WO2014185530A1 - 押圧検出装置及びタッチパネル - Google Patents
押圧検出装置及びタッチパネル Download PDFInfo
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- WO2014185530A1 WO2014185530A1 PCT/JP2014/063100 JP2014063100W WO2014185530A1 WO 2014185530 A1 WO2014185530 A1 WO 2014185530A1 JP 2014063100 W JP2014063100 W JP 2014063100W WO 2014185530 A1 WO2014185530 A1 WO 2014185530A1
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- detection device
- polymer
- piezoelectric
- pressure
- piezoelectric material
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- 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
- G06F3/0414—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using force sensing means to determine a position
- G06F3/04142—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using force sensing means to determine a position the force sensing means being located peripherally, e.g. disposed at the corners or at the side of a touch sensing plate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
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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 OR CALCULATING; 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
- G06F2203/04105—Pressure sensors for measuring the pressure or force exerted on the touch surface without providing the touch position
Definitions
- the present invention relates to a press detection device and a touch panel.
- PZT PBZrO 3 -PbTiO 3 solid solution
- PZT contains lead, so it has a low environmental burden and is highly flexible.
- Molecular piezoelectric materials are being used.
- polymer piezoelectric materials are mainly classified into the following two types. That is, Pauling type polymer represented by nylon 11, polyvinyl fluoride, polyvinyl chloride, polyurea, etc., polyvinylidene fluoride ( ⁇ type) (PVDF), and vinylidene fluoride-trifluoroethylene copolymer (P (VDF-TrFE)) (75/25) and other ferroelectric polymers.
- polymers having optical activity such as polypeptides and polylactic acid
- polylactic acid polymers exhibit piezoelectricity only by mechanical stretching operation.
- polylactic acid has a small volume fraction of side chains with respect to the main chain and a large ratio of permanent dipoles per volume, and can be said to be an ideal polymer among the polymers having helical chirality.
- polylactic acid that exhibits piezoelectricity only by stretching treatment does not require poling treatment and the piezoelectricity is unlikely to decrease for several years.
- a touch panel including a piezoelectric sheet made from polylactic acid has been proposed (for example, International Publication No. 2010/143528, International Publication No. 2011). / 125408 pamphlet, international publication 2012/049969 pamphlet, and international publication 2011/138903 pamphlet).
- An object of the present invention is to provide a press detection device and a touch panel having high detection sensitivity using a polymer piezoelectric material.
- a member to be pressed having a contact surface to which pressure is applied by applying pressure
- a piezoelectric member including a polymeric piezoelectric material is a piezoelectric constant d 14 measured by a displacement method at 25 ° C. is 1 Pm/V more
- the ratio IEb / IEa of the product IEb of the cross-sectional secondary moment Ib and Young's modulus Eb of the member to be pressed and the product IEa of the cross-sectional secondary moment Ia and Young's modulus Ea of the piezoelectric member is in the range of 10 2 to 10 10 .
- a pressure detection device is provided.
- ⁇ 2> The pressure detection device according to ⁇ 1>, wherein the ratio IEb / IEa is in a range of 10 4 to 10 9 .
- ⁇ 3> The press detection device according to ⁇ 1> or ⁇ 2>, wherein the ratio IEb / IEa is in the range of 10 5 to 10 8 .
- ⁇ 4> Support means for supporting the member to be pressed against pressure applied from the contact surface; Support means for supporting the piezoelectric member against pressure applied from the contact surface via the pressed member;
- the press detection device according to any one of ⁇ 1> to ⁇ 3>, further comprising: ⁇ 5> The press detection device according to any one of ⁇ 1> to ⁇ 4>, wherein a direction in which pressure is applied from the contact surface intersects a molecular orientation direction of the polymeric piezoelectric material.
- ⁇ 6> The press detection device according to any one of ⁇ 1> to ⁇ 5>, wherein a thickness of the pressed member is in a range of 0.2 mm to 20 mm.
- ⁇ 7> The press detection device according to any one of ⁇ 1> to ⁇ 6>, wherein a Young's modulus Eb of the member to be pressed is 1 GPa to 200 GPa.
- a Young's modulus Eb of the member to be pressed is 1 GPa to 200 GPa.
- ⁇ 8> The pressure detection according to any one of ⁇ 1> to ⁇ 7>, further including a relaxation portion having a Young's modulus of 0.1 GPa or less on a side opposite to the pressed member side of the piezoelectric member. apparatus.
- the polymeric piezoelectric material includes an optically active helical chiral polymer having a weight average molecular weight of 50,000 to 1,000,000, the crystallinity obtained by DSC method is 20% to 80%, and Any of ⁇ 1> to ⁇ 8>, wherein the product of the normalized molecular orientation MORc and the crystallinity is 40 to 700 when the reference thickness measured by a microwave transmission type molecular orientation meter is 50 ⁇ m.
- the press detection apparatus of Claim 1. ⁇ 10> The press detection device according to any one of ⁇ 1> to ⁇ 9>, wherein an internal haze of the polymeric piezoelectric material with respect to visible light is 10% or less.
- ⁇ 11> The press detection device according to ⁇ 9> or ⁇ 10>, wherein the MORc is 3.5 to 15.0.
- ⁇ 12> The helical chiral polymer according to any one of ⁇ 9> to ⁇ 11>, wherein the helical chiral polymer is a polylactic acid polymer having a main chain including a repeating unit represented by the following formula (1): Press detection device.
- ⁇ 13> The press detection device according to any one of ⁇ 9> to ⁇ 12>, wherein the helical chiral polymer has an optical purity of 95.00% ee or more.
- ⁇ 14> The press detection device according to any one of ⁇ 9> to ⁇ 13>, wherein the content of the helical chiral polymer in the polymer piezoelectric material is 80% by mass or more.
- the polymeric piezoelectric material further includes a stabilizer having one or more functional groups selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group and having a weight average molecular weight of 200 to 60000,
- the pressure detection device according to any one of ⁇ 9> to ⁇ 14>, wherein the stabilizer is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the chiral polymer.
- the press detection device according to ⁇ 15> including a stabilizer having one functional group in one molecule selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group as the stabilizer.
- a touch panel comprising the press detection device according to any one of ⁇ 1> to ⁇ 16> and a display device.
- a press detection device and a touch panel with high detection sensitivity using a polymer piezoelectric material are provided.
- FIG. 1 It is sectional drawing which shows schematically the cross section of the thickness direction about an example of the press detection apparatus which concerns on this embodiment. It is a top view which shows roughly the other side of the contact surface of the press detection apparatus shown in FIG. In an Example, it is a figure which shows schematically the circuit structure used for the measurement of the generated electric charge density.
- a pressure detection device includes a pressed member having a contact surface to which pressure is applied and pressure is applied, and a piezoelectric piezoelectric material disposed opposite the pressed member.
- the inventors preferably have a ratio IEb / IEa between the product IEb of the cross-sectional secondary moment Ib and Young's modulus Eb of the member to be pressed and the product IEa of the cross-sectional secondary moment Ia and Young's modulus Ea of the piezoelectric member. It has been found that by being in the range of 2 to 10 10 , the generated charge density per unit deflection amount is high, that is, the pressure applied to the contact surface of the member to be pressed can be detected with high sensitivity. From the viewpoint of higher detection sensitivity, IEb / IEa is preferably 10 3 or more, more preferably 10 4 or more, and particularly preferably 10 5 or more.
- IEb / IEa is preferably 10 9 or less, more preferably 10 8 or less, and even more preferably 10 7 or less.
- IEB / IEa is preferably 10 4 to 10 9, more preferably from 10 4 to 10 8, and particularly preferably 10 5 to 10 8.
- the piezoelectric member only needs to face at least a part of the member to be pressed.
- the pressurizing means, the portion where the pressurizing means of the member to be pressed contacts, and the piezoelectric member may be arranged on a straight line or may not be arranged on a straight line. Also good.
- the cross-sectional secondary moment is an amount representing the difficulty of deformation of the object with respect to the bending moment.
- the cross-sectional secondary moment (Ib) of the member to be pressed and the cross-sectional secondary moments (Ia) of the piezoelectric member constituting the press detection device of the present embodiment are respectively determined as follows.
- the members (pressurized member and piezoelectric member) are rectangular flat plate members, this member is regarded as a beam having a rectangular cross section.
- the cross-sectional secondary moment I is generally calculated by the following equation (a) based on the member width b and member thickness h.
- the cross section of the member to be pressed or the piezoelectric member is not a short rectangular cross section, it is calculated as a short rectangular cross section, and the secondary moment of the cross section is calculated by a fixed end interval ⁇ (thickness of member thickness) / 12.
- Young's modulus (longitudinal elastic modulus) is a constant that determines how much stress is required per unit strain in the elastic range.
- Each Young's modulus (Eb, Ea) of the member to be pressed and the piezoelectric member constituting the press detection device of the present embodiment is obtained as follows.
- the Young's modulus Ea (longitudinal elastic modulus) of the piezoelectric member and the Young's modulus Eb (longitudinal elastic modulus) of the member to be pressed made of resin are dumbbell-shaped as defined in JIS K6251 by a tensile test method in accordance with JIS K7127. Measured using a test piece of type No.
- the Young's modulus is obtained as the slope of the elastic region (linear part thereof) in the stress strain diagram obtained by this test piece and this test method.
- the Young's modulus of a member to be pressed made of a brittle material such as glass is obtained by a static elastic modulus measurement method based on JIS R1602.
- FIG. 1 is a cross-sectional view schematically showing a cross section in the thickness direction of an example of the press detection device according to the present embodiment
- FIG. 2 is a view (a support frame) opposite to the contact surface of the press detection device shown in FIG. FIG.
- a press detection device 10 is disposed so as to face a base material (a member to be pressed) 6 having a contact surface 6A to which pressure is applied and pressure is applied.
- a piezoelectric member 7 includes a polylactic acid (PLA) film (polymer piezoelectric material) 4 and electrode layers (first electrode layer 2 and second electrode layer 3) provided on both sides of the PLA film 4. It is configured.
- PLA polylactic acid
- electrode layers first electrode layer 2 and second electrode layer 3
- copper foil tapes 22 and 23 with conductive adhesive layers are attached to the first electrode layer 2 and the second electrode layer 3 as lead electrodes, respectively.
- a support frame 5 is provided at the edge of the surface of the substrate 6 opposite to the contact surface 6A as a support means for supporting the substrate 6 against the pressure applied from the contact surface 6A.
- the support frame 5 is affixed to the base material 6 with a double-sided tape, an adhesive agent, an adhesive, etc., for example.
- the support frame 5 is provided at the edge of the surface of the substrate 6, but the present embodiment is not limited to this aspect, and the support frame 5 is provided at the edge of the surface of the piezoelectric member 7. It may be provided.
- the support frame 5 is It may be provided at the edge of the piezoelectric member 7.
- the support frame 5 should just be provided so that the base material 6 can be supported with respect to the pressure applied from 6 A of contact surfaces.
- the support means for supporting the member to be pressed against the pressure applied from the contact surface is not limited to being a support frame, and the member to be pressed against the pressure (preferably May be any means that supports (at least two points).
- the first electrode layer 2 side of the PLA film 4 is attached to the base material 6 via the double-sided tape 1.
- the double-sided tape 1 functions as a support means for supporting the piezoelectric member 7 on the base material 6, and supports the piezoelectric member 7 on the base material 6 against pressure applied via the base material 6 from the contact surface 6 ⁇ / b> A.
- the base material 6 is supported by the support frame 5 and the piezoelectric member 7 is supported by the base material 6 via the double-sided tape 1, so that when the pressure is applied from the contact surface 6 ⁇ / b> A, the base material 6.
- the piezoelectric member 7 bend together.
- the press detection device of the present embodiment preferably has a mode in which the entire main surface of the piezoelectric member 7 is in contact with the main surface of the pressed member 6 via a double-sided tape or the like, but the piezoelectric member 7 is supported at least at two locations. It may be an embodiment. Specifically, if two or more points that support the piezoelectric member 7 with respect to the pressure F (hereinafter referred to as “fulcrum a”) are provided between the pressed member 6 and the piezoelectric member 7 and the covered member. There may be a gap between the pressure member 6.
- the fulcrum a of the piezoelectric member 7 is provided on the member to be pressed 6 as long as the pressure F applied to the member to be pressed 6 is transmitted to the piezoelectric member 7 through the fulcrum ieri.
- the pressing member 6 and the piezoelectric member 7 do not need to be in direct contact, and a member that propagates the pressure F may be interposed between the piezoelectric member 7 and the pressed member 6.
- the fulcrum a of the piezoelectric member 7 preferably has a displacement of 10% or less with respect to the maximum displacement of the piezoelectric member 7 when the pressure F is applied to the contact surface 6A.
- the fulcrum a may be freely displaced in a direction other than the direction of the pressure F.
- the fulcrum a may slide in a direction perpendicular to the pressing direction and parallel to the main surface of the piezoelectric member 7.
- the press detection device in order to displace the pressed member 6 and the piezoelectric member 7 by the pressure applied to the contact surface 6A, a gap for displacement or a portion that can absorb the displacement is provided. It is preferable. Specifically, it is preferable that the press detection device according to the present embodiment further includes a relaxation portion having a Young's modulus of 0.1 GPa or less on the opposite side of the piezoelectric member 7 from the pressed member 6 side. In the press detection device 10 shown in FIGS. 1 and 2, a cavity 11 is provided on the back surface of the piezoelectric member 7 as a relaxation portion.
