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WO2017209080A1 - Film piézoélectrique - Google Patents

Film piézoélectrique Download PDF

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Publication number
WO2017209080A1
WO2017209080A1 PCT/JP2017/019979 JP2017019979W WO2017209080A1 WO 2017209080 A1 WO2017209080 A1 WO 2017209080A1 JP 2017019979 W JP2017019979 W JP 2017019979W WO 2017209080 A1 WO2017209080 A1 WO 2017209080A1
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WIPO (PCT)
Prior art keywords
piezoelectric film
coating layer
piezoelectric
layer
piezoelectricity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/019979
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English (en)
Japanese (ja)
Inventor
浩史 別府
孝伸 矢野
基希 拝師
憲俊 木曽
智剛 梨木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
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Filing date
Publication date
Priority claimed from JP2017104590A external-priority patent/JP2017216450A/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to KR1020187028511A priority Critical patent/KR20190015188A/ko
Priority to CN201780033533.1A priority patent/CN109196673A/zh
Publication of WO2017209080A1 publication Critical patent/WO2017209080A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
    • H10N30/706—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings characterised by the underlying bases, e.g. substrates
    • H10N30/708—Intermediate layers, e.g. barrier, adhesion or growth control buffer layers
    • 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
    • H10N30/857—Macromolecular compositions
    • 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
    • H10N30/302—Sensors

Definitions

  • the present invention relates to a piezoelectric film.
  • a touch panel detects a two-dimensional position on the surface of a finger or pen that touches the surface of the touch panel.
  • finger or pen is simply referred to as “finger”, and the two-dimensional position on the surface of the touch panel of the finger or pen is referred to as “finger XY coordinates”.
  • the pressure touched by the finger cannot be detected.
  • the magnitude of the pressure touched by the finger is considered to be in the Z-axis direction and is referred to as the “Z coordinate of the finger”. That is, regardless of the magnitude of the pressure touched by the finger (Z coordinate of the finger) Only the XY coordinates of the finger touch position are detected.
  • Such a touch panel that can detect the pressure (Z coordinate of the finger) touched by a finger is described in, for example, Japanese Patent Application Laid-Open No. 2010-26938.
  • a laminate in which transparent electrodes are laminated on both sides of a piezoelectric layer containing a polyvinylidene fluoride-tetrafluoroethylene copolymer is used.
  • the thickness of the piezoelectric layer containing the polyvinylidene fluoride-tetrafluoroethylene copolymer is 20 ⁇ m to 300 ⁇ m.
  • the piezoelectric layer containing the polyvinylidene fluoride-tetrafluoroethylene copolymer of Patent Document 1 is described as being produced by a casting method or an extrusion method, a self-supporting film (a film not laminated on another film) )it is conceivable that.
  • Patent Document 1 describes that a piezoelectric layer containing a polyvinylidene fluoride-tetrafluoroethylene copolymer has a haze value (cloudiness value) of 5% to 7% and a total light transmittance of 95%.
  • the haze value and the total light transmittance in the examples of Patent Document 1 are values of the piezoelectric layer alone containing the polyvinylidene fluoride-tetrafluoroethylene copolymer before the transparent electrode is laminated.
  • the visibility of the image on the display on the back of the touch panel is affected at least by the haze value and the total light transmittance of the piezoelectric film. Since the piezoelectric layer containing the polyvinylidene fluoride-tetrafluoroethylene copolymer of Patent Document 1 has a large haze value, the visibility of the display image on the back surface of the touch panel may be lowered.
  • an object of the present invention is to realize a piezoelectric film having a small haze value and a high total light transmittance.
  • the piezoelectric film of the present invention includes a laminate of a base film and a piezoelectric coating layer.
  • the piezoelectric film of the present invention includes an undercoat layer between the base film and the coating layer having piezoelectricity.
  • the piezoelectric film of the present invention includes at least one optical adjustment layer on the surface of the coating layer having piezoelectricity opposite to the base film.
  • the at least one optical adjustment layer means that the optical adjustment layer may be a multilayer film having two or more layers.
  • the piezoelectric film of the present invention includes at least one first optical adjustment layer between the base film and the coating layer having piezoelectricity.
  • the at least one first optical adjustment layer means that the first optical adjustment layer may be a multilayer film of two or more layers.
  • the piezoelectric film of the present invention includes at least one second optical adjustment layer on the surface of the coating layer having piezoelectricity opposite to the first optical adjustment layer.
