WO2023026726A1 - 圧電フィルムおよび圧電素子 - Google Patents
圧電フィルムおよび圧電素子 Download PDFInfo
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- WO2023026726A1 WO2023026726A1 PCT/JP2022/028212 JP2022028212W WO2023026726A1 WO 2023026726 A1 WO2023026726 A1 WO 2023026726A1 JP 2022028212 W JP2022028212 W JP 2022028212W WO 2023026726 A1 WO2023026726 A1 WO 2023026726A1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R17/00—Piezoelectric transducers; Electrostrictive transducers
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R17/00—Piezoelectric transducers; Electrostrictive transducers
- H04R17/005—Piezoelectric transducers; Electrostrictive transducers using a piezoelectric polymer
-
- 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
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
-
- 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
- H10N30/88—Mounts; Supports; Enclosures; Casings
- H10N30/883—Additional insulation means preventing electrical, physical or chemical damage, e.g. protective coatings
Definitions
- the present invention relates to piezoelectric films and piezoelectric elements used in electroacoustic transducers and the like.
- the speakers used in these thin displays are also required to be thin and light.
- flexibility is required for speakers used in such displays.
- the piezoelectric film disclosed in Patent Document 1 includes a polymer composite piezoelectric body in which piezoelectric particles are dispersed in a viscoelastic matrix made of a polymer material having viscoelasticity at room temperature, and a It has a formed thin film electrode and a protective layer formed on the surface of the thin film electrode.
- the piezoelectric layer When a drive voltage is applied to the electrode layer, such a piezoelectric film expands and contracts the polymer composite piezoelectric body due to expansion and contraction of the piezoelectric particles, and vibrates to absorb this expansion and contraction. This vibration causes the piezoelectric film to vibrate the air and convert the electrical signal into sound.
- the piezoelectric layer In order to vibrate the piezoelectric film, the piezoelectric layer is very thin, preferably 300 ⁇ m or less, for example.
- piezoelectric films are often cut into desired shapes and used as cut sheets.
- the piezoelectric layer of the piezoelectric film is very thin, and the distance between the electrode layers is very close.
- dielectric breakdown may occur, and the piezoelectric film may not operate properly.
- dielectric breakdown is a discharge phenomenon accompanied by heat generation, so if dielectric breakdown occurs in a state in which the piezoelectric film is incorporated in a product, it may lead to a serious failure.
- An object of the present invention is to solve such problems of the prior art. It is an object of the present invention to provide a piezoelectric film and a piezoelectric element capable of preventing malfunction due to dielectric breakdown between electrode layers in a piezoelectric film.
- a piezoelectric film having a piezoelectric layer containing piezoelectric particles in a matrix containing a polymer material, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers, having an end surface sealing layer made of a resin-containing material covering the end surface of the piezoelectric film;
- a piezoelectric film having an inter-electrode distance of 30 ⁇ m or more on the end face of the piezoelectric film and having an inter-electrode distance of 103% or more and less than 120% of the thickness of the piezoelectric layer.
- the piezoelectric film in a piezoelectric film having electrode layers on both sides of a piezoelectric layer containing piezoelectric particles in a matrix containing a polymer material, the piezoelectric film can prevent malfunction due to dielectric breakdown between the electrode layers at the ends, and A piezoelectric element can be provided.
- FIG. 1 is a sectional view conceptually showing an example of a piezoelectric film of the present invention
- FIG. 2 is an enlarged view showing an end portion of the piezoelectric film shown in FIG. 1
- FIG. 1 is a diagram conceptually showing an example of a piezoelectric layer used in the piezoelectric film of the present invention
- FIG. It is a conceptual diagram for explaining an example of the method of manufacturing the piezoelectric film of the present invention. It is a conceptual diagram for explaining an example of the method of manufacturing the piezoelectric film of the present invention. It is a conceptual diagram for explaining an example of the method of manufacturing the piezoelectric film of the present invention. It is a conceptual diagram for explaining an example of the method of manufacturing the piezoelectric film of the present invention. It is a conceptual diagram for explaining an example of the method of manufacturing the piezoelectric film of the present invention.
- FIG. 1 is a conceptual diagram of an example of a flat speaker using the piezoelectric film of the present invention
- FIG. FIG. 4 is a conceptual diagram for explaining a shape of a piezoelectric film that is out of the scope of the present invention
- the piezoelectric film of the present invention is A piezoelectric film having a piezoelectric layer containing piezoelectric particles in a matrix containing a polymer material, electrode layers provided on both sides of the piezoelectric layer, and a protective layer provided on the electrode layer, having an end surface sealing layer made of a resin-containing material covering the end surface of the piezoelectric film;
- the piezoelectric film has an inter-electrode distance of 30 ⁇ m or more on the end face of the piezoelectric film, and a distance between the electrodes on the end face of the piezoelectric film of 103% or more and less than 120% of the thickness of the piezoelectric layer.
- Such a piezoelectric film of the present invention is used as an electroacoustic conversion film, for example.
- the piezoelectric film of the present invention is used as diaphragms of electroacoustic transducers such as piezoelectric speakers, microphones and voice sensors.
- electroacoustic transducer when the piezoelectric film is elongated in the plane direction by applying a voltage to the piezoelectric film, the piezoelectric film moves upward (in the sound radiation direction) in order to absorb this expansion, and conversely, When the piezoelectric film shrinks in the plane direction due to voltage application to the piezoelectric film, the piezoelectric film moves downward to absorb this contraction.
- An electroacoustic transducer converts vibration (sound) into an electric signal by the vibration caused by repeated expansion and contraction of this piezoelectric film. It is used for reproducing, converting the vibration of the piezoelectric film by receiving a sound wave into an electric signal, giving a tactile sensation by vibration, and transporting objects.
- applications of piezoelectric film include speakers such as full-range speakers, tweeters, squawkers, and woofers, headphone speakers, noise cancellers, microphones, and pickups (sensors for musical instruments) used in musical instruments such as guitars.
- speakers such as full-range speakers, tweeters, squawkers, and woofers
- headphone speakers noise cancellers
- microphones microphones
- pickups sensors for musical instruments
- the piezoelectric film of the present invention is a non-magnetic material, it can be suitably used as a noise canceller for MRI among noise cancellers.
- the electroacoustic transducer using the piezoelectric film of the present invention is thin, light, and bendable, it has functions as wearable products such as hats, mufflers, and clothes, thin displays such as televisions and digital signage, and audio equipment. It is suitably used for buildings, ceilings of automobiles, curtains, umbrellas, wallpaper, windows and beds.
- FIG. 1 conceptually shows an example of the piezoelectric film of the present invention.
- the piezoelectric film 10 shown in FIG. 1 includes a piezoelectric layer 12, a first electrode layer 14 laminated on one surface of the piezoelectric layer 12, a first protective layer 18 laminated on the first electrode layer 14, It has a second electrode layer 16 laminated on the other surface of the piezoelectric layer 12 , a second protective layer 20 laminated on the second electrode layer 16 , and an end surface sealing layer 30 .
- the piezoelectric film 10 of the present invention is, for example, a long piezoelectric film produced by roll-to-roll, or a cut sheet shape (sheet-like shape) obtained by cutting a large piezoelectric film into a desired shape. is a film of Therefore, the end surface of the piezoelectric film 10 is a cut surface.
- the piezoelectric film 10 preferably has a through hole 18 a through which the first protective layer 18 penetrates to the first electrode layer 14 .
- a conductive first connection member 32 is provided in the through hole 18 a so as to be connected to the first electrode layer 14 .
- a first extraction electrode 34 is provided to connect the first connection member 32 to connect the piezoelectric film 10 to an external power source.
- the second protective layer 20 also has a through hole 20a penetrating to the second electrode layer 16, and a conductive second connecting member 33 is provided in this through hole 20a.
- a second extraction electrode 36 for connecting the piezoelectric film 10 to an external power supply is provided by connecting to the second connection member 33 .
- the piezoelectric layer 12 is a polymer composite piezoelectric body containing piezoelectric particles 26 in a polymer matrix 24 containing a polymer material. is preferred.
- the polymer composite piezoelectric body (piezoelectric layer 12) preferably satisfies the following requirements.
- normal temperature is 0 to 50°C.
- Flexibility For example, when gripping a loosely bent state like a document like a newspaper or magazine for portable use, it is constantly subjected to a relatively slow and large bending deformation of several Hz or less from the outside. become. At this time, if the polymer composite piezoelectric material is hard, a correspondingly large bending stress is generated, and cracks occur at the interface between the polymer matrix and the piezoelectric particles, which may eventually lead to destruction. Therefore, the polymer composite piezoelectric body is required to have appropriate softness.
- the lowest resonance frequency f 0 of a speaker diaphragm is given by the following formula. where s is the stiffness of the vibration system and m is the mass. At this time, as the degree of curvature of the piezoelectric film, that is, the radius of curvature of the curved portion increases, the mechanical stiffness s decreases, so the minimum resonance frequency f 0 decreases. That is, the sound quality (volume and frequency characteristics) of the speaker changes depending on the radius of curvature of the piezoelectric film.
- the polymer composite piezoelectric body is required to behave hard against vibrations of 20 Hz to 20 kHz and softly against vibrations of several Hz or less. Also, the loss tangent of the polymer composite piezoelectric body is required to be moderately large with respect to vibrations of all frequencies of 20 kHz or less.
- polymer solids have a viscoelastic relaxation mechanism, and as temperature rises or frequency falls, large-scale molecular motion causes a decrease (relaxation) in storage elastic modulus (Young's modulus) or a maximum loss elastic modulus (absorption). is observed as Among them, the relaxation caused by the micro-Brownian motion of the molecular chains in the amorphous region is called principal dispersion, and a very large relaxation phenomenon is observed.
- the temperature at which this primary dispersion occurs is the glass transition point (Tg), and the viscoelastic relaxation mechanism appears most prominently.
- the polymer composite piezoelectric body (piezoelectric layer 12), by using a polymer material having a glass transition point at room temperature, in other words, a polymer material having viscoelasticity at room temperature as a matrix, it is possible to suppress vibrations of 20 Hz to 20 kHz. This realizes a polymer composite piezoelectric material that is hard at first and behaves softly with respect to slow vibrations of several Hz or less.
- a polymer material whose glass transition point Tg at a frequency of 1 Hz is at normal temperature for the matrix of the polymer composite piezoelectric material, because this behavior is preferably exhibited.
- the polymer material that forms the matrix 24 preferably has a maximum loss tangent Tan ⁇ of 0.5 or more at a frequency of 1 Hz in a dynamic viscoelasticity test at room temperature.
- the polymer material forming the matrix 24 preferably has a storage elastic modulus (E') at a frequency of 1 Hz measured by dynamic viscoelasticity measurement of 100 MPa or more at 0°C and 10 MPa or less at 50°C.
- E' storage elastic modulus
- the polymeric material that forms the matrix 24 has a dielectric constant of 10 or more at 25°C.
- a voltage is applied to the polymer composite piezoelectric material, a higher electric field is applied to the piezoelectric particles in the polymer matrix, so a large amount of deformation can be expected.
- the polymer material in consideration of ensuring good moisture resistance and the like, it is also suitable for the polymer material to have a dielectric constant of 10 or less at 25°C.
- Polymer materials that satisfy these conditions include cyanoethylated polyvinyl alcohol (cyanoethylated PVA), polyvinyl acetate, polyvinylidene chloride core acrylonitrile, polystyrene-vinylpolyisoprene block copolymer, polyvinylmethylketone, and polybutyl. Methacrylate and the like are preferably exemplified. Commercially available products such as Hybler 5127 (manufactured by Kuraray Co., Ltd.) can also be suitably used as these polymer materials.
- Hybler 5127 manufactured by Kuraray Co., Ltd.
- the piezoelectric layer 12 preferably uses a polymer material having a cyanoethyl group as the matrix 24, and particularly preferably uses cyanoethylated PVA.
- the above-mentioned polymeric materials represented by cyanoethylated PVA are collectively referred to as "polymeric materials having viscoelasticity at room temperature”.
- These polymer materials having viscoelasticity at room temperature may be used alone or in combination (mixed).
- the matrix 24 of the piezoelectric layer 12 may be made of a combination of multiple polymer materials, if necessary.
- the matrix 24 constituting the polymer composite piezoelectric body may be made of a polymer material having viscoelasticity at room temperature as described above for the purpose of adjusting the dielectric properties and mechanical properties, and if necessary, other dielectric materials may be used.
- a flexible polymer material may be added.
- dielectric polymer materials examples include polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, and polyvinylidene fluoride-trifluoroethylene copolymer.
