WO2022196202A1 - 圧電素子 - Google Patents
圧電素子 Download PDFInfo
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- WO2022196202A1 WO2022196202A1 PCT/JP2022/005416 JP2022005416W WO2022196202A1 WO 2022196202 A1 WO2022196202 A1 WO 2022196202A1 JP 2022005416 W JP2022005416 W JP 2022005416W WO 2022196202 A1 WO2022196202 A1 WO 2022196202A1
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- Prior art keywords
- piezoelectric
- layer
- piezoelectric film
- film
- piezoelectric element
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Images
Classifications
-
- 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
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
-
- 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
- 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
- H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
-
- 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
- H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
- H10N30/085—Shaping or machining of piezoelectric or electrostrictive bodies by machining
- H10N30/088—Shaping or machining of piezoelectric or electrostrictive bodies by machining by cutting or dicing
-
- 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
- H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
-
- 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
Definitions
- the present invention relates to piezoelectric elements.
- Piezoelectric elements are used for various purposes as so-called exciters, which vibrate and produce sound by attaching them to various items. For example, by attaching an exciter to an image display panel, a screen, or the like and vibrating them, sound can be produced instead of a speaker.
- the exciter when attaching an exciter to a flexible image display device, a rollable screen, etc., the exciter itself must be flexible (rollable) at least when not in use.
- Patent Document 1 discloses 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 polymer composite piezoelectric body formed on one surface of the polymer composite piezoelectric body.
- An electroacoustic conversion film having a lower electrode lead-out metal foil positioned outside the molecular composite piezoelectric body in the plane direction is described.
- Such a piezoelectric film is film-shaped and has a limited spring constant, so when used as an exciter, the output is insufficient. Therefore, it is conceivable to stack piezoelectric films to increase the spring constant and increase the output.
- An object of the present invention is to solve the problems of the prior art, and to provide a piezoelectric element formed by laminating a plurality of piezoelectric films and capable of preventing the generation of wrinkles.
- a piezoelectric film in which a piezoelectric layer containing piezoelectric particles is sandwiched between electrode layers in a matrix containing a polymer material, and a protective layer is laminated on the surface of the electrode layer that is not in contact with the piezoelectric layer.
- a piezoelectric element having a difference of 4.2 ⁇ m or less between the maximum height in the thickness direction in a region within 43 ⁇ m from the end surface of the piezoelectric film and the height in the thickness direction at a position within 43 ⁇ m from the end surface of the piezoelectric film.
- the piezoelectric film has a difference of 1.4 ⁇ m or less between the maximum height in the thickness direction and the height in the thickness direction at a position 43 ⁇ m inward from the end surface in a region up to 43 ⁇ m inward from the end surface. piezoelectric element.
- the piezoelectric film has a difference of 0.3 ⁇ m or more between the maximum height in the thickness direction and the height in the thickness direction at a position 43 ⁇ m inward from the end surface in a region up to 43 ⁇ m inward from the end surface [1] or [ 2].
- the piezoelectric element according to any one of [1 to 3], wherein the piezoelectric film has a thickness of 20 ⁇ m to 80 ⁇ m.
- a piezoelectric element formed by laminating a plurality of piezoelectric films and capable of preventing the occurrence of wrinkles.
- FIG. 1 is a cross-sectional view conceptually showing an example of a piezoelectric film included in a piezoelectric element
- FIG. FIG. 4 is a partially enlarged view of the vicinity of the end face of the piezoelectric film
- FIG. 4 is a diagram schematically showing another example of the piezoelectric element of the present invention
- FIG. 4 is a diagram schematically showing another example of the piezoelectric element of the present invention
- FIG. 1 is a side view conceptually showing a cutting device used in Examples.
- FIG. FIG. 10 is a front view of FIG. 9;
- FIG. 10 is a diagram for explaining the amount of engagement between the upper blade and the lower blade of the cutting device of FIG. 9;
- 1 is a side view conceptually showing a cutting device used in Examples.
- FIG. 1 is a perspective view conceptually showing a cutting device used in Examples.
- FIG. 1 is a perspective view conceptually showing a cutting device used in Examples.
- FIG. 1 is a perspective view conceptually showing a cutting device used in Examples.
- FIG. 17 is a top view conceptually showing a punching blade of the cutting device of FIG. 16.
- FIG. 20 is a side view conceptually showing a blade of the cutting device of FIG. 19;
- FIG. 3 is a front view conceptually showing the shape of a blade used in a comparative example;
- FIG. 22 is a perspective view of FIG. 21;
- a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
- the piezoelectric element of the present invention is Piezoelectric layers containing piezoelectric particles are sandwiched between electrode layers in a matrix containing a polymer material, and a protective layer is laminated on the surfaces of the electrode layers that are not in contact with the piezoelectric layers.
- the piezoelectric film is a piezoelectric element having a difference of 4.2 ⁇ m or less between the maximum height in the thickness direction in a region up to 43 ⁇ m inward from the end face and the height in the thickness direction at a position 43 ⁇ m inward from the end face.
- FIG. 1 shows a plan view schematically showing an example of the piezoelectric element of the present invention.
- a piezoelectric element 50 shown in FIG. 1 is obtained by laminating a plurality of piezoelectric films 10 .
- three piezoelectric films 10 are laminated. Adjacent piezoelectric films 10 are attached to each other by an adhesive layer 19 .
- the piezoelectric element 50 is adhered to the diaphragm 12 by the adhesion layer 16 to constitute the electroacoustic transducer 70 .
- a power source PS is connected to each piezoelectric film 10 for applying a drive voltage.
- illustration of the protective layer of each piezoelectric film is omitted, but as shown in FIG. 2, each piezoelectric film has a protective layer.
- the piezoelectric film 10 expands and contracts in the plane direction. stretches to Due to the expansion and contraction of the piezoelectric element 14 in the plane direction, the diaphragm 12 bends, and as a result, the diaphragm 12 vibrates in the thickness direction. This vibration in the thickness direction causes the diaphragm 12 to generate sound.
- the diaphragm 12 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 . That is, the electroacoustic transducer 70 can be used as a speaker using the piezoelectric element 50 as an exciter.
- the piezoelectric element 50 shown in FIG. 1 is obtained by laminating three layers of the piezoelectric film 10, the present invention is not limited to this. That is, if the piezoelectric element is formed by laminating a plurality of piezoelectric films 10, the number of laminated piezoelectric films 10 may be two, or four or more. This is the same for the piezoelectric element 56 shown in FIG. 4 and the piezoelectric element 60 shown in FIG. 5, which will be described later.
- the polarization directions of adjacent piezoelectric films 10 are opposite to each other. Therefore, in adjacent piezoelectric films 10, the lower electrode layers 24 face each other and the upper electrode layers 26 face each other. Therefore, the power supply PS always supplies power of the same polarity to the facing electrodes regardless of whether it is an AC power supply or a DC power supply. For example, in the piezoelectric element 50 shown in FIG. 1, electric power of the same polarity is always applied to the upper electrode layer 26 of the lowermost piezoelectric film 10 in the drawing and the upper electrode layer 26 of the second (middle) piezoelectric film 10 .
- the polarization direction of the piezoelectric film 10 can be detected with a d33 meter or the like.
- the polarization direction of the piezoelectric film 10 may be known from the polarization processing conditions described later.
- the piezoelectric film 10 shown in FIG. 2 includes a piezoelectric layer 20 which is a sheet-like material having piezoelectric properties, a lower electrode layer 24 laminated on one surface of the piezoelectric layer 20, and piezoelectric layers of the lower electrode layer 24.
- the piezoelectric layer 20 contains piezoelectric particles 36 in a matrix 34 containing a polymeric material. Also, the lower electrode layer 24 and the upper electrode layer 26 are electrode layers in the present invention. Also, the lower protective layer 28 and the upper protective layer 30 are protective layers in the present invention. As will be described later, the piezoelectric film 10 (piezoelectric layer 20) is preferably polarized in the thickness direction.
- the piezoelectric film 10 has a difference of 4.2 ⁇ m or less between the maximum height in the thickness direction in the region 43 ⁇ m inward from the end face and the height in the thickness direction at the position 43 ⁇ m inward from the end face. be. This point will be described with reference to FIG.
- FIG. 3 is a partially enlarged view showing the vicinity of the end surface of the piezoelectric film 10 in an enlarged manner. As shown in FIG. 3, if H43 is the difference between the position 43 ⁇ m inside from the end surface (side surface) of the piezoelectric film 10 and the maximum height in the area 43 ⁇ m inside from the end surface, then H43 is 4.2 ⁇ m or less. .
- the present inventors have investigated the occurrence of such wrinkles and found that when a piezoelectric film is cut, burr-like projections are sometimes formed at the edges. It was found that when the films were laminated, excessive stress was applied to the piezoelectric film, causing wrinkles.
- the difference H 43 between the position 43 ⁇ m inside from the end surface (side surface) of the piezoelectric film and the maximum height in the area 43 ⁇ m inside from the end surface is 4.2 ⁇ m or less. It can be considered that the height of the protrusions formed at the ends of the piezoelectric film 10 is 4.2 ⁇ m or less.
- the height of the projections formed at the ends of the piezoelectric film 10 By setting the height of the projections formed at the ends of the piezoelectric film 10 to 4.2 ⁇ m or less in this way, it is possible to prevent excessive stress from being applied to the piezoelectric films when a plurality of layers of the piezoelectric films are laminated. , wrinkles can be prevented.
- the difference H43 between the position 43 ⁇ m inside the end face of the piezoelectric film and the maximum height in the region 43 ⁇ m inside the end face is preferably 1.4 ⁇ m or less, more preferably 1.0 ⁇ m or less. preferable.
- H 43 is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more.
- the difference H43 between the position 43 ⁇ m inside the end face of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside the end face is measured as follows. By placing the piezoelectric film on a flat table and scanning the surface from the surface side using a confocal laser scanning microscope, the surface profile was measured, and the height of the position 43 ⁇ m inside from the surface profile and the end face , the difference from the maximum height in the area 43 ⁇ m inside from the end face. Such measurements are taken at 77 points on each side, and the average value is defined as H43 . Such measurements are made on both major surfaces.
- the piezoelectric film after cutting may be subjected to pressure treatment with a roller, heat treatment, laser processing of convex portions, etc., so that the value of H 43 of the piezoelectric film is 4.2 ⁇ m or less.
