WO2015129829A1 - バイモルフ型圧電フィルム - Google Patents
バイモルフ型圧電フィルム Download PDFInfo
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- WO2015129829A1 WO2015129829A1 PCT/JP2015/055713 JP2015055713W WO2015129829A1 WO 2015129829 A1 WO2015129829 A1 WO 2015129829A1 JP 2015055713 W JP2015055713 W JP 2015055713W WO 2015129829 A1 WO2015129829 A1 WO 2015129829A1
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- piezoelectric film
- film
- bimorph
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- piezoelectric
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Classifications
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- H04R17/005—Piezoelectric transducers; Electrostrictive transducers using a piezoelectric polymer
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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
- H10N30/072—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies
- H10N30/073—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies by fusion of metals or by adhesives
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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
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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
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- H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
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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
- H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
- H10N30/302—Sensors
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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
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Definitions
- the present invention relates to a bimorph type piezoelectric film.
- Patent Document 1 discloses a technology that can detect not only the touch position but also the pressing force (that is, the strength of pressing) on the touch panel having a piezoelectric body by utilizing this property. Further, when a pyroelectric material is used as the piezoelectric material, the pyroelectric material has a relatively high piezoelectric constant, so that the detection sensitivity of the pressing force can be increased.
- Patent Document 2 discloses a polarized vinylidene fluoride / tetrafluoroethylene copolymer film for a touch panel or a touch pressure detection as a piezoelectric film.
- a touch panel using a pyroelectric material when a temperature change occurs in the pyroelectric material, a voltage due to the pyroelectric effect is generated, which becomes a noise output (pyroelectric noise). Therefore, the touch panel may malfunction due to a change in environmental temperature. Therefore, it is desired to provide a touch panel in which generation of pyroelectric noise is suppressed.
- a high degree of transparency is required for members used in touch panels.
- the present invention has been made to solve the above-described problem, and provides a bimorph piezoelectric film that is less susceptible to pyroelectric noise due to temperature changes and that can provide a highly transparent touch panel and the like. Objective.
- the present inventors have A first piezoelectric film, Having a pressure-sensitive adhesive sheet or an adhesive layer, and a second piezoelectric film in this order;
- the first piezoelectric film and the second piezoelectric film are:
- the bimorph type piezoelectric film which is arranged so that the surfaces where the charges of the same polarity are generated by the temperature rise are respectively outside, and has a total light transmittance of 90% or more and a total haze value of 8.0% or less.
- the present invention includes the following aspects.
- Item 1 A first piezoelectric film, Having a pressure-sensitive adhesive sheet or an adhesive layer, and a second piezoelectric film in this order;
- the first piezoelectric film and the second piezoelectric film are:
- a bimorph type piezoelectric film which is disposed so that the surfaces where charges of the same polarity are generated by temperature rise are on the outside, and has a total light transmittance of 90% or more and a total haze value of 8.0% or less.
- Item 2. The bimorph piezoelectric film of Item 1, wherein the pressure-sensitive adhesive sheet or adhesive layer has a storage elastic modulus of 0.1 MPa or more, an internal haze value of 0.6% or less, and a thickness of 30 ⁇ m or less.
- the first piezoelectric film and the second piezoelectric film are polarized vinylidene fluoride / tetrafluoroethylene copolymer piezoelectric films, having a total light transmittance of 92% or more and an internal haze of 0.6% or less.
- Item 3. The bimorph piezoelectric film according to Item 1 or 2, wherein the bimorph piezoelectric film has a thickness of 40 ⁇ m or less, and the pressure-sensitive adhesive layer or the adhesive layer has a thickness of 15 ⁇ m or less.
- An input device comprising the bimorph piezoelectric film according to any one of Items 1 to 3.
- Item 6. Item 6.
- An electronic device having the input device according to Item 4 or the speaker according to Item 5.
- the bimorph piezoelectric film of the present invention makes it possible to provide a touch panel that is not easily affected by pyroelectric noise due to temperature changes and has high transparency.
- detection of “touch position” means determination of touch position
- detection of “touch pressure” means presence / absence of pressure, speed, magnitude (strength), Or the change of these, or the determination of these combination is meant.
- touch includes touching, touching, pushing, pushing, and touching.
- polarization means that a surface is charged. That is, the polarizing film can be an electret.
- the bimorph type piezoelectric film of the present invention is A first piezoelectric film, Having a pressure-sensitive adhesive sheet or an adhesive layer, and a second piezoelectric film in this order;
- the first piezoelectric film and the second piezoelectric film are:
- the surfaces where charges of the same polarity are generated by the temperature rise are arranged so as to be outside, and have a total light transmittance of 90% or more and a total haze value of 8.0% or less.
- the bimorph type piezoelectric film of the present invention is a laminate.
- the first piezoelectric film and the second piezoelectric film included in the bimorph piezoelectric film of the present invention are single-layer piezoelectric films.
- the term “single-layer piezoelectric film” means that it is not a pressure-sensitive adhesive sheet or a laminate bonded by an adhesive layer, and is used to distinguish it from a bimorph-type piezoelectric film.
- the first piezoelectric film used in the bimorph type piezoelectric film of the present invention is preferably an organic piezoelectric film.
- the “organic piezoelectric film” is a film (polymer film) formed from a polymer that is an organic substance. Examples of the “organic piezoelectric film” include a polarized vinylidene fluoride polymer film, an odd-chain nylon piezoelectric film, and polylactic acid.
- the “organic piezoelectric film” may contain components other than the polymer.
- the “organic piezoelectric film” includes a film made of the polymer and a film in which an inorganic substance is dispersed in the polymer.
- the content of the polymer in the piezoelectric film of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass.
- the upper limit of the content is not particularly limited, and may be, for example, 100% by mass or 99% by mass.
- the polymer is preferably a vinylidene fluoride polymer.
- the piezoelectric film of the present invention is preferably composed of a polarized vinylidene fluoride polymer film.
- examples of the “vinylidene fluoride polymer film” include a vinylidene fluoride / tetrafluoroethylene copolymer film, a vinylidene fluoride / trifluoroethylene copolymer film, and a polyvinylidene fluoride film.
- the vinylidene fluoride polymer film is preferably a vinylidene fluoride / tetrafluoroethylene copolymer film.
- the “vinylidene fluoride polymer film” may contain an additive usually used for a resin film.
- the “vinylidene fluoride polymer film” is a film composed of a vinylidene fluoride polymer and contains a vinylidene fluoride polymer.
- vinylidene fluoride polymer (1) a copolymer of vinylidene fluoride and one or more monomers copolymerizable therewith; and (2) polyvinylidene fluoride.
- Examples of “monomer copolymerizable with this” in “(1) copolymer of vinylidene fluoride and one or more monomers copolymerizable therewith” include trifluoroethylene, tetrafluoroethylene , Hexafluoropropylene, chlorotrifluoroethylene, and vinyl fluoride.
- the “one or more monomers copolymerizable therewith” or one of them is preferably tetrafluoroethylene.
- Preferable examples of the “vinylidene fluoride polymer” include a vinylidene fluoride / tetrafluoroethylene copolymer.
- the “vinylidene fluoride / tetrafluoroethylene copolymer” may contain repeating units derived from monomers other than vinylidene fluoride and tetrafluoroethylene as long as the properties relating to the present invention are not significantly impaired.
- the “(1) copolymer of vinylidene fluoride and one or more monomers copolymerizable therewith” contains 50 mol% or more (preferably 60 mol% or more) of repeating units derived from vinylidene fluoride. )contains.
- the molar ratio of (repeat unit derived from tetrafluoroethylene) / (repeat unit derived from vinylidene fluoride) in the “vinylidene fluoride / tetrafluoroethylene copolymer” is preferably 5/95 to 36/64. Within the range, more preferably within the range of 15/85 to 25/75, still more preferably within the range of 18/82 to 22/78.
- the “vinylidene fluoride / tetrafluoroethylene copolymer” may contain a repeating unit derived from a monomer other than vinylidene fluoride and tetrafluoroethylene as long as the properties of the present invention are not significantly impaired. Usually, the content of such repeating units is 10 mol% or less. Such a monomer is not limited as long as it is copolymerizable with a vinylidene fluoride monomer or a tetrafluoroethylene monomer.
- Fluoromonomer eg, vinyl fluoride (VF), trifluoroethylene (TrFE), hexafluoropropene (HFP), 1-chloro-1-fluoro-ethylene (1,1-CFE), 1-chloro- 2-fluoro-ethylene (1,2-CFE), 1-chloro-2,2-difluoroethylene (CDFE), chlorotrifluoroethylene (CTFE), trifluorovinyl monomer, 1,1,2-trifluorobutene- 4-bromo-1-butene, 1,1,2-trifluorobutene-4-silane-1-butene, perfluoroalkyl vinyl ether, perfluoromethyl vinyl ether (PMVE), perfluoropropyl vinyl ether (PPVE), perfluoroacrylate, 2, 2,2-trifluoroethyl acrylate, 2- (2) hydrocarbon monomers (eg, ethylene, propylene, maleic anhydride, vinyl ether, vinyl ester, allyl glycidy
- the total light transmittance of the first piezoelectric film is preferably 91% or more, more preferably 93% or more. Although the upper limit of the total light transmittance is not limited, the total light transmittance of the first piezoelectric film is usually 99% or less. In the present specification, the “total light transmittance” is obtained by a light transmission test using a haze meter NDH7000SP CU2II (product name) (Nippon Denka) or an equivalent thereof based on ASTM D1003.
- the total haze value of the first piezoelectric film is preferably 6.0% or less, more preferably 4.0% or less, still more preferably 3.0% or less, and still more preferably 1.5% or less.
- the lower the total haze value the better.
- the lower limit is not limited, but the total haze value of the first piezoelectric film is usually 0.1% or more.
- total haze is based on ASTM D1003, and is determined by haze (HAZE, turbidity) test using haze guard II (product name) (Toyo Seiki Seisakusho) or its equivalent. can get.
