JP2006125396A - Actuator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actuator, which is flexibly and smoothly operated, and of which operation quantity and expansion ratio can be increased. <P>SOLUTION: This actuator comprises a plurality of unit actuators coaxially disposed and comprising cylindrical members 1a, 1b, and 1c disposed coaxially at an interval from one another, and having different diameters, and expansible actuator parts 2 to connect the outer wall of the inner cylindrical member to the inner wall of the outer cylindrical member. It is provided with a means to supply drive energy to the actuator parts 2. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer battery such as a lithium ion secondary battery using a conjugated polymer, a solar battery, a display, a light modulation element, an electrochromic element used for a memory medium, an organic transistor, a functional element used for a sensor, The present invention also relates to actuators used in medical devices, various robots, nursing care devices, data gloves capable of dynamic feedback, and the like.

  A semiconducting or conductive polymer such as a conjugated polymer is excellent in moldability and can be easily formed into a thin film. For this reason, application to various functional elements such as electrochromic elements is expected by combining a semiconducting or conductive polymer thin film with an ion conductive polymer thin film such as a polymer electrolyte. For example, an electrochromic device utilizes a color change caused by carrier injection from an ion conductive polymer thin film to a semiconductor or conductive polymer thin film. Also, it can be used as an actuator using a polymer thin film whose molecular volume is changed by an electrochemical reaction when ions are implanted through a solid electrolyte.

  Such a functional element exhibits a function when a carrier passes through an interface between a semiconducting or conductive polymer thin film and an ion conductive polymer thin film, so that the interface between the two is adhered in a large area. It is important that

  However, in the structure in which two types of polymer thin films are laminated, it is difficult to increase the area of the interface, and it is difficult to improve the response speed and output. Moreover, in many cases, a large electric field or stress is applied to the interface, so that deterioration or peeling is likely to occur, causing a decrease in durability.

  In addition, an actuator using a conjugated polymer thin film or a polymer gel as described above can be operated softly, lightly and flexibly. Therefore, application as an artificial muscle used for a prosthetic limb or an actuator used for a medical device or a nursing robot is expected. However, an actuator using a polymer thin film has a small expansion / contraction rate and operation amount. For example, an actuator that drives polyaniline, which is a conjugated polymer, in an electrolyte solution can provide a driving force that is about an order of magnitude higher than that of living muscles. It is about an order of magnitude smaller than the expansion rate of about 30%. For this reason, it is requested | required that expansion and contraction rate and an operation amount should be expanded further, and the bimorph structure is employ | adopted typically.

  However, since the bimorph structured actuator bends, its usage is limited. Further, since a bending torque is applied to the thin film constituting the actuator, it is difficult to improve the effective output. Note that the expansion / contraction ratio cannot be increased by simply connecting or stacking a plurality of actuators in series along the expansion / contraction direction in order to increase the operation amount.

  An object of the present invention is to provide a functional element that has an element structure having a sufficiently large interface area and high interface durability and can be used favorably as an electrochromic element or an actuator. Another object of the present invention is to provide an actuator that can be operated flexibly and flexibly and that can increase the operation amount and the expansion / contraction rate.

  The actuator according to the present invention is a telescopic actuator that connects a cylindrical member having a different diameter coaxially arranged at an interval, and an outer wall of the inner cylindrical member and an inner wall of the outer cylindrical member. And a means for supplying drive energy to the actuator unit.

  In this actuator, it is preferable that a plurality of unit actuators are coaxially arranged with the inner cylindrical member, the outer cylindrical member, and an actuator portion connecting them as unit actuators.

  Since this actuator operates along the direction of expansion and contraction of the actuator part, it can be used in various forms depending on the arrangement of the actuator part. Further, when a plurality of unit actuators are arranged coaxially, the operation amount can be increased.

  According to the present invention, it is possible to provide a functional element that has an element structure having a sufficiently large interface area and high interface durability, and can be favorably used as an electrochromic element or an actuator. Further, it is possible to provide an actuator that is flexible and operates flexibly, and that can increase the operation amount and the expansion / contraction rate.

  Hereinafter, the present invention will be described in more detail.

  The functional element of the present invention contains a semiconductor or conductive first organic polymer chain and an ion conductive second organic polymer chain.

  Semiconductive or conductive organic polymers are those in which a molecular structure of photocharge generation or carrier transport is bonded in the main chain of an electrically inactive polymer chain or in a pendant form as a side chain. Can be mentioned. The electrically inactive polymer chain is a polyethylene chain, a polyether chain, a polyester chain, a polyamide chain, a polyimide chain, or the like. Examples of the photocharge-generating or carrier-transporting molecular structure include the following. For example, phthalocyanine derivative, naphthalocyanine derivative, azo compound derivative, perylene derivative, indigo derivative, quinacridone derivative, polycyclic quinone derivative (such as anthraquinone), cyanine derivative, fullerene derivative, nitrogen-containing cyclic Compound derivatives (indole, carbazole, oxazole, indoxazole, thiazole, imidazole, pyrazole, oxadiazole, pyrazoline, thiadiazole, triazole, etc.), hydrazone derivatives, triphenylamine derivatives, triphenylmethane derivatives, stilbene derivatives, quinone compound derivatives ( Anthraquinone, diphenoquinone, etc.) and polycyclic aromatic compound derivatives (anthracene, bilene, phenanthrene, coronene, etc.).

  Further, a conjugated polymer may be used. Conjugated polymers include aromatic conjugated polymers (such as polyparaphenylene), aliphatic conjugated polymers (such as polyacetylene), heterocyclic conjugated polymers (such as polypyrrole and polythiophene), and heteroatoms containing heteroatoms. Examples include conjugated polymers (polyaniline, polyphenylene sulfide, etc.). Alternatively, a composite conjugated polymer having a structure in which structural units of these conjugated polymers are alternately bonded, specifically, poly (phenylene vinylene), poly (arylene vinylene), or the like may be used. In addition, oligosilanes such as polysilane and disilanylene, and polymers with alternating electronic structures (disilanylene allylene polymer, (disilanylene) ethenylene polymer, (disilanylene) ethynylene polymer, etc.), phosphorus-based or nitrogen-based inorganic A polymer (polymer such as phthalocyanate polysiloxane) in which an aromatic ligand is coordinated to a polymer chain may be used.

  Examples of ion-conductive organic polymers include polyethers (polyethylene oxide (PEO), etc.), polyesters, polyamines, polyimines, polysulfides, comb-type polyether derivatives having an oligoether chain in the side chain, and polyelectrolyte-type ion conductors. Is mentioned.

  In the functional element of the present invention, a first phase (referred to as A phase) formed by agglomeration of a semiconducting or conductive first organic polymer chain (referred to as organic polymer chain A), and an ion conductive The second phase (referred to as B phase) formed by aggregation of the second organic polymer chain (referred to as organic polymer chain B) forms a three-dimensional co-continuous microphase separation structure, and both phases are at the interface. A chemically bonded multi-component multi-phase polymer molding is used. In the B phase, an organic salt such as a lithium salt or an ammonium salt, an inorganic salt, or a polymer salt such as an ion exchange resin is mixed.

  In order to form a good three-dimensional co-continuous microphase separation structure, the polymer chain A (or a precursor such as a monomer or oligomer) and the polymer chain B (or a precursor such as a monomer or oligomer) are not It is preferable that they are compatible. The chemical bond at the interface between the A phase and the B phase is preferably a covalent bond. Therefore, it is preferable to use an AB type diblock copolymer comprising two kinds of polymer chains A and polymer chains B, or an ABA type or a BAB type triblock copolymer. The molecular weight of each block constituting the block copolymer is preferably 10,000 or more. In some cases, a star-type copolymer or a graft-type copolymer may be used.

