JP2008171823A - Elastic member of semiconductive polymer for actuator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an elastic member of a semiconductive polymer for an actuator, excellent in the voltage dependence and environmental dependence of the electrical resistance. <P>SOLUTION: The elastic member of a semiconductive polymer for an actuator, comprises a conductive composition containing a conductive polymer and a binder polymer. The conductive polymer has a surfactant structure obtained by chemically oxidatively polymerizing its raw monomer with an oxidizing agent in the presence of a surfactant, and is dispersed or in compatibility with the binder polymer. The elastic member of a semiconductive polymer satisfies the following characteristics: (A) the variation between the electrical resistance at an applied voltage of 1 V and the electrical resistance at an applied voltage of 133 V under the environment of 25°C and 50%RH, is 1.34 digits or smaller; (B) the variation between the electrical resistance at an applied voltage of 10 V under the environment of 15°C and 10%RH, and the electrical resistance at an applied voltage of 10 V under the environment of 35°C and 85%RH, is 0.4 digit or smaller; and (C) the electrical resistance at 100% elongation is 1.3 digits or smaller of the electrical resistance at non-elongation. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a semiconductive polymer elastic member of the actuator.

In general, the semi-conductive polymer elastic member, in order to suitably use is the control of the electrical resistance required. Therefore, conventionally, the electrical resistance is controlled by blending an ion conductive agent or an electronic conductive agent with a binder polymer such as resin or rubber.

Since the ionic conductive agent dissolves in the binder polymer, there is an advantage that the variation in conductivity is small, the variation in electric resistance when the voltage is changed is small, and the voltage dependency of the electric resistance is excellent. However, since the ionic conductive agent has a conductivity development mechanism based on ion conduction, if the electric resistance is 1 × 10 ⁷ Ω · cm or more, the ion conduction in the binder polymer is good. The conductivity can be controlled. However, when the electric resistance is less than 1 × 10 ⁷ Ω · cm, ion conduction is difficult to occur, and the conductivity is difficult to control. The ion conductive agent is susceptible to moisture or the like, to vary the electrical resistance 2 digits or more under the conditions of high temperature and high humidity and low temperature and low humidity, poor environmental dependency of electrical resistance, restrictions on use as an actuator There are many.

On the other hand, an electronic conductive agent such as carbon black is less susceptible to moisture and the like, has little fluctuation in electric resistance under conditions of high temperature and high humidity and low temperature and low humidity, and is excellent in environmental dependency of electric resistance and low electric resistance. of the Ru Oh possible. However, since it is difficult to uniformly disperse the electronic conductive agent in the binder polymer, variation in electric resistance is large, and it is difficult to control the conductivity. In addition, even when dispersed relatively uniformly, the mechanism of conductivity development is due to the tunnel effect or hopping phenomenon in which electrons are transmitted between the carbons in the binder polymer by a high voltage, so the electric resistance when the voltage is changed Fluctuation is large and the voltage dependence of electrical resistance is inferior.

The present invention is such made in view of the circumstances, the provision of semi-conductive polymer elastic member for outstanding actuator voltage dependence of the electrical resistance and the environmental dependency of the electrical resistance and an object.

In order to achieve the above object, the semiconductive polymer elastic member for an actuator of the present invention is a semiconductive polymer for an actuator comprising a conductive composition containing a conductive polymer and a binder polymer. An elastic member, wherein the conductive polymer has a surfactant structure obtained by chemical oxidative polymerization of the raw material monomer with an oxidizing agent in the presence of a surfactant, and is dispersed in a binder polymer. dolphins or are compatible, the semi-conductive polymer elastic member, a configuration characterized by satisfying the characteristics of the following (a) ~ (C).
(A) In an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied is 1. 34 digits or less.
(B) Fluctuation between the electrical resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electrical resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH is zero. 4 digits or less.
(C) The electrical resistance when 100% stretched is 1.3 digits or less of the electrical resistance when not stretched.