- the internal haze value of the first piezoelectric film is preferably 6.0% or less, more preferably 4.0% or less, still more preferably 3.0% or less, still more preferably 2.0% or less, particularly preferably. It is 1.5% or less, more particularly preferably 1.0% or less, even more particularly preferably 0.8% or less, still more particularly preferably 0.6% or less, and most preferably 0.4% or less.
- the lower the internal haze value the better.
- the lower limit is not limited, but the internal haze value of the first piezoelectric film is usually 0.1% or more.
- “inner haze” means that in the method for measuring the total haze value, water is put into a glass cell, a film is inserted therein, and the haze value is measured. Is obtained.
- the external haze value of the first piezoelectric film is preferably 3.0% or less, more preferably 1.5% or less, and still more preferably 1.0% or less.
- the lower limit is not limited, but the external haze value of the piezoelectric film of the present invention is usually 0.1% or more.
- the “outer haze value” is calculated by subtracting the internal haze value from the total haze value of the film.
- the piezoelectric property (d33) of the first piezoelectric film is preferably within the range of 40 to 0.1 pC / N, more preferably within the range of 30 to 1 pC / N, and even more preferably within the range of 20 to 2 pC / N. is there.
- the piezoelectric property (d33) of a single film piezoelectric film is measured using a d33 meter (PM300, Piezo test. Ltd) or an equivalent thereof.
- the electromechanical coupling coefficient of the first piezoelectric film is usually in the range of 0.1 to 0.01, preferably in the range of 0.09 to 0.02, more preferably in the range of 0.08 to 0.03. It is.
- the rate of change of the electromechanical coupling coefficient of the first piezoelectric film needs to be 10% or less, preferably 8% or less, more preferably 6% or less.
- the electromechanical coupling coefficient may be abbreviated as kt.
- the “electromechanical coupling coefficient” (kt) of the piezoelectric film is obtained by forming an Al vapor-deposited electrode on both sides of the piezoelectric film, cutting out a 13 mm disk from a predetermined portion of the piezoelectric film, and analyzing an impedance analyzer (Hewlett Packard, 4194A) or Measured using the equivalent, and calculated by the method described in H. Ohigashi et al., “The application of ferroelectric polymer, Ultrasonic transducers in the megahertz range”.
- rate of change of electromechanical coupling coefficient is the rate of change of electromechanical coupling coefficient when heated at 85 ° C. for 10 hours unless otherwise specified.
- the “rate of change of electromechanical coupling coefficient” is (1) measuring the electromechanical coupling coefficient (kt before heating) of the piezoelectric film; (2) heating the piezoelectric film in air at 85 ° C. for 10 hours; (3) Allowing the piezoelectric film to stand at room temperature and cooling to room temperature, and (4) Measuring the electromechanical coupling coefficient (kt after heating) of the piezoelectric film after the heating and cooling.
- Kt before heating” and “kt after heating” are determined by calculating into the following equation.
- room temperature is a temperature within the range of 15 to 35 ° C.
- the thickness of the first piezoelectric film is preferably 40 ⁇ m or less.
- the thickness of the first piezoelectric film is, for example, in the range of 0.5 to 100 ⁇ m, in the range of 0.8 to 50 ⁇ m, in the range of 0.8 to 40 ⁇ m, in the range of 3 to 100 ⁇ m, and in the range of 3 to 50 ⁇ m.
- the first piezoelectric film is preferably Consisting of a polarized vinylidene fluoride polymer film; Yellowness YI value measured according to JIS K7105 is 4 or less; L * is 85 or more in the L * a * b * color system was measured in accordance with JIS K7105, a * is 0.5 or more, and b * is 1.5 or less.
- the first piezoelectric film preferably has a yellowness YI value measured according to JIS K7105 of 4 or less, more preferably 3 or less.
- the lower limit of the YI value is not particularly limited, but is usually about 0.1.
- the YI value of the piezoelectric film can be measured under the conditions of room temperature and normal humidity using a C / 2 light source with a SZ Sigma 90 measuring instrument manufactured by Nippon Denshoku Industries Co., Ltd. by a measuring method based on JIS K7105.
- the first piezoelectric film is preferably L * of 85 or more in the L * a * b * color system was measured in accordance with JIS K7105, and more preferably 90 or more.
- the upper limit of L * is not particularly limited, but is usually about 99.
- the first piezoelectric film is preferably a * is 0.5 or less in the L * a * b * color system was measured in accordance with JIS K7105, more preferably 0.1 or less.
- the lower limit of a * is not particularly limited, but is usually about 0.01.
- the first piezoelectric film is preferably b * of 1.5 or less in the L * a * b * color system was measured in accordance with JIS K7105, more preferably 1.3 or less.
- the lower limit of b * is not particularly limited, but is usually about 0.8.
- L * , a * , and b * of the piezoelectric film are measured by a measuring method based on JIS K7105, using an SZ Sigma 90 measuring instrument manufactured by Nippon Denshoku Co., Ltd. using a C / 2 light source at normal temperature and normal humidity. Can be measured.
- the first piezoelectric film preferably has a retardation value of 1 to 20 nm. By setting the retardation value within the above range, the color of the piezoelectric film can be further suppressed.
- the retardation value of the first piezoelectric film can be measured by using RETS4200RV manufactured by Otsuka Electronics Co., Ltd. under the condition of irradiating light of 550 nm.
- the first piezoelectric film is preferably manufactured using a polymer that satisfies at least one condition selected from the following conditions (1) to (3).
- the following conditions (1) to (3) It is more preferable that the polymer is manufactured using a polymer that satisfies all of the conditions.
- the surfactant content is 100 ppm or less; (2) The content of methylcellulose is 6000 ppm or less; (3) The total of the metal content and the ion content is 200 ppm or less.
- said YI value of the first piezoelectric film may be four or less, L * a * b * a L * 85 or more in a color system, a * Can be 0.5 or more and b * can be 1.5 or less.
- the surfactant when the surfactant is a polymer obtained by emulsion polymerization of the polymer used in the production of the first piezoelectric film, a film is produced using the polymer in which the surfactant remains. It can be included in the piezoelectric film.
- the content of the surfactant is preferably 100 ppm or less.
- the content of the surfactant is preferably 50 ppm or less.
- the lower limit of the surfactant content is not particularly limited, but is usually 0 ppm when the polymer is polymerized by suspension polymerization.
- the content of the surfactant in the first film is determined by measuring the water from which the surfactant is extracted by suspending the polymer in water and then treating with ultrasonic waves for 10 minutes or longer with a DX500 measuring instrument manufactured by Dionex. Can be detected.
- methylcellulose is a polymer in which methylcellulose used in the polymerization remains when the polymer used in the production of the first piezoelectric film is polymerized by suspension polymerization. It can be included in a piezoelectric film by manufacturing a piezoelectric film.
- the methylcellulose content is preferably 6000 ppm or less.
- the methyl cellulose content is more preferably 5000 ppm or less.
- the lower limit of the content of methylcellulose is not particularly limited, but is usually 0 ppm when the polymer is polymerized by emulsion polymerization, and is usually about 3000 ppm or less when the polymer is polymerized by suspension polymerization.
- the content of methylcellulose in the piezoelectric film can be detected by measuring the water from which methylcellulose is extracted by suspending the polymer in water and then treating with ultrasound for 10 minutes or more with a DX500 measuring instrument manufactured by Dionex. .
- the metal and ions can be contained in a polymer polymerized by any of emulsion polymerization and suspension polymerization, and the first piezoelectric film is produced by using the polymer to produce a piezoelectric material. It can be included in the film.
- the total of the metal content and the ion content is preferably 200 ppm or less.
- the total content is more preferably 100 ppm or less.
- the lower limit of the total of the metal content and the ion content is not particularly limited, but is usually about 30 ppm when polymerizing the polymer by emulsion polymerization, and when polymerizing the polymer by suspension polymerization. Usually about 10 ppm.
- the metal content in the piezoelectric film is detected by burning the piezoelectric film with a SPS3000 measuring instrument manufactured by Seiko Instruments Inc., extracting the metal with 0.1 wt% dilute hydrochloric acid, and measuring it with the device. can do.
- the content of ions in the first piezoelectric film is such that the piezoelectric film is finely cut to be in a state close to powder, immersed in water and subjected to ultrasonic treatment for 1 hour or more, and the water from which ions are extracted is manufactured by Dionex. It can be measured by analyzing with a DX500 measuring instrument.
- the first and second piezoelectric films are, for example, Step A of polarizing a non-polarized polymer film (eg, non-polarized vinylidene fluoride polymer film); and subsequent heat treatment of the polarized polymer film (eg, polarized vinylidene fluoride polymer film) Step B It can manufacture by the manufacturing method containing.
- a non-polarized polymer film eg, non-polarized vinylidene fluoride polymer film
- subsequent heat treatment of the polarized polymer film eg, polarized vinylidene fluoride polymer film
- step A the non-polarized polymer film is polarized.
- the “non-polarized polymer film” used in step A can be produced by a known method such as a casting method, a hot press method, or a melt extrusion method.
- the “non-polarized polymer film” used in step A is preferably a film produced by a casting method.
- non-polarized polymer film by the casting method is, for example, (1) A liquid composition is prepared by dissolving or dispersing a polymer (eg, vinylidene fluoride polymer) and desired components (eg, inorganic oxide particles and affinity improver) in a solvent. Process; (2) A process comprising casting (applying) the liquid composition on a substrate; and (3) vaporizing the solvent to form a film.
- a polymer eg, vinylidene fluoride polymer
- desired components eg, inorganic oxide particles and affinity improver
- the dissolution temperature in the preparation of the liquid composition is not particularly limited, but a higher dissolution temperature is preferable because dissolution can be promoted.
- the melting temperature is preferably from room temperature to 80 ° C.
- the solvent include ketone solvents (eg, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, diethyl ketone, dipropyl ketone), ester solvents ( Examples include ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl lactate), ether solvents (eg, tetrahydrofuran, methyltetrahydrofuran, dioxane), and amide solvents (eg, dimethylformamide (DMF), dimethylacetamide). It is done. These solvents may be used alone or in combination of two or more.
