WO2015005420A1 - Feuille piézoélectrique, procédé de fabrication de ladite feuille, et stratifié piézoélectrique - Google Patents

Feuille piézoélectrique, procédé de fabrication de ladite feuille, et stratifié piézoélectrique Download PDF

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Publication number
WO2015005420A1
WO2015005420A1 PCT/JP2014/068411 JP2014068411W WO2015005420A1 WO 2015005420 A1 WO2015005420 A1 WO 2015005420A1 JP 2014068411 W JP2014068411 W JP 2014068411W WO 2015005420 A1 WO2015005420 A1 WO 2015005420A1
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Prior art keywords
piezoelectric
sheet
fiber
inorganic filler
piezoelectric sheet
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PCT/JP2014/068411
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English (en)
Japanese (ja)
Inventor
米田　哲也
幸 山中
善宏 瀬戸口
渡辺　直樹
佳郎 田實
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日本バルカー工業株式会社
学校法人関西大学
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Priority to JP2015526395A priority Critical patent/JPWO2015005420A1/ja
Publication of WO2015005420A1 publication Critical patent/WO2015005420A1/fr

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/092—Forming composite materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/702—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive fibres
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to a piezoelectric sheet having high piezoelectricity, a method for manufacturing the sheet, and a piezoelectric laminate.
  • a piezoelectric material using a polymer material has been studied to have a porous structure by a method such as foaming or stretching or a crystal structure that is easily polarized.
  • a method such as foaming or stretching or a crystal structure that is easily polarized.
  • the polymer material has a porous structure, it exhibits high piezoelectric characteristics.
  • Patent Document 1 discloses a porous resin sheet for piezoelectric / pyroelectric elements containing ceramic particles having a volume porosity of 20 to 75% and a dielectric constant higher than that of a resin component. Has been. However, since a solvent extraction step is required to remove the phase separation agent used in the production process of the porous resin sheet for piezoelectric / pyroelectric elements, industrial practical application has been difficult.
  • Patent Document 2 discloses a piezoelectric film that has been subjected to a polarization treatment after forming a rolled film by mixing dielectric fine powder with polytetrafluoroethylene.
  • Patent Document 3 discloses a piezoelectric element forming sheet material comprising a ceramic component and a thermoplastic resin.
  • Patent Document 4 discloses an energy conversion film made of a stretched thermoplastic resin film containing an inorganic powder.
  • An object of the present invention is to provide a piezoelectric sheet having a high piezoelectric rate and a piezoelectric laminate using the sheet.
  • the present invention relates to the following [1] to [9], for example.
  • [1] A piezoelectric sheet containing a nonwoven fabric or woven fabric formed using fibers containing an organic polymer and containing an inorganic filler.
  • a method for producing a piezoelectric sheet comprising a step of producing a fiber by an electrospinning method from a spinning solution containing an organic polymer and an inorganic filler, and forming a nonwoven fabric or a woven fabric from the fiber.
  • a piezoelectric sheet and a piezoelectric laminate that have a high porosity are effective in retaining piezoelectricity, have high flexibility, have a high amount of charge retention in the sheet, and have excellent piezoelectric characteristics. You can get a body.
  • FIG. 1 is a schematic diagram showing an example of a cross section of the piezoelectric laminate of the present invention.
  • FIG. 2 is a schematic diagram showing an example of a cross section of the piezoelectric laminate of the present invention.
  • FIG. 3 is a schematic diagram showing an example of a cross section of the piezoelectric laminate of the present invention.
  • the piezoelectric sheet of the present invention (hereinafter also referred to as “sheet”) includes a non-woven fabric or a woven fabric formed using fibers containing an organic polymer, and includes an inorganic filler.
  • the piezoelectric sheet of the present invention contains an inorganic filler. For this reason, a piezoelectric sheet having a high charge retention amount in the sheet and excellent piezoelectric characteristics can be obtained.
  • a filler having a dielectric constant higher than that of the organic polymer is preferable from the viewpoint of obtaining a sheet having a high piezoelectric constant.
  • an inorganic filler having a relative dielectric constant ⁇ of 10 to 10,000 is preferable. preferable.