  • the term “at least one second optical adjustment layer” means that the second optical adjustment layer may be a multilayer film including two or more layers.
  • the piezoelectric film of the present invention includes at least one anti-blocking layer between the base film and the coating layer having piezoelectricity.
  • the at least one anti-blocking layer means that the anti-blocking layer may be a multilayer film having two or more layers.
  • the piezoelectric film of the present invention includes at least one anti-blocking layer on the surface of the base film opposite to the piezoelectric coating layer.
  • the piezoelectric film of the present invention includes at least one transparent adhesive layer on the surface of the coating layer having piezoelectricity opposite to the base film.
  • the at least one transparent adhesive layer means that the transparent adhesive layer may be a multilayer film having two or more layers.
  • the piezoelectric film of the present invention includes at least one transparent adhesive layer on the surface of the base film opposite to the piezoelectric coating layer.
  • the coating layer having piezoelectricity contains a fluororesin.
  • the fluororesin is a vinylidene fluoride polymer or a copolymer of two or more of (vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene).
  • the fluororesin is a copolymer of vinylidene fluoride and trifluoroethylene, and the molar ratio of vinylidene fluoride and trifluoroethylene contained in the copolymer is 100 is in the range of (50 to 85) :( 50 to 15).
  • the fluororesin is a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene, and the vinylidene fluoride, trifluoroethylene, and chloro contained in the copolymer
  • the molar ratio of trifluoroethylene is in the range of (63 to 65) :( 27 to 29) :( 10 to 6), based on 100 as a whole.
  • the piezoelectric coating layer is a coating layer obtained by applying and drying a fluororesin solution on a substrate film.
  • the thickness of the coating layer having piezoelectricity is 0.5 ⁇ m to 20 ⁇ m.
  • the material of the base film is polyethylene terephthalate, polyethylene naphthalate, polyolefin, polycycloolefin, cycloolefin copolymer, polycarbonate, polyether sulfone, polyarylate, polyimide, polyamide, polystyrene, It is selected from at least one of polynorbornene.
  • the piezoelectric film of the present invention has a haze value of 5% or less.
  • the piezoelectric film of the present invention has a total light transmittance of 90% or more.
  • the piezoelectric layer of the present invention since the piezoelectric layer is formed by coating, the thickness of the piezoelectric layer is thinner than a piezoelectric layer made of a conventional self-supporting film. Therefore, the increase in the haze value and the decrease in the total light transmittance due to the piezoelectric layer are less than that of the piezoelectric layer made of a self-supporting film. As a result, a piezoelectric film having a small haze value and a high total light transmittance is realized.
  • the piezoelectric film of the present invention is used as a Z-coordinate detection piezoelectric film for a touch panel, it is possible to realize a touch panel having a Z-coordinate (finger pressing force) detection function with good display visibility on the back of the touch panel. it can.
  • FIG. 1 shows a first basic configuration of the piezoelectric film of the present invention.
  • the first basic configuration of the piezoelectric film of the present invention is a piezoelectric film 10 in which a base film 11 is laminated with a coating layer 12 having piezoelectricity.
  • An easy adhesion layer (not shown) may be laminated between the base film 11 and the coating layer 12 having piezoelectricity.
  • FIG. 2 shows a second basic configuration of the piezoelectric film of the present invention. Elements common to the first basic configuration are denoted by the same reference numerals.
  • a second basic configuration of the piezoelectric film of the present invention is a piezoelectric film 20 in which an undercoat layer 13 is laminated on a base film 11 and further a coating layer 12 having piezoelectricity is laminated on the undercoat layer 13. .
  • the undercoat layer 13 (or anchor coat layer) has a function of increasing the adhesion between the base film 11 and the coating layer 12 having piezoelectricity.
  • FIG. 3 shows a third basic configuration of the piezoelectric film of the present invention. Elements common to the first basic configuration are denoted by the same reference numerals.
  • a coating layer 12 having piezoelectricity is laminated on the base film 11, and at least one optical adjustment layer 14 is further laminated on the coating layer 12 having piezoelectricity.
  • This is a piezoelectric film 30.
  • the optical adjustment layer 14 (Index matching layer) (also referred to as a refractive index adjustment layer) has a function of adjusting the reflectance of the piezoelectric film 30.
  • An easy adhesion layer (not shown) may be laminated between the base film 11 and the coating layer 12 having piezoelectricity.
  • FIG. 4 shows a fourth basic configuration of the piezoelectric film of the present invention. Elements common to the first basic configuration are denoted by the same reference numerals.