- an amide solvent which is a solvent widely used for dissolving polyvinylidene fluoride (PVDF) may be used, but the content of the amide solvent in the solvent is desirably 50% or less.
- the liquid composition is cast (applied) onto a substrate by a knife coating method, a cast coating method, a roll coating method, a gravure coating method, a blade coating method, a rod coating method, an air doctor coating method, or a slot die method.
- the conventional method such as the above may be used.
- the gravure coating method or the slot die method is preferable because it is easy to operate, has little variation in film thickness, and is excellent in productivity.
- the base material for example, a polyethylene terephthalate (PET) film can be used.
- the solvent can be vaporized by a conventional drying method such as heating.
- the drying temperature in the vaporization of the solvent can be appropriately determined according to the type of the solvent, but is usually in the range of 20 ° C to 200 ° C, preferably in the range of 40 ° C to 170 ° C.
- the drying temperature may be a constant temperature or may be changed.
- a low temperature eg, 40 to 100 ° C.
- a high temperature eg, 120 to 200 ° C.
- This can be achieved, for example, by dividing the drying zone into several zones and the film (or cast solution before film formation) enters the cold zone and moves to the hot zone.
- the drying zone may be divided into four zones of 50 ° C., 80 ° C., 120 ° C., and 150 ° C., and the film may be continuously moved from the zone of 50 ° C. to the zone of 150 ° C.
- the drying time in the vaporization of the solvent is usually in the range of 1 to 600 seconds, preferably in the range of 10 to 200 seconds.
- non-polarized vinylidene fluoride polymer film (hereinafter sometimes simply referred to as “non-polarized film”) used in Step A is preferably not stretched.
- the non-polarized film is not stretched.
- the first and second piezoelectric films are preferably unstretched piezoelectric films.
- the first and second piezoelectric films thus obtained have high thickness uniformity.
- the first and second piezoelectric films have a variation coefficient of thickness measured at 10 points per 1 cm square over the entire film of ⁇ 20% or less of the average film thickness.
- the non-polarized film used in step A may be heat-treated after film formation.
- Determination of the thickness of the non-polarized film used in step A may be performed according to the piezoelectric film to be obtained.
- the polarization treatment in step A can be performed by a conventional method such as corona discharge treatment.
- the polarization treatment in step A is preferably performed by corona discharge.
- corona discharge either a negative corona or a positive corona may be used, but it is desirable to use a negative corona from the viewpoint of easy polarization of the non-polarized resin film.
- the corona discharge treatment is not particularly limited.
- the nonpolarized film is applied using a linear electrode;
- the application can be performed by using a needle-like electrode to the polarizing film.
- the conditions for the corona discharge treatment may be appropriately set based on common sense in the technical field to which the present invention belongs. If the corona discharge treatment conditions are too weak, the piezoelectricity of the resulting piezoelectric film may be insufficient. On the other hand, if the corona discharge treatment conditions are too strong, the resulting piezoelectric film may have point defects. is there.
- the processing speed is, for example, 10 to 500 cm / min.
- the polarization treatment may be carried out by, for example, sandwiching a flat electrode from both sides of a non-polarized film in addition to corona discharge.
- a DC electric field of 0 to 400 MV / m (preferably 50 to 400 MV / m), and 0.1 second to 60 minutes. The conditions for the application time can be adopted.
- Process B heat treatment process
- Step B the polarized vinylidene fluoride polymer film obtained by the polarization treatment in Step A (hereinafter sometimes simply referred to as a polarized film) is heat-treated.
- the heat treatment in step B can be performed on the polarized film or the portion where polarization has been completed in step A. That is, while performing the polarization process of the process A, the heat treatment of the process B may be performed on the portion where the polarization process has been completed.
- the method of the heat treatment is not particularly limited.
- the polarizing film is sandwiched between two metal plates and the metal plate is heated; the polarizing film roll is heated in a thermostatic bath; -In the production of a polarized film in a roll mode, the metal roller is heated and the polarized film is brought into contact with the heated metal roller; or in a furnace in which the polarized film is heated in a roll-to-roll manner This can be done by passing it through.
- the polarized film may be heat-treated alone, or may be laminated on another type of film or metal foil to form a laminated film, which may be heat-treated. In particular, when the heat treatment is performed at a high temperature, the latter method is preferable because the polarizing film is less likely to wrinkle.
- the temperature of the heat treatment may vary depending on the kind of the polarized film to be heat-treated, and is preferably in the range of (melting point of the polarizing film to be heat-treated) -100 ° C. to (melting point of the polarized film to be heat-treated + 40) ° C. Is within. Specifically, the temperature of the heat treatment is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 90 ° C. or higher. The temperature of the heat treatment is preferably 170 ° C. or lower, more preferably 160 ° C. or lower, and still more preferably 140 ° C. or lower.
- the time for the heat treatment is usually 10 seconds or longer, preferably 0.5 minutes or longer, more preferably 1 minute or longer, and further preferably 2 minutes or longer. Moreover, although the upper limit of the said heat processing time is not limited, Usually, the time of the said heat processing is 60 minutes or less.
- the conditions for the heat treatment are preferably 90 ° C. or more and 1 minute or more.
- the melting point of a film is a maximum value in a heat of fusion curve obtained when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus.
- the non-polarized polymer film is cooled to a predetermined temperature.
- the temperature is preferably in the range of 0 ° C. to 60 ° C. and can be room temperature.
- the cooling rate may be slow cooling or rapid cooling, and rapid cooling is preferable from the viewpoint of productivity.
- the rapid cooling can be performed by means such as air blowing.
- the first piezoelectric film and the second piezoelectric film are bonded to each other by an adhesive sheet or an adhesive layer.
- the pressure-sensitive adhesive sheet is not particularly limited as long as the first piezoelectric film and the second piezoelectric film can be bonded to each other, and can be composed of one or more layers. That is, when the said adhesive sheet consists of one layer, the said adhesive sheet consists of an adhesive layer, and when the said adhesive sheet consists of two or more layers, the both outer layers are adhesive layers. When the said adhesive sheet consists of 3 or more layers, the said adhesive sheet may have a base material layer as an inner layer.
- the base material layer in the said adhesive sheet should just be a transparent film, Preferably, it can be a film of a polyimide, a polyethylene terephthalate, a polybutylene terephthalate, a polycarbonate, a polyparaphenylene sulfide, or a polyamideimide, for example.
- the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet can be a layer containing an acrylic pressure-sensitive adhesive as a pressure-sensitive adhesive.
- the adhesive that forms the adhesive layer may be an acrylic adhesive.
- the pressure-sensitive adhesive layer or adhesive layer used in the bimorph-type piezoelectric film of the present invention is formed, for example, because it contains a polymer having at least one acrylic monomer having an ester group (—COO—) as a structural unit. It is preferable that it is an adhesive layer.
- an acrylic monomer having an ester group (—COO—) for example, a general formula CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 is hydrogen or a methyl group, R 2 is an alkyl group having 1 to 14 carbon atoms) And (meth) acrylates such as hydroxyl group-containing (meth) acrylates.
- alkyl (meth) acrylate represented by the general formula CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 14 carbon atoms).
- R 1 represents hydrogen or a methyl group
- R 2 represents an alkyl group having 1 to 14 carbon atoms.
- the alkyl group R 2 has 1 to 14 carbon atoms from the viewpoint of adhesive strength. It is not preferable that the alkyl group has 15 or more carbon atoms because the adhesive strength may be reduced.
- the alkyl group R 2 preferably has 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
- alkyl (meth) acrylates having 1 to 14 carbon atoms in the alkyl group R 2 alkyl (meth) acrylates having 1 to 3 or 13 to 14 carbon atoms in the alkyl group R 2 are used as a part of the monomer.
- an alkyl (meth) acrylate having 4 to 12 carbon atoms of the alkyl group R 2 as an essential component (eg, 50 to 100 mol%).
- these alkyl groups R 2 may be a straight chain or may be branched.
- the pressure-sensitive adhesive layer or adhesive layer used in the bimorph type piezoelectric film of the present invention is, for example, a pressure-sensitive adhesive layer formed from a polymer having at least one (meth) acrylate containing a hydroxyl group as a structural unit. Or an adhesive layer.
- the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene. Examples include glycol mono (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate.
- a pressure-sensitive adhesive layer containing no carboxylic acid and hydroxyl group may be used. Since carboxylic acid can cause whitening, a pressure-sensitive adhesive layer or an adhesive layer not containing this is preferred.
- the pressure-sensitive adhesive layer or adhesive layer used in the bimorph piezoelectric film of the present invention is, for example, a pressure-sensitive adhesive formed from a polymer in which a crosslinkable site is introduced into the above polymer from the viewpoint of increasing storage elastic modulus.
- a layer or an adhesive layer is also preferred.
- the crosslinking site include thermal crosslinking, chemical crosslinking, and ultraviolet crosslinking.
- it is thermal crosslinking or ultraviolet crosslinking, and as an ultraviolet crosslinking site, excited by ultraviolet irradiation, hydrogen radicals from other parts in the (meth) acrylic copolymer molecule or other (meth) acrylic copolymer molecules. It is possible to adopt a structure capable of pulling out.
- Examples of such a structure include a benzophenone structure, a benzyl structure, an o-benzoylbenzoate structure, a thioxanthone structure, a 3-ketocoumarin structure, a 2-ethylanthraquinone structure, and a camphorquinone structure.
- Such a pressure-sensitive adhesive layer or adhesive layer contains additives that the pressure-sensitive adhesive composition or the adhesive composition forming the layer can normally contain unless the effects of the present invention are significantly impaired. Also good.
- the storage elastic modulus of the pressure-sensitive adhesive sheet or adhesive layer used in the present invention is preferably 0.08 MPa or more, more preferably 0.1 MPa or more, and further preferably 0.12 MPa or more.