- the height difference H 43 is 4.2 ⁇ m or less on the surface of the piezoelectric film of the piezoelectric element that faces another piezoelectric film.
- the piezoelectric element of the present invention can suitably suppress the occurrence of wrinkles, so a thin piezoelectric film can be used.
- the thickness of the piezoelectric film is preferably 20 ⁇ m to 80 ⁇ m, more preferably 20 ⁇ m to 60 ⁇ m, even more preferably 20 ⁇ m to 50 ⁇ m.
- the electrode layer and protective layer of the piezoelectric film are thin from the viewpoint of not restricting expansion and contraction of the piezoelectric layer.
- the piezoelectric layer is preferably thinner from the viewpoint that the voltage (potential difference) required to expand and contract the piezoelectric layer by the same amount is small. That is, from the viewpoint of large expansion and contraction with a small voltage, it is preferable that the piezoelectric film is thin.
- the adjacent piezoelectric films are configured so that the polarization directions are opposite to each other, but the configuration is not limited to this.
- the polarization directions of the piezoelectric layers 20 may all be the same.
- a plurality of sheets of the piezoelectric film 10 are laminated, but the present invention is not limited to this.
- Fig. 5 shows another example of the piezoelectric element. Since the piezoelectric element 56 shown in FIG. 5 uses a plurality of the same members as the piezoelectric element 50 described above, the same members are denoted by the same reference numerals, and the description mainly focuses on different parts.
- the piezoelectric element 56 shown in FIG. 5 is obtained by laminating a plurality of piezoelectric films by folding a long piezoelectric film 10L in the longitudinal direction one or more times, preferably a plurality of times. Moreover, the piezoelectric element 56 adheres the piezoelectric film 10 ⁇ /b>L laminated by folding with the adhesive layer 19 . By folding and stacking one long piezoelectric film 10L polarized in the thickness direction, the polarization direction of the adjacent (facing) piezoelectric films in the stacking direction is as indicated by the arrow in FIG. going in the opposite direction.
- the piezoelectric element 56 can be configured with only one sheet of the long piezoelectric film 10L, only one power source PS is required for applying the drive voltage, and furthermore, the electrodes from the piezoelectric film 10L can be connected. Withdrawals can also be done in one place. Therefore, according to the piezoelectric element 56 shown in FIG. 5, the number of parts can be reduced, the configuration can be simplified, the reliability of the piezoelectric element (module) can be improved, and the cost can be reduced.
- the piezoelectric element 56 shown in FIG. 5 in the piezoelectric element 56 obtained by folding the long piezoelectric film 10L, it is preferable to insert the core rod 58 into the folded portion of the piezoelectric film 10L while contacting the piezoelectric film 10L.
- the lower electrode layer 24 and the upper electrode layer 26 of the piezoelectric film 10L are formed of metal deposition films or the like. If the vapor-deposited metal film is bent at an acute angle, cracks or the like are likely to occur, which may lead to disconnection of the electrode. That is, in the piezoelectric element 56 shown in FIG. 5, cracks or the like easily occur in the electrodes inside the bent portion.
- the piezoelectric element 56 obtained by folding the long piezoelectric film 10L by inserting the core rod 58 into the folded portion of the piezoelectric film 10L, the lower electrode layer 24 and the upper electrode layer 26 are prevented from being folded. By doing so, it is possible to suitably prevent disconnection from occurring.
- the piezoelectric film 10 includes a piezoelectric layer 20, a lower electrode layer 24 laminated on one surface of the piezoelectric layer 20, and a surface of the lower electrode layer 24 opposite to the piezoelectric layer 20. an upper protective layer 28 laminated on the other surface of the piezoelectric layer 20; and an upper protective layer 30 laminated on the surface of the upper electrode layer 26 opposite to the piezoelectric layer 20. have.
- the piezoelectric layer 20 may be a layer made of a known piezoelectric material.
- the piezoelectric layer 20 is preferably a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 containing a polymeric material.
- the material of the polymer composite piezoelectric matrix 34 (matrix and binder) that constitutes the piezoelectric layer 20 it is preferable to use a polymer material that has viscoelasticity at room temperature.
- "ordinary temperature” refers to a temperature range of about 0 to 50.degree.
- the polymer composite piezoelectric body preferably satisfies the following requirements.
- 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. Moreover, stress can be relieved if strain energy can be diffused to the outside as heat. Therefore, it is required that the loss tangent of the polymer composite piezoelectric material is appropriately large.
- the flexible polymer composite piezoelectric material used as an exciter is required to behave hard against vibrations of 20 Hz to 20 kHz and softly against vibrations of several Hz or less.
- 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.
- the spring constant can be easily adjusted by laminating according to the rigidity (hardness, stiffness, spring constant) of the mating material (diaphragm) to be attached. The thinner it is, the more energy efficient it can be.
- polymer solids have a viscoelastic relaxation mechanism, and as the temperature rises or the frequency decreases, large-scale molecular motion causes a decrease (relaxation) in the 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 20), 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 having a glass transition point at room temperature ie, 0 to 50° C. at a frequency of 1 Hz, for the matrix of the polymer composite piezoelectric material, because this behavior is favorably expressed.
- the polymer material having viscoelasticity at room temperature Preferably, a polymer material having a maximum value of 0.5 or more in loss tangent Tan ⁇ at a frequency of 1 Hz in a dynamic viscoelasticity test at normal temperature, ie, 0 to 50° C., is used.
- a polymer material having a maximum value of 0.5 or more in loss tangent Tan ⁇ at a frequency of 1 Hz in a dynamic viscoelasticity test at normal temperature, ie, 0 to 50° C. is used.
- the polymer material having viscoelasticity at room temperature preferably has a storage elastic modulus (E') at a frequency of 1 Hz measured by dynamic viscoelasticity of 100 MPa or more at 0°C and 10 MPa or less at 50°C.
- E' storage elastic modulus
- the polymer material having viscoelasticity at room temperature 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 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.
- polymeric materials having viscoelasticity at room temperature examples include cyanoethylated polyvinyl alcohol (cyanoethylated PVA), polyvinyl acetate, polyvinylidene chloride core acrylonitrile, polystyrene-vinylpolyisoprene block copolymer, and polyvinylmethyl.
- cyanoethylated polyvinyl alcohol cyanoethylated PVA
- polyvinyl acetate polyvinylidene chloride core acrylonitrile
- polystyrene-vinylpolyisoprene block copolymer examples include ketones and polybutyl methacrylate.
- Commercially available products such as Hybler 5127 (manufactured by Kuraray Co., Ltd.) can also be suitably used as these polymer materials.
- the polymer material it is preferable to use a material having a cyanoethyl group, and it is particularly preferable to use cyanoethylated PVA. These polymer materials may be used singly or in combination (mixed).
- the matrix 34 using such a polymer material having viscoelasticity at room temperature may use a plurality of polymer materials together, if necessary. That is, in addition to a viscoelastic material such as cyanoethylated PVA, other dielectric polymer materials may be added to the matrix 34 as necessary for the purpose of adjusting dielectric properties and mechanical properties.
- a viscoelastic material such as cyanoethylated PVA
- other dielectric polymer materials may be added to the matrix 34 as necessary for the purpose of adjusting dielectric properties and mechanical properties.
- 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 rubber and chloroprene rubber are exemplified. Among them, polymer materials having cyanoethyl groups are preferably used. Further, in the matrix 34 of the piezoelectric layer 20, the dielectric polymer added in addition to the material having viscoelasticity at room temperature such as cyanoethylated PVA is not limited to one type, and plural types may be added. .
- the matrix 34 may include thermoplastic resins such as vinyl chloride resin, polyethylene, polystyrene, methacrylic resin, polybutene, and isobutylene, and phenolic resin for the purpose of adjusting the glass transition point Tg. , urea resins, melamine resins, alkyd resins, and thermosetting resins such as mica may be added. Furthermore, a tackifier such as rosin ester, rosin, terpene, terpene phenol, and petroleum resin may be added for the purpose of improving adhesiveness.
- the addition amount is not particularly limited, but the ratio of the material to the matrix 34 is 30% by mass or less. is preferable.
- the characteristics of the polymer material to be added can be expressed without impairing the viscoelastic relaxation mechanism in the matrix 34, so that the dielectric constant can be increased, the heat resistance can be improved, and the adhesion between the piezoelectric particles 36 and the electrode layer can be improved. favorable results can be obtained in terms of
- the piezoelectric layer 20 is a polymeric composite piezoelectric body containing piezoelectric particles 36 in such a matrix 34 .
- the piezoelectric particles 36 are made of ceramic particles having a perovskite or wurtzite crystal structure. Examples of ceramic particles constituting the piezoelectric particles 36 include lead zirconate titanate (PZT), lead zirconate lanthanate titanate (PLZT), barium titanate (BaTiO 3 ), zinc oxide (ZnO), and A solid solution (BFBT) of barium titanate and bismuth ferrite (BiFe 3 ) is exemplified.
- the particle size of the piezoelectric particles 36 is not limited, and may be appropriately selected according to the size of the piezoelectric film 10, the application of the piezoelectric element 50, and the like.
- the particle size of the piezoelectric particles 36 is preferably 1 to 10 ⁇ m. By setting the particle size of the piezoelectric particles 36 within this range, favorable results can be obtained in that the piezoelectric film 10 can achieve both high piezoelectric characteristics and flexibility.
- the piezoelectric particles 36 in the piezoelectric layer 20 are uniformly and regularly dispersed in the matrix 34 in FIG. 2, the present invention is not limited to this. That is, the piezoelectric particles 36 in the piezoelectric layer 20 may be dispersed irregularly in the matrix 34 as long as they are preferably uniformly dispersed.
- the quantitative ratio of the matrix 34 and the piezoelectric particles 36 in the piezoelectric layer 20 is not limited, and the size and thickness of the piezoelectric film 10 in the plane direction, the application of the piezoelectric element 50, and It may be appropriately set according to the characteristics required for the piezoelectric element 50 .
- the volume fraction of the piezoelectric particles 36 in the piezoelectric layer 20 is preferably 30% to 80%, more preferably 50% or more, and therefore more preferably 50% to 80%.
- the thickness of the piezoelectric layer 20 is not particularly limited, and may be appropriately determined according to the application of the piezoelectric element 50 , the number of layers of the piezoelectric film in the piezoelectric element 50 , the properties required of the piezoelectric film 10 , and the like. , should be set.