  • Specific examples of the inorganic filler include titanium oxide, aluminum oxide, barium titanate, lead zirconate titanate, zirconium oxide, cerium oxide, nickel oxide and tin oxide.
  • the average particle diameter of the inorganic filler is preferably 1/1000 to 1/2, more preferably 1/100 to 1/10, of the average fiber diameter of the fiber containing the organic polymer.
  • the average particle diameter of the inorganic filler is within this range, a sheet in which the inorganic filler is uniformly dispersed can be obtained, and the piezoelectric characteristics of the sheet can be improved uniformly.
  • the average particle diameter can be measured by the following method or an equivalent method.
  • the average particle diameter of the inorganic filler is obtained by observing with an electron microscope and calculating the average value.
  • an SEM equipment: S-3400N (manufactured by Hitachi High-Technologies Corporation), magnification: 10,000 times) observation region was selected at random, and this region was observed with SEM, It can be obtained by randomly selecting 20 inorganic fillers, measuring their particle diameters, and calculating the average.
  • the content of the inorganic filler contained in the sheet is preferably 0.1 to 30% by weight, more preferably 0.1 to 15% by weight, still more preferably 0.1 to 10% by weight, based on the total amount of the fiber. It is. If the content of the inorganic filler is within the above range, the piezoelectricity of the sheet can be further increased. When the content of the inorganic filler is less than the lower limit value, a sheet having a high piezoelectric rate may not be obtained. When the inorganic filler content is higher than the upper limit value, the initial value of the piezoelectric rate increases, but the charge retention rate May decrease.
  • the piezoelectric sheet of the present invention is formed using a fiber containing an organic polymer. For this reason, it is possible to obtain a piezoelectric sheet having a high porosity, effective in retaining piezoelectricity, and having high flexibility.
  • Examples of the organic polymer constituting the fiber include polymers having a volume resistivity of 1.0 ⁇ 10 13 ⁇ ⁇ cm or more.
  • polyamide resins (6-nylon, 6,6-nylon, etc.), aromatic Group polyamide resins (such as aramid), polyolefin resins (such as polyethylene and polypropylene), polyester resins (such as polyethylene terephthalate), polyacrylonitrile, phenolic resins, fluorine resins (such as polytetrafluoroethylene and polyvinylidene fluoride) Imide resin (polyimide, polyamideimide, bismaleimide, etc.).
  • an organic polymer that has a high continuous usable temperature does not have a dipole due to a molecule and a crystal structure, or does not have a glass transition point in the operating temperature range of the sheet.
  • the continuously usable temperature can be measured by a continuous use temperature test described in UL746B (UL standard), and is preferably 100 ° C. or higher, and more preferably 200 ° C. or higher.
  • an organic polymer exhibiting water repellency is preferable.
  • polyolefin resin, imide resin, and fluorine resin are preferable, and polytetrafluoroethylene (PTFE) is more preferable.
  • the fiber containing the organic polymer has an average fiber diameter of preferably 0.05 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m, still more preferably 0.3 to 5 ⁇ m.
  • the average fiber diameter is within the above range, a non-woven fabric or woven fabric exhibiting high flexibility can be formed, and a sufficient space for holding electric charge can be formed by increasing the fiber surface area. This is preferable in that the distribution uniformity can be increased.
  • the average fiber diameter is reduced by decreasing the humidity, decreasing the nozzle diameter, increasing the applied voltage, or increasing the voltage density during electrospinning. Tend to be.
  • the average fiber diameter is randomly selected by observing a scanning electron microscope (SEM) region for the fiber (group) to be measured, and observing this region by SEM (magnification: 10,000 times). This is a value calculated based on the measurement results obtained by selecting 20 fibers and measuring the fiber diameter (major axis) of each of these fibers.
  • SEM scanning electron microscope
  • the fiber diameter variation coefficient of the fiber is preferably 0.7 or less, more preferably 0.01 to 0.5.
  • the fiber diameter variation coefficient is within the above range, the fiber diameter of the fiber becomes uniform, and with such a fiber, a sheet having a higher porosity can be obtained, and the charge retention of the obtained sheet can be improved. It is preferable in that it can be increased.
  • the fiber length of the fiber is preferably 0.5 to 100 mm, preferably 1 to 50 mm.
