WO2023090376A1 - Composition de résine, film séché, film durci, dispositif piézoélectrique et procédé de commande d'onde sonore - Google Patents

Composition de résine, film séché, film durci, dispositif piézoélectrique et procédé de commande d'onde sonore Download PDF

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WO2023090376A1
WO2023090376A1 PCT/JP2022/042621 JP2022042621W WO2023090376A1 WO 2023090376 A1 WO2023090376 A1 WO 2023090376A1 JP 2022042621 W JP2022042621 W JP 2022042621W WO 2023090376 A1 WO2023090376 A1 WO 2023090376A1
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resin
resin composition
cured film
film
functional film
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PCT/JP2022/042621
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English (en)
Japanese (ja)
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恭介 鈴木
恭久 石田
恒則 大平
聖也 根本
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株式会社レゾナック
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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00—Piezoelectric transducers; Electrostrictive transducers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials

Definitions

  • the present disclosure relates to resin compositions, dry films, cured films, piezoelectric devices, and sound wave control methods.
  • Piezoelectric devices that transmit and receive sound waves such as ultrasonic waves are used in a wide range of fields, such as ultrasonic imaging devices, obstacle sensing in transportation machines and the like, and fingerprint authentication in electronic devices.
  • a piezoelectric device for example, an ultrasonic device having an acoustic matching portion that is deformed by the stress of the acoustic lens between the ultrasonic element array substrate and the ultrasonic lens is disclosed (for example, Japanese Patent Laid-Open No. 2015-084788 publication, etc.)
  • the function provided on the surface of the member to control the amount of transmission and reflection of sound waves at the interface such as the interface between the member and gas, the interface between the member and liquid, etc.
  • a functional film a functional film capable of controlling an acoustic impedance value to a desired value is desired.
  • the present disclosure provides a resin composition that can obtain a functional film that can widely control acoustic impedance while maintaining flexibility, a dry film, a cured film, a piezoelectric device, and an acoustic wave control method using the same. intended to provide
  • Means for solving the above problems include the following aspects.
  • a resin composition used for manufacturing a functional film for a piezoelectric device A resin composition containing a resin and having an insulating filler content of less than 50% by volume relative to the total solid content of the resin composition.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin is a resin having a polar group.
  • the resin includes at least one selected from the group consisting of epoxy resins, phenoxy resins, polyamideimide resins, acrylic resins, polyester resins, and polyether resins. The described resin composition.
  • the resin composition according to 1. ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the insulating filler has a specific gravity of 6.0 or more.
  • ⁇ 11> The resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a dispersant.
  • ⁇ 13> A dry film obtained by drying the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> A cured film obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 15> A cured film obtained by curing the dried film according to ⁇ 13>.
  • ⁇ 16> The cured film according to ⁇ 14> or ⁇ 15>, wherein the content of the insulating filler is less than 50% by volume with respect to the entire cured film.
  • ⁇ 17> The cured film according to any one of ⁇ 14> to ⁇ 16>, which is a functional film used for an acoustic matching layer, an acoustic lens, a sound wave transmission layer, a sound wave attenuation layer, or a sound wave reflection layer.
  • a piezoelectric element a piezoelectric element; a first functional film comprising the cured film according to any one of ⁇ 14> to ⁇ 17>; Provided on the first functional film, composed of a cured film according to any one of ⁇ 14> to ⁇ 17>, and having a different content rate of the insulating filler from the first functional film a second functional membrane; Piezoelectric device including.
  • the first functional film is a cured film obtained by curing a first resin composition containing a first resin
  • the second functional film is a cured film obtained by curing a second resin composition containing the same type of resin as the first resin,
  • the piezoelectric device according to ⁇ 19> The piezoelectric device according to ⁇ 19>.
  • a sound wave control method comprising: controlling the amount of transmission and reflection of sound waves by providing the cured film according to any one of ⁇ 14> to ⁇ 17> on the surface of a member constituting a piezoelectric device.
  • a resin composition that can obtain a functional film that can widely control acoustic impedance while maintaining flexibility, a dry film, a cured film, a piezoelectric device, and an acoustic wave control method using the same are provided. be.
  • FIG. 2 is a schematic end view showing an acoustic wave transmitting/receiving section in one example of the piezoelectric device according to the first embodiment
  • FIG. 5 is a schematic end view showing a sound wave transmitting/receiving section in another example of the piezoelectric device according to the first embodiment
  • FIG. 11 is a schematic end view showing an acoustic wave transmitting/receiving section in an example of a piezoelectric device according to a second embodiment
  • FIG. 11 is a schematic end view showing an acoustic wave transmitting/receiving section in an example of a piezoelectric device according to a third embodiment
  • the term "process” includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • each component may contain multiple types of applicable substances.
  • the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
  • Particles corresponding to each component in the present disclosure may include a plurality of types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
  • the term “layer” or “film” refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.
  • the term “laminate” indicates stacking layers, and two or more layers may be bonded, or two or more layers may be detachable.
  • “(meth)acryloyl group” means at least one of acryloyl group and methacryloyl group
  • “(meth)acrylic acid” means at least one of acrylic acid and methacrylic acid.
  • the resin composition of the present disclosure is a resin composition used for producing a functional film for a piezoelectric device, which contains a resin and has an insulating filler content of 50% by volume with respect to the total solid content of the resin composition. is less than
  • the total solid content of the resin composition means all components excluding volatile components from the resin composition.
  • the resin composition contains a resin and the content of the insulating filler is less than 50% by volume, thereby obtaining a functional film capable of widely controlling acoustic impedance while maintaining flexibility.
  • the content rate of the insulating filler when the content rate of the insulating filler is less than 50% by volume, the content rate of the resin can be relatively increased compared to the case where the content rate is 50% by volume or more. It becomes easy to obtain a functional film having Further, since the functional film has flexibility, the functional film can easily adhere to the surface of the member, and the functional film can easily follow the deformation of the member provided in contact with the functional film. Moreover, since the content of the insulating filler is less than 50% by volume, the dried film obtained by drying the resin composition also has flexibility. Therefore, the handling property is also improved when the dry film is peeled from the base material, adhered to the surface of the member, and cured to form a cured film.
  • the acoustic impedance of the functional film can be widely controlled by adjusting the content of the insulating filler in the range of 0% by volume or more and less than 50% by volume.
  • a functional film with a low acoustic impedance can be obtained by reducing the content of the insulating filler without changing the types of the resin and the insulating filler, while increasing the content of the insulating filler. can obtain a functional film with high acoustic impedance.
  • the resin composition can provide a functional film that can widely control acoustic impedance while maintaining flexibility, so that it can be easily provided directly on the member of the piezoelectric device.
  • a functional film that can widely control acoustic impedance while maintaining flexibility, so that it can be easily provided directly on the member of the piezoelectric device.
  • another layer such as an adhesive layer or a cushion layer between the member on which the functional film is provided and the functional film, making it easier to control the amount of transmission and reflection of sound waves at the interface.
  • the resin composition of the present disclosure contains at least a resin.
  • the type of resin is not particularly limited, and may be a thermosetting resin, a thermoplastic resin, or a combination thereof.
  • the resin may be in the state of a monomer having a functional group capable of causing a polymerization reaction by heating, or may be in the state of an already polymerized polymer.
  • the resin is preferably a resin having a polar group.
  • a polar group represents an atomic group having polarity due to bonding between atoms having different electronegativities.
