JP2013072829A - Electrochemical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical element suitable for a sensor capable of emitting an electric signal with high signal intensity.SOLUTION: There is provided an electrochemical element comprising: a polymer electrolyte layer consisting of a block copolymer (Z) having a polymer block (A) composed of a structural unit derived from an aromatic vinyl compound and a polymer block (B) composed of a structural unit derived from an olefinic unsaturated compound, in which the polymer block (A) has a functional group represented by the following general formula (1); and two electrodes joined respectively to both surfaces of the polymer electrolyte layer. (In the formula (1), Rto Reach independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)

Description

  The present invention relates to an electrochemical element particularly suitable for a sensor.

  Electrochemical elements that can convert the deformation of the action part and the electrical signal into each other are being developed for various applications. For example, a block copolymer containing a polymer block mainly having a structural unit derived from an aromatic vinyl compound having an ion conductive group and a polymer block that is incompatible with the polymer block is mainly used. It is known that an electrochemical element composed of an action part composed of a molded body as a component and two electrodes joined to the action part is useful as an actuator (see Patent Document 1).

JP 2007-336790 A

A sensor is mentioned as an application of an electrochemical element which has attracted attention in recent years. Such a sensor is required to transmit an electric signal having a high signal intensity due to deformation of the action part, but it has been difficult to transmit a signal intensity that is practical as a sensor in a conventional electrochemical element.
Accordingly, an object of the present invention is to provide an electrochemical element suitable for a sensor capable of transmitting an electric signal having a high signal intensity.

（式中、Ｒ^１〜Ｒ^３はそれぞれ独立して水素原子、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。）
で示される官能基（以下官能基（１）と称する）を有するブロック共重合体（Ｚ）を含有する高分子電解質層と、該高分子電解質層の両面にそれぞれ接合した２つの電極を備える電気化学素子を提供することによって、達成される。 According to the present invention, the object includes a polymer block (A) composed of a structural unit derived from an aromatic vinyl compound and a polymer block (B) composed of a structural unit derived from an olefinically unsaturated compound, And the said polymer block (A) is following General formula (1)

^(Wherein, R 1 to R ³ are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
A polymer electrolyte layer containing a block copolymer (Z) having a functional group represented by (hereinafter referred to as functional group (1)) and two electrodes joined to both sides of the polymer electrolyte layer, respectively. This is achieved by providing a chemical element.

According to the present invention, there is provided an electrochemical element capable of transmitting an electric signal having a high signal intensity when used as a sensor having a polymer electrolyte layer containing the block copolymer (Z) as an action part. Can be provided.
When the electrochemical element of the present invention is used as a sensor, it is considered that a high electrical signal is transmitted as the imidazolium cation derived from the functional group (1) moves due to deformation of the polymer electrolyte layer serving as an action part. ing.

The block copolymer (Z) contained in the polymer electrolyte layer provided in the electrochemical device of the present invention is a polymer block (A ₀ ) comprising a structural unit derived from an aromatic vinyl compound not containing the functional group (1). ) And a block copolymer (Z ₀ ) containing a polymer block (B) composed of a structural unit derived from an olefinically unsaturated compound, and then a functional group is added to the polymer block (A ₀ ) by a known method. It is obtained by introducing (1).

Examples of the aromatic vinyl compound constituting the polymer block (A ₀ ) contained in the block copolymer (Z ₀ ) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 2-methoxy. Styrene, 3-methoxystyrene, 4-methoxystyrene, vinylnaphthalene, vinylanthracene, vinylphenanthrene, vinylbiphenyl, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-butylstyrene, α-pentylstyrene, α -Hexyl styrene, α-heptyl styrene, α-octyl styrene, α-isopropyl styrene, α-tert-butyl styrene, α-isobutyl styrene, α-tert-pentyl styrene, α-neopentyl styrene, 1,1-diphenylethylene 1-methyl-1-na Chiruechiren, 1-methyl-1-biphenylyl ethylene, 4, include α- dimethylstyrene. Of these, styrene and α-methylstyrene are preferable from the viewpoint of economy, ease of polymerization, and ease of introduction of the functional group (1), and α-methylstyrene is more preferable from the viewpoint of radical resistance. These aromatic vinyl compounds may be used alone or in combination of two or more. When a plurality of types of aromatic vinyl compounds are used in combination, the plurality of types of aromatic vinyl compounds are preferably copolymerized randomly to form a polymer block (A ₀ ).

The polymer block (A ₀ ) may contain one or a plurality of other structural units in addition to the structural unit derived from the aromatic vinyl compound as long as the effects of the present invention are not impaired. Examples of the monomer that gives such other structural unit include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, and 4-methyl-1. -Alkenes having 2 to 8 carbon atoms such as pentene, 1-heptene, 2-heptene, 1-octene, 2-octene; butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, Conjugated alkadienes having 4 to 8 carbon atoms such as 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 2,4-heptadiene, 3,5-heptadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl esters of vinyl pivalate and the like; methyl vinyl ether, ethyl vinyl ether, such as isobutyl vinyl ether; and the like. When these monomers are used, it is preferable that the polymer block (A ₀ ) is constituted by random copolymerization with the aromatic vinyl compound.

Among the structural units constituting the polymer block (A ₀ ), the content of the structural unit derived from the aromatic vinyl compound is preferably 60 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more. .

The molecular weight of the polymer block (A ₀ ) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 10,000 to 100,000 as the number average molecular weight in terms of standard polystyrene.