That is, the present inventors have so conducted intensive research voltage dependence of the electrical resistance and obtain a semiconductive polymer elastic member for an actuator having excellent environmental dependency of the electrical resistance. As a result, in an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied is 1. The electrical resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and less than 34 digits, and the electrical resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH When a semiconductive polymer elastic member for an actuator having a fluctuation of 0.4 digits or less and an electrical resistance at 100% elongation of 1.3 digits or less of the electrical resistance when not stretched is used, The inventors have found that the intended purpose can be achieved and have reached the present invention.

The semiconductivity in the semiconductive polymer elastic member for the actuator of the present invention means that the electric resistance measured according to the method described in SRIS 2304 is in the range of 1 × 10 ¹² Ω · cm or less. Means.

As described above, the semi-conductive polymer elastic member for the actuator of the present invention, in the voltage dependence of the electrical resistance in the range of 1V to 133V is 1.34 digits, the change in electric resistance by environmental since 0.4 digits or less and excellent in both characteristics of the environmental dependence of the voltage dependence of the electrical resistance and electrical resistance. Moreover, the semiconductive polymer elastic member for an actuator according to the present invention has an electrical resistance at 100% elongation of 1.3 digits or less of the electrical resistance when not stretched. It exhibits stable electrical characteristics, and there are few electrical fluctuations when used with large deformations and electrical deterioration after long-term use. As a result, the semiconductive polymer elastic member for the actuator of the present invention is capable of controlling the electric resistance due to the applied voltage constant, it is effective as a current control element A Kuchue data. Moreover, it is also effective as a sensor material using such a difference in electrical characteristics.

Further, the electrical resistance of the semiconductive polymer elastic member for the actuator of the present invention is in the range of 10 ⁶ ~10 ¹² Ω · cm, it is possible to provide a good optimal electrical properties.

  Next, an embodiment of the present invention will be described.

The semiconductive polymer elastic member for an actuator of the present invention can be obtained using a conductive composition containing a conductive polymer and a binder polymer.

  The conductive polymer is not particularly limited, but a conductive polymer having a surfactant structure is preferably used.

  The conductive polymer having the surfactant structure can be produced, for example, by a method such as chemical oxidative polymerization with an oxidizing agent in the presence of a conductive polymer raw material monomer and a surfactant.

  The raw material monomer of the conductive polymer is not particularly limited as long as it has conductivity. For example, aniline (including aniline salts such as aniline hydrochloride in addition to aniline derivatives), pyrrole, thiophene, alkylthiophene, Ethylenedioxythiophene, isonaphthothiophene, 3-thiophene-β-ethanesulfonic acid, dichenothiophene, acetylene, paraphenylene, phenynevinylene, furan, selenophene, tellurophene, isothianaphthene, paraphenylene sulfide, paraphenylene oxide, Examples include vinylene sulfide.

  The surfactant is not particularly limited, and examples thereof include anionic surfactants such as long-chain alkyl sulfates, cationic surfactants such as long-chain alkyl ammonium salts, and neutral surfactants. can give. These may be used alone or in combination of two or more.

  Examples of the long-chain alkyl sulfate of the anionic surfactant include dodecyl sulfonic acid, dodecyl benzene sulfonic acid, pentadecyl sulfonic acid, naphthalene sulfonic acid and the like.

  Examples of the long-chain alkylammonium salt of the cationic surfactant include cetyltrimethylammonium bromide.

  Examples of the oxidizing agent include ammonium persulfate, hydrogen peroxide, ferric chloride, and the like.

  The mixing ratio of the raw material monomer and the surfactant of the conductive polymer is preferably a molar ratio of raw material monomer / surfactant = 1 / 0.03 to 1/3, particularly preferably raw material monomer / surfactant. Agent = 1 / 0.05 to 1/2. That is, when the molar ratio of the surfactant is lowered, the compatibility and dispersibility with the binder polymer are lowered, and conversely, when the molar ratio of the surfactant is increased, the effect of the surfactant on the ionic conductivity is increased. This is because the electronic conductivity of the conductive polymer is reduced.

