JP6249852B2 - Dielectric film manufacturing method - Google Patents

Description

  The present invention relates to a transducer using an elastomer material, and more particularly, to a dielectric film used for the transducer.

  Known transducers include actuators, sensors, power generation elements, etc. that convert mechanical energy and electrical energy, or speakers, microphones, etc. that convert acoustic energy and electrical energy. Polymer materials such as dielectric elastomers are useful for constructing a highly flexible, small and lightweight transducer. For example, a transducer can be configured by arranging a pair of electrodes on both sides in the thickness direction of a dielectric film made of a dielectric elastomer.

  In order to increase the electrostatic attraction with respect to the applied voltage and improve the performance of the transducer, it is necessary to increase the relative dielectric constant of the dielectric film. For this reason, as described in Patent Documents 1 and 2, various dielectric films have been proposed in which dielectric particles having a high dielectric constant such as barium titanate are blended into an elastomer.

JP 2008-53527 A International Publication No. 2013/058237 JP 2006-244927 A

  When dielectric particles are blended with the elastomer, the dielectric constant of the dielectric film can be increased. However, when dielectric particles having a large particle size are included, the particles are the starting point and are likely to cause dielectric breakdown. In addition, since the dielectric particles tend to aggregate, it is difficult to uniformly disperse them in the elastomer. In this case, agglomerates in which the dielectric particles agglomerate are the starting points, and dielectric breakdown is likely to occur.

  In recent years, thinning of the dielectric film has been promoted from the viewpoints of improving safety by lowering the applied voltage, reducing the cost of the booster circuit, and expanding applications. As the thickness of the dielectric film decreases, the influence of the size of dielectric particles and the presence of aggregates on the film thickness becomes more significant. Therefore, when the dielectric film is thinned, the reduction of the dielectric breakdown strength due to the dielectric particles becomes a big problem.

  Patent Document 1 discloses a dielectric rubber layer containing dielectric particles having a relative dielectric constant of 200 or more and having a thickness of 10 to 200 μm. However, in Patent Document 1, the dielectric breakdown strength of the dielectric rubber layer is not a problem, and there is no description regarding the particle diameter or dispersion state of the dielectric particles.

  Patent Document 2 discloses a dielectric film including an elastomer and barium titanate particles having a crystallinity of 80% or more, and having a crosslinked structure formed of the elastomer and the barium titanate particles. In the dielectric film described in Patent Document 2, barium titanate particles having a crystallinity of 80% or more are used based on the knowledge that the relative dielectric constant of the barium titanate particles increases as the crystallinity increases. Moreover, aggregation with the barium titanate particles is suppressed by bonding with the elastomer. For this reason, a functional group capable of reacting with the elastomer is required on the surface of the barium titanate particles. Thus, in order to produce the barium titanate particles having a desired crystallinity and functional group, hydrothermal synthesis using supercritical water, as described in Patent Document 2, is not a normal production method. It is necessary to employ a sol-gel method using a high-concentration precursor or a high-concentration precursor. Also, Patent Document 2 does not discuss the reduction in dielectric breakdown strength when the dielectric film is thinned.

  In Patent Document 3, as a composite material used as a gate insulating film of a transistor, a composite material including particles having a 50% diameter in a volume cumulative distribution of 100 nm or less and a relative dielectric constant of 50 or more and an insulating resin Is disclosed. However, the use of the composite material described in Patent Document 3 is not a transducer. For this reason, the matrix is a resin and the composite material is poor in flexibility. Further, the particles blended in the resin are limited to those having a relatively small particle diameter, but the dispersion state of the particles in the matrix is not taken into consideration.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a dielectric film that is flexible, has a large relative dielectric constant, and has a high dielectric breakdown strength even when it is thinned. Another object of the present invention is to provide a transducer that is excellent in dielectric breakdown resistance and can output a large force using the dielectric film.

(1) The dielectric film of the present invention includes an elastomer and dielectric particles, and satisfies the following conditions (A), (B), and (C).
(A) Film development of three straight lines extending in the film thickness direction having a length of 1/2 or more of the length in the film thickness direction of the cross-sectional photograph taken by the scanning electron microscope Draw at a distance of 500 nm in the direction, and for each straight line, count the number of the dielectric particles that intersect the straight line, and divide the number by the length of the straight line to obtain a reference number per 1 μm of the straight line Is calculated, the average value of the reference numbers in the three straight lines is 0.8 / μm or more.
(B) Among the dielectric particles intersecting with the three straight lines in (A), the number of large particles having a particle diameter larger than 1/10 of the thickness of the dielectric film is counted for each straight line, When the number of large particles per 1 μm of the straight line is calculated by dividing the number by the length of the straight line, the average value of the number of large particles in the three straight lines is 0.2 / μm or less. .
(C) A cross-sectional photograph taken in the film thickness direction taken by a scanning electron microscope was provided with a measurement region formed by connecting 100 unit regions of 200 nm square, and the area occupied by the elastomer was measured for each unit region. In this case, the number of the unit regions whose area ratio of the elastomer in the measurement region is 30% or less is 10 or less.

  First, the condition (A) will be described. In FIG. 1, the schematic diagram of the cross-sectional photograph of the dielectric film for demonstrating the conditions (A) in this invention is shown. FIG. 1 is a schematic diagram for explaining a procedure for calculating the reference number of the condition (A). FIG. 1 is not intended to limit the dielectric film of the present invention, including the size, shape, number, arrangement, and thickness of the dielectric film.

  The cross-sectional photograph 100 is a photograph of a cross section in the film thickness direction of the dielectric film taken with a scanning electron microscope (SEM). A large number of dielectric particles 102 are dispersed in the elastomer 101. In order to determine whether or not the condition (A) is satisfactory, first, three straight lines α, β, and γ extending in the vertical direction (thickness direction of the dielectric film) are drawn in an arbitrary portion of the cross-sectional photograph 100. The distance between the three straight lines α, β, and γ in the left-right direction (dielectric film development direction) is 500 nm each. The lengths of the three straight lines α, β, and γ are L μm that is 1/2 or more of the vertical length of the cross-sectional photograph 100. Next, for each of the three straight lines α, β, and γ, the number of dielectric particles 102 that intersect the straight lines α, β, and γ is counted. Here, the number of dielectric particles 102 that intersect with the three straight lines α, β, and γ is X for the straight line α, Y for the straight line β, and Z for the straight line γ. Subsequently, the reference number per 1 μm of each straight line is calculated by dividing each number by the length L μm of the straight line. In this case, the reference number in each straight line is X / L (pieces / μm), Y / L (pieces / μm), and Z / L (pieces / μm). Finally, an average value [(X + Y + Z) / (3L)] of the three reference numbers is calculated. And it is judged whether the obtained average value is 0.8 piece / micrometer or more. In this way, the sufficiency of the condition (A) is determined.

  In condition (A), the average value of the reference number is a value related to the number and size of dielectric particles. If the number of dielectric particles in the elastomer is small, the average value of the reference number becomes small. In this case, the effect of increasing the relative dielectric constant is reduced. Moreover, since the number of dielectric particles tends to decrease when the size of the dielectric particles is large, the average value of the reference numbers becomes small. In this case, dielectric breakdown starting from dielectric particles tends to occur. An average value of the reference number of 0.8 particles / μm or more indicates that the number and size of the dielectric particles are appropriate. That is, the dielectric film has a large relative dielectric constant and is difficult to break down. Thus, the condition (A) serves as an index of the relative dielectric constant and the dielectric breakdown strength.