  Examples of the olefinically unsaturated compound constituting the polymer block (B) include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 4-methyl. C2-C8 alkenes such as -1-pentene, 1-heptene, 2-heptene, 1-octene, 2-octene; butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4- Conjugation with 4 to 8 carbon atoms such as hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 2,4-heptadiene, 3,5-heptadiene, etc. Alkadienes; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters of the acids such as benzyl; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl esters of vinyl pivalate and the like; methyl vinyl ether, ethyl vinyl ether, such as isobutyl vinyl ether; and the like. These olefinically unsaturated compounds may be used alone or in combination of two or more. When a plurality of types of olefinically unsaturated compounds are used in combination, the plurality of types of olefinically unsaturated compounds are preferably copolymerized randomly to form the polymer block (B). Moreover, when using a conjugated alkadiene as an olefinically unsaturated compound, there is no restriction | limiting in particular in the ratio of the structural unit based on a 1, 2- bond and the structural unit based on a 1, 4- bond.

  The polymer block (B) may contain one or more kinds of other structural units in addition to the structural unit derived from the olefinically unsaturated compound as long as the effects of the present invention are not impaired. Examples of the monomer that gives such other structural unit include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinylnaphthalene. These monomers and olefinically unsaturated compounds are preferably copolymerized randomly to constitute the polymer block (B).

  Of the structural units constituting the polymer block (B), the content of the structural unit derived from the olefinically unsaturated compound is preferably 60% by mass or more, more preferably 75% by mass or more, More preferably, it is 90 mass% or more.

  The polymer block (B) is preferably amorphous. Here, the polymer block (B) being amorphous means that the melting point derived from the polymer block (B) is not observed in the viscoelasticity measurement. From the viewpoint of ease of deformation of the polymer electrolyte layer, the softening temperature of the polymer block (B) is preferably 40 ° C. or lower, more preferably 20 ° C. or lower, and 0 ° C. or lower. More preferably.

When the main chain or the side chain has a carbon-carbon double bond after polymerization, as in the case where the olefinically unsaturated compound is a conjugated alkadiene, the carbon-carbon double bond is hydrogenated (hereinafter referred to as “the hydrogenated”). (Referred to as “hydrogenation”). From the viewpoint of improving the deterioration resistance of the electrochemical device of the present invention, the hydrogenation rate of the carbon-carbon double bond is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more. 90 mol% or more is particularly preferable. The hydrogenation rate of the carbon-carbon double bond can be calculated by, for example, an iodine number measurement method, ¹ H-NMR measurement or the like.

  From the viewpoint of flexibility and elongation of the block copolymer (Z), the structural unit constituting the polymer block (B) is an alkene unit having 2 to 8 carbon atoms, a conjugated alkadiene unit having 4 to 8 carbon atoms, and carbon. -It is preferably selected from the group consisting of conjugated alkadiene units having 4 to 8 carbon atoms in which some or all of the carbon double bonds are hydrogenated, and from the viewpoint of economy and ease of polymerization, the number of carbon atoms is 4 to 8 It is more preferable that the conjugated alkadiene unit or a conjugated alkadiene unit having 4 to 8 carbon atoms in which part or all of the carbon-carbon double bond is hydrogenated is selected.

  The molecular weight of the polymer block (B) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 10,000 to 100,000 as the number average molecular weight in terms of standard polystyrene.

The mass ratio of the polymer block (A ₀ ) and the polymer block (B) is preferably in the range of 90:10 to 10:90, more preferably in the range of 80:20 to 15:85, More preferably, it is in the range of 50:50 to 20:80. In such a mass ratio, when the ratio of the polymer block (A ₀ ) is higher than 90% by mass, the shape-retaining property of the polymer electrolyte layer containing the block copolymer (Z) tends to decrease, and the polymer block When the ratio of (A ₀ ) is lower than 10% by mass, the polymer block (A) derived from the polymer block (A ₀ ) hardly forms a continuous phase, and the ionic conductivity tends to be reduced.

As the structure of the block copolymer (Z), when the polymer block (A) is represented by A and the polymer block (B) is represented by B, an AB type diblock copolymer, an ABA type Triblock copolymer, BAB type triblock copolymer, ABAB type tetrablock copolymer, ABABA type pentablock copolymer, B- A-B-A-B type pentablock copolymer, (AB) _n X-type star block copolymer (n represents an integer of 2 or more, X represents a coupling agent residue). These may be used alone or in combination. Each polymer block may be graft-bonded, and it is preferable that the polymer block (B) forms at least a main chain from the viewpoint of production. Among the above, an ABA type triblock copolymer is preferable.

  The block copolymer (Z) is a polymer block (C) comprising a structural unit derived from an aromatic vinyl compound having no ion conductive group in addition to the polymer block (A) and the polymer block (B). May further be contained.

  As the structure of the block copolymer (Z) in the case of further containing the polymer block (C), when the polymer block (C) is represented by C, an ABC type triblock copolymer, A- B-C-A type tetrablock copolymer, A-B-A-C type tetrablock copolymer, B-A-B-C type tetrablock copolymer, A-B-C-B type tetrablock copolymer Examples thereof include a copolymer, a C-A-B-A-C type pentablock copolymer, a C-B-A-B-C type pentablock copolymer, and the like.

As the aromatic vinyl compound constituting the polymer block (C), 4-methylstyrene, 4-tert-butylstyrene, 4, α-dimethylstyrene and the like are preferable. From the viewpoint of suppressing the introduction of the functional group (1) into the polymer block (C) when the functional group (1) is introduced into the polymer block (A ₀ ) of the block copolymer (Z ₀ ), 4 -Tert-butylstyrene is more preferred. Such aromatic vinyl compounds may be used alone or in combination of two or more. When the polymer block (C) is formed by using a plurality of types of aromatic vinyl compounds in combination, the plurality of types of aromatic vinyl compounds may be copolymerized randomly to form the polymer block (C). preferable.

  The polymer block (C) includes a structural unit derived from one or more other monomers in addition to the structural unit derived from the aromatic vinyl compound as long as the effects of the present invention are not impaired. You may go out. Examples of such other monomers include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 4-methyl-1-pentene, 1 -Alkene having 2 to 8 carbon atoms such as heptene, 2-heptene, 1-octene, 2-octene; 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, Conjugated alkadienes having 4 to 8 carbon atoms such as 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 2,4-heptadiene, 3,5-heptadiene; Such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate (meth) Acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl esters of vinyl pivalate and the like; methyl vinyl ether, ethyl vinyl ether, such as isobutyl vinyl ether; and the like. When these monomers are used, it is preferable that the polymer block (C) is constituted by random copolymerization with the aromatic vinyl compound.