  • the fourth basic configuration of the piezoelectric film of the present invention at least one first optical adjustment layer 15 is laminated on the base film 11, and further, at least one first optical adjustment layer 15 is piezoelectric.
  • the piezoelectric film 40 is formed by laminating a coating layer 12 having
  • FIG. 5 shows a fifth basic configuration of the piezoelectric film of the present invention. Elements common to the fourth basic configuration are denoted by the same reference numerals.
  • the fifth basic configuration of the piezoelectric film of the present invention at least one first optical adjustment layer 15 is laminated on the base film 11, and further, at least one first optical adjustment layer 15 is piezoelectric.
  • the piezoelectric film 50 is formed by laminating a coating layer 12 having, and further laminating at least one second optical adjustment layer 16 on the coating layer 12 having piezoelectricity.
  • FIG. 6 shows a sixth basic configuration of the piezoelectric film of the present invention. Elements common to the first basic configuration are denoted by the same reference numerals.
  • the sixth basic configuration of the piezoelectric film of the present invention is that a base film 11 is laminated with at least one anti-blocking layer 17, and further, at least one anti-blocking layer 17 has a piezoelectric coating layer 12.
  • the piezoelectric film 60 is laminated.
  • the anti-blocking layer 17 has a function of preventing the stacked or wound piezoelectric films 60 from being pressure-bonded (blocked).
  • FIG. 7 shows a seventh basic configuration of the piezoelectric film of the present invention. Elements common to the third basic configuration are denoted by the same reference numerals.
  • a coating layer 12 having piezoelectricity is laminated on one surface of the substrate film 11, and at least one optical adjustment layer 14 is further provided on the coating layer 12 having piezoelectricity.
  • the piezoelectric film 70 is laminated and has at least one anti-blocking layer 17 laminated on the other surface of the base film 11.
  • An easy adhesion layer (not shown) may be laminated between the base film 11 and the coating layer 12 having piezoelectricity.
  • FIG. 8 shows an eighth basic configuration of the piezoelectric film of the present invention. Elements common to the first basic configuration are denoted by the same reference numerals.
  • a coating layer 12 having piezoelectricity is laminated on the base film 11, and at least one transparent adhesive layer 18 is further laminated on the coating layer 12 having piezoelectricity.
  • the at least one transparent adhesive layer 18 may be at least one transparent adhesive layer.
  • An easy adhesion layer (not shown) may be laminated between the base film 11 and the coating layer 12 having piezoelectricity.
  • FIG. 9 shows a ninth basic configuration of the piezoelectric film of the present invention. Elements common to the eighth basic configuration are denoted by the same reference numerals.
  • a coating layer 12 having piezoelectricity is laminated on one surface of the substrate film 11, and at least one transparent adhesive layer 18 is formed on the other surface of the substrate film 11.
  • the at least one transparent adhesive layer 18 may be at least one transparent adhesive layer.
  • An easy adhesion layer (not shown) may be laminated between the base film 11 and the coating layer 12 having piezoelectricity.
  • the base film 11 is made of, for example, a polymer film such as polyethylene terephthalate, polyethylene naphthalate, polyolefin, polycycloolefin, cycloolefin copolymer, polycarbonate, polyether sulfone, polyarylate, polyimide, polyamide, polystyrene, and polynorbornene.
  • a polymer film such as polyethylene terephthalate, polyethylene naphthalate, polyolefin, polycycloolefin, cycloolefin copolymer, polycarbonate, polyether sulfone, polyarylate, polyimide, polyamide, polystyrene, and polynorbornene.
  • PET polyethylene terephthalate
  • the thickness of the base film 11 is preferably 10 ⁇ m to 200 ⁇ m, but is not limited thereto. However, if the thickness of the base film 11 is less than 10 ⁇ m, handling may be difficult. Moreover, when the thickness of the base film 11 exceeds 200 ⁇ m, it may be difficult to wind the piezoelectric film (10, 20, 30, 40, 50, 60, 70, 80, 90) into a roll. If the thickness of the substrate film 11 exceeds 200 ⁇ m, the piezoelectric film (10, 20, 30, 40, 50, 60, 70, 80, 90) may be too thick when mounted on a touch panel or the like. There is.
  • the material of the coating layer 12 having piezoelectricity is not particularly limited as long as the surface of the base film 11 can be coated in a thin film and the coated thin film has piezoelectricity. Absent.
  • the coating layer 12 having piezoelectricity desirably exhibits piezoelectricity without performing poling (polarization treatment), but may exhibit piezoelectricity after poling.