- the piezoelectric member 7 (in detail, together with the base 6 depending on the strength of the pressure around the position where the pressure is applied)
- the PLA film 4 contained in the piezoelectric member 7 is displaced, whereby electric charges can be generated.
- a cushioning material may be provided on the back surface of the piezoelectric member 7 as a relaxing part.
- the member to be pressurized (for example, the member to be pressurized 6) is a contact surface (for example, the above-described contact) to which pressure is applied by a pressing unit (for example, the above-described pressing unit 8) such as an operator's finger Surface 6A).
- a pressing unit for example, the above-described pressing unit 8
- the pressurizing unit include a pressurizing member such as a pen-shaped member (for example, a touch pen) and a bar-shaped member in addition to the operator's finger.
- the material to be pressed in the present embodiment is not particularly limited, such as an inorganic material such as glass and an organic material (preferably resin) such as a resin (acrylic resin, vinyl chloride resin, etc.).
- an inorganic material such as glass
- an organic material preferably resin
- a member to be pressed in a form in which an inorganic material layer and an organic material layer are laminated and integrated, or a member to be pressed in a form in which an inorganic material is dispersed in a resin material layer is used. You can also.
- a touch panel is manufactured by stacking the press detection device of the present embodiment on the viewing side of the display device, a highly transparent material is used as the member to be pressed in order to increase the visibility of the display device. preferable.
- the contact surface 6A is a surface with which the pressing means 8 such as an operator's finger contacts.
- the contact surface 6A may be the surface of the pressed member 6 formed as a single layer, or the pressed member 6 is composed of a plurality of materials, and the outermost layer forms the contact surface 6A. May be.
- an electrode may be disposed on the surface of the member to be pressed 6, and a hard coat layer may be formed to improve scratch resistance.
- the pressurized member 6 may have a part of the space inside.
- the product IEb of the cross-sectional secondary moment Ib and the Young's modulus Eb of the pressed member 6 as a whole is obtained, and the ratio IEb of the product of the cross-sectional secondary moment Ia and the Young's modulus Ea of the piezoelectric member 7 is IEb.
- / IEa may be in the range of 10 2 to 10 10 .
- the preferable range of IEb / IEa is as described above.
- the thickness of the member to be pressed 6 is preferably in the range of 0.2 mm to 20 mm, more preferably 0.3 mm to 10 mm, from the viewpoint of suppressing the distortion of the detection signal.
- the Young's modulus Eb of the pressed member (for example, the pressed member 6) in the present embodiment is in a range of 200 GPa or less from the viewpoint of efficiently transmitting the strain generated by the thickness to the strain of the piezoelectric member. It is preferable.
- the Young's modulus Eb of the member to be pressed in this embodiment is preferably in the range of 1 GPa to 200 GPa, and particularly preferably in the range of 3 GPa to 100 GPa.
- the cross-sectional secondary moment Ib of the member to be pressed in the present embodiment is preferably 10 ⁇ 1 mm 4 to 10 7 mm 4 from the viewpoint of efficiently propagating the pressure applied to the contact surface through the piezoelectric member.
- 10 ⁇ 1 mm 4 to 10 6 mm 4 is more preferable, and 10 ⁇ 1 mm 4 to 10 5 mm 4 is more preferable.
- the IEb in this embodiment is preferably 10 GPa ⁇ mm 4 to 10 8 GPa ⁇ mm 4 from the viewpoint of efficiently propagating the pressure applied to the contact surface through the piezoelectric member, and 10 GPa ⁇ mm 4 to 10 7 GPa.
- • mm 4 is more preferable, 10 GPa ⁇ mm 4 to 10 6 GPa ⁇ mm 4 is still more preferable, and 10 2 GPa ⁇ mm 4 to 10 5 GPa ⁇ mm 4 is particularly preferable.
- the Young's modulus Ea of the piezoelectric member (for example, the piezoelectric member 7) in the present embodiment is preferably 1 GPa to 10 GPa, more preferably 1 GPa to 5 GPa, more preferably 2 GPa to 4 GPa, from the viewpoint of the balance between the generated charge density and the strength. Particularly preferred.
- the cross-sectional secondary moment Ia of the piezoelectric member in this embodiment is preferably 10 ⁇ 7 mm 4 to 10 ⁇ 1 mm 4 from the viewpoint of the balance between the generated charge density and the strength, and 10 ⁇ 6 mm 4 to 10 ⁇ . 2 mm 4 is more preferable, and 10 ⁇ 5 mm 4 to 10 ⁇ 3 mm 4 is particularly preferable.
- IEa in this embodiment from the viewpoint of the balance between the generated charge density and strength, preferably 10 -6 GPa ⁇ mm 4 ⁇ 1GPa ⁇ mm 4, 10 -5 GPa ⁇ mm 4 ⁇ 10 -1 GPa ⁇ mm 4 is more preferable, and 10 ⁇ 4 GPa ⁇ mm 4 to 10 ⁇ 2 GPa ⁇ mm 4 is preferable.
- the member to be pressed (pressurized member 6 in FIG. 1) and the piezoelectric member (piezoelectric member 7 in FIG. 1) are provided with the double-sided tape 1 and the first electrode layer 2 as shown in FIG. Or a gap (gap) between the member to be pressed and the piezoelectric member.
- the size of the gap in the direction in which the pressure is applied is preferably 0.1 mm or less. This is because the pressed member comes into contact with the piezoelectric member when the pressed member is bent (displaced) by the pressing unit such as a finger (pressing unit 8 in FIG. 1). This is because the bending of the member propagates to the piezoelectric member, and electric charges are easily generated by the piezoelectric member (specifically, the polymer piezoelectric material included in the piezoelectric member).
- the piezoelectric member (for example, the piezoelectric member 7) in the present embodiment is disposed to face the member to be pressed (for example, the member to be pressed 6), and includes a polymer piezoelectric material (for example, the PLA film 4).
- a polymer piezoelectric material for example, the PLA film 4
- the piezoelectric constant d 14 is 1 Pm/V or more as measured by a displacement method at 25 ° C..
- piezoelectric constant d 14 is one of the tensors of piezoelectricity, and is obtained from the degree of polarization generated in the direction of shear stress when shear stress is applied in the stretch axis direction of the stretched material. . Specifically, the generated charge density per unit shear stress is defined as d 14. Numerical piezoelectric constant d 14 indicating that piezoelectricity is higher the larger. When simply referred to as “piezoelectric constant” in the present application, it refers to “piezoelectric constant d 14 ”.
- the piezoelectric constant d 14 includes one measured by a displacement method (unit: pm / V) and one measured by a resonance method (unit: pC / N).
- the piezoelectric constant (displacement method) of the polymeric piezoelectric material refers to a value measured by the displacement method as follows, for example.
- the polymer piezoelectric material is cut at 40 mm in the stretching direction (MD direction) and 40 mm in the direction orthogonal to the stretching direction (TD direction) to produce a rectangular test piece.
- the obtained test piece is set on a test stand of Showa Vacuum Corp. SIP-600, and Al is vapor-deposited on one surface of the test piece so that the deposition thickness of Al is 50 nm.
- the other surface of the test piece is vapor-deposited in the same manner, and Al is coated on both sides of the test piece to form an Al conductive layer.
- a test piece of 40 mm ⁇ 40 mm with an Al conductive layer formed on both sides is 32 mm in the direction of 45 ° with respect to the stretching direction (MD direction) of the polymer piezoelectric material, and 5 mm in the direction perpendicular to the direction of 45 °. Cut and cut out a rectangular film of 32 mm ⁇ 5 mm. This is a piezoelectric constant measurement sample.
- the piezoelectric constant d 14 measured by the displacement method at 25 ° C. is usually, 1 pm / V or more, preferably more than 4pm / V, more preferably at least 6pm / V, or 8pm / V are particularly preferred.
- the upper limit of the piezoelectric constant d 14 is not particularly limited, from the viewpoint of the balance, such as transparency, which will be described later, preferably 50 Pm/V less in piezoelectric material using a helical chiral polymer, 30pm / V If less is more preferable There is.
- the direction in which pressure is applied from the contact surface for example, the direction 20 in FIG. 1 and the molecular orientation direction of the polymer piezoelectric material (for example, the PLA film 4 in FIG. 1) (for example, in FIG. 2).
- the molecular orientation direction 9) of Since the direction in which pressure is applied from the contact surface and the molecular orientation direction of the polymeric piezoelectric material intersect, the pressure applied by the pressure applied in the thickness direction of the piezoelectric member from the contact surface of the pressed member When the pressure member is bent, a tensile force is applied to the piezoelectric member and the piezoelectric member is distorted. Therefore, electric charges are easily generated in the polymer piezoelectric material.
- the polymeric piezoelectric material in the present embodiment is preferably a helical chiral polymer having optical activity with a weight average molecular weight of 50,000 to 1,000,000 [hereinafter referred to as “optically active polymer (A)” as appropriate. ],
- the crystallinity obtained by DSC method is 20% to 80%, and the standardized molecular orientation MORc when the reference thickness measured by a microwave transmission type molecular orientation meter is 50 ⁇ m and the above-mentioned
- the product with the crystallinity is 40 to 700.
- the helical chiral polymer having optical activity refers to a polymer having molecular optical activity in which the molecular structure is a helical structure.
- examples of the helical chiral polymer having optical activity include polypeptides, cellulose derivatives, polylactic acid resins, polypropylene oxide, poly ( ⁇ -hydroxybutyric acid), and the like.
- examples of the polypeptide include poly (glutarate ⁇ -benzyl), poly (glutarate ⁇ -methyl) and the like.
- the cellulose derivative include cellulose acetate and cyanoethyl cellulose.
- the optically active polymer (A) in the present embodiment preferably has an optical purity of 95.00% ee or more, and 96.00% ee or more, from the viewpoint of improving the piezoelectricity of the polymeric piezoelectric material. Is more preferably 99.00% ee or more, and even more preferably 99.99% ee or more. Desirably, it is 100.00% ee.
- the optical purity of the optically active polymer (A) is a value calculated by the following formula.
- Optical purity (% ee) 100 ⁇
- the value obtained by dividing (multiplying) the value obtained by dividing (dividing) the amount of L-form [mass%] by the total amount of D-form [mass%] of optically active polymer" by "100".
- the value obtained by the method using a high performance liquid chromatography is used for the quantity [mass%] of the L form of an optically active polymer and the quantity [mass%] of the D form of an optically active polymer.
- a compound having a main chain containing a repeating unit represented by the following formula (1) is preferable from the viewpoint of increasing optical purity and improving piezoelectricity.
- Examples of the compound having a repeating unit represented by the formula (1) as a main chain include polylactic acid polymers. Among them, polylactic acid is preferable, and L-lactic acid homopolymer (PLLA) or D-lactic acid homopolymer (PDLA) is most preferable.
- the polylactic acid-based polymer in the present embodiment refers to “polylactic acid (polymer compound consisting only of repeating units derived from a monomer selected from L-lactic acid and D-lactic acid)”, “L-lactic acid or D-lactic acid”. A copolymer of lactic acid and a compound copolymerizable with the L-lactic acid or D-lactic acid ”, or a mixture of both.
- polylactic acid is a polymer in which lactic acid is polymerized by an ester bond and is connected for a long time, a lactide method via lactide, and a direct polymerization method in which lactic acid is heated in a solvent under reduced pressure and polymerized while removing water. It is known that it can be manufactured by, for example.
- examples of the “polylactic acid” include a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, a block copolymer containing at least one polymer of L-lactic acid and D-lactic acid, and L-lactic acid and D-lactic acid. Examples include graft copolymers containing at least one polymer.
- Examples of the “compound copolymerizable with L-lactic acid or D-lactic acid” include glycolic acid, dimethyl glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 2- Hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxycaproic acid, 3-hydroxycaproic acid, 4-hydroxycaproic acid, 5-hydroxycaproic acid, 6-hydroxycaprone Acids, hydroxycarboxylic acids such as 6-hydroxymethylcaproic acid and mandelic acid, glycolides, cyclic esters such as ⁇ -methyl- ⁇ -valerolactone, ⁇ -valerolactone and ⁇ -caprolactone, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, Polycarboxylic acids such as ndecanedioic acid,
- Examples of the “copolymer of L-lactic acid or D-lactic acid and a compound copolymerizable with the L-lactic acid or D-lactic acid” include a block copolymer or graft copolymer having a polylactic acid sequence capable of forming a helical crystal. Can be mentioned.
- the concentration of the structure derived from the copolymer component in the optically active polymer (A) is preferably 20 mol% or less.
- the optically active polymer (A) is a polylactic acid polymer
- the copolymer component is preferably 20 mol% or less based on the total number of moles.
- polylactic acid polymer examples include a method obtained by direct dehydration condensation of lactic acid described in JP-A-59-096123 and JP-A-7-033861, or US Pat. No. 2,668,182. And ring-opening polymerization using lactide, which is a cyclic dimer of lactic acid, described in US Pat. No. 4,057,357 and the like.
- the optically active polymer obtained by each of the above production methods has an optical purity of 95.00% ee or more.
- the optical purity is improved by crystallization operation. It is preferable to polymerize lactide having an optical purity of 95.00% ee or higher.
- the content of the optically active polymer (A) contained in the polymer piezoelectric material in the present embodiment is preferably 80% by mass or more.