  In order to synthesize the block copolymer as described above, after polymer A and polymer B are synthesized in advance, terminal functional groups may be reacted with each other, or polymer B having a functional group introduced at the terminal may be reacted. In the presence of the polymer, the monomer of the polymer A may be polymerized by an appropriate method such as living polymerization. For example, a triblock copolymer or a diblock copolymer can be synthesized by oxidative polymerization of aniline in the presence of polyethylene oxide having an aminophenyloxy group at the terminal. In addition, for example, one polymer incompatible with the other and a precursor oligomer of the other polymer are mixed to form a phase separation structure, and then reacted by heating, light irradiation, or addition of a catalyst to form a final block. A copolymer may be synthesized. In this case, the block copolymer can be synthesized without destroying the phase-separated structure by appropriately selecting the reaction conditions such as reaction at a temperature lower than the glass transition temperature of the block copolymer to be synthesized. .

  The above block copolymer is dissolved in a suitable solvent to prepare a coating solution, and coated on a suitable substrate and dried to form a polymer molded body (thin film) having a three-dimensional co-continuous microphase separation structure. ) Can be produced. Alternatively, the block copolymer may be melted, applied to a suitable substrate, molded, and then cooled to produce a molded body.

  The phase separation structure formed using the block copolymer as described above is different from a simple phase separation structure from a mixture, and is often very regular having unit cells on the order of several nm to several tens of nm. The microstructure is shown. For example, a very regular three-dimensional co-continuous microphase separation structure similar to the crystal structure, called the OBDD structure, is formed. In addition to the OBDD structure, various structures such as a lamellar catenoid structure, a T-surface structure, and a disordered structure are formed. When a three-dimensional network-like phase separation structure is formed, the average diameter of the openings of each phase is generally in the range of about 10 to 100 nm. The average diameter of the opening varies depending on the molecular weight of the block copolymer and the combination of polymer chains. The average diameter of the openings is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 20 nm or less.

In the three-dimensional bicontinuous microphase separation structure, the A phase and the B phase each form a three-dimensional network structure, and these three-dimensional network structures are intertwined with each other. Moreover, since each phase is continuous, it can be considered that all the phase separation domains are connected. In such a phase separation structure, the area of the interface between the A phase and the B phase (interfacial area per unit volume of each phase) is very large, such as several m ² / g, and in some cases about 1000 m ² / g. The area of the interface is preferably 10 m ² / g or more. It is difficult to obtain such a large interfacial area with a phase separation structure from a simple mixture. Thus, in the polymer molded body constituting the functional element of the present invention, the exchange of carriers (electrons, holes or ions) proceeds very smoothly between the A phase and the B phase having a very large interface area. Therefore, it is advantageous for improving response speed and output.

  In the above phase separation structure, each polymer chain aggregates in a state of penetrating the interface between the A phase and the B phase, and the A phase and the B phase are completely joined by chemical bonding. Separation of the interface does not occur unless the molecular chain is broken. Therefore, even if a large electric field or stress is applied to the interface, a decrease in durability can be suppressed.

  In order to stabilize the phase separation structure, a cross-linking agent is added to the polymer material or a crosslinkable group is introduced into the polymer chain, and the polymer material is cross-linked three-dimensionally after the phase separation structure is formed. Also good. By crosslinking in this way, the thermal or mechanical strength of the polymer molded body can be further improved.

  In the functional element of the present invention, as means for supplying electric power to each phase of the polymer molded body, electrodes connected to the A phase and the B phase are used. As the electrode material, an inorganic or organic conductor or semiconductor can be used. The shape of the electrode is not particularly limited, and may be any of a plate shape, a thin film shape, a porous film shape, a rod shape, a fiber shape, a mesh shape, and a dot shape. In this case, by utilizing the difference in the affinity of the electrode material with respect to the A phase and the B phase, the electrode can be contacted with only one of the phases. For example, if the electrode material has a high affinity with the A phase but a low affinity with the B phase, the phase A is formed on the electrode surface in the process of phase separation after coating or melting the block copolymer on the electrode. Since it selectively aggregates, an electrode connected only to the A phase can be formed. Further, in order to give the electrode affinity for either the A phase or the B phase, a homopolymer composed of the same polymer chain as that phase may be formed on the electrode surface. In a practical element structure, another semiconductor or conductive layer may be formed between the electrode and the A phase, or another ion conductive layer may be formed between the electrode and the B phase. It may be inserted.

  Thus, the electrodes are connected to the A phase and the B phase, respectively, and as described above, the A phase and the B phase each form a three-dimensional network structure inside the phase separation structure, and each phase is continuous. . For this reason, the electrical connection state of the functional element of the present invention is equivalent to a conventional element having a laminated structure of the polymer thin film A and the polymer thin film B.

  The functional element of the present invention can be used as, for example, an electrochromic element. Specifically, a polymer having a three-dimensional co-continuous microphase separation structure using a block copolymer comprising a conductive polymer chain A such as polyaniline or polypyrrole and an ion conductive polymer chain B such as polyethylene glycol. An electrochromic element in which a thin film is formed and an electrode connected to each of the A phase and the B phase can be manufactured. In such an electrochromic device, power can be supplied from an electrode, and carriers can be injected into the A phase through the ion conductive B phase, thereby causing a color change in the conductive A phase. This electrochromic element has a high response speed, and a sufficient optical density can be obtained by increasing the thickness of the polymer thin film.

  FIG. 1 shows an example of an electrochromic device according to the present invention. In FIG. 1, a phase separation film 103 is formed by applying a solution of a block copolymer on a transparent electrode 102 formed on a glass substrate 101 and drying it. A counter electrode 105 is formed on the phase separation membrane 103 via an electrolyte layer 104. The electrolyte layer 104 may be a solid electrolyte impregnated with an electrolyte solution, or may be filled with an electrolyte solution.

  Here, a phase separation film composed of another kind of polymer may be provided on the counter electrode 105 side, and the electrochromic phenomenon may be caused simultaneously on the counter electrode 105 side.

  Note that an additive such as a dopant may be unevenly distributed in either the A phase or the B phase in order to improve the performance of the functional element. In order to produce such an element, a block copolymer coating solution is mixed with a dopant having good affinity specifically for either the A phase or the B phase, and only one of the phases is separated during the phase separation process. The dopant can be unevenly distributed. Further, the dopant may be chemically bonded to one polymer chain constituting the block copolymer.

  In the three-dimensional co-continuous microphase separation structure, the bonding points between the polymer chain A and the polymer chain B are formed in a sheet shape at the interface between the A phase and the B phase. Therefore, when a functional molecule is introduced at the bonding point of both polymer chains, an ultrathin film at the molecular level composed of the functional molecule can be formed at the interface between the A phase and the B phase. For example, if a molecule exhibiting electrochromic properties is used as the functional molecule, an electrochromic device with very high efficiency and high-speed response can be formed.

  Similarly, a very thin insulating layer can be formed at the interface between the A phase and the B phase. For example, when oligo (di-t-butoxysiloxane) is aggregated in the form of a sheet at the interface between the A phase and the B phase, and preferably heated while acting an acid catalyst, the elimination of the t-butoxy group and the generated silanol group A dehydration condensation reaction occurs and a silicon oxide film is generated. Thus, the insulating layer formed at the interface can be made very thin and, in principle, no defect occurs. Therefore, it is very useful when forming an electrolytic capacitor or the like.

  Next, the actuator of the present invention uses a polymer molded body in which a phase composed of an organic polymer chain whose molecular volume is changed by an electrochemical reaction and a phase composed of a solid electrolyte form a co-continuous structure.

  Examples of the organic polymer whose molecular volume is changed by an electrochemical reaction include a conductive polymer made of a conjugated polymer such as polyaniline or polypyrrole.

  Examples of the solid electrolyte include an ion conductive polymer such as polyethylene oxide (PEO) and a polymer gel impregnated with an electrolyte solution.

  As the polymer molded body constituting this actuator, one having a three-dimensional co-continuous microphase separation structure using a block copolymer may be used in the same manner as the functional element described above. However, regarding the polymer molded body used in the actuator, the interface between the two polymer phases does not necessarily have to be joined by chemical bonding. For example, a three-dimensionally shaped molded body of polyaniline or polypyrrole may be formed, and the opening may be filled with a polymer gel impregnated with a solid electrolyte or an electrolyte solution. Specifically, an acrylonitrile porous gel impregnated with a propylene carbonate solution of an electrolyte salt can be used.

