JP5528967B2 - Electrode forming paste and polymer transducer using coating film as electrode film - Google Patents

Description

  The present invention relates to an electrode forming paste useful as an electrode film material and a polymer transducer using a coating film formed thereby as an electrode film.

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

  Thus, in many fields, polymer transducers are attracting attention as lightweight and flexible transducers, and various types of polymer transducers have been reported.

  For example, Patent Document 1 discloses a small and flexible actuator element including a cation exchange membrane and electrodes in contact with both surfaces of the ion exchange membrane. In addition, in the patent document 2, the present inventors have disclosed a polymer transducer that is extremely flexible due to a polymer solid electrolyte component having a specific molecular structure. The inventions of Patent Documents 1 and 2 both have a structure in which at least a pair of electrode layers are provided on a polymer solid electrolyte, and a laminate in which an electrode layer is formed on a polymer solid electrolyte using an electroless plating technique. It has a structure.

  On the other hand, regarding the laminated structure, Patent Documents 3 and 4 disclose a polymer transducer using a composition comprising a polymer solid electrolyte and conductive fine particles as an electrode layer. In the operation of these polymer transducers, it is important to form an electric double layer at the interface between the polymer solid electrolyte and a conductive material such as dendritic metal, metal fine particles, and carbon fine particles formed by electroless plating. Show the role. In order to form more electric double layers, a method of forming with such a composition is employed.

  In general, the electroless plating method needs to repeat the noble metal dope and the reduction with the reducing agent several times, and is not industrially suitable. In that respect, the composition of the polymer solid electrolyte and the conductive fine particles disclosed in Patent Documents 3 to 4 and Non-Patent Documents 1 to 3 are used, and from a liquid or paste in which this is dissolved or dispersed in an appropriate medium It is expected that the method of using the obtained film as an electrode film is industrially and economically feasible. Since the paste used in this manner is not yet sufficient in terms of solid content concentration adjustment, storage stability, handling properties, coating properties, etc., a paste having higher practicality is desired.

JP-A-6-6991 JP 2007-336790 A US Patent Application Publication No. 2005/0103706 US Patent Application Publication No. 2006/0266642

Future Materials, 2005, Vol. 5, No. 10, p.14-19 Angelwandte Chemie International Edition, 2005, 44, 2410-2413 Polymer, 2002, 43, p.797-802

  The present invention has been made to solve the above-mentioned problems, and can be prepared to have an arbitrary solid content concentration. The electrode forming paste has excellent handling properties, coating properties, and storage stability, and the electrode forming paste is applied. It is an object of the present invention to provide a uniform and excellent electrode film obtained by processing and drying, and a polymer transducer that can be realized industrially and economically and exhibits excellent performance.

  As a result of intensive studies, the present inventors have found an electrode-forming paste suitable for the production of a polymer transducer, a coating film obtained by drying the electrode-forming paste, and a polymer transducer obtained by using the coating film. It has been found that it has excellent performance, and the present invention has been completed.

（式中、Ｒ^１は水素原子、炭素数１〜８の直鎖状若しくは分岐鎖状のアルキル基又は炭素数６〜１４のアリール基、Ｒ^２は炭素数１〜１０のアルキレン基、１〜３個の置換基を有してもよい炭素数６〜１４のアリーレン基、置換基を有してもよい（ポリ）アルキレングリコール基又は直接結合、Ｒ^３は炭素数１〜４のアルキル基又はアルコキシ基、水素イオンＨ^＋に対するアニオンＹ⁻はＲ^２を介して芳香環と連結されており、ｎ＝１〜３、ｍ＝０〜４、かつ１≦ｍ＋ｎ≦５である）で示される単位を含む重合体ブロック（ａ−１）及びイオン基を有しておらず室温でゴム状の重合体ブロック（ａ−２）を含むブロック共重合体からなる高分子固体電解質（Ａ）と、沸点が１５０℃以上の炭化水素溶媒（Ｂ）と、水酸基、エステル基、カルボニル基、及びアミド基から選ばれる少なくとも一つの官能基を有する沸点が１５０℃以上の有機溶媒（Ｃ）と、導電性微粒子（Ｄ）とを含有していることを特徴とする。 The electrode forming paste according to claim 1, which has been made to achieve the above object, has the following chemical formula (1):

Wherein R ¹ is 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, R ² is an alkylene group having 1 to 10 carbon atoms, 1 to An arylene group having 6 to 14 carbon atoms which may have 3 substituents, a (poly) alkylene glycol group which may have a substituent or a direct bond, R ³ is an alkyl group having 1 to 4 carbon atoms or An alkoxy group, an anion Y ⁻ for hydrogen ion H ⁺ is connected to an aromatic ring via R ² , and n = 1 to 3, m = 0 to 4, and 1 ≦ m + n ≦ 5). a polymer block comprising a (a-1)及beauty ion-radical at room temperature does not have a rubbery polymer block (a-2) a solid polymer electrolyte comprising a block copolymer comprising (a) , Hydrocarbon solvent (B) having a boiling point of 150 ° C. or higher, hydroxyl group, ester group, Boniru group, and at least one of the boiling point of 0.99 ° C. or more organic solvents having a functional group (C) selected from an amido group, characterized in that it contains an electrically conductive fine particles (D).

The electrode forming paste according to claim 2 is the paste according to claim 1, wherein the anion Y ⁻ is an anion selected from a carboxylate anion, a sulfonate anion, and a phosphonate anion. And

  The electrode forming paste according to claim 3 is the electrode forming paste according to claim 1, wherein the conductive fine particles (D) are metal fine particles, metal compound fine particles, conductive carbon fine particles, and / or conductive. It is a polymer powder.

  The electrode film according to claim 4 is characterized in that the electrode forming paste according to claim 1 is dried and solidified to form a film.