  Among the structural units constituting the polymer block (C), the content of the structural unit derived from the aromatic vinyl compound is preferably 60% by mass or more, more preferably 75% by mass or more, and further preferably 90% by mass or more. .

  The polymer block (C) may be crosslinked by a known method as long as the effects of the present invention are not impaired. By crosslinking, the mechanical strength of the polymer electrolyte layer tends to increase.

  The molecular weight of the polymer block (C) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 10,000 to 100,000 as the number average molecular weight in terms of standard polystyrene.

  When the block copolymer (Z) contains the polymer block (C), the content of the polymer block (C) is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. preferable.

The number average molecular weight of the block copolymer (Z ₀ ) is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 15,000 to 1,000,000 as the number average molecular weight in terms of standard polystyrene. The range of 20,000 to 500,000 is more preferable.

  The polymer block (A) has a functional group (1) represented by the following general formula (1).

（式中、Ｒ^１〜Ｒ^３はそれぞれ独立して水素原子、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。）

^(Wherein, R 1 to R ³ are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, An ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group are mentioned.

  The content of the functional group (1) with respect to the structural unit derived from the aromatic vinyl compound constituting the polymer block (A) is preferably in the range of 25 to 100 mol%, more preferably in the range of 30 to 90 mol%, and 40 to 80 mol. More preferably, it is in the range of%. If the content is less than 25 mol%, the performance as an electrochemical element tends to be insufficient, and if it exceeds 100 mol%, the production tends to be difficult.

The block copolymer (Z) preferably has only the functional group (1) as an ion conductive group. From the viewpoint of ease of introduction and sensor performance, the functional group (1) is on the aromatic ring of the structural unit derived from the aromatic vinyl compound constituting the polymer block (A ₀ ) of the block copolymer (Z ₀ ). It is preferable to introduce into.

  The polymer block (B) contained in the block copolymer (Z) is preferably incompatible with the polymer block (A). Since the polymer block (A) and the polymer block (B) are incompatible, the block copolymer (Z) forms a microphase separation structure, and the phase formed by the polymer block (A) is It becomes a migration path of the imidazolium cation possessed by the functional group (1) as an ion channel. Moreover, when a polymer block (B) has a softness | flexibility, elasticity and a softness | flexibility can be provided to a polymer electrolyte layer. It is highly desirable that the polymer block (B) has substantially no functional group (1). In addition, the block copolymer (Z) forms a microphase-separated structure because the polymer electrolyte layer prepared from the block copolymer (Z) by the method described later is used as a measurement sample, and a transition metal such as ruthenium. This can be confirmed by observing with an electron microscope after dyeing.

The block copolymer (Z ₀ ) can be produced by various polymerization methods such as a radical polymerization method, an anionic polymerization method, a cationic polymerization method, and a coordination polymerization method. The living radical polymerization method, the living anion polymerization method, and the living cation polymerization method are preferable, and the living anion polymerization method is more preferable from the viewpoint of easy control of molecular weight, molecular weight distribution, and the like.

Block copolymer (Z ₀₎ is poly (alpha-methylstyrene) comprising a polymer block (A _0), and when it contains a polymer block comprising a conjugated alkadiene (B), ease of manufacture and molecular structure design Living anionic polymerization method is preferable from the viewpoint of properties, for example,
[1] A method of obtaining an ABA type block copolymer by polymerizing conjugated alkadiene using a dianionic polymerization initiator in a tetrahydrofuran solvent and then polymerizing α-methylstyrene under a temperature condition of −78 ° C. (Macromolecules, (1969), 2 (5), 453-458). ;
[2] After α-methylstyrene is polymerized using an anionic polymerization initiator, conjugated alkadiene is polymerized, and then a coupling reaction is performed with a coupling agent such as tetrachlorosilane, and (AB) _n X type A method for obtaining a star block copolymer (Kautsch. Gummi, Kunstst., (1984), 37 (5), 377-399; Polym. Bull., (1984), 12, 71-77). And [3] In a nonpolar solvent, an organolithium compound is used as an initiator, and in the presence of a polar compound having a concentration of 0.1 to 10% by mass, at a concentration of 5 to 50% by mass at −30 to 30 ° C. And a method of polymerizing conjugated alkadiene to the resulting living polymer and then adding a coupling agent to obtain an ABA type triblock copolymer. From the viewpoint of property, the method [3] is more preferable.

Further, in the method of the above-mentioned [1] to [3], adding another aromatic vinyl compound may be introduced polymer block (C) in the block copolymer (Z _0).

When the polymer block (B) has a carbon-carbon double bond, the ease of selective introduction of the functional group (1) into the polymer block (A ₀ ) and the resistance of the polymer electrolyte layer From the standpoint of improving the deterioration, etc., it is preferable to hydrogenate part or all of it.

Examples of the hydrogenation method include a method in which a block copolymer (Z ₀ ) is dissolved in an organic solvent and hydrogen is reacted in the presence of a catalyst. Examples of the organic solvent include hydrocarbons such as cyclohexane, toluene, and benzene; ethers such as tetrahydrofuran and 1,4-dioxane.

Examples of the hydrogenation catalyst (hydrogenation catalyst) include Ziegler catalysts such as nickel-based Ziegler catalysts and cobalt-based Ziegler catalysts, and metallocene catalysts such as titanocene catalysts.
The temperature at the time of hydrogenation is preferably in the range of 0 to 100 ° C, more preferably in the range of 20 to 90 ° C. The hydrogen pressure at the time of hydrogenation is preferably in the range of 10 to 10000 kPa, more preferably in the range of 500 to 3000 kPa.

