WO2023053750A1 - Piezoelectric element, and electro-acoustic converter - Google Patents

Piezoelectric element, and electro-acoustic converter Download PDF

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Publication number
WO2023053750A1
WO2023053750A1 PCT/JP2022/030855 JP2022030855W WO2023053750A1 WO 2023053750 A1 WO2023053750 A1 WO 2023053750A1 JP 2022030855 W JP2022030855 W JP 2022030855W WO 2023053750 A1 WO2023053750 A1 WO 2023053750A1
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Prior art keywords
piezoelectric
layer
piezoelectric element
electrode layer
projecting portion
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PCT/JP2022/030855
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French (fr)
Japanese (ja)
Inventor
栄貴 小沢
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富士フイルム株式会社
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Priority to CN202280060037.6A priority Critical patent/CN117957858A/en
Publication of WO2023053750A1 publication Critical patent/WO2023053750A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B06GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06BMETHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B1/00Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B06B1/02Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
    • B06B1/06Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00Piezoelectric transducers; Electrostrictive transducers
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00Piezoelectric transducers; Electrostrictive transducers
    • H04R17/02Microphones

Definitions

  • the present invention relates to piezoelectric elements and electroacoustic transducers.
  • 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.
  • piezoelectric element As a piezoelectric element, it has been proposed to use a piezoelectric film in which a piezoelectric layer is sandwiched between electrode layers and protective layers. It is also proposed to laminate a plurality of piezoelectric films and use them as a piezoelectric element.
  • Patent Document 1 discloses a polymer composite piezoelectric body in which piezoelectric particles are dispersed in a matrix containing a polymer material, and electrode layers formed on both sides of the polymer composite piezoelectric body, The loss tangent at a frequency of 1 kHz by dynamic viscoelasticity measurement has a maximum value of 0.1 or more in the temperature range of more than 50 ° C. and 150 ° C. or less, and the value at 50 ° C. is 0.08 or more.
  • a piezoelectric film is described.
  • Patent Document 1 describes a piezoelectric element in which a piezoelectric film is folded one or more times to laminate a plurality of piezoelectric films.
  • a piezoelectric element made by folding a piezoelectric film is attached to a diaphragm, and by vibrating the diaphragm, the diaphragm generates sound.
  • a projection projecting in the plane direction is provided from the laminated part in which the piezoelectric films are laminated, and the external power supply is connected to the electrode layer at this projection. is considered.
  • a piezoelectric element formed by laminating piezoelectric films is capable of suppressing variations in sound pressure while suppressing heat generation. and to provide an electroacoustic transducer.
  • a piezoelectric film having a piezoelectric layer, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers is folded once or more to form a piezoelectric film having a plurality of layers,
  • a piezoelectric element formed by lamination In a plan view, the piezoelectric film has a projecting portion projecting from a laminated portion in which two or more layers are stacked, The protruding part has a connection part for connecting the electrode layer and an external power supply,
  • a piezoelectric element and an electroacoustic transducer that can suppress variations in sound pressure while suppressing heat generation in a piezoelectric element formed by laminating piezoelectric films.
  • FIG. 2 is a perspective view of the piezoelectric element shown in FIG. 1;
  • FIG. 2 is a plan view of the piezoelectric element shown in FIG. 1;
  • FIG. 4 is a diagram for explaining the area of a laminated portion, the area of a protruding portion, and the length of a side where the protruding portion and the laminated portion are in contact;
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention;
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention;
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention;
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention;
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention;
  • FIG. 1 is a perspective view of the piezoelectric element shown in FIG.
  • FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention. It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film.
  • 1 is a diagram schematically showing an example of an electroacoustic transducer of the present invention having a piezoelectric element of the present invention; FIG.
  • 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 A piezoelectric film having a piezoelectric layer, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers is folded one or more times to laminate a plurality of piezoelectric films.
  • a piezoelectric element that In a plan view, the piezoelectric film has a projecting portion projecting from a laminated portion in which two or more layers are stacked,
  • the protruding part has a connection part for connecting the electrode layer and an external power supply,
  • the ratio of the area of the projecting portion to the area of the laminated portion is in the range of 0.02 to 0.3, and the length of the side where the projecting portion is in contact with the laminated portion is 4 mm or more.
  • FIG. 1 shows a side view schematically showing an example of the piezoelectric element of the present invention.
  • FIG. 2 shows a perspective view of the piezoelectric element of FIG.
  • FIG. 3 shows a plan view of the piezoelectric element of FIG. Note that the plan view is a view of the piezoelectric film 10 laminated in a plurality of layers and viewed from the lamination direction.
  • the piezoelectric element 50a shown in FIGS. 1 to 3 is obtained by laminating five layers of the piezoelectric film 10 by folding one rectangular piezoelectric film 10 four times in one direction. That is, this piezoelectric element 50a is a laminated piezoelectric element in which five layers of piezoelectric films 10 are laminated. 2, the piezoelectric film 10 has electrode layers on both sides of the piezoelectric layer 20, covering both electrode layers and It has a protective layer. Further, in the following description, the direction in which the piezoelectric film 10 is folded back (horizontal direction in FIG. 1) is referred to as the folding direction.
  • the piezoelectric element 50a has a protruding portion 10a that protrudes outward in the plane direction from a laminated portion 10b in which five layers of piezoelectric films 10 are superimposed. That is, when one piezoelectric film 10 is folded back four times, the piezoelectric element 50a is arranged so that the four layers from the bottom side in FIG. By making the length of the piezoelectric film 10, which is the side layer, longer than the piezoelectric films 10 of the other layers so that one end in the folding direction does not overlap the piezoelectric films 10 of the other layers, the projecting portion 10a is formed. It was established.
  • the layers of the piezoelectric film 10 adjacent to each other in the laminated portion 10b are adhered by the adhesive layer 14.
  • the laminated portion 10b is a region in which two or more layers of piezoelectric films overlap in plan view, ie, when the piezoelectric element is viewed from above (or below) in FIG. That is, as shown in FIG. 3, the area where five layers of the piezoelectric film 10 overlap is the laminated portion 10b.
  • the protruding portion 10a is a region that protrudes in the plane direction from the laminated portion 10b, and is a region that does not overlap with other layers in plan view.
  • the right end of the uppermost layer is the projecting portion 10a.
  • the projecting portion 10a is formed with a connection portion 40 for connecting the first electrode layer 24 and the second electrode layer 26 (hereinafter collectively referred to as electrode layers) to an external electrode. It is In the illustrated example, through holes are formed in the protective layers (the first protective layer 28 and the second protective layer 30) of the protrusion 10a to expose the electrode layer and provide the connecting section 40. As shown in FIG.
  • the method for forming the through-holes is not limited, and known methods such as laser processing, removal by dissolution using a solvent, and mechanical processing such as mechanical polishing may be used depending on the material for forming the protective layer. .
  • the connecting portion 40 is connected to a wiring that is filled with a known conductive material such as a conductive metal paste such as silver paste, a conductive carbon paste, and a conductive nanoink and is connected to an external power supply.
  • a known conductive material such as a conductive metal paste such as silver paste, a conductive carbon paste, and a conductive nanoink.
  • the piezoelectric element 50a of the present invention drives the piezoelectric element 50a by applying a voltage to the electrode layer using an external power source via the connecting portion 40 provided on the projecting portion 10a.
  • the piezoelectric element 50a expands and contracts in the plane direction, bending the diaphragm to which the piezoelectric element 50a is attached, and as a result vibrating the diaphragm to generate sound.
  • the diaphragm vibrates according to the magnitude of the driving voltage applied to the piezoelectric element 50a, and generates sound according to the driving voltage applied to the piezoelectric element 50a. That is, the piezoelectric element 50a can be used as an exciter.
  • the protruding portion 10a when a voltage is applied from the connecting portion 40 between the electrode layer provided on the protruding portion 10a and the external power supply to drive the piezoelectric element 50a, the protruding portion 10a generates heat remarkably. , thermal runaway may occur and continuous drive may not be possible. In order to suppress such heat generation, it is preferable that the area of the projecting portion 10a is large.
  • the length Ya of the side where the projecting portion 10a and the laminated portion 10b are in contact is 4 mm or more.
  • the ratio Ps of the area Sa of the protruding portion 10a to the area Sb of the laminated portion 10b is too small, that is, if the area Sa of the protruding portion 10a is too small, when a voltage is applied to the piezoelectric element 50a, a current is generated in the protruding portion 10a. Density increases. Therefore, the protruding portion 10a generates heat remarkably. Also, if the length Ya of the side where the projecting portion 10a and the laminated portion 10b contact each other is too short, the current density at the projecting portion 10a also becomes high, resulting in significant heat generation at the projecting portion 10a.
  • the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is set to 0.02 or more, that is, the area Sa of the projecting portion 10a is increased. Accordingly, it is possible to suppress an increase in current density in the protruding portion 10a, thereby suppressing heat generation of the protruding portion 10a. Further, by setting the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact with each other to 4 mm or more, it is possible to suppress an increase in the current density in the protruding portion 10a and suppress the heat generation of the protruding portion 10a. .
  • the ratio Ps of the area Sa of the protruding portion 10a to the area Sb of the laminated portion 10b is too large, that is, if the area Sa of the protruding portion 10a is too large, when a plurality of piezoelectric elements 50a having the same specifications are manufactured, , there is a problem that the variation of the sound pressure, especially in the high frequency band, becomes large.
  • the protrusion 10a when the protrusion 10a is provided, when the piezoelectric element 50a is driven, the protrusion 10a also vibrates and generates a sound. It is presumed that the sound pressure generated from the protruding portion 10a varies due to variations, variations in the state of warping, and the like. Since the size of the projecting portion 10a is smaller than the diaphragm to which the piezoelectric element 50a is adhered, the variation in sound pressure generated from the projecting portion 10a has a greater effect especially in a high frequency band.
  • the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is 0.3 or less, that is, the area Sa of the projecting portion 10a is reduced. Therefore, variations in the shape of the projecting portion 10a, variations in the state of warping, etc. can be reduced, and variations in sound pressure can be reduced.
  • the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact is preferably 4 mm or longer, more preferably 10 mm or longer, and even more preferably 20 mm or longer.
  • the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is preferably 0.02 or more, more preferably 0.04 or more, and 0.06 or more. is more preferred.
  • the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is preferably 0.3 or less, more preferably 0.2 or less, and 0.1 or less. More preferred.
  • FIG. 4 is a plan view of the piezoelectric element 50a.
  • the area Sb of the laminated portion 10b and the area Sa of the projecting portion 10a are the areas in plan view.
  • the area Sb of the laminated portion 10b is Lb ⁇ Wb, where Lb is the length in the folded direction of the laminated portion 10b in plan view, and Wb is the width in the direction orthogonal to the folded direction.
  • the area Sa of the projection 10a is La ⁇ Wa.
  • the width Wa of the projecting portion 10a and the width Wb of the laminated portion 10b are the same.
  • the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact is the same as the width Wa of the protruding portion 10a (the width Wb of the laminated portion 10b).
  • the width Wa of the protruding portion 10a is substantially the same as the width Wb of the laminated portion 10b, but it is not limited to this.
  • FIG. 5 shows a plan view of another example of the piezoelectric element of the present invention.
  • a piezoelectric element 50b shown in FIG. 5 has a rectangular laminated portion 10b and a rectangular protruding portion 10a, and the width Wa of the protruding portion 10a is shorter than the width Wb of the laminated portion 10b. Therefore, the length Ya of the side where the protruding portion 10a and the laminated portion 10b contact is the same as the width Wa of the protruding portion 10a.
  • the protruding portion 10a is arranged substantially in the center in the width direction of the laminated portion 10b, but is not limited to this, and is arranged at any position in the width direction of the laminated portion 10b. may be
  • the projecting portion 10a has a substantially square shape, but is not limited to this and may have a rectangular shape.
  • the width direction of the projecting portion 10a may be the long side of the rectangle, or the length direction (folding direction) of the projecting portion 10a may be the long side of the rectangle.
  • the shape of the projecting portion 10a is not limited to a rectangular shape.
  • the shape of the projecting portion 10a may have a polygonal shape such as a hexagonal shape. It may be in shape.
  • the protruding portion 10a is configured to protrude from the laminated portion 10b in the folding direction, but the present invention is not limited to this.
  • the protruding portion 10a may be configured to protrude from the laminated portion 10b in the width direction orthogonal to the folding direction.
  • the length La of the projecting portion 10a in the folding direction is equal to the length Ya of the side where the projecting portion and the laminated portion are in contact with each other.
  • the piezoelectric element is configured to have one projecting portion, but the configuration is not limited to this.
  • FIG. 8 shows a plan view of another example of the piezoelectric element of the present invention.
  • a piezoelectric element 50e shown in FIG. 8 has a rectangular laminated portion 10b and a plurality of rectangular protruding portions 10a arranged on one side of the laminated portion 10b.
  • a connecting portion 40 for connecting the first electrode layer 24 and/or the second electrode layer 26 to an external electrode is formed on each projecting portion 10a.
  • Either one of the first electrode layer 24 and the second electrode layer 26 may be connected to an external electrode in one projecting portion 10a. It is preferable that both the first electrode layer 24 and the second electrode layer 26 are connected to the external electrode in one projecting portion 10a. That is, it is preferable that both the first electrode layer 24 and the second electrode layer 26 are connected to the external electrode in each of the plurality of protrusions 10a.
  • the area Sa of the protrusions 10a is the total area of the plurality of protrusions 10a. That is, the ratio of the total area of the plurality of projecting portions 10a to the area of the laminated portion 10b should be in the range of 0.02 to 0.3.
  • the length Ya of the side where the protruding portion 10a and the laminated portion 10b contact is the length Ya of the side of each protruding portion 10a that contacts the laminated portion 10b. Therefore, in each projecting portion 10a, the length Ya of the side in contact with the laminated portion 10b should be 4 mm or more.
  • the number of protrusions 10a is preferably 12 or less, more preferably 10 or less.
  • the piezoelectric element 50a shown in FIG. 1 is formed by laminating five layers of piezoelectric films 10, but the present invention is not limited to this. That is, the piezoelectric element may have two to four layers of the piezoelectric film 10, or may have six or more layers.
  • the piezoelectric elements 50a to 50e are collectively referred to as the piezoelectric element 50 when there is no need to distinguish them.
  • FIG. 9 shows an enlarged view of a portion of the piezoelectric film 10.
  • the piezoelectric film 10 shown in FIG. 9 includes a piezoelectric layer 20 that is a sheet-like material having piezoelectricity, a second electrode layer 26 that is laminated on one surface of the piezoelectric layer 20 , and a piezoelectric layer of the second electrode layer 26 .
  • the piezoelectric layer 20 is preferably a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 containing a polymeric material, as conceptually shown in FIG.
  • 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 which the adhesive layer 104 is 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. 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. Among them, as the polymer material, it is preferable to use a material having a cyanoethyl group, and it is particularly preferable to use cyanoethylated PVA.
  • the piezoelectric layer 20 preferably uses a polymer material having a cyanoethyl group as the matrix 34, 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 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. Moreover, in the matrix 34 of the piezoelectric layer 20, these dielectric polymer materials are not limited to one type, and a plurality of types may be added.
  • the matrix 34 may also include thermoplastic resins such as vinyl chloride resin, polyethylene, polystyrene, methacrylic resin, polybutene, and isobutylene for the purpose of adjusting the glass transition point Tg, and Thermosetting resins such as phenolic resins, urea resins, melamine resins, alkyd resins, and 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.
  • thermoplastic resins such as vinyl chloride resin, polyethylene, polystyrene, methacrylic resin, polybutene, and isobutylene for the purpose of adjusting the glass transition point Tg
  • Thermosetting resins such as phenolic resins, urea resins, melamine resins, alkyd resins, and mica may be added.
  • a tackifier such as rosin ester, ros
  • 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 layer made of a polymeric composite piezoelectric material containing piezoelectric particles 36 in such a matrix 34 .
  • Piezoelectric particles 36 are dispersed in the matrix 34 .
  • the piezoelectric particles 36 are uniformly (substantially uniformly) dispersed in the matrix 34 .
  • the piezoelectric particles 36 are made of ceramic particles having a perovskite or wurtzite crystal structure.
  • 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.
  • PZT lead zirconate titanate
  • PLAT lead zirconate lanthanate titanate
  • BaTiO 3 barium titanate
  • ZnO zinc oxide
  • BFBT solid solution
  • 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 may be uniformly and regularly dispersed in the matrix 34, or if they are uniformly dispersed, they may be dispersed irregularly in the matrix 34. may have been
  • 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 layer 20 is preferably polarized (poled) in the thickness direction.
  • the piezoelectric layer 20 is a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 made of a polymer material having viscoelasticity at room temperature, such as cyanoethylated PVA, as described above. No restrictions. That is, in the piezoelectric film 10 of the present invention, various known piezoelectric layers can be used as the piezoelectric layer.
  • a high-performance dielectric material containing similar piezoelectric particles 36 in a matrix containing a dielectric polymer material such as the polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer described above may be used.
  • Molecular composite piezoelectric material, piezoelectric layer made of polyvinylidene fluoride, piezoelectric layer made of fluorine resin other than polyvinylidene fluoride, piezoelectric layer made by laminating a film made of poly-L-lactic acid and a film made of poly-D-lactic acid, etc. is also available.
