US20110300393A1 - Dielectric film, process for producing same, and transducer using same - Google Patents
Dielectric film, process for producing same, and transducer using same Download PDFInfo
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- US20110300393A1 US20110300393A1 US13/201,508 US201013201508A US2011300393A1 US 20110300393 A1 US20110300393 A1 US 20110300393A1 US 201013201508 A US201013201508 A US 201013201508A US 2011300393 A1 US2011300393 A1 US 2011300393A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/002—Electrostatic motors
- H02N1/006—Electrostatic motors of the gap-closing type
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/06—Influence generators
- H02N1/08—Influence generators with conductive charge carrier, i.e. capacitor machines
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/025—Diaphragms comprising polymeric materials
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/027—Diaphragms comprising metallic materials
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
- H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
Definitions
- the present invention relates to a dielectric film that is suited for use in transducers such as actuators and sensors, to a process for producing the same, and to a transducer using the same.
- Transducers can be actuators, sensors, electric power generation elements, etc. that perform conversion between mechanical energy and electrical energy.
- transducers can be speakers, microphones, etc. that perform conversion between acoustic energy and electrical energy.
- Polymer materials such as dielectric elastomers are useful for configuring transducers that are high in flexibility, small in size and light in weight.
- An actuator may be configured by, for example, arranging a pair of electrodes on both thickness direction sides of a dielectric film that is formed of a dielectric elastomer.
- electrostatic attractive force between the electrodes increases with an increase of the voltage that is applied between the electrodes, so that the dielectric film that is sandwiched between the electrodes is compressed in the thickness direction and the thickness thereof is reduced.
- the dielectric film correspondingly expands in the direction parallel with the electrode plane.
- the actuator can drive an object to be driven by the expansion and contraction of the dielectric film.
- the dielectric film material silicone rubbers, acrylic rubbers, nitrile rubbers, urethane rubbers, etc. are used (see, for example, Patent Documents 1 and 2).
- Patent Document 1 Published Japanese Translation of PCT application 2003-505865
- Patent Document 2 Published Japanese Translation of PCT application 2001-524278
- Patent Document 3 Japanese Patent No. 3295023
- a silicone rubber for example, has a skeletal structure that is composed of siloxane bonds, the electric resistance thereof is high. For this reason, a dielectric film made of such a silicone rubber hardly undergoes dielectric breakdown even when a high voltage is applied thereto.
- a polydimethylsiloxane-based silicone rubber on the other hand, has low polarity, namely has a small dielectric constant. Therefore, when an actuator is configured using a dielectric film that is composed of such a polydimethylsiloxane-based silicone rubber, the electrostatic attractive force for an applied voltage is so small that sufficient force and displacement are not obtainable.
- an actuator when configured using a dielectric film that has a large dielectric constant, it is possible to store a large amount of charges in a boundary between the dielectric film and each electrode. It follows that the electrostatic attractive force for an applied voltage is large.
- known acrylic rubber and nitrile rubber have a larger dielectric constant than silicone rubber and, therefore, are suited as a dielectric film.
- the electric resistance of acrylic rubber, etc. is smaller than that of silicone rubber. Therefore, when acrylic rubber or the like rubber is used as a dielectric film, a current unavoidably flows through the dielectric film when an applied voltage is high. Hence, charges are not sufficiently accumulated in the film.
- the present invention has been made in view of the foregoing circumstances and is aimed at the provision of a dielectric film that has a large electric resistance and is excellent in durability and of a method for producing the same. It is also an object of the present invention to provide a transducer that uses such a dielectric film and that has large displacement and excellent durability.
- a dielectric film according to the present invention is a dielectric film that is to be interposed between at least a pair of electrodes of a transducer.
- the dielectric film is characterized by including a three-dimensional crosslinked body that is synthesized from an organic metal compound, a rubber polymer which is other than a polydimethyl siloxane and has a functional group which is reactive with the organic metal compound, and an inorganic filler which has a functional group that is reactive with the organic metal compound.
- Patent Document 3 discloses a ceramic composite rubber in which a rubber polymer and an organic metal compound that has an organic functional group which is reactive with the rubber polymer are chemically bonded to each other.
- the ceramic composite rubber does not contain an inorganic filler that is capable of forming a three-dimensional crosslinked body. Namely, in the ceramic composite rubber, a metal oxide that is produced by hydrolysis of an unreacted organic metal compound is merely dispersed in the rubber.
- the three-dimensional crosslinked body of the present invention contains an inorganic filler.
- each of the rubber polymer and inorganic filler has a functional group that is capable of reacting with the organic metal compound. Therefore, during synthesis of the three-dimensional crosslinked body, reactions occur between the rubber polymer and the organic metal compound and between the inorganic filler and the organic metal compound, so that they are chemically bonded to each other.