  • Polar groups include, for example, groups having heteroatoms other than carbon atoms and hydrogen atoms, more specifically, from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, and a silicon atom. Included are groups containing at least one selected heteroatom.
  • the polar group is preferably a group containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. More specifically, the polar group includes an amino group, an amide group, an imide group, a cyano group, a nitro group, an epoxy group, a hydroxy group, a carboxy group, a carbonyl group, a thiol group, a sulfo group, a thionyl group, an ester bond, ether bond, sulfide bond, urethane bond, urea bond, etc., selected from the group consisting of amide group, imide group, epoxy group, hydroxy group, amino group, carboxy group, carbonyl group, ether bond, and urea bond At least one is preferred.
  • the polar group may be present on the main chain of the resin or may be present on the side chain.
  • resins having a polar group include vinyl polymerization resins, acrylic resins, polyamide resins, polyimide resins, polyamideimide resins, polyurethane resins, polyester resins, polyether resins, epoxy resins, oxazine resins, and bismaleimide resins. , phenol resins, unsaturated polyester resins, silicone resins, phenoxy resins, and the like.
  • the resin having a polar group preferably contains at least one selected from the group consisting of polyamideimide resins, epoxy resins, acrylic resins, polyester resins, and polyether resins.
  • a resin having a polar group may be used alone or in combination of two or more.
  • the resin composition may contain a resin having no polar group in addition to the resin having a polar group.
  • resins having no polar group include SBR resin (styrene-butadiene-random copolymer resin), SBS resin (styrene-butadiene block copolymer resin), SIS (styrene-isoprene block copolymer), SEBS (styrene- ethylene/butylene block copolymer resin), SEPS (styrene-ethylene/propylene block copolymer resin) polyethylene, polypropylene, polybutadiene, polyisoprene, polystyrene, cycloolefin polymers, and hydrogenated products thereof.
  • the content of the resin having a polar group with respect to the total amount of the resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. is particularly preferred.
  • the content of the resin having a polar group with respect to the total amount of the resin may be 100% by mass or 95% by mass or less.
  • the resin preferably contains a thermosetting resin, preferably a thermosetting resin having a polar group.
  • the thermosetting resin may have an aromatic ring, or may have a condensed ring in which two or more aromatic rings are condensed. Condensed rings include naphthalene ring, anthracene ring, phenanthrene ring and the like.
  • Thermosetting resins having polar groups include epoxy resins, phenolic resins, melamine resins, urea resins, thermosetting polyimide resins, thermosetting acrylic resins, polyurethane resins, and the like.
  • the thermosetting resin having a polar group is preferably an epoxy resin, a phenol resin, or a thermosetting acrylic resin, more preferably an epoxy resin, from the viewpoint of durability.
  • the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
  • Specific examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and naphthalene type epoxy resin. , anthracene-type epoxy resin, biphenol-type epoxy resin, biphenyl novolac-type epoxy resin, cycloaliphatic epoxy resin, and the like.
  • epoxy resins include those having substituents such as ether groups and alicyclic epoxy groups in the above epoxy resins.
  • an epoxy resin having a heteroatom other than an oxygen atom derived from an epoxy group or a glycidyloxy group of the epoxy resin is preferable.
  • the epoxy resin may be, for example, an epoxy resin containing a nitrogen atom and a hydrogen atom bonded to the nitrogen atom.
  • the epoxy resin may have a heterocyclic structure containing a nitrogen atom and a hydrogen atom bonded to the nitrogen atom.
  • a heterocyclic structure includes, for example, a glycoluril structure.
  • the molecular weight of the epoxy resin is not particularly limited.
  • the content of the epoxy resin with respect to the total amount of the resin may be 80% by mass or more, 90% by mass or more, or 100% by mass. Further, the content of the epoxy resin with respect to the total amount of the resin may be 10% by mass to 90% by mass, may be 20% by mass to 80% by mass, or may be 30% by mass to 80% by mass. It may be 40% by mass to 80% by mass.
  • thermosetting acrylic resin is not particularly limited as long as it has two or more (meth)acryloyl groups in the molecule.
  • thermosetting acrylic resins include polyfunctional (meth)acrylic acid esters such as 1,9-nonanediol diacrylate, ethylene glycol diacrylate, and propylene glycol diacrylate.
  • the resin composition may further contain an acrylic compound other than the thermosetting acrylic resin.
  • acrylic compounds other than thermosetting acrylic resins include acrylic nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, 3-ethoxy propyl acrylate, oxycarbonyl tetramethacrylate, methyl acrylate, isopropyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, n-propyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, ethyl methacrylate, 2-nitro-2-methylpropyl methacrylate, 1 , 1-diethylpropyl methacrylate, methyl methacrylate, isodecyl acrylate, tricyclode
  • the total content of the thermosetting acrylic resin and the acrylic compound other than the thermosetting acrylic resin with respect to the total amount of the resin is 5% by mass to 100% by mass. It may be 10% by mass to 50% by mass.
  • the resin composition may further contain a curing agent.
  • a curing agent such as a peroxide or an azo compound.
  • the resin preferably contains a thermoplastic resin, and preferably contains a thermoplastic resin having a polar group.
  • thermoplastic resins include phenoxy resins, polyamideimide resins, polyethylene resins, polypropylene resins, SBR resins, and the like.
  • the thermoplastic resin is preferably a phenoxy resin, a polyamideimide resin, a polyethylene resin, or an SBR resin, and more preferably a polyamideimide resin, a phenoxy resin, or an SBR resin.
  • the phenoxy resin is not particularly limited as long as it has a phenoxy structure in its molecular structure.
  • the “phenoxy structure” refers to a structure in which an oxygen atom is bonded to a benzene ring, and includes not only a phenoxy group (C 6 H 5 —O—), but also a partially substituted phenoxy group, a phenoxy group Those partially reacted by hydrogenation or the like are also included.
  • phenoxy resins include phenoxy resins having a bisphenol skeleton, phenoxy resins having a novolac skeleton, phenoxy resins having a naphthalene skeleton, and phenoxy resins having a biphenyl skeleton.
  • the phenoxy resin is preferably a phenoxy resin having a bisphenol skeleton from the viewpoint of versatility.
  • phenoxy resins having a bisphenol skeleton include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A and bisphenol F copolymer phenoxy resin, bisphenol S type phenoxy resin, brominated bisphenol A type phenoxy resin, hydrogenated bisphenol A type phenoxy resin and the like. These phenoxy resins may be used alone or in combination of two or more.
  • a polyamideimide resin is a resin that has an amide bond and an imide bond in its main chain.
  • Preferred specific examples of polyamideimide resins include polyamideimide resins having at least one selected from the group consisting of a polyalkylene oxide structure and a polysiloxane structure. These polyamide-imide resins are preferable from the viewpoint of relaxation of stress due to deformation of the polyamide-imide resin.
  • These polyamide-imide resins may be polyamide-imide resins synthesized using, for example, polyalkylene oxide-modified diamines and polysiloxane-modified diamines.
  • the unit structure of the polyalkylene oxide structure that may be contained in the polyamideimide resin is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and having 1 to 4 carbon atoms.
  • An alkylene oxide structure is more preferred.
  • a polypropylene oxide structure is preferable as the polyalkylene oxide structure.
  • the alkylene group in the alkylene oxide structure may be linear or branched.
  • the number of unit structures in the polyalkylene oxide structure may be one, or two or more.