  As means for supplying electric power to each phase of the polymer molded body constituting the actuator, electrodes connected to each of the conductive polymer phase and the solid electrolyte phase are used as in the above-described functional element.

  As an electrode connected to the conductive polymer phase, an electrode made of an electrochemically stable material is used. Specifically, it is preferable to use noble metals (platinum, gold) or carbon. The form of the carbon electrode may be any of film, fiber, and cloth. Note that the electrode is not necessarily provided when the conductive polymer exhibits high conductivity.

The electrode connected to the solid electrolyte phase preferably has a large contact area at the interface with the electrolyte. For example, platinum black and a porous carbon electrode are mentioned. It is preferable to use a porous carbon electrode having a surface area of about 1000 to 2000 cm ² / g.

  Even in this actuator, the area of the interface between the conductive polymer phase and the solid electrolyte phase of the polymer molded body is very large, so that the electrolyte exchange between the solid electrolyte phase and the conductive polymer phase is very smooth. Therefore, it is advantageous for improving the response speed.

  The actuator structure may have a single polymer molded body or a so-called bimorph structure. Examples of the actuator according to the present invention are shown in FIGS.

  The actuator shown in FIG. 2 is obtained by connecting a platinum electrode 202 to one surface of one end of a phase separation membrane 201 and a carbon electrode 203 having a solid electrolyte membrane 204 formed on the other surface. 3 is a so-called bimorph type in which an electrolyte layer 205 is sandwiched between two phase separation films 201 and platinum electrodes 202 are connected to the two phase separation films 201, respectively. Any of the actuators shown in FIGS. 2 and 3 may be sealed with a sealing film.

  Next, an actuator having a novel structure according to the present invention will be described. This actuator has a cylindrical member having a different diameter and is coaxially arranged at an interval, and an extendable actuator portion that connects the outer wall of the inner cylindrical member and the inner wall of the outer cylindrical member to each other. .

  4A, 4B, and 4C show the basic structure of this actuator. (A) is a perspective view, (B) is a diagram in which (A) is broken, and (C) is a diagram seen from an end surface. As shown in FIG. 4, a pair of cylindrical members 1a and 1b having different diameters are arranged coaxially with a gap therebetween, and an outer wall on one end side (right side in the drawing) of the inner cylindrical member 1a is disposed in the gap therebetween. An extendable actuator portion 2 is provided so as to connect the other end side (left side in the figure) inner wall of the outer cylindrical member 1b.

  This actuator is used, for example, immersed in an electrolyte solution. The actuator portion is made of a conductive polymer such as a conjugated polymer, and operates by swelling due to intrusion of electrolyte ions accompanying an electrochemical reaction. In this case, in order to supply drive energy to the actuator unit 2, the entire actuator is immersed in the electrolyte solution in a state in which the actuator unit 2 can be energized, and the counter electrode is immersed in the electrolyte solution and power is supplied from the power source. To do. The actuator unit 2 can be energized, for example, by bonding the actuator unit 2 to the tubular member with a conductive adhesive layer and connecting a lead wire from a power source to the conductive adhesive layer. Then, according to the expansion and contraction of the actuator portions 2 and 2, the outer cylindrical member 1b slides to the right or left in the drawing with respect to the inner cylindrical member 1a.

  In FIG. 4, two cylindrical members are used and two actuator parts are arranged in linear and symmetrical positions. However, these shapes, numbers and arrangements are used as desired. It can be freely selected according to the form.

  In order to increase the operation amount and the expansion / contraction rate in the actuator of the present invention, a plurality of unit actuators are used by using the inner cylindrical member, the outer cylindrical member and the actuator unit connecting them as a unit actuator as shown in FIG. It is preferable to arrange them coaxially.

  5A and 5B show examples of such actuators. As shown in FIG. 5, cylindrical members 1a, 1b, 1c, and 1d having a length of β and different diameters are coaxially arranged at intervals, and one end side (right side in the figure) outer wall of the inner cylindrical member The actuator portion 2 is provided so as to extend and contract so as to connect the inner wall to the other end side (left side in the drawing) of the outer cylindrical member. If each actuator portion contracts by α, the cylindrical member 1b slides by α relative to the cylindrical member 1a, and the cylindrical member 1c slides by α relative to the cylindrical member 1b. The member 1d slides by α relative to the cylindrical member 1c. As a result of the plurality of unit actuators operating in concert as described above, the total operation amount is integrated to 3α. In addition, since the expansion / contraction rate is the ratio of the operation amount to the length β of the cylindrical member, the expansion / contraction rate increases as the operation amount increases. Such an effect cannot be obtained by simply connecting the actuators in series. That is, in the case of connecting in series, the operation amount can be increased, but since the length of the initial state is also long, the expansion / contraction rate cannot be increased. In the actuator of the present invention, in order to increase the expansion / contraction rate effectively, it is preferable that the number of unit actuators is large.

  In the above description, the operation when the actuator portion contracts has been described. However, when the actuator portion extends, only the operation direction is reversed, and the effect of increasing the operation amount and the expansion / contraction rate is the same as described above. can get. Various modifications of the actuator of the present invention can be considered as described below.

  The actuator shown in FIGS. 6A, 6B, and 6C uses two types of actuator portions 2 and 3 to connect the inner cylindrical member 1a and the outer cylindrical member 1b. . The actuator unit 2 connects the right outer wall of the inner cylindrical member 1a and the left inner wall of the outer cylindrical member 1b. The actuator unit 3 connects the left outer wall of the inner cylindrical member 1a and the right inner wall of the outer cylindrical member 1b. And these actuator parts 2 and 3 are operated so that one contracts and the other expands. For example, when the actuator unit 2 is contracted and the actuator unit 3 is extended, the outer cylindrical member 1b slides to the right relative to the inner cylindrical member 1a as shown in FIG. Forward operation). When the actuator unit 2 is extended and the actuator unit 3 is contracted, the outer cylindrical member 1b slides to the left relative to the inner cylindrical member 1a as shown in FIG. 6C. (Reverse operation).

  With this actuator, the operation amount and output during forward operation and reverse operation can be made equal. Here, in the actuator of FIG. 5, there is a possibility that the operation amount and the output obtained when the actuator unit extends are smaller than when the actuator unit contracts. This is because the actuator portion has flexibility and may buckle when a load is applied during expansion. On the other hand, in the actuator of FIG. 6, buckling is unlikely to occur because the contracted actuator portion bears a part of the load during forward operation or reverse operation.

  In the actuator shown in FIGS. 7A and 7B, cylindrical members 4a and 4b having different diameters, which are formed of a material that can be expanded and contracted similarly to the actuator portion, are arranged coaxially with an interval therebetween, and an inner cylinder is formed. The actuator parts 2 and 2 which can be expanded and contracted are provided so as to connect the outer wall on the one end side of the cylindrical member 4a and the inner wall on the other end side of the outer cylindrical member 4b. And when the actuator part 2 shrink | contracts, it act | operates so that the cylindrical members 4a and 4b which serve as an actuator part may extend. This actuator can increase the operation amount and the expansion / contraction rate compared to the actuator in which the cylindrical member does not expand.

  The actuator shown in FIGS. 8A, 8B, and 8C is obtained by arranging the actuator portion 2 at an angle with respect to the central axes of the cylindrical members 1a and 1b. (A) is a whole perspective view, (B) is a figure which shows arrangement | positioning of the actuator part 2 with respect to the inner cylindrical member 1a. In this actuator, as shown in (C), as the actuator portion 2 expands and contracts, the cylindrical member slides in the axial direction and rotates (twists) around the axis.

  In the actuator shown in FIG. 9, the actuator unit 2 is arranged along the circumferential direction of the cylindrical members 1a, 1b, and 1c. In this actuator, for example, when the actuator unit 2 contracts, the cylindrical member rotates in the direction of the arrow about the axis.

