WO2004014987A1 - 導電性高分子の製造方法 - Google Patents
導電性高分子の製造方法 Download PDFInfo
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- WO2004014987A1 WO2004014987A1 PCT/JP2003/010111 JP0310111W WO2004014987A1 WO 2004014987 A1 WO2004014987 A1 WO 2004014987A1 JP 0310111 W JP0310111 W JP 0310111W WO 2004014987 A1 WO2004014987 A1 WO 2004014987A1
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- conductive polymer
- electrolytic
- expansion
- molded article
- actuator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/50—Prostheses not implantable in the body
- A61F2002/5066—Muscles
Definitions
- the present invention relates to a laminate, an electroconductive stretching method of the conductive polymer molded article and the laminate having an excellent stretch ratio, an activator containing the conductive polymer, and uses thereof.
- conductive polymers such as polypyrrole exhibit electrolytic stretching, which is a phenomenon of stretching or deformation due to electrochemical redox. Electrolytic expansion and contraction of this conductive high molecule is expected to be applied to driving artificial muscles, mouth pot arms, artificial hands, artificial legs, powered suits, and actiyu, and has been attracting attention in recent years.
- a method of producing such a conductive polymer which undergoes electrolytic expansion and contraction a method of producing by an electrolytic polymerization method is generally used.
- a working electrode and a counter electrode are placed in an electrolyte solution containing a monomer component such as pyrrole, and then a voltage is applied to both electrodes so that the conductive polymer film acts.
- a method of forming an electrode is usually performed.
- the conductive polymer film obtained by the electrolytic polymerization method can be expanded or contracted or displaced by applying a voltage to the film.
- Such a conductive polymer that expands and contracts can be used as a conductive polymer alone film for applications such as artificial muscles.
- Japanese Patent Application Laid-Open No. H11-169393 shows a feature.
- Kaihei 1 1 1 1 169 394 describes that it is also possible to use an artificial muscle having a polyaniline film formed on both sides of a solid electrolyte former.
- a voltage is applied to the conductive polymer. After that, it is necessary to improve the ratio of the length of the conductive polymer molded article in the initial state at a specific time to the length of the stretched or displaced length, that is, the rate of displacement per specific time. If possible, it is desirable to further enhance practicality.
- the conductive polymer obtained by the electropolymerization method is used as a conductive polymer used in artificial muscles.
- the present invention provides a method for producing a conductive polymer having an excellent stretch ratio per oxidation-reduction cycle, a conductive polymer molded article obtained by the method, and a conductive polymer obtained by the method.
- the present invention is, first, a method for producing a conductive polymer by an electrolytic polymerization method, wherein the conductive polymer has elasticity due to electrochemical oxidation-reduction, and the electrolytic polymerization method is an organic compound.
- the organic compound is selected from the group consisting of (1) a chemical bond consisting of an ether bond, an ester bond, a carbon-halogen bond, and a force-ponate bond.
- a method for producing a conductive polymer containing anion containing a plurality of fluorine atoms bonded to a trifluoromethanesulfonic acid ion and / or a central atom a method for producing a conductive polymer containing anion containing a plurality of fluorine atoms bonded to a trifluoromethanesulfonic acid ion and / or a central atom.
- the conductive polymer obtained by this production method has a large expansion and contraction per oxidation-reduction cycle and can be suitably used for an actuating element which is a driving source for practical use.
- the present invention also provides, secondly, a method for producing a conductive polymer by an electrolytic polymerization method, wherein the conductive polymer has elasticity due to electrochemical oxidation-reduction
- the electrolytic solution includes an anion containing a plurality of fluorine atoms bonded to a trifluoromethanesulfonic acid ion and / or a central atom in the electrolytic solution, and the electrolytic polymerization method uses a metal electrode as a working electrode on which a conductive polymer is formed. It is also a method for producing conductive polymers.
- the conductive polymer obtained by this manufacturing method can greatly exceed the conventional expansion and contraction ratio of 1%, and can generate a larger power than conventional ones. It can be suitably used for an overnight device.
- the present invention is a conductive polymer molded article obtained by the production method.
- the conductive polymer molded article not only has an excellent expansion / contraction rate per oxidation-reduction cycle, but also has an excellent displacement rate per specific time. Therefore, the conductive polymer molded article can be suitably used for an actuator element which is a driving source for practical use.
- the present invention provides a conductive polymer molded article obtained by the production method, comprising trifluoromethanesulfonate ion, anion containing a plurality of fluorine atoms bonded to a central atom, and a sulfonate having 3 or less carbon atoms.
- the present invention is also a laminate including a conductive polymer-containing layer and a solid electrolyte layer.
- the conductive polymer contained in the conductive polymer-containing layer is a conductive polymer obtained by the above-described method for producing a conductive polymer, the laminate has a thickness per oxidation-reduction cycle.
- the present invention relates to an actuating unit including an operating unit, a counter electrode and an electrolyte, wherein the operating unit includes an operating unit including a conductive polymer obtained by the above-described method for producing a conductive polymer. But also.
- the above-mentioned actuate can improve the expansion and contraction rate per one oxidation-reduction cycle of the actuate over the electrolytic expansion and contraction caused by applying a voltage between the counter electrode and the working part, so that it is practically used. It can be suitably used for an actuating element which is a driving source of the device.
- the present invention provides a positioning device, a posture control device, an elevating device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, using the above-described conductive polymer molded product as an actuator element. Or a joint device, and a pressing device used for the pressing portion. Further, the present invention provides a positioning device, a posture control device, a lifting device, a transport device, a moving device, an adjusting device, an adjusting device, a guiding device, or a joint device using the above-described actuator as a driving unit, and a pressing unit. It is also the pressing device used. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is a perspective view showing the appearance of an embodiment of the present invention of the present invention.
- FIG. 2 is a sectional view taken along the line AA of FIG. BEST MODE FOR CARRYING OUT THE INVENTION
- the electrolytic polymerization method is a polymerization method using an electrolytic solution containing an organic compound as a solvent, and the organic compound is a chemical reaction comprising an ether bond, an ester bond, a carbon-halogen bond, and a carbonate bond.
- the electrolyte comprises trifluoromethanesulfonate ions and / or This is a method for producing a conductive polymer containing an anion containing a plurality of fluorine atoms bonded to a core atom.
- an organic compound is contained as a solvent in an electrolytic solution used in an electrolytic polymerization method.
- the organic compound includes at least one chemical bond selected from the group consisting of an ether bond, an ester bond, a carbon bond, and a carbonate bond, and / or a hydroxyl group, a nitro group, a sulfone group, and a hydroxyl group.
- the molecule contains at least one functional group selected from the group of functional groups consisting of a tolyl group. The organic compound contains one or more of these chemical bonds and these functional groups in a molecule.
- the organic compound may include any of a chemical bond selected from the group of the chemical bonds and a functional group selected from the group of the functional groups. Further, the molecule may contain at least one chemical bond selected from the group of chemical bonds and at least one functional group selected from the group of functional groups.
- organic compound examples include the following groups of organic compounds: 1,2 dimethyloxetane, 1,2-diethoxetane, tetrahydrofuran, 21-methyltetrahydrofuran, 1,4-dioxane Organic compounds), arptyrolactone, ethyl acetate, n-butyl acetate, 1-butyl acetate, 1,2-diacetoxetane, 3-methyl-2-oxazolidinone, methyl benzoate, benzoic acid Ethyl, butyl benzoate, getyl phthalate (above, organic compounds containing ester bonds), propylene glycol, ethylene carbonate, dimethyl carbonate, getyl carbonate, methylethyl carbonate (more than, organic compounds containing carbonate bonds) ), Ethylene glycol, butanol, 1-hexano Cyclohexanol, 1-octanol, 1-decanol, 1-dodecanol
- the organic compound containing a hydroxyl group is not particularly limited, but is preferably a polyhydric alcohol or a monohydric alcohol having 4 or more carbon atoms because of its good elasticity.
- the organic compound may have, in addition to the above examples, two or more bonds or functional groups among ether bonds, ester bonds, carbonate bonds, hydroxyl groups, nitro groups, sulfone groups, and nitrile groups in the molecule.
- Organic compounds may be included in any combination.
- an organic compound containing an ester bond is preferable because the obtained conductive polymer has a large expansion and contraction rate.