  • polysiloxane structure that may be contained in the polyamideimide resin
  • a part or all of the silicon atoms of the polysiloxane structure are substituted with an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • a siloxane structure is mentioned.
  • a preferred embodiment of the polyamide-imide resin includes a polyamide-imide resin having a structural unit derived from diimidecarboxylic acid or a derivative thereof and a structural unit derived from an aromatic diisocyanate or an aromatic diamine.
  • the SBR resin is not particularly limited as long as it is a copolymer of styrene and butadiene. Moreover, the ratio of the units derived from styrene and the units derived from butadiene constituting the SBR resin is not limited, nor is the molecular weight of the SBR resin particularly limited.
  • the SBR resin may have an unsaturated double bond of a unit derived from butadiene left in order to react with the thermosetting resin, and the unsaturated double bond is hydrogenated to increase durability. It may be
  • the thermoplastic resin and the thermosetting resin may be combined from the viewpoint of improving the strength of the film after film formation and suppressing curing shrinkage during curing.
  • the content of the thermoplastic resin is preferably 40% by mass or less, may be 30% by mass or less, or may be 20% by mass with respect to the solid content of the resin composition. There may be.
  • the lower limit of the thermoplastic resin content relative to the solid content of the resin composition is not particularly limited, and is, for example, 3% by mass.
  • the content of the thermoplastic resin with respect to the entire resin is, for example, 75% by mass or less, and from the viewpoint of achieving both durability and plasticity, it is 50% by mass or less. and more preferably 35% by mass or less.
  • the lower limit of the content of the thermoplastic resin with respect to the entire resin is not particularly limited, and is, for example, 15% by mass.
  • combinations of the thermoplastic resin and the thermosetting resin include a combination of a phenoxy resin and an epoxy resin, a combination of an SBR resin and an acrylic resin, and the like. mentioned.
  • the total content of the resin in the resin composition is preferably 9% by mass or more, more preferably 10% by mass or more, relative to the solid content of the resin composition. is more preferable, and 13% by mass or more is even more preferable. Further, the total content of the resin in the resin composition may be 100% by mass or less, 99% by mass or less, or 95% by mass or less relative to the solid content of the resin composition. good too. Further, the total content of the resin in the resin composition is preferably 50% by volume or more, preferably 55% by volume or more, relative to the solid content of the resin composition, from the viewpoint of obtaining flexibility of the functional film. It is more preferable that the content is 60% by volume or more. Further, the total content of the resin in the resin composition may be 100% by volume or less, 99% by volume or less, or 95% by volume or less with respect to the solid content of the resin composition. good too.
  • the resin composition of the present disclosure has an insulating filler content of less than 50% by volume relative to the total solid content of the resin composition. That is, the resin composition does not contain an insulating filler, or contains an insulating filler in a range of less than 50% by volume.
  • the resin composition preferably contains an insulating filler in an amount of less than 50% by volume. Including an insulating filler in the resin composition makes it easier to control the acoustic impedance of the resulting functional film.
  • the filler contained in the resin composition is an insulating filler, there is an advantage that a short circuit can be prevented when the resin composition is incorporated in an electronic component and used.
  • insulating fillers examples include oxides such as aluminum oxide, zirconium oxide, titanium oxide, bismuth oxide, silicon dioxide, cerium oxide, tantalum oxide, tungsten oxide, and sintered uranium oxide; barium titanate, tungsten carbide, tungsten, zirconium, and the like.
  • An insulating filler may be used individually by 1 type, or may use 2 or more types together.
  • the insulating filler preferably contains at least one selected from the group consisting of aluminum oxide, zirconium oxide, titanium oxide, bismuth oxide, silicon dioxide, tantalum oxide, and tungsten oxide.
  • the insulating filler is a group consisting of aluminum oxide, zirconium oxide, titanium oxide, barium titanate, tantalum oxide, tungsten oxide, and bismuth oxide from the viewpoint of having a high Young's modulus and a uniform particle shape. It preferably contains at least one more selected, more preferably at least one selected from the group consisting of aluminum oxide, zirconium oxide, tantalum oxide, tungsten oxide, and bismuth oxide.
  • the insulating filler may contain at least one selected from the group consisting of barium titanate, cerium oxide, tungsten oxide, and bismuth oxide. From the viewpoint of acoustic impedance control, the insulating filler may be a combination of an insulating filler with a high Young's modulus and an insulating filler with a low Young's modulus.
  • the volume resistivity of the insulating filler at 25° C. is preferably 1 ⁇ 10 6 ⁇ cm or more, more preferably 1 ⁇ 10 8 ⁇ cm or more, and more preferably 1 ⁇ 10 10 ⁇ cm or more. It is even more preferable to have
  • the volume average particle diameter D50 of the insulating filler is preferably 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, and 2.0 ⁇ m or less from the viewpoint of thinning the resin composition layer. is more preferred.
  • the lower limit of the volume average particle diameter D50 of the insulating filler is not particularly limited, and may be 0.001 ⁇ m or more. From the above viewpoints, the volume average particle diameter D50 of the insulating filler is preferably 0.001 ⁇ m to 5.0 ⁇ m, more preferably 0.001 ⁇ m to 3.0 ⁇ m, and 0.001 ⁇ m to 2.0 ⁇ m. is more preferable.
  • the volume average particle size D50 of the insulating filler is preferably 0.1 ⁇ m or more.
  • the volume average particle diameter D50 of the insulating filler is 0.1 ⁇ m or more, the total surface area of the insulating filler is not too large, and mixing with the resin becomes easy.
  • the volume average particle diameter D50 of the insulating filler is preferably 0.1 ⁇ m to 5.0 ⁇ m, more preferably 1.0 ⁇ m to 5.0 ⁇ m. It is more preferably 0 ⁇ m, further preferably 1.5 ⁇ m to 3.5 ⁇ m.
  • the volume average particle size D50 of the insulating filler contained in the resin composition and the volume average particle size D50 of the insulating filler contained in the functional film formed using the resin composition are calculated as follows.
  • the particle size when the accumulation from the small diameter side is 50% is defined as the volume average particle size D50.
  • the particle size distribution curve of the insulating filler contained in the resin composition is obtained by observing the cross section of the cured product of the resin composition with a scanning electron microscope (SEM) and obtaining the equivalent circle diameter for 20 insulating fillers. can get.
  • a particle size distribution measuring device using a laser light scattering method for example, Co., Ltd. Shimadzu Corporation, "SALD-3000"
  • SALD-3000 a laser light scattering method
  • the shape of the insulating filler is not particularly limited, and may be spherical, powdery, needle-like, fibrous, plate-like, angular, polyhedral, scale-like, or the like. From the viewpoint of thinning the resin composition layer, the shape of the insulating filler is preferably polyhedral or spherical, more preferably spherical. From the viewpoint of thinning the resin composition layer, the aspect ratio of the insulating filler is preferably 5 or less, preferably 4 or less, and more preferably 3 or less. The aspect ratio of the insulating filler contained in the resin composition is obtained by observing the cross section of the cured product of the resin composition with a scanning electron microscope (SEM) and averaging the aspect ratios of 20 insulating fillers. .
  • SEM scanning electron microscope
  • the specific gravity of the insulating filler is not particularly limited, and may be appropriately adjusted according to the application of the resin composition.
  • the specific gravity of the insulating filler may be 2.0 or more, 3.0 or more, 5.0 or more, 6.0 or more, or 7.0. or more.