- fluorine-based polymers such as polyvinylidene fluoride-tetrafluoroethylene copolymer, vinylidene cyanide-vinyl acetate copolymer, cyanoethylcellulose, cyanoethylhydroxysaccharose, cyanoethylhydroxycellulose, cyanoethylhydroxypullulan, cyanoethylmethacrylate, cyanoethylacrylate, cyanoethyl Cyano groups such as hydroxyethylcellulose, cyanoethylamylose, cyanoethylhydroxypropylcellulose, cyanoethyldihydroxypropylcellulose, cyanoethylhydroxypropylamylose, cyanoethylpolyacrylamide, cyanoethylpolyacrylate, cyanoethylpullulan, cyanoethylpolyhydroxymethylene, cyanoethylglycidolpullul
- polymers having cyanoethyl groups and synthetic rubbers such as nitrile rubbers and chloroprene rubbers are exemplified. Among them, polymer materials having cyanoethyl groups are preferably used. Moreover, in the matrix 24 of the piezoelectric layer 12, these dielectric polymer materials are not limited to one type, and a plurality of types may be added.
- thermoplastic resins such as vinyl chloride resins, polyethylene, polystyrene, methacrylic resins, polybutene and isobutylene, phenolic resins, and urea are used for the purpose of adjusting the glass transition point Tg of the matrix 24.
- Thermosetting resins such as resins, melamine resins, alkyd resins and mica may be added.
- a tackifier such as rosin ester, rosin, terpene, terpene phenol, and petroleum resin may be added for the purpose of improving adhesiveness.
- the proportion of the polymer in the matrix 24 is limited to 30% by mass or less. is preferred.
- the characteristics of the polymer material to be added can be expressed without impairing the viscoelastic relaxation mechanism in the matrix 24, so that the dielectric constant can be increased, the heat resistance can be improved, and the adhesion to the piezoelectric particles 26 and the electrode layer can be improved. favorable results can be obtained in terms of
- the polymer composite piezoelectric that forms the piezoelectric layer 12 contains piezoelectric particles 26 in such a polymer matrix.
- Piezoelectric particles 26 are dispersed in a polymer matrix.
- the piezoelectric particles 26 are uniformly (substantially uniformly) dispersed in the polymer matrix.
- the piezoelectric particles 26 are preferably ceramic particles having a perovskite or wurtzite crystal structure.
- Ceramic particles forming the piezoelectric particles 26 include lead zirconate titanate (PZT), lead zirconate lanthanate titanate (PLZT), barium titanate (BaTiO 3 ), zinc oxide (ZnO), and Particles such as a solid solution (BFBT) of barium titanate and bismuth ferrite (BiFe 3 ) are exemplified.
- PZT lead zirconate titanate
- PLAZT lead zirconate lanthanate titanate
- BaTiO 3 barium titanate
- ZnO zinc oxide
- Particles such as a solid solution (BFBT) of barium titanate and bismuth ferrite (BiFe 3 ) are exemplified.
- the particle size of the piezoelectric particles 26 may be appropriately selected according to the size and application of the piezoelectric film 10 .
- the particle size of the piezoelectric particles 26 is preferably 1 to 10 ⁇ m.
- the quantitative ratio between the matrix 24 and the piezoelectric particles 26 in the piezoelectric layer 12 depends on the size and thickness of the piezoelectric film 10 in the plane direction, the application of the piezoelectric film 10, and the characteristics required for the piezoelectric film 10. etc., it may be set as appropriate.
- the volume fraction of the piezoelectric particles 26 in the piezoelectric layer 12 is preferably 30-80%, more preferably 50-80%.
- the thickness of the piezoelectric layer 12 is not limited, and may be appropriately set according to the size of the piezoelectric film 10, the application of the piezoelectric film 10, the properties required of the piezoelectric film 10, and the like. good.
- the thickness of the piezoelectric layer 12 is preferably 8-300 ⁇ m, more preferably 8-200 ⁇ m, still more preferably 10-150 ⁇ m, particularly preferably 15-100 ⁇ m.
- the piezoelectric layer 12 is preferably polarized (poled) in the thickness direction.
- the polarization treatment will be detailed later.
- the laminated film of the piezoelectric film 10 shown in FIG. 1 has the second electrode layer 16 on one side of the piezoelectric layer 12 and the second protective layer 20 on the surface of the second electrode layer 16 , a first electrode layer 14 is provided on the other surface of the piezoelectric layer 12 and a first protective layer 18 is provided on the surface of the first electrode layer 14 .
- the first electrode layer 14 and the second electrode layer 16 form an electrode pair.
- both surfaces of the piezoelectric layer 12 are sandwiched between electrode pairs, that is, the first electrode layer 14 and the second electrode layer 16, and the first protective layer 18 and the second protective layer 20 sandwiched between them.
- the region sandwiched by the first electrode layer 14 and the second electrode layer 16 is driven according to the applied voltage.
- the terms "first” and “second” in the first electrode layer 14, the second electrode layer 16, etc. are used for convenience in describing the piezoelectric film 10 of the present invention. Therefore, the first and the second in the piezoelectric film 10 of the present invention have no technical significance and are irrelevant to the actual usage conditions.
- the piezoelectric film 10 of the present invention includes, for example, an adhesive layer for attaching the electrode layer and the piezoelectric layer 12 and an adhesive layer for attaching the electrode layer and the protective layer. It may have a layer.
- the adhesive may be an adhesive or an adhesive. Also, the same material as the matrix 24, that is, the polymer material obtained by removing the piezoelectric particles 26 from the piezoelectric layer 12, can be suitably used as the adhesive.
- the adhesive layer may be provided on both the first electrode layer 14 side and the second electrode layer 16 side, or may be provided on only one of the first electrode layer 14 side and the second electrode layer 16 side. good.
- the first protective layer 18 and the second protective layer 20 cover the first electrode layer 14 and the second electrode layer 16, and provide the piezoelectric layer 12 with appropriate rigidity and mechanical strength. is responsible for That is, in the piezoelectric film 10 of the present invention, the piezoelectric layer 12 containing the matrix 24 and the piezoelectric particles 26 exhibits excellent flexibility against slow bending deformation, but may may lack rigidity and mechanical strength.
- the piezoelectric film 10 is provided with a first protective layer 18 and a second protective layer 20 to compensate.
- the first protective layer 18 and the second protective layer 20 have the same configuration, except for the arrangement position. Therefore, in the following description, when there is no need to distinguish between the first protective layer 18 and the second protective layer 20, both members are collectively referred to as protective layers.
- the protective layer there are no restrictions on the protective layer, and various sheet-like materials can be used, and various resin films are suitable examples. Among them, polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), polycarbonate (PC), polyphenylene sulfite (PPS), polymethyl methacrylate (PMMA), due to their excellent mechanical properties and heat resistance. ), polyetherimide (PEI), polyimide (PI), polyamide (PA), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), and resin films made of cyclic olefin resins are preferably used. .
- the thickness of the protective layer is also not limited. Also, the thicknesses of the first protective layer 18 and the second protective layer 20 are basically the same, but may be different. If the rigidity of the protective layer is too high, it not only restricts expansion and contraction of the piezoelectric layer 12, but also impairs its flexibility. Therefore, the thinner the protective layer, the better, except when mechanical strength and good handling properties as a sheet are required.
- the thickness of each of the first protective layer 18 and the second protective layer 20 is not more than twice the thickness of the piezoelectric layer 12, favorable results can be achieved in terms of ensuring both rigidity and appropriate flexibility. is obtained.
- the thickness of the piezoelectric layer 12 is 50 ⁇ m and the first protective layer 18 and the second protective layer 20 are made of PET, the thicknesses of the first protective layer 18 and the second protective layer 20 are each preferably 100 ⁇ m or less. , 50 ⁇ m or less, and more preferably 25 ⁇ m or less.
- the first electrode layer 14 is provided between the piezoelectric layer 12 and the first protective layer 18, and the second electrode layer is provided between the piezoelectric layer 12 and the second protective layer 20. 16 are formed respectively. The first electrode layer 14 and the second electrode layer 16 are provided for applying an electric field to the piezoelectric film 10 (piezoelectric layer 12).
- the first electrode layer 14 and the second electrode layer 16 are basically the same except for their positions. Therefore, in the following description, when there is no need to distinguish between the first electrode layer 14 and the second electrode layer 16, both members are collectively referred to as electrode layers.
- the material for forming the electrode layer is not limited, and various conductors can be used. Specifically, carbon, palladium, iron, tin, aluminum, nickel, platinum, gold, silver, copper, chromium, molybdenum, alloys thereof, indium tin oxide, and PEDOT/PPS (polyethylenedioxythiophene-polystyrenesulfone Acid) and other conductive polymers are exemplified. Among them, copper, aluminum, gold, silver, platinum, and indium tin oxide are preferred. Among them, copper is more preferable from the viewpoint of conductivity, cost, flexibility, and the like.
- the method of forming the electrode layer is not limited, and a vapor phase deposition method (vacuum film formation method) such as vacuum deposition and sputtering, a method of forming a film by plating, a method of attaching a foil formed of the above materials, a coating method, or the like.
- a vapor phase deposition method vacuum film formation method
- a method of forming a film by plating a method of attaching a foil formed of the above materials, a coating method, or the like.
- a thin film of copper or aluminum formed by vacuum deposition is preferably used as the electrode layer because the flexibility of the piezoelectric film 10 can be ensured.
- a copper thin film formed by vacuum deposition is particularly preferably used.
- the thicknesses of the first electrode layer 14 and the second electrode layer 16 are not limited. Also, the thicknesses of the first electrode layer 14 and the second electrode layer 16 are basically the same, but may be different.
- the protective layer described above if the rigidity of the electrode layer is too high, not only will the expansion and contraction of the piezoelectric layer 12 be restricted, but the flexibility will also be impaired. Therefore, the thinner the electrode layer, the better, as long as the electrical resistance does not become too high.
- the thickness of the electrode layer is It is preferably 1.2 ⁇ m or less, more preferably 0.3 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the piezoelectric film 10 has a structure in which a piezoelectric layer 12 is sandwiched between a first electrode layer 14 and a second electrode layer 16, and further a first protective layer 18 and a second protective layer 20 are sandwiched.
- the loss tangent (Tan[delta]) at a frequency of 1 Hz by dynamic viscoelasticity measurement has a maximum value of 0.1 or more at room temperature.
- the piezoelectric film 10 preferably has a storage elastic modulus (E') at a frequency of 1 Hz measured by dynamic viscoelasticity measurement of 10 to 30 GPa at 0°C and 1 to 10 GPa at 50°C. Accordingly, the piezoelectric film 10 can have a large frequency dispersion in the storage elastic modulus (E') at room temperature. That is, it can act hard against vibrations of 20 Hz to 20 kHz and soft against vibrations of several Hz or less.
- E' storage elastic modulus
- the piezoelectric film 10 has a product of thickness and storage elastic modulus (E′) at a frequency of 1 Hz measured by dynamic viscoelasticity measurement of 1.0 ⁇ 10 6 to 2.0 ⁇ 10 6 N/m at 0° C. , 1.0 ⁇ 10 5 to 1.0 ⁇ 10 6 N/m at 50°C.
- E′ thickness and storage elastic modulus
- the piezoelectric film 10 preferably has a loss tangent (Tan ⁇ ) of 0.05 or more at 25° C. and a frequency of 1 kHz in a master curve obtained from dynamic viscoelasticity measurement.
- Ton ⁇ loss tangent
- the frequency characteristics of the speaker using the piezoelectric film 10 are smoothed, and the amount of change in sound quality when the lowest resonance frequency f 0 changes as the curvature of the speaker (piezoelectric film 10) changes can be reduced.
- the piezoelectric film 10 has a through hole 18 a through which the first protective layer 18 penetrates to the first electrode layer 14 .
- a conductive first connection member 32 is provided in the through hole 18 a so as to be connected to the first electrode layer 14 .
- a first extraction electrode 34 is provided for connecting the piezoelectric film 10 to an external power supply by connecting to the first connection member 32 .
- the second protective layer 20 also has a similar through hole 20a, in which a conductive second connecting member 33 is provided in connection with the second electrode layer 16.
- a second extraction electrode 36 is provided to connect the second connection member 33 to connect the piezoelectric film 10 to an external power source.
- the first extraction electrode 34 and the second extraction electrode 36 are preferably provided at different positions in the plane direction of the piezoelectric film 10 (laminated film). In FIG. 1, the first extraction electrode 34 and the second extraction electrode 36 are provided at different positions in the direction perpendicular to the plane of the drawing.
- first lead-out electrode 34 and the second lead-out electrode 36 are led out in the same direction.
- the present invention is not limited to this, and various configurations can be used.
- the first extraction electrode 34 and the second extraction electrode 36 may be extracted in opposite directions, or may be extracted so that the first extraction electrode 34 and the second extraction electrode 36 are perpendicular to each other.
- the through hole 18a (through hole 20a) is a first connection member 32 (second connection member 33) that connects the first electrode layer 14 and the first extraction electrode 34 (the second electrode layer and the second extraction electrode 36). is a through hole drilled in the first protective layer 18 (second protective layer 20) to form a .
- the size of the through-hole 18a is not limited, and is sufficiently large according to the materials forming the first electrode layer 14 and the first lead-out electrode 34, the size of the first lead-out electrode 34, the size of the piezoelectric film 10, and the like.
- the size that allows formation of the first connection member 32 capable of providing electrical continuity may be set as appropriate.
- the shape of the through hole 18a is also not limited. Therefore, various shapes such as a truncated cone shape, a cylindrical shape, and a square tubular shape can be used for the through hole.