The block copolymer (Z) is produced by first reacting a block copolymer (Z ₀ ) dissolved in a halogenated hydrocarbon with a sulfonating agent to form a sulfone on the aromatic ring of the polymer block (A ₀ ). An acid group is introduced (hereinafter, a polymer block (A ₀ ) having a sulfonic acid group introduced is referred to as a polymer block (A ₁ )). Examples of the halogenated hydrocarbon include chloroform and dichloromethane, and dichloromethane is preferred from the viewpoint of solubility. Examples of the sulfonating agent include concentrated sulfuric acid and acetyl sulfate, and acetyl sulfate is preferred. Note that. Acetyl sulfate can be easily prepared, for example, by reacting acetic anhydride and concentrated sulfuric acid.

In the block copolymer (Z ₀ ) into which the resulting sulfonic acid group was introduced (hereinafter referred to as block copolymer (Z ₁ )), the content of the sulfonic acid group was ₁ g of the block copolymer (Z ₁ ). Is preferably 0.30 mmol or more, and more preferably 0.40 mmol or more. The content of the sulfonic acid group can be calculated using a titration method.

Next, the obtained block copolymer (Z ₁ ) is subjected to cation exchange treatment to convert the sulfonic acid group of the polymer block (A ₁ ) into the functional group (1). Specifically, by immersing the block copolymer (Z ₁₎ to cation exchange treatment solution, sulfone group of the polymer block (A ₁₎ is converted to a functional group (1), i.e. Weight A block copolymer (Z) in which the combined block (A ₁ ) is converted into the polymer block (A) is obtained. The treatment temperature and treatment time in the cation exchange treatment, and the concentration of the cation source in the cation exchange treatment solution to be used can be appropriately adjusted and are not particularly limited. Examples of the cation exchange solution include 3-ethyl-1-methylimidazolium acetate aqueous solution and 3-ethyl-1,2-dimethylimidazolium acetate aqueous solution. From the viewpoint of enhancing the performance of the electrochemical device, 3-ethyl An aqueous solution of -1-methylimidazolium acetate is preferred. The above cation exchange process creates a polymer electrolyte layer with the block copolymer (Z _1), carried out after the bonding of the further electrodes as required, from the viewpoint of production.

  The polymer electrolyte layer provided in the electrochemical device of the present invention is preferably composed only of the block copolymer (Z), but as long as the effects of the present invention are not impaired, other resins, softeners, water, You may contain an organic solvent and various additives.

  Examples of other resins that the polymer electrolyte layer may contain include, for example, propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene- (1-butene) copolymer Copolymers, propylene-ethylene- (1-butene) copolymers, propylene- (4-methyl-1-pentene) copolymers, ethylene homopolymers such as high-density polyethylene and low-density polyethylene, ethylene- (1-butene) ) Copolymer, ethylene- (1-hexene) copolymer, ethylene- (1-heptene) copolymer, ethylene- (1-octene) copolymer, ethylene- (4-methyl-1-pentene) copolymer Polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester Polyolefin resins such as copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers; polyether resins such as polyoxymethylene and polyphenylene ether resins; polyamide 6, polyamide 6,6, polyamide Polyamide resins such as 6,10, polyamide 11, polyamide 12, polyamide 6,12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, xylene group-containing polyamide; polyethylene terephthalate, polybutylene terephthalate, polynaphthalene terephthalate, etc. Polyester resin: polystyrene, poly α-methyl styrene, poly p-methyl styrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, etc. Styrene resin; polycarbonate resin; natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, chloroprene rubber, acrylic rubber, butyl rubber, acrylonitrile-butadiene rubber, epichlorohydrin rubber, silicone rubber, Examples thereof include rubbers such as fluorine rubber; elastomers such as polyurethane elastomers, polyamide elastomers, polyester elastomers, styrene elastomers, and olefin elastomers.

  Examples of the softener that may be contained in the polymer electrolyte layer include petroleum softeners such as paraffinic, naphthenic, and aroma-based process oils, liquid paraffin, and vegetable oil-based softeners.

  Examples of the organic solvent that may be included in the polymer electrolyte layer include aliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, isopropylbenzene, and diisopropylbenzene; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones such as cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl butyrate, and ethyl lactate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-hexanol, 1 -Alcohol such as octanol; alkylene carbonate such as ethylene carbonate and propylene carbonate; alkylene glycol such as ethylene glycol and propylene glycol; nitric acid such as acetonitrile and propionitrile Yl; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane; amides such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone; dialkyl sulfoxides such as dimethyl sulfoxide; among these, alkylene carbonate, Alkylene glycol and nitrile are preferable, and ethylene carbonate and propylene carbonate are more preferable from the viewpoint of affinity with the polymer block (A). A plurality of these organic solvents may be contained.

  Examples of other various additives that may be included in the polymer electrolyte layer include, for example, phenol stabilizers, ionic stabilizers, phosphorus stabilizers, light stabilizers, antistatic agents, mold release agents, flame retardants, and foaming agents. , Pigments, dyes, brighteners, carbon fibers, talc, calcium carbonate, silica, glass fibers, mica, kaolin, titanium oxide, carbon black, etc., which can be used alone or in combination. May be.

  The content of the block copolymer (Z) in the polymer electrolyte layer is preferably 60% by mass or more, and preferably 70% by mass or more from the viewpoint of ion conductivity and the performance of the electrochemical element. More preferably, it is more preferably 80% by mass or more, and still more preferably 90% by mass or more.