（式中、Ｒ^１は水素原子、炭素数１〜８の直鎖状若しくは分岐鎖状のアルキル基又は炭素数６〜１４のアリール基、Ｒ^２は炭素数１〜１０のアルキレン基、１〜３個の置換基を有してもよい炭素数６〜１４のアリーレン基、置換基を有してもよい（ポリ）アルキレングリコール基又は直接結合、Ｒ^３は炭素数１〜４のアルキル基又はアルコキシ基、水素イオンＨ^＋に対するアニオンＹ⁻はＲ^２を介して芳香環と連結されており、ｎ＝１〜３、ｍ＝０〜４、かつ１≦ｍ＋ｎ≦５である）で示される単位を含む重合体ブロック（ａ−１）及びイオン基を有しておらず室温でゴム状の重合体ブロック（ａ−２）を有するブロック共重合体からなる高分子固体電解質（Ａ）と、沸点が１５０℃以上の炭化水素溶媒（Ｂ）と、水酸基、エステル基、カルボニル基、及びアミド基から選ばれる少なくとも一つの官能基を有する沸点が１５０℃以上の有機溶媒（Ｃ）と、導電性微粒子（Ｄ）とを含有する電極形成用ペーストを乾燥固化し膜状に形成されている一対の電極膜で挟まれていることを特徴とする。 The polymer transducer according to claim 5, wherein the polymer solid electrolyte is:
The following chemical formula (1)

Wherein R ¹ is 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, R ² is an alkylene group having 1 to 10 carbon atoms, 1 to An arylene group having 6 to 14 carbon atoms which may have 3 substituents, a (poly) alkylene glycol group which may have a substituent or a direct bond, R ³ is an alkyl group having 1 to 4 carbon atoms or An alkoxy group, an anion Y ⁻ for hydrogen ion H ⁺ is connected to an aromatic ring via R ² , and n = 1 to 3, m = 0 to 4, and 1 ≦ m + n ≦ 5). a polymer block comprising a (a-1)及beauty ion-radical at room temperature does not have a rubbery polymer block (a-2) a solid polymer electrolyte comprising a block copolymer having (a) A hydrocarbon solvent (B) having a boiling point of 150 ° C. or higher, a hydroxyl group, an ester group, An electrode-forming paste containing an organic solvent (C) having at least one functional group selected from a rubonyl group and an amide group and having a boiling point of 150 ° C. or more and conductive fine particles (D) is dried and solidified into a film shape It is characterized by being sandwiched between a pair of formed electrode films.

  Since the paste for electrode formation of the present invention can be easily adjusted in viscosity, it can exhibit excellent handling properties and coating properties. In addition, the electrode forming paste is a solution in which the polymer solid electrolyte (A) as a component thereof is uniformly dissolved, and the state can be maintained for a long period of time and stably stored. Since the polymer fixed electrolyte (A) contained in the electrode forming paste is stable in a homogeneously dissolved state, the electrode film, which is a homogeneous coating film, can be obtained by applying and drying the electrode forming paste. Can be formed.

  The electrode film of the present invention is homogeneous and can exhibit extremely excellent flexibility and toughness. An electrode film that is easily formed from an electrode-forming paste having high coatability is industrially and economically superior. This electrode film can be suitably used regardless of its shape as an electrode of a polymer transducer.

  The polymer transducer of the present invention is manufactured by an electrode forming paste having excellent performance without requiring a complicated process, and can exhibit high response sensitivity due to excellent flexibility.

It is sectional drawing which shows an example of the polymer transducer to which this invention is applied. It is sectional drawing which shows the example to which the member of the polymer transducer to which this invention is applied was added. It is a schematic diagram which shows the performance measuring method of the polymer transducer to which this invention is applied. It is a figure which shows the correlation of the elapsed time after giving a displacement to the polymer transducer to which this invention is applied, and signal strength. It is a figure which shows the correlation of the elapsed time after giving a displacement to the polymer transducer of the application of this invention, and signal strength.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The electrode forming paste of the present invention comprises a polymer solid electrolyte (A), a hydrocarbon solvent (B) having a boiling point of 150 ° C. or higher, a boiling point of 150 ° C. or higher, a hydroxyl group, a carboxyl group, a carbonyl group and an amide group. The organic solvent (C) and the electroconductive fine particles (D) which have at least one functional group selected from the above and are different from the hydrocarbon solvent (B) are included.

Examples of the aryl group of R ¹ and the arylene group of R ^{2 in} the chemical formula (1) constituting the polymer solid electrolyte (A) include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, and a phenylene group.

Examples of the substituent of R ^{2 in} the chemical formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, Examples thereof include 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 contained in the solid polymer electrolyte (A) represented by the chemical formula (1) is a hydrogen ion, but may be substantially bound to water to become an oxonium ion. In general, it is difficult to distinguish between these. In this specification, these are unified and described as hydrogen ions. Since the hydrogen ion is not bonded to the polymer main chain of the polymer solid electrolyte (A) through a chemical bond, it is movable in the polymer solid electrolyte.

The anion Y ⁻ for the hydrogen ion which is a mobile ion is bonded to the polymer main chain of the polymer solid electrolyte (A). Examples of the anion Y ⁻ 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 acid conjugated anion is preferable, and a sulfonate anion and a phosphonate anion are preferable. In particular, a sulfonate anion is preferable from the viewpoint of easy introduction into a polymer.

  Accordingly, the polymer block (a-1) constituting the polymer solid electrolyte (A) is a polymer comprising styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, 1,1-diphenylethylene, and the like. The polymer block is preferably a polymer block in which a sulfonic acid group is introduced into at least a part of the aromatic ring contained in. Of these, at least one of the aromatic rings of polystyrene and / or poly-α-methylstyrene from the viewpoints of ease of production of block copolymers as precursors, industrial availability, ease of introduction of sulfonic acid groups, and the like. It is more preferable that the polymer block has a sulfonic acid group introduced into the part. Hereinafter, the polymer block (a-1) may be referred to as a sulfonated polystyrene block.

  The amount of the sulfonic acid group introduced is not particularly limited, but from the viewpoint of the handling property of the polymer solid electrolyte (A), the solubility in a solvent, the ion conductivity, and the performance of the resulting polymer transducer, the aromatic ring Is in the range of 10 mol% to 100 mol%, preferably 25 mol% to 80 mol%, more preferably 40 mol% to 70 mol%. This index may be described as a sulfonation rate. Here, the sulfonation rate of 50 mol% indicates that 50 of 100 aromatic rings have sulfonic acid groups introduced therein. When the sulfonation rate is lower than this range, the amount of ionic groups becomes insufficient, and the performance of the resulting polymer transducer is lowered, which is not preferable.