- FIG. 18 As a method for forming the through holes 18a, various known methods can be used depending on the material for forming the first protective layer 18.
- FIG. 18 a method of removing the first protective layer 18 by burning (ablation) with a laser beam such as a laser beam with a wavelength of 10.6 ⁇ m from a carbon dioxide laser to form the through hole 18a is exemplified.
- the through holes 18a may be formed at desired positions in the first protective layer 18 by scanning the formation positions of the through holes 18a in the first protective layer 18 with a laser beam.
- the through-hole 18a with a desired thickness can be formed by adjusting the intensity of the laser beam, the scanning speed (that is, the processing time by the laser beam), and the like.
- a method of forming the through-holes 18a by dissolving the first protective layer 18 using an organic solvent can also be used.
- the through holes 18a can be formed using hexafluoroisoppanol or the like.
- the through holes 18a may be formed at desired positions by using a mask or the like, like etching in photolithography or the like. In this case, by adjusting the processing time and the concentration of the organic solvent, it is possible to form the through holes 18a with a desired thickness.
- a first connection member 32 (second connection member 33) is provided in the through hole 18a.
- the first connection member 32 electrically connects the first electrode layer 14 and the first extraction electrode 34 .
- the first connection member 32 can be made of various conductive materials that can be inserted into the through holes 18a. Specifically, metal paste made by dispersing metal particles such as silver, copper and gold in a binder made of thermosetting resin such as epoxy resin and polyimide, and similar metal particles cured at about room temperature such as acrylic resin.
- a metal paste dispersed in a binder made of a resin, a metal paste thermosetting as a single metal with a complex metal, a metal tape such as a copper foil tape, and a metal member that can be inserted into the through hole 18a are exemplified.
- the first extraction electrode 34 (second extraction electrode 36 ) is wiring for electrically connecting an external power source and the piezoelectric film 10 , electrically connected to the first connection member 32 . Therefore, the first lead-out electrode 34 extends to the outside in the plane direction of the laminated film in which the piezoelectric layer 12, the electrode layer and the protective layer are laminated.
- the first lead-out electrode 34 is also not limited, and there are various types of known electrodes used for wiring that electrically connects electrodes, power supplies, and external devices, such as metal foil such as copper foil and various metal wirings. Available.
- the length of the first lead-out electrode 34 outside the laminated film in the plane direction may be appropriately set according to the application of the piezoelectric film 10, the device to which the piezoelectric film 10 is connected, the installation position of the piezoelectric film 10, and the like. Just do it.
- first extraction electrode 34 and the first connection member 32 may be adhered as necessary.
- the attachment of the first extraction electrode 34 and the first connection member 32 may be performed by a known method. Examples thereof include a method using a conductive sticking agent (adhesive, pressure-sensitive adhesive), a method using a conductive double-sided tape, and the like.
- a metal paste such as silver paste for the first connection member 32 and using a copper foil, a conductive wire, or the like as the first lead-out electrode 34, adhesiveness is imparted to the first lead-out electrode 34 and the first lead-out electrode 34.
- a method of adhering the connection member 32 is also available.
- a through hole is formed in the protective layer, an electrode connection member is provided in the through hole, and an electrode connection member is provided in the protective layer as a preferred mode in which the end surface sealing layer 30 described later can be easily formed on the entire end surface of the laminated film.
- an electrode for connection to an external power supply is extracted.
- the piezoelectric film of the present invention is not limited to this, and various configurations can be used for leading out the electrodes. For example, between the protective layer and the piezoelectric layer, or between the electrode layer and the protective layer, a bar-like or sheet-like (film-like, plate-like) lead wire is provided. , an extraction electrode may be connected.
- the lead wiring may be used as it is as the lead electrode.
- a part of the protective layer and the electrode layer may be protruded from the piezoelectric layer in the plane direction, and the protruding electrode layer may be used as wiring for extraction, and the extraction electrode may be connected thereto.
- the piezoelectric film of the present invention has an end surface sealing layer made of a material containing a resin covering the end surfaces of the piezoelectric film, the distance between the electrodes on the end surfaces of the piezoelectric film is 30 ⁇ m or more, and the piezoelectric layer The distance between the electrodes at the end face of the piezoelectric film is 103% or more and less than 120% of the thickness of the piezoelectric film.
- the piezoelectric film of the present invention can suitably prevent dielectric breakdown (short circuit) between the first electrode layer and the second electrode layer at the ends.
- FIG. 2 is an enlarged view of an end portion of the piezoelectric film 10 shown in FIG.
- the piezoelectric film 10 is formed by stacking the end surfaces of the piezoelectric film 10, that is, the first protective layer 18, the first electrode layer 14, the piezoelectric layer 12, the second electrode layer 16, and the second protective layer 20.
- the end face of the film has an end face sealing layer 30 made of a resin-containing material so as to cover at least the end face.
- the end surface sealing layer 30 is formed from the main surface of the first protective layer 18 to the main surface of the second protective layer 20, so that the end surface of the laminated film is covered in the entire thickness direction. covering the The main surface is the maximum surface of the sheet-like material (layer, film, plate-like material).
- the end faces of the piezoelectric film 10 are not perpendicular to the main faces of the laminated film (the main faces of the first protective layer 18 and the second protective layer 20), but are inclined. Since the end face is slanted, the inter-electrode distance d1 between the first electrode layer 14 and the second electrode layer 16 on the end face exceeds 100% of the thickness t of the piezoelectric layer. If the ratio of the inter-electrode distance d1 between the first electrode layer 14 and the second electrode layer 16 on the end surface of the laminated film to the thickness t of the piezoelectric layer is defined as "ratio p", then in the present invention the ratio p is 103. % or more and less than 120%, and the inter-electrode distance d 1 is 30 ⁇ m or more.
- the piezoelectric film (piezoelectric layer) is very thin, the inter-electrode distance between the first electrode layer and the second electrode layer is very short. Therefore, when a high voltage is applied, air breakdown may occur between the electrode layers on both sides of the piezoelectric layer at the end surfaces of the piezoelectric film, and the piezoelectric film may not operate properly. In addition, dielectric breakdown is a discharge phenomenon accompanied by heat generation, so if dielectric breakdown occurs in a state in which the piezoelectric film is incorporated in a product, it may lead to a serious failure.
- the ratio p is 103% or more and less than 120%, and the distance d 1 between the electrodes is 30 ⁇ m or more.
- the end face of the piezoelectric film is covered with the end face sealing layer 30 to ensure insulation, so that dielectric breakdown does not occur between the electrode layers on both sides of the piezoelectric layer 12 at the end face of the piezoelectric film 10. occurrence can be suppressed. As a result, it is possible to prevent the piezoelectric film from malfunctioning properly due to dielectric breakdown between the electrode layers, and to prevent the failure of the product incorporating the piezoelectric film due to the heat generated due to the dielectric breakdown.
- the ratio p the longer the inter-electrode distance d 1 can be secured with respect to the thickness of the piezoelectric layer 12 .
- the ratio p is set to less than 120%.
- the ratio p is preferably 105% to 115%, more preferably 110% to 115%.
- the inter-electrode distance d 1 is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, and even more preferably 50 ⁇ m or more.
- the inter-electrode distance d 1 on the end face between the first electrode layer 14 and the second electrode layer 16 at the end of the piezoelectric film 10 and the ratio of the inter-electrode distance d 1 to the thickness t of the piezoelectric layer 12 p can be measured by various known methods.
- an SEM Sccanning Electron Microscope
- EDS Electronic X-ray spectrometry
- EDX Energy dispersive X-ray spectrometry
- the SEM is SU8220 manufactured by Hitachi High-Technologies Corporation
- the EDS is XFash 5060FQ manufactured by BRUKER.
- the piezoelectric film is embedded 5 mm or more from the end so as to include the measurement position of the inter-electrode distance d 1 , cut using a microtome, and if necessary Then, the inter-electrode distance d 1 between the first electrode layer 14 and the second electrode layer 16 is measured.
- the piezoelectric film is embedded 5 mm or more from the end so as to include the measurement position of the inter-electrode distance d 1 , and is cut using a microtome. ), the edge of the piezoelectric film 10 is observed by EDS, and the elemental analysis of the edge of the observation region is performed by EDS.
- elemental mapping of the materials forming the first electrode layer 14 and the second electrode layer 16 is performed to obtain an image of the mapping result. For example, when the forming material of the first electrode layer 14 and the second electrode layer 16 is copper, copper mapping is performed from the result of elemental analysis to obtain an image of the result of copper mapping.
- the distance d 1 between the electrodes at the end surface between the first electrode layer 14 and the second electrode layer 16 at the end of the piezoelectric film 10 is measured from the elemental mapping image. do.
- the thickness t of the piezoelectric layer 12 is known from the catalog value of the piezoelectric film 10 or the like, that value may be used.
- the thickness t of the piezoelectric layer 12 may be measured by a known method when the piezoelectric layer 12 is formed in the manufacturing process of the piezoelectric film 10 to be described later.
- the thickness t of the piezoelectric layer 12 may be calculated from the coating thickness and composition of the paint that forms the piezoelectric layer 12 in the manufacturing process of the piezoelectric film 10, which will be described later.
- the thickness t of the piezoelectric layer 12 is may be asked for.
- the thickness t of the piezoelectric layer 12 can be measured by the following method.
- the piezoelectric film 10 is embedded in resin. It is preferable to embed the piezoelectric film 10 in the resin at a distance of 5 mm or more from the cut surface of the piezoelectric film 10 .
- the resin used for embedding may be appropriately set according to the forming material and size (maximum surface area, thickness) of the piezoelectric film 10 . In addition, you may mix and use multiple types of resin used for embedding as needed. After the piezoelectric film 10 is embedded in the resin, the piezoelectric film 10 embedded in the resin is linearly cut at any desired location.
- Cutting may be performed by a known method such as a method using a microtome.
- the cutting is preferably performed at a position where the center of the cut surface in the longitudinal direction is 5 mm or more inside from all the ends (end surfaces) of the piezoelectric film 10 .
- the cut surface is polished. Polishing may be performed by a known method.
- elemental mapping of the forming materials of the first electrode layer 14 and the second electrode layer 16 is performed by the above-described SEM-EDS at the central portion of the cut surface in the longitudinal direction.
- the distance in the thickness direction between the inner surface of the first electrode layer 14 and the inner surface of the second electrode layer 16 is measured at the center of the cut surface in the longitudinal direction, and this distance is used as the cut surface.
- the thickness of the piezoelectric layer 12 at the cut planes is measured at any five cross sections, and the average value is taken as the thickness t of the piezoelectric layer 12 of the piezoelectric film 10 to be measured.
- the cut sheet-like piezoelectric film 10 when the cut sheet-like piezoelectric film 10 is rectangular, it has four end surfaces (cut surfaces). Therefore, for one corner, the ratio p of one end of side A observed by SEM from the direction of arrow a perpendicular to side A, and the side observed by SEM from the direction of arrow b perpendicular to side B The ratio p of one end face of B can be measured. That is, when the piezoelectric film 10 is rectangular, the ratio p of the ends of the piezoelectric film 10 at eight locations in total can be measured with respect to the corners at four locations.
- the piezoelectric film of the present invention is not limited to the rectangular shape described above, and various shapes can be used.
- the planar shape of the piezoelectric film of the present invention ie, the shape of the main surface, may be circular, elliptical, triangular, or polygonal with pentagons or more. Regardless of the shape, the ratio p [%] between the distance d 1 between the electrodes and the thickness t is determined by observing the ends with SEM-EDS and performing elemental mapping of the material forming the electrodes.
- the ratio p is measured from two directions with all the corners as the measurement object, and the average value of all the ratios p (the number of corners ⁇ 2 places) is the ratio p in the piezoelectric film 10 .
- the term “polygon” also includes cases where the corners are curved due to chamfering or the like.
- the ratio p is measured at eight equally divided outer circumferences, and the average value is taken as the ratio p of the piezoelectric film 10 .
- the end face sealing layer 30 is made of a material containing resin and suppresses dielectric breakdown between electrode layers.
- the material for forming the end face sealing layer 30 is not limited, and various known materials can be used as long as they have insulating properties. Examples include polyimide and heat-resistant polyethylene terephthalate.
- thermoplastic resins and ultraviolet (UV) curable resins are preferable as the resin contained in the material of the end face sealing layer 30 .
- thermoplastic resins include polyolefin, polypropylene, polyamide, EVA (ethylene-vinyl acetate copolymer resin), synthetic rubber, and the like.
- UV curable resins include urethane acrylate and epoxy.
- the end surface of the piezoelectric film 10 is coated with, for example, a solution in which a resin material to be the end surface sealing layer 30 is dissolved in a solvent.
- a solution in which a resin material to be the end surface sealing layer 30 is dissolved in a solvent When forming by coating this solution, it takes time to dry and harden. Therefore, the solution may be pulled by surface tension or the like, exposing a part of the end face, and the end face sealing layer 30 covering the entire end face may not be formed.