- the optically active polymer (A) in this embodiment has a weight average molecular weight (Mw) of 50,000 to 1,000,000. If the lower limit of the weight average molecular weight of the optically active polymer (A) is 50,000 or more, the mechanical strength when the optically active polymer is used as a molded article is sufficient.
- the lower limit of the weight average molecular weight of the optically active polymer is preferably 100,000 or more, and more preferably 200,000 or more.
- the upper limit of the weight average molecular weight of the optically active polymer (A) is 1,000,000 or less, it is easier to mold the optically active polymer (for example, to form a film shape by extrusion molding or the like). Become.
- the upper limit of the weight average molecular weight is preferably 800,000 or less, and more preferably 300,000 or less.
- the molecular weight distribution (Mw / Mn) of the optically active polymer (A) is preferably 1.1 to 5, and preferably 1.2 to 4 from the viewpoint of the strength of the polymer piezoelectric material. More preferred. Further, it is preferably 1.4 to 3.
- the weight average molecular weight Mw and molecular weight distribution (Mw / Mn) of the optically active polymer (A) are measured by gel permeation chromatograph (GPC) by the GPC measurement method under the following conditions.
- -GPC measuring device Waters GPC-100 -column- Made by Showa Denko KK, Shodex LF-804 -Sample preparation-
- the optically active polymer (A) is dissolved in a solvent (for example, chloroform) at 40 ° C. to prepare a sample solution having a concentration of 1 mg / ml.
- -Measurement condition- 0.1 ml of the sample solution is introduced into the column at a solvent [chloroform], a temperature of 40 ° C., and a flow rate of 1 ml / min.
- polylactic acid polymer commercially available polylactic acid may be used, and examples thereof include PURASORB (PD, PL) manufactured by PURAC, LACEA (H-100, H-400) manufactured by Mitsui Chemicals, and the like.
- PURASORB PURASORB
- LACEA H-100, H-400
- Mw weight average molecular weight
- the optically active polymer is added by the lactide method or the direct polymerization method. It is preferable to manufacture.
- the polymeric piezoelectric material in the present embodiment contains a compound having a weight average molecular weight of 200 to 60000 having at least one functional group selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group as a stabilizer. Is preferred.
- This stabilizer (B) suppresses the hydrolysis reaction of the helical chiral polymer (this hydrolysis reaction is assumed to proceed, for example, according to the following reaction scheme), and the resulting heat resistance of the piezoelectric material Used to improve
- a functional group capable of interacting with both a hydroxyl group and a carboxy group at least one kind comprising a carbodiimide group, an isocyanate group, and an epoxy group having the following structure: Among them, a carbodiimide group is preferable from the viewpoint of effects.
- the weight average molecular weight of the stabilizer (B) used in this embodiment is preferably 200 to 60000, more preferably 200 to 30000, and further preferably 300 to 18000. If the molecular weight is within the above range, it is presumed that the stabilizer (B) can easily move, and the effect of improving the heat and moisture resistance can be sufficiently obtained.
- a preferred embodiment of the stabilizer (B) is a stabilizer having one or more functional groups selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group, and having a number average molecular weight of 200 to 900.
- the weight average molecular weight of the stabilizer (B1) having a number average molecular weight of 200 to 900 is about 200 to 900, and the number average molecular weight and the weight average molecular weight of the stabilizer (B1) are almost the same value. .
- the stabilizer (B1) specifically, dicyclohexylcarbodiimide, bis-2,6-diisopropylphenylcarbodiimide, hexyl isocyanate, octadecyl isocyanate, 3- (triethoxysilyl) propyl isocyanate, N-glycidyl
- examples thereof include phthalimide, orthophenylphenyl glycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, and the like.
- the stabilizer (B2) include poly (4,4′-dicyclohexylmethanecarbodiimide), poly (tetramethylxylylene carbodiimide), poly (N, N-dimethylphenylcarbodiimide), poly ( N, N'-di-2,6-diisopropylphenylcarbodiimide), diphenylmethane diisocyanate polyisocyanate, 1,6-hexamethylene diisocyanate polyisocyanate, xylylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, phenol novolac epoxy Examples thereof include resins, cresol novolac type epoxy resins, and epoxidized polybutadiene.
- the moisture and heat resistance is particularly improved by including the stabilizer (B1) having a relatively low molecular weight and the stabilizer (B2) having a polyfunctionality and a relatively large molecular weight.
- the stabilizer (B1) is included, and the stabilizer (B1) is 100 parts by mass.
- the stabilizer (B2) is preferably in the range of 10 parts by mass to 150 parts by mass from the viewpoint of achieving both transparency and wet heat resistance, and more preferably in the range of 50 parts by mass to 100 parts by mass. .
- the stabilizer (B) includes a stabilizer (B3) having one functional group in one molecule selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group, and the dimensional stability is improved.
- a stabilizer (B3) having one functional group in one molecule selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group, and the dimensional stability is improved.
- the stabilizer (B3) has only one functional group selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group in one molecule, it has an optical activity having a hydroxyl group or a carboxyl group generated by hydrolysis.
- the part of the polymer (A) is not easily cross-linked with the stabilizer (B3) interposed therebetween.
- the weight average molecular weight of the compound having one functional group selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group in one molecule is preferably 200 to 2000, more preferably 200 to 1500, and more preferably 300 to 900. Further preferred. Specific examples of the compound having one functional group selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group in one molecule include dicyclohexylcarbodiimide, bis-2,6-diisopropylphenylcarbodiimide, hexyl isocyanate, and octadecyl isocyanate.
- the stabilizer (B3) and the stabilizer (B4) having two or more functional groups selected from the group consisting of a carbodiimide group, an epoxy group, and an isocyanate group in one molecule (for example, the aforementioned stabilizer (B2 ) May be used in combination.
- the range of 200 parts by mass is preferable from the viewpoint of balance of transparency, wet heat resistance and dimensional stability, and more preferably in the range of 10 to 100 parts by mass.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the stabilizer (B) are both the same by the measurement method using the gel permeation chromatograph (GPC) described for the optically active polymer (A). Is measured. In addition to GPC, it can be measured by a measuring method such as GC-MS, FAB-MS, ESI-MS, or TOF-MS.
- the addition amount of the stabilizer (B) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the optically active polymer (A). Further, in order to obtain higher reliability (specifically, reliability in a reliability test of 500 hours described later), the addition amount is more preferably 0.7 parts by mass or more. In particular, when aliphatic carbodiimide is used as a stabilizer, 0.01 to 2.8 parts by mass is more preferable from the viewpoint of transparency. When the addition amount is in the above range, the reliability of the piezoelectric material can be improved without significantly impairing the noise inside the polymeric piezoelectric material in the present embodiment. In addition, the said addition amount shows those total amounts, when using 2 or more types of stabilizers (B) together.
- the amount of the stabilizer (B) added is 100 parts by mass of the optically active polymer (A) having optical activity. 0.01 parts by weight to 1.2 parts by weight is preferred, 0.01 parts by weight to 0.7 parts by weight is more preferred, and 0.01 parts by weight to 0.6 parts by weight is even more preferred.
- the polymer piezoelectric material in the present embodiment is a known resin typified by polyvinylidene fluoride, polyethylene resin or polystyrene resin, inorganic fillers such as silica, hydroxyapatite, and montmorillonite, as long as the effects of the present embodiment are not impaired.
- Other components such as a known crystal nucleating agent such as phthalocyanine may be contained.
- an inorganic filler such as hydroxyapatite may be nano-dispersed in the polymer piezoelectric material in order to make the polymer piezoelectric material a transparent film in which voids such as bubbles are suppressed.
- an inorganic filler such as hydroxyapatite
- the inorganic filler a large amount of energy is required for crushing the aggregate, and when the filler is not nano-dispersed, the transparency of the film may be lowered.
- the polymeric piezoelectric material in this embodiment contains an inorganic filler, the content of the inorganic filler with respect to the total mass of the polymeric piezoelectric material is preferably less than 1% by mass.
- the content of the component other than the helical chiral polymer is preferably 20% by mass or less based on the total mass of the polymer piezoelectric material. More preferably, it is 10 mass% or less.
- the crystal accelerator is not particularly limited as long as the effect of promoting crystallization is recognized, but it is desirable to select a substance having a crystal structure having a face spacing close to that of the crystal lattice of the helical chiral polymer. . This is because a substance with a close spacing is more effective as a nucleating agent.
- the organic substance is zinc phenylsulfonate, melamine polyphosphate, melamine cyanurate, zinc phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate,
- examples include inorganic substances such as talc and clay.
- zinc phenylphosphonate is most preferable because the plane spacing is most similar to the plane spacing of polylactic acid and provides a good crystal formation promoting effect.
- the commercially available crystal accelerator can be used. Specific examples include zinc phenylphosphonate; Eco Promote (manufactured by Nissan Chemical Industries, Ltd.) and the like.
- the content of the crystal nucleating agent is usually 0.01 parts by weight to 1.0 part by weight, preferably 0.01 parts by weight to 100 parts by weight of the helical chiral polymer (for example, the optically active polymer (A)). 0.5 parts by mass, particularly preferably from 0.02 parts by mass to 0.2 parts by mass from the viewpoint of a better crystallization promoting effect and maintaining the degree of biomass. If the content of the crystal nucleating agent is less than 0.01 parts by mass, the effect of accelerating crystallization is not sufficient. Tend to decrease.
- a polymeric piezoelectric material does not contain components other than an optically active polymer (A) and a stabilizer (B) from a transparent viewpoint.
- the molecular orientation degree MOR (Molecular Orientation Ratio) is a value indicating the degree of molecular orientation, and is measured by the following microwave measurement method. That is, the sample surface (film surface) is placed in the microwave resonance waveguide of a known microwave molecular orientation degree measuring apparatus (also referred to as a microwave transmission type molecular orientation meter) in the microwave traveling direction. ) To be vertical.
- the sample is rotated by 0 to 360 ° in a plane perpendicular to the traveling direction of the microwave, and the microwave transmitted through the sample is transmitted.
- the degree of molecular orientation MOR is determined by measuring the strength.
- the normalized molecular orientation MORc can be measured with a known molecular orientation meter, for example, a microwave molecular orientation meter MOA-2012A or MOA-6000 manufactured by Oji Scientific Instruments Co., Ltd. at a resonance frequency near 4 GHz or 12 GHz.
- the normalized molecular orientation MORc can be controlled mainly by the heat treatment conditions (heating temperature and heating time) before stretching of the uniaxially stretched film, stretching conditions (stretching temperature and stretching speed), and the like.
- the normalized molecular orientation MORc can be converted into a birefringence ⁇ n obtained by dividing the retardation amount (retardation) by the thickness of the film. Specifically, retardation can be measured using RETS100 manufactured by Otsuka Electronics Co., Ltd. MORc and ⁇ n are approximately in a linear proportional relationship, and when ⁇ n is 0, MORc is 1. For example, when the optically active polymer (A) is a polylactic acid polymer and the birefringence ⁇ n is measured at a measurement wavelength of 550 nm, 2.0, which is the lower limit of the preferred range of the normalized molecular orientation MORc, is birefringence ⁇ n. Can be converted to 0.005.
- the lower limit 40 of the preferred range of the product of normalized molecular orientation MORc and crystallinity of the polymer piezoelectric material is that the product of birefringence ⁇ n and crystallinity of the polymer piezoelectric material is converted to 0.1. Can do.
- the normalized molecular orientation MORc is preferably 3.5 to 15.0, more preferably 4.0 to 15.0, and 6.0 to 10.0. More preferably, it is more preferably 7 to 10.0. If the normalized molecular orientation MORc is in the range of 3.5 to 15.0, there are many polylactic acid molecular chains arranged in the stretching direction. As a result, the rate of formation of oriented crystals increases, and high piezoelectricity is expressed. It becomes possible.
- the crystallinity of the polymer piezoelectric material is determined by the DSC method, and the crystallinity of the polymer piezoelectric material in this embodiment is 20% to 80%, preferably 25% to 70%, more preferably Is preferably 30% to 50%. If the crystallinity is in the above range, the piezoelectricity and transparency of the polymeric piezoelectric material are well balanced, and when the polymeric piezoelectric material is stretched, whitening and breakage are unlikely to occur and it is easy to manufacture.
- the product of the crystallinity of the polymeric piezoelectric material and the normalized molecular orientation MORc is preferably 40 to 700, more preferably 75 to 680, more preferably 90 to 660, more preferably 125 to 650, and more preferably 180 to 350. If the product of the crystallinity of the polymer piezoelectric material and the normalized molecular orientation MORc is in the range of 40 to 700, the balance between piezoelectricity and transparency of the polymer piezoelectric material is good, and dimensional stability And can be suitably used as a piezoelectric element described later.
- the transparency of the polymeric piezoelectric material can be evaluated, for example, by visual observation or haze measurement.
- the haze of the polymer piezoelectric material in the present embodiment is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less, with respect to visible light.
- haze was measured at 25 ° C. using a haze measuring device (TC Density Co., Ltd., TC-HIII DPK) in accordance with JIS-K7105 for a polymeric piezoelectric material having a thickness of 0.05 mm. It is a value when measured by.
- the haze of the polymeric piezoelectric material is preferably as low as possible.
- haze or “inside haze” refers to haze inside a polymeric piezoelectric material.
- the internal haze is haze excluding haze due to the shape of the outer surface of the polymeric piezoelectric material.
- the raw material of the polymeric piezoelectric material in the present embodiment is an optically active polymer (A) such as the polylactic acid-based polymer described above, and other components such as a stabilizer (B) such as a carbodiimide compound as necessary. Are mixed to obtain a mixture. The mixture may be melt kneaded.