- the three-dimensional crosslinked body of the present invention has such a structure in which the rubber polymer is crosslinked with the organic metal compound and the inorganic filler is incorporated in the thus formed crosslinkage.
- the electric resistance of the three-dimensional crosslinked body of the present invention is high. Namely, the electric resistance of the dielectric film of the present invention is high. Therefore, when a voltage is applied between a pair of electrodes between which the dielectric film of the present invention is interposed, an electric current does not easily flow through the dielectric film. For this reason, a large amount of charges can be stored in the dielectric film. As a consequence, electrostatic attractive force increases so that large force and displacement are obtainable in, for example, an actuator.
- the dielectric film of the present invention because an electric current does not easily flow through the dielectric film, generation of Joule heat is suppressed. For this reason, there is low possibility that the dielectric film of the present invention is thermally broken down. Additionally, the dielectric film of the present invention, which has a high electric resistance, does not easily undergo insulation breakdown. Thus, the dielectric film of the present invention has excellent durability. Moreover, it is possible to apply a higher voltage to the dielectric film of the present invention. Therefore, with the dielectric film of the present invention, large force and displacement are obtainable in, for example, an actuator.
- the dielectric film of the present invention uses a rubber polymer that is other than polydimethylsiloxane. Namely, the film uses a rubber polymer that has higher polarity, in other words, a larger dielectric constant, than that of the conventionally employed polydimethylsiloxane-type silicone rubber. Therefore, with the dielectric film of the present invention, large electrostatic attractive force is generated even when an applied voltage is relatively low. As a consequence, a desired force and displacement are obtainable in, for example, an actuator that uses the dielectric film of the present invention.
- a process for producing a dielectric film according to the present invention includes a first solution preparing step that prepares a first solution that contains the rubber polymer, the inorganic filler and, optionally the plasticizer in a solvent that is capable of dissolving the rubber polymer and of chelating the organic metal compound, a second solution preparing step that prepares a second solution by mixing the organic metal compound into the first solution, and a crosslinking step that removes the solvent from the second solution to allow a crosslinking reaction to proceed.
- the organic metal compound hydrolyzes by reaction with water and is polycondensed by dehydration or dealcoholation (sol-gel reaction) to form a three-dimensional crosslinked body.
- the organic metal compound is generally highly reactive with water and difficult to handle.
- the solvent not only can dissolve the rubber polymer and disperse the inorganic filler but also serves to act as a chelating agent.
- the organic metal compound in the solution is chelated.
- the hydrolysis of the organic metal compound is suppressed.
- the solvent is removed. Namely, the chelating agent is removed.
- the dealcoholation of the organic metal compound is accelerated so that the crosslinking by polycondensation proceeds.
- the reaction speed of the organic metal compound can be lowered. Therefore, it is possible to obtain a homogeneous dielectric film.
- the solvent serves to function both as a solvent for dissolving the rubber polymer and dispersing the inorganic filler and as a chelating agent, it is not necessary to separately prepare a solvent and a chelating agent. Therefore, the production step is simplified and is practical.
- a first solution in which the rubber polymer is dissolved and the inorganic filler is dispersed, is previously prepared. Consequently, the dispersibility of the inorganic filler in the second solution is improved so that a homogeneous dielectric film is obtainable.
- a plasticizer may be mixed as needed. Namely, the plasticizer may be or may not be contained in the first solution.
- a transducer of the present invention is characterized by including the above-described dielectric film according to the present invention, and a plurality of electrodes that are arranged via the dielectric film
- the transducer of the present invention includes the above-described dielectric film of the present invention.
- the dielectric film of the present invention has a high electric resistance and, therefore, can store a large amount of charges. For this reason, when the transducer of the present invention is used, for example, as an actuator, large force and displacement can be obtained. Further, there is low possibility that the dielectric film of the present invention is thermally broken down. Additionally, the dielectric film does not easily undergo insulation breakdown. Thus, the dielectric film of the present invention has excellent durability.
- FIG. 1 is schematic cross-sectional view of an actuator which is a first embodiment of a transducer according to the present invention, wherein (a) shows an OFF state and (b) shows an ON state.
- FIG. 2 is schematic cross-sectional view of a capacitive sensor which is a second embodiment of a transducer according to the present invention.
- FIG. 3 is schematic cross-sectional view of an electric power generation element which is a third embodiment of a transducer according to the present invention, wherein (a) shows an expanded state and (b) shows a contracted state.
- FIG. 4 is a front view of an actuator that is mounted on an experimental device.
- FIG. 5 is a V-V cross-sectional view of FIG. 4 .
- the dielectric film, production process thereof and transducer according to the present invention will be described below. It should be noted that the dielectric film, production process thereof and transducer according to the present invention are not limited to the following specific embodiments but may be embodied in various forms that can be modified or improved by those skilled in the art without departing from the gist of the present invention.