  • non-contact type poling and contact type poling as poling (polarization processing).
  • the coating layer 12 is polarized by subjecting the coating layer 12 to corona discharge treatment.
  • contact poling for example, the coating layer 12 is sandwiched between two metal plates, and a voltage is applied between the two metal plates to polarize the coating layer 12.
  • the coating layer 12 having piezoelectricity is made into a solution by dissolving the material of the coating layer 12 having piezoelectricity in a solvent, and is thinly applied to the surface of the base film 11 by a known coating apparatus such as a bar coater or a gravure coater. And then dried.
  • a material containing a fluororesin is preferably used as the material of the coating layer 12 having piezoelectricity.
  • the material containing a fluororesin include a vinylidene fluoride polymer, a vinylidene fluoride / trifluoroethylene copolymer, a vinylidene fluoride / trifluoroethylene / chlorotrifluoroethylene copolymer, hexafluoro Copolymer of propylene and vinylidene fluoride, copolymer of perfluorovinyl ether and vinylidene fluoride, copolymer of tetrafluoroethylene and vinylidene fluoride, copolymer of hexafluoropropylene oxide and vinylidene fluoride, hexafluoropropylene And a copolymer of tetrafluoroethylene and vinylidene fluoride.
  • the material containing a fluororesin is preferably a copolymer of vinylidene fluoride and trifluoroethylene, or a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene.
  • a copolymer of vinylidene fluoride and trifluoroethylene is referred to as a binary copolymer.
  • a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene is referred to as a ternary copolymer.
  • the molar ratio of vinylidene fluoride and trifluoroethylene is 100 as a whole.
  • (50 to 85): (50 to 15) is appropriate.
  • a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene is used as a material for the coating layer 12 having piezoelectricity, vinylidene fluoride, trifluoroethylene
  • the molar ratio of chlorotrifluoroethylene is suitably in the range of (63 to 65) :( 27 to 29) :( 10 to 6) with 100 as a whole.
  • the thickness of the coating layer 12 having piezoelectricity is not limited, but in consideration of the optical characteristics described later, it is preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 0.5 ⁇ m to 5 ⁇ m. Further preferred. If the thickness of the coating layer 12 having piezoelectricity is less than 0.5 ⁇ m, the formed film may be incomplete. If the thickness of the coating layer 12 having piezoelectricity exceeds 20 ⁇ m, the optical characteristics (haze value and total light transmittance) may become inappropriate.
  • the transparent adhesive layer 18 is preferably made of an optical transparent adhesive.
  • the transparent adhesive layer 18 can be formed using a sheet of an optical transparent adhesive.
  • the transparent adhesive layer is preferably made of an optical transparent adhesive.
  • a liquid optical transparent adhesive can be applied and cured by irradiation with ultraviolet rays to form a transparent adhesive layer.
  • the refractive index of the transparent adhesive layer 18 or the transparent adhesive layer is preferably an intermediate value of the refractive indexes of the materials laminated on both sides thereof.
  • the haze value of the piezoelectric film is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, and more preferably 2% or less.
  • the total light transmittance of the piezoelectric film is preferably 90% or more, more preferably 91% or more, and particularly preferably 92% or more. If the haze value of the piezoelectric film exceeds 5%, or if the total light transmittance is less than 90%, the image on the display may not be clearly visible.
  • a transparent electrode can be laminated
  • the optical adjustment layer 14 and the transparent electrode 20 are laminated on the piezoelectric film 10 of FIG.
  • the coating layer 12 having piezoelectricity in the base film 11 has a hard coat layer 22 having an anti-blocking function laminated on the surface on the tie side.
  • the transparent electrode 20 examples include indium-based composite oxides, typically indium tin composite oxide (ITO: Indium Tin Oxide), and indium zinc composite oxide, but doped with tetravalent metal ions or divalent metal ions.
  • ITO Indium Tin Oxide
  • Indium oxide In203
  • Indium composite oxides are characterized by high transmittance of 80% or more in the visible light region (380 to 780 nm) and low surface resistance per unit area (30 to 1000 ⁇ / ⁇ ).
  • the surface resistance value of the indium composite oxide is preferably 300 ⁇ / ⁇ (ohms per square) or less, and more preferably 150 ⁇ / ⁇ .
  • a transparent electrode having a low surface resistance is formed by, for example, forming an amorphous layer of an indium-based composite oxide on a cured resin layer by sputtering or vacuum evaporation, and then heat-treating it at 100 to 200 ° C. It is obtained by changing the crystalline layer to a crystalline layer.