  The number average molecular weight (Mn) of the conductive polymer is preferably in the range of 500 to 100,000, particularly preferably in the range of 1000 to 20000.

  The binder polymer used together with the conductive polymer is not particularly limited, and examples thereof include acrylic-based, urethane-based, fluorine-based, polyamide-based, epoxy-based, rubber-based elastomers or resins. These may be used alone or in combination of two or more. Among these, acrylic and rubber elastomers or resins are preferable in terms of excellent compatibility with the conductive polymer.

  Examples of the acrylic elastomer or resin include polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and known acrylic monomers. Polymerized products and the like can be mentioned.

  Examples of the urethane-based elastomer or resin include ether-based, ester-based, acrylic-based, aliphatic-based urethane, and those obtained by copolymerizing a silicone-based polyol or a fluorine-based polyol. The urethane elastomer or resin may have a urea bond or an imide bond.

  Examples of the fluoroelastomer or resin include polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, and the like. It is done.

  Examples of the polyamide-based elastomer or resin include alcohol-soluble methoxymethylated nylon.

  Examples of the epoxy elastomer or resin include bisphenol A type, epoxy novolac resin, brominated type, polyglycol type, polyamide combined type, silicone modified, amino resin combined type, and alkyd resin combined type.

  Examples of the rubber elastomer or resin include natural rubber (NR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), hydrogenated NBR (H-NBR), styrene butadiene rubber (SBR), and isoprene rubber (IR). ), Urethane rubber, chloroprene rubber (CR), epichlorohydrin rubber (ECO), ethylene propylene diene polymer (EPDM), fluoro rubber, styrene-butadiene block copolymer (SBS), styrene-ethylene-butylene-styrene block A known thermoplastic polymer such as a polymer (SEBS) can be used.

  The number average molecular weight (Mn) of the binder polymer is preferably in the range of 500 to 2,000,000, particularly preferably in the range of 2,000 to 800,000.

  The mixing ratio of the conductive polymer raw material (the total amount of the conductive polymer raw material monomer and the surfactant) and the binder polymer is a weight ratio, and the conductive polymer raw material / binder polymer = 1/99 to 40. The range of / 60 is preferable, and the raw material of the conductive polymer / binder polymer is preferably 4/96 to 35/65. That is, if the weight ratio of the raw material of the conductive polymer is less than 1, the effect on the conductivity is small. Conversely, if the weight ratio of the raw material of the conductive polymer exceeds 40, the conductive composition becomes hard and brittle. This is because the physical properties of the composition are lowered.

  In addition to the conductive polymer and the binder polymer, the conductive composition may contain an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like.

  Examples of the ionic conductive agent include lithium perchlorate, quaternary ammonium salts, borates, surfactants, and the like. These may be used alone or in combination of two or more.

  In addition, the blending ratio of the ionic conductive agent is 100 in total from the viewpoint of physical properties and electrical characteristics. The total of the raw material of the conductive polymer having a surfactant structure (total amount of raw material monomer and surfactant) and the binder polymer is 100. The range of 0.01 to 5 parts is preferable with respect to parts by weight (hereinafter abbreviated as “parts”), particularly preferably 0.5 to 2 parts.

Examples of the electronic conductive agent include carbon black, c-ZnO (conductive zinc oxide), c-TiO ₂ (conductive titanium oxide), c-SnO ₂ (conductive tin oxide), graphite, and the like.

  In addition, the blending ratio of the electronic conductive agent is 5 with respect to a total of 100 parts of the conductive polymer raw material (total amount of raw material monomer and surfactant) and the binder polymer from the viewpoint of physical properties and electrical characteristics. A range of ˜30 parts is preferred, with 8-20 parts being particularly preferred.

  Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, blocked isocyanate, and melamine, epoxy curing agents, polyamine curing agents, and peroxides.