  Next, the material and shape of the cylindrical member and actuator part constituting the actuator of the present invention, and the electrolyte solution and the like will be described.

  The cylindrical member is preferably made of a material that has flexibility but has a sufficiently large longitudinal rigidity, and that does not buckle and deform when a compressive stress is applied. Specifically, polyimide, polyamide (for example, various nylons and aramid resins), polyether (for example, polyoxymethylene), polyester (for example, polyethylene phthalate), vinyl resin (for example, polyvinyl chloride), epoxy resin, phenol resin, fluorine resin (For example, PTFE) and ion exchange resins are preferred. Further, since the cylindrical member rubs against the actuator portion and the other cylindrical member, it is preferable that the surface has a small frictional resistance. From this viewpoint, the material of the cylindrical member is preferably a self-lubricating material such as nylon or fluororesin. A resin mixed with a solid lubricant (for example, tungsten disulfide or molybdenum disulfide) or a resin whose surface is coated with a fluororesin or various lubricants may be used. The cylindrical member may be formed using these resins alone, or may be formed by mixing or alloying a plurality of resins. Generally, pipes made of these resins are used for the cylindrical member, but it is also possible to use a laminate of several resin films and molded into a cylindrical shape. A composite of resin and glass fiber or carbon fiber may be used. A woven fabric or a nonwoven fabric knitted with resin fibers as described above may be used.

  As shown in FIGS. 4 to 9, the shape of the cylindrical member is not particularly limited, although a shape close to a cylinder is generally used. However, it is desirable that the cross-sectional shape is constant in order to ensure smooth operation of the actuator. Further, the cylindrical member located on the innermost side is not necessarily a hollow cylinder, and may be a solid rod.

  In order to increase the rigidity with respect to longitudinal stress and prevent buckling, the cylindrical member is generally preferably a complete cylindrical shape having no cut on the peripheral surface. However, for example, as shown in various examples in FIG. 10, it may have a cross-sectional shape that is not completely closed.

  Further, in order to reduce frictional resistance due to contact with the actuator part or other cylindrical member, a contact area may be reduced by forming a groove or an emboss (microprojection group) on the surface of the cylindrical member. . In particular, it is preferable to form the groove along the long axis direction of the cylindrical member because the cylindrical member is less likely to buckle. In the type of actuator in which the actuator part is immersed in the electrolytic solution, the use of a cylindrical member in which grooves or embosses are formed is advantageous in that the circumference of the electrolytic solution around the actuator part is improved. In order to improve the electrolyte periphery, a large number of slits may be formed in the cylindrical member, or a porous cylindrical member may be used.

  Moreover, as shown in FIG. 11, by providing the cylindrical member 1a with the rib 6 and installing the actuator unit 2 between the two adjacent ribs 6 and 6, the actuator unit 2 and the cylindrical members 1a and 1b The sliding resistance can be reduced. A cylindrical member as shown in FIG. 11 can be manufactured by, for example, an optical modeling method. Further, by the composite stereolithography disclosed in JP-A-7-60843, the cylindrical member can be formed by stereolithography using a predetermined resin, and at the same time, the actuator portion can be formed by stereolithography. .

  As a material for the actuator portion, a shape memory resin, a chemomechanical gel, or a conjugated polymer (for example, polyaniline) can be used.

  In an actuator portion using a shape memory resin, a heating energy or a cooling Peltier element made of a superelastic metal material or an electric heating element such as carbon is installed in a shape memory resin molded body to supply driving energy. The electrothermal element is preferably installed so as not to hinder the deformation of the molded body functioning as the actuator section and to conduct heat well to the molded body.

  As the chemomechanical gel, an electrically responsive chemomechanical gel, for example, a copolymer gel of polyvinyl alcohol and sodium polyacrylate, poly-2-acrylamide-2-methylpropanesulfonic acid gel, acrylonitrile gel, acrylamide gel, or Examples thereof include ion exchange resins (perfluorosulfonic acid, polyethylene sulfonic acid, etc.). A driving electrode made of a platinum thin film, a gold thin film, or a conductive polymer thin film is provided on the surface or surface layer of the electrically responsive chemomechanical gel molded body so as not to hinder the deformation of the gel to supply driving energy. . Further, as the chemomechanical gel, a thermoresponsive chemomechanical gel, for example, an IPN gel of poly-N-isopropylacrylamide and polyacrylamide, or a polyvinyl methyl ether gel can be used. For the thermoresponsive chemomechanical gel, a driving energy is supplied by installing a heating heater or a cooling Peltier element made of a superelastic metal material or an electrothermal element such as carbon. In addition, a gel that is deformed by a change in pH, such as a polysilamine gel, can also be used.

  Examples of the conjugated polymer include heterocyclic conjugated polymers such as doped polypyrrole and polythiophene, and heteroatom-containing conjugated polymers such as polyaniline. In the actuator unit using the conjugated polymer, a conductive material is preferably placed on the compact of the conjugated polymer and immersed in the electrolyte solution, and the counter electrode is immersed in the electrolyte solution, and power is supplied from the power source. When the conjugated polymer constituting the actuator portion is electrochemically oxidized, holes are generated inside. As a result, in order to compensate for electrical neutrality, anions enter the actuator portion from the electrolyte solution. And the swelling by the penetration | invasion of an anion becomes the main cause, and the volume of an actuator part expand | swells. The actuator portion made of such a conjugated polymer is preferable in that the operating speed is faster than that using another chemomechanical gel.

  The electrolyte solution may be an aqueous solution or an organic solvent solution. Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, tetrahydrofuran, 1,4-dioxane, monoglyme, acetone, 4-methyl-2-pentanone, acetylacetone, acetonilyl, propionitol, dimethyl sulfoxide, sulfolane, nitromethane. , Dichloromethane, propylene carbonate, ethylene carbonate, acetic acid, 1,2-dichloroethane, benzonitrile and the like.

When polyaniline is used as the actuator portion, an aqueous solution of an acid such as HCl, HBr, HClO ₄ , H ₂ SO ₄ , HBF ₄ , or benzenesulfonic acid is generally used as the electrolyte solution.

  When a surfactant is added to the electrolyte solution, the permeability of the electrolyte solution to the actuator part and the liquid periphery are improved. The electrolyte solution to which the surfactant is added penetrates into the sliding portion of the actuator, and also exhibits an action of reducing sliding resistance as a lubricant. As the surfactant, a surfactant that does not change due to the electrolyte or electrolytic reaction and does not inhibit the electrolytic reaction of the conjugated polymer is preferable. For example, a fluorine-based surfactant is used. Moreover, it is preferable that the surface of the cylindrical member constituting the actuator also has high affinity with the electrolyte solution. For example, when an aqueous solution is used as the electrolyte solution, it is preferable to hydrophilize the surface of the resin constituting the cylindrical member by plasma discharge treatment, glow discharge treatment, ozone oxidation treatment, or the like. Further, a hydrophilic substance such as polyvinyl alcohol may be applied to the surface of the cylindrical member or chemically bonded.

  Instead of the electrolyte solution, a porous polymer impregnated with the electrolyte solution to form a gel may be used. As the porous polymer, for example, polyacrylonitrile, polyethylene, polypropylene or the like is used. A solid electrolyte may be used instead of the electrolyte solution. If a solid electrolyte is used, an all-solid actuator can be obtained. In such an actuator, since the solid electrolyte is installed in close contact with the actuator portion, the solid electrolyte is preferably flexible and stretchable. Such solid electrolytes include compounds having a polyether skeleton (polyethylene oxide, polypropylene oxide, etc.), compounds having a polyester skeleton (polyethylene succinate, poly-β-propiolactone, etc.), compounds having a polyamine skeleton (polyethyleneimine, etc.) ) And compounds having a polysulfide skeleton (polyalkylene sulfide and the like).