  • the piezoelectric film 10 has a second electrode layer 26 on one surface of the piezoelectric layer 20, and a second protective layer 30 thereon. has a first electrode layer 24 on the surface thereof, and a first protective layer 28 thereon.
  • the first electrode layer 24 and the second electrode layer 26 form an electrode pair.
  • both surfaces of the piezoelectric layer 20 are sandwiched between electrode pairs, that is, the second electrode layer 26 and the first electrode layer 24 , and this laminate is formed into the second protective layer 30 and the first protective layer 28 . It has a configuration sandwiched between.
  • the region sandwiched between the second electrode layer 26 and the first electrode layer 24 expands and contracts according to the applied voltage.
  • the second electrode layer 26 and the second protective layer 30 as well as the first electrode layer 24 and the first protective layer 28 are attached for the sake of convenience in describing the piezoelectric film 10 . Therefore, the first and second aspects of the present invention have no technical significance and are irrelevant to the actual usage conditions.
  • the piezoelectric film 10 includes, in addition to these layers, an adhesive layer for attaching the electrode layer and the piezoelectric layer 20 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.
  • the same material as the matrix 34 that is, the polymer material obtained by removing the piezoelectric particles 36 from the piezoelectric layer 20, can be preferably used as the adhesive.
  • the adhesive layer may be provided on both the first electrode layer 24 side and the second electrode layer 26 side, or may be provided on only one of the first electrode layer 24 side and the second electrode layer 26 side. good.
  • the second protective layer 30 and the first protective layer 28 cover the first electrode layer 24 and the second electrode layer 26, and provide the piezoelectric layer 20 with appropriate rigidity and mechanical strength. is responsible for 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 second protective layer 30 and a first protective layer 28 to compensate.
  • the first protective layer 28 and the second protective layer 30 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 28 and the second protective layer 30, both members are collectively referred to as protective layers.
  • Various sheet materials can be used for the second protective layer 30 and the first protective layer 28 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 second protective layer 30 and the first protective layer 28 are also not limited. Also, the thicknesses of the second protective layer 30 and the first protective layer 28 are basically the same, but may be different. Here, if the rigidity of the second protective layer 30 and the first protective layer 28 is too high, not only will the expansion and contraction of the piezoelectric layer 20 be constrained, but also the flexibility will be impaired. Therefore, the thinner the second protective layer 30 and the first protective layer 28, the better, except when mechanical strength and good handling properties as a sheet-like article are required.
  • the thicknesses of the second protective layer 30 and the first protective layer 28 are not more than twice the thickness of the piezoelectric layer 20, it is possible to ensure both rigidity and appropriate flexibility. favorable results can be obtained.
  • the thickness of the piezoelectric layer 20 is 50 ⁇ m and the second protective layer 30 and the first protective layer 28 are made of PET, the thicknesses of the second protective layer 30 and the first protective layer 28 are preferably 100 ⁇ m or less. 50 ⁇ m or less is more preferable, and 25 ⁇ m or less is even more preferable.
  • the second electrode layer 26 is provided between the piezoelectric layer 20 and the second protective layer 30, and the first electrode layer 24 is provided between the piezoelectric layer 20 and the first protective layer 28. It is formed.
  • the second electrode layer 26 and the first electrode layer 24 are provided for applying voltage to the piezoelectric layer 20 (piezoelectric film 10).
  • the first electrode layer 24 and the second electrode layer 26 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 24 and the second electrode layer 26, both members are collectively referred to as electrode layers.
  • the materials for forming the second electrode layer 26 and the first electrode layer 24 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. Alternatively, conductive polymers such as PEDOT/PPS (polyethylenedioxythiophene-polystyrenesulfonic acid) are also exemplified.
  • PEDOT/PPS polyethylenedioxythiophene-polystyrenesulfonic acid
  • copper, aluminum, gold, silver, platinum, and indium tin oxide are preferably exemplified as the second electrode layer 26 and the first electrode layer 24 .
  • copper is more preferable from the viewpoint of conductivity, cost, flexibility, and the like.
  • the method of forming the second electrode layer 26 and the first electrode layer 24 is not limited, and may be a vapor phase deposition method (vacuum film formation method) such as vacuum deposition or sputtering, a film formation by plating, or the formation of the above materials.
  • a vapor phase deposition method vacuum film formation method
  • sputtering a film formation by plating
  • a variety of known methods are available, such as affixing the foils.
  • thin films of copper, aluminum, or the like formed by vacuum deposition are preferably used as the second electrode layer 26 and the first electrode layer 24 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 second electrode layer 26 and the first electrode layer 24 are not limited. Also, the thicknesses of the second electrode layer 26 and the first electrode layer 24 are basically the same, but may be different.
  • the second protective layer 30 and the first protective layer 28 if the rigidity of the second electrode layer 26 and the first electrode layer 24 is too high, not only will the expansion and contraction of the piezoelectric layer 20 be restricted, Flexibility is also impaired. Therefore, the thinner the second electrode layer 26 and the first electrode layer 24, the better, as long as the electrical resistance does not become too high.
  • the product of the thickness of the second electrode layer 26 and the first electrode layer 24 and the Young's modulus is less than the product of the thickness of the second protective layer 30 and the first protective layer 28 and the Young's modulus , is preferred because it does not significantly impair flexibility.
  • the second protective layer 30 and the first protective layer 28 are made of PET (Young's modulus: about 6.2 GPa), and the second electrode layer 26 and the first electrode layer 24 are made of copper (Young's modulus: about 130 GPa).
  • the thickness of the second protective layer 30 and the first protective layer 28 is 25 ⁇ m
  • the thickness of the second electrode layer 26 and the first electrode layer 24 is preferably 1.2 ⁇ m or less, more preferably 0.3 ⁇ m or less. , it is preferably 0.1 ⁇ m or less.
  • the piezoelectric film 10 includes the piezoelectric layer 20 formed by dispersing the piezoelectric particles 36 in the matrix 34 containing a polymer material, sandwiched between the second electrode layer 26 and the first electrode layer 24, and This laminate has a structure in which the second protective layer 30 and the first protective layer 28 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 (external power source) is connected to the second electrode layer 26 and the first electrode layer 24 of the piezoelectric film 10 to apply a drive voltage for expanding and contracting the piezoelectric film 10 , that is, to supply drive power.
  • the power source may be a DC power source or an AC power source.
  • 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.
  • electrodes are led out from the second electrode layer 26 and the first electrode layer 24 at the projecting portion 10a.
  • the method of extracting electrodes from the second electrode layer 26 and the first electrode layer 24 there are no restrictions on the method of extracting electrodes from the second electrode layer 26 and the first electrode layer 24, and various known methods can be used.
  • a method of connecting a conductor such as a copper foil to the second electrode layer 26 and the first electrode layer 24 to lead the electrodes to the outside and a method of penetrating the second protective layer 30 and the first protective layer 28 by a laser or the like.
  • Examples include a method of forming a hole, filling the through hole with a conductive material, and leading an electrode to the outside.
  • 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.
  • FIG. 10 An example of a method for manufacturing the piezoelectric film 10 will be described below with reference to FIGS. 10 to 12.
  • FIG. 10 An example of a method for manufacturing the piezoelectric film 10 will be described below with reference to FIGS. 10 to 12.
  • FIG. 10 An example of a method for manufacturing the piezoelectric film 10 will be described below with reference to FIGS. 10 to 12.
  • FIG. 10 An example of a method for manufacturing the piezoelectric film 10 will be described below with reference to FIGS. 10 to 12.
  • a sheet-like object 12a having a second protective layer 30 and a second electrode layer 26 formed thereon as shown in FIG. 10 is prepared. Further, a sheet-like material 12c having the first electrode layer 24 formed on the surface of the first protective layer 28 conceptually shown in FIG. 12 is prepared.
  • the sheet 12a may be produced by forming a copper thin film or the like as the second electrode layer 26 on the surface of the second protective layer 30 by vacuum deposition, sputtering, plating, or the like.
  • the sheet 12c may be produced by forming a copper thin film or the like as the first electrode layer 24 on the surface of the first protective layer 28 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 12a and/or the sheet 12c.
  • the sheet-like material 12a and the sheet-like material 12c 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 20 is applied onto the second electrode layer 26 of the sheet 12a, and then cured to form the piezoelectric layer 20.
  • a piezoelectric laminate 12b in which the sheet-like material 12a and the piezoelectric layer 20 are laminated is produced.
  • a piezoelectric layer 20 depending on the material forming the piezoelectric layer 20 .
  • a polymer material such as cyanoethylated PVA is dissolved in an organic solvent, and piezoelectric particles 36 such as PZT particles are added and stirred to prepare a coating material.
  • Organic solvents are not limited, and various organic solvents such as dimethylformamide (DMF), methyl ethyl ketone (MEK), and cyclohexanone can be used.
  • the paint is cast (applied) on the sheet-like material 12a and dried by evaporating the organic solvent.
  • a piezoelectric laminate 12b having the second electrode layer 26 on the second protective layer 30 and the piezoelectric layer 20 laminated on the second electrode layer 26 is produced. do.
  • a piezoelectric layered body 12b as shown in FIG. 11 may be produced by extruding a sheet onto the shaped object 12a and cooling it.
  • the matrix 34 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 20 After the piezoelectric layer 20 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 20 of the piezoelectric laminate 12b having the second electrode layer 26 on the second protective layer 30 and the piezoelectric layer 20 formed on the second electrode layer 26 is subjected to a polarization treatment ( polling).
  • the polarization treatment of the piezoelectric layer 20 may be performed before calendering, but is preferably performed after calendering.
  • the method of polarization treatment of the piezoelectric layer 20 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 24 may be formed before the polarization treatment, and the electric field poling treatment may be performed using the first electrode layer 24 and the second electrode layer 26. .
  • the polarization treatment is preferably performed in the thickness direction of the piezoelectric layer 20, not in the plane direction.
  • the previously prepared sheet-like material 12c is laminated on the piezoelectric layer 20 side of the piezoelectric layered body 12b subjected to the polarization treatment, with the first electrode layer 24 facing the piezoelectric layer 20. do.
  • this laminate is thermocompression bonded using a hot press device, a heating roller, etc., with the first protective layer 28 and the second protective layer 30 sandwiched between them, thereby forming the piezoelectric laminate 12b and the sheet-like material 12c. are bonded together to produce a piezoelectric film 10 as shown in FIG.
  • the piezoelectric film 10 may be produced by bonding the piezoelectric laminate 12b and the sheet-like material 12c together using an adhesive and preferably further pressing them together.
  • the piezoelectric film 10 may be manufactured using the cut-sheet-like sheet-like material 12a and the sheet-like material 12c, etc., or may be manufactured using a roll-to-roll process. good too.
  • the produced piezoelectric film may be cut into a desired shape according to various uses.
  • 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 drive voltage is applied.
  • the adhesive layer 14 for attaching the piezoelectric films to each other various known adhesive layers can be used as long as the adjacent piezoelectric films 10 can be attached. Materials similar to the deposition layer 104 can be used.
  • the electroacoustic transducer of the present invention is This is an electroacoustic transducer in which the piezoelectric element described above is attached to a diaphragm.
  • FIG. 13 shows a diagram schematically showing an example of the electroacoustic transducer of the present invention having the piezoelectric element of the present invention.
  • the electroacoustic transducer 100 shown in FIG. 13 has the above-described piezoelectric element 50a, a diaphragm 102, and a bonding layer 104 for bonding the piezoelectric element 50a to the diaphragm 102.
  • the piezoelectric element 50a is attached to the diaphragm 102 on the laminated portion 9 on the side of the piezoelectric element 50a having the projecting portion 10a.
  • the diaphragm 102 has flexibility as a preferred embodiment.
  • 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.
  • Diaphragm 102 is not limited as long as it preferably has flexibility, and various sheet-like materials (plate-like material, film) can be used.
  • sheet-like materials plate-like material, film
  • 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 diaphragm 102 may be an organic electroluminescence (OLED (Organic Light Emitting Diode)) display, a liquid crystal display, 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 a liquid crystal display
  • micro LED Light Emitting Diode
  • display devices such as inorganic electroluminescence displays can also be suitably used.
  • the diaphragm 102 and the piezoelectric element 50 are adhered by the adhesion layer 104 .
  • the adhesive layer 104 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 diaphragm 102 is bent and vibrated to generate sound. Therefore, in the electroacoustic transducer 100 , it is preferable that the expansion and contraction of the piezoelectric element 50 is directly transmitted to the diaphragm 102 . If a substance having a viscosity that reduces vibration is present between the diaphragm 102 and the piezoelectric element 50, the efficiency of transmission of the expansion and contraction energy of the piezoelectric element 50 to the diaphragm 102 is lowered, resulting in electroacoustic conversion. The driving efficiency of the device 100 is lowered.
  • the sticking layer 104 is preferably an adhesive layer made of an adhesive that provides a solid and hard sticking layer 104 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 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 104 is not limited, and the thickness that provides sufficient adhesive strength (adhesive strength, cohesive strength) may be appropriately set according to the material of the adhesive layer 104 .
  • the thinner the adhesive layer 104 the higher the effect of transmitting the stretching energy (vibrational energy) of the piezoelectric element 50 to the diaphragm 102, and the higher the energy efficiency.
  • the adhesive layer 104 is thick and rigid, it may restrict expansion and contraction of the piezoelectric element 50 .
  • the adhesive layer 104 is preferably thinner.
  • the thickness of the adhesive layer 104 is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, and even more preferably 0.1 to 10 ⁇ m after being attached.
  • the adhesive layer 104 is provided as a preferred embodiment and is not an essential component. Therefore, the electroacoustic transducer 100 does not have the adhesive layer 104, and the diaphragm 102 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 102 when a drive voltage is applied from the power supply. is not transmitted to the diaphragm 102. In this way, when the piezoelectric element 50 expands and contracts independently of the diaphragm 102, the efficiency of vibration of the diaphragm 102 by the piezoelectric element 50 decreases. There is a possibility that the diaphragm 102 cannot be sufficiently vibrated. Considering this point, it is preferable that the vibration plate 102 and the piezoelectric element 50 are adhered with an adhesion layer 104 as shown in FIG.
  • the piezoelectric layer 20 contains the piezoelectric particles 36 in the matrix 34 .
  • a second electrode layer 26 and a first electrode layer 24 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 102 is attached to the piezoelectric film 10 with an adhesive layer 104 . Therefore, the expansion and contraction of the piezoelectric film 10 bends the diaphragm 102, and as a result, the diaphragm 102 vibrates in the thickness direction. Due to this vibration in the thickness direction, the diaphragm 102 generates sound. That is, the diaphragm 102 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 .
  • the sound pressure level can be improved. If the mass of the piezoelectric film 10 is large, the diaphragm 102 will be bent, which may suppress vibration of the diaphragm 102 during driving. On the other hand, if the mass of the piezoelectric film 10 is small, the resonance frequency will be high, possibly suppressing the vibration of the diaphragm 102 at low frequencies. Considering these points, it is preferable to appropriately adjust the mass of the piezoelectric film 10 according to the spring constant of the diaphragm 102 .
  • a piezoelectric film was produced by the method shown in FIGS. 10 to 12 described above. 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
  • 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 5 ⁇ m.
  • a sheet-like material was prepared by vacuum-depositing a copper thin film with a thickness of 0.3 ⁇ 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 0.3 ⁇ m thick copper-deposited 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. Next, the sheet-like material coated with the paint was dried by heating on a hot plate at 120° C.
  • 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 material obtained by vapor-depositing the same thin film on a PET film was laminated on the piezoelectric laminate that had been subjected to the polarization treatment, with the first electrode layer (copper thin film side) facing the piezoelectric layer.
  • the laminate of the piezoelectric laminate and the sheet-like material is thermocompression bonded at a temperature of 120° C. using a laminator device, thereby adhering and bonding the piezoelectric layer and the first electrode layer.
  • a film was produced.
  • Example 1 The produced piezoelectric film was cut into a size of 170 mm x 150 mm, folded four times in the direction of the 170 mm side, and the piezoelectric films were laminated with an adhesive layer (acrylic adhesive) to form a laminated portion of length Lb 30 mm x width Wb 150 mm, A piezoelectric element having a protruding portion with a length La of 9 mm and a width of Wa of 150 mm was produced. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.3. The length Ya of the side where the projecting portion and the laminated portion are in contact is 150 mm. Ten such piezoelectric elements were produced.
  • Example 2 Ten piezoelectric elements were produced in the same manner as in Example 1, except that there were 12 protrusions each having a length La of 11 mm and a width of Wa 10 mm (see FIG. 8). The ratio Ps of the (total) area Sa of the protrusions to the area Sb of the laminated part is 0.29. The length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm. In addition, the first electrode layer and the second electrode layer were connected to the external power source at each of the plurality of projecting portions.
  • Example 3 Ten piezoelectric elements were produced in the same manner as in Example 1, except that 14 projecting portions each having a length La of 9.5 mm and a width of Wa of 10 mm were provided.
  • the ratio Ps of the (total) area Sa of the protrusions to the area Sb of the laminated part is 0.30.
  • the length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm.
  • the first electrode layer and the second electrode layer were connected to the external power source at each of the plurality of projecting portions.