- the organic compound contained as a solvent in the electrolytic solution contains a carbon-halogen bond
- the organic compound may be a halogenated hydrocarbon.
- the octogenated hydrocarbon is not particularly limited as long as at least one hydrogen in the hydrocarbon is substituted with a halogen atom and can be stably present as a liquid under electropolymerization conditions. Not something.
- Examples of the halogenated hydrocarbon include dichloromethane and dichloroethane. As the halogenated hydrocarbon, only one kind can be used as a solvent in the electrolytic solution, but two or more kinds can be used in combination.
- the halogenated hydrocarbon may be used as a mixture with the above organic compound, and a mixed solvent with the organic solvent other than the halogenated hydrocarbon may be used as the solvent in the electrolytic solution.
- a mixture of two or more of the above organic compounds is used as a solvent for the electrolytic solution, an organic compound containing an ether bond, an organic compound containing an ester bond, an organic compound containing a carbonate bond, an organic compound containing a hydroxyl group, Organic compounds having excellent elongation and organic compounds having excellent shrinkage from the group consisting of organic compounds having an organic group, organic compounds having a sulfone group, and organic compounds having a nitrile group.
- the conductive polymer obtained by the electrolytic polymerization can be improved in the expansion and contraction rate per one oxidation-reduction cycle.
- the electrolytic solution used in the electrolytic polymerization method includes an organic compound to be electrolytically polymerized (for example, pyrrole), trifluoromethanesulfonate ion, and nitrogen atom or a central atom.
- the liquid contains an anion containing a plurality of fluorine atoms bonded to the liquid.
- the conductive polymer obtained by the electrolytic polymerization using this electrolytic solution has a stretching rate per oxidation-reduction cycle and a displacement rate per Z or specific time in electrolytic stretching.
- anion containing a plurality of trifluoromethanesulfonate ions and a plurality of fluorine atoms bonded to z or the central atom is incorporated into the conductive polymer.
- the anion containing a plurality of trifluoromethanesulfonic acid ions and a plurality of fluorine atoms bonded to the central atom or the trifluoromethanesulfonate ion is not particularly limited in the content thereof in the electrolytic solution, but may be 0.1 to 30 in the electrolytic solution. % By weight, more preferably 1 to 15% by weight.
- Triflate Ruo b methanesulfonate ion has the formula CF 3 S 0 3 - is a compound represented by.
- An anion containing a plurality of fluorine atoms bonded to a central atom has a structure in which a plurality of fluorine atoms are bonded to a central atom such as boron, phosphorus, antimony, and arsenic.
- the Anion containing a plurality of fluorine atoms bonded to the central atom are not particularly limited, tetrafurfuryl O b borate ion (BF 4 I), the Kisafuruororin acid ion (PF 6 -), the hexa Fluoroantimonate ion (S bF 6 —) and hexafluoro arsenate ion (A s F 6 _) can be exemplified.
- CF 3 S_ ⁇ 3 - preferably when the consideration of safety to human body, CF 3 S0 3 _ and BF 4 - -, BF 4 first and PF 6 are more preferred.
- the anion containing a plurality of fluorine atoms bonded to the central atom may be one kind, or two or more kinds may be used simultaneously in the electrolytic solution. Further, trifluoromethanesulfonic acid ions and anions containing a plurality of fluorine atoms bonded to a plurality of types of central atoms may be simultaneously used in the electrolytic solution.
- the method is used in an electrolytic polymerization method.
- the electrolytic solution contains a conductive polymer monomer in the solution, in addition to the organic compound solvent and the trifluoromethanesulfonic acid ion and / or anion containing a plurality of fluorine atoms bonded to a central atom.
- the electrolyte solution may further contain other known additives such as polyethylene glycol and polyacrylamide.
- the present invention provides, secondly, a method for producing a conductive polymer by an electrolytic polymerization method, wherein the conductive polymer has elasticity due to electrochemical oxidation-reduction, and the electrolytic polymerization method comprises: An electrolytic solution containing trifluoromethanesulfonic acid ion and anion containing a plurality of fluorine atoms bonded to a central atom or a trifluoromethanesulfonate ion is contained in the electrolytic solution, and the electrolytic polymerization method comprises a metal electrode as a working electrode on which a conductive polymer is formed. This is a method for producing a conductive polymer using the same.
- the electrolytic solution used in the electrolytic polymerization method contains, in addition to the organic compound to be electrolytically polymerized (for example, pyrrole), trifluoromethanesulfonic acid ions and / or Includes anions containing multiple fluorine atoms bonded to the atoms.
- anion containing a plurality of trifluoromethanesulfonate ions and / or a plurality of fluorine atoms bonded to the central atom is incorporated into the conductive polymer.
- the anion containing a plurality of trifluoromethanesulfonate ions and a plurality of fluorine atoms bonded to Z or a central atom is not particularly limited in the content thereof in the electrolytic solution, but is contained in the electrolytic solution in an amount of 0.1 to 3%.
- the content is preferably 0% by weight, more preferably 1 to 15% by weight.
- Torifuruorome evening Nsuruhon acid ion a compound represented by the chemical formula CF 3 S_ ⁇ 3.
- An anion containing a plurality of fluorine atoms bonded to the central atom is It has a structure in which multiple fluorine atoms are bonded to central atoms such as boron, phosphorus, antimony, and arsenic.
- the anion containing a plurality of fluorine atoms bonded to the central atom is not particularly limited, but includes tetrafluoroborate ion (BF 4 —), hexafluorophosphate ion (PF 6 —), and hexafluorophosphate ion (PF 6 —).
- xafluoroantimonate ion S bF 6 —
- hexafluoro arsenate ion As F 6 —
- CF 3 S_ ⁇ 3 - preferably when the consideration of safety sex to the human body or the like, CF 3 S0 3 - -, BF 4 _ and PF 6 and BF 4 are more preferable.
- the anion containing a plurality of fluorine atoms bonded to the central atom may be one kind, or two or more kinds may be used simultaneously in the electrolytic solution.
- trifluoromethanesulfonic acid ion and anion containing a plurality of fluorine atoms bonded to a plurality of kinds of central atoms may be simultaneously used in the electrolytic solution.
- a metal electrode is used as a working electrode in which polymerization of a conductive polymer is performed during electrolytic polymerization.
- metal electrodes in the electropolymerization compared to the case of using electrodes mainly composed of non-metallic materials such as ITO glass electrodes and Nesa glass electrodes, the use of the obtained conductive polymer in an active material Evening can develop a large generating power.
- the metal electrode is not particularly limited as long as it is a metal-based electrode, but is selected from the group consisting of Pt, Ti, Au, Ni, Ta, Mo, Cr and W.
- An electrode of a simple metal or an alloy of an element can be suitably used. It is particularly preferable that the metal species contained in the metal electrode is Ni or Ti because the conductive polymer obtained by the above-mentioned production method has a large expansion and contraction rate and a high generating force, and the electrode can be easily obtained.
- the solvent contained in the electrolytic solution at the time of electrolytic polymerization is not particularly limited, but the expansion / contraction rate per oxidation-reduction cycle is 3%.
- an aniline containing a plurality of fluorine atoms with respect to trifluoromethanesulfonate ion and Z or a central atom is required.
- the chemical bond selected from the group consisting of ether bond, ester bond, carbon-halogen bond and force-ponate bond
- at least one or more chemical bond species and / or hydroxyl group, nitro group, sulfone group It is preferable to include, as a solvent for the electrolytic solution, an organic compound containing in its molecule at least one functional group selected from the group of functional groups consisting of nitrile groups. Two or more of these solvents can be used in combination. More preferably, the solvent of the electrolytic solution is a solvent having an ester group.
- the electrolytic polymerization method used in the first and second production methods of the conductive polymer of the present invention can use a known electrolytic polymerization method as a method for electrolytic polymerization of a monomer of the conductive polymer.
- any of the constant potential method, constant current method and electric sweep method can be used.
- the electrolytic polymerization method can be carried out at a current density of 0.01 to 20 mA / cm 2 and a reaction temperature of 170 to 80 ° C., in order to obtain a conductive polymer having good film quality.
- the reaction is performed under the conditions of a current density of 0.1 to 2 mAZ cm 2 and a reaction temperature of 40 to 40 ° C, and more preferably a reaction temperature of 130 to 30 ° C. It is good.