- the upper limit of the storage elastic modulus of the pressure-sensitive adhesive sheet or the adhesive layer used in the present invention is not particularly limited, but the storage elastic modulus of the pressure-sensitive adhesive sheet or the adhesive layer used in the present invention is usually 0.9 MPa or less. .
- the internal haze of the pressure-sensitive adhesive sheet or adhesive layer used in the present invention is preferably 0.6% or less, more preferably 0.5% or less, and still more preferably 0.4% or less.
- the minimum of the internal haze of the adhesive sheet used for this invention or the said adhesive bond layer is not specifically limited, The internal haze of the adhesive sheet used for this invention or an adhesive bond layer is 0.01% or more normally.
- the thickness of the pressure-sensitive adhesive sheet or adhesive layer used in the present invention is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less.
- the thickness of the pressure-sensitive adhesive sheet or pressure-sensitive adhesive used in the present invention is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
- the pressure-sensitive adhesive sheet or the adhesive layer has a storage elastic modulus of 0.1 MPa or more and a thickness of 15 ⁇ m or less.
- Examples of the second piezoelectric film used in the bimorph piezoelectric film of the present invention are the same as those of the first piezoelectric film. Moreover, as a preferable example of the 2nd piezoelectric film used in the bimorph type
- the second piezoelectric film used in the bimorph type piezoelectric film of the present invention may be the same as or different from the first piezoelectric film.
- the piezoelectric characteristic (d33) of the second piezoelectric film approximates the piezoelectric characteristic (d33) of the first piezoelectric film.
- the ratio of [piezoelectric characteristics of the second piezoelectric film (d33) / piezoelectric characteristics of the first piezoelectric film (d33)] is preferably 0.6 to 1.4, more preferably 0. It is within the range of 8 to 1.2.
- the first piezoelectric film and the second piezoelectric film are polarized vinylidene fluoride / tetrafluoroethylene copolymer piezoelectric films and have a total light transmission of 92% or more. Rate, an internal haze value of 0.6% or less, and a thickness of 40 ⁇ m or less.
- the first piezoelectric film and the second piezoelectric film may have different film thicknesses. In that case, it is desirable that the thinner piezoelectric film be positioned outside when bent by touch or the like.
- the first piezoelectric film and the second piezoelectric film are polarized vinylidene fluoride / tetrafluoroethylene copolymer piezoelectric films, having a total light transmittance of 92% or more and an internal haze of 0.6% or less.
- the pressure-sensitive adhesive sheet or the adhesive layer has a storage elastic modulus of 0.1 MPa or more and a thickness of 15 ⁇ m or less.
- the bimorph type piezoelectric film of the present invention can be produced by a conventional production method of a bimorph type piezoelectric film.
- an adhesive sheet is attached to the first piezoelectric film so that the surfaces where charges of the same polarity are generated by temperature rise are outside, and then the second adhesive sheet is attached to the adhesive sheet. It can manufacture by affixing the piezoelectric film of this.
- the sheet-like ones may be stuck together, or may be continuously stuck in a roll-to-roll manner.
- the pressure for bonding is preferably a pressure that does not cause deformation of the piezoelectric film. Moreover, you may heat when sticking.
- the bimorph type piezoelectric film of the present invention is also applied, for example, by applying an adhesive composition to the surface of the first piezoelectric film so that the surfaces where charges of the same polarity are generated by the temperature rise are on the outside. It can manufacture by arrange
- the total light transmittance of the bimorph type piezoelectric film of the present invention is 90% or more, preferably 91% or more, more preferably 92% or more.
- the upper limit of the total light transmittance of the bimorph type piezoelectric film of the present invention is not limited, but the total light transmittance of the bimorph type piezoelectric film of the present invention is usually 99% or less.
- the total haze value of the bimorph type piezoelectric film of the present invention is 8.0% or less, preferably 6.0% or less, more preferably 4.0% or less. Although the upper limit of the total haze value of the bimorph type piezoelectric film of the present invention is not limited, the total haze value of the bimorph type piezoelectric film of the present invention is usually 0.2% or more.
- the thickness of the bimorph type piezoelectric film of the present invention is preferably in the range of 5 to 300 ⁇ m, more preferably in the range of 10 to 120 ⁇ m, and still more preferably in the range of 15 to 90 ⁇ m.
- the piezoelectricity of the bimorph piezoelectric film of the present invention is preferably in the range of 30 to 1500 mV, more preferably in the range of 50 to 1200 mV, and still more preferably in the range of 100 to 1000 mV by the measurement method described later when the load is 300 g. Within range.
- the piezoelectricity of the bimorph piezoelectric film of the present invention is measured by the following method. (Preparation of bimorph type piezoelectric film specimen) The measurement of piezoelectricity is performed by preparing a specimen having an appropriate size (for example, 65 mm long ⁇ 35 mm wide) with ITO (indium tin oxide) attached as a transparent electrode.
- Two ITO electrodes with a length of 65 mm ⁇ width 35 mm ⁇ thickness 50 ⁇ m are prepared, and this is a transparent adhesive layer with a thickness of 10 ⁇ m, one on each of the upper and lower sides of a single-layer piezoelectric film or a bimorph type piezoelectric film 65 mm long ⁇ 35 mm wide.
- Paste using (Neiei Kako MHM-FED10).
- the piezoelectricity of the bimorph type piezoelectric film is measured by the following method. Prepare a glass plate that is 125mm long x 60mm wide x 0.54mm thick, and place both vertical edges 15mm on an acrylic resin frame.
- FIG. 2 shows an outline of this aspect.
- a weight of a constant weight is applied to the central portion, and the resulting piezoelectric signal is measured.
- the resulting piezoelectric signal is measured using the configuration outlined in FIG.
- Japanese data system UDS 5204S is used, and the voltage is read by an integrating circuit.
- thermocouple Measurement of pyroelectric property of bimorph type piezoelectric film
- Attach a thermocouple to the center of the specimen with the same setup as the piezoelectric measurement.
- the temperature change is read with a thermocouple, and the pyroelectric signal is read with the same device as the piezoelectric signal.
- Using a dryer apply hot air to the specimen and measure the voltage generated by raising the temperature from 20 ° C. to 40 ° C. within 0.5 to 1 minute.
- the pyroelectric property of the bimorph piezoelectric film of the present invention is preferably 100 mV or less, more preferably 60 mV or less, and still more preferably 50 mV or less.
- the lower limit of the pyroelectric property of the bimorph type piezoelectric film of the present invention is not particularly limited, but the pyroelectric property of the bimorph type piezoelectric film of the present invention is usually 1 mV or more.
- the piezoelectric / pyroelectric ratio (sometimes referred to herein as the S / N ratio) of the bimorph piezoelectric film of the present invention is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. More preferably, it is 10 or more, particularly preferably 20 or more, more particularly preferably 30 or more, and most preferably 50 or more.
- the upper limit of the S / N ratio is not particularly limited, but the S / N ratio is usually 100 or less.
- FIG. 1 shows one embodiment of the bimorph type piezoelectric film of the present invention.
- the bimorph piezoelectric film 1 is First piezoelectric film 11, Adhesive layer or adhesive layer 12 and second piezoelectric film 13 In this order, The first piezoelectric film 11 and the second piezoelectric film 13 are The surfaces where charges having the same polarity (negative (-) charge)) are generated by the temperature rise are arranged on the outer side.
- the first piezoelectric film 11 and the second piezoelectric film 13 are similarly heated, so that similar charges are generated outside both films. . Therefore, when measuring the potential difference between the upper surface of the first piezoelectric film 11 and the lower surface of the second piezoelectric film 13, the electrical signal due to pyroelectricity is reduced, and the electrical signal due to piezoelectricity can be selectively obtained. is there.
- the first piezoelectric film 11 and the second piezoelectric film 13 are similarly heated. On the other hand, for example, when the pressure shown by the white arrow in FIG.
- the deformation of the first piezoelectric film 11 and the second piezoelectric film 13 is not the same. Therefore, when measuring the potential difference between the upper surface of the first piezoelectric film 11 and the lower surface of the second piezoelectric film 13, the electrical signal due to pyroelectricity is reduced, and the electrical signal due to piezoelectricity can be selectively obtained. It is.
- the bimorph type piezoelectric film of the present invention can be used for a piezoelectric panel (eg, a touch panel (preferably a touch panel capable of detecting a touch pressure)) and the like.
- the touch panel having the bimorph piezoelectric film of the present invention can detect both the touch position and the touch pressure, suppress the generation of pyroelectric noise, and has high transparency.
- the bimorph type piezoelectric film of the present invention can be used for touch panels of all types such as a resistance film type and a capacitance type. When the bimorph type piezoelectric film of the present invention is used for a touch panel, it is not necessarily used for detecting both the touch position and the touch pressure.
- the bimorph type piezoelectric film of the present invention is not necessarily used for the touch position or touch. It may also be used to detect either pressure.
- the piezoelectric panel having the bimorph type piezoelectric film of the present invention has the bimorph type piezoelectric film and electrode of the present invention, preferably, A first electrode (preferably a transparent electrode); The bimorph piezoelectric film of the present invention; A second electrode (preferably a transparent electrode); In this order.
- the first electrode is disposed directly or indirectly on one main surface of the bimorph piezoelectric film of the present invention, and the second electrode is directly or indirectly disposed on the other main surface of the bimorph piezoelectric film of the present invention. Arranged.
- a piezoelectric panel e.g., touch panel (preferably a touch panel capable of detecting touch pressure)
- the time-dependent change in strain of the bimorph piezoelectric film of the present invention is obtained. Since an electrical signal can be obtained, the presence / absence of pressure, speed, size (strength), or a change thereof, or a combination thereof can be determined by using the piezoelectric panel.
- the magnitude of the pressure that is, the static pressure
- the first first piezoelectric film and the second piezoelectric film used for the bimorph type piezoelectric film of the present invention may have pyroelectricity.