- A optically active polymer
- B stabilizer
- a carbodiimide compound as necessary.
- the optically active polymer (A) to be mixed and other components used as necessary are mixed using a melt kneader (manufactured by Toyo Seiki Co., Ltd., Labo Plast Mill), with a mixer rotation speed of 30 rpm to 70 rpm, By melt-kneading for 5 to 20 minutes at 180 ° C. to 250 ° C., a blend of optically active polymer (A) and stabilizer (B), a blend of multiple types of helical chiral polymers, A blend of a helical chiral polymer and other components such as an inorganic filler can be obtained.
- a melt kneader manufactured by Toyo Seiki Co., Ltd., Labo Plast Mill
- the polymer piezoelectric material in the present embodiment is prepared by crystallizing an amorphous sheet containing, for example, an optically active polymer (A) and, if necessary, a stabilizer (B), to obtain a pre-crystallized sheet (crystallized). And a second process of stretching the pre-crystallized sheet mainly in a uniaxial direction.
- an optically active polymer A
- B stabilizer
- the orientation of the helical chiral polymer is promoted, the piezoelectric constant is increased, crystallization proceeds, and the crystal size is increased to increase the haze. Also, the dimensional deformation rate tends to increase due to an increase in internal stress. If force is simply applied to the film, crystals that are not oriented like spherulites are formed. Crystals with low orientation, such as spherulites, increase haze, but are unlikely to contribute to an increase in piezoelectric constant.
- the inside of the sheet is pre-crystallized to form fine crystals before stretching, and then stretched.
- the force applied to the film during stretching can be efficiently applied to the polymer part having low crystallinity between the microcrystals, and the helical chiral polymer is efficiently oriented in the main stretching direction. be able to.
- finely oriented crystals are formed in the polymer portion where the crystallinity between the microcrystals is low, and at the same time, the spherulites generated by the precrystallization are broken down to form spherulites.
- the desired lamellar crystals are oriented in the stretching direction in a daisy chain connected to tie molecular chains, whereby a desired value of MORc can be obtained. For this reason, a sheet having a low haze and dimensional deformation rate can be obtained without greatly reducing the piezoelectric constant.
- the crystallinity of the crystallization raw material is adjusted by the heat treatment time and the heat treatment temperature in the first step, and the stretching speed and the stretching temperature in the second step. is important.
- the helical chiral polymer is a polymer having molecular optical activity.
- the amorphous sheet containing the helical chiral polymer and the carbodilite compound may be commercially available or may be produced by a known film forming means such as extrusion.
- the amorphous sheet may be a single layer or a multilayer.
- the pre-crystallized sheet can be obtained by heat-treating an amorphous sheet containing the optically active polymer (A) and, if necessary, the stabilizer (B) to crystallize it.
- the raw material containing the optically active polymer (A) and the stabilizer (B) is heated to a temperature higher than the glass transition temperature of the helical chiral polymer by extrusion or the like, and extruded into a sheet shape
- a pre-crystallized sheet having a predetermined crystallinity can be obtained by rapidly cooling the sheet extruded by a caster.
- a pre-crystallized pre-crystallized sheet may be sent to a stretching step (second step) described later and set in a stretching apparatus to be stretched (off-line heat treatment), or 2) by heat treatment
- a non-crystallized amorphous sheet is set in a stretching apparatus, heated in a stretching apparatus to be pre-crystallized, and then continuously sent to a stretching process (second process) for stretching.
- Good heat treatment by in-line).
- the heating temperature T for pre-crystallization of the sheet containing the helical chiral polymer in the amorphous state is not particularly limited. However, in order to improve the piezoelectricity and transparency of the polymer piezoelectric material produced by this production method, the glass transition temperature Tg of the chiral polymer and the following formula are preferably satisfied, and the crystallinity is preferably set to 3% to 70%. Tg ⁇ 40 °C ⁇ T ⁇ Tg + 40 °C (Tg represents the glass transition temperature of the helical chiral polymer)
- the heating time for pre-crystallization or the heating time for crystallization when extruding into a sheet form satisfies the desired degree of crystallinity and is the standard for the polymeric piezoelectric material after stretching (after the second step)
- the product of the polymer molecular orientation MORc and the crystallinity of the polymer piezoelectric material after stretching is preferably adjusted to 40 to 700, more preferably 125 to 650, and further preferably 250 to 350.
- the heating time becomes longer the degree of crystallinity after stretching increases, and the normalized molecular orientation MORc after stretching also increases.
- the heating time is shortened, the crystallinity after stretching also decreases, and the normalized molecular orientation MORc after stretching tends to decrease.
- the sheet becomes harder and a greater stretching stress is applied to the sheet, so that the portion with relatively low crystallinity in the sheet also becomes more oriented, and after stretching
- the normalized molecular orientation MORc is also increased.
- the crystallinity of the pre-crystallized sheet before stretching becomes low, the sheet becomes soft and the stretching stress becomes more difficult to be applied to the sheet, so that the portion with relatively low crystallinity in the sheet becomes weakly oriented.
- the normalized molecular orientation MORc after stretching is also considered to be low.
- the heating time varies depending on the heating temperature, the thickness of the sheet, the molecular weight of the resin constituting the sheet, the type or amount of additives, and the like. Further, the substantial heating time for crystallizing the sheet is the preheating when preheating at a temperature at which the amorphous sheet crystallizes in preheating that may be performed before the stretching step (second step) described later. This corresponds to the sum of the time and the heating time in the precrystallization step before preheating.
- the heating time of the amorphous sheet or the heating time when crystallization is performed when the sheet is extruded is normally 5 seconds to 60 minutes, and 1 minute to 30 minutes from the viewpoint of stabilizing the manufacturing conditions. But you can.
- an amorphous sheet containing a polylactic acid polymer as a helical chiral polymer is pre-crystallized, it is preferably heated at 20 ° C. to 170 ° C. for 5 seconds to 60 minutes, and for 1 minute to 30 minutes. But you can.
- the reason why the piezoelectricity and dimensional stability are improved by stretching is that the stress due to stretching is concentrated in a portion where the crystallinity in the pre-crystallized sheet presumed to be in a spherulitic state is relatively high. While the piezoelectric d 14 is improved by being oriented while being broken, it is considered that the stretching stress is applied to a portion having a relatively low crystallinity through the spherulite to promote the orientation and improve the piezoelectric d 14. Because.
- the crystallinity of the sheet after stretching, or when performing the annealing described later is set to 20% to 80%, preferably 40% to 70%. Therefore, the crystallinity of the pre-crystallized sheet immediately before stretching is set to 3% to 70%, preferably 10% to 60%, more preferably 15% to 50%.
- the crystallinity of the pre-crystallized sheet may be the same as the measurement of the crystallinity of the polymeric piezoelectric material in the present embodiment after stretching.
- the thickness of the pre-crystallized sheet is mainly determined by the thickness of the polymeric piezoelectric material to be obtained by stretching in the second step and the stretching ratio, but is preferably 50 ⁇ m to 1000 ⁇ m, more preferably about 200 ⁇ m to 800 ⁇ m. It is.
- the stretching method in the stretching step which is the second step, is not particularly limited, and various stretching methods such as uniaxial stretching, biaxial stretching, and solid phase stretching described later can be used.
- various stretching methods such as uniaxial stretching, biaxial stretching, and solid phase stretching described later can be used.
- the “main surface” means the surface having the largest area among the surfaces of the polymeric piezoelectric material.
- the polymeric piezoelectric material in this embodiment may have two or more main surfaces.
- the polymer piezoelectric material is a plate-like body having two surfaces A each having a surface A of 10 mm ⁇ 0.3 mm square, a surface B having 3 mm ⁇ 0.3 mm square, and a surface C having 10 mm ⁇ 3 mm square.
- the main surface of the polymeric piezoelectric material is a surface C, which has two main surfaces.
- that the area of the main surface is large means that the area of the main surface of the polymeric piezoelectric material is 5 mm 2 or more. Moreover, it is preferable that the area of a main surface is 10 mm ⁇ 2 > or more.
- the molecular chain of polylactic acid polymer contained in the polymer piezoelectric material can be oriented in one direction and aligned with high density, which is higher It is estimated that piezoelectricity can be obtained.
- the glass transition temperature Tg [° C.] of the polymer piezoelectric material and the melting point Tm [° C.] of the polymer piezoelectric material are measured with respect to the polymer piezoelectric material using a differential scanning calorimeter (DSC). From the melting endothermic curve when the temperature is raised at 10 ° C./min, the glass transition temperature (Tg) obtained as the inflection point of the curve and the temperature (Tm) confirmed as the peak value of the endothermic reaction.
- DSC differential scanning calorimeter
- the stretching temperature of the polymeric piezoelectric material is 10 ° C. to 20 ° C. from the glass transition temperature of the polymeric piezoelectric material when the polymeric piezoelectric material is stretched only by a tensile force, such as a uniaxial stretching method or a biaxial stretching method. It is preferable that the temperature range be as high as about ° C.
- the stretching ratio in the stretching treatment is preferably 3 to 30 times, and more preferably 4 to 15 times.
- preheating When stretching the pre-crystallized sheet, preheating may be performed immediately before stretching in order to facilitate stretching of the sheet. This preheating is generally performed in order to soften the sheet before stretching and facilitate stretching, so that the sheet before stretching is crystallized and does not harden the sheet. It is normal. However, as described above, in the present embodiment, since pre-crystallization may be performed before stretching, the pre-heating may be performed together with pre-crystallization. Specifically, preheating and precrystallization can be performed by performing preheating at a temperature higher or longer than the normal temperature in accordance with the heating temperature and heat treatment time in the precrystallization step described above.
- the polymer piezoelectric material after the stretching treatment (after the second step) is subjected to a certain heat treatment (hereinafter also referred to as “annealing treatment”).
- annealing treatment a certain heat treatment
- the preliminary crystallization performed in the above-described preliminary crystallization step may be omitted.
- the temperature of the annealing treatment is preferably approximately 80 ° C. to 160 ° C., more preferably 100 ° C. to 155 ° C.
- the temperature application method of the annealing treatment is not particularly limited, and examples include a method of directly heating using a hot air heater or an infrared heater, a method of heating by immersing the polymer piezoelectric material in a heated liquid such as heated silicon oil, and the like. It is done.
- the temperature application time of the annealing treatment is preferably 1 second to 60 minutes, more preferably 1 second to 300 seconds, and further preferably heating in the range of 1 second to 60 seconds.
- the degree of orientation may decrease due to the growth of spherulites from the molecular chains of the amorphous portion at a temperature higher than the glass transition temperature of the polymeric piezoelectric material. And transparency may be reduced.
- the polymer piezoelectric material annealed as described above is rapidly cooled after the annealing treatment.
- “rapidly cool” means that the annealed polymer piezoelectric material is immersed in ice water or the like immediately after the annealing process and cooled to at least the glass transition point Tg or less. It means that no other treatment is included in the dipping time.
- the rapid cooling method includes a method of immersing the annealed polymer piezoelectric material in a coolant such as ethanol, methanol, or liquid nitrogen containing water, ice water, ethanol, or dry ice, or by spraying a liquid spray with a low vapor pressure to evaporate.
- a coolant such as ethanol, methanol, or liquid nitrogen containing water, ice water, ethanol, or dry ice
- the method of cooling by latent heat is mentioned.
- To continuously cool the polymer piezoelectric material it is possible to rapidly cool the polymer piezoelectric material by bringing it into contact with a metal roll controlled to a temperature not higher than the glass transition temperature Tg of the polymer piezoelectric material. It is. Further, the number of times of cooling may be only once, or may be two or more. Furthermore, annealing and cooling can be alternately repeated.
- the method for producing a polymeric piezoelectric material in the present embodiment includes a step of stretching a sheet containing the optically active polymer (A) and the stabilizer (B) mainly in a uniaxial direction, and a step of annealing. It may be included in this order.
- the stretching process and the annealing process can be the same processes as described above. Moreover, in this manufacturing method, it is not necessary to implement the above-mentioned preliminary crystallization process.
- the piezoelectric member in the present embodiment preferably includes an electrode in addition to the above-described polymer piezoelectric material.
- the piezoelectric member has, as in the piezoelectric member 7, a polymer piezoelectric material (for example, the PLA film 4) having two main surfaces, and electrodes (for example, the first electrode layer 2 and the first electrode layer 2) on the main surface.
- the electrodes only need to be provided on at least two surfaces of the polymeric piezoelectric material.
- the electrode is not particularly limited, and for example, Al, Ag, Au, Cu, an Ag—Pd alloy, ITO, ZnO, IZO (registered trademark), a conductive polymer, or the like is used.
- the piezoelectric member in the present embodiment may be a laminated piezoelectric member having a configuration in which a polymer piezoelectric material and an electrode are repeatedly stacked.
- the unit having two repetitions is a laminated piezoelectric member in which electrodes, polymer piezoelectric material, electrodes, polymer piezoelectric material, and electrodes are stacked in this order.
- one layer of the piezoelectric polymer material may be the polymeric piezoelectric material in this embodiment, and the other layers are not the polymeric piezoelectric material in this embodiment. Also good.
- the laminated piezoelectric element includes a plurality of polymer piezoelectric materials in the present embodiment, if the optical activity of the optically active polymer (A) included in the polymer piezoelectric material in the present embodiment in a certain layer is L-form.