  • the fiber is produced, for example, by an electrospinning method, a melt spinning method, a melt electrospinning method, a spunbond method (melt blow method), a wet method, or a spunlace method.
  • the fiber obtained by the electrospinning method has a fiber diameter. Since the nonwoven fabric or woven fabric formed from such fibers has a high porosity and a high specific surface area, a sheet and a piezoelectric laminate having high piezoelectricity can be obtained.
  • the electrospinning is performed using a spinning solution containing an organic polymer and a solvent, and if necessary, an inorganic filler.
  • the organic polymer is contained, for example, in an amount of 5 to 100% by weight, preferably 5 to 80% by weight, and more preferably 10 to 70% by weight in the spinning solution, although it depends on the kind of the polymer and the spinning method.
  • the said organic polymer may be used individually by 1 type, and may use 2 or more types.
  • the inorganic filler When an inorganic filler is blended in the spinning solution, the inorganic filler is included, for example, in an amount of 0.1 to 30% by weight, preferably 1 to 30% by weight, depending on the type of the inorganic filler. If the content of the inorganic filler is within the above range, the piezoelectricity of the sheet can be further increased. When the content of the inorganic filler is less than the lower limit value, a sheet having a high piezoelectric rate may not be obtained. When the inorganic filler content is higher than the upper limit value, the initial value of the piezoelectric rate increases, but the charge retention rate May decrease.
  • the said inorganic filler may be used individually by 1 type, and may use 2 or more types.
  • the solvent is not particularly limited as long as it can dissolve or disperse the organic polymer.
  • water dimethylacetamide, dimethylformamide, tetrahydrofuran, methylpyrrolidone, xylene, acetone, chloroform, ethylbenzene, cyclohexane, benzene
  • Examples include sulfolane, methanol, ethanol, phenol, pyridine, propylene carbonate, acetonitrile, trichloroethane, hexafluoroisopropanol, and diethyl ether.
  • These solvents may be used individually by 1 type, and may be used as a mixed solvent which combined 2 or more types.
  • the solvent is contained in the spinning solution in an amount of, for example, 0 to 90% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight.
  • the spinning solution may further contain additives other than the organic polymer and inorganic filler, such as a surfactant, a dispersant, a charge adjusting agent, a functional particle, an adhesive, a viscosity adjusting agent, and a fiber forming agent.
  • additives other than the organic polymer and inorganic filler such as a surfactant, a dispersant, a charge adjusting agent, a functional particle, an adhesive, a viscosity adjusting agent, and a fiber forming agent.
  • a surfactant for example, when the organic polymer is PTFE and the solvent is water
  • fiber formation is performed from the viewpoint of maintaining the organic polymer in a fiber shape during spinning. It is preferable that an agent is included.
  • the surfactant examples include a fluorine-based surfactant (that is, a surfactant having a fluorine atom.
  • a fluorine-based surfactant that is, a surfactant having a fluorine atom.
  • an ammonium salt of an acid having a perfluoroalkyl group a hydrocarbon-based surfactant (the main chain is an alkyl group).
  • a surfactant based on silicon a surfactant having a silicon atom.
  • the fluorosurfactant is a footgent (registered trademark) 100 (anionic fluorosurfactant), a footgent (registered trademark) 310 (cationic fluorosurfactant).
  • a footgent registered trademark
  • Megafac F114 anionic fluorosurfactant, manufactured by DIC Corporation
  • Surflon S-231 amphoteric fluorosurfactant, manufactured by Asahi Glass Co., Ltd.
  • the amount used is, for example, 0.01 to 5% by weight, preferably 0.1 to 3% by weight in the spinning solution.
  • the fiber forming agent is preferably a polymer having high solubility in a solvent, such as polyethylene oxide, polyethylene glycol, dextran, alginic acid, chitosan, starch, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide. , Cellulose, and polyvinyl alcohol.
  • a solvent such as polyethylene oxide, polyethylene glycol, dextran, alginic acid, chitosan, starch, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide. , Cellulose, and polyvinyl alcohol.
  • the amount of the fiber-forming agent used is, for example, 0.1 to 15% by weight, preferably 1 to 10% by weight in the spinning solution, although it depends on the viscosity of the solvent and the solubility in the solvent.
  • the spinning solution can be produced by mixing the above-mentioned organic polymer, solvent and, if necessary, additives by a conventionally known method.