  Next, the condition (B) will be described. Of the dielectric particles 102 that intersect the three straight lines α, β, and γ in the condition (A), the number of large particles having a particle diameter larger than 1/10 of the film thickness of the dielectric film is counted. Here, the number of large particles is x for the straight line α, y for the straight line β, and z for the straight line γ. The large particles include agglomerated particles whose particle size is increased by aggregation of a plurality of particles, in addition to single particles having a large particle size. Subsequently, the number of large particles per 1 μm of each straight line is calculated by dividing each number by the length L μm of the straight line. In this case, the number of large particles in each straight line is x / L (number / μm), y / L (number / μm), and z / L (number / μm). Finally, the average value [(x + y + z) / (3L)] of the three large particles is calculated. And it is judged whether the obtained average value is 0.2 piece / micrometer or less. In this way, the satisfaction of the condition (B) is determined.

  In the condition (B), the average value of the number of large particles being 0.2 particles / μm or less indicates that the number of dielectric particles having a large particle diameter with respect to the film thickness is small. In this case, even when the film thickness is small, dielectric breakdown starting from dielectric particles is unlikely to occur. As described above, the condition (B) is an index of dielectric breakdown strength.

  Next, the condition (C) will be described. FIG. 2 shows a schematic diagram of a cross-sectional photograph of a dielectric film for explaining the condition (C) in the present invention. FIG. 3 shows a schematic diagram in which one of the unit regions in FIG. 2 is enlarged. For convenience of explanation, the elastomer and dielectric particles are omitted in FIG. 2 and 3 are schematic diagrams for explaining the unit region and the measurement region of the condition (B). 2 and 3 do not limit the dielectric film of the present invention in any way, including the size, shape, number, arrangement, and thickness of the dielectric film.

  When judging whether or not the condition (C) is satisfactory, first, as shown in FIG. 2, in a cross-sectional photograph 100 in which a cross section in the film thickness direction of the dielectric film is taken with a scanning electron microscope (SEM), a square of 2 μm square is formed. A measurement area M is provided. The measurement area M is divided by 10 unit areas E in the vertical direction × 10 in the horizontal direction (total of 100). The unit region E is a 200 nm square. In the unit region E, the elastomer 101 and the dielectric particles 102 are observed as shown in FIG. Next, for each unit region E, the area occupied by the elastomer 101 is measured. Then, as indicated by hatching in FIG. 2, the number of unit regions E in which the area ratio of the elastomer 101 is 30% or less is counted. Then, it is determined whether or not the number is 10 or less. In this way, the sufficiency of the condition (C) is determined.

  Here, the arrangement method of the unit regions E is not particularly limited. However, from the viewpoint of uniformly detecting the dispersion state of the dielectric particles in the film thickness direction and the film development direction, the same number (10 × 10) of unit regions E are arranged in the film thickness direction and the film development direction. The measurement area M is preferably a square of 2 μm square (see FIG. 2). However, there may be cases where ten unit regions E cannot be arranged in the film thickness direction, such as when the thickness of the dielectric film is less than 2 μm. In this case, the remaining unit regions E that cannot be arranged in the film thickness direction may be arranged in addition to the film development direction.

  In the condition (C) of the present invention, the number of unit regions having an elastomer area ratio of 30% or less is 10 or less, which means that there are many elastomer components or many regions where the elastomer components are continuously present. It shows that. In this case, the polymer network increases elongation and the dielectric film becomes flexible. Thus, the condition (C) is an index of flexibility. In addition, when the dielectric film is flexible, the mechanical strength is not easily lowered even if the expansion and contraction is repeated. For this reason, the flexibility of the dielectric film leads to an improvement in the dielectric breakdown strength during deformation.

  In summary, it can be said that a dielectric film satisfying all the conditions (A), (B), and (C) has a large relative dielectric constant and dielectric breakdown strength and is flexible. That is, by realizing a dispersion form of dielectric particles that satisfies the conditions (A), (B), and (C), the dielectric film is flexible, has a large relative dielectric constant, and has a high dielectric breakdown strength even when the film thickness is small. Can be obtained.

  (2) A transducer according to the present invention includes the dielectric film according to the present invention, and a plurality of electrodes disposed via the dielectric film.

  The transducer of the present invention includes the dielectric film of the present invention. As described above, the relative dielectric constant of the dielectric film of the present invention is large. For this reason, the electrostatic attraction with respect to the applied voltage is large. In addition, the dielectric film of the present invention is flexible. For this reason, according to the transducer of the present invention, a large force and displacement can be obtained with a practical voltage. Moreover, the dielectric film of the present invention has a high dielectric breakdown strength even when it is thinned. Therefore, the transducer of the present invention is excellent in resistance to dielectric breakdown. According to the transducer of the present invention, the provision of the thin dielectric film having a high dielectric breakdown strength enables operation under a lower voltage, improving safety, reducing the cost of the booster circuit, and reducing the size. Can be planned.

It is a schematic diagram of the cross-sectional photograph of the dielectric film for demonstrating the conditions (A) in this invention. It is a schematic diagram of the cross-sectional photograph of the dielectric film for demonstrating the conditions (B) in this invention. It is the schematic diagram which expanded one of the unit area | regions in FIG. It is a perspective view of the speaker which is 1st embodiment of the transducer of this invention. It is VV sectional drawing of FIG. It is a cross-sectional schematic diagram of the actuator which is 2nd embodiment of the transducer of this invention, Comprising: (a) shows a voltage-off state, (b) shows a voltage-on state. It is a top view of the capacitive sensor which is 3rd embodiment of the transducer of this invention. It is VIII-VIII sectional drawing of FIG. It is a cross-sectional schematic diagram of the electric power generation element which is 4th embodiment of the transducer of this invention, Comprising: (a) shows at the time of expansion | extension, (b) shows the time of contraction. It is a SEM photograph of the film thickness direction cross section of the dielectric film (film thickness of 10 micrometers) of Example 2. FIG. It is a front side view of the actuator attached to the measuring device. It is XII-XII sectional drawing of FIG.

  Hereinafter, embodiments of the dielectric film and the transducer of the present invention will be described. The dielectric film and the transducer of the present invention are not limited to the following embodiments, and can be variously modified and improved by those skilled in the art without departing from the gist of the present invention. Can be implemented.

<Dielectric film>
The dielectric film of the present invention includes an elastomer and dielectric particles, and satisfies the above conditions (A), (B), and (C).

[Elastomer]
Elastomers include cross-linked rubbers and thermoplastic elastomers. One of these can be used alone, or two or more can be mixed and used. The elastomer may be appropriately selected according to the performance required for the transducer. For example, from the viewpoint of increasing the electrostatic attractive force with respect to the applied voltage, it is desirable to employ an elastomer having a large polarity, that is, a large relative dielectric constant. Specifically, those having a relative dielectric constant of 2.8 or more (measurement frequency 100 Hz) are suitable. Examples of the elastomer having a large relative dielectric constant include nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), acrylic rubber, natural rubber, isoprene rubber, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic. Examples include acid ester copolymers, butyl rubber, styrene-butadiene rubber, fluorine rubber, epichlorohydrin rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, and urethane rubber. In addition, even if the relative dielectric constant is small, an elastomer having a large electric resistance is desirable because it is difficult to break down when a voltage is applied. Examples of the elastomer having a large electric resistance include silicone rubber and ethylene-propylene-diene copolymer. Further, an elastomer modified by introducing a functional group or the like may be used. As the modified elastomer, for example, carboxyl group-modified nitrile rubber (X-NBR), carboxyl group-modified hydrogenated nitrile rubber (XH-NBR) and the like are suitable. In X-NBR and XH-NBR, the acrylonitrile content (bound AN amount) is preferably 33% by mass or more. The amount of bonded AN is the mass ratio of acrylonitrile when the total mass of the rubber is 100% by mass.

  Thermoplastic elastomers are suitable because they do not contain a cross-linking agent and thus are less likely to contain impurities. Thermoplastic elastomers include styrene (SBS, SEBS, SEPS), olefin (TPO), vinyl chloride (TPVC), urethane (TPU), ester (TPEE), amide (TPAE), Examples include polymers and blends.