  • the upper limit of the specific gravity of the insulating filler is not particularly limited.
  • the specific gravity of the insulating filler may be, for example, 10.0 or less.
  • the specific gravity of the filler is measured according to JIS K 0061: 2001 and JIS Z 8807: 2012 by the ratio of the mass of the measurement sample to the mass of pure water of the same volume under atmospheric pressure. It represents the ratio of the true specific gravity of water to the true specific gravity of water.
  • the specific gravity of the insulating fillers refers to the value of the mixture of the insulating fillers contained in the resin composition.
  • the content of the insulating filler in the total solid content of the resin composition is less than 50% by volume.
  • the content of the insulating filler in the total solid content of the resin composition may be 45% by volume or less, or 35% by volume or less, from the viewpoint of lowering the acoustic impedance of the functional film. It may be vol % or less, or may be 15 vol % or less.
  • the content of the insulating filler in the total solid content of the resin composition may be 1% by volume or more, or 5% by volume or more, from the viewpoint of increasing the acoustic impedance of the functional film. , 15% by volume or more, 25% by volume or more, or 35% by volume or more.
  • the content of the insulating filler in the total solid content of the resin composition is preferably 87% by mass or less, more preferably 70% by mass or less, from the viewpoint of achieving both flexibility and wide acoustic impedance control. More preferably, it is less than 65% by mass. From the viewpoint of lowering the acoustic impedance of the functional film, the content of the insulating filler in the total solid content of the resin composition may be 60% by mass or less, 50% by mass or less, or 40% by mass or less. % by mass or less.
  • the content of the insulating filler in the total solid content of the resin composition may be 1% by mass or more, or 5% by mass or more, from the viewpoint of increasing the acoustic impedance of the functional film. , 20% by mass or more.
  • the resin composition may contain a dispersant from the viewpoint of dispersibility of the insulating filler.
  • the dispersant includes a dispersant having compatibility with the resin.
  • the dispersant includes phosphates, carboxylates, carboxylic acid amine salts, and the like.
  • the content of the dispersant may be 0.01% by mass to 5% by mass, may be 0.05% by mass to 3% by mass, or may be 0.1% by mass with respect to the total solid content of the resin composition. % to 1% by mass, or 0.1% to 0.5% by mass.
  • the content of the dispersant may be 0.01 to 5 parts by mass, 0.1 to 3 parts by mass, or 0.1 to 3 parts by mass with respect to 100 parts by mass of the insulating filler. It may be 3 parts by mass to 2 parts by mass.
  • the resin composition may contain a solvent from the viewpoint of adjusting the viscosity.
  • the solvent is preferably a solvent having a boiling point of 70° C. or higher, and a solvent having a boiling point of 100° C. or higher, from the viewpoint of preventing drying of the composition in the step of applying the composition. is more preferable.
  • the solvent is more preferably a solvent having a boiling point of 300° C. or less in order to suppress the generation of voids.
  • the type of solvent is not particularly limited, and examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, aromatic hydrocarbon-based solvents, ester-based solvents, and nitrile-based solvents.
  • the content of the solvent is preferably 60% by mass or less, more preferably 40% by mass or less, based on the total amount of the resin composition, from the viewpoint of viscosity, shortening of the heating process, and the like. % by mass or less is more preferable.
  • the lower limit of the solvent content is not particularly limited, and the resin composition may not contain a solvent.
  • the solvent content may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more.
  • the resin composition may contain other components as needed.
  • Other components include additives such as coupling agents and thixotropic agents.
  • the total content of the resin and the insulating filler is preferably 90% by mass or more, more preferably 95% by mass or more, and 97% by mass or more relative to the solid content of the resin composition. is more preferred.
  • other components include fillers other than insulating fillers (for example, conductive fillers).
  • the content of the filler other than the insulating filler is not particularly limited, and may be 10% by volume or less, or 5% by volume or less, relative to the solid content of the resin composition. It may be vol% or less, or 1 vol% or less.
  • the type of coupling agent is not particularly limited, and examples of the coupling agent include silane-based compounds, titanium-based compounds, aluminum chelate compounds, aluminum/zirconium-based compounds, and the like. Among them, a silane coupling agent is preferable from the viewpoint of adhesion to a substrate such as glass.
  • a coupling agent may be used individually by 1 type, or may use 2 or more types together. When the resin composition contains a coupling agent, the adhesion of the obtained functional film to the substrate tends to be improved.
  • silane coupling agents examples include silane coupling agents having vinyl groups, epoxy groups, methacrylic groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, isocyanate groups, acid anhydride groups, and the like. Among them, a silane coupling agent having an epoxy group or an amino group is preferable, and a silane coupling agent having an epoxy group or an anilino group is more preferable.
  • a silane cup having an epoxy group or an amino group A ring agent is preferably used, and a silane coupling agent having an epoxy group or an anilino group is more preferably used.
  • silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • silane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltri ethoxysilane and the like.
  • the content of the coupling agent in the resin composition is not particularly limited, and is 0.05% by mass to 5% by mass relative to the solid content of the resin composition. is preferred, and 0.1% by mass to 2.5% by mass is more preferred.
  • Thixotropic agents include 12-hydroxystearic acid, 12-hydroxystearic acid triglyceride, ethylenebisstearic acid amide, hexamethylenebisoleic acid amide, N,N'-distearyladipic acid amide, fumed silica and the like.
  • the thixotropic agents may be used alone or in combination of two or more.
  • the content of the thixotropic agent is not particularly limited, and may be 0.01% by mass to 5% by mass, or may be 0.05% by mass to 3% by mass with respect to the total solid content of the resin composition. , 0.1% by mass to 1% by mass.
  • the resin composition may or may not contain a conductive filler as another component.
  • the content of the conductive filler with respect to the total solid content of the resin composition is preferably less than 1% by volume, more preferably less than 0.1% by volume, from the viewpoint of obtaining a functional film having insulating properties. , more preferably less than 0.01% by volume.
  • the conductive filler refers to a filler having a volume resistivity of less than 1 ⁇ 10 6 ⁇ cm at 25°C. Examples of conductive fillers include metals, conductive metal oxides, carbon black, and the like.
  • the method for preparing the resin composition is not particularly limited, and examples thereof include a method of mixing the above-described components contained in the resin composition in predetermined blending amounts using a mixer or the like.
  • the viscosity of the resin composition is preferably 10 Pa ⁇ s to 300 Pa ⁇ s, more preferably 20 Pa ⁇ s to 250 Pa ⁇ s, and more preferably 30 Pa ⁇ s to 200 Pa ⁇ s at 25° C. from the viewpoint of handling properties. is more preferable.
  • the viscosity of the resin composition was determined according to JIS Z 3284-3: 2014 using an E-type rotational viscometer equipped with an SPP rotor at 25°C and 2.5 revolutions per minute (rpm) for 144 seconds. This is the measured value when rotated, and is the average value of two measurements.
  • the resin composition of the present disclosure is used for producing functional films for piezoelectric devices. Specifically, a cured film obtained by curing a dried film obtained by drying a resin composition, a cured film obtained by curing a resin composition, or the like is used as the functional film. The details of the dry film and the cured film will be described later.
  • the functional film includes an acoustic matching layer, an acoustic lens, a sound wave transmission layer, a sound wave attenuation layer, a sound wave reflection layer, and the like.
  • a functional film obtained using the resin composition of the present disclosure is provided between the plurality of members for the purpose of suppressing reflection of sound waves at the interface of a plurality of members having a large difference in acoustic impedance.