  In addition, the blending ratio of the crosslinking agent is based on 100 parts in total of the conductive polymer raw material (total amount of raw material monomer and surfactant) and the binder polymer from the viewpoint of physical properties, adhesion, and liquid storage property. The range of 1 to 30 parts is preferable, and the range of 3 to 10 parts is particularly preferable.

  In addition to the above components, the conductive composition may contain a crosslinking accelerator, a catalyst, an anti-aging agent, a dopant and the like as necessary.

  Examples of the crosslinking accelerator include sulfenamide-based crosslinking accelerators, dithiocarbamate-based crosslinking accelerators, amines, and organic tin-based catalysts.

  The said electrically conductive composition can be manufactured as follows, for example. That is, first, a conductive polymer is produced according to the method described above. Next, a binder polymer is blended with the conductive polymer, and an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like are blended as necessary. And an electroconductive composition can be obtained by knead | mixing these using kneading machines, such as a roll, a kneader, a Banbury mixer. The conductive polymer is preferably soluble in a solvent or can be present as a colloidal solution, and the binder polymer is preferably soluble in a solvent.

  Furthermore, according to the above-mentioned method, while producing a conductive polymer, you may disperse | distribute this conductive polymer in a binder polymer using a high shear disperser. Use of such a high shear disperser is preferable because the particle size of the conductive polymer becomes smaller and becomes compatible or uniformly finely dispersed in the binder polymer. Further, the particle size (median diameter) of the conductive polymer is preferably 1 μm or less. In the production of the conductive composition, it is desirable that the purification after the synthesis of the conductive polymer is not completely dried in order to prevent aggregation of the conductive polymer.

  Examples of the high shearing disperser include a high-speed bead mill using ceramic beads such as glass and zirconia, a sand mill, a ball mill, a three roll, a pressure kneader, a colloid mill using a grinding force, and the like.

  Examples of the solvent include organic solvents such as m-cresol, methanol, methyl ethyl ketone (MEK), and toluene.

In the present invention, a semi-conductive polymer elastic member for the actuator formed by using the conductive composition, is a feature to meet the characteristics maximum of the following (A) ~ (C).
(A) In an environment of 25 ° C. × 50% RH, fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied (difference between the maximum value and the minimum value of the electric resistance: Voltage dependency) is 1. 34 digits or less.
(B) Fluctuation between the electric resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electric resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH (environment) Dependency) is 0.4 digits or less.
(C) The electrical resistance when 100% stretched is 1.3 digits or less of the electrical resistance when not stretched.

  The evaluation of the voltage dependence of the electrical resistance was performed by measuring the electrical resistance when a voltage of 1 V was applied and the electrical resistance when a voltage of 133 V was applied in an environment of 25 ° C. × 50% RH, respectively. 1V / 133V), and the logarithmic difference of the electrical resistance is indicated as the number of fluctuation digits.

  In addition, the evaluation of the fluctuation (environment dependence) of the electrical resistance due to the environment is based on the electrical resistance at the low temperature and low humidity (15 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × 85%) under the condition of the applied voltage of 10V. % RH), and the logarithmic difference of the electrical resistance is expressed as a variable digit by Log (15 ° C. × 10% RH / 35 ° C. × 85% RH).

In addition, the measurement of the electrical resistance fluctuation before and after 100% elongation was performed by punching a semiconductive polymer elastic member for an actuator using the conductive composition into a strip shape (10 mm width, 100 mm length), Measure the electrical resistance of 10V applied when it is stretched to 100% in an environment of 25 ° C x 50% RH, and change the electrical resistance before and after stretching (by digit). ).

The semiconductive polymer elastic member for an actuator using the conductive composition has an electric resistance of 10 ⁶ to 10 ¹² Ω when a voltage of 10 V is applied in an environment of 25 ° C. × 50% RH. -It is preferable to be in the range of cm. That is, when the electrical resistance is less than 10 ⁶ Ω · cm, since the electric resistance is too low, leakage occurs, the tendency of the advantages of the image is reduced is seen as OA parts, contrary to 10 ¹² Ω · cm This is because the electrical resistance is too high, the charge up occurs and the control as the actuator tends to be difficult.