  The polymer block (a-2) constituting the polymer solid electrolyte (A) needs to be rubbery at room temperature of 25 ° C., that is, having a glass transition temperature (Tg) of 25 ° C. or less. Preferably it is 0 ° C. (Tg is 0 ° C. or less), more preferably -30 ° C., but it is rubbery (Tg is −30 ° C. or less). Thereby, since the coating film obtained by applying and drying the electrode forming paste becomes flexible, a flexible polymer transducer can be obtained. As long as this condition is satisfied, there is no restriction on the polymer block (a-2), 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, water in which some or all of the carbon-carbon double bonds contained in these polyconjugated dienes are hydrogenated Examples thereof include poly (meth) acrylates such as polyconjugated dienes, 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 the sulfonic acid group into the polymer block (a-1) as a property as rubber. It is preferable to use hydrogenated polyisoprene, hydrogenated poly (butadiene-r-isoprene), or polyisobutylene.

The block sequence of the polymer solid electrolyte (A) which is a block copolymer is not particularly limited, but is a (a-1)-(a-2) type diblock copolymer, (a-1)-(a -2)-(a-1), (a-2)-(a-1)-(a-2) triblock copolymer, (a-1)-(a-2)-(a-1) )-(A-2) tetrablock copolymer, (a-1)-(a-2)-(a-1)-(a-2)-(a-1), (a-2)- (A-1)-(a-2)-(a-1)-(a-2) linear block copolymers such as pentablock copolymers, [(a-1)-(a-2) ] _N- X, [(a-2)-(a-1)] _n- X type star-type block copolymer (n is a number exceeding 2, X is a coupling agent residue) Preferably it is either, (a-1)-(a -2)-(a-1) type triblock copolymer is more preferable.

  Since the number average molecular weight of the polymer solid electrolyte (A) is difficult to measure after the sulfonic acid group is introduced, the number average molecular weight before the introduction of the sulfonic acid group may be used as an index. In that case, it is 3000 to 300,000. And preferably 10,000 to 200,000. If the number average molecular weight is lower than this, it is not preferable because the mechanical strength of the polymer solid electrolyte is inferior, and if it is higher than this, the solubility in a solvent is reduced when forming an electrode forming paste. Therefore, it is not preferable.

  The total mass ratio of the polymer block (a-1) and the polymer block (a-2) is preferably 1: 9 to 9: 1. If it is out of this range, the mechanical strength is greatly reduced or the flexibility is lost.

  Moreover, the block copolymer may have a polymer block different from the polymer block (a-1) and the polymer block (a-2) 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, and poly-4-methyl-1-pentene; poly p-methyl styrene, poly p-ethyl styrene, poly Polystyrenes having a substituent 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 , Poly (meth) acrylates such as polybutyl acrylate and poly 2-hydroxyethyl acrylate; halogen-containing poly such as polyvinyl chloride, polytetrafluoroethylene, polyhexafluoropropylene and polyvinylidene fluoride -Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polylactic acid, polyglycolic acid, poly-ε-caprolactone; polyamides such as polyamide-6, polyamide-6,12, polyamide-6T, polyamide-9T , Polyurethanes, polysiloxanes and the like.

  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, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polyamide-6, polyamide-6,12, polyamide-6T, polyamide-9T, polyp-methylstyrene, polyp-adamantylstyrene, poly It is preferable to use a polymer block made of a polymer having a high glass transition temperature such as pt-butylstyrene. In addition, in order to anticipate a function different from a polymer block (a-1) in another polymer block, it is preferable that an ionic group is not included substantially.

  More specific examples of the block copolymer include a polymer block (a-1) in which a sulfonic acid group is directly bonded to the p-position (4 position) of the benzene ring of styrene and / or α-methylstyrene. And a polymer block (a-2) consisting of 1,3-butadiene units and / or isoprene units and partially or entirely hydrogenated of carbon-carbon double bonds, and the block sequence is (a- The triblock copolymer which is 1)-(a-2)-(a-1) can be mentioned.

  The hydrocarbon solvent (B) contained in the electrode forming paste of the present invention needs to have a boiling point of 150 ° C. or higher at normal pressure. Below this range, the electrode forming paste tends to dry, and the workability during coating tends to decrease.

  Examples of the hydrocarbon solvent (B) include saturated or unsaturated hydrocarbons such as octane, nonane, decane, undecane, decene, undecene, α-terpinene, β-terpinene; cumene, o-cymene, m Mention may be made of aromatic hydrocarbons such as -cymene, p-cymene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, o-diisopropylbenzene, m-diisopropylbenzene, p-diisopropylbenzene and mixtures of these isomers. it can. These may be used alone or in combination of two or more.

  The organic solvent (C) contained in the electrode forming paste of the present invention has at least one functional group selected from a hydroxyl group, an ester group, a carbonyl group, and an amide group. Further, it is necessary that the boiling point is 150 ° C. or higher at normal pressure. When the boiling point is 150 ° C. or lower, the paste tends to dry, and the workability during coating tends to decrease.

  Examples of such an organic solvent (C) include 1-hexanol, 1-octanol, 2-octanol, 3-octanol, terpineol, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol. Alcohols such as monobutyl ether, terpineol, cyclohexanol; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate; isophorone, cyclohexanone, 2-octanone, 3-octanone, etc. Ketones: N-methylpyrrolidone, formamide, dimethylphos Amides such as Muamido like.

  As the solvent, it is important to use at least two kinds of hydrocarbon solvent (B) and organic solvent (C). The polymer solid electrolyte (A) contained in the electrode forming paste is composed of a sulfonated polystyrene block (a-1) having a high polarity and a polymer block (a-2) having a low polarity. Because it is a block copolymer, it is difficult to simply dissolve it in a single solvent. On the other hand, if the boiling point is too high, the drying process after applying the electrode-forming paste may take a long time, or the solvent may remain in the coating film. From this viewpoint, the boiling point of the solvent is 300 ° C. or lower, more preferably 250 ° C. or lower.