- the dielectric film of the present invention includes a three-dimensional crosslinked body that is synthesized from an organic metal compound, a rubber polymer that has a functional group which is reactive with the organic metal compound and which is other than a polydimethyl siloxane, and an inorganic filler that has a functional group which is reactive with the organic metal compound.
- the kind of the organic metal compound is not specifically limited.
- the organic metal compound may be liquid or solid.
- Examples of the organic metal compound include metal alkoxide compounds, metal acylate compounds and metal chelate compounds. One compound that is selected from these compounds may be used singly. Alternatively, two or more of these compounds may be used in combination. It is desired that the organic metal compound contains at least one element that is selected from the group consisting of titanium, zirconium, aluminum, silicon, boron, vanadium, manganese, iron, cobalt, germanium, yttrium, niobium, lanthanum, cerium, tantalum, tungsten and magnesium.
- the metal alkoxide compound is represented, for example, by the following general formula (a):
- M represents an atom such as a metal
- R represents at least one of C 1 to C 10 alkyl groups, aryl groups and alkenyl groups and may be the same or different
- m is a valency of the atom M which is a metal or the like element.
- the metal alkoxide compound may also be a polymer that has two or more recurring units of [(MO) n where n is an integer of 2 or more] in the molecule thereof. By changing the number n, it is possible to control compatibility with the rubber polymer, reaction speed, etc. of the metal alkoxide compound. It is advisable, therefore, to select a suitable polymer depending on the kind of the rubber polymer.
- Examples of the atom M such as a metal include titanium, zirconium, aluminum, silicon, iron, copper, tin, barium, strontium, hafnium and boron. Particularly, at least one atom that is selected from titanium, zirconium and aluminum is preferably contained for reasons of good reactivity.
- suitable metal alkoxide include tetra-n-butoxy titanium, tetra-n-butoxy zirconium, tetra-n-butoxy silane, acetoalkoxy aluminum diisopropylate, tetra-1-propoxy titanium, tetraethoxy silane, tetrakis(2-ethylhexyloxy) titanium and titanium butoxide dimer.
- metal acylate compound examples include polyhydroxy titanium stearate and zirconium tributoxy monostearate.
- the metal chelate compound examples include titanium chelate compounds such as titanium diisopropoxy-bis(acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxy-bis(octylene glycolate), titanium diisopropoxy-bis(ethylacetoacetate), titanium diisopropoxy-bis(triethanolaminate) and titanium dibutoxy-bis(triethanolaminate) and zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxy acetylacetonate-bis(ethylacetoacetate) and zirconium dibutoxy-bis(ethylacetoacetate).
- titanium chelate compounds such as titanium diisopropoxy-bis(acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxy-bis(octylene glycolate
- the rubber polymer is other than polydimethylsiloxane and has a functional group that is capable of reacting with the organic metal compound.
- the rubber polymer may be liquid or solid.
- the functional group that is capable of reacting with the organic metal compound include a carboxyl group (—COOH), a hydroxyl group (—OH), an amino group (—NH), an amide (—CONR 1 R 2 ), an epoxy group, a thiol (—SH) and an ester (R 3 C( ⁇ O)OR 4 ). It is preferred that the rubber polymer has one or more of these functional groups.
- a rubber polymer that has high polarity namely a high dielectric constant
- a rubber polymer that has a dielectric constant of 2.8 or more (measuring frequency of 100 Hz) is preferable.
- the rubber polymer that has a high dielectric constant include acrylonitrile-butadiene copolymers (NBR), hydrogenated nitrile rubbers (H-NBR), acrylic rubbers, urethane rubbers, fluorine rubbers, fluorosilicone rubbers, chlorosulfonated polyethylene rubbers, chloroprene rubbers, ethylene-vinyl acetate copolymers and chlorinated polyethylenes. It is desired that these rubbers be used singly or as a mixture of two or more thereof. It is also preferred that the rubber polymer have an unsaturated main chain because of its less tendency to cause insulation breakdown even when applied with a high voltage and of its weatherability.
- the inorganic filler has a functional group that is capable of reacting with the organic metal compound.
- the functional group that is capable of reacting with the organic metal compound include a hydroxyl group (—OH), a carboxyl group (—COOH), an amino group (—NH), an amide (—CONR 1 R 2 ), an epoxy group, a thiol (—SH) and an ester (R 3 C( ⁇ O)OR 4 ), which are similar to the case of the rubber polymer. It is preferred that the inorganic filler have one or more of these functional groups.
- the inorganic filler may be subjected to a surface treatment to increase the number of the functional groups. By so doing, the reactivity of the inorganic filler with the metal alkoxide can be improved.
- examples of the inorganic filler include silica, titanium oxide, barium titanate, calcium carbonate, clay and talc.