The semiconductive polymer elastic member for the actuator formed by using the conductive composition, the electric resistance at 100% elongation, as 1.3 digits of increase in electrical resistance when not extend It is . Ie, the increase in electrical resistance is more than 1.3 orders of magnitude, when used to deform a flexible member, since the electric resistance changes, Ru Karadea the control of the actuator becomes difficult.

Incidentally, the semi-conductive polymer elastic member for the actuator of the present invention, Ru is used in electronic components such as actuator. In addition, the semiconductive polymer elastic member for an actuator of the present invention can be used for a sensor utilizing electric characteristics.

  Next, examples will be described together with comparative examples.

First, the composition shown below used for an Example and a comparative example was prepared. And using these compositions, the conductive coating film or the foam sheet (henceforth "conductive coating film etc.") was produced, and the postscript evaluation was performed.

[ Example Composition 1 ]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and m-cresol. Was added to obtain a polyaniline solution having a surfactant structure. Next, 80 parts of polyurethane as a binder polymer (Carbon-based TPU E980, manufactured by Nippon Milactolan Co., Ltd. ) is dissolved in a solvent (comprising 200 parts of methyl ethyl ketone “ MEK ” and 300 parts of tetrahydrofuran “ THF ” ), and then the above polyaniline solution. 20 parts of the active ingredient (nonvolatile content) was added and kneaded using a high shear disperser (Dyno mill , 3200 rpm, bead particle size 0.8 mm ) to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 2 for Examples ]
Except not using a high shear disperser, the conductive coating film was produced like the composition 1 for an Example .

[Composition 3 for Examples ]
Acrylic fluoropolymer resin (produced by Dainippon Ink and Chemicals, Inc., DEFENSA TR230K) as the binder polymer together with the use of, as the solvent, and using a methyl ethyl ketone (MEK) 200 parts and 300 parts of toluene. Other than that was carried out similarly to the composition 1 for an Example, and produced the electrically conductive coating film.

[ Example Composition 4 ]
First, 1 mol of aniline and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, toluene was added, A polyaniline solution having a surfactant structure was obtained. Next, 80 parts of H-NBR (manufactured by Zeon Corporation, Zetpol 0020) as the binder polymer, 1 part of sulfur as the cross-linking agent, and sulfenamide-based cross-linking accelerator (Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 5 parts, 0.5 part of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) is kneaded using two rolls and dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene. After that, 20 parts of an active ingredient (nonvolatile content) of the polyaniline solution was added to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on the SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[ Example Composition 5 ]
A conductive coating film was prepared in the same manner as Example Composition 4 except that 5 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) was further added as a conductive agent.

[ Example Composition 6 ]
Except for further blending 1 part of a quaternary ammonium salt (tetrabutylammonium hydrogen sulfate: TBAHS) and 1 part of a borate (manufactured by Nippon Carlit Co., Ltd., LR147) as a conductive agent, the same as Example Composition 4 A conductive coating film was prepared.