  Conjugated polymer moldings often have sufficient electrical conductivity, so drive current can be supplied from a drive power source simply by installing power supply leads, etc., in a part of the actuator part. can do. However, in order to give conductivity more reliably, metal (gold, platinum, etc.), carbon, conductive polymer, etc. on the surface or inside of the actuator part, thin film, fiber, It is preferable to install in the form of a mesh or the like. Further, conductive fine particles made of metal or carbon may be dispersed in the molded body constituting the actuator portion. Further, in order to simplify the wiring of the actuator part, it is preferable to make the cylindrical member conductive and to make the adhesive part of the cylindrical member and the actuator part conductive and to connect the actuator parts in series. .

  The shape of the actuator portion may be any of a linear shape (fiber shape), a film shape (strip shape), and a cylindrical shape. The cylindrical actuator portion may be a film wound in a cylindrical shape, or may be a knitted fiber.

  In order to fabricate the actuator according to the present invention, for example, one end of a strip-like or fibrous actuator is bonded to one end of an inner cylindrical member using an adhesive (preferably a conductive adhesive). Is inserted into the outer cylindrical member, and the other end of the strip-like or fibrous actuator is bonded to the other end of the outer cylindrical member using an adhesive (preferably a conductive adhesive). The method can be used.

  The actuator according to the present invention can be manufactured as shown in FIG. 13 using the apparatus shown in FIG. The apparatus shown in FIG. 12 has a core rod 51 that rotatably holds the innermost cylindrical member 1a constituting the actuator, and a nozzle 52 that is slidably held and sprays various coating liquids onto the cylindrical member 1a. .

  As the coating solution, a resin in which the resin constituting the cylindrical member and the actuator unit can be applied such as solution, melt, dispersion, or fine powder is prepared. Also, an adhesive coating solution and a sacrificial layer coating solution to be removed later are prepared. First, while rotating the cylindrical member 1a, after applying the coating solution of the adhesive 11 and the coating solution of the sacrificial layer 15, post-processing such as heat drying and heat fusion is performed. Next, after the application liquid for the actuator unit 2 is applied, post-processing is performed. Similarly, the application liquid of the adhesive 11 and the application liquid of the sacrificial layer 15 and the post-treatment and the application liquid of the cylindrical member 1b and the post-treatment are performed. These steps are repeated as many times as desired. This state is shown in the cross-sectional view of FIG. 13A and the end view of FIG. Next, the sacrificial layer 15 is removed by wet or dry etching. This state is shown in the cross-sectional view of FIG. 13C and the end view of FIG. Thereafter, lead wires are connected to complete the actuator. However, when the cylindrical member and the actuator portion are easily peeled off, it is not always necessary to provide the sacrificial layer.

  In addition, in order to apply | coat a coating liquid, you may use not only the method of spraying from a nozzle as mentioned above but the dip coating method, the brush coating method, and the doctor blade method. In particular, the dip coating method has a large degree of freedom in the shape of the cylindrical member that can be used, and is advantageous for producing an actuator having a small diameter. Moreover, an actuator part and a cylindrical member can also be formed in the internal space of a hollow cylindrical member.

  The position of the actuator of the present invention can be controlled by attaching various sensors such as a strain sensor. For example, a part of the inner and outer cylindrical members may be made conductive to form a capacitor, and a change in capacitance that occurs when these cylindrical members slide relatively may be monitored. For example, when the actuator portion uses electrolytic expansion / contraction such as polyaniline, an induced current flows through the actuator portion when an external stress is applied. Therefore, the external stress can be measured by monitoring the induced current.

  The present invention will be specifically described below based on examples.

Example 1
Polyaniline (basic emeraldine) -PEO-polyaniline (basic emeraldine) by oxidative polymerization of aniline in the presence of polyethylene oxide (PEO) having aminophenyloxy groups at both ends and a weight average molecular weight of about 10,000. A triblock copolymer was obtained. The weight average molecular weight of this triblock copolymer was about 18,000.

  Also, polyaniline (basic emeraldine) -PEO diblock copolymer is obtained by oxidative polymerization of aniline in the presence of polyethylene oxide (PEO) having an aminophenyloxy group at one end and a weight average molecular weight of about 10,000. Got. The diblock copolymer had a weight average molecular weight of about 22,000.

  For comparison, a polyaniline (basic emeraldine) homopolymer was prepared.

The above triblock copolymer was dissolved in toluene, applied onto a substrate and dried, and then peeled from the substrate to obtain a film having a thickness of 30 μm. As a result of TEM observation, this film formed an OBDD type co-continuous phase separation structure. A platinum electrode and a carbon electrode having a surface area of 1300 m ² / g coated with PEO were prepared as electrodes. As shown in FIG. 2, at one end of the phase separation membrane 201, the platinum electrode 202 was attached to one side, and the carbon electrode 203 was attached to the other side with the PEO film 204 side in contact. The phase separation membrane 201 was immersed in a 1 M / L HBF ₄ aqueous solution for 1 hour, and then air-dried overnight at room temperature to produce an actuator.

  Further, an actuator was produced in the same manner as described above using a diblock copolymer instead of the triblock copolymer.

  For comparison, an actuator was prepared in the same manner as described above using a polyaniline homopolymer instead of the triblock copolymer.

  Each actuator was driven with a DC voltage of 1.5 V, and the time required for maximum expansion and contraction was measured. As a result, the actuator using the phase separation membrane of the triblock copolymer and the diblock copolymer reached the maximum expansion and contraction in about 0.1 seconds. On the other hand, an actuator using a polyaniline homopolymer film had a very slow driving time of about 3 seconds and required a maximum expansion and contraction, and had poor repeatability.

Example 2
Two phase-separation membranes of a triblock copolymer having the same thickness of 30 μm as those used in Example 1 were prepared. A crosslinked polyvinyl alcohol film having a thickness of 50 μm was prepared and impregnated with a 1 M / L hydrochloric acid aqueous solution. As shown in FIG. 3, an electrolyte layer 205 made of a crosslinked polyvinyl alcohol membrane was sandwiched between two phase separation membranes 201, and a platinum electrode 202 was attached to each of the two phase separation membranes 201 to produce a bimorph actuator.

  A bimorph actuator was prepared in the same manner as described above using a diblock copolymer instead of the triblock copolymer.

  For comparison, a polymorphic homopolymer was used instead of the triblock copolymer, and a bimorph actuator was produced in the same manner as described above.

  Each actuator was driven with a DC voltage of 1.5 V, and the time required for maximum expansion and contraction was measured. As a result, the actuators using the triblock copolymer phase separation membrane reached the maximum expansion and contraction in about 0.2 seconds, and the actuators using the diblock copolymer phase separation membrane in about 0.1 seconds. On the other hand, an actuator using a polyaniline homopolymer film had a very slow driving time of about 3 seconds and required a maximum expansion and contraction, and had poor repeatability.

Example 3
A mixed solution of polyaniline (basic emeraldine) having a weight average molecular weight of about 100,000 and N-methylpyrrolidinone (NMP) of polymethyl methacrylate was applied to the substrate, dried, and then peeled to obtain a cast film. This film was washed with toluene to elute polymethyl methacrylate to obtain a porous polyaniline film. From the TEM observation, the average pore diameter was about 0.2 μm, and most of the pores were continuous pores. This cast film was immersed in a hydrochloric acid solution of polyvinyl alcohol and then dried to prepare a polyaniline-polyvinyl alcohol composite film having a thickness of 30 μm.

  Using this composite film, a bimorph actuator having the same structure as that shown in FIG. 3 was produced. When this actuator was driven with a DC voltage of 1.5 V, the time required for maximum expansion and contraction was about 0.5 seconds.

Example 4
The electrochromic device shown in FIG. 1 was produced as follows. A toluene solution of the same triblock copolymer used in Example 1 was spin-coated on a glass substrate 101 on which a transparent electrode 102 made of ITO was formed to form a phase separation film 103 having a thickness of 1 μm. . On this phase separation membrane 103, a carbon electrode 105 was placed via a spacer having a thickness of 50 μm. Then, a 1 M / L hydrochloric acid aqueous solution was filled in the gap between the phase separation membrane 103 and the carbon electrode 105 to form an electrolyte layer 104.