  • the transparent electrode 20 is not limited to the above materials, and transparent conductive oxides such as tin zinc oxide, zinc oxide and fluorine-doped tin oxide, and conductive polymers such as polyethylenedioxythiophene can be used.
  • transparent conductive oxides such as tin zinc oxide, zinc oxide and fluorine-doped tin oxide, and conductive polymers such as polyethylenedioxythiophene can be used.
  • the thickness of the coating layer 12 having piezoelectricity examples are 0.5 to 10 ⁇ m, the thickness of the optical adjustment layer 14 is 80 to 160 nm, and the thickness of the transparent electrode 20 is 20 nm or more. Further, the refractive index of the coating layer 12 having piezoelectricity is 1.40 to 1.50, the refractive index of the optical adjustment layer 14 is 1.50 to 1.70, and the refractive index of the transparent electrode 20 is 1.90 to 2.50. 10 is an example. Further, the thickness of the base film 11 is set to 2 to 100 ⁇ m, and the refractive index is set to 1.50 to 1.70. By using the above thickness and refractive index, the difference in reflectance between the transparent electrode 20 and the optical adjustment layer 14 becomes 2.0% or less, and the appearance is improved.
  • the piezoelectric film 10 of Example 1 has the first basic configuration of the piezoelectric film of the present invention.
  • easy adhesion (not shown) is first formed on the surface of a substrate film 11 (polyethylene terephthalate film), and then a copolymer of vinylidene fluoride and trifluoroethylene (binary copolymer) is used. (Coupled) solution.
  • the thickness of the base film 11 (polyethylene terephthalate film) was 23 ⁇ m.
  • a vinylidene fluoride / trifluoroethylene copolymer (binary copolymer) is dissolved in methyl ethyl ketone by ultrasonic waves, and vinylidene fluoride and trifluoroethylene are dissolved.
  • a solution of this copolymer (binary copolymer) was prepared.
  • the molar ratio of vinylidene fluoride and trifluoroethylene contained in the copolymer of vinylidene fluoride and trifluoroethylene (binary copolymer) was 70/30.
  • a solution of a copolymer of vinylidene fluoride and trifluoroethylene (binary copolymer) was coated on the surface of the base film 11 (polyethylene terephthalate film) with a bar coater.
  • the base film 11 (polyethylene terephthalate film) and the undried coating layer were dried at 60 ° C. for 5 minutes to obtain a coating layer 12 having piezoelectricity.
  • the thickness of the coating layer 12 having piezoelectricity after drying was 1 ⁇ m.
  • Example 2 The piezoelectric film 10 of Example 2 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 2 was produced in the same manner as the piezoelectric film 10 of Example 1 except that the thickness of the coating layer 12 having piezoelectricity after drying was 5 ⁇ m.
  • the piezoelectric film 10 of Example 3 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 3 was produced in the same manner as the piezoelectric film 10 of Example 1 except that the thickness of the coating layer 12 having piezoelectricity after drying was 10 ⁇ m.
  • the piezoelectric film 10 of Example 4 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 4 was produced in the same manner as the piezoelectric film 10 of Example 1 except that the thickness of the coating layer 12 having piezoelectricity after drying was 20 ⁇ m.
  • the piezoelectric film 10 of Example 5 has the first basic configuration of the piezoelectric film of the present invention.
  • the molar ratio of vinylidene fluoride and trifluoroethylene contained in the copolymer (binary copolymer) of vinylidene fluoride and trifluoroethylene is 75/25. Except for this, it was produced in the same manner as the piezoelectric film 10 of Example 1.
  • the piezoelectric film 10 of Example 6 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 6 was produced in the same manner as the piezoelectric film 10 of Example 5 except that the thickness of the coating layer 12 having piezoelectricity after drying was 5 ⁇ m.
  • Example 7 The piezoelectric film 10 of Example 7 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 7 was produced in the same manner as the piezoelectric film 10 of Example 5 except that the thickness of the coating layer 12 having piezoelectricity after drying was 10 ⁇ m.
  • the piezoelectric film 10 of Example 8 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 8 is the piezoelectric film of Example 5 except that the thickness of the coating layer 12 having piezoelectricity after drying is 2 ⁇ m and the drying conditions are 135 ° C. and 5 minutes. It was produced in the same manner as film 10.
  • the piezoelectric film 10 of Example 9 has the first basic configuration of the piezoelectric film of the present invention.