  • Example 4 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 37 mm and a width of Wa of 37 mm was provided. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.30. The length Ya of the side where the projecting portion and the laminated portion are in contact is 37 mm.
  • Example 5 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one hexagonal protrusion with a side length of 22.5 mm was provided (see FIG. 6). A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.29. The length Ya of the side where the projecting portion and the laminated portion are in contact is 22.5 cm.
  • Example 6 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 60 mm and a width of Wa 4 mm was provided. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.05. The length Ya of the side where the projecting portion and the laminated portion are in contact is 4 mm.
  • Example 7 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 4 mm and a width of Wa of 25 mm was provided. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.02. The length Ya of the side where the projecting portion and the laminated portion are in contact is 25 mm.
  • Example 1 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 10 mm and a width of Wa of 150 mm was provided. The ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.33. The length Ya of the side where the projecting portion and the laminated portion are in contact is 150 mm.
  • Example 2 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 70 mm and a width of Wa 3 mm was provided. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.05. Moreover, the length Ya of the side where the projecting portion and the laminated portion are in contact is 3 mm.
  • Example 3 Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 4 mm and a width of Wa 10 mm was provided. A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.01. The length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm.
  • An electroacoustic transducer was produced by attaching the surface of the produced piezoelectric element opposite to the projecting portion to a diaphragm.
  • a diaphragm a plate member having a size of 500 mm ⁇ 450 mm, a thickness of 0.8 mm, and material: aluminum (A5052) was used.
  • the horizontal direction of the diaphragm and the longitudinal direction of the piezoelectric element were matched, and the center of the laminated part of the piezoelectric element was aligned with the center of the diaphragm and attached.
  • An acrylic pressure-sensitive adhesive was used as a bonding layer for bonding the piezoelectric element and the diaphragm.
  • a sine sweep signal with a frequency of 1 kHz to 20 kHz and an applied voltage of 50 Vrms was inputted to the piezoelectric element, and the sound pressure was measured with a microphone placed at a distance of 1 m from the center of the diaphragm.
  • the above measurement was performed on 10 specimens, and the difference between the maximum and minimum values of sound pressure at 15 kHz was taken as the sound pressure variation.
  • a sound pressure variation of less than 7 dB satisfies the desired characteristics.
  • 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,

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Abstract

Provided are a piezoelectric element and an electro-acoustic converter which are capable of suppressing sound pressure variability while suppressing heat generation, the piezoelectric element being formed by stacking a piezoelectric film. The piezoelectric element is formed by stacking a plurality of layers of the piezoelectric film, which comprises a piezoelectric layer, electrode layers provided on both surfaces of the piezoelectric layer, and protective layers provided on the electrode layers, by folding back the piezoelectric film one or more times, wherein: in a plan view, the piezoelectric element includes a projecting portion which projects from a stacked portion in which two or more layers of the piezoelectric film overlap one another; the projecting portion has a connecting portion for connecting the electrode layer and an external power source; a ratio of the surface area of the projecting portion to the surface area of the stacked portion lies within a range of 0.02 to 0.3; and a length of an edge where the projecting portion and the stacked portion are in contact with one another is equal to or greater than 4 mm.

Description

圧電素子および電気音響変換器Piezoelectric elements and electroacoustic transducers
 本発明は、圧電素子および電気音響変換器に関する。 The present invention relates to piezoelectric elements and electroacoustic transducers.
 圧電素子は、各種の物品に接触して取り付けることで、物品を振動させて音を出す、いわゆるエキサイター(励起子)として、各種の用途に利用されている。例えば、画像表示パネル、スクリーン等にエキサイターを取り付けて、これらを振動させることで、スピーカーの代わりに音を出すことができる。 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.
 圧電素子として、圧電体層を電極層および保護層で挟持した圧電フィルムを用いることが提案されている。また、圧電フィルムを複数層積層して圧電素子として用いることも提案されている。 As a piezoelectric element, it has been proposed to use a piezoelectric film in which a piezoelectric layer is sandwiched between electrode layers and protective layers. It is also proposed to laminate a plurality of piezoelectric films and use them as a piezoelectric element.
 例えば、特許文献1には、高分子材料を含む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、前記高分子複合圧電体の両面に形成された電極層とを有し、動的粘弾性測定による周波数1kHzでの損失正接が、50℃超150℃以下の温度範囲に0.1以上となる極大値が存在し、かつ、50℃での値が0.08以上である圧電フィルムが記載されている。また、特許文献1には、圧電フィルムを1回以上折り返して、圧電フィルムを複数層、積層した圧電素子が記載されている。 For example, Patent Document 1 discloses a polymer composite piezoelectric body in which piezoelectric particles are dispersed in a matrix containing a polymer material, and electrode layers formed on both sides of the polymer composite piezoelectric body, The loss tangent at a frequency of 1 kHz by dynamic viscoelasticity measurement has a maximum value of 0.1 or more in the temperature range of more than 50 ° C. and 150 ° C. or less, and the value at 50 ° C. is 0.08 or more. A piezoelectric film is described. Further, Patent Document 1 describes a piezoelectric element in which a piezoelectric film is folded one or more times to laminate a plurality of piezoelectric films.
国際公開第2020/196850号WO2020/196850
 圧電フィルムを折り返してなる圧電素子は、振動板に貼付けて、振動板を振動させることで、振動板から音を発生させる。このような圧電素子の電極層に外部電源を接続するために、圧電フィルムが積層された積層部から面方向に突出する突出部を設けて、この突出部にて電極層に外部電源を接続することが考えられている。圧電素子を駆動させるために突出部に設けられた電極層と外部電源との接続部から電圧を印加すると、突出部で顕著に発熱し、最悪の場合、熱暴走を起こし連続駆動できなくなるおそれがある。このような発熱抑制のためには、突出部の面積は広い方が好ましい。 A piezoelectric element made by folding a piezoelectric film is attached to a diaphragm, and by vibrating the diaphragm, the diaphragm generates sound. In order to connect an external power supply to the electrode layer of such a piezoelectric element, a projection projecting in the plane direction is provided from the laminated part in which the piezoelectric films are laminated, and the external power supply is connected to the electrode layer at this projection. is considered. When a voltage is applied from the connection between the electrode layer provided on the protrusion and the external power supply to drive the piezoelectric element, the protrusion generates significant heat, and in the worst case, thermal runaway may occur, preventing continuous driving. be. In order to suppress such heat generation, it is preferable that the area of the projecting portion is large.
 しかしながら、本発明者らの検討によれば、突出部の面積が広い圧電素子を複数個作製して音圧を測定すると、音圧のばらつき、特に高周波帯域における音圧のばらつきが大きくなる問題が生じることがわかった。 However, according to the studies of the present inventors, when a plurality of piezoelectric elements having a large protrusion area are manufactured and the sound pressure is measured, there is a problem that the variation in the sound pressure, especially in the high frequency band, increases. found to occur.
 本発明の課題は、このような従来技術の問題点を解決することにあり、圧電フィルムを積層してなる圧電素子において、発熱を抑制しつつ、音圧のばらつきを抑制することができる圧電素子および電気音響変換器を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art. A piezoelectric element formed by laminating piezoelectric films is capable of suppressing variations in sound pressure while suppressing heat generation. and to provide an electroacoustic transducer.
 上述した課題を解決するために、本発明は、以下の構成を有する。
 [1] 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と、を有する圧電フィルムを1回以上、折り返すことにより、圧電フィルムを、複数層、積層してなる圧電素子であって、
 平面視において、圧電フィルムが2層以上重なる積層部から突出する突出部を有し、
 突出部は、電極層と外部電源とを接続するための接続部を有し、
 積層部の面積に対する突出部の面積の比率が0.02~0.3の範囲であり、かつ、突出部と積層部とが接する辺の長さが4mm以上である、圧電素子。
 [2] 突出部を複数有し、
 積層部の面積に対する突出部の合計面積の比率が0.02~0.3の範囲であり、
 各突出部と積層部が接する辺の長さが4mm以上である、[1]に記載の圧電素子。
 [3] 突出部の数が12個以下である、[2]に記載の圧電素子。
 [4] 平面視における突出部の形状が矩形状である、[1]~[3]のいずれかに記載の圧電素子。
 [5] 圧電体層は、高分子材料を含むマトリックス中に圧電体粒子を含む高分子複合圧電体からなる、[1]~[4]のいずれかに記載の圧電素子。
 [6] [1]~[5]のいずれかに記載の圧電素子を、振動板に貼り付けてなる、電気音響変換器。
 [7] 圧電素子の、突出部を有する側の面の積層部に、振動板に貼り付けられている、[6]に記載の電気音響変換器。
In order to solve the problems described above, the present invention has the following configurations.
[1] A piezoelectric film having a piezoelectric layer, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers is folded once or more to form a piezoelectric film having a plurality of layers, A piezoelectric element formed by lamination,
In a plan view, the piezoelectric film has a projecting portion projecting from a laminated portion in which two or more layers are stacked,
The protruding part has a connection part for connecting the electrode layer and an external power supply,
A piezoelectric element, wherein the ratio of the area of the projecting portion to the area of the laminated portion is in the range of 0.02 to 0.3, and the length of the side where the projecting portion and the laminated portion are in contact is 4 mm or more.
[2] having a plurality of protrusions,
The ratio of the total area of the projecting portion to the area of the laminated portion is in the range of 0.02 to 0.3,
The piezoelectric element according to [1], wherein the length of the side where each projecting portion and the laminated portion are in contact is 4 mm or more.
[3] The piezoelectric element according to [2], wherein the number of protrusions is 12 or less.
[4] The piezoelectric element according to any one of [1] to [3], wherein the projection has a rectangular shape in plan view.
[5] The piezoelectric element according to any one of [1] to [4], wherein the piezoelectric layer is composed of a polymeric composite piezoelectric body containing piezoelectric particles in a matrix containing a polymeric material.
[6] An electroacoustic transducer comprising the piezoelectric element according to any one of [1] to [5] attached to a diaphragm.
[7] The electroacoustic transducer according to [6], wherein the diaphragm is attached to the laminated portion on the side of the piezoelectric element having the projecting portion.
 本発明によれば、圧電フィルムを積層してなる圧電素子において、発熱を抑制しつつ、音圧のばらつきを抑制することができる圧電素子および電気音響変換器を提供することができる。 According to the present invention, it is possible to provide a piezoelectric element and an electroacoustic transducer that can suppress variations in sound pressure while suppressing heat generation in a piezoelectric element formed by laminating piezoelectric films.
本発明の圧電素子の一例を模式的に示す図である。It is a figure which shows typically an example of the piezoelectric element of this invention. 図1に示す圧電素子の斜視図である。FIG. 2 is a perspective view of the piezoelectric element shown in FIG. 1; 図1に示す圧電素子の平面図である。FIG. 2 is a plan view of the piezoelectric element shown in FIG. 1; 積層部の面積、突出部の面積、および、突出部と積層部とが接する辺の長さについて説明するための図である。FIG. 4 is a diagram for explaining the area of a laminated portion, the area of a protruding portion, and the length of a side where the protruding portion and the laminated portion are in contact; 本発明の圧電素子の他の一例を模式的に示す平面図である。FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention; 本発明の圧電素子の他の一例を模式的に示す平面図である。FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention; 本発明の圧電素子の他の一例を模式的に示す平面図である。FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention; 本発明の圧電素子の他の一例を模式的に示す平面図である。FIG. 4 is a plan view schematically showing another example of the piezoelectric element of the present invention; 圧電フィルムの作製方法の一例を説明するための概念図である。It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. 圧電フィルムの作製方法の一例を説明するための概念図である。It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. 圧電フィルムの作製方法の一例を説明するための概念図である。It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. 圧電フィルムの作製方法の一例を説明するための概念図である。It is a conceptual diagram for explaining an example of a method of manufacturing a piezoelectric film. 本発明の圧電素子を有する本発明の電気音響変換器の一例を模式的に示す図である。1 is a diagram schematically showing an example of an electroacoustic transducer of the present invention having a piezoelectric element of the present invention; FIG.
 以下、本発明の圧電素子および電気音響変換器について、添付の図面に示される好適実施例を基に、詳細に説明する。 The piezoelectric element and electroacoustic transducer of the present invention will be described in detail below based on preferred embodiments shown in the accompanying drawings.
 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限定されるものではない。
 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。
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
[圧電素子]
 本発明の圧電素子は、
 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と、を有する圧電フィルムを1回以上、折り返すことにより、圧電フィルムを、複数層、積層してなる圧電素子であって、
 平面視において、圧電フィルムが2層以上重なる積層部から突出する突出部を有し、
 突出部は、電極層と外部電源とを接続するための接続部を有し、
 積層部の面積に対する突出部の面積の比率が0.02~0.3の範囲であり、かつ、突出部と積層部が接する辺の長さが4mm以上である、圧電素子である。
[Piezoelectric element]
The piezoelectric element of the present invention is
A piezoelectric film having a piezoelectric layer, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers is folded one or more times to laminate a plurality of piezoelectric films. A piezoelectric element that
In a plan view, the piezoelectric film has a projecting portion projecting from a laminated portion in which two or more layers are stacked,
The protruding part has a connection part for connecting the electrode layer and an external power supply,
In the piezoelectric element, the ratio of the area of the projecting portion to the area of the laminated portion is in the range of 0.02 to 0.3, and the length of the side where the projecting portion is in contact with the laminated portion is 4 mm or more.
 図1に、本発明の圧電素子の一例を模式的に表す側面図を示す。図2に、図1の圧電素子の斜視図を示す。図3に、図1の圧電素子の平面図を示す。なお、平面図は、圧電フィルム10を複数層積層した積層方向から見た図である。 FIG. 1 shows a side view schematically showing an example of the piezoelectric element of the present invention. FIG. 2 shows a perspective view of the piezoelectric element of FIG. FIG. 3 shows a plan view of the piezoelectric element of FIG. Note that the plan view is a view of the piezoelectric film 10 laminated in a plurality of layers and viewed from the lamination direction.
 図1~図3に示す圧電素子50aは、矩形状の1枚の圧電フィルム10を、一方向に4回、折り返すことにより、5層の圧電フィルム10を積層したものである。すなわち、この圧電素子50aは、5層の圧電フィルム10を積層した積層圧電素子である。
 図2では、図面を簡略化して、圧電素子50aの構成を明瞭に示すために省略するが、圧電フィルム10は、圧電体層20の両面に電極層を有し、両電極層を覆って、保護層を有するものである。
 また、以下の説明では、圧電フィルム10を折り返す方向(図1中左右方向)を折り返し方向という。
The piezoelectric element 50a shown in FIGS. 1 to 3 is obtained by laminating five layers of the piezoelectric film 10 by folding one rectangular piezoelectric film 10 four times in one direction. That is, this piezoelectric element 50a is a laminated piezoelectric element in which five layers of piezoelectric films 10 are laminated.
2, the piezoelectric film 10 has electrode layers on both sides of the piezoelectric layer 20, covering both electrode layers and It has a protective layer.
Further, in the following description, the direction in which the piezoelectric film 10 is folded back (horizontal direction in FIG. 1) is referred to as the folding direction.
 図1に示すとおり、圧電素子50aは、5層の圧電フィルム10が重なる積層部10bから面方向の外側に突出する突出部10aを有する。すなわち、圧電素子50aは、1枚の圧電フィルム10を4回折り返す際に、図1中、下面側の層から4層は、折り返し方向の長さが略同じ長さになるようにし、最上面側の層となる圧電フィルム10の長さを他の層の圧電フィルム10よりも長くして、折り返し方向の一端が他の層の圧電フィルム10と重ならないようにすることで、突出部10aを設けたものである。 As shown in FIG. 1, the piezoelectric element 50a has a protruding portion 10a that protrudes outward in the plane direction from a laminated portion 10b in which five layers of piezoelectric films 10 are superimposed. That is, when one piezoelectric film 10 is folded back four times, the piezoelectric element 50a is arranged so that the four layers from the bottom side in FIG. By making the length of the piezoelectric film 10, which is the side layer, longer than the piezoelectric films 10 of the other layers so that one end in the folding direction does not overlap the piezoelectric films 10 of the other layers, the projecting portion 10a is formed. It was established.
 積層部10bで隣接する圧電フィルム10の層同士は、粘着層14によって貼着されている。 The layers of the piezoelectric film 10 adjacent to each other in the laminated portion 10b are adhered by the adhesive layer 14.
 本発明において、積層部10bとは、平面視において、すなわち、図1において圧電素子を上方(あるいは下方)から見た際に、圧電フィルムが2層以上重なる領域である。すなわち、図3に示すように、圧電フィルム10の層が5層重なる領域が、積層部10bである。 In the present invention, the laminated portion 10b is a region in which two or more layers of piezoelectric films overlap in plan view, ie, when the piezoelectric element is viewed from above (or below) in FIG. That is, as shown in FIG. 3, the area where five layers of the piezoelectric film 10 overlap is the laminated portion 10b.
 一方、突出部10aとは、積層部10bから面方向に突出する領域であり、平面視において、他の層と重なっていない領域である。図1に示す例では、図中、最上層の右側端部が突出部10aである。 On the other hand, the protruding portion 10a is a region that protrudes in the plane direction from the laminated portion 10b, and is a region that does not overlap with other layers in plan view. In the example shown in FIG. 1, the right end of the uppermost layer is the projecting portion 10a.