[Dielectric particles]
As long as the dielectric particles are particles having a relative dielectric constant larger than that of the matrix elastomer, the material, production method and the like are not particularly limited. For example, inorganic particles such as barium titanate, lead zirconate titanate, lanthanum-doped lead zirconate titanate, strontium titanate, bismuth titanate, and bismuth barium titanate are suitable. As the dielectric particles, one kind of these may be used alone, or two or more kinds may be mixed and used. Moreover, you may use the inorganic particle by which the surface was modified by the functional group with high polarity. Examples of the highly polar functional group include functional groups including halogen, amide, cyano group, amine, phosphoric acid, sulfonic acid and the like. For modification with a functional group, a known method such as a dehydration reaction, an ene-thiol reaction, or a hydrolysis reaction may be used. Even when organic particles are used as the dielectric particles, the surface can be modified with a functional group having a high polarity, like the inorganic particles.

  The dielectric constant of the dielectric particles increases as the crystallinity of the particles increases. For example, when barium titanate is used as the dielectric particles, particles having a c-axis to a-axis ratio (c / a ratio) of the crystal lattice of 1.001 or more are preferably used. As such particles, for example, “KZM-50” manufactured by Sakai Chemical Industry Co., Ltd. is commercially available.

  Examples of the method for producing the dielectric particles include a solid phase reaction method, a hydrothermal synthesis method, a sol-gel method, and an oxalic acid method. The method for producing the dielectric particles is not particularly limited. For example, according to the solid phase reaction method, particles with high crystallinity can be obtained, but the particles are likely to aggregate by firing at a high temperature. Even if pulverization is performed after firing, it is difficult to obtain particles having a small particle size. On the other hand, according to the sol-gel method, it is easy to obtain particles having a small particle diameter, but the crystallinity of the obtained particles is low and the relative dielectric constant is small. In this regard, according to the hydrothermal synthesis method, it is easy to obtain particles having a relatively high crystallinity and a small particle size, although not as much as the solid phase reaction method. Therefore, according to the hydrothermal synthesis method, it is easy to produce dielectric particles suitable for the dielectric film of the present invention.

  If the dielectric film contains many particles having a large particle diameter with respect to the film thickness, the particles serve as starting points and easily cause dielectric breakdown. For this reason, in order to improve the dielectric breakdown strength of the dielectric film, it is desirable to make the particle diameter of the dielectric particles smaller than the film thickness. However, as the particle size of the dielectric particles decreases, the dielectric constant of the dielectric particles decreases. For this reason, in order to increase the relative dielectric constant of the dielectric film, it is desirable to increase the particle diameter of the dielectric particles as much as possible. Therefore, the particle diameter of the dielectric particles may be appropriately determined in consideration of the thickness of the dielectric film and the relative dielectric constant to be realized.

  As will be described later, the dielectric film of the present invention is produced by curing a composition in which an elastomer polymer is mixed with a powder of dielectric particles and other components blended as necessary under predetermined conditions. be able to. In this case, from the viewpoint of dielectric breakdown strength of the dielectric film, it is desirable to use a powder whose 95% diameter in the volume cumulative distribution of the particle diameter is 1/10 or less of the film thickness of the dielectric film as the dielectric particle powder. . From the viewpoint of the dielectric constant of the dielectric film, it is desirable to use a powder having a number average particle diameter of 10 nm or more.

  The number average particle diameter and 95% diameter of the powder of dielectric particles can be measured, for example, using a particle size distribution measuring apparatus such as a dynamic light scattering method (DLS). In this specification, the value measured by “ELSZ-0S” manufactured by Otsuka Electronics Co., Ltd. is adopted.

  The content of dielectric particles in the dielectric film may be appropriately determined in consideration of the dielectric constant and flexibility of the dielectric film. For example, the content of the dielectric particles may be 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the elastomer. When the content of the dielectric particles is less than 20 parts by mass, it is difficult to satisfy the condition (A), and the effect of increasing the dielectric constant is small. On the other hand, when it exceeds 200 parts by mass, it is difficult to satisfy the condition (C), the elastic modulus increases, and the flexibility is impaired. Further, since the dispersibility of the dielectric particles is lowered, it is difficult to satisfy the condition (B), and the dielectric breakdown strength may be impaired.

[Other ingredients]
The dielectric film of the present invention may contain other components in addition to the elastomer and dielectric particles. Examples of other components include a crosslinking agent, a reinforcing material, a plasticizer, an antiaging agent, and a coloring agent. For example, when insulating inorganic particles or the like are blended as the reinforcing material, the mechanical strength and electrical resistance of the dielectric film can be increased. Thereby, the dielectric breakdown strength of the dielectric film is further increased, and the durability is improved when the deformation is repeated.

[Physical properties of dielectric film]
The thickness of the dielectric film of the present invention is not particularly limited, but when used for a transducer, it may be 1 μm or more and 100 μm or less. According to the dielectric film of the present invention, the dielectric breakdown strength is high even when the thickness is reduced to 50 μm or less, further 10 μm or less. From the viewpoint of increasing the electrostatic attractive force with respect to the applied voltage, it is desirable that the dielectric film of the present invention has a large relative dielectric constant. For example, the relative dielectric constant is preferably 13 or more. From the viewpoint of flexibility, the elastic modulus of the dielectric film of the present invention is preferably 100 MPa or less. A more preferable elastic modulus is 50 MPa or less. In addition, the elongation at break of the dielectric film of the present invention is preferably 250% or more. In the present specification, the elastic modulus is calculated from a stress-elongation curve obtained by a tensile test specified in JIS K7127: 1999 (the test piece type 2 is used for the test piece). The elongation at break is measured by a tensile test specified in JIS K6251: 2010 (dumbbell-shaped No. 5 is used for the test piece).

[Dielectric film manufacturing method]
The manufacturing method of the dielectric film of the present invention is not particularly limited. For example, the elastomer polymer, the powder of dielectric particles, and other components blended as necessary may be kneaded with a roll or a kneader and formed into a thin film under predetermined conditions. Alternatively, a liquid raw material containing an elastomer polymer, dielectric particles, and other components blended as necessary may be applied on a substrate and cured under predetermined conditions.

  In order to realize a dispersion form of dielectric particles satisfying the above conditions (A), (B), and (C), it is desirable to monodisperse dielectric particles having a small particle diameter as much as possible in the elastomer. For this purpose, it is desirable to adopt the latter method. In this case, a liquid raw material may be prepared by adding a dispersion in which dielectric particles are dispersed in a solvent to a polymer solution obtained by dissolving an elastomer polymer in a solvent.

  As described above, from the viewpoint of improving the dielectric breakdown strength by reducing the number of dielectric particles having a large particle diameter relative to the film thickness, the 95% diameter in the volume cumulative distribution of the particle diameter is 1 / of the film thickness of the dielectric film. It is desirable to use a powder of dielectric particles that is 10 or less. For example, a dispersion of nanometer-size dielectric particles can be produced by mechanochemical treatment of a preliminary dispersion in which a powder of dielectric particles is dispersed in a solvent. The method of mechanochemical treatment is not particularly limited as long as it is a uniform and finely dispersible method. For example, a wet bead mill, wet ball mill, jet mill, kneader, Banbury mixer, planetary mixer, or the like may be used. Of these, wet bead mills and wet ball mills are suitable. The size of the medium to be used is preferably 0.3 mm or less, more preferably 0.1 mm or less. In addition, after the mechanochemical treatment, dielectric particles having a large particle diameter can be removed by filtering the obtained dispersion. By doing so, it is possible to easily produce a dispersion in which a powder of dielectric particles whose 95% diameter in the volume cumulative distribution of particle diameter is 1/10 or less of the film thickness of the dielectric film is dispersed in a solvent. it can.