Examples of the conductive fine particles (D) contained in the electrode forming paste of the present invention include metal fine particles such as gold, silver, copper, platinum, aluminum, nickel; ruthenium oxide (RuO ₂ ), titanium oxide (TiO ₂ ). , Fine metal compound particles such as tin oxide (SnO ₂ ), iridium dioxide (Ir ₂ O ₃ ), tantalum oxide (Ta ₂ O ₅ ), indium-tin composite oxide (ITO), zinc sulfide (ZnS); carbon black, Conductive carbon fine particles such as carbon nanotubes such as single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNT), vapor-grown carbon fibers (VGCF); polyacetylene, polypyrrole, polythiophene, and the like Examples of conductive polymer powders such as derivatives; It can be. These may be used alone or in combination of two or more. Among these, conductive carbon fine particles are preferable from the viewpoints of industrial economy, electrochemical stability when used as a polymer transducer, and the like. From the viewpoint of performance as a polymer transducer, carbon black having a large specific surface area is more preferable. Examples of such carbon black include ketjen black (manufactured by Lion Corporation). The average particle diameter of the conductive fine particles (D) is preferably 1 μm or less, more preferably 0.5 μm or less, preferably 1 nm or more, and more preferably 10 nm or more. The average particle diameter can be determined, for example, by observation with an electron microscope.

  The electrode forming paste is composed of at least four components of a polymer solid electrolyte (A), a hydrocarbon solvent (B), an organic solvent (C), and conductive fine particles (D). On the other hand, a coating made of this electrode forming paste is used. The electrode film which is a film is composed of at least two components of a polymer solid electrolyte (A) and conductive fine particles (D). The hydrocarbon solvent (B) and the organic solvent (C) contained in the electrode forming paste are volatilized in the drying step after coating.

  The composition ratio between the polymer solid electrolyte (A) and the conductive fine particles (D) greatly affects the physical properties of the coating film. For example, the mass ratio is preferably (A) :( D) = 99: 1 to 1:99, and (A) :( D) = from the viewpoints of flexibility and electronic conductivity of the resulting coating film. More preferably, it is 95: 5 to 25:75. When there is more polymer solid electrolyte (A) than this, electronic conductivity will fall, and when there are many electroconductive fine particles (D), there exists a tendency for a softness | flexibility to fall.

The solid content concentration (%) of the electrode forming paste defined by the following formula (2) affects the printing characteristics and handling properties of the paste and a more suitable printing method.
[{(A) + (D)} / {(A) + (B) + (C) + (D)}] × 100 (%) (2)
In formula (2), (A) represents a polymer solid electrolyte, (B) represents a hydrocarbon solvent, (C) represents an organic solvent, and (D) represents the mass of the conductive fine particles.

  As described above, the appropriate solid content concentration depends on the printing method employed. When a screen printing method suitable for the shape of the electrode layer of the polymer transducer of the present invention is used, the appropriate solid content concentration is preferably 3% by mass or more, more preferably 10% by mass or more, and 20 More preferably, it is at least mass%. When the solid content concentration is lower than this, the viscosity of the paste is excessively lowered, so that defects due to dripping tend to occur. On the other hand, when the solid content concentration is higher than 70% by mass, the viscosity of the paste becomes too high, and defects such as scraping tend to occur.

  The mass ratio of the hydrocarbon solvent (B) and the organic solvent (C) in the electrode forming paste of the present invention is not particularly limited, and is determined in consideration of the solubility and dispersibility of the polymer solid electrolyte (A) used. It is what is done. The mass ratio of the hydrocarbon solvent (B) and the organic solvent (C) is, for example, 1:99 to 99: 1, preferably 5:95 to 95: 5, more preferably 15:85 to 85:15. It is a range.

  The electrode forming paste of the present invention is obtained by mixing the polymer solid electrolyte (A), the hydrocarbon solvent (B), the organic solvent (C), and the conductive fine particles (D) by an appropriate method. . The polymer solid electrolyte (A) may be dissolved or dispersed in the hydrocarbon solvent (B) and the organic solvent (C), but it is dissolved from the viewpoint of obtaining a uniform coating film. Is preferable.

  The mixing method is not particularly limited. For example, the conductive fine particles (D) are added to a liquid (vehicle) in which the polymer solid electrolyte (A) is previously dissolved in the hydrocarbon solvent (B) and the organic solvent (C). Examples of the mixing include a kneader such as a stirrer (stirring blade), a bead mill, a ball mill, and a roll mill, and a disperser.

  The electrode forming paste of the present invention can be applied by various methods. Examples of the coating method include a spray method, a dip method, a bar coat method, a doctor blade method, a relief printing method, an intaglio printing method, a lithographic printing method, a screen printing method, and an ink jet method. Of these, the screen printing method is desirable from the viewpoint of the shape required for the coating film and workability.

  Thus, after apply | coating the paste for electrode formation, it is made to dry and the electrode film of this invention can be obtained. Although there is no restriction | limiting in particular about the conditions of drying, For example, it can carry out in the time range of 1 second-1 day under the temperature of 50-150 degreeC. These depend on the composition ratio of the hydrocarbon solvent (B) and the organic solvent (C) used, the polymer solid electrolyte (A), the hydrocarbon solvent (B), the organic solvent (C), and the conductive fine particles (D). To be determined.

  The polymer transducer of the present invention constituted by an electrode film obtained by drying and solidifying an electrode forming paste will be described in detail with reference to FIG. The polymer transducer 1 has a structure in which a pair of electrode layers 3a and 3b insulated at least independently from each other are provided to the polymer solid electrolyte layer 2. This structure is formed by laminating the electrode layer 3a / polymer solid electrolyte layer 2 / electrode layer 3b in this order in the thickness direction. The electrode layer 3a and the electrode layer 3b having a laminated structure are independent electrodes that are insulated from each other. When the polymer transducer 1 is used as a sensor for bending amount or the like, the potential difference generated between the electrode layer 3a and the electrode layer 3b when the polymer transducer 1 is bent is read as a signal and used. When the polymer transducer 1 is used as an actuator, it is driven by applying a potential difference from the outside between the electrode layer 3a and the electrode layer 3a.