There is no particular limitation on the method for producing the polymer electrolyte layer. For example, a solution or suspension of the block copolymer (Z) and, if necessary, the block copolymer (Z) prepared by mixing the above optional components with an appropriate solvent is placed on a plate-like body such as glass. After casting, coating using a coater or applicator or printing using a screen printer or the like, the polymer electrolyte layer can be obtained by removing the solvent.
Solvents include halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as toluene, xylene, benzene, isopropylbenzene, and diisopropylbenzene; aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; ethers such as tetrahydrofuran; methanol, ethanol , 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-hexanol and other alcohols; or a mixed solvent thereof, and a mixed solvent of an aromatic hydrocarbon and an alcohol is preferable.
Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is preferable that it is 20 times or less of a block copolymer (Z). The conditions for removing the solvent are not particularly limited as long as the block copolymer (Z) is not decomposed. For example, a method of drying with hot air in the range of 60 to 140 ° C .; a method of drying under normal pressure in the range of 10 to 30 ° C., and further drying with hot air in the range of 60 to 140 ° C. (especially 80 to 120 ° C.); 10 After drying under normal pressure in the range of -30 ° C, and further drying under reduced pressure in the range of 25-40 ° C; after drying under normal pressure in the range of 10-30 ° C, further 60-140 ° C (Especially, a method of drying under normal pressure in the range of 80 to 120 ° C.).
From the viewpoint of film forming property, a method of drying under normal pressure in the range of 10 to 30 ° C. and then drying at 80 to 120 ° C. under normal pressure is preferable.

  The block copolymer (Z) may be molded by compression molding, roll molding, extrusion molding, injection molding, or the like to form a polymer electrolyte layer.

As another method for preparing the polymer electrolyte layer comprising the block copolymer (Z), the block copolymer (Z ₁ ) is prepared in the same manner as the method for preparing the polymer electrolyte layer from the block copolymer (Z) described above. After forming a layer composed of the block copolymer (Z ₁ ), the sulfonic acid group is converted to the functional group (1) by cation exchange treatment by the above-described method to obtain the block copolymer (Z). A method is mentioned.

The electrochemical device of the present invention comprises a polymer electrolyte layer made of a block copolymer (Z) and two electrodes respectively bonded to both surfaces of the polymer electrolyte layer. As such an electrode, a metal thin film; a resin molded body in which a conductor is dispersed; and the like can be used.
Of these, in the molded resin body in which the conductor is dispersed, when an electrode is used using an elastomer as the resin, the electrode becomes flexible and can be prevented from peeling or breaking due to deformation of the polymer electrolyte layer. preferable. In the sensor application, it is more preferable that the elastomer is a polymer electrolyte because the signal strength value is less likely to change with time when the working portion of the sensor is deformed and the signal strength value is stable. In addition, the polymer electrolyte includes a block copolymer containing a polymer block composed of a structural unit derived from an aromatic vinyl compound having an ion conductive group and a polymer block composed of a structural unit derived from an olefinically unsaturated compound. In the case of a thermoplastic elastomer composed of a coalescence, it is more preferable from the viewpoint of bondability with the polymer electrolyte layer. Such a block copolymer may be a block copolymer (Z) that forms a polymer electrolyte layer provided in the electrochemical device of the present invention.
Examples of the conductor dispersed in the molded body to be an electrode include metals such as gold, silver, copper, platinum, aluminum, and nickel; ruthenium oxide (RuO ₂ ), titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), and dioxide dioxide. Metal oxides such as iridium (IrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), indium-tin composite oxide (ITO); metal sulfides such as zinc sulfide (ZnS); conductivity such as carbon black and carbon nanotubes And carbon; conductive polymers such as polyacetylene, polypyrrole, and polythiophene. From the viewpoint of ease of handling, conductive carbon is preferable, and these may be used alone or in combination of two or more.

  The method for forming the molded body to be the electrode is the same as the method for preparing the polymer electrolyte layer, except that the conductor is dispersed.

  As a method of joining two electrodes to both surfaces of the polymer electrolyte layer, for example, a method of joining by vacuum deposition method of metals, sputtering method, electroplating, chemical plating method, etc., or ink containing electrode material is applied. Examples thereof include a method and a method of pressure-bonding and welding a separately prepared electrode. Among these, from the viewpoint of workability and versatility, a method of applying an ink containing an electrode material is preferable.

  Moreover, after joining an electrode only to one side of a polymer electrolyte layer to make a joined body, two such joined bodies are bonded together by polymer electrolyte layers, so that two on both sides of the polymer electrolyte layer composed of two layers. Two electrodes may be joined to each other. The material and thickness of the two polymer electrolyte layers may be the same or different. The method of bonding the two bonded bodies is preferably thermocompression bonding.

  The shape of the electrochemical device of the present invention is not particularly limited, and examples thereof include membranes, films, sheets, plates, fibers, rods, cubes, cuboids, spheres, rugby balls, and the like, depending on the purpose of use. What is necessary is just to select suitably.

  The electrochemical element of the present invention obtained by the method as described above can be used as, for example, a sensor or a capacitor for detecting pressure, force, displacement, etc., and particularly when used as a sensor, it has a high signal strength. Show.

  Hereinafter, the present invention will be specifically described with reference examples, comparative examples, and examples, but the present invention is not limited thereto. In addition, measuring instruments, measuring methods, and materials used in the following Reference Examples, Examples and Comparative Examples are shown below.

[1] Derived from α-methylstyrene content (% by mass) of block copolymer (Z ₀ ), hydrogenation rate of polymer block (B) and α-methylstyrene in block copolymer (Z ₁ ) Of sulfonic acid group to the structural unit (mol%)
Using a nuclear magnetic resonance apparatus (JNM-LA 400) manufactured by JEOL Ltd., calculated from a ¹ H-NMR spectrum measured using deuterated chloroform alone or a mixture of deuterated tetrahydrofuran and deuterated methanol (mass ratio 80:20) as a solvent. did.