- the working electrode is not particularly limited as long as it can be used for electrolytic polymerization, and an ITO glass electrode, a metal electrode, or the like may be used. it can.
- the conductive polymer monomer contained in the electrolytic solution used in the electrolytic polymerization method may be a polymer obtained by oxidation by electrolytic polymerization.
- the compound is not particularly limited as long as it is a compound that exhibits electrical conductivity when converted to a compound.
- examples include a 5-membered heterocyclic compound such as pyrrole, thiophene, and isothianaphthene, and derivatives thereof such as an alkyl group and an oxyalkyl group. .
- a five-membered heterocyclic compound such as pyrrole and thiophene and a derivative thereof are preferable.
- a conductive polymer containing a pyrrole and / or a pyrrole derivative is preferable because it is easy to produce and has a high conductivity. It is preferable because it is stable as a polymer.
- the above monomers can be used in combination of two or more kinds.
- the conductive polymer produced by the first and second methods of producing the conductive polymer of the present invention is not particularly limited as long as it has elasticity. Polypyrrol, polythiophene, and polya Diphosphorus, polyphenylene film and the like can be used.
- the conductive polymer is a conductive polymer having a molecular chain containing pyrrole and a pyrrole or pyrrole derivative, which is easy to manufacture, is not only stable as a conductive polymer, but also has an electrolytic stretching property. It is preferable because it is excellent.
- the conductive polymer may include, as a dopant, trifluoromethanesulfonate ion contained in the electrolytic solution and an anion containing a plurality of fluorine atoms bonded to Z or a central atom. Therefore, it is thought that it shows an excellent stretching ratio per oxidation-reduction cycle in electrolytic stretching, and also shows an excellent displacement ratio per specific time.
- the conductive polymer may include, in the electrolytic solution, trifluoromethanesulfonate ion and anion containing a plurality of fluorine atoms bonded to Z or a central atom in the electrolytic solution. Since a metal electrode is used as the working electrode of the present invention, it exhibits an excellent expansion and contraction rate per oxidation-reduction cycle in electrolytic expansion and contraction, and can generate a large force by electrolytic expansion and contraction.
- the present invention is also a conductive polymer molded article having a desired shape of the conductive polymer obtained by the first of the above manufacturing methods. That is, a method for producing a conductive polymer, which is a method for producing a conductive polymer having elasticity by electrochemical oxidation-reduction by an electrolytic polymerization method, wherein the electrolytic polymerization method comprises an ether bond, an ester bond, and a carbonate bond. An organic compound containing at least one bond or a functional group of at least one of a hydroxyl group, a nitro group, a sulfon group and a nitrile group, and an electrolyte solution containing Z or octogenated hydrocarbon as a solvent. To the trifluoromethanesulfonate ion and Z or the central atom. T liquor 03/010111
- the shape of the conductive polymer molded article is not particularly limited, and may be a film shape, a tubular shape, a cylindrical shape, a prism, a fiber shape, or the like. It is preferably in the form of a film because it precipitates on the working electrode during polymerization.
- the working electrode is not particularly limited as long as it can be used for electrolytic polymerization, and an IT-based glass electrode, a metal electrode, or the like can be used.
- the expansion and contraction rate of the conventional conductive polymer was only about 1% per one oxidation-reduction cycle in the plane direction.
- the conductive polymer molded article of the present invention contains, as a dopant, trifluoromethanesulfonic acid ion and anion containing a plurality of fluorine atoms bonded to Z or a central atom in the conductive polymer. As a result, it has become possible to exhibit an excellent stretch ratio of 3% or more, particularly 5% or more per oxidation-reduction cycle, in the length direction of the conductive polymer molded article.
- the conductive polymer molded article of the present invention has a stretch ratio of at least 3% in the length direction per redox cycle, and therefore requires a large stretch ratio represented by artificial muscle. Can be suitably used.
- the conductive polymer molded article may appropriately contain a conductive material such as a metal wire or a conductive oxide in order to reduce the resistance value as an operating electrode, in addition to the dopant.
- the conductive polymer molded article which expands and contracts by electrochemical oxidation-reduction, the expansion and contraction rate in one oxidation-reduction cycle of 20 seconds is 3% or more in the length direction.
- the conductive polymer molded article is a method for manufacturing a conductive polymer manufactured by an electrolytic polymerization method, wherein the electrolytic polymerization method includes an ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, Using an electrolytic solution containing at least one bond or a functional group among nitrile groups and / or a halogenated hydrocarbon as a solvent, 20 seconds by including a conductive polymer obtained by the method for manufacturing a conductive polymer containing anion containing a plurality of fluorine atoms bonded to a central ion and / or a central atom in the electrolytic solution.
- this conductive polymer molded product has a stretch ratio of 3% or more in the length direction in one oxidation-reduction cycle.
- this conductive polymer molded product requires a large displacement of the tip of the conductive polymer molded product within a certain period of time after the start of voltage application at one point. Therefore, it can be suitably used for an actuator element which is a driving source for practical use.
- the actuator is an actuator including the conductive polymer molded article, a counter electrode and an electrolyte, and via the electrolyte.
- the apparatus can be configured to include a counter electrode and an electrolyte so that a voltage can be applied between the counter electrode and the conductive polymer molded article.
- a voltage By applying a voltage from one end of the conductive polymer molded article, the stretching rate in one oxidation-reduction cycle of 20 seconds is 3% or more in the length direction, so that artificial muscles and various devices can be used. It can be suitably used in factories that require faster responsiveness, such as a drive unit.
- the present invention is also a conductive polymer molded article in which the conductive polymer obtained by the second of the above-described manufacturing method is formed into a desired shape.
- a method for producing a conductive polymer which is a method for producing a conductive polymer having elasticity by electrochemical redox by an electrolytic polymerization method, wherein the electrolytic polymerization method comprises A method for producing a conductive polymer having an electroconductive polymer by an electrolytic polymerization method, wherein the electropolymerization method comprises the step of forming a trifluoromethanesulfonate ion and a fluorine atom bonded to Z or a central atom.
- the shape of the conductive polymer molded article is not particularly limited, and may be a shape such as a film, a tube, a tube, a prism, and a fiber. Since the conductive polymer is deposited on the working electrode during electrolytic polymerization, the conductive polymer is preferably in the form of a film. When the molded article is in the form of a film, it may be a film obtained by using the conductive polymer of the above-mentioned production method of the present invention.
- the film-shaped body may be formed in a form in which the conductive polymer obtained by the above-described manufacturing method covers the surface of the target article by a known method.
- the present invention is a laminate including a conductive polymer layer and a solid electrolyte layer, and is also a laminate including the conductive polymer in the conductive polymer layer. That is, the invention of the present application is a laminate including a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer layer includes the conductive polymer obtained by the first method for producing a conductive polymer. It can be a laminate containing a polymer. Further, the present invention is a laminate including a conductive polymer layer and a solid electrolyte layer, wherein the conductive polymer layer includes the conductive polymer obtained by the second method for producing a conductive polymer.
- the laminate may include a polymer.
- the electrolyte in the solid electrolyte layer is supplied to the conductive polymer layer, and the conductive polymer layer includes the conductive polymer layer. Since the conductive polymer greatly expands and contracts due to electrochemical oxidation and reduction, a large expansion and contraction rate per oxidation-reduction cycle can be exhibited during electrolytic expansion and contraction. A large expansion ratio per oxidation-reduction cycle can be exhibited during electrolytic expansion. It is preferable that the conductive polymer layer and the solid electrolyte layer in the laminate are in direct contact with each other, but any electrolyte in the solid electrolyte can be transferred to the conductive polymer. If desired, another layer may be interposed.
- the conductive polymer-containing layer may include a substrate or the like that does not significantly hinder electrolytic expansion and contraction, and may also include a conductive oxide or a metal wire.
- the solid electrolyte is not particularly limited, but is preferably an ion-exchange resin because it can be largely driven.
- the ion-exchange resin a known ion-exchange resin can be used.
- a trade name “Naiion” perfluorosulfonic acid resin, manufactured by DuPont
- the laminate is used as an actuator, it is an actuator having a counter electrode and the laminate, wherein the counter electrode and the conductive polymer in the laminate are interposed via a solid electrolyte in the laminate.
- the actuator may be provided with a counter electrode so that a voltage can be applied to the containing layer.