  FIG. 2 shows another polymer transducer 1 to which a member is added. The polymer transducer 10 has current collectors 4a, 4b on the outside of the electrode layers 3a, 3b of the laminated structure of electrode layer 3a / polymer solid electrolyte layer 2 / electrode layer 3b, respectively, in order to reduce the resistance in the longitudinal direction. Is provided. Furthermore, the outer sides of the current collectors 4a and 4b are covered with film base materials 5a and 5b having a function as a protective layer. Here, a laminated structure of the current collector 4a / electrode layer 3a / polymer solid electrolyte layer 2 / electrode layer 3b / current collector 4b is defined as a sensor unit 1A. The current collectors 4 a and 4 b can be disposed outside at least one of the pair of electrode layers 3 a and 3 b constituting the polymer transducer 1, that is, on the opposite side to the polymer solid electrolyte 2.

  The current collectors 4a and 4b are, for example, a metal foil or metal thin film such as gold, silver, copper, platinum, or aluminum; a metal powder such as gold, silver, or nickel; or carbon fine powder such as carbon powder, carbon nanotube, or carbon fiber. A molded article made of a binder resin; for example, a fabric such as woven fabric, paper, and nonwoven fabric, or a polymer film formed with a metal thin film by a method such as sputtering or plating. Among these, from the viewpoint of flexibility, it is preferable that a metal thin film is formed on a film-like molded body, a cloth, a polymer film, or the like made of a metal powder and a binder resin.

  As the film bases 5a and 5b, 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 is appropriately used depending on the application. it can. The film bases 5a and 5b may be removed when the polymer transducer 1 is used, or may be integrated as they are. When used as it is, the film bases 5a and 5b act as a protective layer.

  The shape of the polymer transducer 1 is not particularly limited, and examples thereof include 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.

As shown in FIGS. 1 and 2, the method for producing a membrane-like, film-like, sheet-like, plate-like polymer transducer 1 is, for example, on both surfaces of a polymer solid electrolyte layer 2 formed into a membrane shape. The electrode layers 3a and 3b, which are coating films obtained by applying and drying the electrode forming paste, are bonded together in a state where insulation is ensured (FIG. 1), and current collectors 4a and 4b as required. A method of forming a film by a coating method or the like (FIG. 2);
The electrode layers 3a and 3b that are insulated from each other are formed by applying and drying an electrode forming paste on both surfaces of the polymer solid electrolyte layer 2 formed into a film shape (FIG. 1), and if necessary, a current collector 4a and 4b are formed by a coating method or the like (FIG. 2);
The component which comprises the polymer solid electrolyte layer 2 on it after forming the electrical power collector 4a as needed on the film base material 5a, coating and drying the electrode formation paste, and forming the electrode layer 3a on it A polymer-containing electrolyte layer 2 is formed by coating and drying a solution or dispersion containing, followed by coating and drying an electrode forming paste to form the electrode layer 3b, and then a current collector as necessary 4b is formed, and a film base material 5b is bonded as a cover as necessary (FIG. 2);
Current collectors 4a and 4b are respectively formed on the film bases 5a and 5b as necessary, and electrode forming paste is applied and dried to form electrode layers 3a and 3b, respectively, and then a polymer solid electrolyte A solution or dispersion containing the components constituting the layer 2 is applied to the electrode layers 3a and 3b and dried to form an electrode layer 3a-polymer solid electrolyte layer 2 and an electrode layer 3b-polymer solid electrolyte layer 2. And the like. A method in which two surfaces of the polymer solid electrolyte layers of the film-like precursors formed by forming the laminated structure are hot-pressed and bonded together by lamination (FIG. 2);

  As the solution or dispersion containing the components constituting the polymer solid electrolyte layer 2, for example, a solution or dispersion of the polymer solid electrolyte (A) that is a constituent element of the electrode forming paste of the present invention can be used.

  The thicknesses of the electrode layers 3a and 3b, the polymer solid electrolyte layer 2 of the polymer transducer 1, the current collectors 4a and 4b, and the film bases 5a and 5b disposed as necessary are not particularly limited. It is appropriately adjusted depending on the use of the polymer transducer. However, the thickness of the electrode layers 3a and 3b is preferably in the range of 1 μm to 10 mm, more preferably 5 μm to 1 mm, and still more preferably 10 to 500 μm. The thickness of the polymer solid electrolyte 2 is preferably in the range of 1 μm to 10 mm, more preferably 5 μm to 1 mm, and still more preferably 10 to 500 μm. When the current collectors 4a and 4b shown in FIG. 2 are provided, the thickness is preferably in the range of 1 nm to 1 mm, more preferably 5 nm to 100 μm, and still more preferably 10 nm to 50 μm. Similarly, as the thickness of the film bases 5a and 5b shown in FIG. 2, regardless of whether or not to use as a protective layer as it is, from the viewpoint of easy handling and strength as a protective layer, Preferably they are 1 micrometer-10 mm, More preferably, they are the range of 10 micrometers-1 mm, More preferably, they are the range of 30 micrometers-500 micrometers.

  The polymer transducer 1 of the present invention can operate in air, water, vacuum, and organic solvent. Further, 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 1 of 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 of the present invention can also be used as a deformation sensor or a deformation sensor element that detects fluctuation, displacement, or pressure.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  The preparation of the electrode forming paste of the present invention is shown in Examples 1 to 4, and the production of polymer transducers containing a coating film obtained by applying and drying the paste as electrode films is shown in Examples 5 to 8. .