- the thickness of the piezoelectric layer 20 is preferably 10 to 300 ⁇ m, more preferably 20 to 200 ⁇ m, even more preferably 30 to 150 ⁇ m.
- the piezoelectric film 10 has a lower electrode layer 24 on one surface of the piezoelectric layer 20, a lower protective layer 28 thereon, and the other surface of the piezoelectric layer 20. Furthermore, it has an upper electrode layer 26 and an upper protective layer 30 thereon. Here, the upper electrode layer 26 and the lower electrode layer 24 form an electrode pair.
- both surfaces of the piezoelectric layer 20 are sandwiched between electrode pairs, that is, the lower electrode layer 24 and the upper electrode layer 26, and this laminate is sandwiched between the lower protective layer 28 and the upper protective layer 30.
- It has a configuration
- the region sandwiched between the lower electrode layer 24 and the upper electrode layer 26 expands and contracts according to the applied voltage.
- the lower electrode layer 24 and the lower protective layer 28 , and the upper electrode layer 26 and the upper protective layer 30 are named according to the polarization direction of the piezoelectric layer 20 . Therefore, the lower electrode layer 24 and the upper electrode layer 26, and the lower protective layer 28 and the upper protective layer 30 basically have the same structure.
- the lower protective layer 28 and the upper protective layer 30 cover the upper electrode layer 26 and the lower electrode layer 24, and play the role of imparting appropriate rigidity and mechanical strength to the piezoelectric layer 20. . That is, in the piezoelectric film 10, the piezoelectric layer 20 made up of the matrix 34 and the piezoelectric particles 36 exhibits excellent flexibility against slow bending deformation, but depending on the application, the rigidity may increase. and mechanical strength may be insufficient.
- the piezoelectric film 10 is provided with a lower protective layer 28 and an upper protective layer 30 to compensate.
- Various sheet materials can be used for the lower protective layer 28 and the upper protective layer 30 without limitation, and various resin films are preferably exemplified as examples.
- various resin films are preferably exemplified as examples.
- PET polyethylene terephthalate
- PP polypropylene
- PS polystyrene
- PC polycarbonate
- PPS polyphenylene sulfite
- PMMA polymethyl methacrylate
- PET polyethylene terephthalate
- PET polypropylene
- PS polystyrene
- PC polycarbonate
- PPS polyphenylene sulfite
- PMMA polymethyl methacrylate
- PET polyethylene terephthalate
- PEI polyetherimide
- PI polyimide
- PEN polyethylene naphthalate
- TAC triacetyl cellulose
- cyclic olefin resins and the like are preferably used.
- the thicknesses of the lower protective layer 28 and the upper protective layer 30 are also not limited. Also, although the thicknesses of the lower protective layer 28 and the upper protective layer 30 are basically the same, they may be different. Here, if the rigidity of the lower protective layer 28 and the upper protective layer 30 is too high, not only will the expansion and contraction of the piezoelectric layer 20 be restricted, but also the flexibility will be impaired. Therefore, the thinner the lower protective layer 28 and the upper protective layer 30 are, the better, except for cases where mechanical strength and good handling properties as a sheet-like article are required.
- the thickness of the lower protective layer 28 and the upper protective layer 30 is not more than twice the thickness of the piezoelectric layer 20, both rigidity and appropriate flexibility can be achieved.
- the thickness of the lower protective layer 28 and the upper protective layer 30 is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. It is preferably 25 ⁇ m or less, more preferably 25 ⁇ m or less.
- a lower electrode layer 24 is formed between the piezoelectric layer 20 and the lower protective layer 28, and an upper electrode layer 26 is formed between the piezoelectric layer 20 and the upper protective layer 30, respectively.
- the lower electrode layer 24 and the upper electrode layer 26 are provided for applying voltage to the piezoelectric layer 20 (piezoelectric film 10).
- the materials for forming the lower electrode layer 24 and the upper electrode layer 26 are not limited, and various conductors can be used. Specifically, metals such as carbon, palladium, iron, tin, aluminum, nickel, platinum, gold, silver, copper, titanium, chromium and molybdenum, alloys thereof, laminates and composites of these metals and alloys, Also, indium tin oxide and the like are exemplified. Among them, copper, aluminum, gold, silver, platinum, and indium tin oxide are preferably exemplified as the lower electrode layer 24 and the upper electrode layer 26 .
- the method of forming the lower electrode layer 24 and the upper electrode layer 26 is not limited. Various known methods such as affixing are available.
- thin films of copper, aluminum, etc., formed by vacuum deposition are preferably used as the lower electrode layer 24 and the upper electrode layer 26 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 lower electrode layer 24 and the upper electrode layer 26 are not limited. In addition, although the thicknesses of the lower electrode layer 24 and the upper electrode layer 26 are basically the same, they may be different.
- the piezoelectric film 10 if the product of the thickness of the lower electrode layer 24 and the upper electrode layer 26 and the Young's modulus is less than the product of the thickness of the lower protective layer 28 and the upper protective layer 30 and the Young's modulus, the piezoelectric film 10 is flexible.
- the lower protective layer 28 and the upper protective layer 30 are made of PET (Young's modulus: about 6.2 GPa) and the lower electrode layer 24 and the upper electrode layer 26 are made of copper (Young's modulus: about 130 GPa), the lower protective layer Assuming that the thickness of the layer 28 and the upper protective layer 30 is 25 ⁇ m, the thickness of the lower electrode layer 24 and the upper electrode layer 26 is preferably 1.2 ⁇ m or less, more preferably 0.3 ⁇ m or less, especially 0.1 ⁇ m or less. is preferred.
- the piezoelectric film 10 is formed by sandwiching the piezoelectric layer 20, which is formed by dispersing the piezoelectric particles 36 in the matrix 34 containing a polymer material, between the lower electrode layer 24 and the upper electrode layer 26.
- the body has a structure in which a lower protective layer 28 and an upper protective layer 30 are sandwiched.
- the maximum value of the loss tangent (Tan ⁇ ) at a frequency of 1 Hz by dynamic viscoelasticity measurement preferably exists at room temperature, and the maximum value of 0.1 or more exists at room temperature. more preferred.
- 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. Note that this condition applies to the piezoelectric layer 20 as well. 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 determined by dynamic viscoelasticity measurement of 1.0 ⁇ 10 5 to 2.0 ⁇ 10 6 N/m at 0° C. , 1.0 ⁇ 10 5 to 1.0 ⁇ 10 6 N/m at 50°C. Note that this condition applies to the piezoelectric layer 20 as well. As a result, the piezoelectric film 10 can have appropriate rigidity and mechanical strength within a range that does not impair flexibility and acoustic properties.
- 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. This condition applies to the piezoelectric layer 20 as well. As a result, 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 f0 changes as the curvature of the speaker changes can be reduced.
- Tan ⁇ loss tangent
- the storage elastic modulus (Young's modulus) and loss tangent of the piezoelectric film 10, piezoelectric layer 20, etc. may be measured by known methods.
- the dynamic viscoelasticity measuring device DMS6100 manufactured by SII Nanotechnology Co., Ltd. manufactured by SII Nanotechnology Co., Ltd. (manufactured by SII Nanotechnology Co., Ltd.) may be used for measurement.
- the measurement frequency is 0.1 Hz to 20 Hz (0.1 Hz, 0.2 Hz, 0.5 Hz, 1 Hz, 2 Hz, 5 Hz, 10 Hz and 20 Hz)
- the measurement temperature is -50 to 150 ° C.
- a heating rate of 2° C./min in a nitrogen atmosphere
- a sample size of 40 mm ⁇ 10 mm including the clamping area
- a distance between chucks of 20 mm may be measured by known methods.
- a power source PS is connected to the lower electrode layer 24 and the upper electrode layer 26 of each piezoelectric film 10 to apply a drive voltage for expanding and contracting the piezoelectric film 10, that is, to supply drive power.
- the power supply PS is not limited and may be a DC power supply or an AC power supply.
- the driving voltage may be appropriately set according to the thickness of the piezoelectric layer 20 of the piezoelectric film 10, the forming material, and the like, so that the piezoelectric film 10 can be properly driven.
- the method of extracting electrodes from the lower electrode layer 24 and the upper electrode layer 26 there are no restrictions on the method of extracting electrodes from the lower electrode layer 24 and the upper electrode layer 26, and various known methods can be used. Examples include a method of connecting a conductor such as a copper foil to the lower electrode layer 24 and the upper electrode layer 26 to lead the electrodes to the outside, and a method of forming through holes in the lower protective layer 28 and the upper protective layer 30 by a laser or the like. , a method of filling the through holes with a conductive material and drawing out the electrodes to the outside, and the like. Examples of suitable methods for extracting electrodes include the method described in Japanese Patent Application Laid-Open No. 2014-209724 and the method described in Japanese Patent Application Laid-Open No. 2016-015354.
- the piezoelectric film is adhered by the adhesion layer 19 .
- Various known layers can be used for the adhesive layer 19 as long as the adjacent piezoelectric films 10 can be attached. Therefore, the adhesive layer 19 has fluidity at the time of bonding and then becomes a solid. Even a layer made of an adhesive that is a gel-like (rubber-like) soft solid at the time of bonding and remains gel-like after that. It may be a layer made of an adhesive that does not change its shape, or a layer made of a material that has the characteristics of both an adhesive and an adhesive.
- the piezoelectric element 50 causes the vibration plate 12 to vibrate and generate sound by expanding and contracting a plurality of laminated piezoelectric films 10 . Therefore, the expansion and contraction of each piezoelectric film 10 is preferably directly transmitted to the piezoelectric element 50 . If a substance having a viscosity that reduces vibration exists between the piezoelectric films 10, the efficiency of transmission of the energy of expansion and contraction of the piezoelectric films 10 will be lowered, and the driving efficiency of the piezoelectric element 50 will be lowered.
- the sticking layer 19 is preferably an adhesive layer made of an adhesive that provides a solid and hard sticking layer 19 rather than a sticky layer made of an adhesive.
- an adhesive layer made of a thermoplastic type adhesive such as a polyester adhesive and a styrene-butadiene rubber (SBR) adhesive is suitably exemplified. Adhesion, unlike sticking, is useful in seeking high adhesion temperatures. Further, a thermoplastic type adhesive is suitable because it has "relatively low temperature, short time, and strong adhesion".