 図3に示すように、突出部10aには、第1電極層24および第2電極層26(以下、まとめて、電極層ともいう)と、外部電極とを接続するための接続部40が形成されている。図示例においては、突出部10aの保護層(第1保護層28および第2保護層30)に貫通孔を形成して、電極層を露出させて、接続部40を設けている。貫通孔の形成方法には、制限はなく、保護層の形成材料に応じて、レーザー加工、溶剤を用いた溶解除去、および、機械研磨等の機械的な加工等の公知の方法で行えばよい。 As shown in FIG. 3, the projecting portion 10a is formed with a connection portion 40 for connecting the first electrode layer 24 and the second electrode layer 26 (hereinafter collectively referred to as electrode layers) to an external electrode. It is In the illustrated example, through holes are formed in the protective layers (the first protective layer 28 and the second protective layer 30) of the protrusion 10a to expose the electrode layer and provide the connecting section 40. As shown in FIG. The method for forming the through-holes is not limited, and known methods such as laser processing, removal by dissolution using a solvent, and mechanical processing such as mechanical polishing may be used depending on the material for forming the protective layer. .
 接続部40には、銀ペーストなどの導電性金属ペースト、導電性カーボンペースト、および、導電性ナノインク等の公知の導電性材料を充填して外部電源に接続される配線が接続される。
 なお、突出部10aにおける電極と配線との接続方法には、制限はなく、公知の各種の方法が利用可能である。
The connecting portion 40 is connected to a wiring that is filled with a known conductive material such as a conductive metal paste such as silver paste, a conductive carbon paste, and a conductive nanoink and is connected to an external power supply.
There is no limitation on the method of connecting the electrode and the wiring in the protruding portion 10a, and various known methods can be used.
 本発明の圧電素子50aは、突出部10aに設けられた接続部40を介して外部電源を用いて電極層に電圧を印加することで、圧電素子50aを駆動させる。圧電素子50aが駆動されると、圧電素子50aが面方向に伸縮し、圧電素子50aが貼着された振動板を撓ませて、結果として振動板を振動させて音を発生させる。振動板は、圧電素子50aに印加した駆動電圧の大きさに応じて振動して、圧電素子50aに印加した駆動電圧に応じた音を発生する。
 すなわち、圧電素子50aは、エキサイターとして用いることができる。
The piezoelectric element 50a of the present invention drives the piezoelectric element 50a by applying a voltage to the electrode layer using an external power source via the connecting portion 40 provided on the projecting portion 10a. When the piezoelectric element 50a is driven, the piezoelectric element 50a expands and contracts in the plane direction, bending the diaphragm to which the piezoelectric element 50a is attached, and as a result vibrating the diaphragm to generate sound. The diaphragm vibrates according to the magnitude of the driving voltage applied to the piezoelectric element 50a, and generates sound according to the driving voltage applied to the piezoelectric element 50a.
That is, the piezoelectric element 50a can be used as an exciter.
 ここで、前述のとおり、圧電素子50aを駆動させるために突出部10aに設けられた電極層と外部電源との接続部40から電圧を印加すると、突出部10aで顕著に発熱し、最悪の場合、熱暴走を起こし連続駆動できなくなるおそれがある。このような発熱抑制のためには、突出部10aの面積は広い方が好ましい。 Here, as described above, when a voltage is applied from the connecting portion 40 between the electrode layer provided on the protruding portion 10a and the external power supply to drive the piezoelectric element 50a, the protruding portion 10a generates heat remarkably. , thermal runaway may occur and continuous drive may not be possible. In order to suppress such heat generation, it is preferable that the area of the projecting portion 10a is large.
 しかしながら、本発明者らの検討によれば、突出部10aの面積が広い圧電素子50aを複数個作製して音圧を測定すると、音圧のばらつき、特に高周波帯域における音圧のばらつきが大きくなる問題が生じることがわかった。 However, according to the studies of the present inventors, when a plurality of piezoelectric elements 50a having a large area of the projecting portion 10a are manufactured and the sound pressure is measured, the variation in the sound pressure, especially in the high frequency band, becomes large. It turned out to be a problem.
 これに対して、本発明の圧電素子50aは、積層部10bの面積Sbに対する突出部10aの面積Saの比率Ps(=Sa/Sb)が0.02~0.3の範囲であり、かつ、突出部10aと積層部10bが接する辺の長さYaが4mm以上である。 On the other hand, in the piezoelectric element 50a of the present invention, the ratio Ps (=Sa/Sb) of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is in the range of 0.02 to 0.3, and The length Ya of the side where the projecting portion 10a and the laminated portion 10b are in contact is 4 mm or more.
 積層部10bの面積Sbに対する突出部10aの面積Saの比率Psが小さすぎると、すなわち、突出部10aの面積Saが小さすぎると、圧電素子50aに電圧を印加した際に、突出部10aで電流密度が高くなってしまう。そのため、突出部10aで顕著に発熱してしまう。また、突出部10aと積層部10bが接する辺の長さYaが短かすぎると、やはり、突出部10aで電流密度が高くなってしまい、突出部10aで顕著に発熱してしまう。 If the ratio Ps of the area Sa of the protruding portion 10a to the area Sb of the laminated portion 10b is too small, that is, if the area Sa of the protruding portion 10a is too small, when a voltage is applied to the piezoelectric element 50a, a current is generated in the protruding portion 10a. Density increases. Therefore, the protruding portion 10a generates heat remarkably. Also, if the length Ya of the side where the projecting portion 10a and the laminated portion 10b contact each other is too short, the current density at the projecting portion 10a also becomes high, resulting in significant heat generation at the projecting portion 10a.
 これに対して、本発明の圧電素子は、積層部10bの面積Sbに対する突出部10aの面積Saの比率Psを0.02以上とすることにより、すなわち、突出部10aの面積Saを大きくすることにより、突出部10aで電流密度が高くなることを抑制して、突出部10aの発熱を抑制することができる。また、突出部10aと積層部10bが接する辺の長さYaを4mm以上とすることにより、突出部10aで電流密度が高くなることを抑制して、突出部10aの発熱を抑制することができる。 On the other hand, in the piezoelectric element of the present invention, the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is set to 0.02 or more, that is, the area Sa of the projecting portion 10a is increased. Accordingly, it is possible to suppress an increase in current density in the protruding portion 10a, thereby suppressing heat generation of the protruding portion 10a. Further, by setting the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact with each other to 4 mm or more, it is possible to suppress an increase in the current density in the protruding portion 10a and suppress the heat generation of the protruding portion 10a. .
 一方で、積層部10bの面積Sbに対する突出部10aの面積Saの比率Psが大きすぎると、すなわち、突出部10aの面積Saが大きすぎると、同じ仕様の圧電素子50aを複数個作製した際に、音圧のばらつき、特に高周波帯域における音圧のばらつきが大きくなる問題が生じることがわかった。この点について、突出部10aを有する場合には、圧電素子50aを駆動した際に、突出部10aも振動して音を発生してしまうが、複数の圧電素子間で、突出部10aの形状のばらつき、反り状態のばらつき等があるため、突出部10aから発生する音圧にばらつきが生じるものと推定される。突出部10aの大きさは、圧電素子50aが貼着される振動板よりも小さいため、この突出部10aから発生する音圧のばらつきは、特に、高周波帯域で影響が大きくなる。 On the other hand, if the ratio Ps of the area Sa of the protruding portion 10a to the area Sb of the laminated portion 10b is too large, that is, if the area Sa of the protruding portion 10a is too large, when a plurality of piezoelectric elements 50a having the same specifications are manufactured, , there is a problem that the variation of the sound pressure, especially in the high frequency band, becomes large. Regarding this point, when the protrusion 10a is provided, when the piezoelectric element 50a is driven, the protrusion 10a also vibrates and generates a sound. It is presumed that the sound pressure generated from the protruding portion 10a varies due to variations, variations in the state of warping, and the like. Since the size of the projecting portion 10a is smaller than the diaphragm to which the piezoelectric element 50a is adhered, the variation in sound pressure generated from the projecting portion 10a has a greater effect especially in a high frequency band.
 これに対して、本発明の圧電素子は、積層部10bの面積Sbに対する突出部10aの面積Saの比率Psを0.3以下とすることにより、すなわち、突出部10aの面積Saを小さくすることにより、突出部10aの形状のばらつき、反り状態のばらつき等を小さくすることができ、音圧のばらつきを小さくすることができる。 In contrast, in the piezoelectric element of the present invention, the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is 0.3 or less, that is, the area Sa of the projecting portion 10a is reduced. Therefore, variations in the shape of the projecting portion 10a, variations in the state of warping, etc. can be reduced, and variations in sound pressure can be reduced.
 突出部10aの発熱を抑制する観点から、突出部10aと積層部10bが接する辺の長さYaは、4mm以上が好ましく、10mm以上がより好ましく、20mm以上がさらに好ましい。 From the viewpoint of suppressing heat generation of the protruding portion 10a, the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact is preferably 4 mm or longer, more preferably 10 mm or longer, and even more preferably 20 mm or longer.
 また、突出部10aの発熱を抑制する観点から、積層部10bの面積Sbに対する突出部10aの面積Saの比率Psは、0.02以上が好ましく、0.04以上がより好ましく、0.06以上がさらに好ましい。 From the viewpoint of suppressing heat generation of the projecting portion 10a, the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is preferably 0.02 or more, more preferably 0.04 or more, and 0.06 or more. is more preferred.
 また、音圧のばらつきを抑制する観点から、積層部10bの面積Sbに対する突出部10aの面積Saの比率Psは、0.3以下が好ましく、0.2以下がより好ましく、0.1以下がさらに好ましい。 Further, from the viewpoint of suppressing variations in sound pressure, the ratio Ps of the area Sa of the projecting portion 10a to the area Sb of the laminated portion 10b is preferably 0.3 or less, more preferably 0.2 or less, and 0.1 or less. More preferred.
 図4を用いて図1~図3に示す圧電素子50aの積層部10bの面積Sb、突出部10aの面積Sa、および、突出部と積層部が接する辺の長さYaについて説明する。図4は、圧電素子50aの平面図である。
 積層部10bの面積Sb、および、突出部10aの面積Saは、平面視における面積である。図4に示すように、平面視における積層部10bの折り返し方向の長さをLb、折り返し方向と直交する方向の幅をWbとすると、積層部10bの面積Sbは、Lb×Wbである。また、突出部10aの折り返し方向の長さをLa、折り返し方向と直交する方向の幅をWaとすると、突出部10aの面積Saは、La×Waである。図4に示す例では、突出部10aの幅Waと積層部10bの幅Wbは同じである。
The area Sb of the laminated portion 10b of the piezoelectric element 50a shown in FIGS. 1 to 3, the area Sa of the projecting portion 10a, and the length Ya of the side where the projecting portion contacts the laminated portion will be described with reference to FIG. FIG. 4 is a plan view of the piezoelectric element 50a.
The area Sb of the laminated portion 10b and the area Sa of the projecting portion 10a are the areas in plan view. As shown in FIG. 4, the area Sb of the laminated portion 10b is Lb×Wb, where Lb is the length in the folded direction of the laminated portion 10b in plan view, and Wb is the width in the direction orthogonal to the folded direction. If La is the length of the projection 10a in the folding direction, and Wa is the width in the direction perpendicular to the folding direction, then the area Sa of the projection 10a is La×Wa. In the example shown in FIG. 4, the width Wa of the projecting portion 10a and the width Wb of the laminated portion 10b are the same.
 また、図4に示す例では、突出部10aと積層部10bとが接する辺の長さYaは、突出部10aの幅Wa(積層部10bの幅Wb)と同じである。 In addition, in the example shown in FIG. 4, the length Ya of the side where the protruding portion 10a and the laminated portion 10b are in contact is the same as the width Wa of the protruding portion 10a (the width Wb of the laminated portion 10b).
 ここで、図1~図4に示す例では、突出部10aの幅Waが、積層部10bの幅Wbと略同じ構成としたが、これに限定はされない。 Here, in the examples shown in FIGS. 1 to 4, the width Wa of the protruding portion 10a is substantially the same as the width Wb of the laminated portion 10b, but it is not limited to this.
 図5に本発明の圧電素子の他の一例の平面図を示す。
 図5に示す圧電素子50bは、矩形状の積層部10bと矩形状の突出部10aとを有し、突出部10aの幅Waが積層部10bの幅Wbよりも短い。したがって、突出部10aと積層部10bとが接する辺の長さYaは、突出部10aの幅Waと同じである。
FIG. 5 shows a plan view of another example of the piezoelectric element of the present invention.
A piezoelectric element 50b shown in FIG. 5 has a rectangular laminated portion 10b and a rectangular protruding portion 10a, and the width Wa of the protruding portion 10a is shorter than the width Wb of the laminated portion 10b. Therefore, the length Ya of the side where the protruding portion 10a and the laminated portion 10b contact is the same as the width Wa of the protruding portion 10a.
 なお、図5に示す例では、突出部10aは、積層部10bの幅方向の略中央に配置される構成としたがこれに限定はされず、積層部10bの幅方向のいずれの位置に配置されてもよい。 In the example shown in FIG. 5, the protruding portion 10a is arranged substantially in the center in the width direction of the laminated portion 10b, but is not limited to this, and is arranged at any position in the width direction of the laminated portion 10b. may be
 また、図5に示す例では、突出部10aは略正方形状としたがこれに限定はされず長方形状であってもよい。その際、突出部10aの幅方向が長方形の長辺であってもよいし、突出部10aの長さ方向(折り返し方向)が長方形の長辺であってもよい。 In addition, in the example shown in FIG. 5, the projecting portion 10a has a substantially square shape, but is not limited to this and may have a rectangular shape. In this case, the width direction of the projecting portion 10a may be the long side of the rectangle, or the length direction (folding direction) of the projecting portion 10a may be the long side of the rectangle.
 また、突出部10aの形状は矩形状に限定はされない。例えば、図6に示す圧電素子50cの突出部10aのように、六角形状等の多角形状であってもよいし、あるいは、略円形状、半円形状、楕円形状、および、不定形状等種々の形状であってもよい。 Also, the shape of the projecting portion 10a is not limited to a rectangular shape. For example, like the projecting portion 10a of the piezoelectric element 50c shown in FIG. 6, it may have a polygonal shape such as a hexagonal shape. It may be in shape.
 また、図1等に示す例では、突出部10aは、積層部10bから折り返し方向に突出するように設けられる構成としたがこれに限定はされない。図7に示す圧電素子50dのように、突出部10aは、折り返し方向と直交する幅方向に積層部10bから突出するように設けられる構成としてもよい。図7に示す例のように、突出部10aが矩形状の場合には、突出部10aの折り返し方向の長さLaが、突出部と積層部とが接する辺の長さYaに等しい。 Also, in the example shown in FIG. 1 and the like, the protruding portion 10a is configured to protrude from the laminated portion 10b in the folding direction, but the present invention is not limited to this. Like the piezoelectric element 50d shown in FIG. 7, the protruding portion 10a may be configured to protrude from the laminated portion 10b in the width direction orthogonal to the folding direction. When the projecting portion 10a has a rectangular shape as in the example shown in FIG. 7, the length La of the projecting portion 10a in the folding direction is equal to the length Ya of the side where the projecting portion and the laminated portion are in contact with each other.
 また、図1等に示す例では、圧電素子は1つの突出部を有する構成としたがこれに限定はされない。 Also, in the example shown in FIG. 1 and the like, the piezoelectric element is configured to have one projecting portion, but the configuration is not limited to this.
 図8に本発明の圧電素子の他の一例の平面図を示す。
 図8に示す圧電素子50eは、矩形状の積層部10bと、積層部10bの一辺側に配列される複数の矩形状の突出部10aとを有する。図示は省略するが、各突出部10aには、第1電極層24および/または第2電極層26と、外部電極とを接続するための接続部40が形成される。1つの突出部10aにおいて、第1電極層24および第2電極層26のいずれか一方が外部電極と接続される構成であってもよいが、電流密度を小さくして、発熱を抑制する観点から、1つの突出部10aにおいて、第1電極層24および第2電極層26の両方が外部電極と接続される構成であるのが好ましい。すなわち、複数の突出部10aのそれぞれにおいて、第1電極層24および第2電極層26の両方が外部電極と接続されるのが好ましい。
FIG. 8 shows a plan view of another example of the piezoelectric element of the present invention.
A piezoelectric element 50e shown in FIG. 8 has a rectangular laminated portion 10b and a plurality of rectangular protruding portions 10a arranged on one side of the laminated portion 10b. Although illustration is omitted, a connecting portion 40 for connecting the first electrode layer 24 and/or the second electrode layer 26 to an external electrode is formed on each projecting portion 10a. Either one of the first electrode layer 24 and the second electrode layer 26 may be connected to an external electrode in one projecting portion 10a. It is preferable that both the first electrode layer 24 and the second electrode layer 26 are connected to the external electrode in one projecting portion 10a. That is, it is preferable that both the first electrode layer 24 and the second electrode layer 26 are connected to the external electrode in each of the plurality of protrusions 10a.