The materials used in 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): Kuraray Co., Ltd. “Septon 2002” was dissolved in toluene, washed three times with water, and then washed into a large excess of acetone. What was purified by reprecipitation was used.
(3) Hydrogenation product of poly α-methylstyrene-b-poly (1,3-butadiene) -b-polyα-methylstyrene (mSEBmS): the same as the method disclosed in WO 02/40611 In this manner, a poly α-methylstyrene-b-poly (1,3-butadiene) -b-poly α-methylstyrene type triblock copolymer was synthesized. The obtained triblock copolymer had a number average molecular weight of 76,000 in terms of polystyrene as measured by gel permeation chromatography (GPC), and was determined from nuclear magnetic resonance ( ¹ H-NMR) 1, The amount of 1,4-bond derived from 3-butadiene 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 performed to obtain mSEBmS. The hydrogenation rate of the obtained mSEBmS was 99.6 mol% from ¹ H-NMR.
(4) Acetic anhydride: purchased from Wako Pure Chemical Industries, Ltd. and used as it is.
(5) Concentrated sulfuric acid: purchased from Wako Pure Chemical Industries, Ltd. and used as it is.
(6) Dichloromethane: A product purchased from Kishida Chemical Co., Ltd. and contacted with molecular sieve (4A) was used.
(7) Diisopropylbenzene: purchased from Mitsui Chemicals and used as it is.
(8) 1-Hexanol: purchased from Wako Pure Chemical Industries, Ltd. and used as it was.
(9) Conductive carbon black: “Ketjen Black EC600JD” purchased from Lion Co., Ltd., vacuum-dried at 150 ° C. for 12 hours was used.
(10) Nafion dispersion: “20% Nafion dispersion DE2021 CS type” was purchased from Wako Pure Chemical Industries, Ltd. and used as it was. Nafion is a trade name of perfluorocarbon sulfonic acid polymer manufactured by DuPont.

  Other solvents and reagents used were commercially available products that were purified by general methods as needed.

(Production Example 1)
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 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 concentrated sulfuric acid at 0 ° C. in 155 mL of methylene chloride was gradually added dropwise over 5 minutes. After stirring for 7 hours at 35 ° C., 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 off. 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 in the obtained sulfonated mSEBmS was 49.8 mol% from ¹ H-NMR spectrum measurement, and the proton exchange capacity was 1.08 mmol / g.

(Production Example 2)
In Production Example 1, SEBS was used in place of mSEBmS, and the same procedure was performed except that the reaction time and the amount of the sulfonating agent used were changed to obtain sulfonated SEBS (1). 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.

(Production Example 3)
In Production Example 1, SEPS 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 SEPS (2). The resulting sulfonated SEPS had a styrene unit benzene ring sulfonation rate of 51.2 mol% and a proton exchange capacity of 1.29 mmol / g.

Example 1
20.5 g of the sulfonated mSEBmS obtained in Production Example 1 was stirred and dissolved in a mixed solvent of 63.6 g of diisopropylbenzene and 15.9 g of 1-hexanol. Next, 4.59 g of ketjen black is added to this solution, and dispersion treatment is performed for 30 minutes at a rotor rotational speed of 4500 rpm using a precision dispersion emulsifier (“CLEARMIX CLM-0.8S” manufactured by M Technique Co., Ltd.). By doing this, an electrode forming paste (I) was prepared.

(Example 2)
24 g of the sulfonated mSEBmS obtained in Production Example 1 was stirred and dissolved in a mixed solvent of 21.6 g of diisopropylbenzene and 50.4 g of 1-hexanol. Next, 5.36 g of ketjen black was added to this solution, and a paste (II) for electrode formation was prepared by performing a dispersion treatment for 30 minutes at a rotor rotation speed of 4500 rpm using CLEARMIX CLM-0.8S.

(Example 3)
In Example 2, an electrode forming paste (III) was prepared in the same manner as in Example 2 except that the sulfonated SEBS produced in Production Example 2 was used instead of the sulfonated mSEBmS.

Example 4
In Example 2, an electrode forming paste (IV) was prepared in the same manner as in Example 2 except that the sulfonated SEPS produced in Production Example 3 was used instead of the sulfonated mSEBmS.

(Comparative Example 1)
Although 24 g of sulfonated mSEBmS produced in Production Example 1 was not dissolved when 72 g of diisopropylbenzene was added and stirred, dispersion treatment was performed for 30 minutes at a rotor speed of 1000 rpm using CLEARMIX CLM-0.8S. In the dispersion, an undispersed material was visually confirmed. To this, 5.36 g of ketjen black was added, and paste (V) was prepared by performing a dispersion treatment for 30 minutes at a rotor rotational speed of 4500 rpm using CLEARMIX CLM-0.8S.

(Comparative Example 2)
When 24 g of sulfonated mSEBmS produced in Production Example 1 was added with 72 g of 1-hexanol and stirred, a slightly cloudy dispersion was obtained. In this dispersion, no undispersed material could be visually confirmed. To this, 5.36 g of ketjen black was added, and a paste (VI) was prepared by performing a dispersion treatment for 30 minutes at Claremix CLM-0.8S at a rotor rotational speed of 4500 rpm.

(Comparative Example 3)
24 g of the sulfonated mSEBmS produced in Production Example 1 was stirred and dissolved in a mixed solvent of 21.6 g of toluene and 50.4 g of isobutyl alcohol. Next, 5.36 g of ketjen black was added to this solution, and paste (VII) was prepared by carrying out a dispersion treatment for 30 minutes at a rotor rotation speed of 4500 rpm using CLEARMIX CLM-0.8S.

(Comparative Example 4)
Add 4.47 g of ketjen black to 100 g of Nafion dispersion, which is an aqueous dispersion containing 20 g of Nafion as a component of the polymer solid electrolyte (A), and use Claremix CLM-0.8S at a rotor rotational speed of 4500 rpm. Paste (VIII) was prepared by performing a dispersion treatment for a minute.

  Table 1 shows the composition ratios of the pastes in Examples 1 to 4 and Comparative Examples 1 to 4.

  In Table 1, the numerical value in parentheses is the charged amount (g), and Nafion is the amount of Nafion contained in 100 g of the Nafion dispersion.

(Evaluation of paste and coating film)
Storage stability evaluation and printing characteristic evaluation of the pastes obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were performed.

(1) Evaluation of storage stability of paste Each paste (I) to (VII) is put in a glass bottle and left to stand at 25 ° C. for 10 days in a covered state, and then the state of the paste is visually observed and stirred with a stick. Was confirmed. In this state, “no change” was evaluated as “◯”, “the occurrence or gelation of a gel-like product” was Δ, and “with sediment” was evaluated as “x”.