  • the material of the coating layer 12 having piezoelectricity is a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (ternary copolymer).
  • ternary copolymer was produced in the same manner as the piezoelectric film 10 of Example 1.
  • the coating layer 12 having piezoelectricity In producing the coating layer 12 having piezoelectricity, first, a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (ternary copolymer) is dissolved in methyl isobutyl ketone at room temperature by ultrasonic waves. Then, a solution of a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (ternary copolymer) was prepared.
  • the molar ratio of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene contained in the copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (ternary copolymer) is 64.2 / 27. 1 / 8.7.
  • a solution of a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene was coated on the surface of the base film 11 (polyethylene terephthalate film) with a bar coater.
  • the base film 11 (polyethylene terephthalate film) and the undried coating layer were dried under a drying condition of 60 ° C. for 5 minutes to prepare a coating layer 12 having piezoelectricity.
  • the thickness of the coating layer 12 having piezoelectricity after drying was 1 ⁇ m.
  • the piezoelectric film 10 of Example 10 has the first basic configuration of the piezoelectric film of the present invention.
  • the piezoelectric film 10 of Example 10 was produced in the same manner as the piezoelectric film 10 of Example 9 except that the thickness of the coating layer 12 having piezoelectricity after drying was 5 ⁇ m.
  • the piezoelectric film of Comparative Example 1 is a self-supporting film (having no base film) having a thickness of 40 ⁇ m and made of a vinylidene fluoride polymer (polyvinylidene fluoride).
  • the piezoelectric film of Comparative Example 1 has a thickness of 40 ⁇ m after drying on a surface of a polyethylene terephthalate film obtained by ultrasonically dissolving a vinylidene fluoride polymer (polyvinylidene fluoride) in isobutyl ketone at room temperature. The film was coated, dried and then peeled off from the polyethylene terephthalate film.
  • Table 1 shows the configurations of the piezoelectric film examples and comparative examples of the present invention, the molar ratio and thickness of the piezoelectric coating layer, the haze value of the piezoelectric film, and the total light transmittance.
  • VDF vinylidene fluoride
  • TrFE trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • PET polyethylene terephthalate
  • P () represents a copolymer. Therefore, “P (VDF-TrFE)” means “a copolymer of vinylidene fluoride and trifluoroethylene”.
  • PVDF-TrFE-CTFE means “a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene”.
  • P (VDF-TrFE) / PET base film means “a copolymer of vinylidene fluoride and trifluoroethylene is coated on the surface of the base film 11 made of polyethylene terephthalate”.
  • P (VDF-TrFE-CTFE) / PET base film” is “the surface of the base film 11 made of polyethylene terephthalate is coated with a copolymer of vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene” It means that.
  • PVDF means a polymer of vinylidene fluoride (polyvinylidene fluoride).
  • the piezoelectric films of Examples 1 to 4 have the same configuration and materials, but the thickness of the coating layer 12 having piezoelectricity is different.
  • the haze value tends to increase as the thickness of the coating layer 12 having piezoelectricity increases.
  • the haze value and the total light transmittance of the piezoelectric films of Examples 1 to 4 are all at a level with no problem.
  • the piezoelectric films of Examples 5 to 7 have the same configuration and materials, but the thickness of the coating layer 12 having piezoelectricity is different.
  • the haze value tends to slightly increase as the thickness of the coating layer 12 having piezoelectricity increases.
  • the haze values and total light transmittances of the piezoelectric films of Examples 5 to 7 are all at a level with no problem.
  • the piezoelectric film of Example 8 has the same configuration and material as the piezoelectric film of Example 5, and the thickness of the coating layer 12 is close, but the haze value is greatly different.
  • the reason why the haze value of the piezoelectric film of Example 8 is large is that the drying temperature is 135 ° C. (the drying temperature of other examples is 60 ° C.). Thus, when the drying temperature of the coating layer 12 is increased, the haze value of the piezoelectric film tends to increase.
  • the piezoelectric films of Example 9 and Example 10 have the same configuration and materials, but the thickness of the coating layer 12 having piezoelectricity is different. From Example 9 and Example 10, the haze value tends to increase as the thickness of the coating layer 12 having piezoelectricity increases. However, the haze values and total light transmittances of the piezoelectric films of Example 9 and Example 10 are all at a level with no problem.