  • the spinning solution preferably contains PTFE, a fiber forming agent, and a solvent.
  • spinning liquid include the following spinning liquid (1) (when no inorganic filler is included) and spinning liquid (2) (when an inorganic filler is included).
  • Spinning liquid (1) Spinning liquid containing 30 to 70% by weight, preferably 35 to 60% by weight of PTFE, and 0.1 to 10% by weight, preferably 1 to 7% by weight, of a fiber forming agent.
  • Spinning liquid (2) Containing 1 to 30% by weight, preferably 1 to 20% by weight of inorganic filler, 30 to 60% by weight, preferably 35 to 55% by weight of PTFE, and 0.1 to 10% by weight, preferably Spinning solution containing 1-7% by weight
  • the applied voltage during this electrospinning is preferably 5 to 50 kV, more preferably 10 to 40 kV.
  • the tip diameter (outer diameter) of the spinning nozzle is preferably 0.1 to 2.0 mm, more preferably 0.2 to 1.6 mm, and still more preferably 0.3 to 1.6 mm. More specifically, for example, when the spinning solution (1) is used, the applied voltage is preferably 10 to 50 kV, more preferably 10 to 40 kV, and the tip diameter (outer diameter) of the spinning nozzle is used. ) Is preferably 0.2 to 1.6 mm.
  • the distance between the electrodes is usually about 50 to 800 mm, preferably about 100 to 350 mm.
  • a method for producing the fiber a method for producing a fiber made of PTFE by an electrospinning method will be specifically described.
  • a method for producing the PTFE fiber a conventionally known production method can be employed, and examples thereof include the following methods described in JP-T-2012-515850.
  • a spinning solution comprising PTFE, a fiber forming agent and a solvent and having a viscosity of at least 50,000 cP; Spinning the spinning solution from a nozzle and forming a fiber by electrostatic traction; Collecting the fibers on a collector (eg, a take-up spool) to form a precursor; The method comprising calcining the precursor to form PTFE fibers by removing the solvent and the fiber-forming agent. In this method, an inorganic filler is added to the spinning solution to thereby add PTFE containing the inorganic filler. Fiber can be obtained.
  • the method for producing the sheet of the present invention is not particularly limited as long as a piezoelectric sheet containing a nonwoven fabric or woven fabric formed using a fiber containing an organic polymer and containing an inorganic filler is obtained.
  • an inorganic filler is blended in the spinning solution, and a fiber containing the inorganic filler is produced by an electrospinning method, and then the inorganic filler is produced. Examples thereof include a method of forming a nonwoven fabric or a woven fabric from a fiber containing a filler.
  • the aspect of the sheet of the present invention includes an aspect in which an inorganic filler is dispersed in a fiber and an aspect in which an inorganic filler is supported (attached or bonded) on the fiber surface.
  • the sheet of the present invention is a non-woven fabric or woven fabric composed of fibers containing an inorganic filler to prevent the inorganic filler from falling off during storage and use (under stress). This is preferable.
  • the step of producing the fiber, and the step of collecting the fiber (in the presence of an inorganic filler if necessary) and forming the non-woven fabric may be performed separately, They may be performed simultaneously (that is, the fibers may be accumulated in a sheet form while being produced to form a nonwoven fabric).
  • the step of producing the fiber, and the step of collecting the fiber (in the presence of an inorganic filler if necessary) to form a nonwoven fabric are simultaneously performed.
  • a step of accumulating the fiber in a sheet form (in the presence of an inorganic filler if necessary) by a wet method to form a nonwoven fabric may be performed.
  • the woven fabric In order to form the woven fabric, it can be produced by a method including a step of producing the fiber, and a step of weaving the obtained fiber into a sheet (in the presence of an inorganic filler if necessary) to form a woven fabric.
  • a method for weaving the fiber into a sheet if necessary, in the presence of an inorganic filler
  • a conventionally known weaving method can be used, and methods such as a water jet loom, an air jet loom, and a rapier room can be used.
  • the content of the inorganic filler is 0.1 to 30% by weight, preferably 1 to 30% by weight, based on the total amount of the fiber. If it is in the said range, the piezoelectric rate of a piezoelectric sheet can be raised more.