(2) Evaluation of Printing Properties of Paste The prepared pastes (I) to (VII) were subjected to test printing using a screen printing apparatus (“LS-34TV” manufactured by Neurong Seimitsu Kogyo Co., Ltd.). At this time, a screen made of Tetron (polyester) material, having a pattern size of 20 mm × 20 mm, a milk material thickness of 12 μm, and 250 mesh was used. The substrate was repeatedly test-printed on the corona-treated surface of an unstretched PP film (“GLC-50” manufactured by Tosero Co., Ltd., thickness 50 μm, single-sided corona treatment), and sensory evaluation was performed regarding printing characteristics. “No problem printing is possible” ○, “The screen mesh used for printing is clogged and printability is not good” △ “The paste surface dries in about 10 minutes after starting the printing operation” The evaluation was made according to an index with x indicating “solidified and impossible to print and printability was poor”.

  The pastes obtained in Examples 1 to 4 and Comparative Example 4 were applied onto a film and dried to evaluate the flexibility of the coating films obtained.

(3) Flexibility evaluation of coating film Polyethylene terephthalate (PET) film (Purex A31, manufactured by Teijin DuPont Films, Ltd.) obtained by subjecting pastes (I) to (IV) and (VIII) to release treatment, respectively. The release treatment surface was coated using a block coater with a clearance of 750 μm, and dried on a hot plate at 100 ° C. to obtain a coating film. This coating is cut to a length of 10 mm x 30 mm, and 15 mm in the length direction is clamped and fixed, and the change in the film is observed when the remaining 15 mm part is pushed and bent by about 10 mm by hand. did.

  Table 2 shows the evaluation results of the storage stability evaluation and printing characteristic evaluation of the paste and the flexibility evaluation of the coating film.

  As is apparent from Table 2, the electrode forming pastes of Examples 1 to 4 that satisfy the constituent requirements of the present invention were suitable for printing and easy to handle. Moreover, the coating film obtained by coating and drying this had a flexibility suitable for achieving the flexibility of the polymer transducer.

  On the other hand, in the paste of Comparative Example 1 that does not use the organic solvent (C) that is a constituent requirement, the solid polymer electrolyte (A) does not sufficiently dissolve in the solvent, so that insoluble matter exists, For this reason, it is difficult to say that the properties expected of the paste are satisfied, such as screen clogging during screen printing.

  Furthermore, the paste of Comparative Example 2 that does not use the hydrocarbon solvent (B), which is a constituent requirement, is inferior in storage stability, and screen clogging during screen printing occurs due to the influence of gel content and the like generated during storage. It was hard to say that the properties expected of the paste were satisfied.

  The paste of Comparative Example 3 in which the boiling points of the hydrocarbon solvent (B) and the organic solvent (C) do not satisfy the criteria of the present invention is extremely easy to cause deterioration due to drying, and it is difficult to say that the paste is an excellent paste. It was.

  The paste of Comparative Example 4 using a polymer different from the polymer solid electrolyte (A) used in the present invention was inferior in flexibility when used as a coating film. This indicates that not only an accurate signal is not given even when a polymer transducer is used, but it is damaged due to deformation, so that actual use is difficult.

(Example 5)
Polypropylene films 5a and 5b (non-stretched polypropylene film “GLC50” manufactured by Tosero Co., Ltd.) having a current collector 4a and 4b made of a commercially available silver paste (“Dotite XA-954” manufactured by Fujikura Kasei Co., Ltd.), film thickness 50 μm ) The electrode forming paste (I) prepared in Example 1 was applied thereon using a screen printing apparatus LS-34TV, and then dried at 80 ° C. This process was performed until the thickness of the coating film reached 100 μm to form the electrode films 3a and 3b, thereby forming the laminate (X).
In Example 1, the same operation was performed except that ketjen black was not used, to prepare a polymer solid electrolyte (A) solution. This solution was applied onto the laminate (X) using a screen printing apparatus LS-34TV, and then dried at 80 ° C. to form a polymer solid electrolyte layer 2. This process was performed until the film thickness of the polymer solid electrolyte (A) became 15 μm to form a laminate (Y).
The two layers of the laminate (Y) were overlapped so that the surfaces of the polymer solid electrolyte (A) were bonded to each other, and in this state, the polymer transducer 1 was manufactured by pressing at 100 ° C. for 5 minutes. . At this time, lead wires 12a and 12b were provided for evaluation as a transducer.

(Example 6)
A polymer transducer was manufactured by performing the same operation except that the electrode forming paste (II) prepared in Example 2 was used instead of the electrode forming paste (I) used in Example 5.

(Example 7)
A polymer solid electrolyte (A) solution obtained by performing the same operation except that the electrode forming paste (III) prepared in Example 3 was used as the electrode forming paste and Ketjen Black was not used in Example 3. A polymer transducer was manufactured in the same manner as in Example 5 except that was used.

(Example 8)
Polymer solid electrolyte (A) solution obtained by performing the same operation except that the electrode forming paste (IV) prepared in Example 4 was used as the electrode forming paste and Ketjen Black was not used in Example 4. A polymer transducer was manufactured in the same manner as in Example 5 except that was used.

(Comparative Example 5)
A polymer transducer was manufactured in the same manner as in Example 5 except that the paste (V) prepared in Comparative Example 1 was used instead of the electrode forming paste (I).

(Comparative Example 6)
A polymer transducer was manufactured in the same manner as in Example 5 except that the paste (VI) prepared in Comparative Example 2 was used instead of the electrode forming paste (I).

(Comparative Example 7)
A polymer transducer was manufactured in the same manner as in Example 5 except that the paste (VII) prepared in Comparative Example 3 was used instead of the electrode forming paste (I) used in Example 5.

(Comparative Example 8)
A polymer transducer was manufactured in the same manner as in Example 5 except that the paste (VIII) prepared in Comparative Example 4 was used instead of the electrode forming paste (I).

(Performance test of polymer transducer as a deformation sensor)
Response sensitivity as a deformation sensor is defined as a voltage generated when a constant displacement is applied to the polymer transducer. A schematic diagram of the performance test measurement is shown in FIG.