- the first piezoelectric film, And the second piezoelectric film are arranged so that the surfaces where charges of the same polarity (for example, positive charge and positive charge, or negative charge and negative charge) are generated by the temperature rise are on the outside, respectively.
- a touch panel preferably a touch panel capable of detecting a touch pressure
- a potential difference between two main surfaces of the bimorph piezoelectric film of the present invention is obtained as an electrical signal between the first electrode and the second electrode. In this case, the electrical signal due to pyroelectricity is reduced, and the electrical signal due to piezoelectricity can be selectively obtained.
- the touch panel having the bimorph piezoelectric film of the present invention can be used for an input device and a touch sensor device.
- the input device having the touch panel (that is, the input device having the bimorph piezoelectric film of the present invention) is input based on the touch position, the touch pressure, or both (for example, the pressure (strength) of pressure such as writing pressure) Based input).
- the input device having the touch panel and the touch sensor device can include a position detection unit and a pressure detection unit.
- the input device is an electronic device (eg, mobile phone (eg, smart phone), personal digital assistant (PDA), tablet PC, ATM, automatic ticket vending machine, digitizer, touch pad, car navigation system, FA (factory automation). It can be used for a touch panel display (touch panel monitor) of equipment.
- An electronic device having the input device has an operation and an operation based on the touch position, the touch pressure, or both (for example, an operation such as changing the thickness of a line displayed on the screen according to the writing pressure in paint software). Is possible.
- the touch sensor device can be used for electronic devices (eg, collision sensors, robot cleaners).
- the electronic device may include the touch input device of the present invention or the touch sensor device of the present invention, or may include the touch input device of the present invention or the touch sensor device of the present invention.
- the bimorph type piezoelectric film of the present invention can be deformed by an electric signal to vibrate air, it can be used for a speaker.
- the speaker can be used in, for example, an electronic device exemplified for the input device.
- the bimorph piezoelectric film of the present invention is transparent, the transparent speaker can be braked by using this.
- the transparent speaker can be disposed on a display surface of a mobile phone (eg, a smartphone), a personal digital assistant (PDA), and a tablet PC.
- Example 1 Preparation of piezoelectric film ( preparation of non-polarized film)
- MEK methyl ethyl ketone
- the obtained paint is filtered through a depth bleach type filter having a pore diameter of 3 ⁇ m, and the filtered paint is cast on a PET film using a die coater, dried, and dried to a thickness of 30 ⁇ m, 20 ⁇ m, 15 ⁇ m, And 10 ⁇ m of each polymer film was prepared.
- the drying is divided into 4 zones with the drying device as 1m 2m, and the drying temperature is set to 50 ° C, 80 ° C, 120 ° C and 150 ° C from the entrance side, and the passing speed of each zone is set. It was carried out by setting the peripheral speed to 8 / min and passing the film (or cast paint).
- the polymer film after drying was peeled off from the PET film. (Polarization treatment)
- the polymer film is sandwiched from above and below by a metal electrode, and a DC voltage is applied to the polymer films having thicknesses of 30 ⁇ m, 20 ⁇ m, 15 ⁇ m, and 10 ⁇ m at a room temperature of 300 kV / cm for 5 minutes at room temperature.
- polarized film was heated in a hot air dryer at 90 ° C. for 5 minutes, and then allowed to stand at room temperature and cooled to room temperature, to obtain a single-layer piezoelectric film.
- Total light transmittance The total light transmittance was measured by a light transmittance test using a haze meter NDH7000SP CU2II (product name) (Nippon Denka) based on ASTM D1003.
- the total haze value was measured by a light transmission test using a haze meter NDH7000SP CU2II (product name) (Nippon Denshoku) based on ASTM D1003.
- the internal haze value was obtained by putting water in a glass cell, inserting a film therein, and measuring the haze value in the method for measuring all haze values.
- Adhesive layer is pasted on the side with positive (+) charge of single film piezoelectric film cut out to A4 size, and the other single film piezoelectric film also has positive (+) charge side Was attached to the adhesive layer to prepare a bimorph type piezoelectric film.
- a pressure-sensitive adhesive layer (baseless) was prepared by selecting an acrylic pressure-sensitive adhesive having the following physical properties.
- A1 Film thickness 5 ⁇ m, internal haze 0.3%, storage elastic modulus 0.2 MPa
- A2 Film thickness 10 ⁇ m, internal haze 0.4%, storage elastic modulus 0.2 MPa
- A3 Film thickness 25 ⁇ m, internal haze 0.5%
- A4 Film thickness 40 ⁇ m, internal haze 0.6%
- storage elastic modulus 0.2 MPa A4 was used for the comparative example.
- B1 Film thickness 25 ⁇ m, internal haze 0.4%, storage elastic modulus 0.05 MPa
- B2 Film thickness 25 ⁇ m, internal haze 0.4%
- B3 Film thickness 25 ⁇ m, internal haze 0.4%
- storage modulus 0.65 MPa B3 was used for a comparative example.
- the optical characteristics (total light transmittance, haze value (total haze value, internal haze value)) were measured by the same method as the single film piezoelectric film. Moreover, piezoelectricity and pyroelectricity were measured by the following methods.
- the results of the first and second piezoelectric films with a thickness of 30 ⁇ m are shown in Table 2, and the results of the first and second piezoelectric films with a thickness of 20 ⁇ m, 15 ⁇ m, and 10 ⁇ m are shown in Table 3.
- the test of piezoelectricity and pyroelectricity of the bimorph type piezoelectric film was performed by preparing a specimen having ITO (indium tin oxide) attached as a transparent electrode as follows. Two ITO electrodes with a length of 65 mm ⁇ width 35 mm ⁇ thickness 50 ⁇ m were prepared, and each of them was placed on the top and bottom of a 65 mm long ⁇ 35 mm wide bimorph-type piezoelectric film, each with a 10 ⁇ m thick transparent adhesive layer (MHM made by Niei Kakko). -FED10).
- ITO indium tin oxide
- a glass plate having a length of 125 mm, a width of 60 mm, and a thickness of 0.54 mm was prepared.
- a test piece 65 mm long ⁇ 35 mm wide bimorph type piezoelectric film with ITO
- a 10 mm thick transparent adhesive layer (MHM-FED10 manufactured by NEIEI KAKO).
- FIG. 2 shows an outline of this aspect.
- a piezoelectric signal generated was measured by applying a constant weight to the center portion.
- the resulting piezoelectric signal was measured using the configuration outlined in FIG.
- an oscilloscope a Japanese data system UDS 5204S was used, and the voltage was read by an integrating circuit.
- thermocouple was attached to the center of the specimen with the same setup as the piezoelectric measurement. The temperature change was read with a thermocouple, and the pyroelectric signal was read with the same device as the piezoelectric signal. Using a dryer, hot air was applied to the specimen, and the voltage generated by raising the temperature from 20 ° C. to 40 ° C. within 0.5 to 1 minute was measured.
- the optical characteristics tended to improve as the film thickness was reduced. On the other hand, the S / N ratio was not changed.
- the thickness of the first piezoelectric film and the second piezoelectric film was changed, Transmittance, total haze, piezoelectricity, and pyroelectricity were measured. The results are shown in Table 4.
- the optical characteristics were improved by reducing the total thickness of both. Also, the piezoelectric signal increased when the thickness of the back piezoelectric film was reduced.
- the bimorph piezoelectric film of the present invention can be used for a piezoelectric panel such as a touch panel that can detect a touch pressure, for example.