  When producing a dispersion, the dielectric particles may be surface-treated with a surface modifier in order to improve the dispersibility of the dielectric particles. As the surface modifier, one that chemically bonds to dielectric particles or one that volatilizes when forming a dielectric film is desirable. If the surface modifier alone remains in the dielectric film, it may be ionized to lower the electrical resistance of the dielectric film, leading to a decrease in dielectric breakdown strength. Examples of the surface modifier include silane-based, titanate-based, aluminate-based, and phosphoric acid-based coupling agents.

<Transducer>
The transducer of the present invention includes the dielectric film of the present invention and a plurality of electrodes disposed via the dielectric film. The transducer of the present invention may be configured by alternately laminating a plurality of dielectric films and a plurality of electrodes. An intermediate layer having an intermediate electrical resistance may be interposed between the dielectric film and the electrode. When a laminated structure is employed, a greater force can be generated. The configuration and manufacturing method of the dielectric film of the present invention are as described above. Therefore, the description is omitted here. In the transducer according to the present invention, it is desirable to adopt a preferable aspect of the dielectric film according to the present invention.

  In the transducer of the present invention, the material of the electrode is not particularly limited. It is desirable that the electrode can be expanded and contracted following the deformation of the dielectric film. In this case, the deformation of the dielectric film is not easily regulated by the electrode. Therefore, it becomes easy to obtain a desired output in the transducer of the present invention. For example, the electrode can be formed from a conductive paste or conductive paint in which a conductive material is mixed with a binder such as oil or elastomer. As the conductive material, carbon material such as carbon black, ketjen black, carbon nanotube, graphene, or metal powder such as silver may be used. Further, the electrodes may be formed by knitting carbon fibers or metal fibers in a mesh shape.

  The transducer of the present invention operates as an actuator by applying a voltage between the electrodes to generate stress. Further, when the dielectric film is deformed and the distance between the electrodes is changed, the capacitance is changed. Thereby, the transducer of the present invention functions as a capacitive sensor. Further, by using the electric charge generated when the dielectric film is deformed as a current, the transducer of the present invention also functions as a power generation element. Hereinafter, embodiments of a speaker, an actuator, a capacitive sensor, and a power generation element will be described as embodiments of the transducer of the present invention.

[First embodiment]
An embodiment in which the transducer of the present invention is embodied in a speaker will be described. FIG. 4 shows a perspective view of the speaker of this embodiment. FIG. 5 shows a VV cross-sectional view of FIG. In FIG. 4, it is shown through the front insulating film. First, the configuration of the speaker of this embodiment will be described. As shown in FIGS. 4 and 5, the speaker 2 includes a vibration member 20, a front frame 30 a, and a rear frame 30 b.

  The front frame 30a and the rear frame 30b are each made of resin and have a ring shape. The front frame 30a and the rear frame 30b are disposed to face each other with the peripheral edge portion of the vibration member 20 interposed therebetween. The front frame 30 a and the rear frame 30 b are fixed by eight bolts 31 and eight nuts 32. The set of “bolt 31 -nut 32” is arranged in the circumferential direction of the speaker 2 with a predetermined interval. The bolt 31 penetrates from the front surface of the front frame 30a to the rear surface of the rear frame 30b. The nut 32 is screwed to the penetrating end of the bolt 31.

  The vibration member 20 is interposed between the front frame 30a and the rear frame 30b. The vibration member 20 includes three dielectric films 21a to 21c, four electrodes 22a to 22d, and two insulating films 23a and 23b. In the vibration member 20, the dielectric films 21a to 21c and the electrodes 22a to 22d are alternately stacked.

  Each of the dielectric films 21a to 21c includes a carboxyl group-modified hydrogenated nitrile rubber and barium titanate particles, and has a circular thin film shape. The thickness of the dielectric films 21a to 21c is 20 μm. The dielectric films 21a to 21c are included in the dielectric film of the present invention. Each of the electrodes 22a to 22d contains silicone rubber and silver particles. Each of the electrodes 22a to 22d has a circular thin film shape having a smaller diameter than the dielectric films 21a to 21c. The electrodes 22a to 22d are disposed substantially concentrically with the dielectric films 21a to 21c, respectively. The electrodes 22a to 22d have terminal portions 220a to 220d, respectively. The terminal portions 220a to 220d protrude in the diameter increasing direction from the outer peripheral edges above the electrodes 22a to 22d, respectively. Each of the terminal portions 220a to 220d has a strip shape. A voltage is applied to the terminal portions 220a to 220d from the outside via wiring (not shown). The insulating films 23a and 23b are both made of acrylic rubber and have a circular thin film shape having the same size as the dielectric films 21a to 21c.

  Next, the manufacturing method of the speaker 2 of this embodiment is demonstrated. First, the dielectric films 21a to 21c are prepared. Next, a conductive paint in which silver powder is mixed with silicone rubber is printed on both front and rear surfaces of the dielectric film 21a to form electrodes 22a and 22b. Then, an insulating paint containing acrylic rubber is printed on the front surface of the formed electrode 22a and the entire front surface of the dielectric film 21a where the electrode 22a is not formed, thereby forming the insulating film 23a. Similarly, conductive paint is printed on both the front and rear surfaces of the dielectric film 21c to form the electrodes 22c and 22d. Then, an insulating paint is printed on the rear surface of the formed electrode 22d and the entire rear surface of the dielectric film 21c where the electrode 22d is not formed, thereby forming the insulating film 23b. Then, the dielectric film 21a having the electrodes 22a and 22b and the insulating film 23a, the dielectric film 21b, and the dielectric film 21c having the electrodes 22c and 22d and the insulating film 23b are laminated to produce the vibration member 20. Next, the peripheral part of the produced laminated body is clamped by the front frame 30a and the rear frame 30b. In this state, the front frame 30 a and the rear frame 30 b are fixed by eight bolts 31 and eight nuts 32. In this way, the speaker 2 is manufactured.

  Next, the movement of the speaker 2 of this embodiment will be described. In an initial state, a predetermined bias voltage is applied to the electrodes 22a to 22d via a wiring (not shown). In this state, an AC voltage as a sound electric signal is applied to the electrodes 22a to 22d. Then, the vibration member 20 vibrates in the front-rear direction as shown by the white arrow in FIG. 5 due to the change in the film thickness of the dielectric films 21a to 21c. Thereby, air vibrates and a sound is generated.

  Next, the effect of the speaker 2 of this embodiment is demonstrated. In the speaker 2 of this embodiment, the dielectric films 21a to 21c are flexible and excellent in stretchability. In addition, the dielectric constants of the dielectric films 21a to 21c are large. The electrodes 22a to 22d are also flexible and can be expanded and contracted integrally with the dielectric films 21a to 21c. Therefore, in the speaker 2, the amount of deformation of the vibration member 20 with respect to the applied voltage increases, and the output sound pressure increases. The dielectric films 21a to 21c are thin films having a thickness of 20 μm, but have high dielectric breakdown strength. For this reason, the speaker 2 is excellent in durability. Moreover, since the dielectric films 21a to 21c are thin films, a large sound pressure can be produced at a lower voltage.

  The vibration member 20 includes three dielectric films 21a to 21c stacked via electrodes 22a to 22d. For this reason, compared with the form which has arrange | positioned the electrode on both surfaces of one dielectric film, the deformation amount of the vibration member 20 with respect to an applied voltage becomes large, and the output sound pressure becomes large. Moreover, since each of the dielectric films 21a to 21c has a small film thickness, the speaker 2 is light and small and relatively inexpensive.

[Second Embodiment]
An embodiment in which the transducer of the present invention is embodied in an actuator will be described. FIG. 6 is a schematic cross-sectional view of the actuator of this embodiment. (A) shows a voltage off state, and (b) shows a voltage on state.