  • the heat treatment is performed, for example, by heat-treating a non-woven fabric or woven fabric formed from a fiber obtained from a spinning solution containing a fiber forming agent and a solvent, usually at 200 to 390 ° C. for 30 to 300 minutes. Can do.
  • the solvent and the fiber-forming agent remaining on the nonwoven fabric or woven fabric are removed, and the nonwoven fabric or woven fabric made of only PTFE (when the spinning solution contains an inorganic filler, the inorganic filler is also included). Can be manufactured.
  • an aqueous dispersion containing the fiber may be deposited on a mesh, for example, and formed into a sheet shape.
  • the amount of the fiber used is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the dispersion. If the fiber is used within this range, water can be efficiently utilized in the accumulation (papermaking) process, and the dispersion state of the fiber is improved, so that a uniform wet nonwoven fabric can be obtained.
  • An inorganic filler may be blended in the aqueous dispersion.
  • the amount of the inorganic filler used is preferably 0.01 to 10% by weight, more preferably 0.01 to 1.5% by weight, based on the total amount of the aqueous dispersion. It is. When the inorganic filler is used in an amount within this range, a uniform and large amount of inorganic filler can be supported in the obtained wet nonwoven fabric.
  • the aqueous dispersion is added with a dispersing agent such as a cationic, anionic, or nonionic surfactant, an oil agent, or an antifoaming agent that suppresses the generation of bubbles. Also good.
  • a dispersing agent such as a cationic, anionic, or nonionic surfactant, an oil agent, or an antifoaming agent that suppresses the generation of bubbles. Also good.
  • the sheet manufacturing method of the present invention includes (1) a method of supporting an inorganic filler on a nonwoven fabric or a woven fabric obtained by forming the fiber into a sheet, and (2) an inorganic filler using an electrospinning method.
  • a method of producing a fiber containing an inorganic filler from a spinning solution containing a non-woven fabric or a woven fabric, and (3) a method of forming a non-woven fabric from an aqueous dispersion containing an inorganic filler using a wet method. can be mentioned.
  • the method of supporting the inorganic filler after forming the nonwoven fabric or woven fabric from the fibers is not particularly limited, and may be performed by a conventionally known method.
  • the nonwoven fabric or woven fabric is dispersed in a dispersion in which the inorganic filler is dispersed.
  • the method of immersing is mentioned.
  • the surface of the nonwoven fabric or woven fabric or the inorganic filler may be treated in advance with a hydrophilizing agent or a coupling agent.
  • the supported amount of the inorganic filler is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total weight of the nonwoven fabric or woven fabric.
  • the amount of the inorganic filler used is such that the total amount of the inorganic filler is preferably 0.1 to 30% by weight with respect to the total amount of the fiber, The amount is more preferably 0.1 to 15% by weight, still more preferably 0.1 to 10% by weight. If the inorganic filler is within the above range, the piezoelectricity can be further increased while maintaining the flexibility of the piezoelectric sheet.
  • the basis weight of the sheet of the present invention is preferably 500 g / m 2 or less, more preferably 300 g / m 2 or less, still more preferably 100 g / m 2 or less, particularly preferably 0.1 to 20 g / m 2 .
  • the thickness of the sheet of the present invention is usually 10 ⁇ m to 1 mm, preferably 50 ⁇ m to 500 ⁇ m.
  • the fabric weight and thickness tend to increase when the fiber is produced by, for example, electrospinning, for example, by increasing the spinning time or increasing the number of spinning nozzles. Tends to increase by increasing the number of depositions, increasing the fiber concentration in the aqueous dispersion.
  • the porosity of the non-woven fabric or woven fabric obtained by the method (1) before supporting the inorganic filler is preferably 62% or more, more preferably 77% or more, and further preferably 80 to 99%.
  • the porosity of the sheet of the present invention is preferably 60% or more, more preferably 75% or more, and further preferably 80 to 98%. When the porosity is within the above range, it is preferable in that the charge retention rate is increased.
  • the porosity of the nonwoven fabric or woven fabric made of PTFE when the organic polymer is PTFE is calculated by the following method. (True density of PTFE ⁇ apparent density) ⁇ 100 / true density of PTFE
  • the sheet of the present invention may be either a single layer or a sheet composed of two or more layers having different materials and fiber diameters.