- silica is preferably used because the number of its functional groups is large and because it is relatively inexpensive.
- silica that has been produced by certain methods may contain sodium that is derived from the raw material. When such sodium remains present in a large amount, there is a possibility that sodium ions cause a reduction of the electric resistance.
- the residual amount of sodium is related to the pH of silica. Namely, the pH value tends to increase with an increase of the residual amount of sodium. Therefore, when silica is used, it is desirable to choose silica that has as low a pH value as possible.
- a pH value of 10.5 or less is suitable.
- the pH value is desirably 8.5 or less, more desirably 6.5 or less.
- the term “pH value” is intended to mean a value that is measured by the following method. Silica is first dispersed in water to prepare a dispersion that has a silica concentration of 4% by mass. After dispersion is sufficiently stirred, the pH value of the dispersion is measured with a pH meter.
- a catalyst, a reinforcing agent, a plasticizer, an age resister, a coloring agent, etc. may be mixed therein in addition to the organic metal compound, rubber polymer and inorganic filler.
- a plasticizer can improve the flexibility of the produced three-dimensional crosslinked body, namely the flexibility of the dielectric film of the present invention. As a consequence, the dielectric film of the present invention can be easily stretched.
- the plasticizer is incorporated into the film, it is possible to obtain larger force and displacement in an actuator, for example.
- the plasticizer to be mixed is preferably one which is highly insulative and is sparingly volatile.
- suitable plasticizers include tricresyl phosphate, tris(2-ethylhexyl) trimellitate, chlorinated paraffin, tris(n-octyl) trimellitate, tris(isononyl) trimellitate, tris(isodecyl) trimellitate, dipentaerythritol esters and octyl esters of pyromellitic acid.
- the production process for the dielectric film of the present invention is not specifically limited.
- the dielectric film may be produced by, for example, the methods that are shown in (1) and (2) below.
- a rubber polymer, an inorganic filler and an organic metal compound are kneaded with rolls or a kneader (kneading step), and the kneaded product is formed into a thin film under predetermined conditions (film forming step).
- a first solution that includes a solvent in which a rubber polymer and an inorganic filler are contained is first prepared (first solution preparing step).
- first solution preparing step an organic metal compound, either as such or as a solution in a predetermined solvent, is mixed so as to prepare a second solution (second solution preparing step). Thereafter, the second solution is applied to a substrate and dried under predetermined conditions (film forming step).
- the rubber polymer and inorganic filler may be previously kneaded with rolls or a kneader, and the resulting kneaded mixture is subsequently added to the solvent to prepare the first solution.
- the first solution may be prepared by mixing a solution of the rubber polymer in a solvent with a dispersion of the inorganic filler in a solvent.
- this solvent may be the same as or different from the solvent that is used in the preparation of the first solution.
- a catalyst, a reinforcing agent, a plasticizer, an age resister, a coloring agent, etc. may be added in the kneading step as needed.
- a catalyst, a reinforcing agent, a plasticizer, an age resister, a coloring agent, etc. may be added in the first solution preparing step and second solution preparing step, as needed.
- a mixing amount of the organic metal compound is preferably 0.5 part by mass or more and 40 parts by mass or less per 100 parts by mass of the rubber polymer. When the amount is less than 0.5 part by mass, crosslinking does not proceed sufficiently so that the three-dimensional crosslinked body is not easily produced.
- the mixing amount is preferably 1.5 parts by mass or more. When the amount exceeds 40 parts by mass, on the other hand, crosslinking excessively proceeds so that there is a possibility that the dielectric film becomes hard and the flexibility thereof is deteriorated.
- the mixing amount is preferably 30 parts by mass or less.
- a mixing amount of the inorganic filler is preferably 1 part by mass or more and 40 parts by mass or less per 100 parts by mass of the rubber polymer. When the amount is less than 1 part by mass, flow of electrons cannot be sufficiently interrupted so that the effect of increasing the electric resistance is small.
- the mixing amount is preferably 5 parts by mass or more. When the amount exceeds 40 parts by mass, on the other hand, there is a possibility that the dielectric film becomes hard and the flexibility thereof is deteriorated.
- the mixing amount is preferably 30 parts by mass or less.
- the mixing amount thereof is preferably 1 part by mass or more and 200 parts by mass or less per 100 parts by mass of a total amount of the rubber polymer and the organic metal compound.
- the mixing amount is preferably 5 parts by mass or more.
- the mixing amount exceeds 200 parts by mass, on the other hand, there is a possibility that the compatibility of the plasticizer with the rubber component is deteriorated and bleeding occurs.
- the mixing amount is preferably 150 parts by mass or less.
- the organic metal compound reacts with water in the air or in the reaction system (rubber polymer, solution) to undergo hydrolysis and polycondensation (sol-gel reaction). It is, therefore, desirable to use the organic metal compound in a chelated form using a chelating agent in order to suppress abrupt reaction with water and to form a homogeneous film.