- the present invention is also an electrolytic expansion / contraction method for expanding / contracting the conductive polymer molded article by electrochemical oxidation / reduction of the above-mentioned conductive polymer molded article in an electrolytic solution.
- an excellent expansion and contraction rate can be obtained per oxidation-reduction cycle.
- the above-mentioned electrolytic expansion / contraction method for expanding / contracting a conductive polymer molded article can also provide an excellent displacement ratio per specific time.
- the working electrolyte which is an electrolyte in which the conductive polymer molded article is subjected to electrolytic expansion and contraction, is not particularly limited, but a liquid containing an electrolyte in water, which is a main solvent, may have a concentration of It is preferable because the preparation is easy.
- the electrolytic solution is at least one selected from the group consisting of a trifluoromethanesulfonate ion, an anion containing a plurality of fluorine atoms bonded to a central atom, and a sulfonate having 3 or less carbon atoms.
- An electrolytic solution containing a compound as a working electrolyte can be used.
- the present invention provides a method for producing a conductive polymer, wherein the conductive polymer molded article is a conductive polymer having elasticity due to electrochemical oxidation-reduction produced by an electrolytic polymerization method.
- the electropolymerization method comprises an organic compound containing at least one bond or a functional group of at least one of a ether bond, an ester bond, a carbonate bond, a hydroxyl group, a nitro group, a sulfone group, and a nitrile group, and Z or halogenated carbon.
- a conductive material obtained by a method for producing a conductive polymer containing anion containing a plurality of fluorine atoms bonded to trifluoromethanesulfonate ions and a central atom in the electrolyte is used.
- a conductive polymer molded product containing a conductive polymer as a resin component 3 010111
- the electrolyte containing at least one compound selected from the group consisting of trifluoromethanesulfonate ion, anion containing a plurality of fluorine atoms with respect to the central atom, and a sulfonate having 3 or less carbon atoms as an operating electrolyte.
- the salt used in the electrolytic solution can be used as a salt contained in the electrolytic solution of the solid electrolyte in the laminate of the present invention, and shows an excellent stretching ratio per oxidation-reduction cycle.
- a laminate with a solid electrolyte can be obtained.
- trifluoromethanesulfonate ion contained as an operating electrolyte in an electrolyte solution as an external environment and anion containing a plurality of fluorine atoms bonded to Z or a central atom are required.
- Triflate Ruo Lome chest sulfonic acid ion a chemical formula CF 3 S 0 3 compound represented by _.
- an anion containing a plurality of fluorine atoms with respect to the central atom is an ion having a structure in which a plurality of fluorine atoms of the central atom are bonded to atoms such as boron, phosphorus, antimony, and arsenic.
- the sulfonate having 3 or less carbon atoms is not particularly limited as long as it is a salt of a sulfonic acid having 3 or less carbon atoms.
- sodium methanesulfonate and sodium ethanesulfonate can be used.
- the present invention also relates to an electrolytic stretching method for expanding and contracting the conductive polymer molded article by electrochemical oxidation reduction of the conductive polymer molded article in an electrolytic solution, wherein the electrolytic solution mainly comprises sodium chloride.
- An electrolytic stretching method which is an aqueous solution containing a suitable electrolyte, may be used.
- the electrolytic solution mainly contains sodium chloride, which is an electrolyte contained in a biological component, it is possible to operate in a state in which a body fluid in a living body and the electrolytic solution are easily interchangeable.
- the temperature of the electrolytic solution or the solid electrolyte that undergoes electrolytic expansion and contraction in the present invention is not particularly limited. However, in order to expand and contract the conductive polymer at a higher speed, the temperature is preferably 20 to 100 °. (:, More preferably 50 to 80 ° C.).
- the invention of the present application is also an actuating device including an operating portion, an electrolyte and a counter electrode, wherein the operating portion includes the conductive polymer obtained by the first or second method for producing a conductive polymer. It's a night of akuchiyue.
- the actuator is not particularly limited as long as it includes an operating part, an electrolyte, and a counter electrode as a device configuration, but a shaft attached to the operating part is provided in a housing so that liquid does not leak during operation. It is preferable to use a packed actuator or an actuator equipped with a housing that can be expanded and contracted according to the operation of the operating part, because it does not cause leakage of electrolyte or the like.
- the work 1 is a cylindrical work, and the outermost layer is formed of a housing made of a flexible material such as urethane rubber.
- a lead 8 for applying a potential to the operating section 3 inside the actuator and leads 7 and 7 ′ for applying a potential to the counter electrode.
- Factory 1 has a column-shaped operating portion 3 in an internal space of a casing 2 formed of a flexible material.
- a concave portion 23 is formed on the inner surface of the bottom portion 22 of the housing 2.
- One end of the operating part 3 is fitted into the recess 23 via the conductive connection plate 4 so that the operating part is Attached to body 2.
- the operating unit 3 is fixed to the housing 2 by joining the other end of the operating unit 3 to the inner surface of the distal end 21 of the housing 2.
- columnar counter electrodes 51 and 52 are fitted near the inner surface of the side wall of the housing 2 with the counter electrode fitting recesses 24 and 25 provided at the bottom 22.
- the remaining internal space excluding the counter electrodes 51 and 52 and the operating part 3 is filled with the electrolyte 6.
- the power supply 9 is connected to the counter electrodes 51 and 52 via the leads 7 and 7 ′, and is connected to the conductive connection plate 4 in contact with the operating section 3 via the lead 8.
- a voltage can be applied between the counter electrodes 51, 52 and the operating section 3, and the operating section 3 can be expanded and contracted electrolytically.
- a force F can be generated at the distal end 21 and can be suitably used as an artificial muscle.
- the tip 21 of the actuator 1 may or may not be joined to the tip of the operating section 3 on the inner surface.
- the force acts to shrink the housing 2 formed of a flexible material into the inside of the actuator due to the shrinkage stress.
- the operating portion 3 electrolytically expands and contracts, so that the distal end portion 21 can expand and contract following the electrolytic expansion and contraction of the operating portion 3.
- the operating portion is not particularly limited as long as it includes the above-described conductive polymer and undergoes electrolytic expansion and contraction by applying a voltage. It is preferable that the operating portion exhibits an elasticity of 5% or more when a voltage is applied.
- the actuating section expands and contracts by 5% or more when a voltage is applied, so that it is possible to obtain an actuation that expands and contracts by 5% or more.
- the operating portion may appropriately include a conductive material such as a metal wire or a conductive oxide in order to reduce a resistance value as an operating electrode in addition to the dopant.
- the flexible material forming the housing 2 is not particularly limited.
- the flexible material The material can be appropriately selected according to the elongation rate of the product, preferably a synthetic resin having an elongation of 5% or more, and more preferably a synthetic resin having an elongation of 20% or more.
- the flexible material for example, silicon-based resin, urethane-based resin, silicon-based rubber, urethane-based rubber, or the like can be used.
- the flexible material also has a function of preventing the electrolyte from leaking to the outside of the actuator, it is preferable that the flexible material has solvent resistance.
- the actuator 1 has a structure in which the operating part is sealed by the housing 2, so it has a longer operating time than a structure in which a rod-like body that transmits force penetrates the housing. Since there is no leakage of electrolyte due to use, it is excellent for use as mechanical parts such as artificial muscles.
- the shape of the actuator of the present invention is not particularly limited. Although the actuator is formed in a cylindrical shape in FIG.
- the shape of the actuator can be formed in a shape corresponding to the usage state, such as a polygonal column such as a prism or a hexagon, a cone, a plate, or a rectangular parallelepiped, in addition to the cylinder.
- the working part installed inside the actuator of the present invention is not limited to a column, but may be a polygonal pillar such as a prism or a hexagon, a cone, a rectangular parallelepiped, or the like. It can be made into an appropriate shape according to.
- the operating portion may be a conductive polymer film obtained on the working electrode by electrolytic polymerization as it is, or may be formed into a desired shape by performing molding such as lamination.
- the counter electrode is not limited to a columnar shape, but may be a plate shape or the like.
- the electrolyte contained in the capsule of the present invention may be a liquid or a solid electrolyte.
- the solvent may be water or an organic solvent.However, since the rate of volatilization is relatively low, handling is easy, and large expansion and contraction can be obtained. Therefore, it is preferably an aqueous solvent.