- the thickness of the adhesive layer 19 is not limited, and a thickness capable of exhibiting sufficient adhesive force may be appropriately set according to the material forming the adhesive layer 19 .
- the thinner the adhesive layer 19 is, the higher the effect of transmitting the expansion and contraction energy of the piezoelectric film 10 and the higher the energy efficiency.
- the adhesive layer 19 is thick and rigid, it may restrict the expansion and contraction of the piezoelectric film 10 .
- the adhesive layer 19 is preferably thinner than the piezoelectric layer 20 . That is, in the piezoelectric element 50, the adhesive layer 19 is preferably hard and thin.
- the thickness of the adhesive layer 19 is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, even more preferably 0.1 to 10 ⁇ m after being attached.
- the polarization directions of adjacent piezoelectric films are opposite to each other, and there is no risk of short-circuiting between the adjacent piezoelectric films 10, so the adhesive layer 19 can be made thinner.
- the spring constant of the adhesive layer 19 is equal to or less than the spring constant of the piezoelectric film 10 .
- the product of the thickness of the adhesive layer 19 and the storage elastic modulus (E′) at a frequency of 1 Hz by dynamic viscoelasticity measurement is 2.0 ⁇ 10 6 N/m or less at 0° C. and 50 It is preferably 1.0 ⁇ 10 6 N/m or less at °C.
- the internal loss at a frequency of 1 Hz by dynamic viscoelasticity measurement of the adhesive layer is 1.0 or less at 25 ° C. for the adhesive layer 19 , and for the adhesive layer 19 . is preferably 0.1 or less at 25°C.
- the diaphragm 12 preferably has flexibility.
- having flexibility is synonymous with having flexibility in general interpretation, and indicates that it is possible to bend and bend, specifically , indicating that it can be bent and stretched without fracture and damage.
- the vibration plate 12 is not particularly limited as long as it preferably has flexibility, and various sheet-like materials (plate-like material, film) can be used.
- Examples include polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), polycarbonate (PC), polyphenylene sulfite (PPS), polymethyl methacrylate (PMMA), polyetherimide (PEI), polyimide (PI), Resin films composed of polyethylene naphthalate (PEN), triacetyl cellulose (TAC), cyclic olefin resins, etc.; expanded polystyrene, expanded plastics composed of expanded styrene, expanded polyethylene, etc.; Examples include various corrugated cardboard materials made by pasting paperboards of the above.
- the vibration plate 12 may be an organic electroluminescence (OLED (Organic Light Emitting Diode)) display, a liquid crystal display, or a micro LED (Light Emitting Diode) display as long as it has flexibility. , and display devices such as inorganic electroluminescence displays can also be suitably used.
- OLED Organic Light Emitting Diode
- liquid crystal display or a micro LED (Light Emitting Diode) display as long as it has flexibility.
- micro LED Light Emitting Diode
- ⁇ Adhesion layer> In the electroacoustic transducer 70 shown in FIG. 1, as a preferred embodiment, the diaphragm 12 and the piezoelectric element 50 are adhered by the adhesion layer 16 .
- the adhesive layer 16 has fluidity at the time of bonding and then becomes a solid. Even a layer made of an adhesive, which is a gel-like (rubber-like) soft solid at the time of bonding, remains gel-like after that. It may be a layer made of an adhesive that does not change its shape, or a layer made of a material that has the characteristics of both an adhesive and an adhesive.
- the electroacoustic transducer 70 by expanding and contracting the piezoelectric element 50, the diaphragm 12 is bent and vibrated to generate sound. Therefore, in the electroacoustic transducer 70 , it is preferable that the expansion and contraction of the piezoelectric element 50 is directly transmitted to the diaphragm 12 . If a substance having a viscosity that reduces vibration is present between the diaphragm 12 and the piezoelectric element 50, the efficiency of transmission of the energy of expansion and contraction of the piezoelectric element 50 to the diaphragm 12 is lowered, resulting in electroacoustic conversion. The driving efficiency of the device 70 is lowered.
- the sticking layer 16 is preferably an adhesive layer made of an adhesive that provides a solid and hard sticking layer 16 rather than a sticky layer made of an adhesive.
- a more preferable adhesive layer 16 is, specifically, an adhesive layer made of a thermoplastic type adhesive such as a polyester adhesive and a styrene-butadiene rubber (SBR) adhesive. Adhesion, unlike sticking, is useful in seeking high adhesion temperatures. Further, a thermoplastic type adhesive is suitable because it has "relatively low temperature, short time, and strong adhesion".
- the thickness of the adhesive layer 16 is not limited, and the thickness may be appropriately set according to the material of the adhesive layer 16 so that sufficient adhesive strength (adhesive strength, cohesive strength) can be obtained.
- adhesive strength adheresive strength, cohesive strength
- the thinner the adhesive layer 16 the higher the effect of transmitting the stretching energy (vibrational energy) of the piezoelectric element 50 to the diaphragm 12, thereby increasing the energy efficiency.
- the adhesive layer 16 is thick and rigid, it may restrict expansion and contraction of the piezoelectric element 50 .
- the adhesive layer 16 is preferably thinner.
- the thickness of the adhesive layer 16 is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, even more preferably 0.1 to 10 ⁇ m after being attached.
- the adhesion layer 16 is provided as a preferable aspect, and is not an essential component. Therefore, the electroacoustic transducer 70 does not have the adhesive layer 16, and the vibration plate 12 and the piezoelectric element 50 may be fixed using known crimping means, fastening means, fixing means, or the like.
- the shape of the piezoelectric element 50 is rectangular in plan view, the four corners may be fastened with members such as bolts and nuts to form an electroacoustic transducer, or the four corners and the central portion may be bolted together.
- the electroacoustic transducer may be configured by fastening with a member such as a nut.
- the piezoelectric element 50 expands and contracts independently of the diaphragm 12, and in some cases, only the piezoelectric element 50 bends and the piezoelectric element The expansion and contraction of 50 is not transmitted to the diaphragm 12. - ⁇ In this way, when the piezoelectric element 50 expands and contracts independently of the diaphragm 12, the efficiency of vibration of the diaphragm 12 by the piezoelectric element 50 decreases. There is a possibility that the diaphragm 12 cannot be sufficiently vibrated. Considering this point, it is preferable that the vibration plate 12 and the piezoelectric element 50 are adhered with the adhesion layer 16 as shown in FIG.
- piezoelectric layer 20 includes piezoelectric particles 36 in matrix 34 .
- a lower electrode layer 24 and an upper electrode layer 26 are provided so as to sandwich the piezoelectric layer 20 in the thickness direction.
- the piezoelectric particles 36 expand and contract in the polarization direction according to the applied voltage.
- the piezoelectric film 10 shrinks in the thickness direction.
- the piezoelectric film 10 also expands and contracts in the in-plane direction. This expansion and contraction is about 0.01 to 0.1%.
- the thickness of the piezoelectric layer 20 is preferably about 10-300 ⁇ m. Therefore, the expansion and contraction in the thickness direction is as small as about 0.3 ⁇ m at maximum.
- the piezoelectric film 10, that is, the piezoelectric layer 20 has a size much larger than its thickness in the planar direction. Therefore, for example, if the length of the piezoelectric film 10 is 20 cm, the piezoelectric film 10 expands and contracts by about 0.2 mm at maximum due to voltage application.
- the diaphragm 12 is attached to the piezoelectric film 10 with an adhesive layer 16 . Therefore, the expansion and contraction of the piezoelectric film 10 bends the diaphragm 12, and as a result, the diaphragm 12 vibrates in the thickness direction. This vibration in the thickness direction causes the diaphragm 12 to generate sound. That is, the diaphragm 12 vibrates according to the magnitude of the voltage (driving voltage) applied to the piezoelectric film 10 and generates sound according to the driving voltage applied to the piezoelectric film 10 .
- a general piezoelectric film made of a polymeric material such as PVDF has in-plane anisotropy in piezoelectric properties, and anisotropy in the amount of expansion and contraction in the plane direction when a voltage is applied.
- the piezoelectric film 10 has no in-plane anisotropy in the piezoelectric properties and expands and contracts isotropically in all directions in the in-plane direction. That is, in the piezoelectric element 50 shown in FIG. 1, the piezoelectric film 10 expands and contracts isotropically two-dimensionally.
- the vibration plate 12 vibrates with a greater force than in the case of laminating general piezoelectric films such as PVDF that expands and contracts greatly only in one direction. and produce a louder and more beautiful sound.
- the size of the piezoelectric element 50 in the plane direction and the size of the diaphragm 12 in the plane direction are substantially the same, but the size is not limited to this.
- the size of the piezoelectric film 50 in the plane direction may be smaller than the size of the diaphragm 12 in the plane direction.
- a sheet-like object 10a having a lower electrode layer 24 formed on a lower protective layer 28 is prepared.
- This sheet-like object 10a may be produced by forming a copper thin film or the like as the lower electrode layer 24 on the surface of the lower protective layer 28 by vacuum deposition, sputtering, plating, or the like. If the lower protective layer 28 is very thin and has poor handling properties, the lower protective layer 28 with a separator (temporary support) may be used as necessary.
- the separator PET or the like having a thickness of 25 ⁇ m to 100 ⁇ m can be used. The separator may be removed after the upper electrode layer 26 and the upper protective layer 30 are thermocompressed and before laminating any member on the lower protective layer 28 .
- a coating material is prepared by dissolving a polymer material as a matrix material in an organic solvent, adding piezoelectric particles 36 such as PZT particles, and stirring and dispersing the mixture.
- Organic solvents other than the above substances are not limited and various organic solvents can be used.
- the paint is cast (applied) on the sheet-like material 10a and dried by evaporating the organic solvent.
- the laminate 10b having the lower electrode layer 24 on the lower protective layer 28 and the piezoelectric layer 20 on the lower electrode layer 24 is produced.
- the lower electrode layer 24 refers to the electrode on the substrate side when the piezoelectric layer 20 is applied, and does not indicate the vertical positional relationship in the laminate.
- the matrix 34 may be added with a dielectric polymer material other than a viscoelastic material such as cyanoethylated PVA.
- a dielectric polymer material other than a viscoelastic material such as cyanoethylated PVA.
- the piezoelectric layer 20 is preferably subjected to polarization treatment (poling). )I do.