  • the functional film may be used as an acoustic matching layer.
  • the resin composition of the present disclosure is applied not only at the interface between a plurality of members, but also at the interface between a member and gas, the interface between a member and liquid, etc., for the purpose of controlling the amount of sound wave transmission and sound wave reflection.
  • You may use the functional film obtained by using.
  • a functional film obtained using the resin composition of the present disclosure may be provided on the surface of the member, and the functional film may be used as a sound wave transmission layer, a sound wave attenuation layer, a sound wave reflection layer, or the like. good.
  • these functional films may be acoustic lenses that converge or diverge acoustic waves propagating within the piezoelectric device.
  • the sound wave may be an ultrasonic wave.
  • an ultrasonic wave is a sound wave with a frequency of 20 kHz or higher.
  • the piezoelectric device is not particularly limited as long as it has a piezoelectric element.
  • Piezoelectric devices include, for example, ultrasonic sensors, and specific examples include TOF (Time of Flight) sensors, fingerprint authentication sensors, touch sensors, ultrasonic diagnostic imaging devices, haptics devices, and ultrasonic flowmeters. etc.
  • the dry film of the present disclosure is a film obtained by drying the resin composition described above. Specifically, for example, the above-mentioned resin composition is applied to at least a part of the surface of the base material or the functional film installation target surface of the functional film installation target member to form a resin composition layer, and the resin composition By drying the layer, a dry film is obtained.
  • the member to be provided with the functional film may be a piezoelectric element used in a piezoelectric device, or may be another member, and may be a dry film or a cured film obtained using the above resin composition. There may be.
  • the method of applying the resin composition is not particularly limited, and examples thereof include a spray method, a screen printing method, a spin coating method, a spin coating method, a bar coating method, and the like.
  • the substrate to which the resin composition is applied is not particularly limited, and includes glass, metal, resin material, metal deposition film, metal oxide, ceramic, nonwoven fabric, glass fiber, aramid fiber, carbon fiber, glass fiber prepreg, aramid fiber prepreg, carbon fiber prepreg and the like.
  • the method of drying the resin composition layer is not particularly limited, and includes a method of heat-treating using a device such as a hot plate and an oven, and a method of natural drying.
  • the conditions for drying by heat treatment are not particularly limited as long as the solvent in the resin composition is sufficiently volatilized. .
  • the average thickness of the dry film is, for example, 4 ⁇ m to 500 ⁇ m, may be 10 ⁇ m to 300 ⁇ m, may be 20 ⁇ m to 200 ⁇ m, or may be 4 ⁇ m to 50 ⁇ m.
  • the average thickness of the dry film is measured using, for example, a micrometer, and obtained as the arithmetic mean value of the thickness at any five points.
  • the maximum height Rz of the dry film is preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, even more preferably 6.0 ⁇ m or less, 5.0 ⁇ m or less is particularly preferred, and 3.5 ⁇ m or less is extremely preferred.
  • the arithmetic mean roughness Ra of the dry film is preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, more preferably 0.6 ⁇ m, from the viewpoint of adhesion to the surface on which the functional film is to be installed. It is more preferably 0.5 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the arithmetic mean roughness Ra and the maximum height Rz of the dry film are values obtained in the same manner as the arithmetic mean roughness Ra and the maximum height Rz of the cured film, which will be described later.
  • the cured film of the present disclosure may be a film obtained by curing the dry film described above, or may be a film obtained by curing the resin composition described above.
  • the cured film may be a film whose hardness is increased by having a chemical structure different from that before curing due to a chemical reaction. It may be a film whose hardness is increased by solidification.
  • the cured film is a film obtained by curing a dry film formed on the surface of the base material
  • the dry film peeled off from the surface of the base material is placed on the functional film installation target surface of the functional film installation target member.
  • a cured film may be obtained by providing it on at least a part and curing it, or after obtaining a cured film by curing a dry film on the substrate, the cured film may be peeled off from the surface of the substrate.
  • the dry film peeled off from the surface of the base material is provided on at least a part of the functional film-installed surface of the functional film-installed target member and cured. is preferred.
  • the dry film obtained using the resin composition described above has flexibility, the dry film is not easily cracked even after the process of peeling it off from the base material and providing it on the surface of the member, and adheres closely to the surface of the member. It is easy to handle, so it is easy to handle.
  • the cured film may be a film obtained by curing a laminate in which a plurality of dry films are laminated. Specifically, dried films formed on a plurality of different substrates may be separated from the respective substrates and then bonded together to obtain an integrated cured film by curing. Alternatively, the resin composition may be further coated on the dry film and dried to obtain a laminated body in which a plurality of dried films are laminated, and the cured film may be obtained by curing the laminated body.
  • the cured film may be obtained by curing the resin composition without going through the drying film.
  • the cured film may be obtained by curing the resin composition without passing through the drying film.
  • the volatile component is removed during the process of curing the resin composition, even if the cured film is obtained without drying the film. good.
  • a resin composition layer is formed by applying the resin composition to at least a part of the functional film installation target surface of the functional film installation target member.
  • a cured film may be obtained by curing the resin composition layer.
  • a cured film may be obtained by applying the resin composition to at least a part of the surface of the substrate to form a resin composition layer, and curing the resin composition layer.
  • the cured film when the cured film is obtained by curing a resin composition, the cured film, which is a molded body of the resin composition, may be obtained by, for example, injection molding, extrusion molding, or the like.
  • the method of curing to obtain a cured film is not particularly limited, and curing can be performed by heat treatment or the like. Curing by heat treatment includes box type dryers, hot air conveyor type dryers, quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, laminators, heat It can be carried out using a plate press or the like. Alternatively, a cured film may be obtained by curing the resin composition by heat treatment during molding using a molding machine such as an injection molding machine or an extrusion molding machine.
  • a molding machine such as an injection molding machine or an extrusion molding machine.
  • the average thickness of the cured film is, for example, 4 ⁇ m to 500 ⁇ m, may be 10 ⁇ m to 300 ⁇ m, may be 20 ⁇ m to 200 ⁇ m, or may be 4 ⁇ m to 50 ⁇ m.
  • the average thickness of the cured film may exceed 500 ⁇ m, may be 500 ⁇ m to 5 mm, may be 800 ⁇ m to 4 mm, or may be 1 mm to 3 mm.
  • the cured film when used as an acoustic lens, the cured film may have an average thickness of 3 mm to 6 mm.
  • the average thickness of the cured film is measured using, for example, a micrometer, and obtained as an arithmetic mean value of thicknesses at arbitrary five locations.
  • the maximum height Rz of the cured film is preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, even more preferably 6.0 ⁇ m or less, 5.0 ⁇ m or less is particularly preferred, and 3.5 ⁇ m or less is extremely preferred.
  • the arithmetic mean roughness Ra of the cured film is preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less, more preferably 0.6 ⁇ m, from the viewpoint of adhesion to the surface on which the functional film is to be installed. It is more preferably 0.5 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the arithmetic mean roughness Ra and the maximum height Rz of the cured film are values obtained based on JIS B 0601:2013. Specifically, it is a value measured using a 3D microscope (eg VR-3200 manufactured by Keyence, 12 times magnification). Regarding the measurement conditions of the arithmetic mean roughness Ra and the maximum height Rz, the measurement length is set to 20 mm, and the average value of the values obtained by measuring three points is used as the arithmetic mean roughness Ra and the maximum height Rz.