- the optically active polymer (A) contained in the polymer piezoelectric material of the other layer may be L-form or D-form.
- the arrangement of the polymeric piezoelectric material can be appropriately adjusted according to the use of the piezoelectric member.
- the first layer of the polymeric piezoelectric material containing the L-type optically active polymer (A) as the main component contains the L-type optically active polymer (A) as the main component via the electrode.
- the uniaxial stretching direction (main stretching direction) of the first polymeric piezoelectric material intersects the uniaxial stretching direction (main stretching direction) of the second polymeric piezoelectric material. It is preferable to make them orthogonal, since the directions of displacement of the first polymeric piezoelectric material and the second polymeric piezoelectric material can be made uniform, and the piezoelectricity of the entire laminated piezoelectric member is increased.
- the first layer of the polymeric piezoelectric material containing the L-type optically active polymer (A) as the main component contains the D-type optically active polymer (A) as the main component via the electrode.
- the uniaxial stretching direction (main stretching direction) of the first polymeric piezoelectric material is substantially the same as the uniaxial stretching direction (main stretching direction) of the second polymeric piezoelectric material. Arranging them in parallel is preferable because the direction of displacement of the first polymeric piezoelectric material and the second polymeric piezoelectric material can be made uniform, and the piezoelectricity of the entire laminated piezoelectric member is enhanced.
- the press detection device of the present embodiment can be used as a touch panel in combination with a display device. That is, a touch panel according to an embodiment of the present invention includes the press detection device of the present embodiment and a display device (for example, a liquid crystal display panel, an organic electroluminescence display panel, etc.).
- a display device for example, a liquid crystal display panel, an organic electroluminescence display panel, etc.
- the positional relationship between the press detection device of the present embodiment and the display device is not particularly limited.
- the press detection device of the present embodiment is a position overlapping the display device as viewed from the side viewing the display device (hereinafter also referred to as “viewing side”) (preferably the viewing side of the display device; hereinafter the same).
- the press detection apparatus of this embodiment may be provided with only one with respect to one display apparatus, and may be provided with two or more.
- the press detection device of the present embodiment when the press detection device of the present embodiment is disposed at a position overlapping the display device when viewed from the viewing side, an electrode having transparency is preferable as an electrode that can be included in the piezoelectric member of the press detection device.
- the press detection device of the present embodiment when the press detection device of the present embodiment is arranged at a position overlapping the display device when viewed from the viewing side, as a pressed member included in the press detection device, in order to increase the visibility of the display device, It is preferable to use a member having transparency.
- “transparency” specifically means that the internal haze is 20% or less (total light transmittance is 80% or more).
- a display device As an example of the touch panel according to the present embodiment, A display device; A position detection device arranged on the viewing side with respect to the display device; A pressure-sensitive device arranged at a position not overlapping the display device when viewed from the viewing side; With The form in which at least one of a position detection apparatus and a pressure-sensitive apparatus contains the press detection apparatus of this embodiment is mentioned.
- the position detection device refers to a device that detects a position touched by a position input means such as a finger or a touch pen.
- the “position” includes a position in the X-axis direction and the Y-axis direction that are parallel to the display surface of the display device and orthogonal to each other, and a position in the Z-axis direction perpendicular to the display surface of the display device. Can be mentioned.
- This “position in the Z-axis direction” represents the depth pushed by the position input means. This depth corresponds to the pressure (pressing) pushed in by the position input means.
- the press detection device of this embodiment is suitable as a position detection device for detecting a position in the Z-axis direction. In this case, the position input means corresponds to the pressurizing means in the present embodiment.
- the pressure-sensitive device refers to a device that is disposed at a position that does not overlap with the display device when viewed from the viewing side, and that detects a pressure applied by a pressing means such as a finger.
- the pressure-sensitive device may be a device for amplifying or attenuating the pressure detected by the position detection device.
- the operator of the touch panel performs position input to the position detection device with one hand (or finger), and simultaneously applies pressure to the pressure sensitive device with the other hand (or finger).
- the detected pressure can be amplified or attenuated.
- Two or more pressure sensitive devices are preferably provided for one display device, and more preferably three or more pressure sensitive devices are provided.
- the pressure sensitive device is provided in at least three of the four locations adjacent to the four corners of the display device.
- the pressure detection device of the present embodiment is suitable as at least one of the pressure sensitive devices.
- the press detection device of the present embodiment may be included only in the position detection device, may be included only in the pressure sensitive device, or may be included in both.
- the press detection device of the present embodiment when the press detection device of the present embodiment is included in both the position detection device and the pressure sensitive device, the pressed member of the press detection device included in the position detection device, and the pressure sensitivity
- the member to be pressed of the pressure detection device included in the device may be a common member.
- the first piezoelectric member is positioned at a position overlapping the display device when viewed from the viewing side with respect to one pressed member (for example, a glass substrate, a resin substrate, etc.).
- a member is provided and the second piezoelectric member is provided at a position that does not overlap the display device when viewed from the viewing side.
- only one or a plurality of the first piezoelectric members and the second piezoelectric members may be provided.
- a piezoelectric member that extends from a position overlapping the display device to a position not overlapping the display device as viewed from the viewing side is provided for one pressed member. Examples are also included.
- the press detection device according to one embodiment of the present invention (hereinafter, also referred to as “first embodiment”) has been described above.
- first embodiment a press detection device
- second embodiment a press detection device
- the press detection device includes a pressed member having a contact surface to which pressure is applied and pressure is applied, and a polymer piezoelectric material disposed opposite the pressed member.
- a product IEb of the cross-sectional secondary moment Ib and Young's modulus Eb of the member to be pressed is in the range of 10 GPa ⁇ mm 4 to 10 8 GPa ⁇ mm 4 .
- the press detection device according to the second embodiment can also be used as a touch panel in combination with a display device.
- the preferable aspect of a touch panel is the same as the preferable aspect of the touch panel using the press detection apparatus which concerns on 1st Embodiment.
- the pressure detection device according to the second embodiment is not limited to IEb / IEa being in the range of 10 2 to 10 10 , but IEb may be in the range of 10 GPa ⁇ mm 4 to 10 8 GPa ⁇ mm 4. is necessary. Except for this point, the press detection device according to the second embodiment is the same as the press detection device according to the first embodiment.
- the preferable aspect of the press detection apparatus according to the second embodiment is the same as the preferable form of the press detection apparatus according to the first embodiment.
- IEb is preferably 10 GPa ⁇ mm 4 to 10 7 GPa ⁇ mm 4, more preferably 10 GPa ⁇ mm 4 to 10 6 GPa ⁇ mm 4 , and 10 2 GPa ⁇ mm 4 to 10 5 GPa ⁇ mm. 4 is particularly preferred.
- Stabilizer B1- having the following structure as stabilizer (B) with respect to 100 parts by mass of polylactic acid resin (registered trademark LACEEA, H-400 (weight average molecular weight Mw: 200,000)) manufactured by Mitsui Chemicals, Inc. 0.1 parts by mass of 1 was added and dry blended to prepare a raw material.
- polylactic acid resin registered trademark LACEEA, H-400 (weight average molecular weight Mw: 200,000
- the prepared raw material is put into an extruder hopper, extruded from a T die while being heated to 220 ° C to 230 ° C, and brought into contact with a cast roll at 55 ° C for 0.5 minutes to produce a pre-crystallized sheet having a thickness of 150 ⁇ m. Filmed (pre-crystallization step). The crystallinity of the pre-crystallized sheet was measured and found to be 5.63%. The obtained pre-crystallized sheet was stretched by roll-to-roll while being heated to 70 ° C. at a stretching speed of 1650 mm / min, and uniaxially stretched in the MD direction up to 3.3 times (stretching step). The thickness of the obtained film was 0.05 mm. Thereafter, the uniaxially stretched film was roll-rolled and brought into contact with a roll heated to 130 ° C. for 60 seconds and annealed to produce a polymer piezoelectric material (PLA film) (annealing process).
- PLA film polymer pie
- ⁇ Melting point, crystallinity> A polymeric piezoelectric material is accurately weighed to 10 mg, and heated to 140 ° C. at a temperature rising rate of 500 ° C./min using a differential scanning calorimeter (DSC-1 manufactured by PerkinElmer Co.). The temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve. The melting point Tm and crystallinity were obtained from the obtained melting curve.
- the term “inside haze” as used in the present application refers to the inside haze of the polymer piezoelectric material, and the measurement method is a general method. Specifically, the internal haze value of the polymeric piezoelectric material of this example was measured by measuring the light transmittance in the thickness direction using the following apparatus under the following measurement conditions. More specifically, the haze (H2) is measured in advance by sandwiching only silicon oil (Shin-Etsu Silicone (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., model number: KF96-100CS) between two glass plates.
- Si oil Shin-Etsu Silicone (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., model number: KF96-100CS
- ⁇ Normalized molecular orientation MORc> The normalized molecular orientation MORc was measured by a microwave molecular orientation meter MOA-6000 manufactured by Oji Scientific Instruments. The reference thickness tc was set to 50 ⁇ m.
- Example 1 A PLA film having a width of 50 mm and a length of 90 mm is cut out from the produced polymer piezoelectric material (PLA film), and Al vapor-deposited electrode layers (thickness is set to 50 nm) are formed on the front and back of the cut-out PLA film.
- a piezoelectric member was prepared.
- These Al vapor-deposited electrode layers were formed using SIP-600 manufactured by Showa Vacuum Co., Ltd. in the same manner as the Al vapor-deposited layer in the measurement of the piezoelectric constant (displacement method) described above.
- a PVC plate made by Takiron Co., Ltd. having a size (length ⁇ width ⁇ thickness) shown in Table 2 below was prepared.
- the value obtained when the principal surface of each member was installed horizontally and the axis was defined in the horizontal direction was defined as the secondary moment of section.
- the Young's modulus (Ea, Eb) of the piezoelectric member and the member to be pressed (base material) is measured by a tensile test method based on JIS K7127, respectively. And measured.
- the Young's modulus of the piezoelectric member and the member to be pressed (base material) was determined as the slope of the elastic region (linear part thereof) in the stress-strain diagram obtained by the test piece and the test method, respectively.
- a press detection device having the same configuration as the press detection device 10 shown in FIG. 1 was produced using the piezoelectric member and the pressed member (base material).
- the support frame 5 a member made of a rigid vinyl chloride having a square frame shape in which a tetrahedron having a size of 100 mm ⁇ 54 mm ⁇ thickness 6 mm is cut out from the center of a tetrahedron having a size of 130 mm ⁇ 80 mm ⁇ thickness 6 mm is used. It was.
- the member to be pressed (base material) 6 and the support frame 5 were arranged so that their outer circumferences overlapped, and both were bonded with a double-sided tape (not shown).
- the fixed end interval in the width direction of the pressed member (base material) 6 is 54 mm.
- the piezoelectric member 7 and the member to be pressed (base material) 6 are arranged so that their centers overlap (that is, the center of the piezoelectric member 7 and the center of the inner periphery of the support frame 5 overlap). And both were bonded with a double-sided tape 1.
- a copper foil tape with a conductive adhesive layer was attached to the Al vapor-deposited electrode layers on both sides of the piezoelectric member to achieve electrical conduction.
- ⁇ Generated charge density per unit deflection> 1 is connected to a load cell of a crosshead portion of a tensile tester Tensilon RTG 1250 manufactured by A & D. A method for measuring the generated charge density per unit deflection will be described. 1 is brought into contact with the center of the contact surface 6A of the substrate 6 perpendicularly to the contact surface 6A, and is pressed against the substrate 6 at a crosshead speed of 5 mm per minute. Is applied. The pressing pressure is measured by a load cell of a tensile tester. When the pressing pressure reaches 5N corresponding to the pressing force of a human finger, the moving direction of the cross head is reversed to reduce the pressing pressure.
- the traveling direction of the crosshead is reversed again. Increase pressure and decrease force when 5N is reached. This cycle is repeated 10 times, and the amount of charge generated at that time is read through the circuit shown in FIG. Further, the amount of deflection is converted into the amount of deflection by reading the output voltage of the tensile tester with an AD converter and using a proportional constant. A value obtained by dividing (maximum value ⁇ minimum value) of the generated charge density by (maximum value ⁇ minimum value) of the deflection amount was defined as a generated charge density per unit deflection amount.
- Example 2 A press detection device was prepared and evaluated in the same manner as in Example 1 except that the piezoelectric member and the member to be pressed (base material) were changed as shown in Table 2. The results are shown in Table 2 below.
- Example 2 (Explanation of Table 2) ⁇ Section moment of inertia is the value when the main surface is installed horizontally and the axis is defined in the horizontal direction.
- a PVC plate (thickness is as shown in Table 2) manufactured by Takiron Co., Ltd. was used as the substrate.
- Example 5 and Comparative Example 1 a polyvinyl chloride plate “Uni Sunday” (thickness is as shown in Table 2) manufactured by Hikari Co., Ltd. was used as the substrate.
- the notation “(numerical value a) E (numerical value b)” represents “(numerical value a) ⁇ 10 (numerical value b) ”.
- the notation “5.2E-04” represents 5.2 ⁇ 10 ⁇ 4 .