  As shown in FIG. 6, the actuator 1 includes a dielectric film 10, electrodes 11a and 11b, and wirings 12a and 12b. The dielectric film 10 includes silicone rubber and barium titanate particles, and has a circular thin film shape. The thickness of the dielectric film 10 is 50 μm. The dielectric film 10 is included in the dielectric film of the present invention. The electrode 11a is disposed so as to cover substantially the entire top surface of the dielectric film 10. Similarly, the electrode 11 b is disposed so as to cover substantially the entire lower surface of the dielectric film 10. The electrodes 11a and 11b are connected to the power supply 13 via wirings 12a and 12b, respectively. The electrodes 11a and 11b include acrylic rubber and carbon black. Each of the electrodes 11a and 11b has a thickness of 10 μm.

  When switching from the off state to the on state, a voltage is applied between the pair of electrodes 11a and 11b. By applying a voltage, the thickness of the dielectric film 10 is reduced, and the thickness of the dielectric film 10 is extended in the diameter-expanding direction as indicated by the white arrow in FIG. Thereby, the actuator 1 outputs the driving force in the vertical direction and the horizontal direction in the drawing.

  According to this embodiment, the dielectric film 10 is flexible and excellent in stretchability. In addition, the dielectric constant of the dielectric film 10 is large. The electrodes 11a and 11b are also flexible and can be expanded and contracted integrally with the dielectric film 10. Therefore, according to the actuator 1, since the deformation amount of the dielectric film 10 with respect to the applied voltage is large, a large force and displacement amount can be obtained. Further, the dielectric breakdown strength of the dielectric film 10 is large. For this reason, the actuator 1 is excellent in dielectric breakdown resistance.

[Third embodiment]
An embodiment in which the transducer of the present invention is embodied in a capacitive sensor will be described. First, the configuration of the capacitive sensor of this embodiment will be described. FIG. 7 shows a top view of the capacitive sensor. FIG. 8 is a sectional view taken along line VIII-VIII in FIG. As shown in FIGS. 7 and 8, the capacitive sensor 4 includes a dielectric film 40, a pair of electrodes 41a and 41b, wirings 42a and 42b, and cover films 43a and 43b.

  The dielectric film 40 includes urethane rubber and barium titanate particles, and has a strip shape extending in the left-right direction. The thickness of the dielectric film 40 is 20 μm. The dielectric film 40 is included in the dielectric film of the present invention.

  The electrode 41a has a rectangular shape. Three electrodes 41a are formed on the upper surface of the dielectric film 40 by screen printing. Similarly, the electrode 41b has a rectangular shape. Three electrodes 41b are formed on the lower surface of the dielectric film 40 so as to face the electrode 41a with the dielectric film 40 interposed therebetween. The electrode 41 b is screen-printed on the lower surface of the dielectric film 40. Thus, three pairs of electrodes 41a and 41b are arranged with the dielectric film 40 interposed therebetween. The electrodes 41a and 41b include acrylic rubber and carbon black. Each of the electrodes 41a and 41b has a thickness of 10 μm.

  The wiring 42 a is connected to each of the electrodes 41 a formed on the upper surface of the dielectric film 40. The electrode 41a and the connector 44 are connected by the wiring 42a. The wiring 42a is formed on the upper surface of the dielectric film 40 by screen printing. Similarly, the wiring 42b is connected to each of the electrodes 41b formed on the lower surface of the dielectric film 40 (indicated by a dotted line in FIG. 7). The electrode 41b and a connector (not shown) are connected by the wiring 42b. The wiring 42b is formed on the lower surface of the dielectric film 40 by screen printing. The wirings 42a and 42b include acrylic rubber and silver particles.

  The cover film 43a is made of acrylic rubber and has a strip shape extending in the left-right direction. The cover film 43a covers the top surfaces of the dielectric film 40, the electrode 41a, and the wiring 42a. Similarly, the cover film 43b is made of acrylic rubber and has a strip shape extending in the left-right direction. The cover film 43b covers the lower surface of the dielectric film 40, the electrode 41b, and the wiring 42b.

  Next, the movement of the capacitive sensor 4 will be described. For example, when the capacitive sensor 4 is pressed from above, the dielectric film 40, the electrode 41a, and the cover film 43a are united and curved downward. Due to the compression, the thickness of the dielectric film 40 is reduced. As a result, the capacitance between the electrodes 41a and 41b increases. By this capacitance change, deformation due to compression is detected.

  Next, the function and effect of the capacitive sensor 4 will be described. According to this embodiment, the dielectric film 40 is flexible and excellent in stretchability. In addition, the dielectric constant of the dielectric film 40 is large. The electrodes 41 a and 41 b and the wirings 42 a and 42 b are also flexible and can be expanded and contracted integrally with the dielectric film 40. Therefore, the response of the capacitive sensor 4 is good. Further, the dielectric breakdown strength of the dielectric film 40 is high. For this reason, the capacitive sensor 4 is excellent in resistance to dielectric breakdown. The capacitive sensor 4 has three pairs of electrodes 41 a and 41 b that are opposed to each other with the dielectric film 40 narrowed. However, the number, size, shape, arrangement, etc. of the electrodes may be determined as appropriate according to the application.

[Fourth embodiment]
An embodiment in which the transducer of the present invention is embodied in a power generation element will be described. In FIG. 9, the cross-sectional schematic diagram of the electric power generating element of this embodiment is shown. (A) shows the time of expansion, and (b) shows the time of contraction.

  As shown in FIG. 9, the power generation element 6 includes a dielectric film 60, electrodes 61a and 61b, and wirings 62a to 62c. The dielectric film 60 includes urethane rubber and barium titanate particles, and has a circular thin film shape. The thickness of the dielectric film 60 is 50 μm. The dielectric film 60 is included in the dielectric film of the present invention. The electrode 61a is disposed so as to cover substantially the entire top surface of the dielectric film 60. Similarly, the electrode 61b is disposed so as to cover substantially the entire lower surface of the dielectric film 60. Wirings 62a and 62b are connected to the electrode 61a. That is, the electrode 61a is connected to an external load (not shown) through the wiring 62a. The electrode 61a is connected to a power source (not shown) through the wiring 62b. The electrode 61b is grounded by the wiring 62c. Each of the electrodes 61a and 61b includes acrylic rubber and carbon black. Each of the electrodes 61a and 61b has a thickness of 10 μm.

  Next, the movement of the power generation element 6 will be described. 9A, when the power generating element 6 is compressed and the dielectric film 60 is extended in a direction parallel to the surfaces of the electrodes 61a and 61b, the thickness of the dielectric film 60 is reduced. Charge is stored between 61a and 61b. Thereafter, when the compressive force is removed, as shown in FIG. 9B, the dielectric film 60 contracts due to the elastic restoring force of the dielectric film 60, and the thickness increases. At that time, the stored charge is discharged through the wiring 62a.

  Next, the effect of the power generating element 6 will be described. According to this embodiment, the dielectric film 60 has a high relative dielectric constant and a high dielectric breakdown strength. For this reason, the power generation element 6 can store a large amount of electric charge between the electrodes 61a and 61b and is excellent in durability. Moreover, the dielectric film 60 is flexible and excellent in stretchability. In addition, the electrodes 61a and 61b are also flexible and can be expanded and contracted integrally with the dielectric film 60. For this reason, the whole power generating element 6 is flexible, and the movement of the dielectric film 60 is not easily restricted by the electrodes 61a and 61b.

  Next, the present invention will be described more specifically with reference to examples.