  • the density of the cured film is preferably 1.1 g/cm 3 or less, more preferably 0.8 g/cm 3 to 1.0 g/cm 3 , and more preferably 0.8 g/cm 3 to 1.0 g/cm 3 . /cm 3 to 0.9 g/cm 3 .
  • the density of the cured film is preferably 2.0 g/cm 3 or more, more preferably 3.0 g/cm 3 to 8.0 g/cm 3 , from the viewpoint of increasing the acoustic impedance. It is more preferably 0.0 g/cm 3 to 7.0 g/cm 3 .
  • the cured film may have a density of 0.8 g/cm 3 to 8.0 g/cm 3 or 0.8 g/cm 3 to 7.0 g/cm 3 .
  • the density of the cured film can be determined, for example, by preparing a 10 mm square sample and measuring the average thickness and mass of the sample.
  • the sound velocity in the cured film is, for example, in the range of 1000 m / s to 6000 m / s, may be in the range of 1100 m / s to 5000 m / s, and may be in the range of 1200 m / s to 4000 m / s. .
  • the speed of sound in the cured film can be obtained by using an ultrasonic sonic meter (ZX-5, manufactured by Minnesota Japan) and inputting the thickness of the cured film measured using a micrometer.
  • the volume resistivity of the cured film is, for example, in the range of 1.0 ⁇ 10 6 ⁇ cm or more, and may be in the range of 1.0 ⁇ 10 7 ⁇ cm or more. It may be in the range of 8 ⁇ cm or more.
  • the volume resistivity is measured with an insulation resistance meter (for example, Advantest, 8340A), and the volume resistivity is calculated from the area and thickness of the electrode contact surface. can be calculated.
  • the elastic modulus of the cured film at 50° C. is preferably high from the viewpoint of preventing scratches during film formation, preferably 0.1 GPa to 2.0 GPa, more preferably 0.1 GPa to 1.5 GPa. , 0.1 GPa to 1.0 GPa.
  • the elastic modulus of the cured film at 50° C. can be obtained by measurement using a viscoelasticity measuring apparatus RSA-3 (TA Instruments) under the conditions of a temperature increase rate of 10° C./min and a frequency of 1 Hz in tensile mode.
  • the content of the insulating filler with respect to the entire cured film is preferably less than 50% by volume from the viewpoint of achieving both flexibility and wide acoustic impedance control.
  • the content of the insulating filler with respect to the entire cured film may be 45% by volume or less, 35% by volume or less, or 25% by volume or less from the viewpoint of lowering the acoustic impedance. It may be 15% by volume or less.
  • the content of the insulating filler with respect to the entire cured film may be 1% by volume or more, 5% by volume or more, or 15% by volume or more from the viewpoint of increasing the acoustic impedance. It may be 25% by volume or more, or 35% by volume or more.
  • the content of the insulating filler in the entire cured film is preferably 87% by mass or less, more preferably 70% by mass or less, more preferably 65% by mass, from the viewpoint of achieving both flexibility and wide acoustic impedance control. % is more preferable. From the viewpoint of lowering the acoustic impedance, the content of the insulating filler in the entire cured film may be 60% by mass or less, 50% by mass or less, or 40% by mass or less. In addition, the content of the insulating filler with respect to the entire cured film may be 1% by mass or more, 5% by mass or more, or 20% by mass or more from the viewpoint of increasing the acoustic impedance. good.
  • the acoustic impedance of the cured film is, for example, in the range of 1.0 ⁇ 10 6 kg/m 2 s to 15.0 ⁇ 10 6 kg/m 2 s, and 1.3 ⁇ 10 6 kg/m 2 s to 15.0 ⁇ 10 6 kg/m 2 s. It may be in the range of 12.0 ⁇ 10 6 kg/m 2 s, or in the range of 1.5 ⁇ 10 6 kg/m 2 s to 10.0 ⁇ 10 6 kg/m 2 s.
  • the cured film of the present disclosure is used as a functional film for piezoelectric devices. Specifically, it can be suitably used as the above-described acoustic matching layer, acoustic lens, sound wave transmission layer, sound wave attenuation layer, sound wave reflection layer, and the like.
  • a piezoelectric device of the present disclosure includes a piezoelectric element and a functional film made of the cured film described above.
  • the functional film may be provided in contact with the piezoelectric element, may be provided on the piezoelectric element via another layer, or may be provided on another member constituting the piezoelectric device.
  • the piezoelectric device of the present disclosure includes a piezoelectric element, a first functional film made of the above-described cured film, and provided in contact with the first functional film, and made of the above-described cured film and having an insulating filler content of and a second functional film different from the first functional film.
  • the first functional film is the second functional film from the viewpoint of adhesion between the first functional film and the second functional film.
  • a cured film obtained by curing a first resin composition containing one resin, and a second functional film obtained by curing a second resin composition containing the same type of resin as the first resin It is preferable that it is a cured film.
  • the resin composition forming the second functional film contains at least one resin of the same type as the resin contained in the resin composition forming the first functional film.
  • the same type of resin means two resins having the same main skeleton, and specifically includes epoxy resins, phenoxy resins, and the like.
  • the first functional film is the second functional film from the viewpoint of adhesion between the first functional film and the second functional film.
  • a cured film obtained by curing a first resin composition containing one resin, and a second functional film obtained by curing a second resin composition containing the same resin as the first resin It is more preferable that it is a cured film. That is, it is more preferable that the resin composition forming the second functional film contains the same resin as at least one of the resins contained in the resin composition forming the first functional film.
  • the piezoelectric device is provided in contact with the surface of the first functional film opposite to the second functional film, and is composed of the above-described cured film and has an insulating filler content similar to that of the first functional film. may further have a different third functional membrane. That is, the piezoelectric device may have three or more layers of functional films made of the aforementioned cured films.
  • the first functional film contains the first resin. It is preferable that it is a cured film obtained by curing a resin composition, and that the third functional film is a cured film obtained by curing a third resin composition containing the same kind of resin as the first resin. . In other words, it is preferable that the resin composition forming the third functional film contains at least one resin of the same type as the resin contained in the resin composition forming the first functional film.
  • the first functional film is a cured film obtained by curing a first resin composition containing a first resin
  • the second functional film is a second functional film.
  • a third resin composition which is a cured film obtained by curing a second resin composition containing the same resin as the first resin, and wherein the third functional film contains the same resin as the first resin. is more preferably a cured film obtained by curing the That is, a resin of the same kind as at least one of the resins contained in the resin composition forming the first functional film is added to the resin composition forming the second functional film and the resin forming the third functional film. More preferably the composition comprises.
  • the first functional film includes the first resin. It is a cured film obtained by curing the first resin composition, and the third functional film is a cured film obtained by curing a third resin composition containing the same resin as the first resin. is more preferred. That is, it is more preferable that the resin composition forming the third functional film contains the same resin as at least one of the resins contained in the resin composition forming the first functional film.
  • the first functional film is a cured film obtained by curing a first resin composition containing a first resin
  • the second functional film is a second functional film.
  • a cured film obtained by curing a second resin composition containing the same resin as the first resin, and the third functional film is formed by curing a third resin composition containing the same resin as the first resin. It is particularly preferable that it is a cured film formed by That is, a resin of the same kind as at least one of the resins contained in the resin composition forming the first functional film is added to the resin composition forming the second functional film and the resin forming the third functional film. It is particularly preferred that the composition comprises.
