherein the electrode includes a conductive substance and a binder, and at least one component of the binder is a solid polymer electrolyte containing the cation.
4. The polymer contained in the polymer solid electrolyte has the following chemical formula (1)
   

   

   (In the formula (1), each of R ¹ to R ³ is independently a hydrogen atom, a fluorine atom, a linear or branched chain having 1 to 8 carbon atoms, and a part or all of the hydrogen atoms are Represents an alkyl group which may be substituted with a fluorine atom or an aryl group having 6 to 14 carbon atoms, and an anion Y ⁻ with respect to the cation X ⁺ is linked to the polymer main chain forming the polymer directly or via R ^4. R ⁴ has 1 to 10 carbon atoms, and part or all of the hydrogen atoms may be an alkylene group which may be substituted with a fluorine atom, or a carbon which may have 1 to 3 substituents. An arylene group having 6 to 14 carbon atoms, or a (poly) alkylene glycol group having 2 to 50 carbon atoms which may have a substituent and part or all of the hydrogen atoms may be substituted with fluorine atoms Represents.)
   The polymer transducer according to claim 2, comprising a repeating unit represented by:
5. The polymer contained in the polymer solid electrolyte has the following chemical formula (2)
   

   

   (In the formula (2), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the anion Y ⁻ for the cation X ⁺ is R ⁵ is coupled to the aromatic ring through a, R ⁵ is an alkylene group having 1 to 10 carbon atoms, 1 to 3 substituents the carbon atoms, which may have 6 to 14 arylene group, a substituted group (Poly) alkylene glycol group or a direct bond, which may have a hydrogen atom, R ⁶ represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, n represents a number of 1 to 3, m represents 1 to 4 is a number satisfying m + n being 5.)
   It is a block copolymer having a polymer block (A) containing a unit represented by the formula (1) and a polymer block (B) which has substantially no ionic group and is rubbery at 25 ° C. The polymer transducer according to claim 2, wherein
6. The polymer block (A) includes a repeating unit in which an anion in which an ionic group is directly bonded to the 4-position of a benzene ring of styrene and / or α-methylstyrene to form an ionic group is a sulfonate anion, 6. The polymer transducer according to claim 5, wherein the block (B) comprises 1,3-butadiene units and / or isoprene units in which part or all of carbon-carbon double bonds may be hydrogenated.
7. The polymer transducer according to claim 4, wherein the cation X ⁺ is an onium cation selected from an imidazolium cation, a pyridinium cation, and an ammonium cation.
8. A polymer block (a) comprising at least one of a styrene unit and an α-methylstyrene unit, and a 1,3-butadiene unit and an isoprene unit in which a part or all of carbon-carbon double bonds may be hydrogenated. For the block copolymer (c) having at least one polymer block (b), sulfonated at least a part of the benzene ring of the styrene unit and α-methylstyrene unit,
   The cation proton of the sulfonic acid group bonded to the benzene ring acts on at least one selected from imidazolium salts, pyridinium salts, and ammonium salts having an acid conjugate anion having a larger acid dissociation constant than toluenesulfonic acid. To produce an onium cation selected from an imidazolium cation, a pyridinium cation, and an ammonium cation, thereby producing a solid polymer electrolyte.
9. A laminate in which an electrode having a polymer having a sulfonic acid group as a binder and an electrolyte layer formed of a polymer having a sulfonic acid group is laminated with a conjugate anion of an acid having an acid dissociation constant larger than that of ammonia, amine or sulfonic acid. A method for producing a polymer transducer, comprising a step of immersing in a solution containing at least one selected from an imidazolium salt, a pyridinium salt, and an ammonium salt.