<Manufacture of dielectric film>
[Example 1]
First, carboxyl group-modified hydrogenated nitrile rubber (“Terban (registered trademark) XT8889” manufactured by LANXESS) was dissolved in acetylacetone to prepare a polymer solution having a solid concentration of 12% by mass. Next, in the prepared polymer solution, 5 parts by mass of an organometallic compound tetrakis (2-ethylhexyloxy) titanium as a crosslinking agent A and titanium dioxide (TiO ₂ ) sol 5 as a reinforcing material with respect to 100 parts by mass of the polymer. Part by mass. Subsequently, a liquid raw material was prepared by adding a dispersion of barium titanate particles to this solution. The dispersion of the barium titanate particles was added so that the barium titanate particles were 20 parts by mass with respect to 100 parts by mass of the polymer. Then, the prepared liquid raw material was applied onto a substrate, dried, and then heated at 150 ° C. for about 60 minutes to obtain a dielectric film. Three types of dielectric films having thicknesses of 3 μm, 10 μm, and 50 μm were manufactured.

  A dispersion of barium titanate particles was produced as follows. First, powder of barium titanate particles (“BT-TO-020RF” manufactured by Toda Kogyo Co., Ltd., manufactured by hydrothermal synthesis method, c / a ratio = 1.002) was added to the solvent acetylacetone to prepare a preliminary dispersion. Prepared. Next, the preliminary dispersion was subjected to mechanochemical treatment using a wet bead mill (“Research Lab” manufactured by Willy et Bacofen, media diameter: 0.1 mm). The liquid after the treatment was passed through a filter (“LPJ-MPX-006-N2” manufactured by Loki Techno Co., Ltd.) to obtain a dispersion.

  The powder of barium titanate particles used is referred to as powder A. The number average particle diameter of the barium titanate particles (dielectric particles) in the dispersion of the manufactured barium titanate particles was 20 nm, and the 95% diameter was 150 nm. For the particle size distribution, a particle size distribution measuring device “ELSZ-0S” manufactured by Otsuka Electronics Co., Ltd. was used, using a measuring solution adjusted so that the barium titanate particles in the dispersion became 7% by mass. (Hereinafter the same).

The TiO ₂ sol was produced as follows. First, 174 mL of 2-methoxyethanol was added to 0.01 mol of tetrai-propoxytitanium, an organometallic compound, and stirred at 125 ° C. for 2 hours. Next, 180 mL of 2-methoxyethanol and 5.4 mol of water were added to this solution and stirred at 70 ° C. for 5 hours. Thereafter, the solution was filtered, and the obtained solid content was dispersed in acetylacetone to obtain a TiO ₂ sol.

[Examples 2 to 4]
A dielectric film was produced in the same manner as in Example 1 except that the blending amount of the dispersion of barium titanate particles, that is, the blending amount of the barium titanate particles was changed.

[Example 5]
As the powder of barium titanate particles, “KZM-50” manufactured by Sakai Chemical Industry Co., Ltd. (manufactured by hydrothermal synthesis method, c / a ratio = 1.005) and blending amount of barium titanate particles A dielectric film was produced in the same manner as in Example 1 except that the amount was 60 parts by mass. The used powder of barium titanate particles is referred to as powder B. The number average particle diameter of the barium titanate particles in the dispersion of the manufactured barium titanate particles was 50 nm, and the 95% diameter was 300 nm.

[Example 6]
First, a dispersion of barium titanate particles was added to A liquid of silicone rubber (“KE-1935” manufactured by Shin-Etsu Chemical Co., Ltd.) and stirred with a stirrer. To this, a B liquid of silicone rubber (same as above) was added and further stirred to prepare a liquid raw material. The dispersion of barium titanate particles was added so that the barium titanate particles were 150 parts by mass with respect to 100 parts by mass of the polymer. Next, the prepared liquid raw material was applied onto a substrate, dried, and then heated at 150 ° C. for about 60 minutes to obtain a dielectric film. Three types of dielectric films having thicknesses of 3 μm, 10 μm, and 50 μm were manufactured.

  A dispersion of barium titanate particles was produced as follows. First, the same powder A as in Example 1 was put into ethanol and dispersed using an ultrasonic disperser. A surface modifier, desilyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and distilled water were added thereto, and the mixture was stirred at 80 ° C. for 2 hours to perform surface treatment of the barium titanate particles. The addition amount of desilyltrimethoxysilane was 0.02 mol with respect to 1 mol of barium titanate particles, and the addition amount of distilled water was 0.001 mol with respect to 1 mol of barium titanate particles. Next, the liquid after the treatment was filtered, and the obtained solid content was put into toluene. This liquid was dispersed using an ultrasonic disperser to prepare a preliminary dispersion. Subsequently, the preliminary dispersion was subjected to mechanochemical treatment using a wet bead mill (same as above). The treated liquid was passed through a filter (same as above) to obtain a dispersion. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 49 nm, and the 95% diameter was 295 nm.

[Example 7]
First, urethane rubber (“N5230” manufactured by Nippon Polyurethane Industry Co., Ltd.) was dissolved in acetylacetone to prepare a polymer solution having a solid content concentration of 12% by mass. Next, 1 mass part of polyisocyanate ("Coronate (registered trademark) L" manufactured by the same company) as a crosslinking agent B was mixed with the prepared polymer solution with respect to 100 mass parts of the polymer content. Subsequently, the same dispersion of barium titanate particles as in Example 1 was added to this solution to prepare a liquid raw material. The dispersion of barium titanate particles was added so that the barium titanate particles were 150 parts by mass with respect to 100 parts by mass of the polymer. Then, the prepared liquid raw material was applied onto a substrate, dried, and then heated at 150 ° C. for about 60 minutes to obtain a dielectric film. Three types of dielectric films having thicknesses of 3 μm, 10 μm, and 50 μm were manufactured.

[Example 8]
A dielectric film was produced in the same manner as in Example 5 except that the surface treatment of the barium titanate particles was performed when producing the dispersion of the barium titanate particles. A dispersion of barium titanate particles was produced as follows. First, the same powder B as in Example 5 was added to acetylacetone to prepare a preliminary dispersion, and a surface modifier, tri-n-octylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and barium titanate was added. Particle surface treatment was performed. The amount of tri-n-octylphosphine oxide added was 0.01 mol with respect to 1 mol of barium titanate particles. Next, the preliminary dispersion was subjected to mechanochemical treatment using a wet bead mill (same as above). The treated liquid was passed through a filter (same as above) to obtain a dispersion. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 48 nm, and the 95% diameter was 180 nm.

[Comparative Example 1]
A dielectric film was produced in the same manner as in Example 1 except that the dispersion of barium titanate particles was not blended.

[Comparative Examples 2 and 3]
A dielectric film was produced in the same manner as in Example 1 except that the blending amount of the dispersion of barium titanate particles, that is, the blending amount of the barium titanate particles was changed.

[Comparative Example 4]
In the production of the dispersion of barium titanate particles with 60 parts by mass of the barium titanate particles, the preliminary dispersion was not a wet bead mill but an ultrasonic disperser (manufactured by Sharp Corporation, ultrasonic oscillator) A dielectric film was produced in the same manner as in Example 1 except that the treatment was performed using “UT304R” and the ultrasonic oscillator “UI304R”, and the liquid after the treatment was not filtered. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 24 nm, and the 95% diameter was 3800 nm.

[Comparative Example 5]
A dielectric film was produced in the same manner as in Example 5 except that in the production of the dispersion of barium titanate particles, the liquid after the treatment was not filtered. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 50 nm, and the 95% diameter was 2480 nm.

[Comparative Example 6]
As a powder of barium titanate particles, “BT-HP9DX-100” (manufactured by solid phase reaction method, c / a ratio = 1.005) manufactured by Kyoritsu Material Co., Ltd., and blending of barium titanate particles A dielectric film was produced in the same manner as in Example 1 except that the amount was 60 parts by mass. The powder of barium titanate particles used is referred to as powder C. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 180 nm, and the 95% diameter was 1000 nm.