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Abstract
Description
ところで、特許文献2では、圧電フィルムとして、タッチパネル用又はタッチ圧検出用の分極化フッ化ビニリデン/テトラフルオロエチレン共重合体フィルムが開示されている。
一方、近年、タッチパネルに用いられる部材には、高度な透明性が求められている。
第1の圧電フィルム、
粘着シート、又は接着剤層、及び
第2の圧電フィルム
を、この順で有し、
前記第1の圧電フィルム、及び前記第2の圧電フィルムは、
温度上昇によって同じ極性の電荷が生じる面がそれぞれ外側になるように配置されてあり、且つ
90%以上の全光線透過率、及び8.0%以下の全ヘイズ値を有する
バイモルフ型圧電フィルム
によって、前記課題が解決できることを見出し、本発明を完成するに至った。
粘着シート、又は接着剤層、及び
第2の圧電フィルム
を、この順で有し、
前記第1の圧電フィルム、及び前記第2の圧電フィルムは、
温度上昇によって同じ極性の電荷が生じる面がそれぞれ外側になるように配置されてあり、且つ
90%以上の全光線透過率、及び8.0%以下の全ヘイズ値を有する
バイモルフ型圧電フィルム。
項2. 前記粘着シート、又は接着剤層が、0.1MPa以上の貯蔵弾性率、0.6%以下の内部ヘイズ値、及び30μm以下の厚さを有する項1のバイモルフ型圧電フィルム
項3. 前記第1の圧電フィルム、及び前記第2の圧電フィルムが、分極化フッ化ビニリデン/テトラフルオロエチレン共重合体圧電フィルムであり、92%以上の全光透過率、0.6%以下の内部ヘイズ値、40μm以下の厚さを有し、且つ
前記粘着剤層、又は前記接着剤層が15μm以下の厚さを有する
項1又は2に記載のバイモルフ型圧電フィルム。
項4. 項1~3のいずれか1項に記載のバイモルフ型圧電フィルムを有する入力装置。
項5. 項1~3のいずれか1項に記載のバイモルフ型圧電フィルムを有するスピーカー。
項6. 項4に記載の入力装置、又は項5に記載のスピーカーを有する電子機器。
本明細書中、「タッチ位置」の「検出」は、タッチ位置の決定を意味し、一方、「タッチ圧」の「検出」は、押圧の有無、速度、大きさ(強弱)、又はこれらの変化、或いはこれらの組み合わせの決定を意味する。
本明細書中、用語「タッチ」は、触れること、触れられること、押すこと、押されること、及び接触すること、を包含する。
本明細書中、用語「分極化」は、表面に電荷を付与されていることを意味する。すなわち、分極化フィルムは、エレクトレットであることができる。
本発明のバイモルフ型圧電フィルムは、
第1の圧電フィルム、
粘着シート、又は接着剤層、及び
第2の圧電フィルム
を、この順で有し、
前記第1の圧電フィルム、及び前記第2の圧電フィルムは、
温度上昇によって同じ極性の電荷が生じる面がそれぞれ外側になるように配置されてあり、且つ
90%以上の全光線透過率、及び8.0%以下の全ヘイズ値を有する。
本発明のバイモルフ型圧電フィルムが有する第1の圧電フィルム、及び第2の圧電フィルムは、単層圧電フィルムである。ここで、用語「単層圧電フィルム」は、粘着シート、又は接着剤層によって貼り合わせられた積層体ではないことを意味し、バイモルフ型圧電フィルムと区別することを意図して用いられる。
本発明の圧電フィルムにおける当該重合体の含有量は、好ましくは、80質量%以上、より好ましくは85質量%以上、更に好ましくは90質量%である。当該含有量の上限は特に制限されず、例えば、100質量%であってもよいし、99質量%であってもよい。
当該重合体は、好ましくは、フッ化ビニリデン系重合体である。
本発明の圧電フィルムは、好ましくは分極化フッ化ビニリデン系重合体フィルムからなる。
本明細書中、「フッ化ビニリデン系重合体フィルム」の例としては、フッ化ビニリデン/テトラフルオロエチレン共重合体フィルム、フッ化ビニリデン/トリフロオロエチレン共重合体フィルム、及びポリフッ化ビニリデンフィルムが挙げられる。
前記フッ化ビニリデン系重合体フィルムは、好ましくはフッ化ビニリデン/テトラフルオロエチレン共重合体フィルムである。
当該「フッ化ビニリデン系重合体フィルム」は、樹脂フィルムに通常用いられる添加剤を含有してもよい。
(1)フッ化ビニリデンと、これと共重合可能な1種以上のモノマーと、の共重合体;及び
(2)ポリフッ化ビニリデン
が挙げられる
当該「これと共重合可能な1種以上のモノマー」又はそのうちの1種は、好ましくはテトラフルオロエチレンである。
当該「フッ化ビニリデン系重合体」の好ましい例としては、フッ化ビニリデン/テトラフルオロエチレン共重合体が挙げられる。
当該「フッ化ビニリデン/テトラフルオロエチレン共重合体」は、本発明に関する性質が著しく損なわれない限りにおいて、フッ化ビニリデン及びテトラフルオロエチレン以外のモノマーに由来する繰り返し単位を含有してもよい。
前記「(1)フッ化ビニリデンと、これと共重合可能な1種以上のモノマーと、の共重合体」は、フッ化ビニリデンに由来する繰り返し単位を50モル%以上(好ましくは60モル%以上)含有する。
前記「フッ化ビニリデン/テトラフルオロエチレン共重合体」における(テトラフルオロエチレンに由来する繰り返し単位)/(フッ化ビニリデンに由来する繰り返し単位)のモル比は、好ましくは5/95~36/64の範囲内、より好ましくは15/85~25/75の範囲内、更に好ましくは18/82~22/78の範囲内である。
(1)フルオロモノマー(例、ビニルフルオリド(VF)、トリフルオロエチレン(TrFE)、ヘキサフルオロプロペン(HFP)、1-クロロ-1-フルオロ-エチレン(1,1-CFE)、1-クロロ-2-フルオロ-エチレン(1,2-CFE)、1-クロロ-2,2-ジフルオロエチレン(CDFE)、クロロトリフルオロエチレン(CTFE)、トリフルオロビニルモノマー、1,1,2-トリフルオロブテン-4-ブロモ-1-ブテン、1,1,2-トリフルオロブテン-4-シラン-1-ブテン、ペルフルオロアルキルビニルエーテル、ペルフルオロメチルビニルエーテル(PMVE)、ペルフルオロプロピルビニルエーテル(PPVE)、ペルフルオロアクリラート、2,2,2-トリフルオロエチルアクリラート、2-(ペルフルオロヘキシル)エチルアクリラート);並びに
(2)炭化水素系モノマー(例、エチレン、プロピレン、無水マレイン酸、ビニルエーテル、ビニルエステル、アリルグリシジルエーテル、アクリル酸系モノマー、メタクリル酸系モノマー、酢酸ビニルが挙げられる。
第1の圧電フィルムの全光線透過率は、好ましくは91%以上、より好ましくは93%以上である。当該全光線透過率の上限は限定されないが、第1の圧電フィルムの全光線透過率は、通常99%以下である。
本明細書中、「全光線透過率」は、ASTM D1003に基づき、ヘイズメーターNDH7000SP CU2II(製品名)(日本電飾)又はその同等品を使用した光透過性試験によって得られる。
本明細書中、「全ヘイズ値」(total haze)は、ASTM D1003に準拠し、ヘイズガードII(製品名)(東洋精機製作所)又はその同等品を使用したヘイズ(HAZE、濁度)試験によって得られる。
本明細書中、「内部ヘイズ値」(inner haze)は、前記全ヘイズ値の測定方法において、ガラス製セルの中に水を入れて、その中にフィルムを挿入し、ヘイズ値を測定することにより、得られる。
本明細書中、「外部ヘイズ値」(outer haze)は、フィルムの全ヘイズ値から内部へイズ値を差し引くことで算出される。
本明細書中、単膜圧電フィルムの圧電特性(d33)は、d33メーター(PM300、Piezo test.Ltd)、又はその同等品を用いて測定される。
第1の圧電フィルムの電気機械結合係数の変化率は、10%以下である必要があり、好ましくは8%以下であり、より好ましくは6%以下である。
本明細書中、電気機械結合係数をktと略記する場合がある。
当該「電気機械結合係数の変化率」は、
(1)圧電フィルムの電気機械結合係数(加熱前のkt)を測定すること、
(2)圧電フィルムを、空気中で、85℃で10時間加熱すること、
(3)圧電フィルムを室温で放置して室温まで冷却すること、及び
(4)前記加熱及び前記冷却後の圧電フィルムの電気機械結合係数(加熱後のkt)を測定すること
を実施し、測定された「加熱前のkt」及び「加熱後のkt」を次式に算入することによって決定される。
電気機械結合係数の変化量(%)=
((加熱後のkt-加熱前のkt)/加熱前のkt)×100
電気機械結合係数の変化率(%)=|電気機械結合係数の変化量(%)|
本明細書中、「室温」は、15~35℃の範囲内の温度である。
分極化フッ化ビニリデン系重合体フィルムからなり;
JIS K7105に準拠して測定した黄色度YI値が4以下であり;
JIS K7105に準拠して測定したL*a*b*表色系におけるL*が85以上、a*が0.5以上、及びb*が1.5以下である。
このようなYI値、並びにL*、a*、及びb*を示すことにより、色味が抑制され、タッチパネル等に使用したときに、表示装置の視認性が高い圧電フィルムとすることができる。
圧電フィルムのYI値は、JIS K7105に準拠した測定方法により、日本電色工業社製SZシグマ90測定器により、C/2光源を用いて、室温・常湿の条件で測定することができる。
圧電フィルムのL*、a*、及びb*は、JIS K7105に準拠した測定方法により、日本電色社製SZシグマ90測定器により、常温・常湿の条件で、C/2光源を用いて測定することができる。
前記第1の圧電フィルムのリタデーション値は、大塚電子株式会社製RETS4200RVを用い、550nmの光を照射する条件により測定することができる。
(1)界面活性剤の含有量が100ppm以下である;
(2)メチルセルロースの含有量が6000ppm以下である;
(3)金属の含有量と、イオンの含有量との合計が200ppm以下である。
前記第1の圧電フィルムを上述の構成とすることにより、前記第1の圧電フィルムのYI値を4以下とすることができ、L*a*b*表色系におけるL*を85以上、a*を0.5以上、及びb*を1.5以下とすることが可能となる。
前記界面活性剤の含有量は、100ppm以下であることが好ましい。当該界面活性剤の含有量は、50ppm以下であることが好ましい。また、界面活性剤の含有量の下限は、特に限定されないが、懸濁重合によりポリマーを重合する場合は通常0ppmである。