  • the sheet obtained as described above can be subjected to polarization treatment to inject charges into the sheet.
  • a conventionally known method can be used, and is not particularly limited, and examples thereof include voltage application processing such as DC voltage application processing and AC voltage application processing, and corona discharge processing.
  • the injected charge is concentrated in the pores existing in the nonwoven fabric or woven fabric to induce polarization.
  • the internally polarized sheet can take out electric charges through the front and back surfaces of the sheet by applying a compressive load in the sheet thickness direction. That is, charge transfer occurs with respect to the external load (electric circuit), and an electromotive force is obtained.
  • the piezoelectric laminate according to the present invention includes the piezoelectric sheet, and a surface coating layer laminated on at least one of the front and back surfaces of the outer surface of the piezoelectric sheet, and the surface coating layer
  • the volume resistivity is 1 ⁇ 10 13 ⁇ ⁇ cm or more. Since the surface covering layer works to prevent the electric charge held in the piezoelectric sheet from being attenuated by being electrically connected to the external environment, it is effective for holding the piezoelectric rate of the piezoelectric laminate of the present invention. Function.
  • volume resistivity of the surface coating layer is usually 1 ⁇ 10 13 ⁇ ⁇ cm or more, preferably 1 ⁇ 10 14 ⁇ ⁇ cm or more. If it exists in this range, it is preferable at the point of the improvement of the long-term charge retention in a piezoelectric sheet.
  • the volume resistivity can be measured based on the double ring electrode method using a single surface coating layer (film).
  • the elastic modulus of the surface coating layer is preferably different from that of the piezoelectric sheet, and may be higher or lower than that of the piezoelectric sheet.
  • the difference in elastic modulus between the surface coating layer and the piezoelectric sheet is usually 10 MPa or more, preferably 50 MPa or more. If it exists in this range, it is preferable at the point which can induce a nonlinear deformation at the time of sheet compression.
  • the relative dielectric constant of the surface coating layer is usually preferably 2 to 100. If the relative dielectric constant is within this range, when the electric charge is applied by the polarization treatment, specifically, corona discharge, the electric charge is concentrated inside the surface coating layer having a high dielectric constant, and the surface coating layer and the piezoelectric layer are piezoelectric. Charge is also retained at the interface of the conductive sheet.
  • the thickness of the surface coating layer is usually 1 ⁇ m or more, and preferably 30% or less of the thickness of the piezoelectric sheet.
  • the thickness is 1 ⁇ m or less, the handleability of the film for the surface coating layer is poor, and problems such as a decrease in insulation due to film defects (pinholes) may occur.
  • the thickness is 30% or more of the thickness of the piezoelectric sheet, the cost for injecting charges into the piezoelectric sheet is increased, and specifically, the corona discharge voltage is set high. Therefore, the industrial application tends to be difficult.
  • the surface coating layer is formed on both surfaces of the piezoelectric sheet, if the thickness of each surface coating layer is made different from each other, nonlinear deformation is induced with respect to compressive strain, and high piezoelectricity is exhibited. This is preferable because it is possible.
  • thermosetting resin examples include polyimide, epoxy resin, thermosetting rubber (eg, vinylidene fluoride rubber, silicone rubber), polyurethane, phenol resin, imide resin (eg, polyimide, polyamideimide, bismaleimide), silicone resin. Is mentioned.
  • thermoplastic resin examples include acrylic resin, methacrylic resin, polypropylene, polyamide, vinyl chloride resin, silicone resin, fluorine resin (for example, polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), Polyvinylidene fluoride (PVDF), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP)), nylon, polystyrene, high density polyethylene, low density polyethylene, polyphenylene Examples thereof include sulfide, polyethylene oxide, polysulfone, and polyvinylidene chloride.
  • fluorine resin for example, polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), Polyvinylidene fluoride (PVDF), tetrafluor
  • the surface coating layer can be formed by a conventionally known method. For example, when a thermosetting resin is used, at least one side of the front and back surfaces of the piezoelectric sheet, that is, one side or both sides, is cured with the thermosetting resin. It can be formed by applying and drying a solution obtained by dissolving an agent in a solvent. Moreover, it can also form by apply
  • the surface coating layer preferably covers the front and back surfaces of the piezoelectric sheet from the viewpoint of obtaining a piezoelectric laminate that retains electric charge for a long time and retains a high piezoelectric rate. The back surface and the end surface are preferably covered.