[Comparative Example 7]
As the powder of barium titanate particles, “BT-HP9DX-400” (manufactured by solid phase reaction method, c / a ratio = 1.005) manufactured by Kyoritsu Material Co., Ltd., blending amount of barium titanate particles A dielectric film was produced in the same manner as in Example 1, except that 60 parts by mass was not filtered and the liquid after the treatment was not filtered. The powder of barium titanate particles used is referred to as powder D. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 590 nm, and the 95% diameter was 6000 nm.

[Comparative Example 8]
A dielectric film was produced in the same manner as in Example 6 except that the dispersion of barium titanate particles was not blended.

[Comparative Example 9]
A dispersion of barium titanate particles was produced in the same manner as in Example 6 except that the same powder C as in Comparative Example 6 was used as the barium titanate particle powder, and a dielectric film was produced. The number average particle diameter of the barium titanate particles in the produced barium titanate particle dispersion was 280 nm, and the 95% diameter was 1985 nm.

[Comparative Example 10]
A dielectric film was produced in the same manner as in Example 7 except that the dispersion of barium titanate particles was not blended.

[Comparative Example 11]
A dielectric film was produced in the same manner as in Example 7 except that the same dispersion of barium titanate particles as in Comparative Example 6 using Powder C was blended.

[Comparative Example 12]
First, 100 parts by mass of a bisphenol A type epoxy resin (“jER (registered trademark) 828” manufactured by Mitsubishi Chemical Corporation) and a phenol novolac resin (“BRG # 558” manufactured by Showa Denko KK) 4.8 as a curing agent are used. A polymer solution was prepared by adding parts by mass. Next, the same dispersion of barium titanate particles as in Example 5 was added to the prepared polymer solution to prepare a liquid raw material. The dispersion of the barium titanate particles was added so that the barium titanate particles were 60 parts by mass with respect to 100 parts by mass of the polymer content. Then, the prepared liquid raw material was applied onto a substrate, dried, and then heated at 150 ° C. for about 60 minutes to obtain a dielectric film. Three types of dielectric films having thicknesses of 3 μm, 10 μm, and 50 μm were manufactured.

  About the kind and compounding quantity of the raw material which were used for manufacture of the dielectric film of an Example and a comparative example, it shows in Table 1 and Table 2 below collectively.

<Evaluation of dielectric film>
The manufactured dielectric film was evaluated according to the following items. The evaluation results of the dielectric film are summarized in Tables 1 and 2 below.

[Satisfaction of conditions (A), (B), (C)]
About the manufactured dielectric film, the SEM photograph of the film thickness direction cross section was image | photographed, and it was investigated whether conditions (A), (B), (C) were satisfy | filled. First, each dielectric film was embedded with an epoxy resin, and a cross section in the film thickness direction was cut out by a microtome. Next, an SEM photograph of the cross section was taken (magnification 1000 to 5000 times). As an example of the SEM photograph, FIG. 10 shows an SEM photograph of a cross section in the film thickness direction of the dielectric film of Example 2 having a film thickness of 10 μm. As shown in FIG. 10, in the dielectric film of Example 2, it was confirmed that minute barium titanate particles were dispersed substantially uniformly in the elastomer.

1. Condition (A)
As shown in FIG. 10, first, three straight lines having a length of 2 μm extending in the film thickness direction were drawn at an interval of 500 nm in the region on the right side of the SEM photograph. Next, for each straight line, the number of barium titanate particles intersecting with the straight line was counted (indicated by a black line in FIG. 10). Subsequently, the number obtained was divided by the length of the straight line, and the reference number was calculated for each straight line. Then, the average value of the three reference numbers was calculated.

2. Condition (B)
Among the barium titanate particles that intersect with the three straight lines in the condition (A), the number of large particles having a particle diameter larger than 1/10 of the film thickness of the dielectric film, that is, the particle diameter exceeding 1 μm was counted. Next, the obtained number was divided by the length of the straight line, and the number of large particles was calculated for each straight line. And the average value of the number of three large particles was computed.

3. Condition (C)
As shown in FIG. 10, first, a 2 μm square measurement area was provided in the left area of the SEM photograph. Next, the measurement area was divided into 100 200 nm square unit areas (10 vertical × 10 horizontal). Subsequently, each unit area was converted into a black and white bitmap using binary image analysis software. Then, for each unit region, the area ratio occupied by the elastomer was calculated from the number of pixels of the elastomer and the barium titanate particles.

[Relative permittivity]
As for the dielectric constant of the dielectric film, the dielectric film is placed in a sample holder (Solartron, type 12962A), and a dielectric constant measurement interface (made by the company, type 1296) and a frequency response analyzer (made by the company, type 1255B) Was used together (frequency: 100 Hz).

[Elastic modulus]
The elastic modulus of the dielectric film was calculated from a stress-elongation curve obtained by conducting a tensile test specified in JIS K7127: 1999. The test piece type 2 was used for the test piece.

[Elongation at cutting]
The elongation at break of the dielectric film was measured by performing a tensile test specified in JIS K6251: 2010. Dumbbell-shaped No. 5 was used for the test piece.

[Volume resistivity]
The volume resistivity of the dielectric film was measured according to the parallel terminal electrode method defined in JIS K6271: 2008. The measurement was performed by applying a DC voltage of 100V.

<Evaluation of actuator characteristics>
Using the manufactured dielectric film, an actuator which is one form of the transducer was manufactured, and the actuator characteristics were evaluated. First, a conductive paint was prepared by mixing and dispersing carbon black in an acrylic rubber polymer solution. Next, the conductive paint was screen-printed on both sides of the manufactured dielectric film in the thickness direction to form electrodes. An actuator including the dielectric film of the embodiment is included in the transducer of the present invention.

  As the characteristics of the manufactured actuator, the dielectric breakdown strength and the maximum generated stress were measured. First, a measuring apparatus and a measuring method will be described. FIG. 11 shows a front side view of the actuator attached to the measuring apparatus. FIG. 12 is a cross-sectional view taken along the line XII-XII in FIG.

  As shown in FIGS. 11 and 12, the upper end of the actuator 5 is held by an upper chuck 52 in the measuring apparatus. The lower end of the actuator 5 is gripped by the lower chuck 53. The actuator 5 is attached between the upper chuck 52 and the lower chuck 53 in a state in which the actuator 5 is previously stretched in the vertical direction (stretching ratio 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 51a and 51b. The dielectric film 50 has a rectangular thin film shape with a length of 50 mm and a width of 25 mm in a natural state. The electrodes 51a and 51b are arranged to face each other in the front and back direction with the dielectric film 50 interposed therebetween. The electrodes 51a and 51b are in a natural state and each have a rectangular thin film shape with a length of 40 mm, a width of 25 mm, and a thickness of 10 μm. The electrodes 51a and 51b are arranged in a state shifted by 10 mm in the vertical direction. That is, the electrodes 51a and 51b overlap with each other through the dielectric film 50 in a range of 30 mm length and 25 mm width. A wiring (not shown) is connected to the lower end of the electrode 51a. Similarly, a wiring (not shown) is connected to the upper end of the electrode 51b. The electrodes 51a and 51b are connected to a power source (not shown) through each wiring.

  When a voltage is applied between the electrodes 51a and 51b, an electrostatic attractive force is generated between the electrodes 51a and 51b, and the dielectric film 50 is compressed. Thereby, the thickness of the dielectric film 50 becomes thin and extends in the extending direction (vertical direction). Due to the extension of the dielectric film 50, the stretching force in the vertical direction decreases. The stretching force decreased before and after the voltage application was measured with a load cell, and used as the generated stress. The generated stress was measured until the applied voltage was increased stepwise until the dielectric film 50 was broken. The generated stress immediately before the dielectric film 50 was broken was defined as the maximum generated stress. Further, a value obtained by dividing the voltage value at that time by the film thickness of the dielectric film 50 was taken as the dielectric breakdown strength. The measurement results of dielectric breakdown strength and maximum generated stress are summarized in Tables 1 and 2 below.