  Further, an electrochromic device was produced in the same manner as described above using a diblock copolymer instead of the triblock copolymer.

  For comparison, an electrochromic device was prepared in the same manner as described above using a polyaniline homopolymer instead of a triblock copolymer.

  The response speed of these electrochromic devices was measured. As a result, compared with the response speed of the device using the polyaniline homopolymer, the response speed of the device using the triblock copolymer is about 12 times, and the response speed of the device using the diblock copolymer is about 9 times. Obtained.

  Next, three types of electrochromic elements were produced in the same manner as described above except that the electrolyte layer 104 was filled with polyvinyl alcohol impregnated with hydrochloric acid instead of the aqueous hydrochloric acid solution.

  The response speed of these electrochromic devices was measured. As a result, the response speed of the device using the triblock copolymer is about 8 times that of the device using the polyaniline homopolymer, and about 11 times that of the device using the diblock copolymer. Obtained.

Example 5
A mixed solution of 13.3 mL of alinine and 150 mL of 1.33 mol / mL hydrochloric acid was kept at −5 ° C., and 26.7 mL of an aqueous solution in which 15.33 g of ammonium persulfate was dissolved was dropped into this solution over 1 hour. Stir. The precipitate was filtered off, washed with 1M aqueous hydrochloric acid until the filtrate became colorless, and further washed thoroughly with pure water. The obtained solid was put into 1M aqueous ammonia and stirred well. The precipitate was again filtered off, washed several times with aqueous ammonia, and further washed with water. Vacuum drying gave 4.5 g of basic emeraldine powder.

  NMP was put into a mortar, and the basic emeraldine powder was added little by little and stirred well to dissolve in a proportion of 8 wt%. This solution was applied in a uniform thickness on a horizontally placed slide glass plate and dried at 50 ° C. to obtain a thin film having a thickness of about 35 μm. This thin film was uniaxially stretched while being heated to 130 ° C. and stretched about 3 times. The obtained emeraldine thin film was cut into a strip shape having a length of 6 cm and a width of 3 mm and used as the actuator part 2. On the other hand, cylindrical members 1a, 1b, 1c and 1d made of nylon pipes having different diameters were prepared.

  Using these, an actuator was manufactured as follows. As shown in FIG. 14 (A), the conductive adhesive layer 11 was applied to the outer wall of the upper end portion of the inner cylindrical member, and the upper end portion of the strip-like actuator portion 2 was bonded to the four portions. This was inserted into the outer cylindrical member, the conductive adhesive layer 11 was applied to the inner wall of the lower end portion of the outer cylindrical member, and the lower end portion of the strip-like actuator portion 2 was adhered at the four locations. By repeating these operations, an actuator as shown in FIGS. 14B and 14C was produced.

Next, as shown in FIG. 14D, a lead wire was connected to the conductive adhesive layer of the obtained actuator 10, and the actuator was immersed upright in an electrolyte solution 31 made of 1M HBF ₄ aqueous solution. Further, the counter electrode 21 made of Pt was immersed in the electrolyte solution 31. And the actuator part 2 and the counter electrode 21 were connected to DC power supply via the lead wire.

  When a voltage was applied to the actuator portion of the actuator to cause contraction, the maximum operation amount was 5.2 mm, and the expansion / contraction rate was 8.7%. For comparison, when a single actuator unit consisting of a strip-shaped emeraldine film with a length of 6 cm and a width of 3 mm was operated under the same conditions, the maximum operation amount was 1.7 mm and the expansion / contraction rate was 2.8%. It was. As described above, in the actuator of the present invention, both the operation amount and the expansion / contraction rate increased about three times as compared with the actuator unit alone.

  Further, when the actuator of FIG. 14 was operated under the same conditions as described above while being compliant along a circumference having a radius of 5 cm, the expansion / contraction ratio was 7.8%.

  Next, the actuator of FIG. 14 was wrapped in a rubber bag (not shown) having a thickness of 10 μm, and the inside thereof was filled with the same electrolyte solution. When this actuator was operated under the same conditions as described above, the expansion / contraction rate was 8.5%.

  In addition, when 0.1% of fluorine-based surfactant (manufactured by 3M, Fluorad FC-430) was added to the electrolyte solution and the actuator was operated, the expansion / contraction speed increased 1.5 times. In addition, the hysteresis is reduced when the extension operation and the contraction operation are repeated. This is presumably because the sliding resistance between the tubular members and between the tubular member and the actuator portion was reduced by adding the surfactant. Similar results were obtained when Fluorad FC-95, Fluorad FC-98, Fluorad FC-134, and Fluorad FC-170C (all manufactured by 3M) were used as the fluorosurfactant.

Further, even when the electrolyte solution was changed to an aqueous solution of HCl, HBr, HClO ₄ , H ₂ SO ₄ , or benzenesulfonic acid, the same effect of increasing the operation amount and the expansion / contraction rate was obtained.

Example 6
15A, 15B, and 15B, which are obtained by cutting the emeraldine thin film prepared in Example 5 into a strip shape having a length of 6 cm and a width of 1.5 mm as an actuator portion. The actuator shown in C) was produced. In this embodiment, the actuator portion 2 that connects the upper end outer wall of the inner cylindrical member and the lower end inner wall of the outer cylindrical member, and the lower end outer wall of the inner cylindrical member and the upper end inner wall of the outer cylindrical member The actuator parts 3 to be connected are alternately arranged along the circumferential direction. And these actuator parts 2 and 3 are operated so that one contracts and the other expands.

  Similarly to Example 5 (FIG. 14D), the obtained actuator was immersed in an electrolyte solution in an upright state, and the counter electrode was immersed and connected to a DC power source.

  When this actuator was operated so that the actuator unit 2 contracted and the actuator unit 3 extended, the operating amount was 5.3 mm at the maximum and the expansion / contraction rate was 8.8%. Both the stretch rate and the stretch rate increased about 3 times. On the other hand, when this actuator was operated so that the actuator portion 2 was extended and the actuator portion 3 was contracted, the same amount of operation and expansion / contraction rate were obtained just as the operating direction was reversed. In the actuator of Example 5, the operation amount when the actuator portion was operated to expand was about 65% of the operation amount when the actuator portion was operated to contract. From the above, it can be seen that the actuator of the present embodiment is preferable in that almost the same operation amount and expansion / contraction rate can be obtained when the operation direction is normal or reverse.

  Further, when the actuator shown in FIG. 15 was operated under the same condition as described above along the circumference of 5 cm radius, the expansion / contraction ratio was 7.8%.

  Next, the actuator of FIG. 15 was wrapped in a rubber bag having a thickness of 10 μm, and the inside thereof was filled with an electrolyte solution. When this actuator was operated under the same conditions as described above, the expansion / contraction ratio was 7.9%.

  When the actuator was operated by adding 0.5% of a fluorosurfactant (manufactured by 3M, Fluorad FC-430) to the electrolyte solution, the expansion / contraction speed increased 1.6 times. In addition, the hysteresis is reduced when the extension operation and the contraction operation are repeated.

Example 7
16A, 16B, and 16C are used in the same manner as in Example 5 by using the emeraldine thin film produced in Example 5 wound in a cylindrical shape of 6 cm in length as the actuator portion 2. An actuator was produced. Similarly to Example 5 (FIG. 14D), the obtained actuator was immersed in an electrolyte solution in an upright state, and the counter electrode was immersed and connected to a DC power source.

  When this actuator was operated so that the actuator part contracted, the expansion / contraction rate was 9.1%, which was about three times that of the actuator part alone.

  Further, when the actuator shown in FIG. 16 was driven in the same manner along the circumference with a radius of 5 cm, the elongation was 8.5%.

  Next, the actuator of FIG. 16 was wrapped with a rubber bag having a thickness of 10 μm, and the inside thereof was filled with an electrolyte solution. When this actuator was operated under the same conditions as described above, the expansion / contraction rate was 8.1%.