 複数の突出部10aを有する構成の場合には、突出部10aの面積Saは、複数の突出部10aの合計面積である。すなわち、積層部10bの面積に対する、複数の突出部10aの合計面積の比率が、0.02~0.3の範囲であればよい。 In the case of a configuration having a plurality of protrusions 10a, the area Sa of the protrusions 10a is the total area of the plurality of protrusions 10a. That is, the ratio of the total area of the plurality of projecting portions 10a to the area of the laminated portion 10b should be in the range of 0.02 to 0.3.
 また、突出部10aと積層部10bとが接する辺の長さYaは、各突出部10aにおける、積層部10bと接する辺の長さYaである。したがって、各突出部10aにおいて、積層部10bと接する辺の長さYaが4mm以上であればよい。 Also, the length Ya of the side where the protruding portion 10a and the laminated portion 10b contact is the length Ya of the side of each protruding portion 10a that contacts the laminated portion 10b. Therefore, in each projecting portion 10a, the length Ya of the side in contact with the laminated portion 10b should be 4 mm or more.
 圧電素子が複数の突出部10aを有する構成の場合に、突出部10aの数が多すぎると、音が発生する箇所が増えて、音圧のばらつきが大きくなるおそれがある。そのため、突出部10aの数は、12個以下であることが好ましく、10個以下がより好ましい。 In the case where the piezoelectric element has a plurality of projecting portions 10a, if the number of projecting portions 10a is too large, the number of locations where sound is generated increases, and there is a risk that the sound pressure will vary greatly. Therefore, the number of protrusions 10a is preferably 12 or less, more preferably 10 or less.
 また、図1に示す圧電素子50aは、圧電フィルム10を、5層、積層したものであるが、本発明は、これに制限はされない。すなわち、圧電素子は、圧電フィルム10を、2層~4層有するものであってもよく、あるいは、6層以上であってもよい。 The piezoelectric element 50a shown in FIG. 1 is formed by laminating five layers of piezoelectric films 10, but the present invention is not limited to this. That is, the piezoelectric element may have two to four layers of the piezoelectric film 10, or may have six or more layers.
 以下、本発明の圧電素子の構成要素について説明する。なお、以下の説明において、区別する必要がない場合には、圧電素子50a~50eをまとめて圧電素子50ともいう。 The constituent elements of the piezoelectric element of the present invention will be described below. In the following description, the piezoelectric elements 50a to 50e are collectively referred to as the piezoelectric element 50 when there is no need to distinguish them.
 図9に、圧電フィルム10の一部を拡大して示す。
 図9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第2電極層26と、第2電極層26の圧電体層20と反対側の面に積層される第2保護層30と、圧電体層20の他方の面に積層される第1電極層24と、第1電極層24の圧電体層20と反対側の面に積層される第1保護層28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。
FIG. 9 shows an enlarged view of a portion of the piezoelectric film 10. As shown in FIG.
The piezoelectric film 10 shown in FIG. 9 includes a piezoelectric layer 20 that is a sheet-like material having piezoelectricity, a second electrode layer 26 that is laminated on one surface of the piezoelectric layer 20 , and a piezoelectric layer of the second electrode layer 26 . A second protective layer 30 laminated on the surface opposite to the body layer 20, a first electrode layer 24 laminated on the other surface of the piezoelectric layer 20, and the first electrode layer 24 opposite to the piezoelectric layer 20. and a first protective layer 28 laminated on the side surface. That is, the piezoelectric film 10 has a configuration in which the piezoelectric layer 20 is sandwiched between electrode layers, and a protective layer is laminated on the surface of the electrode layer that is not in contact with the piezoelectric layer.
 本発明において、圧電体層20は、公知の圧電体層が、各種、利用可能である。
 本発明において、圧電体層20は、図9に概念的に示すように、高分子材料を含むマトリックス34中に、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。
In the present invention, various known piezoelectric layers can be used as the piezoelectric layer 20 .
In the present invention, the piezoelectric layer 20 is preferably a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 containing a polymeric material, as conceptually shown in FIG.
 圧電体層20を構成する高分子複合圧電体のマトリックス34(マトリックス兼バインダ)の材料として、常温で粘弾性を有する高分子材料を用いるのが好ましい。なお、本明細書において、「常温」とは、0~50℃程度の温度域を指す。 As 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. In this specification, "ordinary temperature" refers to a temperature range of about 0 to 50.degree.
 ここで、高分子複合圧電体(圧電体層20)は、次の用件を具備したもの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。
Here, the polymer composite piezoelectric body (piezoelectric layer 20) preferably satisfies the following requirements.
(i) 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.
 以上をまとめると、エキサイターとして用いるフレキシブルな高分子複合圧電体は、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求められる。また、高分子複合圧電体の損失正接は、20kHz以下の全ての周波数の振動に対して、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104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。
In summary, 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. 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.
Furthermore, it is preferable that the spring constant can be easily adjusted by laminating according to the rigidity (hardness, stiffness, spring constant) of the mating material (diaphragm) to which the adhesive layer 104 is attached. The thinner it is, the more energy efficient it can be.
 一般に、高分子固体は粘弾性緩和機構を有しており、温度上昇あるいは周波数の低下とともに大きなスケールの分子運動が貯蔵弾性率(ヤング率)の低下(緩和)あるいは損失弾性率の極大(吸収)として観測される。その中でも、非晶質領域の分子鎖のミクロブラウン運動によって引き起こされる緩和は、主分散と呼ばれ、非常に大きな緩和現象が見られる。この主分散が起きる温度がガラス転移点(Tg)であり、最も粘弾性緩和機構が顕著に現れる。
 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。
In general, 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.
In 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. In particular, it is preferable to use 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.
 常温で粘弾性を有する高分子材料としては、公知の各種のものが利用可能である。好ましくは、常温、すなわち0~50℃において、動的粘弾性試験による周波数1Hzにおける損失正接Tanδの極大値が、0.5以上有る高分子材料を用いる。
 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、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。
Various known materials can be used as 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 δ at a frequency of 1 Hz in a dynamic viscoelasticity test at normal temperature, ie, 0 to 50° C., is used.
As a result, when the polymer composite piezoelectric body is slowly bent by an external force, the stress concentration at the interface between the polymer matrix and the piezoelectric particles at the maximum bending moment is relaxed, and high flexibility can be expected.
 また、常温で粘弾性を有する高分子材料は、動的粘弾性測定による周波数1Hzでの貯蔵弾性率(E’)が、0℃において100MPa以上、50℃において10MPa以下、であるのが好ましい。
 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。
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.
As a result, the bending moment generated when the polymeric composite piezoelectric body is slowly bent by an external force can be reduced, and at the same time, it can behave rigidly against acoustic vibrations of 20 Hz to 20 kHz.
 また、常温で粘弾性を有する高分子材料は、比誘電率が25℃において10以上有ると、より好適である。これにより、高分子複合圧電体に電圧を印加した際に、マトリックス中の圧電体粒子にはより高い電界が掛かるため、大きな変形量が期待できる。
 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。
Further, it is more preferable that the polymer material having viscoelasticity at room temperature has a dielectric constant of 10 or more at 25°C. As a result, when 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.
On the other hand, however, 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.
 このような条件を満たす常温で粘弾性を有する高分子材料としては、シアノエチル化ポリビニルアルコール(シアノエチル化PVA)、ポリ酢酸ビニル、ポリビニリデンクロライドコアクリロニトリル、ポリスチレン-ビニルポリイソプレンブロック共重合体、ポリビニルメチルケトン、および、ポリブチルメタクリレート等が例示される。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。なかでも、高分子材料としては,シアノエチル基を有する材料を用いることが好ましく、シアノエチル化PVAを用いるのが特に好ましい。 Examples of polymeric materials having viscoelasticity at room temperature that meet these conditions include cyanoethylated polyvinyl alcohol (cyanoethylated PVA), polyvinyl acetate, polyvinylidene chloride core acrylonitrile, polystyrene-vinylpolyisoprene block copolymer, and polyvinylmethyl. 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. Among them, as the polymer material, it is preferable to use a material having a cyanoethyl group, and it is particularly preferable to use cyanoethylated PVA.
 常温で粘弾性を有する高分子材料としては、シアノエチル基を有する高分子材料を用いるのが好ましく、シアノエチル化PVAを用いるのが特に好ましい。すなわち、本発明において、圧電体層20は、マトリックス34として、シアノエチル基を有する高分子材料を用いるのが好ましく、シアノエチル化PVAを用いるのが特に好ましい。
 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。
As the polymer material having viscoelasticity at room temperature, it is preferable to use a polymer material having a cyanoethyl group, and it is particularly preferable to use cyanoethylated PVA. That is, in the present invention, the piezoelectric layer 20 preferably uses a polymer material having a cyanoethyl group as the matrix 34, and particularly preferably uses cyanoethylated PVA.
In the following description, the above-mentioned polymeric materials represented by cyanoethylated PVA are collectively referred to as "polymeric materials having viscoelasticity at room temperature".
 なお、これらの常温で粘弾性を有する高分子材料は、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。 These polymer materials having viscoelasticity at room temperature may be used alone or in combination (mixed).
 このような常温で粘弾性を有する高分子材料を用いるマトリックス34は、必要に応じて、複数の高分子材料を併用してもよい。
 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。
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.
 添加可能な誘電性高分子材料としては、一例として、ポリフッ化ビニリデン、フッ化ビニリデン-テトラフルオロエチレン共重合体、フッ化ビニリデン-トリフルオロエチレン共重合体、ポリフッ化ビニリデン-トリフルオロエチレン共重合体およびポリフッ化ビニリデン-テトラフルオロエチレン共重合体等のフッ素系高分子、シアン化ビニリデン-酢酸ビニル共重合体、シアノエチルセルロース、シアノエチルヒドロキシサッカロース、シアノエチルヒドロキシセルロース、シアノエチルヒドロキシプルラン、シアノエチルメタクリレート、シアノエチルアクリレート、シアノエチルヒドロキシエチルセルロース、シアノエチルアミロース、シアノエチルヒドロキシプロピルセルロース、シアノエチルジヒドロキシプロピルセルロース、シアノエチルヒドロキシプロピルアミロース、シアノエチルポリアクリルアミド、シアノエチルポリアクリレート、シアノエチルプルラン、シアノエチルポリヒドロキシメチレン、シアノエチルグリシドールプルラン、シアノエチルサッカロースおよびシアノエチルソルビトール等のシアノ基またはシアノエチル基を有するポリマー、ならびに、ニトリルゴムやクロロプレンゴム等の合成ゴム等が例示される。
 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、これらの誘電性高分子材料は、1種に限定はされず、複数種を添加してもよい。
Examples of dielectric polymer materials that can be added include polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, and polyvinylidene fluoride-trifluoroethylene copolymer. and 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, cyanoethylglycidolpullulan, cyanoethylsaccharose and cyanoethylsorbitol. Alternatively, 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.
Moreover, in the matrix 34 of the piezoelectric layer 20, these dielectric polymer materials are not limited to one type, and a plurality of types may be added.
 また、マトリックス34には、誘電性高分子材料以外にも、ガラス転移点Tgを調節する目的で、塩化ビニル樹脂、ポリエチレン、ポリスチレン、メタクリル樹脂、ポリブテン、および、イソブチレン等の熱可塑性樹脂、ならびに、フェノール樹脂、尿素樹脂、メラミン樹脂、アルキド樹脂、および、マイカ等の熱硬化性樹脂を添加しても良い。
 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。
In addition to the dielectric polymer material, the matrix 34 may also include thermoplastic resins such as vinyl chloride resin, polyethylene, polystyrene, methacrylic resin, polybutene, and isobutylene for the purpose of adjusting the glass transition point Tg, and Thermosetting resins such as phenolic resins, urea resins, melamine resins, alkyd resins, and 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.
 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等の粘弾性を有する高分子材料以外の材料を添加する際の添加量には、特に限定は無いが、マトリックス34に占める割合で30質量%以下とするのが好ましい。
 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。
When adding a material other than a polymer material having viscoelasticity, such as cyanoethylated PVA, to the matrix 34 of the piezoelectric layer 20, 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.
As a result, 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
 圧電体層20は、このようなマトリックス34に、圧電体粒子36を含む、高分子複合圧電体からなる層である。圧電体粒子36は、マトリックス34に分散されている。好ましくは、圧電体粒子36は、マトリックス34に均一(略均一)に分散される。
 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。
The piezoelectric layer 20 is a layer made of a polymeric composite piezoelectric material containing piezoelectric particles 36 in such a matrix 34 . Piezoelectric particles 36 are dispersed in the matrix 34 . Preferably, the piezoelectric particles 36 are uniformly (substantially uniformly) dispersed in the 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.
 このような圧電体粒子36の粒径には制限はなく、圧電フィルム10のサイズ、および、圧電素子50の用途等に応じて、適宜、選択すれば良い。圧電体粒子36の粒径は、1~10μmが好ましい。
 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。
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 μm.
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.
 なお、圧電体層20中の圧電体粒子36は、マトリックス34中に、均一かつ規則性を持って分散されていてもよいし、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。 The piezoelectric particles 36 in the piezoelectric layer 20 may be uniformly and regularly dispersed in the matrix 34, or if they are uniformly dispersed, they may be dispersed irregularly in the matrix 34. may have been
 圧電フィルム10において、圧電体層20中におけるマトリックス34と圧電体粒子36との量比には、制限はなく、圧電フィルム10の面方向の大きさおよび厚さ、圧電素子50の用途、ならびに、圧電素子50に要求される特性等に応じて、適宜、設定すればよい。
 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。
In the piezoelectric film 10, 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%.
By setting the amount ratio between the matrix 34 and the piezoelectric particles 36 within the above range, favorable results can be obtained in terms of achieving both high piezoelectric characteristics and flexibility.
 圧電フィルム10において、圧電体層20の厚さには、特に限定はなく、圧電素子50の用途、圧電素子50における圧電フィルムの積層数、圧電フィルム10に要求される特性等に応じて、適宜、設定すればよい。
 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。
In the piezoelectric film 10 , 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 thicker the piezoelectric layer 20 is, the more advantageous it is in terms of rigidity such as stiffness of the so-called sheet-like material, but the voltage (potential difference) required to expand and contract the piezoelectric film 10 by the same amount is increased.
The thickness of the piezoelectric layer 20 is preferably 10 to 300 μm, more preferably 20 to 200 μm, even more preferably 30 to 150 μm.
By setting the thickness of the piezoelectric layer 20 within the above range, favorable results can be obtained in terms of ensuring both rigidity and appropriate flexibility.
 また、圧電体層20は、厚さ方向に分極処理(ポーリング)されているのが好ましい。 Also, the piezoelectric layer 20 is preferably polarized (poled) in the thickness direction.
 なお、本発明において、圧電体層20は、上述したような、シアノエチル化PVAのような常温で粘弾性を有する高分子材料からなるマトリックス34に、圧電体粒子36を含む高分子複合圧電体に制限はされない。
 すなわち、本発明の圧電フィルム10において、圧電体層は、公知の圧電体層が、各種、利用可能である。
In the present invention, the piezoelectric layer 20 is a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 made of a polymer material having viscoelasticity at room temperature, such as cyanoethylated PVA, as described above. No restrictions.
That is, in the piezoelectric film 10 of the present invention, various known piezoelectric layers can be used as the piezoelectric layer.
 一例として、上述したポリフッ化ビニリデン、フッ化ビニリデン-テトラフルオロエチレン共重合体およびフッ化ビニリデン-トリフルオロエチレン共重合体等の誘電性高分子材料を含むマトリックスに同様の圧電体粒子36を含む高分子複合圧電体、ポリフッ化ビニリデンからなる圧電体層、ポリフッ化ビニリデン以外のフッ素樹脂からなる圧電体層、および、ポリL乳酸からなるフィルムとポリD乳酸からなるフィルムとを積層した圧電体層等も利用可能である。
 しかしながら、上述のように、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ことができ、優れた音響特性が得られる、可撓性に優れる等の点で、上述したシアノエチル化PVAのような常温で粘弾性を有する高分子材料からなるマトリックス34に、圧電体粒子36を含む高分子複合圧電体が、好適に利用される。
As an example, a high-performance dielectric material containing similar piezoelectric particles 36 in a matrix containing a dielectric polymer material such as the polyvinylidene fluoride, vinylidene fluoride-tetrafluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer described above may be used. Molecular composite piezoelectric material, piezoelectric layer made of polyvinylidene fluoride, piezoelectric layer made of fluorine resin other than polyvinylidene fluoride, piezoelectric layer made by laminating a film made of poly-L-lactic acid and a film made of poly-D-lactic acid, etc. is also available.
However, as described above, it is hard against vibrations of 20 Hz to 20 kHz, and can behave softly against slow vibrations of several Hz or less, and has excellent acoustic characteristics and excellent flexibility. Therefore, a polymeric composite piezoelectric body containing piezoelectric particles 36 in a matrix 34 made of a polymeric material having viscoelasticity at room temperature, such as the cyanoethylated PVA described above, is preferably used.
 図9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、第2電極層26を有し、その上に第2保護層30を有し、圧電体層20の他方の面に、第1電極層24を有し、その上に第1保護層28を有してなる構成を有する。ここで、第1電極層24と第2電極層26とが電極対を形成する。 As shown in FIG. 9, the piezoelectric film 10 has a second electrode layer 26 on one surface of the piezoelectric layer 20, and a second protective layer 30 thereon. has a first electrode layer 24 on the surface thereof, and a first protective layer 28 thereon. Here, the first electrode layer 24 and the second electrode layer 26 form an electrode pair.