- a metal alkoxide compound has high reactivity and, hence, is desired to be used in a chelated form.
- a metal acylate compound is not so reactive as compared with the metal alkoxide compound and, therefore, the necessity for chelating is low.
- a first solution that includes a predetermined solvent in which the rubber polymer and the inorganic filler are contained is first prepared (first solution preparing step).
- first solution preparing step an organic metal compound in a chelated form is mixed so as to obtain a second solution (second solution preparing step).
- second solution preparing step an organic metal compound in a chelated form is mixed so as to obtain a second solution (second solution preparing step).
- second solution is applied to a substrate and dried under predetermined conditions to remove the chelating agent and to allow a crosslinking reaction to proceed (crosslinking step).
- the chelating agent examples include ⁇ -diketones such as acetyl acetone, benzoyl acetone and dibenzoylmethane, ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate, triethanolamine, lactic acid, 2-etylhexane-1,3-diol and 1,3-hexanediol.
- the chelating agent is desirably used in an amount of 10 parts by mass or more and 100,000 parts by mass or less per 100 parts by mass of the organic metal compound. When the amount is less than 10 parts by mass, the organic metal compound cannot be sufficiently chelated.
- the mixing amount is preferably 50 parts by mass or more. When the amount exceeds 100,000 parts by mass, it becomes difficult to remove the chelating agent and, therefore, the drying, for example, must be performed excessively.
- the mixing amount is preferably 8,000 parts by mass or less.
- a first solution that contains the rubber polymer and the inorganic filler in a solvent that is capable of dissolving the rubber polymer and of chelating the organic metal compound is first prepared (first solution preparing step). Then, the organic metal compound is mixed into the first solution to prepare a second solution (second solution preparing step). Thereafter, the solvent is removed from the second solution to allow a crosslinking reaction to proceed (crosslinking step).
- the solvent may consist only of the chelating agent or may be a mixture of the chelating agent and other solvent.
- the crosslinking step it is only necessary to apply the second solution to a substrate and dry it. By so doing, a dielectric film in the form of a thin film may be produced.
- a temperature of the crosslinking step may be appropriately determined according to the type of solvent in consideration of the reaction speed, etc. For example, room temperature may be employed. However, a temperature that is not lower than the boiling point of the solvent may be desirably used.
- the production process for the dielectric film may include the following three steps. At first, a first solution that contains the rubber polymer, the inorganic filler and the plasticizer in a solvent that is capable of dissolving the rubber polymer and of chelating the organic metal compound is prepared (first solution preparing step). Then, the organic metal compound is mixed into the first solution to prepare a second solution (second solution preparing step). Thereafter, the solvent is removed from the second solution to allow a crosslinking reaction to proceed (crosslinking step).
- the transducer of the present invention includes the dielectric film according to the present invention, and a plurality of electrodes that are arranged via the dielectric film.
- the constitution and process for production of the dielectric film of the present invention are as described above and the description thereof is omitted here.
- the transducer of the present invention it is desired that the preferred embodiments of the dielectric film of the present invention be also employed.
- a thickness of the dielectric film may be appropriately determined according to, for example, the intended use thereof.
- the thickness of the transducer be thin from the standpoint of compactness of the actuator, capability of driving at a low voltage, large displacement, etc.
- the thickness of the dielectric film be 1 ⁇ M or more and 1,000 ⁇ M (1 mm) or less, more preferably 5 ⁇ m or more and 200 ⁇ m or less.
- the material for the electrode is not specifically limited. It is possible to use, for example, an electrode that is obtainable by applying a paste or paint which is a mixture of: an electrically conductive material formed by a carbonaceous material, such as carbon black or carbon nanotubes, or a metal; and a binder such as oil or an elastomer. Alternatively, an electrode may be used that is obtainable by weaving a carbonaceous material or a metal into mesh. It is desired that the electrode be expandable/contractible in conformity with the expansion/contraction of the dielectric film. When the electrode is expanded/contracted together with the dielectric film, deformation of the dielectric film is not disturbed by the electrode. As a consequence, when the transducer of the present invention is used as an actuator, for example, desired displacement may be easily achieved.
- the transducer of the present invention is designed such that a plurality of the dielectric films and electrodes are alternately laminated, it is possible to generate larger force. Therefore, when such a laminated structure is employed, a high output of an actuator, for example, can be obtained. By this, a member to be driven can be driven with a larger force.
- FIG. 1 shows a cross-sectional schematic view of an actuator of the first embodiment, in which (a) shows an OFF state and (b) shows an ON state.
- the actuator 1 includes a dielectric film 10 and electrodes 11 a and 11 b .