[2] Measurement of number average molecular weight Gel permeation chromatography (GPC) was measured under the following conditions, and calculated in terms of standard polystyrene.
Equipment: Gel permeation chromatograph (HLC-8020) manufactured by Tosoh Corporation
Column: TSK-GEL SuperMultipore HZ-M 4.6 mm (ID) x 15.0 cm (L) connected in series by Tosoh Guard column: TSK guard column SuperMP (HZ) -M 4.6 mm (ID) x 2.0 cm (L) )
Eluent: Tetrahydrofuran, flow rate 1.0 ml / min Calibration curve: prepared using standard polystyrene Detection method: Differential refractive index (RI)

[3] the block copolymer _{(Z 1)} content block copolymer sulfonic acid group _(Z 1) Weigh P (g), it was completely dissolved in 100 times by mass of tetrahydrofuran. To this solution was added an excess amount of saturated aqueous sodium chloride solution, and then a few drops of phenolphthalein solution were added. Titrate with 0.01 M NaOH standard aqueous solution, and from the amount Q (ml) of NaOH standard aqueous solution required for titration, the content of sulfonic acid groups (sulfone per ₁ g of block copolymer (Z ₁ )) from the following formula: The number of moles of acid groups was determined.
Content of sulfonic acid group: f (mmol / g) = 0.01 Q / P

[4] Measurement of residual ratio of sulfonic acid groups in block copolymers (Z-1) to (Z-3) and block copolymers (Y-1) to (Y-5) In a glass container that can be sealed The joined bodies prepared in Examples 1 to 3 and Comparative Examples 3 to 7 were put in, an excessive amount of an aqueous sodium chloride solution was added, and then a few drops of a phenolphthalein solution were added. Titrate with 0.01 M NaOH standard aqueous solution, and from the amount R (ml) of NaOH standard aqueous solution required for the titration, block copolymers ((Z-1) to (Z- 3) The residual ratio of sulfonic acid groups in (Y-1) to (Y-5)) (number of moles of sulfonic acid groups per 1 g of block copolymer) was determined.
Residual rate of sulfonic acid group (mmol / g) = 0.01 R / S
S is the mass of the block copolymer after the cation exchange treatment contained in the joined body after the cation exchange treatment, and was calculated by estimating the specific gravity of the block copolymer as 1 g / cm ³ from the volume of the polymer electrolyte layer. .

[5] Measurement of signal strength of sensor The sensors produced in Examples 1 to 3 and Comparative Examples 1 to 7 were kept at 80 ° C. and 50% in a thermo-hygrostat (manufactured by Espec Corp., small environmental tester, SH-221). R. H. For 15 hours.
Measurement is performed by fixing a sensor between leaf springs and controlling the operation with a stage controller (manufactured by Sigma Koki Co., Ltd., SHOT-202) (manufactured by Sigma Koki Co., Ltd., stepping motor drive small actuator, SGSP) -13ACT-BO), 1 mm bending deformation was applied and the deformation was maintained for 20 seconds. The voltage generated at this time was evaluated by monitoring with a voltmeter, and the maximum value of the voltage indicated during deformation was measured. Signal strength was taken. In addition, the displacement amount in bending deformation was measured with a laser displacement meter (manufactured by Keyence Corporation, CCD laser displacement meter, LK-G3000).

[Reference Example 1: Production of block copolymer (Z ₀ -1)]
An α-methylstyrene polymer block (polymer block (A ₀ )) and a butadiene polymer block (polymer block (B)) are converted into (A ₀ )-() in the same manner as previously reported (WO 02/40611). A triblock copolymer bonded in the order of B)-(A ₀ ) was synthesized.
The triblock copolymer was dissolved in cyclohexane, charged into a pressure vessel and purged with nitrogen, and then subjected to a hydrogenation reaction at a hydrogen pressure of 981 kPa and 80 ° C. in the presence of a nickel-based Ziegler catalyst to produce a block copolymer (Z ₀ ). As a result, a block copolymer (Z ₀ -1) was obtained. The number average molecular weight (standard polystyrene conversion) of the obtained block copolymer (Z ₀ -1) is 127,700, the hydrogenation rate of the polymer block (B) is 98.9%, and the α-methylstyrene polymer block The content of was 40% by mass.

[Reference Example 2: Production of block copolymer (Z ₁ -1)]
55 g of the block copolymer (Z ₀ -1) obtained in Reference Example 1 was placed in a 3 L reaction vessel equipped with a stirrer and dried at 2 Pa and 30 ° C. for 1 hour, and then the system was replaced with nitrogen. Thereafter, 3 L of dichloromethane was added and dissolved by stirring at 35 ° C. for 2 hours. After dissolution, a sulfonating agent (acetyl sulfate) obtained by reacting 34.7 ml of acetic anhydride and 77.5 ml of sulfuric acid at 0 ° C. in 155 ml of dichloromethane was 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 precipitate a solid. The precipitated solid was washed with distilled water for 30 minutes and then filtered off. This washing and filtration are repeated until there is no change in the pH of the washing water, and the solid matter collected by filtration at the end is dried at 2 Pa and 30 ° C. for 12 hours to form a block copolymer (Z ₁ ) block copolymer (Z ₁ ). Z ₁ -1) was obtained. The content of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene of the obtained block copolymer (Z ₁ -1) was 50.0 mol% from the ¹ H-NMR spectrum. Was also 1.42 mmol / g was measured according block copolymer _(Z 1 -1) content of sulfonic acid groups in the.

[Reference Example 3: Production of block copolymer (Z ₀ -2)]
An α-methylstyrene polymer block (polymer block (A ₀ )) and a butadiene polymer block (polymer block (B)) are (A ₀ ) in the same manner as previously reported (Japanese Patent Laid-Open No. 2007-336790). A triblock copolymer bonded in the order of-(B)-(A ₀ ) was synthesized.
Subjected to hydrogenation reaction such triblock copolymer in the same manner as in Reference Example 1 to give a block copolymer (Z ₀₎ is a block copolymer (Z 0 _-2). The number average molecular weight (standard polystyrene conversion) of the obtained block copolymer (Z ₀ -2) is 78,000, the hydrogenation rate of the polymer block (B) is 99.7%, and the α-methylstyrene polymer block The content of was 28% by mass.