 すなわち、圧電フィルム10は、圧電体層20の両面を電極対、すなわち、第2電極層26および第1電極層24で挟持し、この積層体を、第2保護層30および第1保護層28で挟持してなる構成を有する。
 このように、圧電フィルム10において、第2電極層26および第1電極層24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、第2電極層26および第2保護層30、ならびに、第1電極層24および第1保護層28は、圧電フィルム10を説明するために、便宜的に付しているものである。従って、本発明における第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。
That is, in the piezoelectric film 10 , both surfaces of the piezoelectric layer 20 are sandwiched between electrode pairs, that is, the second electrode layer 26 and the first electrode layer 24 , and this laminate is formed into the second protective layer 30 and the first protective layer 28 . It has a configuration sandwiched between.
Thus, in the piezoelectric film 10, the region sandwiched between the second electrode layer 26 and the first electrode layer 24 expands and contracts according to the applied voltage.
The second electrode layer 26 and the second protective layer 30 as well as the first electrode layer 24 and the first protective layer 28 are attached for the sake of convenience in describing the piezoelectric film 10 . Therefore, the first and second aspects of the present invention have no technical significance and are irrelevant to the actual usage conditions.
 本発明において圧電フィルム10は、これらの層に加えて、例えば、電極層と圧電体層20とを貼着するための貼着層、および、電極層と保護層とを貼着するための貼着層を有してもよい。
 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20から圧電体粒子36を除いた高分子材料すなわちマトリックス34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24側および第2電極層26側の両方に有してもよく、第1電極層24側および第2電極層26側の一方のみに有してもよい。
In the present invention, the piezoelectric film 10 includes, in addition to these layers, an adhesive layer for attaching the electrode layer and the piezoelectric layer 20 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 34, that is, the polymer material obtained by removing the piezoelectric particles 36 from the piezoelectric layer 20, can be preferably used as the adhesive. The adhesive layer may be provided on both the first electrode layer 24 side and the second electrode layer 26 side, or may be provided on only one of the first electrode layer 24 side and the second electrode layer 26 side. good.
 圧電フィルム10において、第2保護層30および第1保護層28は、第1電極層24および第2電極層26を被覆すると共に、圧電体層20に適度な剛性と機械的強度を付与する役目を担っている。すなわち、圧電フィルム10において、マトリックス34と圧電体粒子36とからなる圧電体層20は、ゆっくりとした曲げ変形に対しては、非常に優れた可撓性を示す一方で、用途によっては、剛性や機械的強度が不足する場合がある。圧電フィルム10は、それを補うために第2保護層30および第1保護層28が設けられる。
 第1保護層28と第2保護層30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28および第2保護層30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。
In the piezoelectric film 10, the second protective layer 30 and the first protective layer 28 cover the first electrode layer 24 and the second electrode layer 26, and provide the piezoelectric layer 20 with appropriate rigidity and mechanical strength. is responsible for 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 second protective layer 30 and a first protective layer 28 to compensate.
The first protective layer 28 and the second protective layer 30 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 28 and the second protective layer 30, both members are collectively referred to as protective layers.
 第2保護層30および第1保護層28には、制限はなく、各種のシート状物が利用可能であり、一例として、各種の樹脂フィルムが好適に例示される。
 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。
Various sheet materials can be used for the second protective layer 30 and the first protective layer 28 without limitation, and various resin films are preferably exemplified as 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), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), cyclic olefin resins, and the like are preferably used.
 第2保護層30および第1保護層28の厚さにも、制限はない。また、第2保護層30および第1保護層28の厚さは、基本的に同じであるが、異なってもよい。
 ここで、第2保護層30および第1保護層28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、第2保護層30および第1保護層28は、薄いほど有利である。
The thicknesses of the second protective layer 30 and the first protective layer 28 are also not limited. Also, the thicknesses of the second protective layer 30 and the first protective layer 28 are basically the same, but may be different.
Here, if the rigidity of the second protective layer 30 and the first protective layer 28 is too high, not only will the expansion and contraction of the piezoelectric layer 20 be constrained, but also the flexibility will be impaired. Therefore, the thinner the second protective layer 30 and the first protective layer 28, the better, except when mechanical strength and good handling properties as a sheet-like article are required.
 圧電フィルム10においては、第2保護層30および第1保護層28の厚さが、圧電体層20の厚さの2倍以下であれば、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。
 例えば、圧電体層20の厚さが50μmで第2保護層30および第1保護層28がPETからなる場合、第2保護層30および第1保護層28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。
In the piezoelectric film 10, if the thicknesses of the second protective layer 30 and the first protective layer 28 are not more than twice the thickness of the piezoelectric layer 20, it is possible to ensure both rigidity and appropriate flexibility. favorable results can be obtained.
For example, when the thickness of the piezoelectric layer 20 is 50 μm and the second protective layer 30 and the first protective layer 28 are made of PET, the thicknesses of the second protective layer 30 and the first protective layer 28 are preferably 100 μm or less. 50 μm or less is more preferable, and 25 μm or less is even more preferable.
 圧電フィルム10において、圧電体層20と第2保護層30との間には第2電極層26が、圧電体層20と第1保護層28との間には第1電極層24が、それぞれ形成される。 第2電極層26および第1電極層24は、圧電体層20(圧電フィルム10)に電圧を印加するために設けられる。 In the piezoelectric film 10, the second electrode layer 26 is provided between the piezoelectric layer 20 and the second protective layer 30, and the first electrode layer 24 is provided between the piezoelectric layer 20 and the first protective layer 28. It is formed. The second electrode layer 26 and the first electrode layer 24 are provided for applying voltage to the piezoelectric layer 20 (piezoelectric film 10).
 第1電極層24および第2電極層26は、位置が異なる以外は、基本的に同じものである。従って、以下の説明においては、第1電極層24および第2電極層26を区別する必要がない場合には、両部材をまとめて、電極層ともいう。 The first electrode layer 24 and the second electrode layer 26 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 24 and the second electrode layer 26, both members are collectively referred to as electrode layers.
 本発明において、第2電極層26および第1電極層24の形成材料には制限はなく、各種の導電体が利用可能である。具体的には、炭素、パラジウム、鉄、錫、アルミニウム、ニッケル、白金、金、銀、銅、チタン、クロムおよびモリブデン等の金属、これらの合金、これらの金属および合金の積層体および複合体、ならびに、酸化インジウムスズ等が例示される。あるいは、PEDOT/PPS(ポリエチレンジオキシチオフェン-ポリスチレンスルホン酸)などの導電性高分子も例示される。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、第2電極層26および第1電極層24として好適に例示される。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。 In the present invention, the materials for forming the second electrode layer 26 and the first electrode layer 24 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. Alternatively, conductive polymers such as PEDOT/PPS (polyethylenedioxythiophene-polystyrenesulfonic acid) are also exemplified. Among them, copper, aluminum, gold, silver, platinum, and indium tin oxide are preferably exemplified as the second electrode layer 26 and the first electrode layer 24 . Among them, copper is more preferable from the viewpoint of conductivity, cost, flexibility, and the like.
 また、第2電極層26および第1電極層24の形成方法にも制限はなく、真空蒸着およびスパッタリング等の気相堆積法(真空成膜法)、めっきによる成膜、ならびに、上記材料で形成された箔を貼着する方法等、公知の方法が、各種、利用可能である。 In addition, the method of forming the second electrode layer 26 and the first electrode layer 24 is not limited, and may be a vapor phase deposition method (vacuum film formation method) such as vacuum deposition or sputtering, a film formation by plating, or the formation of the above materials. A variety of known methods are available, such as affixing the foils.
 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およびアルミニウム等の薄膜は、第2電極層26および第1電極層24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。 In particular, thin films of copper, aluminum, or the like formed by vacuum deposition are preferably used as the second electrode layer 26 and the first electrode layer 24 because the flexibility of the piezoelectric film 10 can be ensured. be. Among them, a copper thin film formed by vacuum deposition is particularly preferably used.
 第2電極層26および第1電極層24の厚さには、制限はない。また、第2電極層26および第1電極層24の厚さは、基本的に同じであるが、異なってもよい。
 ここで、前述の第2保護層30および第1保護層28と同様に、第2電極層26および第1電極層24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、第2電極層26および第1電極層24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。
The thicknesses of the second electrode layer 26 and the first electrode layer 24 are not limited. Also, the thicknesses of the second electrode layer 26 and the first electrode layer 24 are basically the same, but may be different.
Here, as with the second protective layer 30 and the first protective layer 28, if the rigidity of the second electrode layer 26 and the first electrode layer 24 is too high, not only will the expansion and contraction of the piezoelectric layer 20 be restricted, Flexibility is also impaired. Therefore, the thinner the second electrode layer 26 and the first electrode layer 24, the better, as long as the electrical resistance does not become too high.
 圧電フィルム10においては、第2電極層26および第1電極層24の厚さと、ヤング率との積が、第2保護層30および第1保護層28の厚さとヤング率との積を下回れば、可撓性を大きく損なうことがないため、好適である。
 例えば、第2保護層30および第1保護層28がPET(ヤング率:約6.2GPa)で、第2電極層26および第1電極層24が銅(ヤング率:約130GPa)からなる組み合わせの場合、第2保護層30および第1保護層28の厚さが25μmだとすると、第2電極層26および第1電極層24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。
In the piezoelectric film 10, if the product of the thickness of the second electrode layer 26 and the first electrode layer 24 and the Young's modulus is less than the product of the thickness of the second protective layer 30 and the first protective layer 28 and the Young's modulus , is preferred because it does not significantly impair flexibility.
For example, the second protective layer 30 and the first protective layer 28 are made of PET (Young's modulus: about 6.2 GPa), and the second electrode layer 26 and the first electrode layer 24 are made of copper (Young's modulus: about 130 GPa). In this case, if the thickness of the second protective layer 30 and the first protective layer 28 is 25 μm, the thickness of the second electrode layer 26 and the first electrode layer 24 is preferably 1.2 μm or less, more preferably 0.3 μm or less. , it is preferably 0.1 μm or less.
 上述したように、圧電フィルム10は、高分子材料を含むマトリックス34に圧電体粒子36を分散してなる圧電体層20を、第2電極層26および第1電極層24で挟持し、さらに、この積層体を、第2保護層30および第1保護層28を挟持してなる構成を有する。
 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。
As described above, the piezoelectric film 10 includes the piezoelectric layer 20 formed by dispersing the piezoelectric particles 36 in the matrix 34 containing a polymer material, sandwiched between the second electrode layer 26 and the first electrode layer 24, and This laminate has a structure in which the second protective layer 30 and the first protective layer 28 are sandwiched.
In such a piezoelectric film 10, the maximum value of the loss tangent (Tan δ) 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.
As a result, even if the piezoelectric film 10 is subjected to a relatively slow and large bending deformation of several Hz or less from the outside, the strain energy can be effectively diffused to the outside as heat. It is possible to prevent cracks from occurring at the interface of
 圧電フィルム10は、動的粘弾性測定による周波数1Hzでの貯蔵弾性率(E’)が、0℃において10~30GPa、50℃において1~10GPaであるのが好ましい。なお、この条件に関しては、圧電体層20も同様である。
 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。
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.
 また、圧電フィルム10は、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1.0×105~2.0×106N/m、50℃において1.0×105~1.0×106N/mであるのが好ましい。なお、この条件に関しては、圧電体層20も同様である。
 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。
In addition, 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.
 さらに、圧電フィルム10は、動的粘弾性測定から得られたマスターカーブにおいて、25℃、周波数1kHzにおける損失正接(Tanδ)が、0.05以上であるのが好ましい。この条件に関しては、圧電体層20も同様である。
 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fが変化した際の音質の変化量も小さくできる。
Furthermore, the piezoelectric film 10 preferably has a loss tangent (Tan δ) 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.
 なお、本発明において、圧電フィルム10および圧電体層20等の貯蔵弾性率(ヤング率)および損失正接は、公知の方法で測定すればよい。一例として、エスアイアイ・ナノテクノロジー社製(SIIナノテクノロジー社製)の動的粘弾性測定装置DMS6100を用いて測定すればよい。
 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。
In the present invention, 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. As an example, the dynamic viscoelasticity measuring device DMS6100 manufactured by SII Nanotechnology Co., Ltd. (manufactured by SII Nanotechnology Co., Ltd.) may be used for measurement.
As an example of the measurement conditions, 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), and 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), and a distance between chucks of 20 mm.
 圧電素子50において、圧電フィルム10の第2電極層26および第1電極層24には、圧電フィルム10を伸縮させる駆動電圧を印加すなわち駆動電力を供給する、電源(外部電源)が接続される。
 電源には、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。
In the piezoelectric element 50 , a power source (external power source) is connected to the second electrode layer 26 and the first electrode layer 24 of the piezoelectric film 10 to apply a drive voltage for expanding and contracting the piezoelectric film 10 , that is, to supply drive power.
There are no restrictions on the power source, and it may be a DC power source or an AC power source. Also, 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.
 前述のとおり、第2電極層26および第1電極層24から電極の引き出しは、突出部10aにおいて行われる。第2電極層26および第1電極層24から電極の引き出し方法には、制限はなく、公知の各種の方法が利用可能である。
 一例として、第2電極層26および第1電極層24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、レーザ等によって第2保護層30および第1保護層28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。
As described above, electrodes are led out from the second electrode layer 26 and the first electrode layer 24 at the projecting portion 10a. There are no restrictions on the method of extracting electrodes from the second electrode layer 26 and the first electrode layer 24, and various known methods can be used.
As an example, a method of connecting a conductor such as a copper foil to the second electrode layer 26 and the first electrode layer 24 to lead the electrodes to the outside, and a method of penetrating the second protective layer 30 and the first protective layer 28 by a laser or the like. Examples include a method of forming a hole, filling the through hole with a conductive material, and leading an electrode to the outside.
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.
 以下、図10~図12を参照して、圧電フィルム10の製造方法の一例を説明する。 An example of a method for manufacturing the piezoelectric film 10 will be described below with reference to FIGS. 10 to 12. FIG.
 まず、図10に示す、第2保護層30の表面に第2電極層26が形成されたシート状物12aを準備する。さらに、図12に概念的に示す、第1保護層28の表面に第1電極層24が形成されたシート状物12cを準備する。 First, a sheet-like object 12a having a second protective layer 30 and a second electrode layer 26 formed thereon as shown in FIG. 10 is prepared. Further, a sheet-like material 12c having the first electrode layer 24 formed on the surface of the first protective layer 28 conceptually shown in FIG. 12 is prepared.
 シート状物12aは、第2保護層30の表面に、真空蒸着、スパッタリング、めっき等によって第2電極層26として銅薄膜等を形成して、作製すればよい。同様に、シート状物12cは、第1保護層28の表面に、真空蒸着、スパッタリング、めっき等によって第1電極層24として銅薄膜等を形成して、作製すればよい。
 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12aおよび/またはシート状物12cとして利用してもよい。
 シート状物12aおよびシート状物12cは、同じものでもよく、異なるものでもよい。
The sheet 12a may be produced by forming a copper thin film or the like as the second electrode layer 26 on the surface of the second protective layer 30 by vacuum deposition, sputtering, plating, or the like. Similarly, the sheet 12c may be produced by forming a copper thin film or the like as the first electrode layer 24 on the surface of the first protective layer 28 by vacuum deposition, sputtering, plating, or the like.
Alternatively, a commercially available sheet having a copper thin film or the like formed on a protective layer may be used as the sheet 12a and/or the sheet 12c.
The sheet-like material 12a and the sheet-like material 12c may be the same or different.
 なお、保護層が非常に薄く、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)付きの保護層を用いても良い。なお、セパレータとしては、厚さ25~100μmのPET等を用いることができる。セパレータは、電極層および保護層の熱圧着後、取り除けばよい。 In addition, when the protective layer is very thin and the handling property is poor, a protective layer with a separator (temporary support) may be used as necessary. As the separator, PET or the like having a thickness of 25 to 100 μm can be used. The separator may be removed after the electrode layer and protective layer are thermocompression bonded.
 次いで、図11に示すように、シート状物12aの第2電極層26上に、圧電体層20となる塗料(塗布組成物)を塗布した後、硬化して圧電体層20を形成する。これにより、シート状物12aと圧電体層20とを積層した圧電積層体12bを作製する。 Next, as shown in FIG. 11, a paint (coating composition) that will form the piezoelectric layer 20 is applied onto the second electrode layer 26 of the sheet 12a, and then cured to form the piezoelectric layer 20. As a result, a piezoelectric laminate 12b in which the sheet-like material 12a and the piezoelectric layer 20 are laminated is produced.
 圧電体層20の形成は、圧電体層20を形成する材料に応じて、各種の方法が利用可能である。
 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36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(MEK)、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12aを準備し、かつ、塗料を調製したら、この塗料をシート状物12a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11に示すように、第2保護層30の上に第2電極層26を有し、第2電極層26の上に圧電体層20を積層してなる圧電積層体12bを作製する。
Various methods can be used for forming the piezoelectric layer 20 depending on the material forming the piezoelectric layer 20 .