- the dielectric film 10 is a three-dimensional crosslinked body (dielectric film of the present invention) that has been synthesized from tetrakis(2-ethylhexyloxy) titanium (metal alkoxide compound), hydrogenated nitrile rubber that has carboxyl groups (rubber polymer) and silica (inorganic filler).
- the electrodes 11 a and 11 b are fixed to upper and lower sides of the dielectric film 10 , respectively.
- the electrodes 11 a and 11 b are connected to a power source 12 through wires.
- the actuator is turned from the OFF state to the ON state when a voltage is applied between the paired electrodes 11 a and 11 b .
- the thickness of the dielectric film 10 is reduced and, therefore, correspondingly expands in the direction parallel with the planes of the electrodes 11 a and 11 b as shown by the white arrows in FIG. 1( b ).
- the actuator 1 can output driving forces in the up-down direction and left-right direction.
- the electric resistance of the dielectric film 10 is high.
- a high voltage is applied between the electrodes 11 a and 11 b , therefore, an electric current does not easily flow through the dielectric film 10 .
- a large amount of charges can be stored in the dielectric film 10 .
- large electrostatic attractive force is generated so that large force and displacement are obtainable.
- generation of Joule heat is suppressed.
- the dielectric film 10 does not easily undergo insulation breakdown.
- the actuator 1 has excellent durability. Incidentally, insulation breakdown strength of the dielectric film 10 is improved when the dielectric film 10 is arranged in the state where it is stretched in the surface-extending direction thereof. In this case, since it is possible to apply a higher voltage, large force and displacement are obtainable.
- FIG. 2 shows a cross-sectional schematic view of a capacitive sensor of the second embodiment.
- the capacitive sensor 2 includes a dielectric film 20 , electrodes 21 a and 21 b and a substrate 22 .
- the dielectric film 20 is a three-dimensional crosslinked body (dielectric film of the present invention) that has been synthesized from tetrakis(2-ethylhexyloxy) titanium (metal alkoxide compound), hydrogenated nitrile rubber that has carboxyl groups (rubber polymer) and silica (inorganic filler).
- the dielectric film 20 is in the form of a strip that extends in the left-right direction.
- the dielectric film 20 is disposed on an upper surface of the substrate 22 via the electrode 21 b .
- the electrodes 21 a and 21 b are each in the form of a strip that extends in the left-right direction.
- the electrodes 21 a and 21 b are fixed to upper and lower sides of the dielectric film 20 , respectively.
- the electrodes 21 a and 21 b are connected to wires (not shown).
- the substrate 22 is an insulative flexible film and is in the form of a strip that extends in the left-right direction.
- the substrate 22 is fixed to a lower side of the electrode 21 b.
- the capacitance of the capacitive sensor 2 may be determined from the following equation (I):
- the electric resistance of the dielectric film 20 is high. Therefore, even when the capacitance between the electrodes 21 a and 21 b becomes high as a result of application of a large compression force, an electric current does not easily flow through the dielectric film 20 . For this reason, it is possible to precisely detect the amount and position of the applied load. In addition, because an electric current does not easily flow through the dielectric film 20 , generation of Joule heat is suppressed. For this reason, there is low possibility that the dielectric film 20 is thermally broken down. Further, the dielectric film 20 does not easily undergo insulation breakdown. Thus, the capacitive sensor 2 has excellent durability.
- FIG. 3 shows a cross-sectional schematic view of an electric power generation element of the third embodiment, in which (a) shows an expanded state and (b) shows a contracted state.
- the electric power generation element 3 includes a dielectric film 30 and electrodes 31 a and 31 b .
- the dielectric film 30 is a three-dimensional crosslinked body (dielectric film of the present invention) that has been synthesized from tetrakis(2-ethylhexyloxy) titanium (metal alkoxide compound), hydrogenated nitrile rubber that has carboxyl groups (rubber polymer) and silica (inorganic filler).
- the electrodes 31 a and 31 b are fixed to upper and lower sides of the dielectric film 30 , respectively.
- the electrodes 31 a and 31 b are connected to wires and the electrode 31 b is grounded.
- the electric resistance of the dielectric film 30 is high. Therefore, even when the amount of compression is large, an electric current does not easily flow through the dielectric film 30 so that a large amount of charges are stored between the electrodes 31 a and 31 b . For this reason, it is possible to generate a large amount of power. In addition, because an electric current does not easily flow through the dielectric film 30 , generation of Joule heat is suppressed. For this reason, there is low possibility that the dielectric film 30 is thermally broken down. Further, the dielectric film 30 does not easily undergo insulation breakdown. Thus, the electric power generation element 3 has excellent durability.
- Dielectric films of Examples 1 to 10 were produced from the raw materials that are shown in Table 1.
- a carboxyl group-containing hydrogenated nitrile rubber (THERBAN (registered trademark) XT8889 manufactured by LANXESS Inc.) and the specified silica were kneaded with a roll kneader to prepare a rubber composition.