[ Example Composition 7 ]
First, 1 mol of pyrrole and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 0.1 mol of an oxidizing agent (ferric chloride), and then unreacted substances were removed with methanol. Was added and filtered to remove moisture, thereby obtaining a polypyrrole solution having a surfactant structure. Next, 80 parts of polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980) as a binder polymer is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then the effective component (nonvolatile content) of the polypyrrole solution is dissolved. ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[ Example Composition 8 ]
First, 1 mol of 3,4-ethylenedioxythiophene and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 0.2 mol of an oxidizing agent (ammonium persulfate) and then unreacted with methanol. The product was removed, and toluene was added to obtain a polythiophene solution having a surfactant structure. Next, 80 parts of a polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980), which is a binder polymer, is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF). ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[ Example Composition 9 ]
First, 1 mol of aniline and 0.3 mol of a surfactant (pentadecylbenzenesulfonic acid) are oxidized and polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances are removed with methanol, and toluene is added. Thus, a polyaniline solution having a surfactant structure was obtained. Next, 80 parts of a polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980), which is a binder polymer, is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF). ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[ Example Composition 1 0 ]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) are oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), and then an unreacted substance is removed with methanol. A polyaniline having a structure was obtained. Next, in an undried state, 20 parts of an active ingredient (non-volatile content) of polyaniline having this surfactant structure, 90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), polymer polyol (manufactured by Mitsui Chemicals, 10 parts of POP31-28), 0.5 part of tertiary amine catalyst (manufactured by Kao Corporation, Kaorizer No. 31), 0.05 part of tertiary amine catalyst (manufactured by Tosoh Corporation, Toyocat HX-35), a blowing agent (water), 2 parts of silicone foam stabilizer (Nippon Unicar Co., L-5309) were combined distribution and 2 parts were kneaded using a three-roll mill. And 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Ltd., Sumidur 44V20) was added to this, mixed using a casting machine, cast and foamed into a mold at 80 ° C., and then at 80 ° C. for 30 minutes. Heat treatment was performed to produce a 5-fold foamed sheet (300 mm × 300 mm, thickness 10 mm).

[Composition A for Comparative Example ]
100 parts of epichlorohydrin rubber (Osaka Soda Co., Ltd., Epichromer CG), 2 parts of a quaternary ammonium salt (LBA Co., Ltd., TBAHS) as a conductive agent, 10 parts of an acid acceptor (zinc oxide), and a thiourea crosslinking accelerator 3 parts (manufactured by Sanshin Chemical Co., Ltd., Sunseller 22C) were mixed and kneaded using three rolls, and then dissolved in 300 parts of methyl ethyl ketone (MEK) and 150 parts of toluene to prepare a composition (coating solution). Prepared. And after apply | coating this composition (coating liquid) on the SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[Composition B for Comparative Example ]
100 parts of polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980) was dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then acetylene black (made by Denki Kagaku Kogyo, 7 parts of Denka Black HS100) were blended and kneaded using three rolls to prepare a composition. And this was heat-crosslinked at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm on a SUS304 plate.

[Composition C for Comparative Example ]
The amount of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) was changed to 20 parts. Other than that was carried out similarly to the composition B, and produced the electroconductive coating film.

[Composition D for Comparative Example ]
Silicone in which carbon was dispersed (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.

[ Comparative Example E]
First, 1 mol of aniline and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidized and polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and filtration was performed three times. The water was completely removed at 100 ° C. for 30 minutes to obtain polyaniline having a surfactant structure. Next, 80 parts of H-NBR (manufactured by Zeon Corporation, Zetpol 0020) as the binder polymer, 1 part of sulfur as the cross-linking agent, and sulfenamide-based cross-linking accelerator (Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 5 parts, 0.5 part of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) is kneaded using two rolls and dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene. After that, polyaniline having the surfactant structure was added and kneaded with three rolls to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on the SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[Composition F for Comparative Example ]
90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and 0.5 part of tertiary amine catalyst (manufactured by Kao Corporation, Kaulizer No. 31) And 0.05 parts of a tertiary amine catalyst (Toyocat HX-35, manufactured by Tosoh Corporation), 2 parts of a foaming agent (water), and 2 parts of a silicone foam stabilizer (manufactured by Nihon Unicar Company, Ltd., L-5309) And 3 parts of ketjen black were blended and kneaded using three rolls. And 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Sumidur 44V20) and 20.5 parts of tolylene diisocyanate (Mitsui Chemicals Co., Ltd., TDI-80) are added to this and mixed using a casting machine. Then, it was cast and foamed into a mold set at 80 ° C., and then heat-treated at 80 ° C. for 30 minutes to prepare a 5-fold foamed sheet (300 mm × 300 mm, thickness 10 mm).