Reference Example 4: Production of a block copolymer _Z 1 -2)]
55 g of the polymer (Z ₀ -2) obtained in Reference Example 3 was placed in a 3 L reaction vessel equipped with a stirrer, dried at 2 Pa and 30 ° C. for 1 hour, and then the system was replaced with nitrogen. 3 L was added and dissolved by stirring at 35 ° C. for 2 hours. After dissolution, a sulfonating agent (acetyl sulfate) obtained by reacting 28.1 ml of acetic anhydride and 12.6 ml of sulfuric acid at 0 ° C. in 56.1 ml of dichloromethane was 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 precipitate a solid. The precipitated solid was washed with distilled water for 30 minutes and then filtered off. This washing and filtration are repeated until there is no change in the pH of the washing water, and the solid matter collected by filtration at the end is dried at 2 Pa and 30 ° C. for 12 hours to form a block copolymer (Z ₁ ) block copolymer (Z ₁ ). Z _1-2 ) was obtained. The content of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene of the obtained block copolymer (Z ₁ -2) was 49.8 mol% from the ¹ H-NMR spectrum. Was also 1.08 mmol / g was measured according block copolymer _(Z 1 -2) content of sulfonic acid groups in the.

[Comparative Example 1]
[1] An electrolyte solution is prepared by dissolving 50 g of the block copolymer (Z ₁ -1) obtained by the method of Reference Example 2 in 200 g of a diisopropylbenzene / 1-hexanol mixed solvent (mass ratio 8/2). did. On the other hand, 4.4 g of ketjen black was further added to 250 g of the electrolyte solution prepared in the same manner, and mixed using a homogenizer to obtain an electrode dispersion.
[2] The electrode dispersion liquid is printed using a screen printer on the collector electrode of a soft film (thickness: 200 μm) provided with a collector electrode (thickness: 10 μm) using a commercially available silver paste, and then dried at 80 ° C. The process was repeated to form a layered electrode having a thickness of 100 μm.
[3] After the electrolyte solution is printed on the electrode formed by the above operation [2] using a screen printer, the step of drying at 100 ° C. is repeated to form a polymer electrolyte layer having a thickness of 15 μm. Thus, a joined body was obtained in which the collector electrode / electrode / polymer electrolyte layer were joined in this order.
[4] The two bonded bodies obtained by the operation of [3] above are overlapped so that the polymer electrolyte layers are in contact with each other, and are pressure-bonded at 100 ° C. and 0.5 MPa for 5 minutes to form a block copolymer (Z ₁ A comparative sensor 1 having -1) as a polymer electrolyte layer was obtained.
[5] The lead wires were connected to the two collector electrodes of the comparative sensor 1, respectively, and evaluation as a sensor was performed.

[Example 1]
[1] The joined body obtained in the same manner as in [1] to [3] of Comparative Example 1 was immersed in a 3-ethyl-1-methylimidazolium acetate aqueous solution prepared at 0.2 M for 1 hour at room temperature. The functional group (1) in which the proton of the sulfonic acid group is exchanged with the 3-ethyl-1-methylimidazolium cation in the block copolymer (Z ₁ -1) in the polymer electrolyte layer provided in the joined body (hereinafter referred to as “the functional group (1)”) And converted to a functional group (1-1)).
Next, the joined body was washed with distilled water until the pH no longer changed, and then air-dried for 12 hours. A joined body having a combination (referred to as “union (Z-1)”) was obtained.
[2] Two block assemblies obtained by the operation of [1] above are superposed so that the polymer electrolyte layers are in contact with each other, and pressure-bonded at 100 ° C. for 5 minutes at 0.5 MPa, thereby producing a block copolymer A sensor 1 comprising the electrochemical element of the present invention comprising (Z-1) as a polymer electrolyte layer was obtained.
[3] Lead wires were connected to the two collector electrodes of the sensor 1, respectively, and evaluation as a sensor was performed.
[4] Detected by measuring the residual ratio of sulfonic acid groups not subjected to cation exchange in the block copolymer (Z-1) in the polymer electrolyte layer provided in the joined body prepared in the same manner as in [1] above Was not. From this, the content (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -1) is α in the block copolymer (Z-1). -It was judged that it was equal to the content rate (mol%) of the functional group (1-1) with respect to the structural unit derived from methylstyrene.

[Comparative Example 2]
Instead of the block copolymer (Z 1 _-1), except that the block copolymer obtained in Reference Example 4 (Z 1 _-2) 50 g was used to prepare a conjugate in the same manner as in Comparative Example 1 Thereafter, the comparative sensor 2 was produced from the joined body and evaluated.

[Example 2]
[1] instead of the block copolymer _(Z 1 -1), Reference Example 4 in the obtained block copolymer _(Z 1 -2) [1] except using 50g of Examples 1 to [3 In the same manner as described above, a joined body comprising a block copolymer (Z) having a functional group (1-1) (hereinafter referred to as “block copolymer (Z-2)”) as a polymer electrolyte layer is prepared. Then, the sensor 2 which consists of the electrochemical element of this invention was produced from this joined body, and evaluation was performed.
[2] Using the joined body separately produced in the same manner as in the above [1], the residual ratio of sulfonic acid groups not subjected to cation exchange in the block copolymer (Z-2) in the polymer electrolyte layer was measured. However, it was not detected. From this, the content (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Z-2). -It was judged that it was equal to the content rate (mol%) of the functional group (1-1) with respect to the structural unit derived from methylstyrene.