- the hardening time can be shortened and the surface tension can be reduced. It is possible to prevent the solution from being partially exposed due to the pulling of the solution by such as. This makes it possible to easily form the edge sealing layer 30 covering the entire edge surface.
- the end face sealing layer 30 is not particularly limited in thickness, shape, etc., as long as dielectric breakdown between electrode layers can be suppressed.
- the end face sealing layer 30 covers part of the main surface of the first protective layer 18, the entire end face in the thickness direction, and part of the main surface of the second protective layer 20.
- it is not limited to this, and it is preferable to cover at least the entire end surface of the piezoelectric film 10 .
- the thickness d 3 (see FIG. 2) of the edge sealing layer 30 in the plane direction from the edge of the piezoelectric film 10 is preferably 5 ⁇ m to 20 ⁇ m, more preferably 10 ⁇ m to 15 ⁇ m. is more preferred. It should be noted that there is a limit to increasing the thickness d3 of the end face sealing layer 30 in the plane direction from the viewpoint of productivity. From this point, it is preferable to set the upper limit of the thickness d3 within the above range.
- the thickness d 2 of the end face sealing layer 30 formed on the main surface of the protective layer is preferably 50 ⁇ m or less, more preferably 10 ⁇ m to 40 ⁇ m, even more preferably 10 ⁇ m to 20 ⁇ m.
- the width d 4 in the plane direction of the end face sealing layer 30 formed on the main surface of the first protective layer 18 and the second protective layer 20 The average value of the width d 5 in the surface direction of the end face sealing layer 30 formed on the main surface of is preferably 3000 ⁇ m or less, more preferably 100 ⁇ m to 2000 ⁇ m, even more preferably 500 ⁇ m to 1500 ⁇ m.
- the cross-sectional shape of the end face of the end face sealing layer 30 is substantially linear, but is not limited to this, and may be substantially circular, elliptical, or the like.
- the end face sealing layer 30 only needs to cover at least a part of the end face of the piezoelectric film 10 in the circumferential direction, and preferably covers the entire circumferential direction. That is, the edge sealing layer 30 preferably covers the entire edge surface of the piezoelectric film 10 .
- FIG. 4 An example of a method for manufacturing the piezoelectric film 10 of the present invention will be described below with reference to conceptual diagrams of FIGS. 4 to 10.
- FIG. 4 a sheet-like object 42 having a second protective layer 20 and a second electrode layer 16 formed thereon as shown in FIG. 4 is prepared. Further, a sheet 40 having the first electrode layer 14 formed on the surface of the first protective layer 18 conceptually shown in FIG. 6 is prepared.
- the sheet 42 may be produced by forming a copper thin film or the like as the second electrode layer 16 on the surface of the second protective layer 20 by vacuum deposition, sputtering, plating, or the like.
- the sheet 40 may be produced by forming a copper thin film or the like as the first electrode layer 14 on the surface of the first protective layer 18 by vacuum deposition, sputtering, plating, or the like.
- a commercially available sheet having a copper thin film or the like formed on a protective layer may be used as the sheet 42 and/or the sheet 40 .
- the sheet-like material 42 and the sheet-like material 40 may be the same or different.
- a protective layer with a separator temporary support
- PET or the like having a thickness of 25 to 100 ⁇ m can be used as the separator.
- the separator may be removed after the electrode layer and protective layer are thermocompression bonded.
- a paint (coating composition) that will form the piezoelectric layer 12 is applied onto the second electrode layer 16 of the sheet 42 and cured to form the piezoelectric layer 12 .
- a piezoelectric laminate 46 in which the sheet-like material 42 and the piezoelectric layer 12 are laminated is produced.
- Various methods can be used to form the piezoelectric layer 12 depending on the material forming the piezoelectric layer 12 .
- the polymer material such as cyanoethylated PVA described above is dissolved in an organic solvent, and then piezoelectric particles 26 such as PZT particles are added and stirred to prepare a paint.
- Organic solvents are not limited, and various organic solvents such as dimethylformamide (DMF), methyl ethyl ketone, and cyclohexanone can be used.
- the paint is cast (applied) onto the sheet 42 and dried by evaporating the organic solvent.
- a piezoelectric laminate 46 having the second electrode layer 16 on the second protective layer 20 and the piezoelectric layer 12 laminated on the second electrode layer 16 is produced. do.
- the matrix 24 may be added with a polymeric piezoelectric material such as PVDF, in addition to the polymeric material having viscoelasticity at room temperature.
- a polymeric piezoelectric material such as PVDF
- the polymeric piezoelectric materials to be added to the paint may be dissolved.
- the polymer piezoelectric material to be added may be added to a polymer material that has been melted by heating and has viscoelasticity at room temperature, and then melted by heating.
- the piezoelectric layer 12 After the piezoelectric layer 12 is formed, it may be calendered, if desired. Calendering may be performed once or multiple times. As is well known, calendering is a process in which a surface to be treated is heated and pressed by a hot press, hot rollers, or the like to flatten the surface.
- the piezoelectric layer 12 of the piezoelectric laminate 46 having the second electrode layer 16 on the second protective layer 20 and the piezoelectric layer 12 formed on the second electrode layer 16 is subjected to a polarization treatment ( polling).
- the polarization treatment of the piezoelectric layer 12 may be performed before calendering, but is preferably performed after calendering.
- the method of polarization treatment of the piezoelectric layer 12 is not limited, and known methods can be used. For example, electric field poling, in which a DC electric field is directly applied to an object to be polarized, is exemplified.
- the first electrode layer 14 may be formed before the polarization treatment, and the electric field poling treatment may be performed using the first electrode layer 14 and the second electrode layer 16. Moreover, in the piezoelectric film 10 of the present invention, it is preferable that the polarization treatment is performed not in the surface direction of the piezoelectric layer 12 but in the thickness direction.
- the previously prepared sheet 40 is laminated on the piezoelectric layer 12 side of the piezoelectric laminate 46 that has been subjected to the polarization treatment, with the first electrode layer 14 facing the piezoelectric layer 12 . do. Furthermore, this laminated body is thermocompression bonded using a hot press device, a heating roller, etc., with the first protective layer 18 and the second protective layer 20 sandwiched between them, to form the piezoelectric laminated body 46 and the sheet-like material 40. are bonded together to produce a large-sized (long) laminated film 48 as shown in FIG. Alternatively, the laminated film 48 may be produced by bonding the piezoelectric laminate 46 and the sheet-like material 40 together with an adhesive, preferably by pressing them together.
- the laminated film 48 may be produced using the cut sheet-like sheet 42 and the sheet 40, or may be produced using roll to roll. good too.
- the produced large-sized laminated film 48 is cut into a predetermined shape, for example, a rectangle, to form a cut sheet.
- the laminated film 48 is cut so that the end face is oblique to the main surface.
- the angle at that time may be adjusted so that the ratio p of the inter-electrode distance d 1 at the end surface of the laminated film 49 (piezoelectric film 10 ) to the thickness t of the piezoelectric layer 12 is 103% or more and less than 120%.
- the end surface sealing layer 30 is formed on the end surface of the laminated film 49 .
- a method for forming the end surface sealing layer 30 on the end surface of the laminated film 49 is not limited, and a known forming method (film formation method) according to the material for forming the end surface sealing layer 30 can be used. Examples include a method of attaching an insulating adhesive tape, a method of applying and drying a liquid obtained by dissolving a material for the end surface sealing layer 30, and a method of applying a liquid obtained by melting a material for the end surface sealing layer 30. Examples include a method of curing, a method of dissolving the resin that forms the end face sealing layer 30 in a solvent, and spraying and drying the solution.
- thermoplastic resin or a UV curable resin is used as the material for the edge sealing layer 30
- a liquid obtained by melting the material for the edge sealing layer 30 is applied and then cooled or irradiated with UV.
- the end face sealing layer 30 may be formed by curing with a heat.
- the method of applying the liquid at this time is not limited, and various known methods can be used. Examples include spray coating and dip coating. Moreover, as described above, the end face sealing layer 30 may be formed up to the main surface of the first protective layer 18 and/or the second protective layer 20, if necessary.
- the piezoelectric film of the present invention can be produced.
- the piezoelectric film 10 produced in this manner is polarized in the thickness direction rather than in the plane direction, and excellent piezoelectric properties can be obtained without stretching after the polarization treatment. Therefore, the piezoelectric film 10 has no in-plane anisotropy in piezoelectric properties, and expands and contracts isotropically in all directions in the plane direction when a driving voltage is applied.
- a process of drawing out the electrodes may be performed. That is, as shown in FIG. 10, a through hole 18a is formed in the first protective layer 18, and a first connection member 32 is formed in the through hole 18a to connect the first extraction electrode 34 thereto. Further, a through hole 20a is formed in the second protective layer 20, and a second connecting member 33 is formed in the through hole 20a to connect the second extraction electrode 36. As shown in FIG. The method of forming the through hole 18a and the through hole 20a, the first connecting member 32 and the second connecting member 33, and the first extraction electrode 34 and the second extraction electrode 36 is as described above.
- FIG. 11 conceptually shows an example of a flat plate-type piezoelectric speaker using the piezoelectric film 10 of the present invention.
- This piezoelectric speaker 60 is a flat plate-type piezoelectric speaker that uses the piezoelectric film 10 as a diaphragm that converts an electrical signal into vibrational energy. Note that the piezoelectric speaker 60 can also be used as a microphone, a sensor, and the like.
- the piezoelectric speaker 60 includes a piezoelectric film 10 , a case 62 , a viscoelastic support 64 and a frame 68 .
- the case 62 is a thin housing made of plastic or the like and having one side open. Examples of the shape of the housing include rectangular parallelepiped, cubic, and cylindrical.
- the frame body 68 is a frame material that engages with the open side of the case 62 and has a through hole in the center that has the same shape as the open side of the case 62 .
- the viscoelastic support 64 has appropriate viscosity and elasticity, supports the piezoelectric film 10, and provides a constant mechanical bias at any location on the piezoelectric film, thereby allowing the piezoelectric film 10 to move back and forth without waste. It is for conversion into motion (motion in the direction perpendicular to the plane of the film). Examples include wool felt, non-woven fabric such as wool felt including PET, glass wool, and the like.
- the piezoelectric speaker 60 accommodates a viscoelastic support 64 in a case 62 , covers the case 62 and the viscoelastic support 64 with the piezoelectric film 10 , and surrounds the piezoelectric film 10 with a frame 68 on the upper end surface of the case 62 .
- the frame body 68 is fixed to the case 62 in a state of being pressed against.
- the height (thickness) of the viscoelastic support 64 is greater than the height of the inner surface of the case 62 . Therefore, in the piezoelectric speaker 60 , the viscoelastic support 64 is pressed downward by the piezoelectric film 10 and held in a reduced thickness at the periphery of the viscoelastic support 64 . Similarly, the curvature of the piezoelectric film 10 sharply changes in the peripheral portion of the viscoelastic support 64 , and a rising portion that becomes lower toward the periphery of the viscoelastic support 64 is formed in the piezoelectric film 10 . Furthermore, the central region of the piezoelectric film 10 is pressed by the square prism-shaped viscoelastic support 64 to form a (substantially) planar shape.
- the piezoelectric speaker 60 when the piezoelectric film 10 expands in the plane direction due to the application of the driving voltage to the first electrode layer 14 and the second electrode layer 16, the viscoelastic support 64 acts to absorb the expansion. Thus, the rising portion of the piezoelectric film 10 changes its angle in the rising direction. As a result, the piezoelectric film 10 having planar portions moves upward. Conversely, when the piezoelectric film 10 shrinks in the plane direction due to the application of the drive voltage to the first electrode layer 14 and the second electrode layer 16, the rising portion of the piezoelectric film 10 collapses in order to absorb this contraction. Change the angle in the direction (direction closer to the plane). As a result, the piezoelectric film 10 having planar portions moves downward. The piezoelectric speaker 60 generates sound by vibrating the piezoelectric film 10 .
- the piezoelectric film 10 conversion from stretching motion to vibration can also be achieved by holding the piezoelectric film 10 in a curved state. Therefore, the piezoelectric film 10 can be made to function as a flexible piezoelectric speaker by simply holding it in a curved state instead of the rigid flat piezoelectric speaker 60 shown in FIG.
- a piezoelectric speaker using such a piezoelectric film 10 can take advantage of its good flexibility and can be rolled up or folded and accommodated in a bag or the like. Therefore, according to the piezoelectric film 10, it is possible to realize an easily portable piezoelectric speaker even if it has a certain size. Moreover, as described above, the piezoelectric film 10 is excellent in softness and flexibility, and has no in-plane anisotropy of piezoelectric properties. Therefore, the piezoelectric film 10 has little change in sound quality when bent in any direction, and also has little change in sound quality with respect to changes in curvature.
- the piezoelectric speaker using the piezoelectric film 10 has a high degree of freedom in installation location, and can be attached to various articles as described above.
- a so-called wearable speaker can be realized by attaching the piezoelectric film 10 in a curved state to a clothing item such as clothes or a portable item such as a bag.
- the piezoelectric film of the present invention by attaching the piezoelectric film of the present invention to a flexible display device such as a flexible organic EL display device or a flexible liquid crystal display device, the It can also be used as a speaker.