- the method of polarization treatment of the piezoelectric layer 20 is not limited, and known methods can be used.
- the surface of the piezoelectric layer 20 may be smoothed by using a heating roller or the like, which is a calendering treatment. By performing this calendering process, the thermocompression bonding process, which will be described later, can be performed smoothly.
- the sheet-like object 10c having the upper electrode layer 26 formed on the upper protective layer 30 is prepared.
- This sheet-like object 10c may be produced by forming a copper thin film or the like as the upper electrode layer 26 on the surface of the upper protective layer 30 by vacuum deposition, sputtering, plating, or the like.
- the upper electrode layer 26 is directed toward the piezoelectric layer 20, and the sheet-like material 10c is laminated on the laminate 10b for which the polarization treatment of the piezoelectric layer 20 has been completed. Further, the laminate of the laminate 10b and the sheet material 10c is thermocompression bonded by a heat press device, a pair of heat rollers, or the like, with the upper protective layer 30 and the lower protective layer 28 sandwiched therebetween.
- a laminate in which the electrode layer and the protective layer are laminated on both sides of the piezoelectric layer 20 is produced.
- Such a laminate may be produced using a cut sheet-like sheet material, or may be produced by roll to roll (hereinafter also referred to as RtoR).
- the produced laminate is cut into a desired shape according to various uses to obtain a piezoelectric film.
- the cutting conditions such as the type of cutting device, the type of blade, the pressing force of the blade, and the cutting speed, the position 43 ⁇ m inside from the end surface of the piezoelectric film.
- the difference H 43 from the maximum height in the region from the end face to the inner side of 43 ⁇ m is within the above range.
- a piezoelectric element is fabricated by laminating a plurality of piezoelectric films thus obtained via an adhesive layer.
- Example 1 [Preparation of piezoelectric film] A piezoelectric film as shown in FIG. 2 was produced by the method shown in FIGS. 6 to 8 described above. First, cyanoethylated PVA (manufactured by Shin-Etsu Chemical Co., Ltd., CR-V) was dissolved in methyl ethyl ketone (MEK) at the following composition ratio. After that, PZT particles were added to this solution in the following compositional ratio and dispersed with a propeller mixer (rotation speed: 2000 rpm) to prepare a paint for forming a piezoelectric layer.
- MEK methyl ethyl ketone
- ⁇ PZT particles 1000 parts by mass ⁇ Cyanoethylated PVA ⁇ 100 parts by mass ⁇ MEK ⁇ 600 parts by mass
- the PZT particles used were obtained by sintering a commercially available PZT raw material powder at 1000 to 1200° C. and then pulverizing and classifying the sintered particles to an average particle size of 3.5 ⁇ m.
- a long PET film having a width of 23 cm and a thickness of 4 ⁇ m was vacuum-deposited with a copper thin film having a thickness of 0.1 ⁇ m to prepare a sheet as shown in FIG. That is, in this example, the lower electrode layer and the upper electrode layer are 0.1 m-thick copper-deposited thin films, and the lower protective layer and the upper protective layer are 4 ⁇ m-thick PET films.
- a PET film with a separator (temporary support PET) having a thickness of 50 ⁇ m was used, and after the thin film electrode and the protective layer were thermally compressed, the separator of each protective layer was removed. Removed.
- a slide coater was used to apply the previously prepared paint for forming the piezoelectric layer.
- the paint was applied so that the thickness of the coating film after drying was 40 ⁇ m.
- the sheet-like material coated with the coating material was heated and dried in an oven at 120° C. to evaporate MEK.
- a laminate having a lower electrode layer made of copper on a lower protective layer made of PET and a piezoelectric layer having a thickness of 40 ⁇ m was formed thereon as shown in FIG. 7 was produced. .
- the piezoelectric layer of this laminate was subjected to polarization treatment by a known method.
- the polarization treatment was performed so that the polarization direction was the thickness direction of the piezoelectric layer.
- the same sheet-like material obtained by vacuum-depositing a copper thin film on a PET film was laminated on the laminate that had been subjected to the polarization treatment.
- the laminated body and the sheet-like material are thermocompressed at 120° C. using a laminator to bond the piezoelectric layer, the lower electrode layer, and the upper electrode layer, and the piezoelectric layer is attached to the lower electrode layer.
- a piezoelectric film as shown in FIG. 2 was produced by sandwiching between the electrode layer and the upper electrode layer, and sandwiching this laminate between the lower protective layer and the upper protective layer.
- this piezoelectric film was cut into a rectangular shape with a planar shape of 25 ⁇ 20 cm.
- FIG. 9 is a side view conceptually showing the cutting device 100a.
- 10 is a front view of FIG. 9.
- FIG. A cutting device 100a shown in FIGS. 9 and 10 is a cutting device using Goebel circular blades, and has an upper blade 102a and a lower blade 104a having blades on the peripheral surface of a cylindrical drum.
- the upper blade 102a is provided with a blade 103a so as to protrude radially from the peripheral surface of the drum.
- the lower blade 104a has a groove formed on the peripheral surface of the drum, and a blade 105a is provided at the corner of the groove.
- the upper blade 102a and the lower blade 104a are arranged so that the blades are engaged with each other, and the piezoelectric film 10 is cut by inserting the piezoelectric film 10 between the upper blade 102a and the lower blade 104a.
- the meshing amount between the upper blade 102a and the lower blade 104a is 0.5 mm.
- the diameter of the cutting edge of the upper blade 102a is 65 mm.
- the diameter of the cutting edge of the lower blade 104a is 50 mm.
- the shape of the blade 103a of the upper blade 102a and the shape of the blade 105a of the lower blade 104a are as shown in FIG.
- the shaft of the upper blade 102a and the shaft of the lower blade 104a are connected by a belt, and when one is rotated, the other is also rotated.
- the piezoelectric film 10 is inserted between the upper blade 102a and the lower blade 104a of such a cutting device 100a, and the shaft of the lower blade 104a is rotated by hand to cut the piezoelectric film 10 to a size of 25 cm ⁇ 20 cm. A piezoelectric film 10 was obtained.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 0.3 ⁇ m
- H 43 on the back side was 0.3 ⁇ m.
- the surface facing the upper blade 102a was defined as the front surface
- the surface facing the lower blade 104a was defined as the back surface.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- Example 2 A piezoelectric element was produced in the same manner as in Example 1, except that a cutting device 100b as shown in FIGS. 12 and 13 was used as a cutting device for cutting the piezoelectric film.
- FIG. 12 is a side view conceptually showing the cutting device 100b.
- 13 is a front view of FIG. 12.
- FIG. A cutting device 100b shown in FIGS. 12 and 13 is a cutting device using a straight round blade, and has an upper blade 102b and a lower blade 104b having blades on the circumferential surface of a cylindrical drum.
- the upper blade 102b is provided with a blade 103b so as to protrude radially from the peripheral surface of the drum.
- the lower blade 104b has a groove formed on the peripheral surface of the drum, and a blade 105b is provided at the corner of the groove.
- the upper blade 102b and the lower blade 104b are arranged so that the blades are engaged with each other, and the piezoelectric film 10 is cut by inserting the piezoelectric film 10 between the upper blade 102b and the lower blade 104b.
- the meshing amount between the upper blade 102b and the lower blade 104b is 0.7 mm.
- the diameter of the cutting edge of the upper blade 102b is 150 mm.
- the cutting edge diameter of the lower blade 104b is 135 mm.
- the shape of the blade 103b of the upper blade 102b and the shape of the blade 105b of the lower blade 104b are as shown in FIG.
- the shaft of the upper blade 102b and the shaft of the lower blade 104b are connected by a belt, and when one is rotated, the other is also rotated.
- the piezoelectric film 10 is inserted between the upper blade 102b and the lower blade 104b of such a cutting device 100b, and the shaft of the lower blade 104b is rotated by hand to cut the piezoelectric film 10 into a size of 25 cm ⁇ 20 cm. A piezoelectric film 10 was obtained.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 0.6 ⁇ m
- H 43 on the back side was 1.4 ⁇ m.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- Example 3 A piezoelectric element was produced in the same manner as in Example 1, except that a cutting device 100c as shown in FIG. 15 was used as a cutting device for cutting the piezoelectric film.
- FIG. 15 is a perspective view conceptually showing the cutting device 100c.
- FC-4200-60 manufactured by Graphtec which is a so-called cutting plotter, was used.
- the cutting device 100c has a table 106 on which a member to be cut is placed, two guide portions 108 arranged along two opposite sides of the table 106, an arm portion 110, and a head 112.
- the arm portion 110 extends from one guide portion 108 to the other guide portion 108 , is engaged with the two guide portions 108 , and is guided by the two guide portions 108 to move above the table 106 . parallel to , in the extending direction of the guide portion 108 .
- the head 112 is engaged with the arm portion 110 and is guided by the arm portion 110 so as to be movable in the extending direction of the arm portion 110 . Further, the head 112 holds a blade 113, and the blade edge contacts the member (piezoelectric film 10) placed on the table 106 to be cut.
- the cutting device 100c cuts the piezoelectric film 10 by moving the arm portion 110 and the head 112 to move the blade 113 on the piezoelectric film 10 placed on the table 106 .
- CB15UA (manufactured by Graphtec) was used as the blade 113 .
- the shape of the blade 113 is as shown in FIG.
- the piezoelectric film 10 was cut using such a cutting device 100c to obtain the piezoelectric film 10 with a size of 25 cm x 20 cm.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 1.4 ⁇ m
- H 43 on the back side was 0 ⁇ m.
- the surface on the side of the blade 113 was defined as the front surface
- the surface on the side of the table 106 was defined as the back surface.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- Example 4 A piezoelectric element was produced in the same manner as in Example 1, except that a cutting device 100d as shown in FIG. 16 was used as a cutting device for cutting the piezoelectric film.
- FIG. 16 is a perspective view conceptually showing the cutting device 100d.
- a cutting device 100d shown in FIG. 16 is a cutting device that uses a punching blade (Thomson blade).
- FIG. 17 shows a top view of the punching blade 122
- FIG. 18 shows a side view of FIG.
- the cutting device 100d has a punching blade 122 having a rectangular planar shape. cut out to
- the shape of the punching blade 122 is as shown in FIG.