前記第1のフィルム中の界面活性剤の含有量は、ダイオネクス社製DX500測定器により、ポリマーを水に懸濁させたのち超音波で10分以上処理を行い界面活性剤を抽出した水を測定して検出することができる。
前記メチルセルロースの含有量は、6000ppm以下であることが好ましい。当該メチルセルロースの含有量は、5000ppm以下であることがより好ましい。また、メチルセルロースの含有量の下限は、特に限定されないが、乳化重合によりポリマーを重合する場合は通常0ppmであり、懸濁重合によりポリマーを重合する場合は通常3000ppm以下程度である。
圧電フィルム中のメチルセルロースの含有量は、ダイオネクス社製DX500測定器により、ポリマーを水に懸濁させたのち超音波で10分以上処理を行いメチルセルロースを抽出した水を測定して検出することができる。
前記金属の含有量と、イオンの含有量との合計は、200ppm以下であることが好ましい。当該含有量の合計は、100ppm以下であることがより好ましい。また、前記金属の含有量と、イオンの含有量との合計の下限は、特に限定されないが、乳化重合によりポリマーを重合する場合は通常30ppm程度であり、懸濁重合によりポリマーを重合する場合は通常10ppm程度である。
前記金属としては、特に限定されないが、例えば、Fe、Cr等が挙げられる。
また、イオンとしては、特に限定されないが、例えば、SO4 2-、Cl-等が挙げられる。
圧電フィルム中の金属の含有量は、セイコーインストルメンツ社製SPS3000測定器により、圧電フィルムを燃焼させたのち、0.1wt%の希塩酸で金属を抽出し、それを当該装置で測定することで検出することができる。
また、前記第1の圧電フィルム中のイオンの含有量は、圧電フィルムを細かく切って粉末に近い状態にし、水中に浸漬させて1hr以上超音波処理を施し、イオンを抽出した水をダイオネクス社製DX500測定器により分析することにより測定することができる。
第1、及び第2の圧電フィルムは、例えば、
非分極の重合体フィルム(例、非分極のフッ化ビニリデン系重合体フィルム)を分極処理する工程A;及びその後の
分極化重合体フィルム(例、分極化フッ化ビニリデン系重合体フィルム)を熱処理する工程B
を含む
製造方法
によって製造できる。
工程Aでは、非分極の重合体フィルムを分極処理する。
(1)溶媒中に、重合体(例、フッ化ビニリデン系重合体)、並びに所望による成分(例、無機酸化物粒子、及び親和性向上剤)を溶解又は分散させて液状組成物を調製する工程;
(2)前記液状組成物を基材上に流延(塗布)する工程;及び
(3)前記溶媒を気化させて、フィルムを形成させる工程
を含む製造方法である。
また、かかる着色を防止する意味から、前記溶媒の好ましい例としては、ケトン系溶媒(例、メチルエチルケトン(MEK)、メチルイソブチルケトン(MIBK)、アセトン、ジエチルケトン、ジプロピルケトン)、エステル系溶媒(例、酢酸エチル、酢酸メチル、酢酸プロピル、酢酸ブチル、乳酸エチル)、エーテル系溶媒(例、テトラヒドロフラン、メチルテトラヒドロフラン、ジオキサン)、及びアミド系溶媒(例、ジメチルホルムアミド(DMF)、ジメチルアセトアミド)が挙げられる。これらの溶媒は、単独で、又は2種以上を組み合わせて用いられ得る。前記溶媒として、ポリフッ化ビニリデン(PVDF)の溶解に汎用される溶媒であるアミド系溶媒を用いてもよいが、溶媒中のアミド系溶媒の含有率は50%以下であることが望ましい。
前記溶媒の気化における乾燥温度は溶媒の種類等に応じて適宜決定され得るが、通常、20℃~200℃の範囲内であり、好ましくは40℃~170℃の範囲内である。
当該乾燥温度は一定温度であってもよいが、変化させてもよい。乾燥温度を低温(例、40~100℃)から高温(例、120~200℃)へと変化させることにより、得られるフィルムのヘイズ値を下げることができる。これは、例えば、乾燥ゾーンを数ゾーンに分割し、フィルム(又はフィルム形成前の流延された溶液)が低温のゾーンへ入って高温のゾーンに移動することによって実現できる。
具体的には、例えば、乾燥ゾーンを50℃、80℃、120℃、及び150℃の4ゾーンに分割し、フィルムを50℃のゾーンから150℃のゾーンへ連続的に移動させればよい。
前記溶媒の気化における乾燥時間は、通常1~600秒間の範囲内、好ましくは10~200秒間の範囲内である。
このようにして得られる第1、及び第2の圧電フィルムは、その厚さの均一性が高い。具体的に好ましくは、第1、及び第2の圧電フィルムは、フィルム全体に渡って1cm四方毎に10箇所において測定した厚さの変動係数が、平均膜厚の±20%以下である。
コロナ放電には、負コロナ及び正コロナのいずれを用いてもよいが、非分極樹脂フィルムの分極しやすさの観点から負コロナを用いることが望ましい。
コロナ放電処理の条件は、本発明が属する技術分野の常識に基づいて、適宜設定すればよい。コロナ放電処理の条件が弱すぎると、得られる圧電フィルムの圧電性が不充分になる虞があり、一方、コロナ放電処理の条件が強すぎると、得られる圧電フィルムが点状欠陥を有する虞がある。
例えば、線状電極を用いてロール・ツー・ロールで連続印加を実施する場合は、線状電極と非分極フィルムの間の距離、フィルム膜厚等によって異なるが、例えば、-15~-25kVの直流電界である。処理速度は、例えば、10~500cm/分である。
工程Bは、前記工程Aの後に実施される。工程Bでは、工程Aの分極処理で得られた分極化フッ化ビニリデン系重合体フィルム(以下、単に分極化フィルムと称する場合がある。)を熱処理する。
工程Bの熱処理は、前記分極化フィルム又は工程Aにおいて分極を完了した部分に対して行うことができる。すなわち、工程Aの分極処理を実施しながら、当該分極処理を終えた部分に対して工程Bの熱処理を実施してもよい。
熱処理の方法は、特に限定されないが、例えば、分極化フィルムを2枚の金属板で挟み、当該金属板を加熱すること;分極化フィルムのロールを恒温槽中で加熱すること;又はロール・ツー・ロール方式での分極化フィルムの生産において、金属ローラーを加熱し、分極化フィルムを、当該加熱した金属ローラーに接触させること;又は分極化フィルムを加熱した炉の中にロール・ツー・ロールで通していくことにより行うことができる。この際、分極化フィルムは単体で熱処理してもよいし、或いは別種のフィルム又は金属箔上に重ねて積層フィルムを作成し、これを熱処理してもよい。とりわけ、高温で熱処理する場合には後者の方法のほうが、分極化フィルムにしわが入りにくいので好ましい。
前記熱処理の温度は、熱処理される分極化フィルムの種類によって異なる場合があり、好ましくは(熱処理される分極化フィルムの融点-100)℃~(熱処理される分極化フィルムの融点+40)℃の範囲内である。
前記熱処理の温度は、具体的には、好ましくは80℃以上、より好ましくは85℃以上、更に好ましくは90℃以上である。
また、前記熱処理の温度は、好ましくは170℃以下、より好ましくは160℃以下、更に好ましくは140℃以下である。
前記熱処理の時間は、通常、10秒間以上、好ましくは0.5分間以上、より好ましくは1分間以上、更に好ましくは2分間以上である。
また、前記熱処理の時間の上限は限定されないが、通常、前記熱処理の時間は60分間以下である。
前記熱処理の条件は、好ましくは90℃以上で1分間以上である。
本明細書中、フィルムの融点とは、示差走査熱量測定(DSC)装置を用い、10℃/分の速度で昇温したときに得られる融解熱曲線における極大値である。
当該粘着シートは、第1の圧電フィルム及び第2の圧電フィルムを互いに貼り合わせられるものであれば特に限定されず、1又は2以上の層からなることができる。すなわち、当該粘着シートが1層からなる場合、当該粘着シートは粘着剤層からなり、及び当該粘着シートが2以上の層からなる場合、その両外層が粘着剤層である。当該粘着シートが3以上の層からなる場合、当該粘着シートは内層として基材層を有していてもよい。
当該粘着シートにおける基材層は、透明なフィルムであればよく、好ましくは、例えば、ポリイミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリパラフェニレンスルフィド、又はポリアミドイミドのフィルムであることができる。
当該粘着シートにおける粘着剤層は、粘着剤としてアクリル系粘着剤を含有する層であることができる。
前記接着剤層を形成する接着剤は、アクリル系接着剤であることができる。
アルキル(メタ)アクリレートは、粘着力の観点から、アルキル基R2の炭素数が1~14とされる。アルキル基の炭素数が15以上であると、粘着力が低下する可能性があるので好ましくない。このアルキル基R2は、炭素数が1~12であることが好ましく、炭素数が4~12であることが好ましく、炭素数が4~8であることがより好ましい。
また、アルキル基R2の炭素数が1~14のアルキル(メタ)アクリレートのうち、アルキル基R2の炭素数が1~3又は13~14のアルキル(メタ)アクリレートをモノマーの一部分として用いてもよいが、アルキル基R2の炭素数が4~12のアルキル(メタ)アクリレートを必須として(例えば50~100モル%)用いることが好ましい。
なお、これらのアルキル基R2は、直鎖であっても、分岐鎖であってもよい。
また、本発明のバイモルフ型圧電フィルムにおいて用いられる第2の圧電フィルムの好ましい例としては、前記第1の圧電フィルムの好ましい例と同様のものが例示される。
本発明のバイモルフ型圧電フィルムにおいて用いられる第2の圧電フィルムは、前記第1の圧電フィルムと同じものであってもよく、異なるものであってもよい。
前記第1の圧電フィルム、及び前記第2の圧電フィルムは、分極化フッ化ビニリデン/テトラフルオロエチレン共重合体圧電フィルムであり、92%以上の全光透過率、0.6%以下の内部ヘイズ値、及び40μm以下の厚さを有し、且つ
前記粘着シート、又は前記接着剤層は、0.1MPa以上の貯蔵弾性率、及び15μm以下の厚さを有する。