- the electrolysis When the liquid is a solid electrolyte, it may be a polymer electrolyte or a completely solid solid electrolyte, but a gel polymer electrolyte is preferred because of its high ionic conductivity in the electrolyte.
- the electrolyte may be an electrolyte containing at least one compound selected from the group consisting of trifluoromethanesulfonate ion, anion containing a plurality of fluorine atoms with respect to a central atom, and a sulfonate having 3 or less carbon atoms. Actuyue is preferred because it allows for a larger expansion and contraction per redox cycle.
- a laminate of a conductive polymer-containing layer and a solid electrolyte may be used as the operating portion and the electrolyte.
- the conductive polymer in the layer expands and contracts greatly.
- the counter electrode may be installed so that a voltage can be applied between the counter electrode and the conductive polymer-containing layer via the solid electrolyte, and the installation place is not particularly limited.
- the actuator can obtain a large expansion and contraction rate by including the above-mentioned conductive polymer in the internal working portion, so that it can be used even when the displacement is small. It can be suitably used as an artificial muscle, which is a use requiring a large displacement. In other words, until now, an actuary using a conductive polymer as a drive unit could only be used for applications requiring a small displacement, but an actuary of the present invention uses a conductive polymer. The application can be expanded to applications where displacement of artificial muscles etc. is large.
- the actuator can be used as a linear actuator. For example, a member for transmitting a force, such as a metal wire, is connected to a distal end 21 of the actuator 1 in FIG. 1 via a driving connector.
- the actuator of the present invention By attaching, it can be used as a drive device. Further, by pressing the front end 21 against the control object, the actuator of the present invention can be used. Can be used as a pressing device.
- the actuator of the present invention is an actuator in which a conductive polymer is driven by electricity, and is silent as it is driven. Therefore, the actuator is suitable as a driving unit or a pressing unit in an indoor use device.
- the actuator is lighter than the conventional linear actuator due to fewer metal parts, so the positioning device, the attitude control device, the elevating device, the transport device, the moving device, the adjusting device, the adjusting device, It can be suitably used as a drive unit of a guidance device and a joint device.
- the conductive polymer molded article and laminate of the present invention can be suitably used for artificial muscles, mouth pot arms, power suits, artificial hands and artificial legs.
- Industrial equipment such as control equipment, soft manipulators, underwater valves, and soft transport equipment; underwater vehicles such as goldfish; or objects used in water such as moving fishing baits or hobby supplies such as propulsion fins.
- the conductive polymer molded product and the laminate of the present invention can be suitably used.
- the first or second method for producing the conductive polymer described above is used.
- An artificial muscle, a robot arm and a prosthesis used as a drive unit, using the obtained conductive polymer as a conductive polymer molded article containing a base resin or a laminate containing a resin component of a conductive polymer layer. can be.
- the conductive polymer obtained by the first or second method for producing a conductive polymer described above is Tweezers, scissors, forceps, snares, and lasers used as a drive unit were formed of a conductive polymer molded article containing the base resin or a laminate containing the conductive polymer layer as a resin component. It can be a medical device including a zames, a spatula, and a clip. Further, when the conductive polymer molded article and the laminate of the present invention are used for the above-described sensor or repair tool, the conductive polymer can be obtained by the first or second method for producing a conductive polymer described above.
- a sensor and a repair tool including inspection and repair, using a conductive polymer molded product containing a base resin as a conductive polymer molded product containing a base resin or a laminate containing a resin component of a conductive polymer layer as a drive unit. It can be.
- the conductive polymer molded article and the laminate of the present invention are used for the above-mentioned industrial equipment, the conductive polymer obtained by the first or second method for producing a conductive polymer described above is used as the conductive polymer.
- Health appliances, hygrometers, hygrometer control devices, and soft manipulators that use a conductive polymer molded article containing a base resin or a laminate containing a conductive polymer layer as a resin component as a drive unit It can be industrial equipment including underwater valves and soft transport equipment. Further, when the conductive polymer molded article and the laminate of the present invention are used for the above-mentioned article used in water, the conductive polymer can be obtained by the first or second method for producing a conductive polymer described above.
- the conductive polymer molded article and the laminate of the present invention can generate displacement, so that they can be used as an actuator.
- those not coated with a resin or the like can be used as an actuator capable of linear displacement in an electrolytic solution.
- the stretch ratio of the conductive polymer layer at the time of electrolytic expansion or contraction is equal to or higher than that. If it is a solid electrolyte layer with elasticity, It can be used as an actor that makes a great displacement.
- one of the upper and lower layers when the conductive polymer layer is used as the intermediate layer has an elasticity smaller than the elasticity of the conductive polymer layer during electrolytic expansion and contraction.
- the solid electrolyte layer or the resin layer does not expand and contract as compared with the conductive polymer layer, and thus can be used as an actuator for bending displacement.
- the actuator that generates a linear displacement or a bending displacement is used as a driving unit that generates a linear driving force or a driving unit that generates a driving force for moving a track-type orbit consisting of an arc. be able to. Further, the actuator can be used as a pressing portion that operates linearly.
- the invention of the present invention is OA equipment, antenna, equipment to put people such as bed and chair, medical equipment, engine, optical equipment, fixture, side trimmer, vehicle, lifting equipment, food processing equipment, cleaning equipment, Measuring equipment, inspection equipment, control equipment, machine tools, processing machines, electronic equipment, electron microscopes, electric razors, electric toothbrushes, manipulators, masts, play equipment, amusement equipment, riding simulation equipment, vehicle occupant holding equipment and aircraft
- the actuator is a drive unit or an arc unit that generates a linear drive force in valves, brakes, and buckles that are used in general machines including the above-described devices such as OA devices and measurement devices. It can be used as a driving unit for generating a driving force for moving on a track-type orbit composed of, or as a pressing unit for performing a linear operation.
- a driving unit of a positioning device in general, in machinery and equipment, a driving unit of an attitude control device, a driving unit of a lifting device, a driving unit of a transport device, a driving unit of a moving device.
- the actuator can be suitably used as a driving unit of an adjusting device for adjusting the amount or direction, a driving unit of an adjusting device such as a shaft, a driving unit of a guiding device, and a pressing unit of a pressing device.
- the actuator can be suitably used as a drive unit in a joint device, such as a joint unit that can be directly driven, such as a joint intermediate member, or a drive unit that applies rotational motion to a joint.
- the actuator of the present invention is, for example, a drive unit for an ink jet part in an ink jet printer such as a CAD printer, a drive unit for displacing the optical axis direction of the light beam of the printer, and a disk drive device such as an external storage device.
- the actuator of the present invention is, for example, a driving unit of a driving mechanism for moving and installing a measuring unit and a feeding unit such as moving a high frequency feeding unit such as a frequency shared antenna for radio astronomy to a second focal point, and a vehicle. It can be suitably used for a drive unit of a lift mechanism in a mast antenna such as a mounted pneumatically operated telescopic mast (telescopic coping mast).
- the actuator of the present invention is, for example, a driving unit of a massage unit of a chair-shaped massage machine, a driving unit of a nursing or medical bed, a driving unit of a posture control device of an electric reclining chair, a massage machine, a comfortable chair, and the like.
- Backrest of reclining chair used for the work ⁇ Drive section of telescopic rod that allows the Ottoman to be moved up and down, backrest of chair and nursing bed, etc. It can be suitably used as a drive unit used for turning drive of a bed or a bed of a nursery bed or a nursing care bed, and a drive unit for controlling the posture of an upright chair.
- the actuator of the present invention includes, for example, a driving unit of an examination device, a driving unit of a pressure measuring device such as a blood pressure used in an extracorporeal blood treatment device, a driving unit of a catheter, an endoscope device, forceps, and the like.
- the drive unit of a cataract surgery device using sound waves the drive unit of a movement device such as a jaw movement device, the drive unit of the means for relatively expanding and contracting the chassis member of the hoist for the disabled, and the raising and lowering of a nursing bed, It can be suitably used for a drive unit for controlling movement and posture.
- the actuator according to the present invention includes, for example, a drive unit of a vibration isolator that attenuates vibration transmitted from a vibration generating unit such as an engine to a vibration receiving unit such as a frame, and a dynamic valve for an intake and exhaust valve of an internal combustion engine. It can be suitably used as a drive unit of a valve device, a drive unit of a fuel control device of an engine, and a drive unit of a fuel supply device of an engine such as a diesel engine.