- the piezoelectric film 10 was cut using such a cutting device 100d to obtain a piezoelectric film 10 with a size of 25 cm x 20 cm.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 0.5 ⁇ m
- H 43 on the back side was 4.2 ⁇ m.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- Example 1 A piezoelectric element was produced in the same manner as in Example 1, except that a cutting device 100e as shown in FIG. 19 was used as a cutting device for cutting the piezoelectric film.
- FIG. 19 is a perspective view conceptually showing the cutting device 100e.
- the cutting device 100e is DN-T61 manufactured by Kokuyo Co., Ltd., and is a cutting device using a rotary cutter.
- the cutting device 100e includes a table 130, a guide portion 132 extending above the table 130 in one direction parallel to the table 130, and a head engaged with the guide portion 132 and movable in the extending direction of the guide portion 132. 134 and .
- the head 134 has a circular blade 135 as shown in FIG. 20. As the head 134 moves, the circular blade 135 rotates to cut the member (piezoelectric film 10) placed on the table 130 to be cut.
- the blade used was RB45-1 manufactured by Olfa.
- the piezoelectric film 10 was cut using such a cutting device 100e to obtain the piezoelectric film 10 with a size of 25 cm ⁇ 20 cm.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 1.9 ⁇ m and H 43 on the back side was 8.5 ⁇ m.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- Example 2 A piezoelectric element was produced in the same manner as in Example 1, except that a cutter knife was used as a cutting device for cutting the piezoelectric film. As a cutter knife, XA-1 manufactured by Olfa was used. The blade used was SB50K manufactured by Olfa.
- FIG. 21 shows a sectional view of the blade 140 of the cutter knife
- FIG. 22 shows a perspective view of the blade 140 of the cutter knife.
- the piezoelectric film 10 was cut using such a cutter knife to obtain the piezoelectric film 10 with a size of 25 cm x 20 cm.
- H 43 between the position 43 ⁇ m inside from the end face (side surface) of the piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end face was measured by the method described above.
- H 43 on the front side was 2.8 ⁇ m
- H 43 on the back side was 8.7 ⁇ m.
- This piezoelectric film was folded four times in a direction of 25 cm at intervals of 5 cm. In the area where the piezoelectric films were laminated, the adjacent piezoelectric films were adhered with the adhesion layer.
- the adhesive layer LIOELM TSU0041SI manufactured by Toyochem Co., Ltd. was used. Moreover, the thickness of the adhesive layer after curing was set to 25 ⁇ m. As a result, a rectangular piezoelectric element having a planar shape of 5 ⁇ 20 cm was produced by laminating five layers by folding the piezoelectric film.
- H 43 is preferably 1.4 ⁇ m or less.
- Example 5 Using the same cutting device 100a as in Example 1, the piezoelectric film was cut into 5 rectangles each having a planar shape of 5 ⁇ 20 cm, and the 5 piezoelectric films were laminated with an adhesive layer to fabricate a piezoelectric element.
- the difference H 43 between the position 43 ⁇ m inside from the end surface (side surface) of each piezoelectric film and the maximum height in the region up to 43 ⁇ m inside from the end surface was measured by the method described above.
- the H43 on the front side of the first sheet was 0.3 ⁇ m
- the H43 on the back side was 0.3 ⁇ m
- the H43 on the front side of the second sheet was 0.3 ⁇ m
- the H43 on the back side was 0.3 ⁇ m.
- H 43 on the front side of the third sheet was 0.3 ⁇ m
- H 43 on the back side was 0.3 ⁇ m.
- the H 43 on the front side of the fourth sheet was 0.3 ⁇ m, and the H 43 on the back side was 0.3 ⁇ m.
- H 43 on the front side of the fifth sheet was 0.3 ⁇ m, and H 43 on the back side was 0.3 ⁇ m.
- the order of the piezoelectric films was set such that the first film was placed on one side of the stack, the second film, the third film, and so on from the first film. Further, when cutting the piezoelectric film, the surface on the side of the upper blade 102a was used as the front surface, and the surface on the side of the lower blade 104a was used as the back surface.
- the piezoelectric element 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,
- Reference Signs List 10 10L piezoelectric film 10a, 10c sheet 10b laminate 12 diaphragm 16, 19 adhesive layer 20 piezoelectric layer 24 lower electrode layer 26 upper electrode layer 28 lower protective layer 30 upper protective layer 34 matrix 36 piezoelectric particles 50 , 56, 60 piezoelectric element 58 core rod 70 electroacoustic transducer 100a to 100e cutting device 102a, 102b upper blade 103a, 103b, 105a, 105b, 113, 140 blade 104a, 104b lower blade 106, 120, 130 table 108, 132 Guide portion 110 Arm portion 112, 134 Head 122 Punching blade 135 Round blade
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Abstract
Description
例えば、特許文献1には、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、高分子複合圧電体の一方の面に形成された、面積が高分子複合圧電体以下である上部薄膜電極、上部薄膜電極の表面に形成される、面積が上部薄膜電極以上である上部保護層、高分子複合圧電体の上部薄膜電極の逆面に形成される、面積が高分子複合圧電体以下である下部薄膜電極、および、下部薄膜電極の表面に形成される、面積が下部薄膜電極以上である下部保護層を有する圧電積層体と、上部薄膜電極の一部に積層されて、少なくとも一部が高分子複合圧電体の面方向外部に位置する上部電極引出し用金属箔と、下部薄膜電極の一部に積層されて、少なくとも一部が高分子複合圧電体の面方向外部に位置する下部電極引出し用金属箔と、を有する電気音響変換フィルムが記載されている。
[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を電極層で挟持し、電極層の圧電体層が接触していない面には保護層が積層されている圧電フィルムを、複数層、積層して、隣接する圧電フィルムを貼着層で貼着した構成を有する圧電素子において、
圧電フィルムは端面から43μm内側までの領域における厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、4.2μm以下である圧電素子。
[2] 圧電フィルムは端面から43μm内側までの領域において、厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、1.4μm以下である[1]に記載の圧電素子。
[3] 圧電フィルムは端面から43μm内側までの領域において、厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、0.3μm以上である[1]または[2]に記載の圧電素子。
[4] 圧電フィルムの厚さが20μm~80μmである、[1~3]のいずれかに記載の圧電素子。
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。
本発明の圧電素子は、
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を電極層で挟持し、電極層の圧電体層が接触していない面には保護層が積層されている圧電フィルムを、複数層、積層して、隣接する圧電フィルムを貼着層で貼着した構成を有する圧電素子において、
圧電フィルムは端面から43μm内側までの領域における厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、4.2μm以下である圧電素子である。