本発明のバイモルフ型圧電フィルムは、例えば、温度上昇によって同じ極性の電荷が生じる面がそれぞれ外側になるようにして、第1の圧電フィルムに粘着シートを貼り付け、次いで、当該粘着シートに第2の圧電フィルムを貼り付けることによって製造できる。粘着シート、粘着剤塗布したフィルムを貼りあわせる場合、シート状にしたもの同士を貼りあわせてもよいし、ロールtoロールで連続的に貼りあわせてもよい。貼りあわせる場合の圧力としては圧電フィルムに変形が見られない程度の圧力が好ましい。また、張り付ける際に加温してもよい。
本発明のバイモルフ型圧電フィルムの圧電性は、次の方法により測定される。
(バイモルフ型圧電フィルムの供試体の用意)
圧電性の測定は、次のように、適当な大きさ(例、縦65mm×横35mm)の、透明電極としてITO(酸化インジウムスズ)を貼り付けた供試体を用意して行う。
縦65mm×横35mm×厚み50μmのITO電極を2枚用意し、これを縦65mm×横35mmの単層圧電フィルム又はバイモルフ型圧電フィルムの上下に、それぞれ1枚ずつ、厚さ10μmの透明粘着層(日栄化工製 MHM-FED10)を用いて貼り付ける。
(バイモルフ型圧電フィルムの圧電性の測定)
バイモルフ型圧電フィルムの圧電性は、次の方法で測定される。
縦125mm×横60mm×厚さ0.54mmのガラス板を用意し、その縦の両端15mmをアクリル樹脂製の枠に載せる。
そのガラス板の下面に、供試体(縦65mm×横35mmのITO付きバイモルフ型圧電フィルム)を厚さ10mmの透明粘着層(日栄化工製MHM-FED10)で貼り付ける。
図2にこの態様の概要を示す。
中心部に重りで一定重さの荷重をかけて、生じる圧電信号を測定する。
生じる圧電信号の測定は、図3に概要を示す構成を用いる。
ここで、オシロスコープとして、日本データシステムUDS 5204Sを用いて、積分回路で電圧を読み取る。
圧電性の測定と同一のセットアップで、供試体の中心部に熱電対を取り付ける。
熱電対で温度変化を読み取り、焦電信号は圧電信号と同じ装置で電圧を読み取る。
ドライヤーを用いて、供試体に熱風をあてて、0.5~1分の間に20℃から40℃まで温度を上昇させて発生する電圧を測定する。
バイモルフ型圧電フィルム1は、
第1の圧電フィルム11、
粘着剤層、又は接着剤層12、及び
第2の圧電フィルム13
を、この順で有し、
前記第1の圧電フィルム11、及び前記第2の圧電フィルム13は、
温度上昇によって同じ極性の電荷(陰(-)電荷))が生じる面がそれぞれ外側になるように配置されている。
本発明のバイモルフ型圧電フィルム1に温度変化が生じたときは、第1の圧電フィルム11と第2の圧電フィルム13が同様に昇温する。一方、例えば、図1の白抜き矢印に示す押圧を加えた場合、第1の圧電フィルム11と第2の圧電フィルム13の変形は同様ではない。従って、第1の圧電フィルム11の上面と第2の圧電フィルム13の下面の電位差を測定する場合、焦電性による電気信号が低減されて、圧電性による電気信号を選択的に得ることが可能である。
圧電パネル
本発明のバイモルフ型圧電フィルムは、圧電パネル(例、タッチパネル(好ましくは、タッチ圧を検出できるタッチパネル))等に使用できる。
本発明のバイモルフ型圧電フィルムを有するタッチパネルは、タッチ位置及びタッチ圧の両方を検出でき、焦電ノイズの発生が抑制され、かつ透明性が高い。
本発明のバイモルフ型圧電フィルムは、抵抗膜方式、及び静電容量方式等の、あらゆる方式のタッチパネルに使用できる。
本発明のバイモルフ型圧電フィルムは、タッチパネルに使用されるとき、必ずしも、タッチ位置及びタッチ圧の両方の検出のために使用される必要は無く、本発明のバイモルフ型圧電フィルムは、タッチ位置又はタッチ圧のいずれかの検出にも使用されてもよい。
本発明のバイモルフ型圧電フィルムを有する圧電パネルは、本発明のバイモルフ型圧電フィルム及び電極を有し、好ましくは、
第1の電極(好ましくは、透明電極)と、
本発明のバイモルフ型圧電フィルムと、
第2の電極(好ましくは、透明電極)と、
をこの順で有する。
第1の電極は本発明のバイモルフ型圧電フィルムの一方の主面上に直接又は間接的に配置され、及び
第2の電極は本発明のバイモルフ型圧電フィルムの他方の主面上に直接又は間接的に配置される。
当該タッチセンサー装置は、電子機器(例、衝突センサー、ロボット掃除機)に用いることができる。
当該電子機器は、本発明のタッチ入力装置、又は本発明のタッチセンサー装置を備えることができ、或いは本発明のタッチ入力装置、又は本発明のタッチセンサー装置からなることもできる。
圧電フィルムの調製
(非分極フィルムの調製)
フッ化ビニリデン/テトラフルオロエチレン共重合体(TFE/VDF=20/80)を、メチルエチルケトン(MEK)に溶解させ、固形分24wt%の塗料を調製した。
得られた塗料を孔径3μmのデプスブリーツタイプのフィルターでろ過し、ろ過した塗料をダイコーターを用いてPETフィルム上に流延(キャスティング)し、乾燥を行って、厚さ30μm、20μm、15μm、及び10μmの各重合体フィルムを調製した。
この際、乾燥は、乾燥装置を1ゾーン2mとして4ゾーンに分割し、それぞれの乾燥温度を、入り口側から50℃、80℃、120℃、及び150℃に設定し、各ゾーンの通過速度を周速8/minに設定して、フィルム(又は流延された塗料)を通過させることによって、実施した。乾燥後の重合体フィルムをPETフィルムから剥離した。
(分極処理)
重合体フィルムを、金属電極で前記重合体フィルムを上下から挟み、厚さ30μm、20μm、15μm、及び10μmの前記重合体フィルムに対して300kV/cmの条件で、直流電圧を室温で5分間印加して分極し、分極化フィルムを得た。
(熱処理)
その後、当該分極化フィルムを、90℃で5分間、熱風乾燥機中で、加熱し、次いで室温で放置して室温まで冷却して、単層圧電フィルムを得た。
全光線透過率は、ASTM D1003に基づき、ヘイズメーターNDH7000SP CU2II(製品名)(日本電飾)を使用した光透過性試験によって測定した。
全ヘイズ値は、ASTM D1003に基づき、ヘイズメーターNDH7000SP CU2II(製品名)(日本電飾)を使用した光透過性試験によって測定した。
内部ヘイズ値は、前記全ヘイズ値の測定方法において、ガラス製セルの中に水を入れて、その中にフィルムを挿入し、ヘイズ値を測定することにより、得た。
単膜圧電フィルムの圧電性(圧電特性(d33))は、d33メーター(PM300 Piezo test.Ltd )を用いて測定した。
A4サイズに切り出した単膜圧電フィルムの陽(+)電荷をもった側に粘着剤層を貼り付け、もう一方の単膜圧電フィルムも陽(+)電荷をもった側を粘着剤層に貼り付けてバイモルフ型圧電フィルムを作成した。
粘着剤層(基材レス)は下記の物性をもつアクリル系粘着剤を選定して、用意した。
A1: 膜厚5μm、内部ヘイズ0.3%、貯蔵弾性率0.2MPa
A2: 膜厚10μm、内部ヘイズ0.4%、貯蔵弾性率0.2MPa
A3: 膜厚25μm、内部ヘイズ0.5%、貯蔵弾性率0.2MPa
A4: 膜厚40μm、内部ヘイズ0.6%、貯蔵弾性率0.2MPa
なお、A4は、比較例に用いた。
B2: 膜厚25μm、内部ヘイズ0.4%、貯蔵弾性率0.09MPa
B3: 膜厚25μm、内部ヘイズ0.4%、貯蔵弾性率0.65MPa
なお、B3は比較例に用いた。
また、圧電性、及び焦電性を次の方法で測定した。
第1及び第2の圧電フィルムの厚さ30μmの結果を表2に示し、並びに第1及び第2の圧電フィルムの厚さ20μm、15μm、及び10μmの結果を表3に示す。
バイモルフ型圧電フィルムの圧電性、及び焦電性の試験は、次のように、透明電極としてITO(酸化インジウムスズ)を貼り付けた供試体を用意して行った。
縦65mm×横35mm×厚み50μmのITO電極を2枚用意し、これを縦65mm×横35mmのバイモルフ型圧電フィルムの上下に、それぞれ1枚ずつ、厚さ10μmの透明粘着層(日栄化工製 MHM-FED10)を用いて貼り付けた。
縦125mm×横60mm×厚さ0.54mmのガラス板を用意し、その縦の両端15mmをアクリル樹脂製の枠に載せた。
そのガラス板の下面に、供試体(縦65mm×横35mmのITO付きバイモルフ型圧電フィルム)を厚さ10mmの透明粘着層(日栄化工製MHM-FED10)で貼り付けた。
図2にこの態様の概要を示す。
中心部に重りで一定重さの荷重をかけて、生じる圧電信号を測定した。
生じる圧電信号の測定は、図3に概要を示す構成を用いた。
ここで、オシロスコープとして、日本データシステムUDS 5204Sを用いて、積分回路で電圧を読み取った。
圧電性の測定と同一のセットアップで、供試体の中心部に熱電対を取り付けた。
熱電対で温度変化を読み取り、焦電信号は圧電信号と同じ装置で電圧を読み取った。
ドライヤーを用いて、供試体に熱風をあてて、0.5~1分の間に20℃から40℃まで温度を上昇させて発生した電圧を測定した。
また、貯蔵弾性率が0.08MPaを下回ると圧電信号が弱くなり、十分なS/N比がとれなくなった。
Claims (7)
- 第1の圧電フィルム、
粘着剤層、又は接着剤層、及び
第2の圧電フィルム
を、この順で有し、
前記第1の圧電フィルム、及び前記第2の圧電フィルムは、
温度上昇によって同じ極性の電荷が生じる面がそれぞれ外側になるように配置されてあり、且つ
90%以上の全光線透過率、及び8.0%以下の全ヘイズを有する
バイモルフ型圧電フィルム。 - 前記粘着剤層、又は接着剤層が、0.1MPa以上の貯蔵弾性率、0.6%以下の内部ヘイズ値、及び30μm以下の厚さを有する請求項1のバイモルフ型圧電フィルム
- 前記第1の圧電フィルム、及び前記第2の圧電フィルムが、分極化フッ化ビニリデン/テトラフルオロエチレン共重合体圧電フィルムであり、92%以上の全光透過率、0.6%以下の内部ヘイズ、及び40μm以下の厚さを有し、
且つ前記粘着剤層、又は前記接着剤層が15μm以下の厚さを有する
請求項1又は2に記載のバイモルフ型圧電フィルム。 - 請求項1~3のいずれか1項に記載の圧電フィルムを有する圧電パネル。
- 請求項1~3のいずれか1項に記載のバイモルフ型圧電フィルムを有する入力装置。
- 請求項1~3のいずれか1項に記載のバイモルフ型圧電フィルムを有するスピーカー。
- 請求項6に記載の入力装置、又は請求項7に記載のスピーカーを有する電子機器。
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