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Abstract
Description
現在知られている高分子圧電材料は、主に以下の2種類に大別される。すなわち、ナイロン11、ポリフッ化ビニル、ポリ塩化ビニル、ポリ尿素などに代表されるポーリング型高分子と、ポリフッ化ビニリデン(β型)(PVDF)と、フッ化ビニリデン-トリフルオロエチレン共重合体(P(VDF-TrFE))(75/25)などに代表される強誘電性高分子との2種類である。
光学活性を有する高分子の中でも、ポリ乳酸のような高分子結晶の圧電性は、螺旋軸方向に存在するC=O結合の永久双極子に起因するとされている。特にポリ乳酸は、主鎖に対する側鎖の体積分率が小さく、体積あたりの永久双極子の割合が大きく、ヘリカルキラリティをもつ高分子の中でも理想的な高分子といえる。
延伸処理のみで圧電性を発現するポリ乳酸は、ポーリング処理が不要で、圧電率は数年にわたり減少しにくいことが知られている。
<1> 加圧手段が接触して圧力が加えられる接触面を有する被加圧部材と、
前記被加圧部材に対向して配置され、25℃において変位法で測定した圧電定数d14が1pm/V以上である高分子圧電材料を含む圧電部材と、
を備え、
前記被加圧部材の断面2次モーメントIb及びヤング率Ebの積IEbと、前記圧電部材の断面2次モーメントIa及びヤング率Eaの積IEaとの比IEb/IEaが102~1010の範囲にある、押圧検出装置。
<2> 前記比IEb/IEaが104~109の範囲にある、<1>に記載の押圧検出装置。
<3> 前記比IEb/IEaが105~108の範囲にある、<1>または<2>に記載の押圧検出装置。
<4> 前記接触面から加えられる圧力に対して前記被加圧部材を支持する支持手段と、
前記接触面から前記被加圧部材を介して加えられる圧力に対して前記圧電部材を支持する支持手段と、
をさらに備える、<1>~<3>のいずれか1項に記載の押圧検出装置。
<5> 前記接触面から圧力が加えられる方向と、前記高分子圧電材料の分子配向方向とが交差する、<1>~<4>のいずれか1項に記載の押圧検出装置。
<6> 前記被加圧部材の厚さが0.2mm~20mmの範囲にある、<1>~<5>のいずれか1項に記載の押圧検出装置。
<7> 前記被加圧部材のヤング率Ebが1GPa~200GPaである、<1>~<6>のいずれか1項に記載の押圧検出装置。
<8> 前記圧電部材の前記被加圧部材側とは反対側に、ヤング率が0.1GPa以下の緩和部をさらに有する、<1>~<7>のいずれか1項に記載の押圧検出装置。
<9> 前記高分子圧電材料が、重量平均分子量が5万~100万である光学活性を有するヘリカルキラル高分子を含み、DSC法で得られる結晶化度が20%~80%であり、かつ、マイクロ波透過型分子配向計で測定される基準厚さを50μmとしたときの規格化分子配向MORcと前記結晶化度との積が40~700である、<1>~<8>のいずれか1項に記載の押圧検出装置。
<10> 前記高分子圧電材料の可視光線に対する内部ヘイズが10%以下である、<1>~<9>のいずれか1項に記載の押圧検出装置。
<11> 前記MORcが3.5~15.0である、<9>又は<10>に記載の押圧検出装置。
<12> 前記ヘリカルキラル高分子が、下記式(1)で表される繰り返し単位を含む主鎖を有するポリ乳酸系高分子である、<9>~<11>のいずれか1項に記載の押圧検出装置。
<14> 前記高分子圧電材料中における前記ヘリカルキラル高分子の含有量が80質量%以上である、<9>~<13>のいずれか1項に記載の押圧検出装置。
<15> 前記高分子圧電材料が、カルボジイミド基、エポキシ基、及びイソシアネート基からなる群から選ばれる1種類以上の官能基を有する重量平均分子量が200~60000の安定化剤をさらに含み、前記ヘリカルキラル高分子100質量部に対して前記安定化剤が0.01質量部~10質量部含まれる、<9>~<14>のいずれか1項に記載の押圧検出装置。
<16> 前記安定化剤として、カルボジイミド基、エポキシ基、及びイソシアネート基からなる群から選ばれる官能基を1分子内に1つ有する安定化剤を含む、<15>に記載の押圧検出装置。
<17> <1>~<16>のいずれか1項に記載の押圧検出装置と、表示装置とを有する、タッチパネル。
本発明の一実施形態に係る押圧検出装置は、加圧手段が接触して圧力が加えられる接触面を有する被加圧部材と、前記被加圧部材に対向して配置され、高分子圧電材料を含む圧電部材と、を備え、前記被加圧部材の断面2次モーメントIb及びヤング率Ebの積IEbと、前記圧電部材の断面2次モーメントIa及びヤング率Eaの積IEaとの比IEb/IEaが102~1010の範囲にある。
IEb/IEaは、104~109が好ましく、104~108がより好ましく、105~108が特に好ましい。
なお、本実施形態において、圧電部材は被加圧部材の少なくとも一部分に対して対向していればよい。また、本実施形態において、加圧手段と、被加圧部材の加圧手段が接触する部分と、圧電部材とが、一直線上に配置されていてもよいし、一直線上に配置されていなくてもよい。
断面2次モーメントは、曲げモーメントに対する物体の変形のしにくさを表した量である。
本実施形態の押圧検出装置を構成する、被加圧部材の断面2次モーメント(Ib)、及び、圧電部材の各断面2次モーメント(Ia)は、それぞれ、以下のようにして求められる。
部材(被加圧部材及び圧電部材)が矩形平板状の部材である場合、この部材は、その断面が矩形断面である梁とみなされる。この場合、断面2次モーメントIは、部材の幅b及び部材の厚みhに基づき、下記式(a)によって一般的に算出される。
I=(b×h3)/12 ・・・ 式(a)
但し、部材(例えば、後述の被加圧部材(基材)6)が支持手段(例えば、後述の支持枠5)によって支持されることにより、加えられる圧力に対して部材の幅のうちの一部(以下「固定端間隔」ともいう;例えば、後述の支持枠5の内周よりも内側の部分)のみが変形する場合には、その部材の断面2次モーメントは、固定端間隔×(部材の厚さの3乗)/12によって算出される。
ヤング率(Young's modulus、縦弾性係数)は、弾性範囲で単位ひずみあたり、どれだけ応力が必要かの値を決める定数である。
本実施形態の押圧検出装置を構成する被加圧部材及び圧電部材の各ヤング率(Eb、Ea)は、以下のようにして求められる。
圧電部材のヤング率Ea(縦弾性係数)や、樹脂からなる被加圧部材のヤング率Eb(縦弾性係数)は、JIS K7127に準拠した引張試験方法により、JIS K6251の規定されるダンベル状1号形の試験片を用いて計測する。ヤング率は、本試験片および本試験方法により得られた応力ひずみ線図における弾性域(の線形部)の傾きとして求める。ガラスのような脆性材料からなる被加圧部材のヤング率は、JIS R1602に準拠する静的弾性率測定方法により求める。
図1は、本実施形態に係る押圧検出装置の一例について厚さ方向の断面を概略的に示す断面図であり、図2は、図1に示す押圧検出装置の接触面の反対側(支持枠側)を示す概略平面図である。
この一例では、さらに、第1電極層2及び第2電極層3には、それぞれ、引出電極として導電性粘着層付きの銅箔テープ22、23が貼り付けられている。
なお、この一例では、支持枠5が基材6の面の縁部に設けられているが、本実施形態はこの態様には限定されず、支持枠5が圧電部材7の面の縁部に設けられていてもよい。例えば、基材6のサイズと圧電部材7のサイズとが近い場合(同サイズである場合を含む)や、基材6のサイズよりも圧電部材7のサイズが大きい場合には、支持枠5は圧電部材7の縁部に設けられていてもよい。要するに、支持枠5は、接触面6Aから加えられる圧力に対して基材6を支持できるように設けられていればよい。
また、本実施形態において、接触面から加えられる圧力に対して被加圧部材を支持する支持手段は、支持枠であることには制限されず、上記圧力に対して被加圧部材を(好ましくは2点以上で)支持する手段であればよい。
なお、圧電部材7を基材6に支持する支持手段としては、両面テープに代えて、接着剤、粘着剤などのその他の支持手段を用いることもできる。
なお、圧電部材7の支点aが被加圧部材6上に設けられているとは、被加圧部材6に加えられた圧力Fが支点аを通じて圧電部材7に伝播する態様であれば、被加圧部材6と圧電部材7が直接接触している必要はなく、圧力Fを伝播する部材が圧電部材7と被加圧部材6との間に介在してもよい。
本実施形態における被加圧部材(例えば上記被加圧部材6)は、操作者の指などの加圧手段(例えば上記加圧手段8)が接触して圧力が加えられる接触面(例えば上記接触面6A)を有する。
なお、加圧手段の例としては、操作者の指以外にも、ペン状部材(例えばタッチペン)、棒状部材等の加圧用部材も挙げられる。
また、被加圧部材としては、無機材料層及び有機材料層とが積層され一体化した形態の被加圧部材や、樹脂材料層中に無機材料を分散した形態の被加圧部材を用いることもできる。
また、本実施形態の押圧検出装置を表示装置の視認側に重ねてタッチパネルを作製する場合は、表示装置の視認性を高めるため、被加圧部材としては、透明性が高い材料を用いることが好ましい。
また、本実施形態におけるIEbは、接触面に加えられた圧力を圧電部材により効率的に伝播させる観点から、10GPa・mm4~108GPa・mm4が好ましく、10GPa・mm4~107GPa・mm4がより好ましく、10GPa・mm4~106GPa・mm4が更に好ましく、102GPa・mm4~105GPa・mm4が特に好ましい。
また、本実施形態における圧電部材の断面2次モーメントIaは、発生電荷密度と強度とのバランスの観点から、10-7mm4~10-1mm4が好ましく、10-6mm4~10-2mm4がより好ましく、10-5mm4~10-3mm4が特に好ましい。
また、本実施形態におけるIEaは、発生電荷密度と強度とのバランスの観点から、10-6GPa・mm4~1GPa・mm4が好ましく、10-5GPa・mm4~10-1GPa・mm4がより好ましく、10-4GPa・mm4~10-2GPa・mm4が好ましい。
本実施形態における圧電部材(例えば上記圧電部材7)は、被加圧部材(例えば上記被加圧部材6)に対向して配置されており、高分子圧電材料(例えば上記PLAフィルム4)を含む。
本実施形態における高分子圧電材料としては、例えば、25℃において変位法で測定した圧電定数d14が1pm/V以上である高分子圧電材料を用いることができる。
ここで、「圧電定数d14」とは、圧電率のテンソルの一つであり、延伸した材料の延伸軸方向に、ずり応力を印加したとき、ずり応力の方向に生じた分極の程度から求める。具体的には、単位ずり応力あたりの発生電荷密度をd14と定義する。圧電定数d14の数値が大きいほど圧電性が高いことを表す。本願において単に『圧電定数』と称するときは、「圧電定数d14」を指す。
本実施形態において、高分子圧電材料の圧電定数(変位法)は、例えば次のようにして変位法により測定される値をいう。
接触面から圧力が加えられる方向と、高分子圧電材料の分子配向方向とが交差していることで、被加圧部材の接触面から圧電部材の厚さ方向に加えられた圧力によって、被加圧部材が撓むことにより、圧電部材に引張力が働いてこの圧電部材が歪むので、高分子圧電材料に電荷が発生しやすい。
光学活性を有するヘリカルキラル高分子としては、例えば、ポリペプチド、セルロース誘導体、ポリ乳酸系樹脂、ポリプロピレンオキシド、ポリ(β―ヒドロキシ酪酸)等を挙げることができる。
前記ポリペプチドとしては、例えば、ポリ(グルタル酸γ-ベンジル)、ポリ(グルタル酸γ-メチル)等が挙げられる。
前記セルロース誘導体としては、例えば、酢酸セルロース、シアノエチルセルロース等が挙げられる。
光学純度(%ee)=100×|L体量-D体量|/(L体量+D体量)
すなわち、『「光学活性高分子のL体の量〔質量%〕と光学活性高分子(A)のD体の量〔質量%〕との量差(絶対値)」を「光学活性高分子のL体の量〔質量%〕と光学活性高分子のD体の量〔質量%〕との合計量」で割った(除した)数値』に、『100』をかけた(乗じた)値を、光学純度とする。
本実施形態における光学活性高分子(A)は、重量平均分子量(Mw)が、5万~100万である。光学活性高分子(A)の重量平均分子量の下限が5万以上であれば光学活性高分子を成型体としたときの機械的強度が十分となる。光学活性高分子の重量平均分子量の下限は、10万以上であることが好ましく、20万以上であることがさらに好ましい。一方、光学活性高分子(A)の重量平均分子量の上限が100万以下であると、光学活性高分子を成形すること(例えば、押出成型などによりフィルム形状などに成形すること)がより容易となる。重量平均分子量の上限は、80万以下であることが好ましく、30万以下であることがさらに好ましい。
-GPC測定装置-
Waters社製GPC-100
-カラム-
昭和電工社製、Shodex LF-804
-サンプルの調製-
光学活性高分子(A)を40℃で溶媒(例えば、クロロホルム)へ溶解させ、濃度1mg/mlのサンプル溶液を準備する。
-測定条件-