- the actuator of the present invention includes, for example, a driving unit of a calibration device of an imaging device with a camera shake correction function, a driving unit of a lens driving mechanism such as a home video camera lens, and a moving lens of an optical device such as a still camera or a video camera.
- Drive unit for the mechanism that drives the group drive unit for the autofocus unit of the camera, drive unit for the lens barrel used in imaging devices such as cameras and video cameras, and drive unit for the auto-guider that captures light from the optical telescope , Stereoscopic visual acuity lens, binoculars, etc., a lens drive mechanism of an optical device having two optical systems or a drive unit of a lens barrel, wavelength conversion of a fiber type wavelength variable filter used for optical communication, optical information processing, optical measurement, etc. It can be suitably used for a driving unit or a pressing unit for applying a compressive force to a fiber, a driving unit for an optical axis aligning device, and a driving unit for a camera mechanism.
- the actuator of the present invention can be suitably used, for example, for a pressing portion of a fixing tool such as fixing a hose fitting to a hose body.
- the actuator of the present invention includes, for example, a driving unit such as a winding spring of a vehicle suspension, a driving unit of a fuel filler opener for unlocking a fuel filler lid of a vehicle, and a driving unit for extending and retracting a bulldozer blade.
- the present invention can be suitably used for a drive unit of a drive unit for automatically switching a gear ratio of a transmission for an automobile and for automatically connecting and disconnecting a clutch.
- the actuator of the present invention includes, for example, a driving unit of a lifting device of a wheelchair with a seat plate lifting device, a driving unit of a lifting device for eliminating a step, a driving unit of a lifting and transferring device, a medical bed, an electric bed, an electric table, Electric chair, nursing bed, lifting table, CT scanner, 0111
- the present invention can be suitably used for a truck cabin tilt device, a drive unit for lifting and lowering a lift and the like, various types of lifting and lowering machinery, and a drive unit for a loading / unloading device of a special vehicle for transporting heavy loads.
- the actuator of the present invention can be suitably used, for example, as a driving unit of a discharge amount adjusting mechanism such as a food discharge nozzle device of a food processing apparatus.
- the actuator of the invention of the present application can be suitably used, for example, as a drive unit for elevating and lowering a truck or a cleaning unit of a cleaning device.
- the actuator according to the present invention is, for example, a driving unit of a measuring unit of a three-dimensional measuring device for measuring the shape of a surface, a driving unit of a stage device, a driving unit of a sensor unit such as a detection system for detecting a tire operating characteristic, and a force sensor.
- the drive unit of the device that gives the initial speed of the shock response evaluation device the drive unit of the piston drive device of the piston cylinder of the device that includes the borehole permeability test device, the drive unit that moves in the elevation direction of the concentrating and tracking type power generator, Alignment is required for the drive unit of the oscillating device of the tuning mirror of the sapphire laser and the oscillation wavelength switching mechanism of the measurement device including the gas concentration measurement device, the inspection device of the printed circuit board, and the inspection device of the flat panel display such as the liquid crystal and PDP.
- Driving unit of an adjustable aperture device used in charged particle beam systems such as systems, driving unit of a support or detection unit of a measurement target in a flatness measuring instrument, and assembly of micro devices, semiconductor exposure It can be suitably used for the drive unit of a precision positioning device such as a device, a semiconductor inspection device, and a three-dimensional shape measuring device.
- the actuator of the present invention can be suitably used, for example, as a driving unit for an electric razor and a driving unit for a fumigation toothbrush.
- the actuator of the present invention is, for example, an imaging device for a three-dimensional object or a drive unit of a device for adjusting the depth of focus of a readout optical system shared by CD and DVD.
- the drive target surface is made into an active curved surface by a plurality of actuators.
- a movable unit having at least one of a driving unit of a variable mirror and a magnetic head such as an optical pickup which can easily change a focal position by approximately forming a desired curved surface by deforming the shape, and linearly moving a moving unit.
- Drive units for disk drives that can operate, magnetic tape heads such as linear tape storage systems, drive units for the head feed mechanism of the assembly, and electrophotographic copiers, printers, facsimile machines, etc.
- a drive unit of an optical disk master exposure apparatus a drive unit of a head drive unit that drives an optical head, a drive unit of an information recording / reproducing apparatus that records information on a recording medium or reproduces information recorded on the recording medium,
- it can be suitably used as a drive unit for opening and closing a circuit breaker or a breaker (a power distribution circuit breaker or a breaker).
- the actuator of the present invention is, for example, a driving unit of a rubber composition press-molding vulcanizing apparatus, and a driving unit of a part aligning apparatus for performing single-row / single-layering of transferred parts and aligning them in a predetermined posture.
- Drive unit of compression molding equipment drive unit of holding mechanism of welding device, drive unit of bag making and filling machine, drive unit of machine tool such as machining center, drive unit of molding machine such as injection molding machine and press machine, printing device
- Driving unit for fluid application equipment such as coating equipment and lacquer spraying equipment, driving unit for manufacturing equipment that manufactures camshafts, etc., driving unit for hoisting equipment for covering materials, and drive for the tuft-restrictor in shuttleless looms Equipment, needle drive system of tufting machine, looper drive system, drive unit such as knife drive system, drive unit of polishing machine that grinds parts such as force grinder and ultra-precision parts, and loom
- a drive unit of a pig frame braking device a drive unit of an opening device forming an opening of a warp for inserting a weft in a loom, a drive unit of a protective sheet peeling device such as a semiconductor substrate, a drive unit of a threading device, Linear control for shifter-fork drive selection in torsion racing
- Drive unit of equipment drive unit of horizontal moving mechanism of anneal window drive unit, support for glass hearth forehearth Arm drive unit, drive unit for moving the rack of the exposure apparatus such as the method for forming the fluorescent screen of the empty picture tube, drive unit for the torch arm of the pole bonding device, drive unit for the bonding head in the XY direction, Driving unit for component mounting process and measurement / inspection process in mounting of chip components and measurement using probe, lifting / lowering driving unit for cleaning tool support of substrate cleaning device, driving for moving detection head to scan glass substrate Drive of the positioning device of the exposure equipment that transfers parts and patterns onto the substrate, drive of the fine positioning device in the sub-micron order in the field of precision processing, etc.Measurement of chemical mechanical polishing tools Exposure apparatus and scanning device used in manufacturing a drive unit of a positioning device of an apparatus, a circuit device such as a conductive circuit element or a liquid crystal display element in a lithography process.
- a reference grid plate of a light beam scanning apparatus is set to the light
- the present invention can be suitably used for a drive unit for displacing the beam in the optical axis direction and a drive unit of a transfer device for transferring the beam in the transverse direction of the conveyor into the article processing unit.
- the actuator of the present invention can be suitably used, for example, as a drive unit of a probe positioning device of a scanning probe microscope such as an electron microscope, and a drive unit of a sample fine-movement device for an electron microscope.
- the actuator of the present invention is, for example, a drive unit of a joint mechanism typified by an automatic welding pot, a robot arm wrist of an industrial robot or a nursing robot, or a manipulator, and a joint other than a direct drive type.
- Drive unit A small object can be arbitrarily placed in the drive unit of the motion conversion mechanism of the slide opening / closing type chuck device used as a hand for robots, etc.
- a drive unit of a micromanipulator for operation, a drive unit of an artificial limb such as an electric prosthesis having a plurality of fingers that can be opened and closed, a drive unit of a handling mouth pot, a drive unit of a prosthetic device, and a drive unit of a power suit.
- the actuator of the present invention can be suitably used, for example, as a pressing portion of a device for pressing an upper rotary blade or a lower rotary blade of a side trimmer.
- the actuary of the present invention is, for example, a drive unit for amusement equipment such as a pachinko machine, a drive unit for an amusement device such as a doll or a pet mouth pot, and a drive unit for a simulation device of a boarding simulation device. It can be suitably used for.
- the actuator of the present invention can be used, for example, in a valve driving section of a valve used in a general machine including the above-mentioned equipment and the like.