- a flexible display device such as a flexible organic EL display device or a flexible liquid crystal display device
- the piezoelectric film 10 expands and contracts in the plane direction when a voltage is applied, and this expansion and contraction in the plane direction suitably vibrates in the thickness direction. It expresses good acoustic characteristics that can output sound.
- the piezoelectric film may not have the first protective layer 18 and/or the second protective layer 20 if there is no possibility of short circuit.
- piezoelectric films without the first protective layer 18 and/or the second protective layer 20 may be laminated via an insulating layer.
- the laminate of the piezoelectric films 10 may be adhered to a diaphragm, and the laminate of the piezoelectric films 10 may be used to vibrate the diaphragm to produce a speaker that outputs sound. That is, in this case, the laminate of the piezoelectric films 10 acts as a so-called exciter that outputs sound by vibrating the diaphragm.
- the laminate of the piezoelectric films 10 acts as a so-called exciter that outputs sound by vibrating the diaphragm.
- the individual piezoelectric films 10 expand and contract in the plane direction, and the expansion and contraction of each piezoelectric film 10 causes the entire laminate of the piezoelectric films 10 to expand and contract in the plane direction.
- the expansion and contraction of the laminate of the piezoelectric film 10 in the planar direction bends the diaphragm to which the laminate is attached, and as a result, the diaphragm vibrates in the thickness direction.
- This vibration in the thickness direction causes the diaphragm to generate sound.
- the diaphragm vibrates according to the magnitude of the driving voltage applied to the piezoelectric film 10 and generates sound according to the driving voltage applied to the piezoelectric film 10 . Therefore, at this time, the piezoelectric film 10 itself does not output sound.
- the number of laminated piezoelectric films 10 is not limited. do it. It is also possible to use one sheet of piezoelectric film 10 as a similar exciter (piezoelectric element) as long as it has sufficient stretching force.
- the vibration plate that is vibrated by the laminate of the piezoelectric films 10 there are no restrictions on the vibration plate that is vibrated by the laminate of the piezoelectric films 10, and various sheet-like materials (plate-like materials, films) can be used. Examples include resin films such as polyethylene terephthalate (PET), foamed plastics such as polystyrene foam, paper materials such as cardboard, glass plates, and wood. Furthermore, a device such as a display device may be used as the diaphragm as long as it can be bent sufficiently.
- PET polyethylene terephthalate
- foamed plastics such as polystyrene foam
- paper materials such as cardboard, glass plates, and wood.
- a device such as a display device may be used as the diaphragm as long as it can be bent sufficiently.
- the adjacent piezoelectric films are adhered with an adhesive layer (adhesive).
- the laminate of the piezoelectric films 10 and the diaphragm are adhered with an adhesion layer.
- the adhesive layer There are no restrictions on the adhesive layer, and various layers that can be used to attach objects to be attached to each other can be used. Therefore, the sticking layer may be made of a pressure-sensitive adhesive or an adhesive.
- an adhesive layer is used which consists of an adhesive, which after application results in a solid and hard adhesive layer. The above points are the same for a laminated body formed by folding a long piezoelectric film 10 described later.
- the polarization direction of each laminated piezoelectric film 10 is not limited. As described above, the polarization direction of the piezoelectric film 10 is the polarization direction in the thickness direction. Therefore, in the laminate of piezoelectric films 10, the polarization direction may be the same for all the piezoelectric films 10, or there may be piezoelectric films having different polarization directions.
- the piezoelectric films 10 are preferably laminated so that the polarization directions of the adjacent piezoelectric films 10 are opposite to each other.
- the polarity of the voltage applied to the piezoelectric layer 12 depends on the polarization direction of the piezoelectric layer 12 . Therefore, regardless of whether the polarization direction is from the first electrode layer 14 to the second electrode layer 16 or from the second electrode layer 16 to the first electrode layer 14, the first electrode is The polarity of layer 14 and the polarity of second electrode layer 16 are made the same.
- the adjacent piezoelectric films 10 have opposite polarization directions, even if the electrode layers of the adjacent piezoelectric films 10 are in contact with each other, the contacting electrode layers have the same polarity, which may cause a short circuit. do not have.
- the laminate (piezoelectric element) of the piezoelectric film 10 may have a configuration in which a plurality of piezoelectric films 10 are laminated by folding the long piezoelectric film 10 one or more times, preferably multiple times.
- a piezoelectric element in which the long piezoelectric film 10 is folded and laminated has the following advantages. That is, in a piezoelectric element in which a plurality of cut-sheet piezoelectric films 10 are laminated, the first electrode layer 14 and the second electrode layer 16 must be connected to the driving power supply for each piezoelectric film. On the other hand, in the structure in which the long piezoelectric film 10 is folded and laminated, the laminated body can be configured with only one long piezoelectric film 10 .
- the long piezoelectric film 10 is folded and laminated, only one power source is required for applying the driving voltage, and the electrode may be led out from the piezoelectric film 10 at one place. Furthermore, in the structure in which the long piezoelectric films 10 are folded and laminated, the polarization directions of adjacent piezoelectric films 10 are inevitably opposite to each other.
- a large laminated film was produced by the method shown in FIGS. First, cyanoethylated PVA (CR-V, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in dimethylformamide (DMF) at the following compositional ratio. After that, PZT particles as piezoelectric particles were added to this solution at the following composition ratio, and the mixture was stirred with a propeller mixer (rotation speed: 2000 rpm) to prepare a paint for forming a piezoelectric layer.
- DMF dimethylformamide
- ⁇ PZT particles ⁇ 300 parts by mass ⁇ Cyanoethylated PVA ⁇ 30 parts by mass ⁇ DMF ⁇ 70 parts by mass
- Mixed powder obtained by wet-mixing in a ball mill was fired at 800° C. for 5 hours and then pulverized.
- a sheet-like material was prepared by vacuum-depositing a copper thin film with a thickness of 0.1 ⁇ m on a PET film with a thickness of 4 ⁇ m. That is, in this example, the first electrode layer and the second electrode layer are 0.1 m-thick copper-evaporated thin films, and the first protective layer and the second protective layer are 4 ⁇ m-thick PET films. Using a slide coater, the previously prepared paint for forming the piezoelectric layer was applied onto the second electrode layer (copper-deposited thin film) of the sheet-like material. In addition, the paint was applied so that the thickness of the coating film after drying was 50 ⁇ m.
- the sheet-like material coated with the paint was dried by heating on a hot plate at 120° C. to evaporate the DMF.
- a piezoelectric laminate having a second electrode layer made of copper on a second protective layer made of PET and a piezoelectric layer (polymer composite piezoelectric layer) having a thickness of 50 ⁇ m thereon is produced. bottom.
- the produced piezoelectric layer was subjected to polarization treatment in the thickness direction.
- a sheet-like product obtained by vapor-depositing the same thin film on a PET film was laminated on the polarized laminate with the first electrode layer (copper thin film side) facing the piezoelectric layer.
- the laminate of the laminate and the sheet-like material is thermocompressed at a temperature of 120° C. using a laminator, thereby adhering and adhering the composite piezoelectric body and the first electrode layer, as shown in FIG.
- a large-sized laminated film as shown in was produced.
- Examples 1 to 4 and Comparative Examples 1 to 3 The produced laminate film was cut into pieces of 210 ⁇ 300 mm by variously changing the cutter blade and cutting angle to be used to produce a cut sheet-like laminate film.
- the inter-electrode distance d 1 at the end face between the first electrode layer and the second electrode layer at the end and the thickness t of the piezoelectric layer were measured by the above-described method using SEM-EDS.
- the ratio p [%] between the inter-electrode distance d1 and the thickness t was calculated.
- SEM-EDS measurement SU8220 manufactured by Hitachi High-Technologies Corporation was used as the SEM, and XFash 5060FQ manufactured by BRUKER was used as the EDS.
- an edge sealing layer was formed on the edge of the cut laminate film so as to cover the entire edge, thereby producing a piezoelectric film.
- a thermoplastic resin (EVA) was used as the material for the edge sealing layer, and the solution applied to the edges was cooled and cured.
- a UV curable resin (urethane acrylate) was used as the material of the end face sealing layer, and the solution applied to the end was cooled and cured.
- end faces were not sealed.
- the thickness d 2 of the end face sealing layer formed on the main surface of the protective layer was set to 50 ⁇ m in Examples 1-3 and Comparative Examples 1-2, and 100 ⁇ m in Example 4.
- Wiring was connected to the electrode layer of the produced piezoelectric film.
- a piezoelectric film is placed in an anechoic chamber, and a voltage that makes the electric field between the piezoelectric film electrode layers 3 V/ ⁇ m is applied as an input signal through a power amplifier. recorded the sound.
- the examples of the present invention can suppress dielectric breakdown compared to the comparative examples.
- dielectric breakdown occurred between the electrode layers at the end face when a high voltage was applied, and no sound was produced.
- Comparative Example 1 it can be seen from Comparative Example 1 that if the ratio p is too large, the end faces cannot be properly sealed, and dielectric breakdown is likely to occur.
- the thickness d 2 of the end face sealing layer is preferably 50 ⁇ m or less. From the above results, the effect of the present invention is clear.
- the piezoelectric film of the present invention can be used, for example, in various sensors such as sound wave sensors, ultrasonic sensors, pressure sensors, tactile sensors, strain sensors and vibration sensors (especially for infrastructure inspection such as crack detection and manufacturing site inspection such as foreign matter contamination detection). useful), acoustic devices such as microphones, pickups, speakers and exciters (specific applications include noise cancellers (used in cars, trains, airplanes, robots, etc.), artificial vocal cords, buzzers for preventing insects and vermin from entering , furniture, wallpaper, photographs, helmets, goggles, headrests, signage, robots, etc.), automobiles, smartphones, smart watches, haptics used for games, etc.
- sensors such as sound wave sensors, ultrasonic sensors, pressure sensors, tactile sensors, strain sensors and vibration sensors (especially for infrastructure inspection such as crack detection and manufacturing site inspection such as foreign matter contamination detection).