この圧電素子14の面方向の伸縮によって、振動板12が撓み、その結果、振動板12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12は、音を発生する。振動板12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。
すなわち、この電気音響変換器70は、圧電素子50をエキサイターとして用いるスピーカーとして用いることができる。
図2に示す圧電フィルム10は、圧電性を有するシート状物である圧電体層20と、圧電体層20の一方の面に積層される下部電極層24と、下部電極層24の圧電体層20と反対側の面に積層される下部保護層28と、圧電体層20の他方の面に積層される上部電極層26と、上部電極層26の圧電体層20と反対側の面に積層される上部保護層30と、を有する。すなわち、圧電フィルム10は、圧電体層20を電極層で挟持し、電極層の圧電体層が接触していない面に保護層が積層された構成を有する。
後述するが、圧電フィルム10(圧電体層20)は、好ましい態様として、厚さ方向に分極されている。
図3に示すように、圧電フィルム10の端面(側面)から43μm内側の位置と、端面から43μm内側までの領域における最大高さとの差をH43とすると、H43が4.2μm以下である。
圧電フィルムを平坦なテーブル上に載置し、表面側から共焦点レーザー走査型顕微鏡を用いて表面を走査することで、表面のプロファイルを計測し、表面プロファイルから端面から43μm内側の位置の高さと、端面から43μm内側までの領域における最大高さとの差を求める。このような測定を各辺側で77箇所測定し、平均値をH43とする。このような測定を両主面で行う。
厚さ方向に分極された長尺な1枚の圧電フィルム10Lを、折り返して積層することで、積層方向に隣接(対面)する圧電フィルムの分極方向は、図5中に矢印で示すように、逆方向になる。
そのため、図5に示す圧電素子56によれば、部品点数を低減し、かつ、構成を簡略化して、圧電素子(モジュール)としての信頼性を向上し、さらに、コストダウンを図ることができる。
圧電フィルム10Lの下部電極層24および上部電極層26は、金属の蒸着膜等で形成される。金属の蒸着膜は、鋭角で折り曲げられると、ヒビ(クラック)等が入りやすく、電極が断線してしまう可能性がある。すなわち、図5に示す圧電素子56では、屈曲部の内側において、電極にヒビ等が入り易い。
これに対して、長尺な圧電フィルム10Lを折り返した圧電素子56において、圧電フィルム10Lの折り返し部に芯棒58を挿入することにより、下部電極層24および上部電極層26が折り曲げられることを防止して、断線が生じることを好適に防止できる。
前述のとおり、圧電フィルム10は、圧電体層20と、圧電体層20の一方の面に積層される下部電極層24と、下部電極層24の圧電体層20と反対側の面に積層される下部保護層28と、圧電体層20の他方の面に積層される上部電極層26と、上部電極層26の圧電体層20と反対側の面に積層される上部保護層30と、を有する。
圧電体層20は、公知の圧電体からなる層であればよい。本発明において、圧電体層20は、高分子材料を含むマトリックス34に、圧電体粒子36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。
さらに、貼り付ける相手材(振動板)の剛性(硬さ、コシ、バネ定数)に合わせて、積層することで、簡便にバネ定数を調節できるのが好ましく、その際、貼着層16は薄ければ薄いほど、エネルギー効率を高めることができる。
高分子複合圧電体(圧電体層20)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でのガラス転移点が常温、すなわち、0~50℃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と圧電体粒子との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。
なお、これらの高分子材料は、1種のみを用いてもよく、複数種を併用(混合)して用いてもよい。
すなわち、マトリックス34には、誘電特性や機械特性の調節等を目的として、シアノエチル化PVA等の粘弾性材料に加え、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20のマトリックス34において、シアノエチル化PVA等の常温で粘弾性を有する材料に加えて添加される誘電性ポリマーは、1種に限定はされず、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34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36および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36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36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)等が例示される。
圧電体粒子36の粒径をこの範囲とすることにより、圧電フィルム10が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。
すなわち、圧電体層20中の圧電体粒子36は、好ましくは均一に分散されていれば、マトリックス34中に不規則に分散されていてもよい。
圧電体層20中における圧電体粒子36の体積分率は、30~80%が好ましく、50%以上がより好ましく、従って、50~80%とするのが、さらに好ましい。
マトリックス34と圧電体粒子36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20が厚いほど、いわゆるシート状物のコシの強さなどの剛性等の点では有利であるが、同じ量だけ圧電フィルム10を伸縮させるために必要な電圧(電位差)は大きくなる。
圧電体層20の厚さは、10~300μmが好ましく、20~200μmがより好ましく、30~150μmがさらに好ましい。
圧電体層20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。
図2に示すように、圧電フィルム10は、このような圧電体層20の一面に、下部電極層24を有し、その上に下部保護層28を有し、圧電体層20の他方の面に、上部電極層26を有し、その上に上部保護層30を有してなる構成を有する。ここで、上部電極層26と下部電極層24とが電極対を形成する。
このように、圧電フィルム10において、下部電極層24および上部電極層26で挾持された領域は、印加された電圧に応じて伸縮される。
なお、下部電極層24および下部保護層28、ならびに、上部電極層26および上部保護層30は、圧電体層20の分極方向に応じて名称を付しているものである。従って、下部電極層24と上部電極層26、ならびに、下部保護層28と上部保護層30とは基本的に同様の構成を有する。
中でも、優れた機械的特性および耐熱性を有するなどの理由により、ポリエチレンテレフタレート(PET)、ポリプロピレン(PP)、ポリスチレン(PS)、ポリカーボネート(PC)、ポリフェニレンサルファイト(PPS)、ポリメチルメタクリレート(PMMA)、ポリエーテルイミド(PEI)、ポリイミド(PI)、ポリエチレンナフタレート(PEN)、トリアセチルセルロース(TAC)、および、環状オレフィン系樹脂等からなる樹脂フィルムが、好適に利用される。
ここで、下部保護層28および上部保護層30の剛性が高過ぎると、圧電体層20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、下部保護層28および上部保護層30は、薄いほど有利である。
例えば、圧電体層20の厚さが50μmで下部保護層28および上部保護層30がPETからなる場合、下部保護層28および上部保護層30の厚さは、100μm以下が好ましく、50μm以下がより好ましく、25μm以下がさらに好ましい。
下部電極層24および上部電極層26の厚さには、制限はない。また、下部電極層24および上部電極層26の厚さは、基本的に同じであるが、異なってもよい。
例えば、下部保護層28および上部保護層30がPET(ヤング率:約6.2GPa)で、下部電極層24および上部電極層26が銅(ヤング率:約130GPa)からなる組み合わせの場合、下部保護層28および上部保護層30の厚さが25μmだとすると、下部電極層24および上部電極層26の厚さは、1.2μm以下が好ましく、0.3μm以下がより好ましく、中でも0.1μm以下とするのが好ましい。
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)の極大値が常温に存在するのが好ましく、0.1以上となる極大値が常温に存在するのがより好ましい。
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を用いたスピーカの周波数特性が平滑になり、スピーカ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。
測定条件としては、一例として、測定周波数は0.1Hz~20Hz(0.1Hz、0.2Hz、0.5Hz、1Hz、2Hz、5Hz、10Hzおよび20Hz)が、測定温度は-50~150℃が、昇温速度は2℃/分(窒素雰囲気中)が、サンプルサイズは40mm×10mm(クランプ領域込み)が、チャック間距離は20mmが、それぞれ、例示される。
電源PSには、制限はなく、直流電源でも交流電源でもよい。また、駆動電圧も、圧電フィルム10の圧電体層20の厚さおよび形成材料等に応じて、圧電フィルム10を適正に駆動できる駆動電圧を、適宜、設定すればよい。
一例として、下部電極層24および上部電極層26に銅箔等の導電体を接続して外部に電極を引き出す方法、および、レーザ等によって下部保護層28および上部保護層30に貫通孔を形成して、この貫通孔に導電性材料を充填して外部に電極を引き出す方法、等が例示される。
好適な電極の引き出し方法として、特開2014-209724号公報に記載される方法、および、特開2016-015354号公報に記載される方法等が例示される。
圧電素子において、圧電フィルムは貼着層19によって貼着される。
貼着層19は、隣接する圧電フィルム10を貼着可能であれば、公知のものが、各種、利用可能である。
従って、貼着層19は、貼り合わせる際には流動性を有し、その後、固体になる、接着剤からなる層でも、貼り合わせる際にゲル状(ゴム状)の柔らかい固体で、その後もゲル状の状態が変化しない、粘着剤からなる層でも、接着剤と粘着剤との両方の特徴を持った材料からなる層でもよい。
この点を考慮すると、貼着層19は、粘着剤からなる粘着剤層よりも、固体で硬い貼着層19が得られる、接着剤からなる接着剤層であるのが好ましい。より好ましい貼着層19としては、具体的には、ポリエステル系接着剤およびスチレン・ブタジエンゴム(SBR)系接着剤等の熱可塑タイプの接着剤からなる貼着層が好適に例示される。
接着は、粘着とは異なり、高い接着温度を求める際に有用である。また、熱可塑タイプの接着剤は『比較的低温、短時間、および、強接着』を兼ね備えており、好適である。
ここで、図1に示す圧電素子50は、貼着層19が薄い方が、圧電フィルム10の伸縮エネルギーの伝達効果を高くして、エネルギー効率を高くできる。また、貼着層19が厚く剛性が高いと、圧電フィルム10の伸縮を拘束する可能性もある。
この点を考慮すると、貼着層19は、圧電体層20よりも薄いのが好ましい。すなわち、圧電素子50において、貼着層19は、硬く、薄いのが好ましい。具体的には、貼着層19の厚さは、貼着後の厚さで0.1~50μmが好ましく、0.1~30μmがより好ましく、0.1~10μmがさらに好ましい。
なお、図1に示す圧電素子50は、隣接する圧電フィルムの分極方向が互いに逆であり、隣接する圧電フィルム10同士がショートする恐れが無いので、貼着層19を薄くできる。
具体的には、貼着層19の厚さと、動的粘弾性測定による周波数1Hzでの貯蔵弾性率(E’)との積が、0℃において2.0×106N/m以下、50℃において1.0×106N/m以下であるのが好ましい。
また、貼着層の動的粘弾性測定による周波数1Hzでの内部損失が、粘着剤からなる貼着層19の場合には25℃において1.0以下、接着剤からなる貼着層19の場合には25℃において0.1以下であるのが好ましい。
上述した圧電素子50を有する電気音響変換器70において、振動板12は、好ましい態様として、可撓性を有するものである。なお、本発明において、可撓性を有するとは、一般的な解釈における可撓性を有すると同義であり、曲げること、および、撓めることが可能であることを示し、具体的には、破壊および損傷を生じることなく、曲げ伸ばしができることを示す。
振動板12は、好ましくは可撓性を有するものであれば、制限はなく、各種のシート状物(板状物、フィルム)が利用可能である。
一例として、ポリエチレンテレフタレート(PET)、ポリプロピレン(PP)、ポリスチレン(PS)、ポリカーボネート(PC)、ポリフェニレンサルファイト(PPS)、ポリメチルメタクリレート(PMMA)、ポリエーテルイミド(PEI)、ポリイミド(PI)、ポリエチレンナフタレート(PEN)、トリアセチルセルロース(TAC)および環状オレフィン系樹脂等からなる樹脂フィルム、発泡ポリスチレン、発泡スチレンおよび発泡ポリエチレン等からなる発泡プラスチック、ならびに、波状にした板紙の片面または両面に他の板紙をはりつけてなる各種の段ボール材等が例示される。
また、電気音響変換器70では、可撓性を有するものであれば、振動板12として、有機エレクトロルミネセンス(OLED(Organic Light Emitting Diode))ディスプレイ、液晶ディスプレイ、マイクロLED(Light Emitting Diode)ディスプレイ、および、無機エレクトロルミネセンスディスプレイなどの表示デバイス等も好適に利用可能である。