- a valve driving section of a reliquefaction apparatus for evaporating helium gas a bellows type sensor Drive unit for pressure control valve, drive unit for opening device to drive pig iron frame, drive unit for vacuum gate valve, drive unit for solenoid operated control valve for hydraulic system, motion transmission device using pivot lever incorporated
- the present invention can be suitably used for a drive unit of a valve, a drive unit of a valve of a movable nozzle of a rocket, a drive unit of a suck back valve, and a drive unit of a pressure regulating valve unit.
- the actuator of the present invention can be used, for example, as a pressing portion of a brake used in a general machine including the above-mentioned devices and the like.
- a brake for emergency use, security use, stop use, etc. can be suitably used for a pressing portion of a braking device suitable for use in a brake, and a pressing portion of a brake structure or a brake system.
- the actuator of the present invention can be used, for example, as a pressing portion of a lock device used in general machines including the above-described devices and the like, for example, a pressing portion of a mechanical lock device, a pressing portion of a steering lock device for a vehicle. , And a pressing portion of a power transmission device having a load limiting mechanism and a coupling release mechanism.
- a monomer and a salt of a dopant ion described in Table 1 are dissolved in a solvent described in Table 1 by a known stirring method, and the monomer of the conductive polymer is adjusted to 0.25 mol, and An electrolytic solution containing the punt salt at the concentration shown in Table 1 was prepared.
- electrolytic polymerization was performed by a constant current method having a polymer current density shown in Table 1. By this electropolymerization, a film-shaped conductive polymer molded article of Example 1 having the conductivity and the film thickness shown in Table 1 was obtained.
- Example 15 the film-like conductive polymer molded articles of Examples 2 to 40, and Examples 44 and 45 were obtained in the same manner as in Example 1. Was done.
- the monomer of the conductive polymer was pyrrole and 3-methylthiophene in a mixing ratio of 1/1 (mol / mol).
- Example 41 The film-form conductivity of Example 41 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used and that the Ti electrode, which was a metal electrode, was used as the working electrode. A polymer molded article was obtained. As the metal electrode in the present application, a commercially available metal electrode was used. (Example 4 2)
- Example 42 The film-form conductivity of Example 42 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used, and the Ni electrode, which was a metal electrode, was used as the working electrode. A polymer molded article was obtained.
- Example 43 The film-form conductivity of Example 43 was obtained by performing the same method as in Example 1 except that the electropolymerization conditions shown in Table 5 were used, and that the Ni electrode, which was a metal electrode, was used as the working electrode. A polymer molded article was obtained.
- Example 1 Except that the electropolymerization conditions of Tables 5 and 6 were used, the same procedures as in Example 1 were performed to obtain the film-shaped conductive polymer molded articles of Comparative Examples 1 to 4.
- the salt of the dopant ion described in Table 7 was dissolved in the solvent described in Table 1 by a known stirring method to contain the monomeric pyrrole at a concentration of 0.225 mol / l.
- An electrolytic solution containing monopant salt at the concentration shown in Table 1 was prepared.
- a metal electrode made of a metal of the metal type shown in Table 1 was used as the working electrode, and a Pt electrode was used as the counter electrode, and electrolytic polymerization was performed by the galvanostatic method with the polymerization current density shown in Table 1. went.
- electrolytic polymerization a film-shaped conductive polymer molded article of Example 46 having the following formula was obtained.
- Example 46 Except for performing the electropolymerization conditions shown in Tables 7, 8, and 10, the same method as in Example 46 was used to obtain a film-shaped conductive polymer molded article of each example.
- Comparative Examples 5 to 16 The film-like conductive polymer molded articles of Comparative Examples 5 to 16 were prepared in the same manner as in Example 46 except that the electropolymerization conditions shown in Tables 9 and 10 were used, and that a glass electrode was used. Obtained.
- Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 7 Comparative example 8 Comparative example 10 Comparative example 9 Using electrodes
- Non-metallic electrode type I TO I TO Solvent MeB MeB DME MeB H20 H20 Polymerization flow density
- TBACF 3 S0 3 triflate Ruo b methanesulfonic acid Tetorabuchirua Nmoniumu
- dopant salt B CF 3 S0 3 Li (Torifuruorome evening lithium Nsuruhon acid) dopant salt C: TBABF 4 (tetrafluoropropoxy O b borate tetra Petit Ruan monitor ⁇ beam) dopant salt D: TBAPFG (to Kisafuruororin tetracalcium Petit Ruan monitor ⁇ G) Dopant salt E: sodium p-toluenesulfonate
- Dopant salt F sodium benzenesulfonate
- PEG polyethylene glycol (molecular weight: 200)
- SF Sulfolane
- Me Sa methyl salicylate
- Tables 1 to 5 show the results.
- the displacement ratio per specific time was measured by the following measurement method, respectively.
- the result of the displacement rate per specific time Table 6 shows.
- the electric conductivity and the film thickness of the molded conductive polymers of Examples 1 to 45 and Comparative Examples 1 to 4 were measured by known methods.
- the film-shaped conductive polymer molded products obtained in Examples 1 to 43 and Comparative Examples 1 and 2 were used as working electrodes having a length of 15 mm and a width of 2 mm, and a platinum plate was used as a counter electrode. the end portion, holds the working electrode in the electrolyte, and connected to a power source via a lead, the potential (-.. 0. 9 tens 0. 7 V v s Ag / Ag +) 1 cycle
- the amount of displacement (displaced length) was measured by applying voltage.
- the difference in displacement obtained by the working electrode extending and contracting in one cycle of application one oxidation-reduction cycle
- the rate was determined.
- electrolyte TEAPF 6 a tetrafluoropropoxy O pyrophosphate tetra- ethyl ammonium Niu unsalted represents ethanesulfonic acid sodium and E t S 0 3 N a.
- the film-shaped conductive polymer moldings obtained in Examples 44 and 45 and Comparative Examples 3 and 4 were used as working electrodes having a length of 15 mm and a width of 2 mm, and a platinum plate was used as a counter electrode. At the end, hold the working electrode in the electrolyte and connect it to the power supply via the lead, and set the potential (+0.9 V vs. AgZAg + or 0.9 V v. Ag / Ag + ), And the displacement 20 seconds after the start of application
- the film-shaped conductive polymer molded products obtained in Examples 46 to 62 and Comparative Examples 5 to 16 were used as working electrodes having a length of 15 mm and a width of 2 mm, a platinum plate was used as a counter electrode, and the conductive polymer was used. A weight is hung on the end of each molded article, the other end is held in the working electrolyte, connected to a power supply via a lead, and the electric potential (0.9 to 10.
- the expansion / contraction ratio with respect to the load weight was measured, and the generated force was measured by converting the measured value into a unit cross-sectional area.
- the conductive polymer molded articles of Examples 59 to 62 and Comparative Examples 15 and 16 and the conductive polymer molded articles of Examples 46 to 62 and Comparative Examples 5 to 16 were obtained.
- the displacement was measured by the same method as the measurement of the expansion and contraction ratio of each, and the maximum generating force of each conductive polymer molded product was obtained.
- the maximum generated force in Table 10 is measured by measuring the expansion / contraction ratio while changing the weight of the weight, and within the range of contraction, the film-shaped conductive polymer molded product immediately before being cut by the weight of the weight. Displaying power.
- the conductivity and the film thickness of the conductive polymer molded products of Examples 46 to 62 and Comparative Examples 5 to 16 were measured by a known method.
- Example 4 The conductive polymer molded article of Examples 6 to 58 corresponds to a conductive polymer molded article manufactured under the same electrolytic polymerization conditions except that an ITO glass electrode, which is a nonmetallic electrode, was used as an electrode.
- the generated force ratio [generated force of the example] Z [generated force of the comparative example]) when the same expansion ratio was shown was calculated. The results are shown in Tables 6-8.
- the conductive polymer molded products of Examples 1 to 45 are conductive polymer molded products containing, as a resin component, the conductive polymer obtained by the first method for producing a conductive polymer of the present invention. is there.
- the conductive polymer molded article of Example 15 used an electrolyte in which trifluoromethanesulfonate ion was used as a dopant anion, and the solvent was a mixed solvent (1: 2) of ethylene carbonate and propylene-one-ponate.
- This is a conductive polymer molded article obtained by a method for producing a conductive polymer by an electrolytic polymerization method.
- the conductive polymer molded product of Comparative Example 1 was a conductive polymer molded product in which the solvent of the electrolytic solution was water, and was electrolytically polymerized with an electrolytic solution containing conventional dopant, p-toluenesulfonate. is there.