  • the piezoelectric device includes an ultrasonic wave transmitting/receiving section that uses the functional film made of the above-described cured film as an acoustic matching layer that suppresses reflection of sound waves at the interface of a plurality of members having a large difference in acoustic impedance. It is an example of a sound wave diagnostic imaging device.
  • FIG. 1 shows a schematic end view showing an acoustic wave transmitting/receiving section in an example of the piezoelectric device according to the first embodiment.
  • the sound wave transmitting/receiving unit 10 is provided in contact with an element substrate 12 having a plurality of piezoelectric elements installed on one surface of a base substrate and a surface 12A of the element substrate 12 on the piezoelectric element side. and an acoustic lens 16 provided in contact with the surface of the acoustic matching layer 14 opposite to the element substrate 12 .
  • the element substrate 12 and the acoustic lens 16 known ones are used.
  • ultrasonic waves emitted from the piezoelectric elements of the element substrate 12 pass through the acoustic matching layer 14 and pass through the acoustic lens 16 to be converged and reach the object.
  • the ultrasonic waves reflected by the object pass through the acoustic lens 16 and the acoustic matching layer 14 and are received by the piezoelectric elements of the element substrate 12 .
  • the acoustic matching layer 14 is provided and the functional film made of the above-described cured film is used as the acoustic matching layer 14, even if the acoustic impedance difference between the piezoelectric element and the acoustic lens 16 is large, the piezoelectric Reflection of ultrasonic waves at the interface between the element and the acoustic lens 16 is suppressed.
  • the acoustic matching layer 14 can be provided in contact with both the element substrate 12 and the acoustic lens 16 .
  • both the acoustic matching layer 14 and the acoustic lens 16 may be functional films made of the aforementioned cured film, or only the acoustic lens 16 may be made of the functional film made of the aforementioned cured film.
  • both the acoustic impedance of the acoustic matching layer 14 and the acoustic impedance of the acoustic lens 16 are set to desired values, respectively, and the interface can suppress the reflection in
  • the acoustic impedance difference between the acoustic matching layer 14 and the acoustic lens 16 is, for example, the content rate of the insulating filler in the cured film used as the acoustic matching layer 14, the content rate of the insulating filler in the cured film used as the acoustic lens 16, may be controlled by adjusting the The content rate of the insulating filler in the cured film used as the acoustic matching layer 14 and the content rate of the insulating filler in the cured film used as the acoustic lens 16 may be adjusted to have different values, or may be the same value. can be adjusted to The composition of
  • the acoustic matching layer may have a multilayer structure.
  • the acoustic wave transmitting/receiving unit 20 shown in FIG. The acoustic matching layer 26, which is provided in contact with the surface opposite to the element substrate 12 in the above, is a functional film made of the above-described cured film and has a different insulating filler content from the acoustic matching layer 24, and an acoustic matching layer and an acoustic lens 28 provided in contact with the surface opposite to the acoustic matching layer 24 in 26 .
  • both the acoustic matching layer 24 and the acoustic matching layer 26 are functional films made of the above-described cured film, and the contents of the insulating filler are different from each other, so that the piezoelectric element Even if the acoustic impedance difference between the piezoelectric element and the acoustic lens 28 is large, reflection of ultrasonic waves at the interface between the piezoelectric element and the acoustic lens 28 is suppressed.
  • the acoustic impedance of the acoustic matching layer 24 is set to a value close to the acoustic impedance of the piezoelectric element between the acoustic impedance of the piezoelectric element and the acoustic impedance of the acoustic lens 28, and the acoustic impedance of the acoustic matching layer 26 is By setting the impedance between the acoustic impedance of the piezoelectric element and the acoustic impedance of the acoustic lens 28 to a value close to the acoustic impedance of the acoustic lens 28, the acoustic impedance difference at the interface is reduced and the reflection of ultrasonic waves is suppressed.
  • the acoustic matching layer is not limited to the two-layer structure as shown in FIG. 2, and may have a structure of three or more layers.
  • a piezoelectric device is a sonic flowmeter having an sonic wave transmitting/receiving section that uses the functional film made of the above-described cured film as a sonic wave transmitting layer that promotes the transmission of sonic waves on the surface of a member and suppresses the reflection thereof.
  • FIG. 3 shows a schematic end view showing a sound wave transmitting/receiving section in an example of the piezoelectric device according to the second embodiment.
  • the sound wave transmitting/receiving unit 30 is provided in contact with an element substrate 32 having a plurality of piezoelectric elements provided on one surface of a base substrate, and a surface 32A of the element substrate 32 on the side of the piezoelectric elements. It has a protective layer 34 that protects the piezoelectric element of the substrate 32 from fluid, and a sound wave transmission layer 36 provided in contact with the surface of the protective layer 34 opposite to the element substrate 32 .
  • the sound wave transmission layer 36 is provided, for example, inside the flow channel of the sonic flowmeter, and the surface of the sound wave transmission layer 36 opposite to the protective layer 34 directly contacts the fluid to be measured.
  • two sonic wave transmitting/receiving units 30 are provided in the flow channel, and the sonic wave transmitted from one sonic wave transmitting/receiving unit 30 is received by the other sonic wave transmitting/receiving unit 30, Measure fluid velocity.
  • the pair of sound wave transmitting/receiving units 30 are arranged, for example, so that the sound wave transmitting layer 36 side faces each other via the flow path.
  • sound waves emitted from the piezoelectric elements of the element substrate 32 pass through the protective layer 34 and the sound wave transmission layer 36 and propagate to the fluid that is in direct contact with the sound wave transmission layer 36 .
  • the sound wave transmitting/receiving unit 30 that receives sound waves the sound wave propagating through the fluid enters from the sound wave transmission layer 36 and reaches the element substrate 32 by passing through the sound wave transmission layer 36 and the protective layer 34 .
  • the sound wave transmission layer 36 is provided, and the sound wave transmission layer 36 is a functional film made of the above-described cured film, so that even if the acoustic impedance difference between the protective layer 34 and the fluid is large, the protection Reflection of sound waves on the surface of layer 34 is suppressed. Specifically, by setting the acoustic impedance of the sound wave transmission layer 36 to a value close to the average value of the acoustic impedance of the protective layer 34 and the acoustic impedance of the fluid, the acoustic impedance difference at the interface is reduced, and the sound wave is reflected. is suppressed.
  • the cured film described above is flexible and can be directly provided on the protective layer 34 without passing through another layer such as an adhesive layer, it is easy to control the acoustic impedance difference at the interface, and the sound waves at the interface can be easily controlled. It is easy to suppress reflection. By suppressing the reflection of sound waves at the interface, the sound waves transmitted from one piezoelectric element efficiently reach the other piezoelectric element, thereby increasing the sensitivity of the sonic flowmeter.
  • both the sound wave transmission layer 36 and the protective layer 34 may be functional films made of the aforementioned cured film. Also, the sound wave transmission layer 36 may have a multilayer structure.
  • the piezoelectric device according to the third embodiment is an example of a fingerprint authentication sensor having a sound wave transmitting/receiving section that uses the above functional film made of the cured film as a sound wave attenuation layer that suppresses the transmission of sound waves on the surface of the member.
  • FIG. 4 shows a schematic end view showing an acoustic wave transmitting/receiving section in an example of the piezoelectric device according to the third embodiment.