- the thus prepared rubber composition was then dissolved in acetyl acetone.
- tetrakis(2-ethylhexyloxy) titanium as an organic metal compound was added to be mixed.
- the acetyl acetone served not only as a solvent for dissolving the carboxyl group-containing hydrogenated nitrile rubber (rubber polymer) but also as a chelating agent for the tetrakis(2-ethylhexyloxy) titanium (metal alkoxide compound).
- the mixture solution was thereafter applied to a substrate, dried and heated at 150° C. for about 60 minutes to obtain each dielectric film.
- Each of the dielectric films had a thickness of about 40 ⁇ m.
- Dielectric films of Reference Examples 1 and 2 were produced from the raw materials that are shown in Table 1.
- the dielectric films of Examples 1 to 10 differ from those of Reference Examples 1 and 2 in the presence or absence of silica.
- a carboxyl group-containing hydrogenated nitrile rubber (same as above) was dissolved in acetyl acetone.
- tetrakis(2-ethylhexyloxy) titanium was added to be mixed.
- the mixture solution was thereafter applied to a substrate, dried and heated at 150° C. for about 60 minutes to obtain each dielectric film.
- Each of the dielectric films had a thickness of about 40 ⁇ m.
- Dielectric films of Examples 11 to 16 were produced from the raw materials that are shown in Table 2 in the same manner as that for the production of the dielectric films of Examples 1 to 10 except that the kind of inorganic filler was changed. Each of the dielectric films had a thickness of about 40 ⁇ m.
- Dielectric films of Examples 17 to 21 were produced from the raw materials that are shown in Table 3 in the same manner as that for the production of the dielectric films of Examples 1 to 10 except that a plasticizer was mixed.
- a carboxyl group-containing hydrogenated nitrile rubber (same as above) and silica (b) that is described hereinafter were kneaded with a roll kneader to prepare a rubber composition.
- the thus prepared rubber composition was then dissolved in acetyl acetone.
- tetrakis(2-ethylhexyloxy) titanium and the specified plasticizer were added to be mixed.
- the mixture solution was thereafter applied to a substrate, dried and heated at 150° C. for about 60 minutes to obtain each dielectric film.
- Each of the dielectric films had a thickness of about 40 ⁇ M.
- Dielectric films of Examples 22 to 25 were produced from the raw materials that are shown in Table 4 in the same manner as that for the production of the dielectric films of Examples 1 to 10 except that the kind of the organic metal compound was changed. Each of the dielectric films had a thickness of about 40 ⁇ m.
- Dielectric films of Comparative Examples 1 and 2 were produced from the raw materials that are shown in Table 5. At first, the specified raw materials were mixed and dispersed with a roll kneader to prepare a rubber composition. The thus prepared rubber composition was then shaped into a thin sheet, fed into a mold, and subjected to press-crosslinking at 175° C. for about 30 minutes to obtain each dielectric film. Each of the dielectric films had a thickness of about 50 ⁇ m.
- Silica shown in Tables 1, 3 and 4 are as follows.
- Silicone rubber “DMS-V31” (manufactured by Gelest, Inc.)
- Nitrile rubber “Nipol (registered trademark) 1042” (manufactured by ZEON CORPORATION)
- Methyl-H-siloxane “TSF484” (manufactured by GE Toshiba Silicones Co., Ltd.)
- Retarder “Surfynol (registered trademark) 61” manufactured by Nissin Chemical Industry Co., Ltd.
- Platinum catalyst “SIP6830.0” manufactured by Gelest, Inc.
- Vulcanization aid Zinc Oxide Grade 2 (manufactured by Mitsui Mining & Smelting Co., Ltd)
- Stearic acid “LUNAC (registered trademark) S30” (manufactured by Kao Corporation)
- Tetraethylthiuram disulfide “Sanceler (registered trademark) TET-G” (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)
- N-Cyclohexyl-2-benzothiazyl sulfenamide “Sanceler (registered trademark) CZ-GS” (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)
- Sulfur “SULFAX T-10” manufactured by TURUMI CHEMICAL INDUSTRY CO., LTD.)
- any of the dielectric films of Examples has a high electric resistance, namely has high insulative properties.
- the electric resistance of Example 1 is higher than that of Reference Example 1 and the electric resistances of Examples 2 to 5, 8 and 10 are higher than that of Reference Example 2.
- the dielectric films of Examples that contain silica each have a higher electric resistance as compared with the dielectric films of Reference Examples that do not contain silica.
- the electric resistance of Examples 11 to 16 is higher than that of Reference Example 2.
- the dielectric films of Examples that contain an inorganic filler each have a higher electric resistance as compared with the dielectric films of Reference Examples that do not contain an inorganic filler.