  • the self-supporting film of the vinylidene fluoride polymer (polyvinylidene fluoride) of Comparative Example 1 has a considerably higher haze value than the piezoelectric films of Examples 1 to 10 of the present invention. Therefore, there is a high possibility that the visibility of the image on the display is lowered. However, the total light transmittance of the piezoelectric film of Comparative Example 1 is hardly different from the piezoelectric films of Examples 1 to 10 of the present invention. From Comparative Example 1, it can be seen that even if the haze value increases, the total light transmittance does not always decrease.
  • the film thickness of less than 1 ⁇ m was measured by observing the cross section using a transmission electron microscope (H-7650, manufactured by Hitachi, Ltd.). The thickness of the film or film exceeding 1 ⁇ m was measured using a film thickness meter (Digital Dial Gauge DG-205 manufactured by Peacock).
  • Example 11 to 16 Further, assuming that the transparent electrode 20 is laminated on the piezoelectric film 10 of the present application as shown in FIG. 10, the piezoelectricity when the optical adjustment layer 14 is disposed between the piezoelectric film 10 and the transparent electrode 20 is shown. The thickness and refractive index of the coating layer 12, the optical adjustment layer 14, and the transparent electrode 20 were measured.
  • the piezoelectric film 10 is the same as the above example, and is a PET film coated with a copolymer of vinylidene fluoride and trifluoroethylene.
  • the optical adjustment layer 14 may have a refractive index of 1.54, 1.62, 1.7. Since the manufacturing method differs depending on the refractive index, each refractive index will be described.
  • the refractive index is 1.54
  • a thermosetting resin having a weight ratio of 2: 2: 1 of melamine resin: alkyd resin: organosilane condensate (refractive index of light) is formed on one surface of the coating layer 12 having piezoelectricity.
  • n 1.54
  • the optical adjustment layer 14 having a thickness of 120 nm was formed.
  • an optical adjustment composition containing 47 parts by mass of ultraviolet curable resin, 57 parts by mass of zirconia oxide particles (median diameter 40 nm) and PGME on one surface of the coating layer 12 having piezoelectricity (Manufactured by JSR, “OPSTAR Z7412”, solid content: 12% by mass) was applied using a gravure coater, and immediately heated and dried at 60 ° C. for 1 minute in a windless state (less than 0.1 m / s). Then, the curing process was performed by irradiating ultraviolet rays with an integrated light amount of 250 mJ / cm 2 with a high-pressure mercury lamp.
  • the optical adjustment layer 14 having a thickness of 90, 120, or 150 nm and a refractive index of 1.62 was formed on the coating layer 12 having piezoelectricity.
  • melamine resin: alkyd resin: organosilane condensate 2: 2: 1
  • the mixing amount of the TiO 2 fine particles was adjusted so that the refractive index of the resin composition was 1.70.
  • the said resin composition was apply
  • the transparent electrode 20 was formed by sputtering indium tin oxide. The results are shown in Table 2.
  • the “first layer” is the piezoelectric coating layer 12
  • the “second layer” is the optical adjustment layer 14
  • the “third layer” is the transparent electrode 20.
  • the thickness of the coating layer 12 having piezoelectricity is 0.5 to 10 ⁇ m
  • the thickness of the optical adjustment layer 14 is 80 to 160 nm
  • the thickness of the transparent electrode 20 is 20 nm or more.
  • the refractive index of the coating layer 12 having piezoelectricity is 1.40 to 1.50
  • the refractive index of the optical adjustment layer 14 is 1.50 to 1.70
  • the refractive index of the transparent electrode 20 is 1.90 to 2.50. It is 10.
  • the difference in reflectance between the transparent electrode 20 and the optical adjustment layer 14 was 2% or less, and the appearance was good.
  • the transparent electrode 20 is etched into a desired electrode or the like as necessary.
  • the refractive index of the optical adjustment layer 14 was the portion where the transparent electrode 20 was removed by etching. Therefore, the reflectance difference was calculated
  • the optical adjustment layer 14 is obtained by diluting silica sol (Colcoat P, Colcoat P) with ethanol so that the solid content concentration becomes 2%. Is applied to one of the coating layers 12 having a property by a silica coating method, and then dried and cured at 150 ° C. for 2 minutes to form a layer having a thickness of 120 nm (SiO 2 film, light refractive index of 1.46). ) To form an optical adjustment layer 14.
  • the manufacturing method of the other configuration is the same as that of the example.
  • the transparent electrode 20 When the transparent electrode 20 is provided on the coating layer 12 having piezoelectricity, the transparent electrode 20 may be colored yellow or brown to impair the appearance.