The electrical resistance was measured using the conductive coating film and the like thus obtained. In addition, the voltage dependence and environmental dependence of the electrical resistance were also evaluated. These results are shown in Tables 1 to 3 below.

[Electric resistance]
In an environment of 25 ° C. × 50% RH, the electrical resistance of the conductive coating film and the like when a voltage of 1 V was applied and when a voltage of 133 V was applied was measured according to SRIS 2304.

(Voltage dependency)
In accordance with the evaluation of the electrical resistance, the electrical resistance when a voltage of 1V was applied and the electrical resistance when a voltage of 133V were applied were measured in an environment of 25 ° C. × 50% RH, respectively. 133V), the difference in electrical resistance is indicated by the number of fluctuation digits.

(Environment dependency)
According to the evaluation of the electrical resistance, the electrical resistance at low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at high temperature and high humidity (35 ° C. × 85% RH) are measured, respectively. Differences are shown in variable digits. The applied voltage at this time is 10V.

〔Particle size〕
The particle size (median diameter) of the conductive polymer dispersed in the binder polymer was measured using a particle size distribution meter LA920 manufactured by Horiba. In addition, about the thing which has not mix | blended the conductive polymer, the particle size (median diameter) of the electrically conductive agent was measured. In addition, since a filler other than carbon is used in combination, “−” is displayed for those in which the particle size of the conductive polymer cannot be measured accurately.

[Electric resistance fluctuation before and after 100% extension]
When the conductive coating film made of each of the above compositions is punched into a strip (10 mm width, 100 mm length), an electrode is applied to the marked line portion, and stretched to 100% in an environment of 25 ° C. × 50% RH The electrical resistance was measured, and the electrical resistance fluctuation (digit) before and after stretching was determined. The applied voltage at this time is 10V.

From the results of the above table, the compositions B, C, D, and F for the comparative examples containing the electronic conductive agent have a remarkably large change in electrical resistance before and after 100% elongation, whereas the conductive polymer (surfactant structure) It can be seen that the composition for example 1 to 10 using the conductive polymer having) has a very small variation in electrical resistance before and after 100% elongation. This is because Comparative Examples Compositions B, C, D, and F are dispersed with an electronic conductive agent that becomes a conductive path, while Examples Compositions 10 to 10 have conductive characteristics that become a conductive path. sex polymer, Ru seems because it is uniformly dispersed in the connected state in a binder polymer.

Claims (4)

A semiconductive polymer elastic member for an actuator using a conductive composition containing a conductive polymer and a binder polymer, wherein the conductive polymer contains the raw material monomer in the presence of a surfactant. It has a surfactant structure obtained by chemical oxidative polymerization with an oxidant, and is dispersed in or compatible with the binder polymer. The semiconductive polymer elastic member has the following (A ) ~ semiconductive polymer elastic member for the actuator to satisfy the characteristics of (C).
(A) In an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied is 1. 34 digits or less.
(B) Fluctuation between the electrical resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electrical resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH is zero. .4 digits or less.
(C) The electrical resistance when 100% stretched is 1.3 digits or less of the electrical resistance when not stretched. The semiconductive polymer elastic member, under 25 ℃ × 50% RH environment, according to claim 1, wherein 10V electric resistance when a voltage was applied for are within the scope of 10 ⁶ ~10 ¹² Ω · cm Semiconductive polymer elastic member for actuators of The binder polymer is soluble in the solvent, and the conductive polymer, a semi-conductive high for an actuator according to claim 1 or 2, wherein those which may be present as a soluble or colloidal solution in a solvent or binder solution Molecular elastic member. The conductive polymer, either dispersed in particle size of less than 1μm in the binder polymer, or semi-conductive high for the actuator according to any one of claims 1 to 3, which is compatible with the binder polymer Molecular elastic member.