  Further, ten cylindrical members were used, and actuators (the number of unit actuators = 9) were produced by connecting them with a cylindrical actuator portion similar to the above. Immerse this actuator in an electrolyte solution in an upright state, immerse the counter electrode and connect it to a DC power supply, and operate it so that the actuator part contracts. About 9 times. In addition, when this actuator is wrapped in a rubber bag with a thickness of 10 μm and filled with an electrolyte solution and operated under the same conditions as described above, both the operation amount and the expansion / contraction rate are about 8 times that of the actuator unit alone. Increased.

Example 8
Instead of the cylindrical actuator portion used in Example 7, an actuator was manufactured using the actuator portion 2 having the shape shown in FIGS.

  The actuator portion of FIG. 17A is obtained by winding an emeraldine thin film into a cylindrical shape having a length of 6 cm.

  The actuator portion shown in FIG. 17B is obtained by knitting an emeraldine thin film with a width of 1 mm and knitting it into a cylindrical shape with a coarse mesh.

  The actuator part of FIG. 17 (C) is an emeraldine thin film made of fibers having a length of 6 cm and a width of 0.2 mm. It is.

  The actuator portion shown in FIG. 17D is obtained by winding a cloth knitted with an emeraldine thin film as a fiber having a width of 0.2 mm into a cylindrical shape and hardening the end portion with a conductive paste 11.

  In the same manner as in Example 5 (FIG. 14D), each of the obtained actuators was immersed in an electrolyte solution in an upright state, and the counter electrode was immersed and connected to a DC power source. When these actuators were operated so that the actuator portion contracted, both the operation amount and the expansion / contraction rate increased about three times as compared with the actuator portion alone.

  Further, in the actuator using the actuator portion of FIG. 17A, the expansion / contraction rate was 9.3%, which was slightly improved from Example 7. Moreover, the expansion / contraction speed was faster than that of Example 7. This is because by cutting the cylindrical actuator part, the circumferential contraction escapes, tightening of the cylindrical member inscribed by the actuator part is relaxed, and the sliding resistance between the actuator part and the cylindrical member is reduced. This is probably due to the improved penetration of the electrolyte solution. In the actuator using the actuator part of FIGS. 17B to 17D, the same effect was obtained by improving the flexibility of the actuator part and improving the penetration of the electrolyte solution. For example, with the actuator of 17 (C), the extension speed was 1.2 times that of Example 7.

  Also, in any actuator, the actuator part is operated in a state where it is bent along the circumference of a radius of 5 cm, and the actuator part is encased in a rubber film having a thickness of 10 μm and filled with an electrolyte solution. The expansion ratio was about 3 times that of the single substance.

Example 9
In this example, an actuator was manufactured using a highly conductive actuator part.

  The carbon mesh solution impregnated with the polyaniline solution synthesized in Example 5 was impregnated, dried at 50 ° C., uniaxially stretched while being heated at 130 ° C., and stretched about 3 times. When this was used as an actuator portion and an actuator was manufactured and operated in the same manner as in Example 5, the drive voltage required to obtain the same operation amount was reduced by 10%. This is presumably because the electrical conductivity of the polyaniline film was improved by the carbon mesh, and the voltage drop due to resistance was alleviated. Further, since the carbon mesh is a structure in which carbon fibers are assembled in an oblique lattice shape, the expansion and contraction of polyaniline was not hindered. The same effect was obtained when a carbon fiber assembled in a coil shape was used.

  Next, a 20 μm thick film was prepared using the polyaniline solution synthesized in Example 5, and after depositing 15 nm thick gold to form a zigzag conductive pattern 12 as shown in FIG. Furthermore, the polyaniline solution was apply | coated and it was set as the film of thickness 40 micrometers. This film was uniaxially stretched while being heated at 130 ° C. and stretched about 3 times. When this was used as the actuator portion 2 to produce and operate an actuator in the same manner as in Example 1, the driving voltage required to obtain the same amount of operation decreased by 10%. This is presumably because the conductivity of the polyaniline film was improved by the gold conductor pattern 12 and the voltage drop due to resistance was alleviated. Moreover, since the gold electrode was deposited in a zigzag shape, the expansion and contraction of the polyaniline film was not hindered.

  The polyaniline thin film produced in Example 1 was formed into a cylindrical shape by winding it. As shown in FIG. 19A or 19B, a solid electrolyte membrane 13 made of crosslinked polyethylene oxide impregnated with an acid aqueous solution was formed in a spiral or zigzag shape on the surface of a cylindrical polyaniline thin film. Further, gold was vapor-deposited on the solid electrolyte film 13 to form the conductor pattern 12 to obtain the actuator unit 2. When these actuator parts were used to make and operate the actuators, they worked well. Since the solid electrolyte membrane 13 and the gold conductor pattern 12 were formed in a spiral shape or a zigzag shape as described above, expansion / contraction of the polyaniline film was not hindered.

Example 10
The emeraldine thin film produced in Example 5 was cut into a strip shape having a width of 3 mm and a length of 1 cm, and used as the actuator unit 2. As shown in FIG. 9, the actuator part 2 was arrange | positioned along the circumferential direction of cylindrical member 1a, 1b, 1c, and the actuator was produced.

  When this actuator was operated, the outer cylindrical member 1c was rotated 12.5 degrees with respect to the inner cylindrical member. This rotation angle was about twice the rotation angle of the unit actuator composed of the cylindrical members 1a and 1b and the actuator portion 2 connecting them.

  When 0.1% of fluorinated surfactant (Fluorad FC-430, manufactured by 3M) was added to the electrolyte solution and the actuator was operated, the expansion / contraction speed increased 1.5 times, and the expansion and contraction operations were performed. Hysteresis when repeated was reduced.

Example 11
Electropolymerization was performed using a mixed aqueous solution of pyrrole and sodium dodecylbenzenesulfonate to form a polypyrrole film on the electrode. A 30 μm thick polypyrrole film was peeled from the electrode. Using this polypyrrole film as an actuator part, an actuator was produced in the same manner as in Example 5. When this actuator was operated in an electrolyte solution of sodium dodecylbenzenesulfonate, an expansion / contraction ratio about three times that of the actuator unit alone was obtained.

  When 0.1% of fluorinated surfactant (Fluorad FC-430, manufactured by 3M) was added to the electrolyte solution and the actuator was operated, the expansion / contraction speed increased 1.5 times, and the expansion and contraction operations were performed. Hysteresis when repeated was reduced.

Example 12
When a polyaniline thin film containing 10% polypyrrole was used as an actuator part and an actuator was manufactured and operated in the same manner as in Example 5, the expansion / contraction speed increased by 10%.

Example 13
After mixing 97 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate and 0.5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, degassing and purging with nitrogen, a distance of 15 cm A crosslinked poly (2-hydroxyethyl methacrylate), which is a hydrophilic polymer, was synthesized by irradiating with an ultraviolet ray from an 80 W / cm high-pressure mercury lamp for 3 minutes and 30 seconds to cure. This crosslinked poly (2-hydroxyethyl methacrylate) was molded into a cylindrical shape and used as a cylindrical member, and an actuator was produced in the same manner as in Example 5. When this actuator was operated, the operation was smooth because the wettability of the cylindrical member to the electrolyte solution was excellent.

Example 14
An actuator was manufactured by a spin coating method using the apparatus shown in FIG. 12 as shown in FIG. The following solutions were prepared as coating solutions for forming each part of the actuator.

Tubular member: Polyvinyl chloride in tetrahydrofuran solution Actuator: Basic emeraldine in N-methylpyrrolidone solution Sacrificial layer: Polyvinylpyrrolidone aqueous solution Adhesive layer: Epoxy adhesive As a core rod 51 in FIG. A real rod was used. The solution was applied sequentially while rotating the core rod. During the coating, heating was performed using an infrared lamp to promote drying of the coating solution. The adhesive was completely cured by heating and drying at 60 ° C. It was immersed in a 40 degreeC warm water tank, and the sacrificial layer was removed using ultrasonic cleaning as needed. An actuator was manufactured by connecting a drive lead wire to the actuator portion.