- the conductive polymer molded article of Example 15 was subjected to electrolytic expansion and contraction using sodium chloride, which is a conventional working environment, as a working electrolyte, the expansion ratio was 3.1% as shown in Table 2.
- the expansion and contraction ratio was 1.3%.
- the conductive polymer molded article of Example 15 has one oxidation-reduction cycle even in an aqueous sodium chloride solution, which is a conventional operating environment, as compared with a conventional conductive polymer molded article containing a dopant. Good expansion and contraction with a stretch ratio of about 2.4 times per unit was achieved.
- the conductive polymer molded articles were respectively the conductive polymer molded articles obtained by the method for producing a conductive polymer of the present invention.
- the conductive polymer molded article was expanded and contracted by electrochemical oxidation-reduction of one redox cycle, and as a result, as shown in Tables 1 to 5, the expansion ratio was 5% or more.
- the conductive polymer was a polymer having a high conductivity obtained by electrolytic polymerization with an electrolyte containing p-toluenesulfonic acid ion, which is a conventional dopant, in which the solvent of the electrolyte was water.
- the expansion and contraction ratio was as low as 1.0%. That is, the conductive polymer molded article of the present invention is at least one selected from the group consisting of trifluoromethanesulfonate ion, a fluorine atom bonded to a central atom, and a sulfonate having 3 or less carbon atoms.
- the conductive polymer molded articles of Examples 44 and 45 are the conductive polymer obtained by the production method of the present invention corresponding to the conductive polymer molded articles of Examples 15 and 4, respectively. It is a molded product.
- the conductive polymer molded articles of Comparative Examples 3 and 4 are conductive polymer molded articles corresponding to Comparative Examples 1 and 2, respectively.
- the conductive polymer molded article of Comparative Example 3 had an expansion / contraction ratio of 0.4% per specific time, whereas the conductive polymer molded article of Example 36 had a contraction rate of 0.4%.
- the expansion and contraction rate per specific time was improved by 1.7%, about 4 times.
- the conductive polymer molded article of the present invention electrolytic stretching with a rapid displacement can be realized.
- an electrolytic environment containing at least one compound selected from the group consisting of trifluoromethanesulfonate ion, anion containing a plurality of fluorine atoms with respect to the central atom, and a sulfonate having 3 or less carbon atoms in the working environment of electrolytic stretching.
- the conductive polymer molded article of Comparative Example 4 had an expansion / contraction ratio of 0.4% per specific time, whereas the conductive polymer molded article of The expansion and contraction rate per hour was improved by 3.9%, about 10 times.
- the conductive polymer molded articles of Examples 46 to 62 are conductive polymer molded articles containing, as a resin component, the conductive polymer obtained by the second step of the method for producing a conductive polymer of the present invention. .
- Example 4 The conductive polymer molded articles of 6 to 58 have a 3 to 5% expansion / contraction, which is a shrinkage per oxidation-reduction cycle, which was not obtained by using the conventional conductive polymer.
- the generated force showed a large value of 3.9 to 15.6 MPa, and it was a conductive polymer molded article having an excellent balance between expansion and contraction rate and generated force.
- the conductive polymer molded articles of Examples 46 to 58 use metal electrodes, and thus are 2.0 to 10.5 times as large as the corresponding examples using non-metal electrodes. This is an excellent improvement in generating power.
- Example 59 to 62 an excellent maximum power of 13.4 to 18.4 MPa was obtained, but in Comparative Examples 17 and 18, The maximum generated force was 0.7 MPa and 3.5 MPa.
- the maximum generated force refers to the generated force immediately before the film-shaped conductive polymer molded product is cut by the weight within the shrinking range by measuring the expansion / contraction ratio while changing the weight of the weight.
- the contraction ratio (shrinkage ratio) of the conductive polymer molded article was measured as the expansion and contraction ratio. Rate. Industrial applicability
- the conductive polymer obtained by the method for producing a conductive polymer according to the present invention can expand and contract at an excellent expansion and contraction ratio due to electrolytic expansion and contraction. Therefore, the conductive polymer is superior in practicability because it performs a larger motion than before, and is useful for applications such as artificial muscles, robot arms, and artificial hands.
- a conductive polymer molded article, a laminate, and an actuate using the conductive polymer obtained by the method for producing a conductive polymer of the present invention expand and contract at an excellent expansion and contraction ratio due to electrolytic expansion and contraction.
- the conductive polymer molded article obtained by the method for producing a conductive polymer according to the present invention has trifluoromethanesulfonate ion and central atom in the working environment of electrolytic expansion and contraction.
- the conductive polymer molded article containing the conductive polymer as a resin component obtained by the first method of the present invention for producing a conductive polymer is used as a working environment for electrolytic expansion and contraction, by using trifluoromethanesulfonic acid.
- Conductivity by electrochemical oxidation-reduction in an electrolyte containing at least one compound selected from the group consisting of ions, ions containing a plurality of fluorine atoms with respect to the central atom, and sulfonates having 3 or less carbon atoms By stretching a polymer molded article, it exhibits a stretch rate per specific time of about 10 times or more as compared to a conventional conductive polymer molded article having elasticity. Therefore, this conductive polymer molded product can be used as a drive part for applications that require a fast response to displacement commands.
- the conductive polymer molded article containing the conductive polymer obtained as the resin component by the second method of the present invention for producing a conductive polymer is a conventional conductive polymer molded article having elasticity.
- a superior expansion / reduction rate per oxidation-reduction cycle is exhibited during electrolytic expansion and contraction, and excellent power generation is obtained.
- the obtained power is twice or more superior to that of the conductive polymer obtained by electrolytic polymerization using the nonmetal electrode.
- the conductive polymer molded article is suitable for applications such as micromachines and artificial muscles.
- the conductive polymer molded article is further suitable as a micromachine because of its high mechanical strength.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Manipulator (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03784596.3A EP1550689B1 (en) | 2002-08-09 | 2003-08-08 | Process for producing conductive polymer |
AU2003254887A AU2003254887A1 (en) | 2002-08-09 | 2003-08-08 | Process for producing conductive polymer |
US10/523,985 US20060076540A1 (en) | 2002-08-09 | 2003-08-08 | Process for producing conductive polymer |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
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JP2002-233617 | 2002-08-09 | ||
JP2002233617 | 2002-08-09 | ||
JP2002265859 | 2002-09-11 | ||
JP2002-265859 | 2002-09-11 | ||
JP2002-289365 | 2002-10-02 | ||
JP2002289365 | 2002-10-02 | ||
JP2002307472 | 2002-10-22 | ||
JP2002-307559 | 2002-10-22 | ||
JP2002-307472 | 2002-10-22 | ||
JP2002307559 | 2002-10-22 |
Publications (1)
Publication Number | Publication Date |
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WO2004014987A1 true WO2004014987A1 (ja) | 2004-02-19 |
Family
ID=31721819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2003/010111 WO2004014987A1 (ja) | 2002-08-09 | 2003-08-08 | 導電性高分子の製造方法 |
Country Status (4)
Country | Link |
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US (1) | US20060076540A1 (ja) |
EP (1) | EP1550689B1 (ja) |
AU (1) | AU2003254887A1 (ja) |
WO (1) | WO2004014987A1 (ja) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005116998A1 (ja) * | 2004-05-27 | 2005-12-08 | Sanyo Electric Co., Ltd | レンズ駆動装置および光ピックアップ装置 |
WO2012133315A1 (ja) * | 2011-03-28 | 2012-10-04 | 富士フイルム株式会社 | 導電性組成物、当該組成物を用いた導電性膜及びその製造方法 |
JP2012251132A (ja) * | 2011-03-28 | 2012-12-20 | Fujifilm Corp | 導電性組成物、当該組成物を用いた導電性膜及びその製造方法 |
US9445501B2 (en) | 2011-03-28 | 2016-09-13 | Fujifilm Corporation | Electrically conductive composition, electrically conductive film using the composition and a method of producing the same |
Also Published As
Publication number | Publication date |
---|---|
AU2003254887A1 (en) | 2004-02-25 |
EP1550689A4 (en) | 2008-10-08 |
EP1550689B1 (en) | 2013-04-24 |
EP1550689A1 (en) | 2005-07-06 |
US20060076540A1 (en) | 2006-04-13 |
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