  For the polymer transducers 1 obtained in Examples 5 to 8 and Comparative Examples 5 to 8, among the sensor unit 1A (20 mm × 20 mm), 10 mm in the length direction is sandwiched between the clamps 11a and 11b, and the deformation sensor length is The measurement cell was made free for 10 mm. The lead wires 12a and 12b were connected to a voltmeter ("NR-ST04" manufactured by Keyence Corporation). In this state, a voltage generated by applying a displacement of 1 mm from the diaphragm 13b of the displacement generator 13 via the drive transmission member 13a at a location 5 mm from the fixed end of the polymer transducer 1 was measured with a data logger. . At this time, the amount of displacement at a displacement point P of 5 mm from the fixed end of the polymer transducer 1 was simultaneously measured using a laser displacement meter 14 (“LK-G155” manufactured by Keyence Corporation). The deformation was released 20 seconds after the deformation started.

  Examples 5 to 8 are shown in FIGS. 4A to 4D, and Comparative Examples 5 to 8 are shown in FIGS. ). The performance as a deformation sensor obtained from FIGS. 4 and 5 was determined based on the following criteria. The signal retention rate was defined by how much signal strength (voltage value) was retained immediately before the cancellation of deformation among the initial signal strengths.

  “Initial signal strength> 0.75 mV / mm, and the signal retention rate after 20 seconds (immediately before the deformation is released) is 50% or more”, “Initial signal strength> 0.25 mV / mm, and 20 seconds (deformation) Evaluate according to the indicators that "the signal retention rate is 50% or more until immediately before release" is "Good", "regardless of the initial signal, the signal retention rate is less than 50%" is "△", and "It does not function as a deformation sensor" is x. did. The evaluation results in Examples 5 to 8 and Comparative Examples 5 to 8 are shown in Table 3.

  As is apparent from Table 3, the polymer transducers of Examples 5 to 8 that satisfy the constituent requirements of the present invention exhibited excellent performance.

  The polymer transducer of Comparative Example 5 that does not use the organic solvent (C), which is a constituent requirement, has a characteristic as a sensor that detects deformation such that a signal can be held while holding the deformation. It was insufficient.

  The polymer transducer of Comparative Example 6 that does not use the constituent hydrocarbon solvent (B) showed good initial signal strength, but was poor in signal retention and had sufficient characteristics as a sensor for detecting deformation. It was hard to say that.

  The polymer transducer of Comparative Example 7 in which the boiling points of the hydrocarbon solvent (B) and the organic solvent (C) did not satisfy the criteria of the present invention showed relatively good characteristics, but the paste was extremely denatured by drying. The result was easy to cause and difficult to use substantially.

  The polymer transducer of Comparative Example 8 using a polymer different from the polymer solid electrolyte (A) used in the present invention functioned as a deformation sensor because internal damage such as cracking of the electrode layer occurred during the test. It is estimated that there was not.

  The electrode forming paste of the present invention exhibits characteristics suitable for printing and is useful as an electrode material for polymer transducers. The coating film obtained by applying and drying the electrode forming paste is used as an electrode film for a polymer transducer, and is used as a polymer transducer that exhibits sufficient flexibility and high response sensitivity. This polymer transducer can be suitably used as a flexible sensor for measuring various deformations and displacements.

  1 is a polymer transducer, 1A is a sensor unit, 2 is a polymer solid electrolyte layer, 3a and 3b are electrode layers, 4a and 4b are current collectors, 5a and 5b are film substrates, 11a and 11b are clips, 12a, 12b is a lead wire, 13 is a displacement generator, 13a is a drive transmission member, 13b is a diaphragm, 14 is a laser displacement meter, and P is a displacement point.

Claims (5)

The following chemical formula (1)

Wherein R ¹ is 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, R ² is an alkylene group having 1 to 10 carbon atoms, 1 to An arylene group having 6 to 14 carbon atoms which may have 3 substituents, a (poly) alkylene glycol group which may have a substituent or a direct bond, R ³ is an alkyl group having 1 to 4 carbon atoms or An alkoxy group, an anion Y ⁻ for hydrogen ion H ⁺ is connected to an aromatic ring via R ² , and n = 1 to 3, m = 0 to 4, and 1 ≦ m + n ≦ 5)
Polymer block (a-1)及beauty rubbery polymer block (a-2) a solid polymer electrolyte comprising a block copolymer containing at room temperature does not have an ion-radical containing in unit represented (A) and
A hydrocarbon solvent (B) having a boiling point of 150 ° C. or higher;
An organic solvent (C) having a boiling point of 150 ° C. or higher and having at least one functional group selected from a hydroxyl group, an ester group, a carbonyl group, and an amide group;
An electrode-forming paste comprising conductive fine particles (D). The anion Y ^- is a carboxylate anion, a sulfonate anion, the electrode forming paste according to claim 1, characterized in that an anion selected from phosphonate anion.   The electrode forming paste according to claim 1, wherein the conductive fine particles (D) are metal fine particles, metal compound fine particles, conductive carbon fine particles, and / or conductive polymer powder.   An electrode film, wherein the electrode forming paste according to claim 1 is dried and solidified to form a film. The polymer solid electrolyte
The following chemical formula (1)

Wherein R ¹ is 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, R ² is an alkylene group having 1 to 10 carbon atoms, 1 to An arylene group having 6 to 14 carbon atoms which may have 3 substituents, a (poly) alkylene glycol group which may have a substituent or a direct bond, R ³ is an alkyl group having 1 to 4 carbon atoms or An alkoxy group, an anion Y ⁻ for hydrogen ion H ⁺ is connected to an aromatic ring via R ² , and n = 1 to 3, m = 0 to 4, and 1 ≦ m + n ≦ 5). a polymer block comprising a (a-1)及beauty ion-radical at room temperature does not have a rubbery polymer block (a-2) a solid polymer electrolyte comprising a block copolymer having (a) A hydrocarbon solvent (B) having a boiling point of 150 ° C. or higher, a hydroxyl group, an ester group, An electrode-forming paste containing an organic solvent (C) having at least one functional group selected from a rubonyl group and an amide group and having a boiling point of 150 ° C. or more and conductive fine particles (D) is dried and solidified into a film shape A polymer transducer characterized by being sandwiched between a pair of formed electrode films.

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