  • the optical adjustment layer 14 As shown in Table 2, it was found that the difference in reflectance can be reduced and the appearance is not impaired. It has been found that even if a configuration in which the optical adjustment layer 14 and the transparent electrode 20 are laminated on the piezoelectric film 10 is disposed on the front surface of the display, the appearance of the display is hardly impaired.
  • the use of the piezoelectric film of the present invention is not limited, but it is particularly suitably used as a piezoelectric film for detecting the Z coordinate (pressure touched by a finger) of a touch panel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Human Computer Interaction (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film piézoélectrique 10 qui est pourvu d'un stratifié d'un film de base 11 et d'une couche de revêtement 12 ayant une piézoélectricité. La couche de revêtement 12 ayant une piézoélectricité contient une fluororésine. La fluororésine est un polymère de fluorure de vinylidène ou un copolymère d'au moins deux composés choisis parmi le fluorure de vinylidène, le trifluoroéthylène et le chlorotrifluoroéthylène. La couche de revêtement 12 ayant une piézoélectricité est obtenue par application d'une solution de la fluororésine sur le film de base 11 et séchage de la solution sur celui-ci. Ce film piézoélectrique 10 permet d'obtenir un film piézoélectrique qui présente une faible valeur de trouble et une transmittance optique totale élevée.
PCT/JP2017/019979 2016-05-30 2017-05-30 Film piézoélectrique Ceased WO2017209080A1 (fr)

Priority Applications (2)

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KR1020187028511A KR20190015188A (ko) 2016-05-30 2017-05-30 압전 필름
CN201780033533.1A CN109196673A (zh) 2016-05-30 2017-05-30 压电薄膜

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JP2016-107050 2016-05-30
JP2017104590A JP2017216450A (ja) 2016-05-30 2017-05-26 圧電フィルム
JP2017-104590 2017-05-26

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10381546B2 (en) * 2014-02-26 2019-08-13 Daikin Industries, Ltd. Bimorph-type piezoelectric film
JPWO2023219090A1 (fr) * 2022-05-11 2023-11-16
EP3943292B1 (fr) * 2019-03-20 2024-07-10 Nitto Denko Corporation Dispositif piézoélectrique stratifié, et procédé de fabrication du dispositif piézoélectrique

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Publication number Priority date Publication date Assignee Title
US20130062998A1 (en) * 2011-09-09 2013-03-14 Dvx, Llc Piezopolymer transducer with matching layer
WO2014168188A1 (fr) * 2013-04-10 2014-10-16 三井化学株式会社 Stratifié
WO2015053345A1 (fr) * 2013-10-08 2015-04-16 ダイキン工業株式会社 Panneau piézoélectrique transparent
JP2015214053A (ja) * 2014-05-09 2015-12-03 日東電工株式会社 積層体
JP2015215734A (ja) * 2014-05-09 2015-12-03 日東電工株式会社 タッチパネル用シートセンサー

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130062998A1 (en) * 2011-09-09 2013-03-14 Dvx, Llc Piezopolymer transducer with matching layer
WO2014168188A1 (fr) * 2013-04-10 2014-10-16 三井化学株式会社 Stratifié
WO2015053345A1 (fr) * 2013-10-08 2015-04-16 ダイキン工業株式会社 Panneau piézoélectrique transparent
JP2015214053A (ja) * 2014-05-09 2015-12-03 日東電工株式会社 積層体
JP2015215734A (ja) * 2014-05-09 2015-12-03 日東電工株式会社 タッチパネル用シートセンサー

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10381546B2 (en) * 2014-02-26 2019-08-13 Daikin Industries, Ltd. Bimorph-type piezoelectric film
EP3943292B1 (fr) * 2019-03-20 2024-07-10 Nitto Denko Corporation Dispositif piézoélectrique stratifié, et procédé de fabrication du dispositif piézoélectrique
US12414472B2 (en) 2019-03-20 2025-09-09 Nitto Denko Corporation Layered structure, piezoelectric device using the same, and method of manufacturing piezoelectric device
JPWO2023219090A1 (fr) * 2022-05-11 2023-11-16
WO2023219090A1 (fr) * 2022-05-11 2023-11-16 株式会社クレハ Film piézoélectrique multicouche, dispositif et procédé de production de film piézoélectrique multicouche
JP7742489B2 (ja) 2022-05-11 2025-09-19 株式会社クレハ 積層圧電フィルム、デバイス、及び積層圧電フィルムの製造方法

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