- acoustic devices such as microphones, pickups, speakers and exciters (specific applications include noise cancellers (used in cars, trains, airplanes, robots,
- piezoelectric film 12 piezoelectric layer 14 first electrode layer 16 second electrode layer 18 first protective layer 18a, 20a through hole 20 second protective layer 24 polymer matrix 26 piezoelectric particles 30 end face sealing layer 32 first connecting member 33 second connection member 34 first extraction electrode 36 second extraction electrode 40, 42 sheet-like object 46 piezoelectric laminate 48 laminate film 60 piezoelectric speaker 62 case 64 viscoelastic support 68 frame d1 distance between electrodes d2 main surface d3 Thickness of edge sealing layer in surface direction d4 , d5 Width of edge sealing layer on main surface t Thickness of piezoelectric layer
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Abstract
Description
特許文献1に開示される圧電フィルムは、常温で粘弾性を有する高分子材料からなる粘弾性マトリックス中に圧電体粒子を分散してなる高分子複合圧電体と、高分子複合圧電体の両面に形成された薄膜電極と、薄膜電極の表面に形成された保護層とを有する。
[1] 高分子材料を含むマトリックス中に圧電体粒子を含む圧電体層と、圧電体層の両面に設けられる電極層と、電極層上に設けられる保護層を有する、圧電フィルムであって、
圧電フィルムの端面を覆う、樹脂を含む材料からなる端面封止層を有し、
圧電フィルムの端面における電極間距離が30μm以上であり、かつ、圧電体層の厚みに対する、圧電フィルムの端面における電極間距離が103%以上120%未満である、圧電フィルム。
[2] 端面封止層の材料が熱可塑性樹脂を含む、[1]に記載の圧電フィルム。
[3] 端面封止層の材料が紫外線硬化性の樹脂を含む、[1]または[2]に記載の圧電フィルム。
[4] 保護層の主面上に形成されている端面封止層の厚みが50μm以下である、[1]~[3]のいずれか一項に記載の圧電フィルム。
[5] 端面封止層の、圧電フィルムの主面上における面方向の幅が、100μm以上5000μm以下である、[1]~[4]のいずれかに記載の圧電フィルム。
[6] 端面封止層の、圧電フィルムの端面からの面方向の厚みが、50μm以下である、[1]~[5]のいずれかに記載の圧電フィルム。
[7] [1]~[6]のいずれかに記載の圧電フィルムを、複数層、積層したものである、圧電素子。
[8] [1]~[6]のいずれかに記載の圧電フィルムを、1回以上、折り返すことにより、圧電フィルムを、複数層、積層したものである、圧電素子。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に制限されるものではない。また、以下に示す図は、いずれも、本発明を説明するための概念的な図であって、各層の厚さ、構成部材の大きさ、および、構成部材の位置関係等は、実際の物とは異なる。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明の圧電フィルムは、
高分子材料を含むマトリックス中に圧電体粒子を含む圧電体層と、圧電体層の両面に設けられる電極層と、電極層上に設けられる保護層を有する、圧電フィルムであって、
圧電フィルムの端面を覆う、樹脂を含む材料からなる端面封止層を有し、
圧電フィルムの端面における電極間距離が30μm以上であり、かつ、圧電体層の厚みに対する、圧電フィルムの端面における電極間距離が103%以上120%未満である、圧電フィルムである。
電気音響変換器は、圧電フィルムへの電圧印加によって、圧電フィルムが面方向に伸長すると、この伸長分を吸収するために、圧電フィルムが、上方(音の放射方向)に移動し、逆に、圧電フィルムへの電圧印加によって、圧電フィルムが面方向に収縮すると、この収縮分を吸収するために、圧電フィルムが、下方に移動する。
電気音響変換器は、この圧電フィルムの伸縮の繰り返しによる振動により、振動(音)と電気信号とを変換するものであり、圧電フィルムに電気信号を入力して電気信号に応じた振動により音を再生したり、音波を受けることによる圧電フィルムの振動を電気信号に変換したり、振動による触感付与や物体の輸送に利用される。
具体的には、圧電フィルムの用途としては、フルレンジスピーカー、ツイーター、スコーカー、ウーハーなどのスピーカー、ヘッドホン用スピーカー、ノイズキャンセラー、マイクロフォン、および、ギター等の楽器に用いられるピックアップ(楽器用センサー)などの各種の音響デバイスが挙げられる。また、本発明の圧電フィルムは非磁性体であるため、ノイズキャンセラーのなかでもMRI用ノイズキャンセラーとして好適に用いることが可能である。
また、本発明の圧電フィルムを利用する電気音響変換器は薄く、軽く、曲がるため、帽子、マフラーおよび衣服といったウェアラブル製品、テレビおよびデジタルサイネージなどの薄型ディスプレイ、ならびに、音響機器等としての機能を有する建築物、自動車の天井、カーテン、傘、壁紙、窓およびベッドなどに好適に利用される。
図1に示す圧電フィルム10は、圧電体層12と、圧電体層12の一方の面に積層される第1電極層14と、第1電極層14に積層される第1保護層18と、圧電体層12の他方の面に積層される第2電極層16と、第2電極層16に積層される第2保護層20と、端面封止層30と、を有する。
第2保護層20も、第2電極層16まで貫通する貫通孔20aを有し、この貫通孔20aには、導電性の第2接続部材33が設けられる。また、同様に、この第2接続部材33に接続して、圧電フィルム10を外部の電源に接続するための第2引出電極36が設けられる。
本発明の圧電フィルム10において、圧電体層12は、図3に概念的に示すように、高分子材料を含む高分子マトリックス24中に、圧電体粒子26を含む、高分子複合圧電体であるのが好ましい。
(i) 可撓性
例えば、携帯用として新聞や雑誌のように書類感覚で緩く撓めた状態で把持する場合、絶えず外部から、数Hz以下の比較的ゆっくりとした、大きな曲げ変形を受けることになる。この時、高分子複合圧電体が硬いと、その分、大きな曲げ応力が発生し、高分子マトリックスと圧電体粒子との界面で亀裂が発生し、やがて破壊に繋がる恐れがある。従って、高分子複合圧電体には適度な柔らかさが求められる。また、歪みエネルギーを熱として外部へ拡散できれば応力を緩和することができる。従って、高分子複合圧電体の損失正接が適度に大きいことが求められる。
(ii) 音質
スピーカーは、20Hz~20kHzのオーディオ帯域の周波数で圧電体粒子を振動させ、その振動エネルギーによって振動板(高分子複合圧電体)全体が一体となって振動することで音が再生される。従って、振動エネルギーの伝達効率を高めるために高分子複合圧電体には適度な硬さが求められる。また、スピーカーの周波数特性が平滑であれば、曲率の変化に伴い最低共振周波数f0が変化した際の音質の変化量も小さくなる。従って、高分子複合圧電体の損失正接は適度に大きいことが求められる。
このとき、圧電フィルムの湾曲程度すなわち湾曲部の曲率半径が大きくなるほど機械的なスチフネスsが下がるため、最低共振周波数f0は小さくなる。すなわち、圧電フィルムの曲率半径によってスピーカーの音質(音量、周波数特性)が変わることになる。
高分子複合圧電体(圧電体層12)において、ガラス転移点が常温にある高分子材料、言い換えると、常温で粘弾性を有する高分子材料をマトリックスに用いることで、20Hz~20kHzの振動に対しては硬く、数Hz以下の遅い振動に対しては柔らかく振舞う高分子複合圧電体が実現する。特に、この振舞いが好適に発現する等の点で、周波数1Hzでのガラス転移点Tgが常温にある高分子材料を、高分子複合圧電体のマトリックスに用いるのが好ましい。
これにより、高分子複合圧電体が外力によってゆっくりと曲げられた際に、最大曲げモーメント部における高分子マトリックス/圧電体粒子界面の応力集中が緩和され、高い可撓性が期待できる。
これにより、高分子複合圧電体が外力によってゆっくりと曲げられた際に発生する曲げモーメントが低減できると同時に、20Hz~20kHzの音響振動に対しては硬く振る舞うことができる。
しかしながら、その反面、良好な耐湿性の確保等を考慮すると、高分子材料は、比誘電率が25℃において10以下であるのも、好適である。
また、これらの高分子材料としては、ハイブラー5127(クラレ社製)などの市販品も、好適に利用可能である。
以下の説明では、シアノエチル化PVAを代表とする上述の高分子材料を、まとめて『常温で粘弾性を有する高分子材料』とも言う。
すなわち、高分子複合圧電体を構成するマトリックス24には、誘電特性や機械的特性の調節等を目的として、上述した常温で粘弾性を有する高分子材料に加え、必要に応じて、その他の誘電性高分子材料を添加しても良い。
中でも、シアノエチル基を有する高分子材料は、好適に利用される。
また、圧電体層12のマトリックス24において、これらの誘電性高分子材料は、1種に制限はされず、複数種を添加してもよい。
さらに、粘着性を向上する目的で、ロジンエステル、ロジン、テルペン、テルペンフェノール、および、石油樹脂等の粘着付与剤を添加しても良い。
これにより、マトリックス24における粘弾性緩和機構を損なうことなく、添加する高分子材料の特性を発現できるため、高誘電率化、耐熱性の向上、圧電体粒子26や電極層との密着性向上等の点で好ましい結果を得ることができる。
圧電体粒子26は、好ましくは、ペロブスカイト型またはウルツ鉱型の結晶構造を有するセラミックス粒子からなるものである。
圧電体粒子26を構成するセラミックス粒子としては、例えば、チタン酸ジルコン酸鉛(PZT)、チタン酸ジルコン酸ランタン酸鉛(PLZT)、チタン酸バリウム(BaTiO3)、酸化亜鉛(ZnO)、および、チタン酸バリウムとビスマスフェライト(BiFe3)との固溶体(BFBT)等の粒子が例示される。
圧電体粒子26の粒径を上記範囲とすることにより、高い圧電特性とフレキシビリティとを両立できる等の点で好ましい結果を得ることができる。
圧電体層12中における圧電体粒子26の体積分率は、30~80%が好ましく、50~80%がより好ましい。
マトリックス24と圧電体粒子26との量比を上記範囲とすることにより、高い圧電特性とフレキシビリティとを両立できる等の点で好ましい結果を得ることができる。
圧電体層12の厚さは、8~300μmが好ましく、8~200μmがより好ましく、10~150μmがさらに好ましく、特に15~100μmが好ましい。
圧電体層12の厚さを、上記範囲とすることにより、剛性の確保と適度な柔軟性との両立等の点で好ましい結果を得ることができる。
言い換えれば、本発明の圧電フィルム10を構成する積層フィルムは、圧電体層12の両面を電極対、すなわち、第1電極層14および第2電極層16で挟持し、さらに、第1保護層18および第2保護層20で挟持してなる構成を有する。
このように、第1電極層14および第2電極層16で挾持された領域は、印加された電圧に応じて駆動される。
従って、本発明の圧電フィルム10における第1および第2には、技術的な意味は無く、また、実際の使用状態とは無関係である。
貼着剤は、接着剤でも粘着剤でもよい。また、貼着剤は、圧電体層12から圧電体粒子26を除いた高分子材料すなわちマトリックス24と同じ材料も、好適に利用可能である。なお、貼着層は、第1電極層14側および第2電極層16側の両方に有してもよく、第1電極層14側および第2電極層16側の一方のみに有してもよい。
第1保護層18と第2保護層20とは、配置位置が異なるのみで、構成は同じである。従って、以下の説明においては、第1保護層18および第2保護層20を区別する必要がない場合には、両部材をまとめて、保護層ともいう。
保護層の剛性が高過ぎると、圧電体層12の伸縮を拘束するばかりか、可撓性も損なわれる。そのため、機械的強度やシート状物としての良好なハンドリング性が要求される場合を除けば、保護層は、薄いほど有利である。
例えば、圧電体層12の厚さが50μmで第1保護層18および第2保護層20がPETからなる場合、第1保護層18および第2保護層20の厚さはそれぞれ、100μm以下が好ましく、50μm以下がより好ましく、中でも25μm以下とするのが好ましい。
中でも、銅、アルミニウム、金、銀、白金、および、酸化インジウムスズは、好適に例示される。その中でも、導電性、コストおよび可撓性等の観点から銅がより好ましい。
中でも特に、圧電フィルム10の可撓性が確保できる等の理由で、真空蒸着によって成膜された銅やアルミニウムの薄膜は、電極層として、好適に利用される。その中でも特に、真空蒸着による銅の薄膜は、好適に利用される。
ここで、上述した保護層と同様に、電極層の剛性が高過ぎると、圧電体層12の伸縮を拘束するばかりか、可撓性も損なわれる。そのため、電極層は、電気抵抗が高くなり過ぎない範囲であれば、薄いほど有利である。
例えば、保護層がPET(ヤング率:約6.2GPa)で、電極層が銅(ヤング率:約130GPa)からなる組み合わせの場合、保護層の厚さが25μmだとすると、電極層の厚さは、1.2μm以下が好ましく、0.3μm以下がより好ましく、0.1μm以下とするのがさらに好ましい。
このような圧電フィルム10は、動的粘弾性測定による周波数1Hzでの損失正接(Tanδ)が0.1以上となる極大値が常温に存在するのが好ましい。
これにより、圧電フィルム10が外部から数Hz以下の比較的ゆっくりとした、大きな曲げ変形を受けたとしても、歪みエネルギーを効果的に熱として外部へ拡散できるため、高分子マトリックスと圧電体粒子との界面で亀裂が発生するのを防ぐことができる。
これにより、常温で圧電フィルム10が貯蔵弾性率(E’)に大きな周波数分散を有することができる。すなわち、20Hz~20kHzの振動に対しては硬く、数Hz以下の振動に対しては柔らかく振る舞うことができる。