図1に示す電気音響変換器70においては、好ましい態様として、このような振動板12と、圧電素子50とは、貼着層16によって貼着されている。
従って、貼着層16は、貼り合わせる際には流動性を有し、その後、固体になる、接着剤からなる層でも、貼り合わせる際にゲル状(ゴム状)の柔らかい固体で、その後もゲル状の状態が変化しない、粘着剤からなる層でも、接着剤と粘着剤との両方の特徴を持った材料からなる層でもよい。
この点を考慮すると、貼着層16は、粘着剤からなる粘着剤層よりも、固体で硬い貼着層16が得られる、接着剤からなる接着剤層であるのが好ましい。より好ましい貼着層16としては、具体的には、ポリエステル系接着剤およびスチレン・ブタジエンゴム(SBR)系接着剤等の熱可塑タイプの接着剤からなる貼着層が例示される。
接着は、粘着とは異なり、高い接着温度を求める際に有用である。また、熱可塑タイプの接着剤は『比較的低温、短時間、および、強接着』を兼ね備えており、好適である。
ここで、電気音響変換器70においては、貼着層16が薄い方が、振動板12に伝達する圧電素子50の伸縮エネルギー(振動エネルギー)の伝達効果を高くして、エネルギー効率を高くできる。また、貼着層16が厚く剛性が高いと、圧電素子50の伸縮を拘束する可能性もある。
この点を考慮すると、貼着層16は、薄い方が好ましい。具体的には、貼着層16の厚さは、貼着後の厚さで0.1~50μmが好ましく、0.1~30μmがより好ましく、0.1~10μmがさらに好ましい。
従って、電気音響変換器70は、貼着層16を有さず、公知の圧着手段、締結手段、および、固定手段等を用いて、振動板12と圧電素子50とを固定してもよい。例えば、圧電素子50の平面視の形状が矩形である場合には、四隅をボルトナットのような部材で締結して電気音響変換器を構成してもよく、または、四隅と中心部とをボルトナットのような部材で締結して電気音響変換器を構成してもよい。
この点を考慮すると、振動板12と圧電素子50とは、図1に示すように、貼着層16で貼着するのが好ましい。
このような圧電体層20を有する圧電フィルム10の下部電極層24および上部電極層26に電圧を印加すると、印加した電圧に応じて圧電体粒子36が分極方向に伸縮する。その結果、圧電フィルム10(圧電体層20)が厚さ方向に収縮する。同時に、ポアゾン比の関係で、圧電フィルム10は、面内方向にも伸縮する。この伸縮は、0.01~0.1%程度である。
これに対して、圧電フィルム10すなわち圧電体層20は、面方向には、厚さよりもはるかに大きなサイズを有する。従って、例えば、圧電フィルム10の長さが20cmであれば、電圧の印加によって、最大で0.2mm程度、圧電フィルム10は伸縮する。
この厚さ方向の振動によって、振動板12は、音を発生する。すなわち、振動板12は、圧電フィルム10に印加した電圧(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。
これに対して、図1に示す圧電素子50において、圧電フィルム10は、圧電特性に面内異方性がなく、面内方向では全方向に等方的に伸縮する。すなわち、図1に示す圧電素子50において、圧電フィルム10は、等方的に二次元的に伸縮する。
このような等方的に二次元的に伸縮する圧電フィルム10によれば、一方向にしか大きく伸縮しないPVDF等の一般的な圧電フィルムを積層した場合に比べ、大きな力で振動板12を振動することができ、より大きく、かつ、美しい音を発生できる。
下部保護層28が非常に薄く、ハンドリング性が悪い時などは、必要に応じて、セパレータ(仮支持体)付きの下部保護層28を用いても良い。なお、セパレータとしては、厚さ25μm~100μmのPET等を用いることができる。セパレータは、上部電極層26および上部保護層30を熱圧着した後、下部保護層28に何らかの部材を積層する前に、取り除けばよい。
上記物質以外の有機溶媒としては制限はなく各種の有機溶媒が利用可能である。
マトリックス34に、これらの高分子材料を添加する際には、上述した塗料に添加する高分子材料を溶解すればよい。
なお、この分極処理の前に、圧電体層20の表面を加熱ローラ等を用いて平滑化する、カレンダー処理を施してもよい。このカレンダー処理を施すことで、後述する熱圧着工程がスムーズに行える。
さらに、この積層体10bとシート状物10cとの積層体を、上部保護層30と下部保護層28とを挟持するようにして、加熱プレス装置や加熱ローラ対等で熱圧着する。
このような積層体は、カットシート状のシート状物を用いて製造を行っても良いし、ロール・トゥ・ロール(Roll to Roll 以下、RtoRともいう)によって作製されてもよい。
[圧電フィルムの作製]
上述した図6~図8に示す方法によって、図2に示すような圧電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(信越化学工業社製、CR-V)をメチルエチルケトン(MEK)に溶解した。その後、この溶液に、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)で分散させて、圧電体層を形成するための塗料を調製した。
・PZT粒子・・・・・・・・・・・1000質量部
・シアノエチル化PVA・・・・・・・100質量部
・MEK・・・・・・・・・・・・・・600質量部
なお、PZT粒子は、市販のPZT原料粉を1000~1200℃で焼結した後、これを平均粒径3.5μmになるように解砕および分級処理したものを用いた。
なお、プロセス中、良好なハンドリングを得るために、PETフィルムには厚さ50μmのセパレータ(仮支持体PET)付きのものを用い、薄膜電極および保護層の熱圧着後に、各保護層のセパレータを取り除いた。
次いで、シート状物の上に塗料を塗布した物を、120℃のオーブンで加熱乾燥することでMEKを蒸発させた。これにより、図7に示すような、PET製の下部保護層の上に銅製の下部電極層を有し、その上に、厚さが40μmの圧電体層を形成してなる積層体を作製した。
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120℃で熱圧着することで、圧電体層と下部電極層および上部電極層とを接着して、圧電体層を下部電極層と上部電極層とで挟持し、この積層体を、下部保護層と上部保護層とで挟持した、図2に示すような圧電フィルムを作製した。
図9および図10に示す裁断装置100aは、ゲーベル丸刃を用いる裁断装置であり、円筒状のドラムの周面に刃を有する上刃102aおよび下刃104aを有する。上刃102aは、ドラムの周面から径方向に突出するように刃103aが設けられている。下刃104aは、ドラムの周面に溝が形成されており、溝の角部に刃105aが設けられている。上刃102aおよび下刃104aは、互いの刃が噛み合うように配置されており、圧電フィルム10を上刃102aと下刃104aとの間に挿通させることにより、圧電フィルム10を裁断する。図11に示すように、上刃102aと下刃104aとの噛合い量は0.5mmである。また、上刃102aの刃先の直径は65mmである。下刃104aの刃先の直径は50mmである。
測定の結果、表面側のH43は0.3μm、裏面側のH43は0.3μmであった。
なお、圧電フィルムを裁断する際に上刃102a側となる面を表面とし、下刃104a側となる面を裏面とした。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
圧電フィルムを裁断する裁断装置として、図12および図13に示すような裁断装置100bを用いた以外は実施例1と同様にして、圧電素子を作製した。
図12および図13に示す裁断装置100bは、ストレート丸刃を用いる裁断装置であり、円筒状のドラムの周面に刃を有する上刃102bおよび下刃104bを有する。上刃102bは、ドラムの周面から径方向に突出するように刃103bが設けられている。下刃104bは、ドラムの周面に溝が形成されており、溝の角部に刃105bが設けられている。上刃102bおよび下刃104bは、互いの刃が噛み合うように配置されており、圧電フィルム10を上刃102bと下刃104bとの間に挿通させることにより、圧電フィルム10を裁断する。図14に示すように、上刃102bと下刃104bとの噛合い量は0.7mmである。また、上刃102bの刃先の直径は150mmである。下刃104bの刃先の直径は135mmである。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
圧電フィルムを裁断する裁断装置として、図15に示すような裁断装置100cを用いた以外は実施例1と同様にして、圧電素子を作製した。
裁断装置100cとしては、いわゆるカッティングプロッターである、グラフテック製FC-4200-60を用いた。裁断装置100cは、裁断する部材を載置するテーブル106と、テーブル106の対向する2辺に沿って配置される2つのガイド部108と、アーム部110と、ヘッド112と、を有する。
なお、圧電フィルムを裁断する際に刃113側となる面を表面とし、テーブル106側となる面を裏面とした。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
圧電フィルムを裁断する裁断装置として、図16に示すような裁断装置100dを用いた以外は実施例1と同様にして、圧電素子を作製した。
図16に示す裁断装置100dは、打抜き刃(トムソン刃)を用いる裁断装置である。
図17に打抜き刃122の上面図を示し、図18に図17の側面図を示す。
裁断装置100dは、平面形状が矩形状の打抜き刃122を有し、裁断装置100dのテーブル120上に載置された圧電フィルム10に、打抜き刃122を押圧することで、圧電フィルム10を矩形状に切り抜く。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
圧電フィルムを裁断する裁断装置として、図19に示すような裁断装置100eを用いた以外は実施例1と同様にして、圧電素子を作製した。
裁断装置100eは、コクヨ製DN-T61で、ロータリーカッターを用いる裁断装置である。裁断装置100eは、テーブル130と、テーブル130の上方で、テーブル130に平行な一方向に延在するガイド部132と、ガイド部132に係合されガイド部132の延在方向に移動可能なヘッド134と、を有する。ヘッド134は、図20に示すような丸刃135を有し、ヘッド134の移動とともに丸刃135が回転してテーブル130に載置された裁断する部材(圧電フィルム10)を裁断する。刃は、オルファ製RB45-1を用いた。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
圧電フィルムを裁断する裁断装置として、カッターナイフを用いた以外は実施例1と同様にして、圧電素子を作製した。カッターナイフはオルファ製XA-1を用いた。また、刃はオルファ製SB50Kを用いた。
これにより、圧電フィルムを折り返して5層を積層した、平面形状が5×20cmの長方形の圧電素子を作製した。
作製した各実施例および比較例の圧電素子の表面および裏面を目視で観察し、シワの有無を以下の基準で評価した。
・A:シワおよびスジが見られない。
・B:端辺に略平行にスジが見られるが、シワは見られない。
・C:端辺から面方向の内側に向かうシワが見られる。
結果を表1に示す。
実施例1と同様の裁断装置100aを用いて、圧電フィルムを、平面形状が5×20cmの長方形に5枚切り出し、5枚の圧電フィルムを粘着層で積層して圧電素子を作製した。
測定の結果、1枚目の表面側のH43は0.3μm、裏面側のH43は0.3μm、2枚目の表面側のH43は0.3μm、裏面側のH43は0.3μm、3枚目の表面側のH43は0.3μm、裏面側のH43は0.3μmであった。4枚目の表面側のH43は0.3μm、裏面側のH43は0.3μmであった。5枚目の表面側のH43は0.3μm、裏面側のH43は0.3μmであった。
なお、圧電フィルムの順序は、積層した際の一方の側を1枚目とし、1枚目から順に2枚目、3枚目~とした。また、圧電フィルムを裁断する際に上刃102a側の面を表面とし、下刃104a側の面を裏面とした。
以上から本発明の効果は明らかである。
10a、10c シート状物
10b 積層体
12 振動板
16、19 貼着層
20 圧電体層
24 下部電極層
26 上部電極層
28 下部保護層
30 上部保護層
34 マトリックス
36 圧電体粒子
50、56、60 圧電素子
58 芯棒
70 電気音響変換器
100a~100e 裁断装置
102a、102b 上刃
103a、103b、105a、105b、113、140 刃
104a、104b 下刃
106、120、130 テーブル
108、132 ガイド部
110 アーム部
112、134 ヘッド
122 抜打ち刃
135 丸刃
Claims (4)
- 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を電極層で挟持し、前記電極層の前記圧電体層が接触していない面には保護層が積層されている圧電フィルムを、複数層、積層して、隣接する前記圧電フィルムを貼着層で貼着した構成を有する圧電素子において、
前記圧電フィルムは端面から43μm内側までの領域における厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、4.2μm以下である圧電素子。 - 前記圧電フィルムは端面から43μm内側までの領域において、厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、1.4μm以下である請求項1に記載の圧電素子。
- 前記圧電フィルムは端面から43μm内側までの領域において、厚み方向の最大高さと、端面から43μm内側の位置での厚み方向の高さとの差が、0.3μm以上である請求項1または2に記載の圧電素子。
- 前記圧電フィルムの厚さが20μm~80μmである、請求項1~3のいずれか一項に記載の圧電素子。
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