[Example 3]
[1] In place of [3-ethyl-1-methylimidazolium acetate aqueous solution], [1] of Example 2 except that 3-Methyl-1,2-dimethylimidazolium acetate aqueous solution prepared to 0.2 M was used Similarly, the functional group (1) (hereinafter referred to as “functional group (1−2) obtained by exchanging protons of the sulfonic acid group of the block copolymer (Z ₁ -2) with 3-ethyl-1,2-dimethylimidazolium cation”. 2) ") is prepared as a polymer electrolyte layer, and then the joined body is prepared from the joined body having the block copolymer (Z) (hereinafter referred to as" block copolymer (Z-3) "). A sensor 3 comprising the electrochemical device of the present invention was obtained and evaluated.
[2] When the remaining rate of sulfonic acid groups not subjected to cation exchange in the block copolymer (Z-3) in the polymer electrolyte layer was measured using a joined body separately prepared in the same manner as in [1] above. Not detected. From this, the content rate (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Z-3). -It was judged that it was equal to the content rate (mol%) of the functional group (1-2) with respect to the structural unit derived from methylstyrene.

[Comparative Example 3]
[1] A block copolymer (Z ₁ ) was prepared in the same manner as in [1] of Example 2 except that ammonia water prepared to 0.5 M was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. -2) After producing a joined body comprising a block copolymer (Y-1) having a functional group (W-1) obtained by exchanging protons of a sulfonic acid group for an ammonium cation, such a joined body The comparative sensor 3 was obtained from and evaluated.
[2] Using the joined body separately prepared in the same manner as in the above [1], the residual ratio of sulfonic acid groups not subjected to cation exchange in the block copolymer (Y-1) in the polymer electrolyte layer was measured. Not detected. From this, the content rate (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Y-1). -It judged that it was equal to the content rate (mol%) of the functional group (W-1) with respect to the structural unit derived from methylstyrene.

[Comparative Example 4]
[1] A block co-polymerization was carried out in the same manner as in [1] of Example 2, except that an aqueous solution of tetramethylammonium hydroxide prepared to 0.5 M was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. coalescing produce conjugates comprising (Z 1 _-2) block copolymer having a proton functional groups that are replaced tetramethylammonium cation of the sulfonic acid group (W-2) of the (Y-2) as the polymer electrolyte layer After that, the comparative sensor 4 was obtained from the joined body and evaluated.
[2] Using a joined body separately prepared in the same manner as in the above [1], the residual ratio of sulfonic acid groups not subjected to cation exchange in the block copolymer (Y-2) in the polymer electrolyte layer was measured. Not detected. From this, the content rate (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Y-2). -It was judged that it was equal to the content rate (mol%) of the functional group (W-2) with respect to the structural unit derived from methylstyrene.

[Comparative Example 5]
[1] A block copolymer (Z) was prepared in the same manner as in [1] of Example 2 except that an aqueous solution of lithium chloride prepared to 0.5 M was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. _1-2 ) After producing a joined body comprising a block copolymer (Y-3) having a functional group (W-3) obtained by exchanging protons of a sulfonic acid group for a lithium cation, such a joined body. The comparative sensor 5 was obtained from the body and evaluated.
[2] When the remaining rate of sulfonic acid groups not subjected to cation exchange in the block copolymer (Y-3) in the polymer electrolyte layer was measured using a joined body prepared separately as in [1] above. Not detected. From this, the content (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the polymer (Z ₁ -2) is changed to α-methylstyrene in the polymer (Y-3). It was judged to be equal to the content (mol%) of the functional group (W-3) with respect to the derived structural unit.

[Comparative Example 6]
[1] A block copolymer in the same manner as in [1] of Example 2, except that a sodium hydroxide aqueous solution prepared to 0.5 M was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. After (Z 1 _-2) block copolymer having a proton functional groups that are replaced sodium cations of the sulfonic acid group (W-4) of the (Y-4) was prepared conjugates comprising a polymer electrolyte layer, The comparative sensor 6 was obtained from the joined body and evaluated.
[2] When the remaining rate of sulfonic acid groups not subjected to cation exchange in the block copolymer (Y-4) in the polymer electrolyte layer was measured using a joined body prepared separately as in [1] above. Not detected. From this, the content rate (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Y-4). -It judged that it was equal to the content rate (mol%) of the functional group (W-4) with respect to the structural unit derived from methylstyrene.

[Comparative Example 7]
[1] A block copolymer in the same manner as in [1] of Example 2 except that a potassium hydroxide aqueous solution prepared to 0.5 M was used instead of the aqueous solution of 3-ethyl-1-methylimidazolium acetate. After (Z 1 _-2) block copolymer having a functional group is replaced with potassium cations proton of the sulfonic acid group (W-5) of the (Y-5) was prepared conjugates comprising a polymer electrolyte layer, The comparative sensor 7 was obtained from the joined body and evaluated.
[2] When the remaining rate of sulfonic acid groups not subjected to cation exchange in the block copolymer (Y-5) in the polymer electrolyte layer was measured using a joined body separately prepared in the same manner as in [1] above. Not detected. From this, the content (mol%) of the sulfonic acid group with respect to the structural unit derived from α-methylstyrene in the block copolymer (Z ₁ -2) is the α in the block copolymer (Y-5). -It was judged that it was equal to the content rate (mol%) of the functional group (W-5) with respect to the structural unit derived from methylstyrene.

  Table 1 shows the signal intensities of the sensors obtained in Examples 1 to 3 and Comparative Examples 1 to 8.

  As is clear from Table 1, the sensors of Examples 1 to 3 exhibit higher signal strength than the sensors of Comparative Examples 1 to 7.

  The sensor using the electrochemical element of the present invention can emit an electric signal having a high signal intensity, and can be suitably used as, for example, a deformation sensor.

Claims (1)

It contains a polymer block (A) composed of a structural unit derived from an aromatic vinyl compound and a polymer block (B) composed of a structural unit derived from an olefinically unsaturated compound, and the polymer block (A) is General formula (1)

^(Wherein, R 1 to R ³ are each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
An electrochemical element comprising a polymer electrolyte layer containing a block copolymer (Z) having a functional group represented by formula (1) and two electrodes respectively bonded to both surfaces of the polymer electrolyte layer.