これにより、圧電フィルム10が可撓性および音響特性を損なわない範囲で、適度な剛性と機械的強度を備えることができる。
これにより、圧電フィルム10を用いたスピーカーの周波数特性が平滑になり、スピーカー(圧電フィルム10)の曲率の変化に伴い最低共振周波数f0が変化した際の音質の変化量も小さくできる。
同様に、第2保護層20も、同様の貫通孔20aを有し、この貫通孔20aには、第2電極層16に接続して、導電性の第2接続部材33が設けられる。また、同様に、この第2接続部材33に接続して、圧電フィルム10を外部の電源に接続するための、第2引出電極36が設けられる。
第1引出電極34と第2引出電極36とは、圧電フィルム10(積層フィルム)の面方向に、異なる位置に設けられることが好ましい。図1においては、第1引出電極34と第2引出電極36とは、図中紙面に直交する方向の異なる位置に設けられる。
例えば、第1引出電極34と第2引出電極36とが逆方向に引き出されてもよく、第1引出電極34と第2引出電極36とが直交するように引き出されてもよい。
貫通孔18aの大きさには、制限はなく、第1電極層14および第1引出電極34の形成材料、第1引出電極34の大きさ、圧電フィルム10の大きさ等に応じて、十分な導通を得られる第1接続部材32を形成可能な大きさを、適宜、設定すればよい。
貫通孔18aの形状にも、制限はない。従って、貫通孔は、円錐台状、円筒状および角筒状等の各種の形状が利用可能である。
一例として、炭酸ガスレーザによる波長10.6μmのレーザ光などのレーザ光によって焼き飛ばす(アブレーション)ことによって第1保護層18を除去して、貫通孔18aを形成する方法が例示される。例えば、第1保護層18における貫通孔18aの形成位置をレーザ光で走査することにより、第1保護層18の所望の位置に貫通孔18aを形成すればよい。この際においては、レーザ光の強度や走査速度(すなわちレーザ光による処理時間)等を調節することで、所望の厚さの貫通孔18aを形成できる。
また、有機溶剤を用いて第1保護層18を溶解することで、貫通孔18aを形成する方法も利用可能である。例えば、第1保護層18がPETであれば、ヘキサフルオロイソプパノール等を用いて、貫通孔18aを形成できる。溶剤を用いる場合には、フォトリソグラフィ等におけるエッチングと同様に、マスク等を用いることにより、所望の位置に貫通孔18aを形成すればよい。この際においては、処理時間や有機溶剤の濃度を調節することで、所望の厚さの貫通孔18aを形成できる。
本発明の圧電フィルム10において、第1接続部材32は、貫通孔18aに挿入可能な導電性を有する材料からなるものが、各種、利用可能である。
具体的には、銀、銅および金などの金属粒子を、エポキシ樹脂、ポリイミドなどの熱硬化性樹脂からなるバインダに分散してなる金属ペースト、同様の金属粒子をアクリル樹脂などの室温程度で硬化する樹脂からなるバインダに分散してなる金属ペースト、錯体金属により金属単体で熱硬化する金属ペースト、銅箔テープなどの金属テープ、および、貫通孔18aに挿入可能な金属部材等が例示される。
第1引出電極34にも、制限はなく、銅箔等の金属箔、各種の金属配線など、電極等と電源および外部装置とを電気的に導通する配線に用いられる公知のものが、各種、利用可能である。
また、積層フィルムの面方向の外部における第1引出電極34の長さは、圧電フィルム10の用途、圧電フィルム10が接続される機器、圧電フィルム10の設置位置等に応じて、適宜、設定すればよい。
一例として、導電性の貼着剤(接着剤、粘着剤)を用いる方法、導電性の両面テープを用いる方法等が例示される。また、第1接続部材32に銀ペースト等の金属ペーストを用い、銅箔および導電性ワイヤー等を第1引出電極34として用いることで、接着性を持たせて、第1引出電極34と第1接続部材32とを貼着する方法も利用可能である。
しかしながら、本発明の圧電フィルムは、これに制限はされず、電極の引き出しは、各種の構成が利用可能である。
例えば、保護層と圧電体層との間、または、電極層と保護層との間に、棒状およびシート状(フィルム状、板状)等の引き出し用の配線を設け、この引き出し用の配線に、引出電極を接続してもよい。または、引き出し用の配線を、そのまま引出電極として用いてもよい。あるいは、保護層および電極層の一部を面方向に圧電体層から突出させ、突出した電極層を引き出し用の配線として、此処に引出電極を接続してもよい。
本発明の圧電フィルムは、このような構成を有することにより、端部における第1電極層と第2電極層との絶縁破壊(ショート(短絡))を好適に防止できる。
図2に示すように、圧電フィルム10は、圧電フィルム10の端面、すなわち、第1保護層18、第1電極層14、圧電体層12、第2電極層16および第2保護層20の積層フィルムの端面には、少なくともこの端面を覆うように形成されている、樹脂を含む材料からなる端面封止層30を有する。図2に示す例では、端面封止層30は、第1保護層18の主面上から第2保護層20の主面上にかけて形成されることで、積層フィルムの端面の厚さ方向の全域を覆っている。なお、主面とは、シート状物(層、フィルム、板状物)の最大面である。
一例として、EDS(Energy dispersive X-ray spectrometry、エネルギー分散型X線分析装置(EDX))を搭載したSEM(Scanning Electron Microscope、走査型電子顕微鏡)を用いて、圧電フィルム10の端面すなわち切断面の端部を観察して、電極層を形成する材料の元素マッピングを行って測定する方法が例示される。SEMおよびEDXは、市販品を用いればよい。一例として、SEMは日立ハイテクノロジーズ社製のSU8220が、EDSは、BRUKER社製のXFash 5060FQが、それぞれ、例示される。
その際、電極間距離d1を測定するために、電極間距離d1の測定位置を含むように圧電フィルムを端部より5mm以上包埋して、ミクロトームを用いた切断、および、必要に応じて研磨を行い、第1電極層14と第2電極層16との電極間距離d1の測定を行う。
次いで、元素分析の結果から、第1電極層14および第2電極層16の形成材料の元素マッピングを行い、マッピング結果の画像を得る。例えば、第1電極層14および第2電極層16の形成材料が銅である場合には、元素分析の結果から銅マッピングを行い、銅マッピングの結果の画像を得る。
あるいは、後述する圧電フィルム10の製造工程において、圧電体層12を形成した時点で、公知の方法で圧電体層12の厚みtを測定してもよい。あるいは、後述する圧電フィルム10の製造工程において、圧電体層12となる塗料の塗布厚および組成から、圧電体層12の厚みtを算出してもよい。あるいは、圧電体層12を形成した時点で、全厚を測定して、その後、一部で圧電体層12を除去して、厚さを測定し、その差から、圧電体層12の厚みtを求めてもよい。
圧電フィルム10を樹脂に包埋する。樹脂による包埋は、圧電フィルム10の切断面から5mm以上、樹脂で包埋するように行うのが好ましい。包埋に用いる樹脂は、圧電フィルム10の形成材料および大きさ(最大面の面積、厚さ)等に応じて、適宜、設定すればよい。なお、包埋に用いる樹脂は、必要に応じて、複数種を混合して用いてもよい。
圧電フィルム10を樹脂に包埋したら、樹脂に包埋した圧電フィルム10を、任意の場所で直線状に切断する。切断は、ミクロトーム等を使う方法の公知の方法で行えばよい。
なお、切断は、切断面の長手方向の中心が、圧電フィルム10の全ての端部(端面)から5mm以上、内側となる位置で行うのが好ましい。
次いで、必要に応じて切断面を研磨する。研磨は、公知の方法で行えばよい。
さらに、切断面の長手方向の中心部において、上述したSEM-EDSによる第1電極層14および第2電極層16の形成材料の元素マッピングを行う。次いで、元素マッピングの画像から、切断面の長手方向の中心で、第1電極層14の内面と第2電極層16の内面との厚さ方向の距離を測定し、この距離を、その切断面における圧電フィルムの厚みtとする。
このような圧電体層12の切断面における厚さの測定を、任意の5断面で行い、その平均値を、測定対象となる圧電フィルム10の圧電体層12の厚みtとする。
p[%]=(d/t)×100
すなわち、圧電フィルム10が矩形である場合には、4か所の角部に対して、合計で8か所の圧電フィルム10の端部の比率pが測定できる。
いずれの形状であっても、電極間距離d1と、厚みtとの比率p[%]は、端部をSEM-EDSで観察して、電極の形成材料の元素マッピングを行う、上述の方法で測定すればよい。
本発明においては、圧電フィルムが多角形の場合には、全ての角部を測定対象として、2方向から比率pを測定し、全ての比率p(角部の数×2か所)の平均値を、圧電フィルム10における比率pとする。なお、多角形とは、面取り等によって角部が曲線状になっている場合も含む。また、圧電フィルムが円形および楕円形などの多角形以外の場合には、外周を等分した8か所において比率pを測定し、その平均値を、圧電フィルム10における比率pとする。
端面封止層30の形成材料には、制限はなく、絶縁性を有する材料であれば、公知の各種の材料が利用可能である。一例として、ポリイミド、および、耐熱性のポリエチレンテレフタレート等が例示される。
熱可塑性樹脂としては、ポリオレフィン、ポリプロピレン、ポリアミド、EVA(エチレン・酢酸ビニル共重合樹脂)、合成ゴム等が例示される。
UV硬化性樹脂としては、ウレタンアクリレート、エポキシ等が例示される。
なお、厚みd3は、次にように規定する。
圧電フィルムの一方の主面から他方の主面を測定範囲とし(=圧電フィルムの厚さの範囲)、均等に5等分振り分けをした箇所にて、圧電フィルムの端面から端面封止層の端部までの水平方向の厚さを測定する。得られた5つの測定データの平均をその切断面における厚みd3とする。これを5断面に対し行い、その平均を最終的なd3として規定する。
まず、図4に示す、第2保護層20の表面に第2電極層16が形成されたシート状物42を準備する。さらに、図6に概念的に示す、第1保護層18の表面に第1電極層14が形成されたシート状物40を準備する。
あるいは、保護層の上に銅薄膜等が形成された市販品をシート状物を、シート状物42および/またはシート状物40として利用してもよい。
シート状物42およびシート状物40は、同じものでもよく、異なるものでもよい。
一例として、まず、有機溶媒に、上述したシアノエチル化PVA等の高分子材料を溶解し、さらに、PZT粒子等の圧電体粒子26を添加し、攪拌して塗料を調製する。
有機溶媒には制限はなく、ジメチルホルムアミド(DMF)、メチルエチルケトン、および、シクロヘキサノン等の各種の有機溶媒が利用可能である。
シート状物42を準備し、かつ、塗料を調製したら、この塗料をシート状物42にキャスティング(塗布)して、有機溶媒を蒸発して乾燥する。これにより、図5に示すように、第2保護層20の上に第2電極層16を有し、第2電極層16の上に圧電体層12を積層してなる圧電積層体46を作製する。
あるいは高分子材料が加熱溶融可能な物であれば、高分子材料を加熱溶融して、これに圧電体粒子26を添加してなる溶融物を作製し、押し出し成形等によって、図4に示すシート状物42の上にシート状に押し出し、冷却することにより、図5に示すような、圧電積層体46を作製してもよい。
マトリックス24に、これらの高分子圧電材料を添加する際には、上記塗料に添加する高分子圧電材料を溶解すればよい。あるいは、加熱溶融した常温で粘弾性を有する高分子材料に、添加する高分子圧電材料を添加して加熱溶融すればよい。
周知のように、カレンダ処理とは、加熱プレスや加熱ローラ等によって、被処理面を加熱しつつ押圧して、平坦化等を施す処理である。
圧電体層12の分極処理の方法には制限はなく、公知の方法が利用可能である。例えば、分極処理を行う対象に、直接、直流電界を印加する、電界ポーリングが例示される。なお、電界ポーリングを行う場合には、分極処理の前に、第1電極層14を形成して、第1電極層14および第2電極層16を利用して、電界ポーリング処理を行ってもよい。
また、本発明の圧電フィルム10においては、分極処理は、圧電体層12の面方向ではなく、厚さ方向に分極を行うのが好ましい。
さらに、この積層体を、第1保護層18および第2保護層20を挟持するようにして、加熱プレス装置および加熱ローラ等を用いて熱圧着して、圧電積層体46とシート状物40とを貼り合わせ、図7に示すような、大判(長尺)の積層フィルム48を作製する。
あるいは、圧電積層体46とシート状物40とを、接着剤を用いて貼り合わせて、好ましくは、さらに圧着して、積層フィルム48を作製してもよい。
積層フィルム49の端面への端面封止層30の形成方法には、制限はなく、端面封止層30の形成材料に応じた、公知の形成方法(成膜方法)が利用可能である。
一例として、絶縁性の粘着テープを貼着する方法、端面封止層30となる材料を溶解した液体を塗布して乾燥する方法、端面封止層30となる材料を溶融した液体を塗布して硬化する方法、端面封止層30となる樹脂を溶剤に溶して、スプレーして乾燥させる方法等が例示される。前述のとおり、端面封止層30の材料として、熱可塑性樹脂またはUV硬化性樹脂を用いる場合には、端面封止層30となる材料を溶融した液体を塗布して、冷却またはUV照射を行って硬化させて端面封止層30を形成すればよい。
また、前述のとおり、必要に応じて、端面封止層30は、第1保護層18および/または第2保護層20の主面まで形成してもよい。
このようにして作製される圧電フィルム10は、面方向ではなく厚さ方向に分極されており、かつ、分極処理後に延伸処理をしなくても大きな圧電特性が得られる。そのため、圧電フィルム10は、圧電特性に面内異方性がなく、駆動電圧を印加すると、面方向では全方向に等方的に伸縮する。
なお、貫通孔18aおよび貫通孔20a、第1接続部材32および第2接続部材33、ならびに、第1引出電極34および第2引出電極36の形成方法は、上述したとおりである。
図11に、本発明の圧電フィルム10を利用する、平板型の圧電スピーカーの一例を概念的に示す。
この圧電スピーカー60は、圧電フィルム10を、電気信号を振動エネルギーに変換する振動板として用いる、平板型の圧電スピーカーである。なお、圧電スピーカー60は、マイクロフォンおよびセンサー等として使用することも可能である。
ケース62は、プラスチック等で形成される、一面が開放する薄い筐体である。筐体の形状としては、直方体状、立方体状、および、円筒状とが例示される。
また、枠体68は、中央にケース62の開放面と同形状の貫通孔を有する、ケース62の開放面側に係合する枠材である。
粘弾性支持体64は、適度な粘性と弾性を有し、圧電フィルム10を支持すると共に、圧電フィルムのどの場所でも一定の機械的バイアスを与えることによって、圧電フィルム10の伸縮運動を無駄なく前後運動(フィルムの面に垂直な方向の運動)に変換させるためのものである。一例として、羊毛のフェルトおよびPET等を含んだ羊毛のフェルトなどの不織布、ならびに、グラスウール等が例示される。