- each of the dielectric films of Examples 17 to 21 in which a plasticizer was mixed has high electric resistance.
- the electric resistance of the dielectric film in which the conventional silicone rubber is used (Comparative Example 1) is high while the electric resistance of the dielectric film in which nitrile rubber is used (Comparative Example 2) is low, as shown Table 5.
- Actuators were next prepared using each of the dielectric films of Examples, Reference Examples and Comparative Examples and their maximum generated stresses and maximum field strengths were measured. Description will be first made of an experiment device and an experiment method.
- Actuators were prepared by bonding an electrode formed by a mixture of an acrylic rubber with carbon black to each of the front and back surfaces of each of the dielectric films of Examples, Reference Examples and Comparative Examples.
- the prepared actuators will be hereinafter referred to as “actuators of Examples”, etc. in correspondence with the types of the dielectric films.
- FIG. 4 A front view of an actuator mounted to an experiment device is shown in FIG. 4 .
- FIG. 5 is a V-V sectional view of FIG. 4 .
- an upper end of an actuator 5 is held by an upper chuck 52 , while a lower end of the actuator 5 is held by a lower chuck 53 .
- the actuator 5 is mounted between the upper chuck 52 and the lower chuck 53 in the state where the film is stretched in the upper-lower direction beforehand (stretching rate: 25%).
- a load cell (not shown) is disposed above the upper chuck 52 .
- the actuator 5 includes a dielectric film 50 and a pair of electrodes 51 a and 51 b .
- the dielectric film 50 in a free state is a rectangular film that is 50 mm long, 25 mm wide and about 40 ⁇ m thick.
- the electrodes 51 a and 51 b are arranged so as to face each other with the dielectric film 50 being sandwiched therebetween.
- Each of the electrodes 51 a and 51 b in a free state is a rectangular film that is 40 mm long, 25 mm wide and about 10 ⁇ m thick.
- the electrodes 51 a and 51 b are arranged in the state where they are offset by 10 mm in the upper-lower direction.
- the electrodes 51 a and 51 b overlap with each other through the dielectric film 50 over the area of 30 mm length and 25 mm width.
- a wire (not shown) is connected to a lower end of the electrode 51 a .
- a wire (not shown) is connected to an upper end of the electrode 51 b .
- the electrodes 51 a and 51 b are connected to a power source (not shown) through the wires.
- the maximum generated stresses of the actuators of Examples are larger than those of the actuators of Comparative Examples. It is also seen that the generated stress of the actuator of Comparative Example 1 in which the dielectric film made of a silicone rubber is used is small, though the maximum field strength is very high.
- the maximum generated stress of Example 1 is larger than that of Reference Example 1 and the maximum generated stresses of Examples 2 to 5, 8 and 10 are larger than that of Reference Example 2.
- Examples 11 to 16 in Table 2 and Reference Example 2 in which the mixing amount of the metal alkoxide compound is the same the maximum generated stresses of Examples 11 to 16 are larger than that of Reference Example 2.
- the maximum generated stress is also large in Examples 17 to 21 in which a plasticizer is used.
- the electric resistances of the dielectric films of Examples are high. Therefore, the actuators of Examples can store a large amount of charges. Further, the dielectric films each also have high resistance to insulation breakdown, so that breakage by Joule heat can be suppressed. Therefore, it is possible to apply a high voltage to the actuators of Examples. It is considered that the actuators of Examples could output large force for the above reasons.
- the dielectric film of the present invention may be widely used in transducers such as actuators, sensors, electric power generation elements, etc. that perform conversion between mechanical energy and electrical energy, as well as speakers, microphones, noise cancellers etc. that perform conversion between acoustic energy and electrical energy.
- the dielectric film is suited for flexible actuators that are used, for example, in artificial muscle for industrial, medical or rehabilitation robots; in small pumps that are used for, for example, electronic part coolers and medical purposes; and in medical instruments.
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PCT/JP2010/065200 WO2011033956A1 (fr) | 2009-09-18 | 2010-09-06 | Film diélectrique, son procédé de fabrication et transducteur l'utilisant |
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EP (1) | EP2390998A4 (fr) |
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Also Published As
Publication number | Publication date |
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WO2011033956A1 (fr) | 2011-03-24 |
JP5558876B2 (ja) | 2014-07-23 |
EP2390998A4 (fr) | 2014-05-21 |
KR20120042723A (ko) | 2012-05-03 |
US20160312002A1 (en) | 2016-10-27 |
US10035897B2 (en) | 2018-07-31 |
CN102405590B (zh) | 2014-12-03 |
JP2011084712A (ja) | 2011-04-28 |
CN102405590A (zh) | 2012-04-04 |
KR101344608B1 (ko) | 2013-12-26 |
EP2390998A1 (fr) | 2011-11-30 |
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