サンプル溶液0.1mlを溶媒〔クロロホルム〕、温度40℃、1ml/分の流速でカラムに導入する。
本実施形態における高分子圧電材料は、安定化剤として、カルボジイミド基、エポキシ基、及びイソシアネート基からなる群より選ばれる1種類以上の官能基を有する重量平均分子量が200~60000の化合物を含むことが好ましい。
この安定化剤(B)は、前記ヘリカルキラル高分子の加水分解反応(この加水分解反応は、例えば下記反応スキームにて進行するものと推定される)を抑制し、得られる圧電材料の耐湿熱性を改良するために用いられる。
また、安定化剤(B2)としては、具体的には、ポリ(4,4’-ジシクロヘキシルメタンカルボジイミド)、ポリ(テトラメチルキシリレンカルボジイミド)、ポリ(N,N-ジメチルフェニルカルボジイミド)、ポリ(N,N’-ジ-2,6-ジイソプロピルフェニルカルボジイミド)、ジフェニルメタンジイソシアネート系ポリイソシアネート、1 ,6-ヘキサメチレンジイソシアネート系ポリイソシアネート、キシリレンジイソシアネート系ポリイソシアネート、イソホロンジイソシアネート系ポリイソシアネート、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、エポキシ化ポリブタジエン等が挙げられる。
カルボジイミド基、エポキシ基、及びイソシアネート基からなる群から選ばれる官能基を1分子内に1つ有する化合物の具体例としては、ジシクロヘキシルカルボジイミド、ビス-2,6-ジイソプロピルフェニルカルボジイミド、ヘキシルイソシアネート、オクタデシルイソシアネート、イソシアン酸3-(トリエトキシシリル)プロピル、N-グリシジルフタルイミド、オルソフェニルフェニルグリシジルエーテル、フェニルグリシジルエーテル、p-t-ブチルフェニルグリシジルエーテルが挙げられる。これらの中でも、ジシクロヘキシルカルボジイミド、ビス-2,6-ジイソプロピルフェニルカルボジイミドが好ましく、ビス-2,6-ジイソプロピルフェニルカルボジイミドがさらに好ましい。
上記安定化剤(B)の数平均分子量(Mn)と重量平均分子量(Mw)は、いずれも、光学活性高分子(A)について記載したゲル浸透クロマトグラフ(GPC)を用いた測定方法により同様に測定される。なおGPC以外にもGC-MS,FAB-MS,ESI-MS,TOF-MSなどの測定方法でも測定することができる。
なお、上記添加量は、安定化剤(B)を2種以上併用する場合、それらの総量を示す。
一方、内部ヘイズを低くし、かつ圧電定数を高めるか又は維持するという観点からは、安定化剤(B)の添加量は、光学活性を有する光学活性高分子(A)100質量部に対して0.01質量部~1.2質量部が好ましく、0.01質量部~0.7質量部がさらに好ましく、0.01質量部~0.6質量部がさらにより好ましい。
本実施形態における高分子圧電材料は、本実施形態の効果を損なわない限度において、ポリフッ化ビニリデン、ポリエチレン樹脂やポリスチレン樹脂に代表される公知の樹脂や、シリカ、ヒドロキシアパタイト、モンモリロナイト等の無機フィラー、フタロシアニン等の公知の結晶核剤等他の成分を含有していてもよい。
例えば、高分子圧電材料を、気泡等のボイドの発生を抑えた透明なフィルムとするために、高分子圧電材料中に、ヒドロキシアパタイト等の無機フィラーをナノ分散してもよい。但し、無機のフィラーをナノ分散させるためには、凝集塊の解砕に大きなエネルギーが必要であり、また、フィラーがナノ分散しない場合、フィルムの透明度が低下する場合がある。本実施形態における高分子圧電材料が無機フィラーを含有するとき、高分子圧電材料全質量に対する無機フィラーの含有量は、1質量%未満とすることが好ましい。なお、高分子圧電材料がヘリカルキラル高分子以外の成分を含む場合、ヘリカルキラル高分子以外の成分の含有量は、高分子圧電材料全質量中に対して、20質量%以下であることが好ましく、10質量%以下であることがより好ましい。
結晶促進剤は、結晶化促進の効果が認められるものであれば、特に限定されないが、ヘリカルキラル高分子の結晶格子の面間隔に近い面間隔を持つ結晶構造を有する物質を選択することが望ましい。面間隔が近い物質ほど核剤としての効果が高いからである。例えば、ヘリカルキラル高分子としてポリ乳酸系高分子を用いた場合、有機系物質であるフェニルスルホン酸亜鉛、ポリリン酸メラミン、メラミンシアヌレート、フェニルホスホン酸亜鉛、フェニルホスホン酸カルシウム、フェニルホスホン酸マグネシウム、無機系物質のタルク、クレー等が挙げられる。それらのうちでも、最も面間隔がポリ乳酸の面間隔に類似し、良好な結晶形成促進効果が得られるフェニルホスホン酸亜鉛が好ましい。なお、使用する結晶促進剤は、市販されているものを用いることができる。具体的には例えば、フェニルホスホン酸亜鉛;エコプロモート(日産化学工業(株)製)等が挙げられる。
本実施形態における高分子圧電材料は、高度に分子が配向している。この配向を表す指標として、「分子配向度MOR」がある。分子配向度MOR(Molecular Orientation Ratio)は、分子の配向の度合いを示す値であり、以下のようなマイクロ波測定法により測定される。すなわち、試料(フィルム)を、周知のマイクロ波分子配向度測定装置(マイクロ波透過型分子配向計ともいう)のマイクロ波共振導波管中に、マイクロ波の進行方向に前記試料面(フィルム面)が垂直になるように配置する。そして、振動方向が一方向に偏ったマイクロ波を試料に連続的に照射した状態で、試料をマイクロ波の進行方向と垂直な面内で0~360°回転させて、試料を透過したマイクロ波強度を測定することにより分子配向度MORを求める。
MORc=(tc/t)×(MOR-1)+1
(tc:補正したい基準厚さ、t:試料厚さ)
規格化分子配向MORcは、公知の分子配向計、例えば王子計測機器株式会社製マイクロ波方式分子配向計MOA-2012AやMOA-6000等により、4GHzもしくは12GHz近傍の共振周波数で測定することができる。
例えば、光学活性高分子(A)がポリ乳酸系高分子で複屈折率Δnを測定波長550nmで測定した場合、規格化分子配向MORcの好ましい範囲の下限である2.0は、複屈折率Δn 0.005に変換できる。また高分子圧電材料の規格化分子配向MORcと結晶化度の積の好ましい範囲の下限である40は、高分子圧電材料の複屈折率Δnと結晶化度の積が0.1に変換することができる。
本実施形態における高分子圧電材料は、規格化分子配向MORcが3.5~15.0であることが好ましく、4.0~15.0であることがより好ましく、6.0~10.0であることがさらに好ましく、7~10.0であることがさらにより好ましい。規格化分子配向MORcが3.5~15.0の範囲にあれば、延伸方向に配列するポリ乳酸分子鎖が多く、その結果、配向結晶の生成する率が高くなり、高い圧電性を発現することが可能となる。
高分子圧電材料の結晶化度は、DSC法によって求められるものであり、本実施形態における高分子圧電材料の結晶化度は20%~80%であり、好ましくは25%~70%、さらに好ましくは30%~50%が好ましい。前記範囲に結晶化度があれば、高分子圧電材料の圧電性、透明性のバランスがよく、また高分子圧電材料を延伸するときに、白化や破断がおきにくく製造しやすい。
高分子圧電材料の結晶化度と規格化分子配向MORcとの積は好ましくは40~700、さらに好ましくは75~680、さらに好ましくは90~660、さらに好ましくは125~650、さらに好ましくは180~350である。高分子圧電材料の結晶化度と、規格化分子配向MORcとの積が40~700の範囲にあれば、高分子圧電材料の圧電性と透明性とのバランスが良好であり、かつ寸法安定性も高く、後述する圧電素子として好適に用いることができる。
高分子圧電材料の透明性は、例えば、目視観察やヘイズ測定により評価することができる。本実施形態における高分子圧電材料のヘイズは、可視光線に対する内部ヘイズが10%以下であることが好ましく、5%以下であることがより好ましく、1%以下であることが特に好ましい。ここで、ヘイズは、厚さ0.05mmの高分子圧電材料に対して、JIS-K7105に準拠して、ヘイズ測定機〔(有)東京電色製、TC-HIII DPK〕を用いて25℃で測定したときの値である。高分子圧電材料のヘイズは、低ければ低いほどよいが、圧電定数などとのバランスの観点からは、0.01%~10%であることが好ましく、0.1%~5%であることがより好ましく、0.1%~1%であることが特に好ましい。なお本願でいう「ヘイズ」または「内部へイズ」とは、高分子圧電材料の内部へイズをいう。内部へイズとは、高分子圧電材料の外表面の形状によるヘイズを除外したヘイズである。
本実施形態における高分子圧電材料の原料は、既述のポリ乳酸系高分子などの光学活性高分子(A)、必要に応じて、カルボジイミド化合物などの安定化剤(B)等の他の成分を混合して、混合物とすることにより得られる。混合物は溶融混練をしてもよい。具体的には、混合する光学活性高分子(A)と必要に応じて用いられる他の成分とを、溶融混練機〔東洋精機社製、ラボプラストミル〕を用い、ミキサー回転数30rpm~70rpm、180℃~250℃の条件で、5分~20分間溶融混練することで、光学活性高分子(A)と安定化剤(B)とのブレンド体、複数種のヘリカルキラル高分子のブレンド体、ヘリカルキラル高分子と無機フィラーなどの他の成分とのブレンド体等を得ることができる。
予備結晶化シートは、光学活性高分子(A)と、必要に応じて安定化剤(B)とを含む非晶状態のシートを加熱処理して結晶化させることで得ることができる。また、押出成形法などで光学活性高分子(A)と安定化剤(B)とを含む原料を、ヘリカルキラル高分子のガラス転移温度よりも高い温度に加熱しシート状に押出成形した後、キャスターで押し出されたシートを急冷することで、所定の結晶化度を有する予備結晶化シートを得ることもできる。
Tg-40℃≦T≦Tg+40℃
(Tgは、前記ヘリカルキラル高分子のガラス転移温度を表す)
第二の工程である、延伸工程における延伸方法は特に制限されず、1軸延伸、2軸延伸、後述する固相延伸などの種々の延伸方法を用いることができる。高分子圧電材料を延伸することにより、主面の面積が大きな高分子圧電材料を得ることができる。
圧電定数を向上させる観点から、延伸処理を施した後(前記第二の工程の後)の高分子圧電材料を、一定の熱処理(以下「アニール処理」とも称する)することが好ましい。なおアニール処理により主に結晶化する場合は、前述の予備結晶化工程で行う予備結晶化を省略できる場合がある。
より好ましい態様の圧電部材は、上記圧電部材7のように、高分子圧電材料(例えば上記PLAフィルム4)が2つの主面を有し、当該主面に電極(例えば上記第1電極層2及び第2電極層3)が設けられた構成の圧電部材である。電極は、高分子圧電材料の少なくとも2つの面に備えられていればよい。
前記電極としては、特に制限されないが、例えば、Al、Ag、Au、Cu、Ag-Pd合金、ITO、ZnO、IZO(登録商標)、導電性ポリマー等が用いられる。
積層型の圧電部材の例としては、電極と高分子圧電材料とのユニットを繰り返し重ね、最後に電極で覆われていない高分子圧電材料の主面を電極で覆ったものが挙げられる。具体的にはユニットの繰り返しが2回のものは、電極、高分子圧電材料、電極、高分子圧電材料、電極をこの順で重ねた積層型の圧電部材である。積層型の圧電部材に用いられる高分子圧電材料はそのうち1層の高分子圧電材料が本実施形態における高分子圧電材料であればよく、その他の層は本実施形態における高分子圧電材料でなくてもよい。
また、積層圧電素子に複数の本実施形態における高分子圧電材料が含まれる場合は、ある層の本実施形態における高分子圧電材料に含まれる光学活性高分子(A)の光学活性がL体ならば、他の層の高分子圧電材料に含まれる光学活性高分子(A)はL体であってもD体であってもよい。高分子圧電材料の配置は圧電部材の用途に応じて適宜調整することができる。
即ち、本発明の一実施形態に係るタッチパネルは、本実施形態の押圧検出装置と、表示装置(例えば、液晶表示パネル、有機エレクトロルミネッセンス表示パネル、等)と、を備える。
上記タッチパネルにおいて、本実施形態の押圧検出装置と、表示装置と、の位置関係には特に制限はない。
例えば、上記タッチパネルにおいて、本実施形態の押圧検出装置は、表示装置を視認する側(以下、「視認側」ともいう)からみて、表示装置に重なる位置(好ましくは表示装置の視認側。以下同じ。)に配置されていてもよいし、表示装置に重ならない位置(例えば、表示装置に隣接する位置。以下同じ)に配置されていてもよいし、表示装置に重なる位置及び表示装置に重ならない位置の両方に配置されていてもよい。
また、上記タッチパネルにおいて、本実施形態の押圧検出装置は、表示装置1つに対し、1つのみ備えられていてもよいし、複数備えられていてもよい。
上記タッチパネルにおいて、本実施形態の押圧検出装置が、視認側からみて表示装置に重なる位置に配置される場合、表示装置の視認性を高めるため、押圧検出装置に含まれる被加圧部材としては、透明性がある部材を用いることが好ましい。
電極及び被加圧部材について、「透明性がある」とは、具体的には、内部ヘイズが20%以下(全光線透過率が80%以上)であることをいう。