そのため、圧電スピーカー60では、粘弾性支持体64の周辺部では、粘弾性支持体64が圧電フィルム10によって下方に押圧されて厚さが薄くなった状態で、保持される。また、同じく粘弾性支持体64の周辺部において、圧電フィルム10の曲率が急激に変動し、圧電フィルム10に、粘弾性支持体64の周辺に向かって低くなる立上がり部が形成される。さらに、圧電フィルム10の中央領域は四角柱状の粘弾性支持体64に押圧されて、(略)平面状になっている。
逆に、第1電極層14および第2電極層16への駆動電圧の印加によって、圧電フィルム10が面方向に収縮すると、この収縮分を吸収するために、圧電フィルム10の立上がり部が、倒れる方向(平面に近くなる方向)に角度を変える。その結果、平面状の部分を有する圧電フィルム10は、下方に移動する。
圧電スピーカー60は、この圧電フィルム10の振動によって、音を発生する。
従って、圧電フィルム10は、図11に示すような剛性を有する平板状の圧電スピーカー60ではなく、単に湾曲状態で保持することでも、可撓性を有する圧電スピーカーとして機能させることができる。
また、上述のように、圧電フィルム10は、柔軟性および可撓性に優れ、しかも、面内に圧電特性の異方性が無い。そのため、圧電フィルム10は、どの方向に屈曲させても音質の変化が少なく、しかも、曲率の変化に対する音質変化も少ない。従って、圧電フィルム10を利用する圧電スピーカーは、設置場所の自由度が高く、また、上述したように、様々な物品に取り付けることが可能である。例えば、圧電フィルム10を、湾曲状態で洋服など衣料品およびカバンなどの携帯品等に装着することで、いわゆるウェアラブルなスピーカーを実現できる。
良好な音響特性すなわち圧電による高い伸縮性能を発現する圧電フィルム10は、複数枚を積層することにより、振動板等の被振動体を振動させる圧電素子としても、良好に作用する。
なお、圧電フィルム10を積層する際には、短絡(ショート)の可能性が無ければ、圧電フィルムは第1保護層18および/または第2保護層20を有さなくてもよい。または、第1保護層18および/または第2保護層20を有さない圧電フィルムを、絶縁層を介して積層してもよい。
積層した圧電フィルム10に駆動電圧を印加することで、個々の圧電フィルム10が面方向に伸縮し、各圧電フィルム10の伸縮によって、圧電フィルム10の積層体全体が面方向に伸縮する。圧電フィルム10の積層体の面方向の伸縮によって、積層体が貼着された振動板が撓み、その結果、振動板が、厚さ方向に振動する。この厚さ方向の振動によって、振動板は、音を発生する。振動板は、圧電フィルム10に印加した駆動電圧の大きさに応じて振動して、圧電フィルム10に印加した駆動電圧に応じた音を発生する。
従って、この際には、圧電フィルム10自身は、音を出力しない。
なお、十分な伸縮力を有するものであれば、1枚の圧電フィルム10を、同様のエキサイター(圧電素子)として用いることも可能である。
一例として、ポリエチレンテレフタレート(PET)等からなる樹脂フィルム、発泡ポリスチレン等からなる発泡プラスチック、段ボール材等の紙材、ガラス板、および、木材等が例示される。さらに、十分に撓ませることができるものであれば、振動板として、表示デバイス等の機器を用いてもよい。
貼着層には制限はなく、貼着対象となる物同士を貼着できるものが、各種、利用可能である。従って、貼着層は、粘着剤からなるものでも接着剤からなるものでもよい。好ましくは、貼着後に固体で硬い貼着層が得られる、接着剤からなる接着剤層を用いる。
以上の点に関しては、後述する長尺な圧電フィルム10を折り返してなる積層体でも、同様である。
従って、圧電フィルム10の積層体において、分極方向は、全ての圧電フィルム10で同方向であってもよく、分極方向が異なる圧電フィルムが存在してもよい。
圧電フィルム10において、圧電体層12に印加する電圧の極性は、圧電体層12の分極方向に応じたものとなる。従って、分極方向が第1電極層14から第2電極層16に向かう場合でも、第2電極層16から第1電極層14に向かう場合でも、積層される全ての圧電フィルム10において、第1電極層14の極性および第2電極層16の極性を、同極性にする。
従って、隣接する圧電フィルム10同士で、分極方向を互いに逆にすることで、隣接する圧電フィルム10の電極層同士が接触しても、接触する電極層は同極性であるので、ショートする恐れがない。
長尺な圧電フィルム10を折り返して積層した圧電素子は、以下のような利点を有する。
すなわち、カットシート状の圧電フィルム10を、複数枚、積層した圧電素子では、1枚の圧電フィルム毎に、第1電極層14および第2電極層16を、駆動電源に接続する必要がある。これに対して、長尺な圧電フィルム10を折り返して積層した構成では、一枚の長尺な圧電フィルム10のみで積層体を構成できる。また、長尺な圧電フィルム10を折り返して積層した構成では、駆動電圧を印加するための電源が1個で済み、さらに、圧電フィルム10からの電極の引き出しも、1か所でよい。
さらに、長尺な圧電フィルム10を折り返して積層した構成では、必然的に、隣接する圧電フィルム10同士で、分極方向が互いに逆になる。
図4~図7に示す方法で、大判の積層フィルムを作製した。
まず、下記の組成比で、シアノエチル化PVA(CR-V 信越化学工業社製)をジメチルホルムアミド(DMF)に溶解した。その後、この溶液に、圧電体粒子としてPZT粒子を下記の組成比で添加して、プロペラミキサー(回転数2000rpm)で攪拌して、圧電体層を形成するための塗料を調製した。
・PZT粒子・・・・・・・・・・・300質量部
・シアノエチル化PVA・・・・・・・30質量部
・DMF・・・・・・・・・・・・・・70質量部
なお、PZT粒子は、主成分となるPb酸化物、Zr酸化物およびTi酸化物の粉末を、Pb=1モルに対し、Zr=0.52モル、Ti=0.48モルとなるように、ボールミルで湿式混合してなる混合粉を、800℃で5時間、焼成した後、解砕処理したものを用いた。
シート状物の第2電極層(銅蒸着薄膜)の上に、スライドコーターを用いて、先に調製した圧電体層を形成するための塗料を塗布した。なお、塗料は、乾燥後の塗膜の膜厚が50μmになるように、塗布した。
次いで、シート状物に塗料を塗布した物を、120℃のホットプレート上で加熱乾燥することでDMFを蒸発させた。これにより、PET製の第2保護層の上に銅製の第2電極層を有し、その上に、厚さが50μmの圧電体層(高分子複合圧電体層)を有する圧電積層体を作製した。
次いで、積層体とシート状物との積層体を、ラミネータ装置を用いて、温度120℃で熱圧着することで、複合圧電体と第1電極層とを貼着して接着して、図7に示すような大判の積層フィルムを作製した。
作製した積層フィルムを、使用するカッター刃および切断角度を、種々、変更して、210×300mmに切り出して、カットシート状の積層フィルムを作製した。
作製した各積層フィルムについて、端部における第1電極層と第2電極層との端面における電極間距離d1、および、圧電体層の厚みtを、SEM-EDSを用いる上述した方法で測定し、電極間距離d1と厚みtとの比率p[%]を算出した。なお、SEM-EDSによる測定において、SEMは日立ハイテクノロジーズ社製のSU8220を用い、EDSは、BRUKER社製のXFash 5060FQを用いた。
実施例1~2、4および比較例1~2については、端面封止層の材料として熱可塑性樹脂(EVA)を用いて、端部に塗布した溶液を冷却して硬化させた。また、実施例3については、端面封止層の材料としてUV硬化性樹脂(ウレタンアクリレート)を用いて、端部に塗布した溶液を冷却して硬化させた。また、比較例3は端面の封止を行わなかった。
<封止の可否>
端面封止層による、積層フィルム端面の封止の可否を、光学顕微鏡にて観察した。積層フィルムの端面4辺を端面に対して垂直な方向から光学顕微鏡にて観察し、封止層から端面の一部が露出している長さを計測した。封止層に覆われておらず端面が露出している長さの合計が、積層フィルム端面4辺の合計長さの5%以下で合った場合を封止できていると判断し、5%よりも多い場合は封止できていないと判断した。
作製した圧電フィルムの電極層に配線を接続した。圧電フィルムを無響音室に置き、入力信号として圧電フィルム電極層間の電界が3V/μmとなる電圧をパワーアンプを通して印加し、圧電フィルムの中心から垂直に50cm離れた距離に置かれたマイクロフォンで音を録音した。
A:問題なく音が鳴った
B:放電音がした後、音が鳴った
作製した圧電フィルムを5層積層し、電極層に配線を行い、圧電素子を作製した。この際、圧電素子の積層サイズは50×200mmとし、積層数は5層とした。作製した圧電素子をエキサイターとして振動板に貼り付けて音圧を測定した。振動板としては、厚さ0.8mm、縦450mm×横500mmのアルミニウム板(A5052P)を用いた。振動板の横方向と圧電素子の長手方向を一致させて、振動板の中央に圧電素子の積層部中心を合わせて貼着した。圧電素子に対し、周波数5~10kHz、印加電圧50Vrmsのサインスイープ信号を入力し、振動板の中心から1m離れた距離に置かれたマイクロフォンで音圧を測定し、各周波数の音圧の平均を代表音圧とした。
A:85dB以上
B:80dB以上~85dB未満
C:80dB未満
結果を下記の表1に示す。
以上の結果より、本発明の効果は明らかである。
12 圧電体層
14 第1電極層
16 第2電極層
18 第1保護層
18a、20a 貫通孔
20 第2保護層
24 高分子マトリックス
26 圧電体粒子
30 端面封止層
32 第1接続部材
33 第2接続部材
34 第1引出電極
36 第2引出電極
40、42 シート状物
46 圧電積層体
48 積層フィルム
60 圧電スピーカー
62 ケース
64 粘弾性支持体
68 枠体
d1 電極間距離
d2 主面上における端面封止層の厚み
d3 端面封止層の面方向の厚み
d4、d5 主面上における端面封止層の幅
t 圧電体層の厚さ
Claims (8)
- 高分子材料を含むマトリックス中に圧電体粒子を含む圧電体層と、前記圧電体層の両面に設けられる電極層と、前記電極層上に設けられる保護層を有する、圧電フィルムであって、
前記圧電フィルムの端面を覆う、樹脂を含む材料からなる端面封止層を有し、
前記圧電フィルムの端面における電極間距離が30μm以上であり、かつ、前記圧電体層の厚みに対する、前記圧電フィルムの端面における電極間距離が103%以上120%未満である、圧電フィルム。 - 前記端面封止層の材料が熱可塑性樹脂を含む、請求項1に記載の圧電フィルム。
- 前記端面封止層の材料が紫外線硬化性の樹脂を含む、請求項1に記載の圧電フィルム。
- 前記保護層の主面上に形成されている前記端面封止層の厚みが50μm以下である、請求項1に記載の圧電フィルム。
- 前記端面封止層の、前記圧電フィルムの主面上における面方向の幅が、100μm以上5000μm以下である、請求項1に記載の圧電フィルム。
- 前記端面封止層の、前記圧電フィルムの端面からの面方向の厚みが、50μm以下である、請求項1に記載の圧電フィルム。
- 請求項1~6のいずれか一項に記載の圧電フィルムを、複数層、積層したものである、圧電素子。
- 請求項1~6のいずれか一項に記載の圧電フィルムを、1回以上、折り返すことにより、前記圧電フィルムを、複数層、積層したものである、圧電素子。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2005050830A (ja) * | 2002-07-12 | 2005-02-24 | Ngk Insulators Ltd | 圧電/電歪膜型素子、及びその製造方法 |
US20050248235A1 (en) * | 2001-07-30 | 2005-11-10 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive element and piezoelectric/electrostrictive device |
US20180152168A1 (en) * | 2016-11-30 | 2018-05-31 | Samsung Electro-Mechanics Co., Ltd. | Bulk acoustic wave resonator |
WO2020095812A1 (ja) * | 2018-11-08 | 2020-05-14 | 富士フイルム株式会社 | 積層圧電素子および電気音響変換器 |
WO2021100428A1 (ja) * | 2019-11-22 | 2021-05-27 | 富士フイルム株式会社 | 電気音響変換器 |
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- 2022-07-20 WO PCT/JP2022/028212 patent/WO2023026726A1/ja active Application Filing
- 2022-07-20 JP JP2023543746A patent/JPWO2023026726A1/ja active Pending
- 2022-07-20 CN CN202280053776.2A patent/CN117813841A/zh active Pending
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050248235A1 (en) * | 2001-07-30 | 2005-11-10 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive element and piezoelectric/electrostrictive device |
JP2005050830A (ja) * | 2002-07-12 | 2005-02-24 | Ngk Insulators Ltd | 圧電/電歪膜型素子、及びその製造方法 |
US20180152168A1 (en) * | 2016-11-30 | 2018-05-31 | Samsung Electro-Mechanics Co., Ltd. | Bulk acoustic wave resonator |
WO2020095812A1 (ja) * | 2018-11-08 | 2020-05-14 | 富士フイルム株式会社 | 積層圧電素子および電気音響変換器 |
WO2021100428A1 (ja) * | 2019-11-22 | 2021-05-27 | 富士フイルム株式会社 | 電気音響変換器 |
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TW202310463A (zh) | 2023-03-01 |
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