As an example, first, a polymer material such as cyanoethylated PVA is dissolved in an organic solvent, and piezoelectric particles 36 such as PZT particles are added and stirred to prepare a coating material.
Organic solvents are not limited, and various organic solvents such as dimethylformamide (DMF), methyl ethyl ketone (MEK), and cyclohexanone can be used.
After the sheet-like material 12a is prepared and the paint is prepared, the paint is cast (applied) on the sheet-like material 12a and dried by evaporating the organic solvent. As a result, as shown in FIG. 11, a piezoelectric laminate 12b having the second electrode layer 26 on the second protective layer 30 and the piezoelectric layer 20 laminated on the second electrode layer 26 is produced. do.
 塗料のキャスティング方法には制限はなく、バーコーター、スライドコーターおよびドクターナイフ等の公知の方法(塗布装置)が、全て、利用可能である。
 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36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10に示すシート状物12aの上にシート状に押し出し、冷却することにより、図11に示すような、圧電積層体12bを作製してもよい。
There are no restrictions on the method of casting the coating material, and known methods (coating equipment) such as bar coaters, slide coaters and doctor knives can all be used.
Alternatively, if the polymer material is heat-meltable, the polymer material is heat-melted and the piezoelectric particles 36 are added to prepare a melt, which is then extruded into the sheet shown in FIG. A piezoelectric layered body 12b as shown in FIG. 11 may be produced by extruding a sheet onto the shaped object 12a and cooling it.
 なお、上述のように、圧電体層20において、マトリックス34には、常温で粘弾性を有する高分子材料以外にも、PVDF等の高分子圧電材料を添加しても良い。
 マトリックス34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。
As described above, in the piezoelectric layer 20, the matrix 34 may be added with a polymeric piezoelectric material such as PVDF, in addition to the polymeric material having viscoelasticity at room temperature.
When these polymeric piezoelectric materials are added to the matrix 34, the polymeric piezoelectric materials to be added to the paint may be dissolved. Alternatively, 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.
 圧電体層20を形成したら、必要に応じて、カレンダ処理を行ってもよい。カレンダ処理は、1回でもよく、複数回、行ってもよい。
 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。
After the piezoelectric layer 20 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.
 次いで、第2保護層30の上に第2電極層26を有し、第2電極層26の上に圧電体層20を形成してなる圧電積層体12bの圧電体層20に、分極処理(ポーリング)を行う。圧電体層20の分極処理は、カレンダ処理の前に行ってもよいが、カレンダ処理を行った後に行うのが好ましい。
 圧電体層20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24を形成して、第1電極層24および第2電極層26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20の面方向ではなく、厚さ方向に分極を行うのが好ましい。
Next, the piezoelectric layer 20 of the piezoelectric laminate 12b having the second electrode layer 26 on the second protective layer 30 and the piezoelectric layer 20 formed on the second electrode layer 26 is subjected to a polarization treatment ( polling). The polarization treatment of the piezoelectric layer 20 may be performed before calendering, but is preferably performed after calendering.
The method of polarization treatment of the piezoelectric layer 20 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. When electric field poling is performed, the first electrode layer 24 may be formed before the polarization treatment, and the electric field poling treatment may be performed using the first electrode layer 24 and the second electrode layer 26. .
Moreover, in the piezoelectric film 10 of the present invention, the polarization treatment is preferably performed in the thickness direction of the piezoelectric layer 20, not in the plane direction.
 次いで、図12に示すように、分極処理を行った圧電積層体12bの圧電体層20側に、先に準備したシート状物12cを、第1電極層24を圧電体層20に向けて積層する。
 さらに、この積層体を、第1保護層28および第2保護層30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12bとシート状物12cとを貼り合わせ、図9に示すような、圧電フィルム10を作製する。
 あるいは、圧電積層体12bとシート状物12c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、圧電フィルム10を作製してもよい。
Next, as shown in FIG. 12, the previously prepared sheet-like material 12c is laminated on the piezoelectric layer 20 side of the piezoelectric layered body 12b subjected to the polarization treatment, with the first electrode layer 24 facing the piezoelectric layer 20. do.
Further, this laminate is thermocompression bonded using a hot press device, a heating roller, etc., with the first protective layer 28 and the second protective layer 30 sandwiched between them, thereby forming the piezoelectric laminate 12b and the sheet-like material 12c. are bonded together to produce a piezoelectric film 10 as shown in FIG.
Alternatively, the piezoelectric film 10 may be produced by bonding the piezoelectric laminate 12b and the sheet-like material 12c together using an adhesive and preferably further pressing them together.
 なお、この圧電フィルム10は、カットシート状のシート状物12aおよびシート状物12c等を用いて製造してもよく、あるいは、ロール・トゥ・ロール(Roll to Roll)を利用して製造してもよい。 The piezoelectric film 10 may be manufactured using the cut-sheet-like sheet-like material 12a and the sheet-like material 12c, etc., or may be manufactured using a roll-to-roll process. good too.
 作製された圧電フィルムは、各種用途に合わせて、所望の形状に裁断されてもよい。
 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。
The produced piezoelectric film may be cut into a desired shape according to various uses.
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 drive voltage is applied.
 圧電フィルム同士を貼着する粘着層14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、利用可能であり、後述する振動板と圧電素子とを貼着する貼着層104と同様の材料を用いることができる。 As the adhesive layer 14 for attaching the piezoelectric films to each other, various known adhesive layers can be used as long as the adjacent piezoelectric films 10 can be attached. Materials similar to the deposition layer 104 can be used.
[電気音響変換器]
 本発明の電気音響変換器は、
 上述した圧電素子を、振動板に貼り付けてなる、電気音響変換器である。
[Electroacoustic transducer]
The electroacoustic transducer of the present invention is
This is an electroacoustic transducer in which the piezoelectric element described above is attached to a diaphragm.
 図13に、本発明の圧電素子を有する本発明の電気音響変換器の一例を模式的に表す図を示す。 FIG. 13 shows a diagram schematically showing an example of the electroacoustic transducer of the present invention having the piezoelectric element of the present invention.
 図13に示す電気音響変換器100は、上述した圧電素子50aと、振動板102と、圧電素子50aを振動板102に貼り付ける貼着層104と、を有する。図13に示す例では、好ましい態様として、圧電素子50aの、突出部10aを有する側の面の積層部に9、振動板102に貼り付けられている。 The electroacoustic transducer 100 shown in FIG. 13 has the above-described piezoelectric element 50a, a diaphragm 102, and a bonding layer 104 for bonding the piezoelectric element 50a to the diaphragm 102. In the example shown in FIG. 13, as a preferred mode, the piezoelectric element 50a is attached to the diaphragm 102 on the laminated portion 9 on the side of the piezoelectric element 50a having the projecting portion 10a.
 このような電気音響変換器100は、圧電素子50aの圧電フィルム10に駆動電圧を印加することで、圧電フィルム10が面方向に伸縮し、この圧電フィルム10の伸縮によって、圧電素子50aが面方向に伸縮する。
 この圧電素子50aの面方向の伸縮によって、振動板102が撓み、その結果、振動板102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102は、音を発生する。振動板102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。
In such an electroacoustic transducer 100, when a drive voltage is applied to the piezoelectric film 10 of the piezoelectric element 50a, the piezoelectric film 10 expands and contracts in the plane direction. stretches to
Due to the expansion and contraction of the piezoelectric element 50a in the plane direction, the diaphragm 102 bends, and as a result, the diaphragm 102 vibrates in the thickness direction. Due to this vibration in the thickness direction, the diaphragm 102 generates sound. The diaphragm 102 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 .
 振動板102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。 The diaphragm 102 has flexibility as a preferred embodiment. In the present invention, 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.
 振動板102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。
Diaphragm 102 is not 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.
 また、電気音響変換器100では、可撓性を有するものであれば、振動板102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。 In the electroacoustic transducer 100, the diaphragm 102 may be an organic electroluminescence (OLED (Organic Light Emitting Diode)) display, a liquid crystal display, 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.
 電気音響変換器100においては、振動板102と、圧電素子50とは、貼着層104によって貼着されている。 In the electroacoustic transducer 100 , the diaphragm 102 and the piezoelectric element 50 are adhered by the adhesion layer 104 .
 貼着層104は、振動板102と圧電素子50と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104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。
Various known layers can be used for the adhesive layer 104 as long as the diaphragm 102 and the piezoelectric element 50 can be adhered.
Therefore, the adhesive layer 104 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.
 ここで、電気音響変換器100では、圧電素子50を伸縮させることで、振動板102を撓ませ振動させて、音を発生させる。従って、電気音響変換器100では、圧電素子50の伸縮が、直接的に振動板102に伝達されるのが好ましい。振動板102と圧電素子50との間に、振動を緩和するような粘性を有する物質が存在すると、振動板102への圧電素子50の伸縮のエネルギーの伝達効率が低くなってしまい、電気音響変換器100の駆動効率が低下してしまう。
 この点を考慮すると、貼着層104は、粘着剤からなる粘着剤層よりも、固体で硬い貼着層104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104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。
Here, in the electroacoustic transducer 100, by expanding and contracting the piezoelectric element 50, the diaphragm 102 is bent and vibrated to generate sound. Therefore, in the electroacoustic transducer 100 , it is preferable that the expansion and contraction of the piezoelectric element 50 is directly transmitted to the diaphragm 102 . If a substance having a viscosity that reduces vibration is present between the diaphragm 102 and the piezoelectric element 50, the efficiency of transmission of the expansion and contraction energy of the piezoelectric element 50 to the diaphragm 102 is lowered, resulting in electroacoustic conversion. The driving efficiency of the device 100 is lowered.
Considering this point, the sticking layer 104 is preferably an adhesive layer made of an adhesive that provides a solid and hard sticking layer 104 rather than a sticky layer made of an adhesive. As a more preferable adhesive layer 104, specifically, an adhesive layer made of a thermoplastic type adhesive such as a polyester adhesive and a styrene-butadiene rubber (SBR) adhesive is 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".
 貼着層104の厚さには、制限はなく、貼着層104の材料に応じて、十分な貼着力(接着力、粘着力)が得られる厚さを、適宜、設定すればよい。
 ここで、電気音響変換器100においては、貼着層104が薄い方が、振動板102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104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104は、薄い方が好ましい。具体的には、貼着層104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。
The thickness of the adhesive layer 104 is not limited, and the thickness that provides sufficient adhesive strength (adhesive strength, cohesive strength) may be appropriately set according to the material of the adhesive layer 104 .
Here, in the electroacoustic transducer 100, the thinner the adhesive layer 104, the higher the effect of transmitting the stretching energy (vibrational energy) of the piezoelectric element 50 to the diaphragm 102, and the higher the energy efficiency. Also, if the adhesive layer 104 is thick and rigid, it may restrict expansion and contraction of the piezoelectric element 50 .
Considering this point, the adhesive layer 104 is preferably thinner. Specifically, the thickness of the adhesive layer 104 is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, and even more preferably 0.1 to 10 μm after being attached.
 なお、電気音響変換器100において、貼着層104は、好ましい態様として設けられるものであり、必須の構成要素ではない。
 従って、電気音響変換器100は、貼着層104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102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。
Note that in the electroacoustic transducer 100, the adhesive layer 104 is provided as a preferred embodiment and is not an essential component.
Therefore, the electroacoustic transducer 100 does not have the adhesive layer 104, and the diaphragm 102 and the piezoelectric element 50 may be fixed using known crimping means, fastening means, fixing means, or the like. For example, when 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.
 しかしながら、この場合には、電源から駆動電圧を印加した際に、振動板102に対して圧電素子50が独立して伸縮してしまい、場合によっては、圧電素子50のみが撓んで、圧電素子50の伸縮が振動板102に伝わらない。このように、振動板102に対して圧電素子50が独立して伸縮した場合には、圧電素子50による振動板102の振動効率が低下してしまい。振動板102を十分に振動させられなくなってしまう可能性がある。
 この点を考慮すると、振動板102と圧電素子50とは、図13に示すように、貼着層104で貼着するのが好ましい。
However, in this case, the piezoelectric element 50 expands and contracts independently of the diaphragm 102 when a drive voltage is applied from the power supply. is not transmitted to the diaphragm 102. In this way, when the piezoelectric element 50 expands and contracts independently of the diaphragm 102, the efficiency of vibration of the diaphragm 102 by the piezoelectric element 50 decreases. There is a possibility that the diaphragm 102 cannot be sufficiently vibrated.
Considering this point, it is preferable that the vibration plate 102 and the piezoelectric element 50 are adhered with an adhesion layer 104 as shown in FIG.
 ここで、上述したように、圧電体層20は、マトリックス34に圧電体粒子36を含むものである。また、圧電体層20を厚さ方向で挟むように、第2電極層26および第1電極層24が設けられる。
 このような圧電体層20を有する圧電フィルム10の第2電極層26および第1電極層24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。
Here, as described above, the piezoelectric layer 20 contains the piezoelectric particles 36 in the matrix 34 . A second electrode layer 26 and a first electrode layer 24 are provided so as to sandwich the piezoelectric layer 20 in the thickness direction.
When a voltage is applied to the second electrode layer 26 and the first electrode layer 24 of the piezoelectric film 10 having such a piezoelectric layer 20, the piezoelectric particles 36 expand and contract in the polarization direction according to the applied voltage. As a result, the piezoelectric film 10 (piezoelectric layer 20) shrinks in the thickness direction. At the same time, due to the Poisson's ratio, the piezoelectric film 10 also expands and contracts in the in-plane direction. This expansion and contraction is about 0.01 to 0.1%.
 上述したように、圧電体層20の厚さは、好ましくは10~300μm程度である。従って、厚さ方向の伸縮は、最大でも0.3μm程度と非常に小さい。
 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。
As described above, the thickness of the piezoelectric layer 20 is preferably about 10-300 μm. Therefore, the expansion and contraction in the thickness direction is as small as about 0.3 μm at maximum.
On the other hand, 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.
 振動板102は、貼着層104によって圧電フィルム10に貼着されている。従って、圧電フィルム10の伸縮によって、振動板102は撓み、その結果、振動板102は、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102は、音を発生する。すなわち、振動板102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。
The diaphragm 102 is attached to the piezoelectric film 10 with an adhesive layer 104 . Therefore, the expansion and contraction of the piezoelectric film 10 bends the diaphragm 102, and as a result, the diaphragm 102 vibrates in the thickness direction.
Due to this vibration in the thickness direction, the diaphragm 102 generates sound. That is, the diaphragm 102 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 .
 また、振動板102のばね定数に応じて、圧電フィルム10の質量を調整することで、音圧レベルを向上させることができる。圧電フィルム10の質量が大きいと、振動板102が撓んでしまうため、駆動時の振動板102の振動を抑制する可能性がある。一方、圧電フィルム10の質量が小さいと、共振周波数が高くなり、低周波数における振動板102の振動を抑制する可能性がある。これらの点を考慮すると、圧電フィルム10の質量は、振動板102のばね定数に応じて、適切に調整することが好ましい。 Further, by adjusting the mass of the piezoelectric film 10 according to the spring constant of the diaphragm 102, the sound pressure level can be improved. If the mass of the piezoelectric film 10 is large, the diaphragm 102 will be bent, which may suppress vibration of the diaphragm 102 during driving. On the other hand, if the mass of the piezoelectric film 10 is small, the resonance frequency will be high, possibly suppressing the vibration of the diaphragm 102 at low frequencies. Considering these points, it is preferable to appropriately adjust the mass of the piezoelectric film 10 according to the spring constant of the diaphragm 102 .
 以上、本発明の圧電素子について詳細に説明したが、本発明は上述の例に限定はされず、本発明の要旨を逸脱しない範囲において、各種の改良や変更を行ってもよいのは、もちろんである。 Although the piezoelectric element of the present invention has been described in detail above, the present invention is not limited to the above examples, and various improvements and modifications may be made without departing from the gist of the present invention. is.
 以下、本発明の具体的実施例を挙げ、本発明についてより詳細に説明する。なお、本発明はこの実施例に限定されるものでなく、以下の実施例に示す材料、使用量、割合、処理内容、処理手順などは、本発明の趣旨を逸脱しない限り適宜変更することができる。 Hereinafter, the present invention will be described in more detail by giving specific examples of the present invention. The present invention is not limited to this example, and the materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. can.
 [圧電フィルムの作製]
 上述した図10~図12に示す方法によって、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(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、市販のPZT原料粉を1000~1200℃で焼結した後、これを平均粒径5μmになるように解砕および分級処理したものを用いた。
[Preparation of piezoelectric film]
A piezoelectric film was produced by the method shown in FIGS. 10 to 12 described above.
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.
・PZT particles・・・・・・・・・・300 parts by mass ・Cyanoethylated PVA・・・・・・・・30 parts by mass ・DMF・・・・・・・・・・・・70 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 5 μm.
 一方、厚さ4μmのPETフィルムに、厚さ0.3μmの銅薄膜を真空蒸着してなるシート状物を用意した。すなわち、本例においては、第1電極層および第2電極層は、厚さ0.3μmの銅蒸着薄膜であり、第1保護層および第2保護層は、厚さ4μmのPETフィルムとなる。
 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。
On the other hand, a sheet-like material was prepared by vacuum-depositing a copper thin film with a thickness of 0.3 μm on a PET film with a thickness of 4 μm. That is, in this example, the first electrode layer and the second electrode layer are 0.3 μm thick copper-deposited thin films, and the first protective layer and the second protective layer are 4 μm 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 μm.