  • the sound wave transmitting/receiving unit 40 is provided in contact with an element substrate 42 having a plurality of piezoelectric elements provided on one surface of a base substrate, and a surface 42A of the element substrate 42 on the piezoelectric element side.
  • an integrated circuit layer 48 disposed in contact with the .
  • the surface of the protective layer 44 opposite to the element substrate 42 is in direct contact with, for example, a fingerprint to be measured.
  • ultrasonic waves emitted from the piezoelectric elements of the element substrate 42 pass through the protective layer 44 and reach the uneven portions of the fingerprint to be measured. Then, the ultrasonic waves reflected by the object to be measured pass through the protective layer 44 again and are received by the piezoelectric elements of the element substrate 42 .
  • the integrated circuit layer 48 is a layer having a piezoelectric device control function, and is easily affected by vibrations such as ultrasonic waves. Therefore, it is preferable that vibrations such as ultrasonic waves do not propagate to the integrated circuit layer 48 .
  • the sound wave attenuation layer 46 is provided, and the functional film made of the above-described cured film is used as the sound wave attenuation layer 46, so that the ultrasonic wave transmitted through the element substrate 42 is attenuated by the sound wave attenuation layer 46.
  • the integrated circuit layer 48 is protected from ultrasonic vibrations.
  • the sound wave attenuation layer 46 is used to protect the integrated circuit layer 48 from ultrasonic vibrations, but the present invention is not limited to this.
  • a functional film made of the aforementioned cured film may be provided as a sound wave reflecting layer that promotes reflection of sound waves on the surface of the member.
  • the sound wave control method of the present disclosure is a sound wave control method that controls the amount of transmission and reflection of sound waves by providing the above-described cured film on the surface of a member that constitutes a piezoelectric device. For example, by adjusting the content of the insulating filler with respect to the total solid content of the resin composition used for producing the cured film according to the acoustic impedance of the member on which the cured film is to be provided, the amount of the insulating filler in the cured film is adjusted. The content is adjusted, and as a result, a cured film having an acoustic impedance value adjusted to a desired value is obtained. By providing a cured film having an adjusted acoustic impedance value on the surface of the member, the amount of transmission and reflection of sound waves on the surface of the member can be controlled.
  • the above-mentioned cured film whose acoustic impedance is adjusted to a value close to the average value of the acoustic impedances of the plurality of members is placed between the plurality of members.
  • the transmission amount of sound waves at the interface can be increased and the reflection amount can be controlled to be low.
  • the above-mentioned curing agent with adjusted acoustic impedance is used.
  • the film on the surface of the member the amount of transmission and reflection of sound waves on the surface is controlled.
  • ⁇ Resin 1 Epoxy resin (YL-983U (trade name), Mitsubishi Chemical Corporation)
  • Resin 2 Phenoxy resin (YP-50 (trade name), Nippon Steel Chemical & Materials Co., Ltd.)
  • Resin 3 Acrylic resin (Viscoat #260 (trade name), Osaka Organic Chemical Industry Co., Ltd.)
  • Resin 4 SBR resin (Dynaron 2324P (trade name), JSR Corporation)
  • Resin 5 Polyurethane resin (KU-7008 (trade name), Showa Denko Materials Co., Ltd.)
  • Curing agent 1 triethylenetetramine (Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Curing agent 2 Peroxide (Perbutyl-P (trade name), NOF Corporation)
  • Dispersant 1 Phosphate (BYK-9010 (trade name), BYK Chemie Japan Co., Ltd.)
  • Dispersant 1 Phosphate (BYK-9010 (trade name), BYK Chemie Japan Co.
  • Example 4 The obtained resin composition was applied to a release PET film so as to have a thickness of 100 ⁇ m after drying, and dried at 100° C. for 20 minutes to obtain a dry film. The obtained dried film was peeled off, cut into a predetermined size, superimposed, and processed with a hot plate press (temperature 170° C., pressure 2 MPa, time 30 minutes) to obtain a cured film having a thickness of 3 mm.
  • a hot plate press temperature 170° C., pressure 2 MPa, time 30 minutes
  • Example 5 The resulting resin composition was poured into a mold having a thickness of 3 mm, cured at 90° C. for 3 hours, and then removed from the mold to obtain a cured film.
  • Acoustic impedance was calculated from the following formula from the values of the density and sound velocity of the cured film obtained by measurement. Table 1 shows the results.
  • Formula: Acoustic Impedance Sound Velocity x Density
  • the resin compositions of Examples can provide functional films that can widely control acoustic impedance while maintaining flexibility.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine utilisée pour produire un film fonctionnel pour un dispositif piézoélectrique, et qui comprend une résine, le rapport de teneur en charge isolante étant inférieur à 50 % en volume des solides totaux de la composition de résine.
PCT/JP2022/042621 2021-11-17 2022-11-16 Composition de résine, film séché, film durci, dispositif piézoélectrique et procédé de commande d'onde sonore WO2023090376A1 (fr)

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PCT/JP2022/042621 WO2023090376A1 (fr) 2021-11-17 2022-11-16 Composition de résine, film séché, film durci, dispositif piézoélectrique et procédé de commande d'onde sonore

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006340007A (ja) * 2005-06-01 2006-12-14 Kyocera Corp 薄膜バルク音響波共振子およびフィルタならびに通信装置
JP2007189342A (ja) * 2006-01-11 2007-07-26 Toshiba Corp アレイ式超音波プローブおよび超音波診断装置
JP2008263419A (ja) * 2007-04-12 2008-10-30 Matsushita Electric Ind Co Ltd 音響整合体、超音波送受波器、および超音波流速流量計
JP2012034160A (ja) * 2010-07-30 2012-02-16 Konica Minolta Medical & Graphic Inc 超音波探触子用バッキング材、それを用いた超音波探触子、及び超音波医用画像診断装置
JP2021062170A (ja) * 2019-10-17 2021-04-22 コニカミノルタ株式会社 超音波プローブ、超音波診断装置およびバッキング材の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3459846B2 (ja) * 1994-08-25 2003-10-27 オリンパス光学工業株式会社 超音波探触子
JP4319644B2 (ja) * 2004-06-15 2009-08-26 株式会社東芝 音響バッキング組成物、超音波プローブ、及び超音波診断装置
JP4171038B2 (ja) * 2006-10-31 2008-10-22 株式会社東芝 超音波プローブおよび超音波診断装置
JP6002524B2 (ja) * 2012-09-28 2016-10-05 住友理工株式会社 トランスデューサ
JP6838941B2 (ja) * 2016-05-27 2021-03-03 オリンパス株式会社 超音波振動子および超音波内視鏡装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006340007A (ja) * 2005-06-01 2006-12-14 Kyocera Corp 薄膜バルク音響波共振子およびフィルタならびに通信装置
JP2007189342A (ja) * 2006-01-11 2007-07-26 Toshiba Corp アレイ式超音波プローブおよび超音波診断装置
JP2008263419A (ja) * 2007-04-12 2008-10-30 Matsushita Electric Ind Co Ltd 音響整合体、超音波送受波器、および超音波流速流量計
JP2012034160A (ja) * 2010-07-30 2012-02-16 Konica Minolta Medical & Graphic Inc 超音波探触子用バッキング材、それを用いた超音波探触子、及び超音波医用画像診断装置
JP2021062170A (ja) * 2019-10-17 2021-04-22 コニカミノルタ株式会社 超音波プローブ、超音波診断装置およびバッキング材の製造方法

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