  • the “front and back surfaces of the piezoelectric sheet” means two surfaces having the largest area among the outer surfaces (six surfaces) of the sheet, and the “end surface of the piezoelectric sheet” Of the outer surfaces (six surfaces) of the sheet, the four surfaces excluding the front and back surfaces.
  • the curing agent crosslinking agent
  • a conventionally known curing agent can be used.
  • 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Perhexa 25B (NOF) Product)
  • triallyl isocyanurate (trade name: TAIC (manufactured by NOF Corporation)
  • the amount of the curing agent used is usually 1 to 20% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the resin.
  • solvent used here examples include tetrahydrofuran (THF), toluene, benzene, acetone, and ethylbenzene.
  • THF tetrahydrofuran
  • the amount of the solvent used is usually 100 to 5000 parts by weight, preferably 200 to 3000 parts by weight with respect to 100 parts by weight of the resin.
  • the surface coating layer may be formed (laminated) by directly applying a liquid containing a thermosetting resin and a curing agent to the surface of the piezoelectric sheet and drying it.
  • a method of forming a surface coating layer (film for) and laminating it by thermocompression bonding with the piezoelectric sheet may be used.
  • thermoplastic resin a thermosetting resin or a photocurable resin
  • a conventionally known molding method for example, a molding machine such as a single-screw or twin-screw extruder.
  • a molding machine such as a single-screw or twin-screw extruder.
  • molding in a film form etc. with a pressure molding machine, T-die, etc. is mentioned, for example.
  • the molding temperature is usually about the same as the melting temperature of the resin, and in the case of a thermosetting resin, it is usually about the same as the curing temperature of the resin.
  • a surface coating layer is laminated on one side of a piezoelectric sheet (FIG. 1), a surface coating layer is laminated on the front and back surfaces of a piezoelectric sheet (FIG. 2), piezoelectricity Examples include those in which a surface coating layer is formed on the front and back surfaces and end surfaces of the sheet (FIG. 3).
  • the piezoelectric laminate according to the present invention can form a new interface capable of holding electric charges between the piezoelectric sheet and the surface coating layer, and thus is effective in improving the piezoelectric rate and is held at such an interface. The amount of charges that can be held synergistically by moving the charges to the hollow structure of the piezoelectric sheet is increased, which contributes to an improvement in piezoelectricity.
  • the piezoelectric laminate of the present invention includes a non-woven fabric or a woven fabric formed using a fiber containing an organic polymer, and contains a piezoelectric sheet containing an inorganic filler, so that it has high flexibility and charge response even at a minute stress. Produce.
  • the piezoelectric laminated body of the present invention has an electromotive force generated by pressure, vibration, sensing materials such as actuators, vibration bodies, pressure sensors, vibration force sensors, and pressure sensors that can be used in automobiles, outdoors, and factories. It can be used as a power generation material used as a power source.
  • a method of storing the electromotive force in a power storage mechanism and using it is also included.
  • the piezoelectric laminate of the present invention can induce a non-linear deformation with respect to the compressive strain at the time of charge extraction by providing a difference in elastic modulus between the piezoelectric sheet and the surface coating layer. It can be about 100 to 400 (unit: d 33 (pC / N)).
  • a conventionally known layer or the like other than the piezoelectric sheet and the surface coating layer may exist.
  • Example 1 Production of piezoelectric sheet and piezoelectric laminate comprising titanium oxide-containing PTFE fiber obtained by electrospinning (titanium oxide content: 20 wt%)
  • a piezoelectric sheet that is a nonwoven fabric sheet is obtained by accumulating PTFE fibers containing titanium oxide in a sheet shape by the electrospinning method described in JP-T-2012-515850 using the following spinning solution and then heat-treating the sheet. (Piezoelectric layer) was manufactured.
  • the porosity was measured based on the following method. Apparent appearance calculated using the weight of a test piece cut out of a 4 cm square (4 cm length, 4 cm width) of a piezoelectric sheet and the thickness measured by a micrometer (LITEMATEC VL-50, manufactured by Mitutoyo Corporation) It calculated by the following formula using the density.