Next, the sheet-like material coated with the paint was dried by heating on a hot plate at 120° C. to evaporate the DMF. As a result, 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 μm thereon is produced. bottom.
 作製した圧電体層を、厚さ方向に分極処理した。 The produced piezoelectric layer was subjected to polarization treatment in the thickness direction.
 分極処理を行った圧電積層体の上に、第1電極層(銅薄膜側)を圧電体層に向けて、PETフィルムに同薄膜を蒸着したシート状物を積層した。
 次いで、圧電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、圧電体層と第1電極層とを貼着して接着して、圧電フィルムを作製した。
A sheet-like material obtained by vapor-depositing the same thin film on a PET film was laminated on the piezoelectric laminate that had been subjected to the polarization treatment, with the first electrode layer (copper thin film side) facing the piezoelectric layer.
Next, the laminate of the piezoelectric laminate and the sheet-like material is thermocompression bonded at a temperature of 120° C. using a laminator device, thereby adhering and bonding the piezoelectric layer and the first electrode layer. A film was produced.
 [実施例1]
 作製した圧電フィルムを170mm×150mmに切り出し、170mmの辺の方向に4回折り返して、圧電フィルム同士を粘着層(アクリル系粘着剤)で積層して、長さLb30mm×幅Wb150mmの積層部と、長さLa9mm×幅Wa150mmの突出部を有する圧電素子を作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.3である。また、突出部と積層部とが接する辺の長さYaは150mmである。
 このような圧電素子を10個作製した。
[Example 1]
The produced piezoelectric film was cut into a size of 170 mm x 150 mm, folded four times in the direction of the 170 mm side, and the piezoelectric films were laminated with an adhesive layer (acrylic adhesive) to form a laminated portion of length Lb 30 mm x width Wb 150 mm, A piezoelectric element having a protruding portion with a length La of 9 mm and a width of Wa of 150 mm was produced.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.3. The length Ya of the side where the projecting portion and the laminated portion are in contact is 150 mm.
Ten such piezoelectric elements were produced.
 [実施例2]
 長さLa11mm×幅Wa10mmの突出部を12個有する構成(図8参照)とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の(合計)面積Saの比率Psは、0.29である。また、突出部と積層部とが接する辺の長さYaは10mmである。
 なお、複数の突出部それぞれにおいて第1電極層および第2電極層と外部電源とを接続した。
[Example 2]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that there were 12 protrusions each having a length La of 11 mm and a width of Wa 10 mm (see FIG. 8).
The ratio Ps of the (total) area Sa of the protrusions to the area Sb of the laminated part is 0.29. The length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm.
In addition, the first electrode layer and the second electrode layer were connected to the external power source at each of the plurality of projecting portions.
 [実施例3]
 長さLa9.5mm×幅Wa10mmの突出部を14個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の(合計)面積Saの比率Psは、0.30である。また、突出部と積層部とが接する辺の長さYaは10mmである。
 なお、複数の突出部それぞれにおいて第1電極層および第2電極層と外部電源とを接続した。
[Example 3]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that 14 projecting portions each having a length La of 9.5 mm and a width of Wa of 10 mm were provided.
The ratio Ps of the (total) area Sa of the protrusions to the area Sb of the laminated part is 0.30. The length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm.
In addition, the first electrode layer and the second electrode layer were connected to the external power source at each of the plurality of projecting portions.
 [実施例4]
 長さLa37mm×幅Wa37mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.30である。また、突出部と積層部とが接する辺の長さYaは37mmである。
[Example 4]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 37 mm and a width of Wa of 37 mm was provided.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.30. The length Ya of the side where the projecting portion and the laminated portion are in contact is 37 mm.
 [実施例5]
 1辺の長さが22.5mmの六角形の突出部を1個有する構成(図6参照)とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.29である。また、突出部と積層部とが接する辺の長さYaは22.5cmである。
[Example 5]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one hexagonal protrusion with a side length of 22.5 mm was provided (see FIG. 6).
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.29. The length Ya of the side where the projecting portion and the laminated portion are in contact is 22.5 cm.
 [実施例6]
 長さLa60mm×幅Wa4mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.05である。また、突出部と積層部とが接する辺の長さYaは4mmである。
[Example 6]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 60 mm and a width of Wa 4 mm was provided.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.05. The length Ya of the side where the projecting portion and the laminated portion are in contact is 4 mm.
 [実施例7]
 長さLa4mm×幅Wa25mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.02である。また、突出部と積層部とが接する辺の長さYaは25mmである。
[Example 7]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 4 mm and a width of Wa of 25 mm was provided.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.02. The length Ya of the side where the projecting portion and the laminated portion are in contact is 25 mm.
 [比較例1]
 長さLa10mm×幅Wa150mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは0.33である。また、突出部と積層部とが接する辺の長さYaは150mmである。
[Comparative Example 1]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 10 mm and a width of Wa of 150 mm was provided.
The ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.33. The length Ya of the side where the projecting portion and the laminated portion are in contact is 150 mm.
 [比較例2]
 長さLa70mm×幅Wa3mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.05である。また、突出部と積層部とが接する辺の長さYaは3mmである。
[Comparative Example 2]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 70 mm and a width of Wa 3 mm was provided.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.05. Moreover, the length Ya of the side where the projecting portion and the laminated portion are in contact is 3 mm.
 [比較例3]
 長さLa4mm×幅Wa10mmの突出部を1個有する構成とした以外は、実施例1と同様にして圧電素子を10個、作製した。
 積層部の面積Sbに対する突出部の面積Saの比率Psは、0.01である。また、突出部と積層部とが接する辺の長さYaは10mmである。
[Comparative Example 3]
Ten piezoelectric elements were produced in the same manner as in Example 1, except that one projecting portion having a length La of 4 mm and a width of Wa 10 mm was provided.
A ratio Ps of the area Sa of the projecting portion to the area Sb of the laminated portion is 0.01. The length Ya of the side where the projecting portion and the laminated portion are in contact is 10 mm.
[評価]
 作製した各実施例および比較例の電気音響変換器について、音圧のばらつき、および、到達温度を評価した。
[evaluation]
The variation in sound pressure and the temperature reached were evaluated for the fabricated electroacoustic transducers of Examples and Comparative Examples.
<音圧>
 作製した圧電素子の、突出部とは反対側の面を振動板に貼着し、電気音響変換器を作製した。振動板としては、大きさ500mm×450mm、厚さ0.8mm、材質:アルミニウム(A5052)の板状部材を用いた。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の中心を合わせて貼着した。圧電素子と振動板とを貼着する貼着層としては、アクリル系粘着剤を用いた。
<Sound pressure>
An electroacoustic transducer was produced by attaching the surface of the produced piezoelectric element opposite to the projecting portion to a diaphragm. As the diaphragm, a plate member having a size of 500 mm×450 mm, a thickness of 0.8 mm, and material: aluminum (A5052) was used. The horizontal direction of the diaphragm and the longitudinal direction of the piezoelectric element were matched, and the center of the laminated part of the piezoelectric element was aligned with the center of the diaphragm and attached. An acrylic pressure-sensitive adhesive was used as a bonding layer for bonding the piezoelectric element and the diaphragm.
 圧電素子に対し、周波数1kHz~20kHz、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た。
 上記測定を10検体について行い、15kHzにおける音圧の最大値と最小値との差を音圧ばらつきとした。音圧ばらつきが7dB未満であれば、所望の特性を満たす。
A sine sweep signal with a frequency of 1 kHz to 20 kHz and an applied voltage of 50 Vrms was inputted to the piezoelectric element, and the sound pressure was measured with a microphone placed at a distance of 1 m from the center of the diaphragm.
The above measurement was performed on 10 specimens, and the difference between the maximum and minimum values of sound pressure at 15 kHz was taken as the sound pressure variation. A sound pressure variation of less than 7 dB satisfies the desired characteristics.
<到達温度>
 音圧測定時と同様、作製した圧電素子を振動板に貼り付けた状態で、印加電圧40VrmsのSN2信号(JEITAが定めたノイズ信号の規格)を入力し、30分後の圧電素子表面の到達温度をサーモグラフィ(Keysight Technologies社製 U5855A)により測定した。また、圧電素子の温度の測定箇所は最高到達温度を示した任意の位置とした。到達温度が50℃以下であれば所望の特性を満たす。
 結果を表1に示す。
<Achievement temperature>
In the same way as when measuring the sound pressure, with the fabricated piezoelectric element attached to the diaphragm, an SN2 signal (noise signal standard defined by JEITA) with an applied voltage of 40 Vrms is input, and the arrival of the piezoelectric element surface after 30 minutes. The temperature was measured by thermography (U5855A manufactured by Keysight Technologies). Also, the temperature of the piezoelectric element was measured at an arbitrary position where the highest temperature was reached. If the temperature reached is 50° C. or lower, the desired characteristics are satisfied.
Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1から、本発明の実施例は比較例に比べて音圧のばらつきが小さく、かつ、到達温度が低いことがわかる。比較例1は突出部の面積比率が大きいためばらつきが大きくなることがわかる。比較例2は突出部と積層部とが接する辺の長さが短いため到達温度が高くなることがわかる。比較例3は突出部の面積比率が小さいため到達温度が高くなることがわかる。 From Table 1, it can be seen that the examples of the present invention have smaller variations in sound pressure and reach lower temperatures than the comparative examples. It can be seen that in Comparative Example 1, since the area ratio of the protruding portion is large, the variation is large. It can be seen that in Comparative Example 2, the reaching temperature is high because the length of the side where the protruding portion and the laminated portion are in contact is short. It can be seen that Comparative Example 3 has a small area ratio of the protruding portion, so that the reaching temperature is high.
 また、実施例1~5の対比から、突出部の面積が略同じ場合には、突出部と積層部とが接する辺の長さが長いほど到達温度が低くなることがわかる。
 また、実施例1と実施例6,7との対比から、突出部の面積比率が小さいほど音圧ばらつきが小さいことがわかる。
 以上から本発明の効果は明らかである。
In addition, from the comparison of Examples 1 to 5, it can be seen that when the areas of the projecting portions are substantially the same, the longer the side where the projecting portion and the laminated portion are in contact with each other, the lower the attained temperature.
Also, from the comparison between Example 1 and Examples 6 and 7, it can be seen that the smaller the area ratio of the protrusions, the smaller the sound pressure variation.
From the above, the effect of the present invention is clear.
 本発明の圧電素子は、例えば、音波センサー、超音波センサー、圧力センサー、触覚センサー、歪みセンサーおよび振動センサー等の各種センサー(特に、ひび検知等のインフラ点検や異物混入検知等の製造現場検査に有用である)、マイクロフォン、ピックアップ、スピーカーおよびエキサイター等の音響デバイス(具体的な用途としては、ノイズキャンセラー(車、電車、飛行機、ロボット等に使用)、人工声帯、害虫・害獣侵入防止用ブザー、家具、壁紙、写真、ヘルメット、ゴーグル、ヘッドレスト、サイネージ、ロボットなどが例示される)、自動車、スマートフォン、スマートウォッチ、ゲーム等に適用して用いるハプティクス、超音波探触子およびハイドロホン等の超音波トランスデューサ、水滴付着防止、輸送、攪拌、分散、研磨等に用いるアクチュエータ、容器、乗り物、建物、スキーおよびラケット等のスポーツ用具に用いる制振材(ダンパー)、ならびに、道路、床、マットレス、椅子、靴、タイヤ、車輪およびパソコンキーボード等に適用して用いる振動発電装置として好適に使用することができる。 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. Ultrasonic probes and hydrophones Acoustic transducers, actuators used for water drop adhesion prevention, transport, agitation, dispersion, polishing, etc., dampers used in containers, vehicles, buildings, sports equipment such as skis and rackets, and roads, floors, mattresses, and chairs , shoes, tires, wheels, and personal computer keyboards.
 10 圧電フィルム
 10a 突出部
 10b 積層部
 12a、12c シート状物
 12b 圧電積層体
 14 粘着層
 20 圧電体層
 24 第1電極層
 26 第2電極層
 28 第1保護層
 30 第2保護層
 34 マトリックス
 36 圧電体粒子
 40 接続部
 50a~50e 圧電素子
 100 電気音響変換器
 102 振動板
 104 貼着層
REFERENCE SIGNS LIST 10 Piezoelectric film 10a Projecting portion 10b Laminated portion 12a, 12c Sheet-like object 12b Piezoelectric laminate 14 Adhesive layer 20 Piezoelectric layer 24 First electrode layer 26 Second electrode layer 28 First protective layer 30 Second protective layer 34 Matrix 36 Piezoelectric body particle 40 connection part 50a to 50e piezoelectric element 100 electroacoustic transducer 102 diaphragm 104 adhesion layer

Claims (7)

  1.  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と、を有する圧電フィルムを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、積層してなる圧電素子であって、
     平面視において、前記圧電フィルムが2層以上重なる積層部から突出する突出部を有し、
     前記突出部は、前記電極層と外部電源とを接続するための接続部を有し、
     前記積層部の面積に対する前記突出部の面積の比率が0.02~0.3の範囲であり、かつ、前記突出部と前記積層部とが接する辺の長さが4mm以上である、圧電素子。
    By folding a piezoelectric film having a piezoelectric layer, electrode layers provided on both sides of the piezoelectric layer, and protective layers provided on the electrode layers one or more times, the piezoelectric film is formed into a plurality of layers, A piezoelectric element formed by lamination,
    In plan view, the piezoelectric film has a projecting portion projecting from a laminated portion in which two or more layers are overlapped,
    the projecting portion has a connection portion for connecting the electrode layer and an external power supply,
    The piezoelectric element, wherein the ratio of the area of the protrusion to the area of the laminate is in the range of 0.02 to 0.3, and the length of the side where the protrusion and the laminate are in contact is 4 mm or more. .
  2.  前記突出部を複数有し、
     前記積層部の面積に対する前記突出部の合計面積の比率が0.02~0.3の範囲であり、
     各前記突出部と前記積層部が接する辺の長さが4mm以上である、請求項1に記載の圧電素子。
    Having a plurality of protrusions,
    The ratio of the total area of the protrusions to the area of the laminate is in the range of 0.02 to 0.3,
    2. The piezoelectric element according to claim 1, wherein the length of the side where each of the projecting portions and the laminated portion are in contact is 4 mm or longer.
  3.  前記突出部の数が12個以下である、請求項2に記載の圧電素子。 The piezoelectric element according to claim 2, wherein the number of protrusions is 12 or less.
  4.  平面視における突出部の形状が矩形状である、請求項1に記載の圧電素子。 The piezoelectric element according to claim 1, wherein the protrusion has a rectangular shape in plan view.
  5.  前記圧電体層は、高分子材料を含むマトリックス中に圧電体粒子を含む高分子複合圧電体からなる、請求項1に記載の圧電素子。 2. The piezoelectric element according to claim 1, wherein the piezoelectric layer is composed of a polymeric composite piezoelectric body containing piezoelectric particles in a matrix containing a polymeric material.
  6.  請求項1~5のいずれか一項に記載の圧電素子を、振動板に貼り付けてなる、電気音響変換器。 An electroacoustic transducer in which the piezoelectric element according to any one of claims 1 to 5 is attached to a diaphragm.
  7.  前記圧電素子の、前記突出部を有する側の面の前記積層部に、前記振動板に貼り付けられている、請求項6に記載の電気音響変換器。 The electroacoustic transducer according to claim 6, wherein the diaphragm is attached to the laminated portion on the side of the piezoelectric element having the protrusion.
PCT/JP2022/030855 2021-09-28 2022-08-15 Piezoelectric element, and electro-acoustic converter WO2023053750A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054486A (en) * 1983-09-05 1985-03-28 Toshiba Corp Lead wire connecting portion of polymer element
WO2014157006A1 (en) * 2013-03-29 2014-10-02 富士フイルム株式会社 Electroacoustic conversion film
JP2015070110A (en) * 2013-09-30 2015-04-13 株式会社村田製作所 Piezoelectric device and method of manufacturing piezoelectric device
WO2020095812A1 (en) * 2018-11-08 2020-05-14 富士フイルム株式会社 Laminated piezoelectric element and electro-acoustic transducer
WO2021225071A1 (en) * 2020-05-07 2021-11-11 富士フイルム株式会社 Piezoelectric element and piezoelectric speaker

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054486A (en) * 1983-09-05 1985-03-28 Toshiba Corp Lead wire connecting portion of polymer element
WO2014157006A1 (en) * 2013-03-29 2014-10-02 富士フイルム株式会社 Electroacoustic conversion film
JP2015070110A (en) * 2013-09-30 2015-04-13 株式会社村田製作所 Piezoelectric device and method of manufacturing piezoelectric device
WO2020095812A1 (en) * 2018-11-08 2020-05-14 富士フイルム株式会社 Laminated piezoelectric element and electro-acoustic transducer
WO2021225071A1 (en) * 2020-05-07 2021-11-11 富士フイルム株式会社 Piezoelectric element and piezoelectric speaker

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