When the obtained actuator was dipped in a 1M HClO ₄ aqueous solution to which 0.1% of a surfactant (manufactured by 3M, trade name Fluorad FC-430) was added, it was driven to expand and contract satisfactorily.

Example 15
An actuator was produced by dip coating. Note that the coating liquid used is the same as that in Example 14, and the state in which the coating liquid is applied is substantially the same as in FIG. First, a coating solution for forming each part of the actuator was prepared.

Cylindrical member: Polyvinyl chloride in tetrahydrofuran solution (liquid a)
Actuator part: N-methylpyrrolidone solution of basic emeraldine (liquid b)
Sacrificial layer: Polyvinylpyrrolidone aqueous solution (liquid c)
Adhesive layer: Epoxy adhesive (d liquid)
A cylindrical solid rod made of vinyl chloride resin was used as the innermost cylindrical member. One end of the chlorinated resin rod was supported, and only the portion where the adhesive layer was formed was immersed in d solution, and then pulled up and dried to form the adhesive layer. The other end of the chlorinated resin rod was supported, and only the portion for forming the sacrificial layer was immersed in the liquid c, and then pulled up and dried to form a sacrificial layer. After the chlorinated resin rod was immersed in the liquid b, it was pulled up and dried to form an actuator part. The other end of the chlorinated resin rod was supported, and only the portion where the adhesive layer was formed was immersed in d solution, and then pulled up and dried to form the adhesive layer. One end of the chlorinated resin rod was supported, and only the portion for forming the sacrificial layer was immersed in the liquid c, and then pulled up and dried to form a sacrificial layer. After immersing the chlorinated resin rod in the liquid a, it was pulled up and dried to form an outer cylindrical member. In this way, a unit actuator having a pair of cylindrical members and an actuator portion for connecting them was formed.

Further, the above operation was repeated three times. Excess coating solution adhering to the end face was removed. The adhesive was completely cured by heating and drying at 60 ° C. It was immersed in a 40 degreeC warm water tank, and the sacrificial layer was removed using ultrasonic cleaning as needed. An actuator was manufactured by connecting a drive lead wire to the actuator portion. When the produced actuator was dipped and driven in a 1M HClO ₄ aqueous solution to which 0.1% of a surfactant (trade name Fluorad FC-430: manufactured by 3M) was added, it was stretched well.

  This method is very effective for forming a thin actuator having a diameter of 2 to 3 mm using a thin resin filament as the innermost cylindrical member.

  After the dip coating as described above, the actuator was manufactured by heating to 130 ° C. and extending about 3 times in the axial direction. When this actuator was operated, the expansion / contraction ratio was 1.5 times. .

  Next, as a liquid for forming a cylindrical member, a viscous solution (J. Non-Crystal. Solids) in which epoxy silane, methacryloxy silane, alkoxy titanium, a methacrylate monomer, and a peroxide polymerization catalyst are mixed and reacted. 63 (1984) 283-293), an actuator was prepared in the same manner as above except that the coating solution was cured by heating at 120 ° C. after coating the solution a. The manufactured actuator had high hydrophilicity of the cylindrical member, and was excellent in wettability with the electrolyte solution.

  Further, an actuator was manufactured in the same manner as described above except that carbon black was mixed with the liquid a for forming the cylindrical member and the liquid d for forming the adhesive layer. In the obtained actuator, since the cylindrical member and the adhesive layer contain conductive carbon black, all the cylindrical members and the actuator portions are electrically connected in series. Therefore, it was possible to operate with a simple wiring by simply connecting a lead wire for supplying driving power to one portion of either the cylindrical member or the actuator portion.

Example 16
An actuator was manufactured by the dip coating method in the same manner as in Example 15 except that a cylindrical hollow rod made of vinyl chloride was used as the first cylindrical member to which the coating solution was applied. As shown in FIG. 20, in this actuator, tubular members 1a, 1b, 1c and an actuator portion 2 for connecting them are formed on the outer surface of the first tubular member 1x, and the tubular member 1a ′ is similarly formed on the inner surface. 1b ', 1c' and an actuator part 2 for connecting them are formed. Thus, if an actuator is produced by a dip coating method using a cylindrical hollow rod, unit actuators can be easily stacked.

Example 17
When the dip coating method is employed as in Examples 15 and 16, actuators can be manufactured using various cylindrical shapes as the first cylindrical member to which the coating liquid is applied.

  For example, when a solid rod made of vinyl chloride having various shapes as shown in FIG. 21 is used as the innermost cylindrical member 1a and an actuator is manufactured and operated in the same manner as in Example 15, it operates satisfactorily. did. In addition, these actuators have improved strength against compressive stress.

  Similarly, when a hollow rod made of vinyl chloride having various shapes as shown in FIG. 22 was used as the first cylindrical member 1x, an actuator was manufactured and operated in the same manner as in Example 16, and it worked well. . These actuators also improved the strength against compressive stress.

  Further, when the dip coating method is adopted, a plurality of cylindrical members can be fixed to the frame and simultaneously dip coated. Then, after being separated from the frame, the sacrificial layer is removed and wiring is formed, whereby the actuator can be manufactured.

Sectional drawing which shows the electrochromic element which concerns on this invention. Sectional drawing which shows the actuator which concerns on this invention. Sectional drawing which shows the other actuator which concerns on this invention. The perspective view, fracture | rupture figure, and end elevation which show the actuator which concerns on this invention. FIG. 3 is an operation explanatory diagram of an actuator according to the present invention. FIG. 3 is an operation explanatory diagram of an actuator according to the present invention. FIG. 3 is an operation explanatory diagram of an actuator according to the present invention. The whole perspective view which shows the actuator which concerns on this invention, the perspective view of an inner side cylindrical member, and operation | movement explanatory drawing. The end view of the actuator concerning the present invention. The figure which shows the example of the cross section of the cylindrical member which comprises the actuator which concerns on this invention. The end view of the actuator concerning the present invention. The perspective view which shows the production apparatus of the actuator which concerns on this invention. Sectional drawing and end elevation which show the manufacturing method of the actuator based on this invention using the apparatus of FIG. FIG. 10 is a partial perspective view, a cross-sectional view, an end view, and an explanatory diagram showing a use state of an actuator in Example 5. FIG. 10 is an end view and a cross-sectional view of an actuator in Example 6. FIG. 10 is a partial perspective view, a cross-sectional view, and an end view of an actuator in Embodiment 7. FIG. 10 is a perspective view of an actuator unit used in Example 8. 10 is a plan view of an actuator unit used in Example 9. FIG. FIG. 10 is a perspective view of an actuator unit used in Example 9. Sectional drawing of the actuator in Example 16. FIG. The end view of the cylindrical member used in Example 17. FIG. The end view of the cylindrical member used in Example 17. FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1a, 1b, 1c, 1d, 1x, 4a, 4b ... Cylindrical member, 2, 3 ... Actuator part, 6 ... Rib, 10 ... Actuator, 11 ... Adhesive layer, 12 ... Conductor pattern, 13 ... Solid electrolyte, 21 ... Counter electrode 31 ... electrolyte solution 51 ... core rod 52 ... nozzle 101 ... glass substrate 102 ... transparent electrode 103 ... phase separation membrane 104 ... electrolyte layer 105 ... counter electrode 201 ... phase separation membrane 202 ... platinum Electrode 203 ... carbon electrode 204 ... solid electrolyte membrane 205 ... electrolyte layer

Claims (2)

  A cylindrical member having a different diameter arranged coaxially with an interval, an expandable / contractible actuator unit that connects an outer wall of the inner cylindrical member and an inner wall of the outer cylindrical member, and the actuator unit And an actuator for supplying driving energy to the actuator.   The actuator according to claim 1, wherein the plurality of unit actuators are coaxially arranged with an inner cylindrical member, an outer cylindrical member, and an actuator portion connecting them as unit actuators.

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