<Applicability to speakers>
In the evaluation of the actuator, the dielectric film having a maximum generated stress of 2.8 MPa or more and a dielectric breakdown strength of 70 V / μm or more when the film thickness is 10 μm exhibits excellent sound pressure characteristics when used for a speaker. Excellent durability. Therefore, the applicability of the dielectric film to the speaker was evaluated from the viewpoint of the maximum generated stress and the dielectric breakdown strength. In other words, a case where the above characteristics are satisfied is applicable (indicated in circles in Tables 1 and 2 below), and a case where it is not satisfied is not applicable (indicated in Tables 1 and 2 below). .

Tables 1 and 2 collectively show the types and amounts of raw materials used in the production of the dielectric film, and the evaluation results of the dielectric film, actuator characteristics, and applicability to speakers. Table 1 shows examples and Table 2 shows comparative examples.

  About the dielectric film of the Example, it manufactured using the dispersion liquid which the powder of the barium titanate particle | grains whose 95% diameter is 1/10 or less of the film thickness of a dielectric film disperse | distributed to the solvent. Thereby, all the dielectric films of an Example satisfy | fill all conditions (A)-(C). Therefore, in the dielectric film of the example, both the relative dielectric constant and the dielectric breakdown strength were increased. According to the dielectric film of the example, it was confirmed that a high dielectric breakdown strength can be maintained even in the case of a thin film of 10 μm or less. In addition, all of the dielectric films of the examples had a large volume resistivity. Further, the elastic modulus of the dielectric film of the example was 49 MPa at the maximum. Thus, since the dielectric film of an Example is flexible, when an actuator is comprised, it is easy to deform | transform. For this reason, it was confirmed that the actuator of an Example can output a big force. Further, comparing Example 5 and Example 8, the dielectric film of Example 8 in which the surface treatment was performed on the barium titanate particles had a higher dielectric breakdown strength due to improved dispersibility of the particles. It was.

  On the other hand, the dielectric films of Comparative Examples 1, 8, and 10 do not contain barium titanate particles. For this reason, the dielectric constants of the dielectric films of Comparative Examples 1, 8, and 10 were small. Therefore, even if the actuator was configured using the dielectric films of Comparative Examples 1, 8, and 10, the generated stress was small and a sufficient force could not be output. On the other hand, barium titanate particles are blended in the dielectric films of Comparative Examples 2 to 7, 9, and 11. Therefore, the relative dielectric constant increased accordingly. However, the dielectric film of Comparative Example 2 does not satisfy the condition (A) because the blending amount of the barium titanate particles is small. For this reason, the effect of improving the dielectric constant was small, and the generated stress of the actuator was small. On the contrary, the dielectric film of Comparative Example 3 does not satisfy the condition (C) because the blending amount of the barium titanate particles is large. For this reason, the elastic modulus increased and the elongation decreased. In the case of a thin film of 10 μm or less, the condition (B) is not satisfied. For this reason, the dielectric breakdown strength was reduced.

  The dispersions used for the production of the dielectric films of Comparative Examples 4 to 7, 9, and 11 contain many barium titanate particles having a large particle size. For this reason, it becomes difficult to satisfy the condition (B) as the film thickness decreases. When the condition (B) was not satisfied, the dielectric breakdown strength was reduced.

  The matrix of the dielectric film of Comparative Example 12 is not an elastomer but a resin. For this reason, in the dielectric film of Comparative Example 12, the elastic modulus was significantly increased. Therefore, even if the actuator was configured using the dielectric film of Comparative Example 12, it was hardly deformed and the force could not be extracted.

  It was confirmed that the dielectric films of all the examples satisfy the desired actuator characteristics and are suitable for speakers. On the other hand, none of the dielectric films of the comparative examples satisfied the desired actuator characteristics, and thus were not applicable to speakers.

  The transducer using the dielectric film of the present invention is widely used as an actuator, a sensor, a power generation element, etc. for converting mechanical energy and electric energy, or a speaker, a microphone, a noise canceller, etc. for converting acoustic energy and electric energy. be able to.

1: Actuator (transducer), 10: Dielectric film, 11a, 11b: Electrode, 12a, 12b: Wiring, 13: Power supply.
2: speaker (transducer), 20: vibration member, 21a-21c: dielectric film, 22a-22d: electrode, 23a, 23b: insulating film, 220a-220d: terminal portion, 30a: front frame, 30b: rear frame, 31: bolt, 32: nut.
4: Capacitance type sensor (transducer), 40: dielectric film, 41a, 41b: electrode, 42a, 42b: wiring, 43a, 43b: cover film, 44: connector.
5: Actuator (transducer), 50: Dielectric film, 51a, 51b: Electrode, 52: Upper chuck, 53: Lower chuck
6: power generation element (transducer), 60: dielectric film, 61a, 61b: electrode, 62a to 62c: wiring.
100: cross-sectional photograph, 101: elastomer, 102: dielectric particles, E: unit area, M: measurement area.

Claims (6)

An elastomer, comprising: a dielectric particle, a, of the following (A), a (B), the method of manufacturing conditions induced film that meets the (C),
A pre-dispersion in which a powder of dielectric particles produced by a hydrothermal synthesis method is dispersed in a solvent, a mechanochemical treatment, and then a filter treatment to produce a dispersion of dielectric particles;
Adding the dispersion to a polymer solution in which an elastomer polymer is dissolved in a solvent to prepare a liquid raw material;
Curing the liquid material to obtain a dielectric film;
Have
A method for producing a dielectric film, wherein a 95% diameter in a volume cumulative distribution of the dielectric particles in the dispersion is 1/10 or less of a film thickness of the dielectric film .
(A) Film development of three straight lines extending in the film thickness direction having a length of 1/2 or more of the length in the film thickness direction of the cross-sectional photograph taken by the scanning electron microscope Draw at a distance of 500 nm in the direction, and for each straight line, count the number of the dielectric particles that intersect the straight line, and divide the number by the length of the straight line to obtain a reference number per 1 μm of the straight line Is calculated, the average value of the reference numbers in the three straight lines is 0.8 / μm or more.
(B) Among the dielectric particles intersecting with the three straight lines in (A), the number of large particles having a particle diameter larger than 1/10 of the thickness of the dielectric film is counted for each straight line, When the number of large particles per 1 μm of the straight line is calculated by dividing the number by the length of the straight line, the average value of the number of large particles in the three straight lines is 0.2 / μm or less. .
(C) A cross-sectional photograph taken in the film thickness direction taken by a scanning electron microscope was provided with a measurement region formed by connecting 100 unit regions of 200 nm square, and the area occupied by the elastomer was measured for each unit region. In this case, the number of the unit regions whose area ratio of the elastomer in the measurement region is 30% or less is 10 or less. The method for manufacturing a dielectric film according to claim 1, wherein the film thickness of the dielectric film is 1 μm or more and 100 μm or less. The method for manufacturing a dielectric film according to claim 1 , wherein the elastic modulus of the dielectric film is 100 MPa or less. 4. The method for producing a dielectric film according to claim 1, wherein a content of the dielectric particles in the dielectric film is 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the elastomer. . It said dielectric particles include barium titanate, lead zirconate titanate, lanthanum-doped lead zirconate titanate, strontium titanate, claims 1 to 4 is bismuth titanate, one or more selected from bismuth titanate Barium A method for producing a dielectric film according to any one of the above. The elastomer is nitrile rubber, hydrogenated nitrile rubber, acrylic rubber, natural rubber, isoprene rubber, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic ester copolymer, butyl rubber, styrene - butadiene rubber, fluorine rubber, silicone rubber, according to epichlorohydrin rubber, chloroprene rubber, or chlorinated polyethylene, claims 1 to 5 chlorosulfonated polyethylene, and one or more selected from urethane rubber in which A method of manufacturing a dielectric film.