  • Thermosetting resin (fluorine rubber G912 manufactured by Daikin Industries, Ltd.) (fluorine concentration: 70.5% by weight, specific gravity (23 ° C): 1.91 (JISK6268), Mooney viscosity (on the front and back surfaces and end surfaces of the obtained piezoelectric sheet) ML1 + 10 ⁇ 100 ° C): approx.
  • the volume resistivity of this surface coating layer was 1.0 ⁇ 10 13 ⁇ ⁇ cm.
  • the volume resistivity of the surface coating layer used in the examples is also the same value.
  • the volume resistivity of the surface coating layer was measured based on the double ring electrode method using the surface coating layer alone.
  • the piezoelectric laminate was subjected to polarization treatment by corona discharge for 3 minutes at room temperature with a distance of 12.5 mm between electrodes and a voltage between electrodes of 3 kV using a corona discharge device manufactured by Kasuga Electric Co., and then both sides of the laminate.
  • a rectangular electrode made of aluminum foil manufactured by Mitsubishi Aluminum Co., Ltd., FOIL, 11 ⁇ m was provided to prepare a sample for evaluation.
  • Example 2 Production of piezoelectric sheet and piezoelectric laminate comprising titanium oxide-containing PTFE fibers obtained by electrospinning (titanium oxide content: 10 wt%) A piezoelectric sheet and a piezoelectric laminate were produced by performing the same operations as in Example 1 except that the following spinning solution was used, and the same physical properties as in Example 1 were measured using these. The results are also shown in Table 1.
  • Example 3 Production of piezoelectric sheet and piezoelectric laminate comprising titanium oxide-containing PTFE fibers obtained by electrospinning (titanium oxide content: 5 wt%) A piezoelectric sheet and a piezoelectric laminate were produced by performing the same operations as in Example 1 except that the following spinning solution was used, and the same physical properties as in Example 1 were measured using these. The results are also shown in Table 2.
  • Example 4 Production of piezoelectric sheet and piezoelectric laminate comprising titanium oxide-containing PTFE fiber obtained by electrospinning (titanium oxide content: 1 wt%) A piezoelectric sheet and a piezoelectric laminate were produced by performing the same operations as in Example 1 except that the following spinning solution was used, and the same physical properties as in Example 1 were measured using these. The results are also shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille piézoélectrique, un procédé de fabrication de ladite feuille, et un stratifié piézoélectrique, la feuille piézoélectrique contenant un tissu non tissé ou un tissu tissé formé au moyen de fibres contenant un polymère organique, ainsi qu'une charge inorganique.
PCT/JP2014/068411 2013-07-10 2014-07-10 Feuille piézoélectrique, procédé de fabrication de ladite feuille, et stratifié piézoélectrique WO2015005420A1 (fr)

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JP2017152468A (ja) * 2016-02-23 2017-08-31 東京応化工業株式会社 圧電素子、センサ、アクチュエータ、及び圧電素子の製造方法
JP2018064097A (ja) * 2016-10-12 2018-04-19 Ntn株式会社 圧電素子およびその製造方法
WO2018092708A1 (fr) * 2016-11-15 2018-05-24 日本バルカー工業株式会社 Feuille d'élément piézoélectrique et procédé permettant de fabriquer cette dernière
WO2022097547A1 (fr) * 2020-11-04 2022-05-12 東レ株式会社 Composition de résine, tissu non tissé et produit textile obtenus à l'aide de celle-ci, séparateur pour élément de stockage d'énergie, batterie rechargeable et condensateur à double couche électrique

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WO2017138542A1 (fr) * 2016-02-09 2017-08-17 日本バルカー工業株式会社 Capteur de vibrations, procédé de mesure de vibrations, et kit de préparation d'un capteur de vibrations
JPWO2017138542A1 (ja) * 2016-02-09 2018-12-06 株式会社バルカー 振動センサー、振動測定方法および振動センサー作製用キット
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WO2022097547A1 (fr) * 2020-11-04 2022-05-12 東レ株式会社 Composition de résine, tissu non tissé et produit textile obtenus à l'aide de celle-ci, séparateur pour élément de stockage d'énergie, batterie rechargeable et condensateur à double couche électrique

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