表示装置と、
表示装置に対して視認側に配置された位置検出装置と、
視認側からみて該表示装置に重ならない位置に配置された感圧装置と、
を備え、
位置検出装置及び感圧装置の少なくとも一方が、本実施形態の押圧検出装置を含む形態が挙げられる。
感圧装置は、位置検出装置で検出された押圧を増幅又は減衰させるための装置とすることもできる。この場合、タッチパネルの操作者が、一方の手(又は指)によって位置検出装置に対して位置入力を行うと同時に、他方の手(又は指)によって感圧装置に圧を加え、位置検出装置によって検出された押圧を増幅又は減衰させることができる。
感圧装置は、表示装置1つに対し、2つ以上備えられることが好ましく、3つ以上備えられることがより好ましい。例えば、視認側からみた表示装置(表示面)の形状が矩形形状である場合、感圧装置は表示装置の4隅に隣接する4か所のうち、少なくとも3か所に備えられることが好ましい。本実施形態の押圧検出装置は、上記感圧装置の少なくとも1つとして好適である。
また、上記一例に係るタッチパネルにおいて、本実施形態の押圧検出装置が、位置検出装置及び感圧装置の両方に含まれる場合、位置検出装置に含まれる押圧検出装置の被加圧部材と、感圧装置に含まれる押圧検出装置の被加圧部材と、が共通する部材であってもよい。
両者が共通する部材である場合の具体的な態様としては、一つの被加圧部材(例えば、ガラス基板、樹脂基板、等)に対し、視認側からみて表示装置に重なる位置に第1の圧電部材を設け、視認側からみて表示装置に重ならない位置に第2の圧電部材を設けた態様が挙げられる。この態様において、第1の圧電部材及び第2の圧電部材は、それぞれ、1つのみ設けてもよいし、複数設けてもよい。
また、両者が共通する部材である場合の具体的な態様としては、一つの被加圧部材に対し、視認側からみて、表示装置に重なる位置から表示装置に重ならない位置にかけてまたがる圧電部材を設けた態様も挙げられる。
第2実施形態に係る押圧検出装置は、加圧手段が接触して圧力が加えられる接触面を有する被加圧部材と、前記被加圧部材に対向して配置され、高分子圧電材料を含む圧電部材と、を備え、前記被加圧部材の断面2次モーメントIb及びヤング率Ebの積IEbが、10GPa・mm4~108GPa・mm4の範囲にある。
第2実施形態に係る押圧検出装置も、第1実施形態に係る押圧検出装置と同様に、表示装置と組み合わせてタッチパネルとして用いることができる。タッチパネルの好ましい態様は、第1実施形態に係る押圧検出装置を用いたタッチパネルの好ましい態様と同様である。
第2実施形態に係る押圧検出装置は、IEb/IEaが102~1010の範囲にあることには限定されないが、IEbが10GPa・mm4~108GPa・mm4の範囲にあることが必要である。第2実施形態に係る押圧検出装置は、この点以外は第1実施形態に係る押圧検出装置と同様である。第2実施形態に係る押圧検出装置の好ましい態様も第1実施形態に係る押圧検出装置の好ましい形態と同様である。第2実施形態において、IEbは、10GPa・mm4~107GPa・mm4が好ましく、10GPa・mm4~106GPa・mm4がより好ましく、102GPa・mm4~105GPa・mm4が特に好ましい。
三井化学(株)製ポリ乳酸系樹脂(登録商標 LACEA、H-400(重量平均分子量Mw:20万)100質量部に対して、安定化剤(B)として下記構造を有する安定化剤B1-1を0.1質量部添加し、ドライブレンドして原料を作製した。
得られた予備結晶化シートを70℃に加熱しながらロールツーロールで、延伸速度1650mm/分で延伸を開始し、3.3倍までMD方向に一軸延伸した(延伸工程)。得られたフィルムの厚さは0.05mmであった。
その後、前記一軸延伸フィルムを、ロールツーロールで、130℃に加熱したロール上に60秒間接触させアニール処理し、高分子圧電材料(PLAフィルム)を作製した(アニール処理工程)。
以上のようにして得られた高分子圧電材料について、重量平均分子量、融点(Tm)、結晶化度、内部ヘイズ、MORc、圧電定数d14を測定した。結果を表1に示す。
具体的には、次のようにして測定した。
前述したGPC測定方法により、高分子圧電材料に含まれる樹脂(光学活性高分子)の分子量分布(Mw/Mn)及び重量平均分子量(Mw)を算出した。
結果を表1に示した。
高分子圧電材料を、10mg正確に秤量し、示差走査型熱量計(パーキンエルマー社製DSC-1)を用い、昇温速度500℃/分の条件で140℃まで昇温し、さらに昇温速度10℃/分の条件で200℃まで昇温して融解曲線を得た。得られた融解曲線から融点Tm及び結晶化度を得た。
本願でいう「内部へイズ」とは高分子圧電材料の内部へイズのことをいい、測定方法は一般的な方法で測定される。
具体的には、本実施例の高分子圧電材料の内部ヘイズ値は、下記測定条件下で下記装置を用いて、厚さ方向の光透過性を測定することにより、測定した。より詳細には、予めガラス板2枚の間に、シリコンオイル(信越化学工業株式会社製信越シリコーン(商標)、型番:KF96-100CS)のみを挟んでヘイズ(H2)を測定し、次にシリコンオイルで表面を均一に塗らした高分子圧電材料を、ガラス板2枚で挟んでヘイズ(H3)を測定し、下記式のようにこれらの差をとることで本実施例の高分子圧電材料の内部ヘイズ(H1)を得た。
内部ヘイズ(H1)=ヘイズ(H3)-ヘイズ(H2)
上記ヘイズ(H2)及び上記ヘイズ(H3)は、下記測定条件下で下記装置を用いて、厚さ方向の光透過性を測定することにより測定した。
測定装置:東京電色社製、HAZE METER TC-HIIIDPK
試料サイズ:幅3mm×長さ30mm、厚さ0.05mm
測定条件:JIS-K7105に準拠
測定温度:室温(25℃)
規格化分子配向MORcは、王子計測機器株式会社製マイクロ波方式分子配向計MOA-6000により測定した。基準厚さtcは、50μmに設定した。
前述した測定方法(変位法)により、高分子圧電材料の圧電定数d14を測定した。
前記作製した高分子圧電材料(PLAフィルム)から、幅50mm、長さ90mmのPLAフィルムを切り出し、切り出したPLAフィルムの表裏にAl蒸着電極層(厚さはいずれも50nmとした)を形成することにより、圧電部材を準備した。これらのAl蒸着電極層は、前述した圧電定数(変位法)の測定におけるAl蒸着層と同様に、(株)昭和真空製SIP-600を用いて形成した。
また、被加圧部材(基材)として、下記表2に示すサイズ(長さ×幅×厚さ)のタキロン(株)製の塩ビプレートを準備した。
上記圧電部材の断面二次モーメント(Ia)を、圧電部材の厚み及び幅に基づいて前述の式(a)に従って求めた。
また上記被加圧部材(基材)の断面二次モーメント(Ib)を、上記被加圧部材(基材)の厚み及び後述の幅方向の固定端間隔に基づいて、数式「Ib=固定端間隔×(部材の厚さの3乗)/12」に従って求めた。
ここでは、各部材の主面を水平に設置し、水平方向に軸を定義したときの値を断面2次モーメントとした。
上記圧電部材及び上記被加圧部材(基材)のヤング率(Ea、Eb)を、それぞれ、JIS K7127に準拠した引張試験方法により、JIS K6251の規定されるダンベル状1号形の試験片を用いて計測した。上記圧電部材及び上記被加圧部材(基材)のヤング率は、それぞれ、本試験片および本試験方法により得られた応力ひずみ線図における弾性域(の線形部)の傾きとして求めた。
上記圧電部材及び上記被加圧部材(基材)を用い、図1に示す押圧検出装置10と同様の構成を有する押圧検出装置を作製した。
ここで、支持枠5としては、130mm×80mm×厚さ6mmサイズの四面体の中心部から100mm×54mm×厚さ6mmサイズの四面体を切り抜いた四角枠状の、硬質塩化ビニル製部材を用いた。
また、被加圧部材(基材)6と支持枠5とを、それぞれの外周が重なるように配置し、両者を両面テープ(不図示)で貼り合せた。この例では、被加圧部材(基材)6の幅方向の固定端間隔は、54mmとなる。
また、圧電部材7と被加圧部材(基材)6とを、それぞれの中心が重なるように配置し(即ち、圧電部材7の中心と支持枠5の内周の中心とが重なるように配置し)、両者を両面テープ1で貼り合わせた。
また、圧電部材の両面のAl蒸着電極層には、導電性粘着層付きの銅箔テープを貼り付けて電気的導通を図った。
上記銅箔テープに図3に示す回路に含まれる銅線をハンダ付けで接続することにより、上記押圧検出装置を図3に示す回路に接続した。
本回路では、圧電効果により発生した電荷を、回路内の100nFのコンデンサ13に蓄電し、コンデンサ13の両端電圧を、OPアンプ12からなるバッファーアンプを介して、AD変換装置14で読み取る。読み取った電圧値に、回路内のコンデンサ13の静電容量100nFを乗じた値が発生電荷量となる。さらに発生電荷を、Al蒸着電極の面積(45cm2(=5cm×9cm))で割った値が発生電荷密度となる。
以上により発生電荷密度を測定した。
図1に示す加圧手段8としての押出棒は、エーアンドディ社製引張試験機テンシロンRTG1250のクロスヘッド部のロードセルに接続されている。
単位たわみ当たりの発生電荷密度の測定方法を説明する。
図1に示す加圧手段8(ここでは押出棒)を基材6の接触面6Aの中央部に、接触面6Aに垂直に接触させ、クロスヘッドスピード毎分5mmで、基材6に押し圧を印加する。押し圧は、引張試験機のロードセルで計測され、押し圧力が、人間の指の押力に相当する5Nに達したら、クロスヘッドの進行方向を反転させて押し圧力を減じる。押し圧力が0Nに達したら、再度、クロスヘッドの進行方向を反転させる。押し圧力を増大させ5Nに達したら力を減じる。
このサイクルを10サイクル行い、その際に発生した電荷量を、図3に示した回路を介して読み取る。また撓み量は、引張試験機の出力電圧をAD変換器で読み取り、比例定数を用いて、撓み量に変換する。
発生電荷密度の(最大値-最小値)を、撓み量の(最大値-最小値)で割った値を単位撓み量当たりの発生電荷密度とした。
圧電部材及び被加圧部材(基材)を表2のように変更したこと以外は実施例1と同様にして押圧検出装置を作製し、評価を行った。
結果を下記表2に示す。
・断面2次モーメントは、主面を水平に設置し、水平方向に軸を定義した時の値である。
・実施例1~4では、基材として、タキロン(株)製の塩ビプレート(厚さは表2のとおり)を用いた。
・実施例5及び比較例1では、基材として、(株)光製の塩ビプレート「ユニサンデー」(厚さは表2のとおり)を用いた。
・「(数値a)E(数値b)」の表記は、「(数値a)×10(数値b)」を表す。例えば、「5.2E-04」との表記は、5.2×10-4を表す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (17)
- 加圧手段が接触して圧力が加えられる接触面を有する被加圧部材と、
前記被加圧部材に対向して配置され、25℃において変位法で測定した圧電定数d14が1pm/V以上である高分子圧電材料を含む圧電部材と、
を備え、
前記被加圧部材の断面2次モーメントIb及びヤング率Ebの積IEbと、前記圧電部材の断面2次モーメントIa及びヤング率Eaの積IEaとの比IEb/IEaが102~1010の範囲にある、押圧検出装置。 - 前記比IEb/IEaが104~109の範囲にある、請求項1に記載の押圧検出装置。
- 前記比IEb/IEaが105~108の範囲にある、請求項1または請求項2に記載の押圧検出装置。
- 前記接触面から加えられる圧力に対して前記被加圧部材を支持する支持手段と、
前記接触面から前記被加圧部材を介して加えられる圧力に対して前記圧電部材を支持する支持手段と、
をさらに備える、請求項1または請求項2に記載の押圧検出装置。 - 前記接触面から圧力が加えられる方向と、前記高分子圧電材料の分子配向方向とが交差する、請求項1または請求項2に記載の押圧検出装置。
- 前記被加圧部材の厚さが0.2mm~20mmの範囲にある、請求項1または請求項2に記載の押圧検出装置。
- 前記被加圧部材のヤング率Ebが1GPa~200GPaである、請求項1または請求項2に記載の押圧検出装置。
- 前記圧電部材の前記被加圧部材側とは反対側に、ヤング率が0.1GPa以下の緩和部をさらに備える、請求項1または請求項2に記載の押圧検出装置。
- 前記高分子圧電材料が、重量平均分子量が5万~100万である光学活性を有するヘリカルキラル高分子を含み、DSC法で得られる結晶化度が20%~80%であり、かつ、マイクロ波透過型分子配向計で測定される基準厚さを50μmとしたときの規格化分子配向MORcと前記結晶化度との積が40~700である、請求項1または請求項2に記載の押圧検出装置。
- 前記高分子圧電材料の可視光線に対する内部ヘイズが10%以下である、請求項1または請求項2に記載の押圧検出装置。
- 前記MORcが3.5~15.0である、請求項9に記載の押圧検出装置。
- 前記ヘリカルキラル高分子は、光学純度が95.00%ee以上である、請求項9に記載の押圧検出装置。
- 前記高分子圧電材料中における前記ヘリカルキラル高分子の含有量が80質量%以上である、請求項9に記載の押圧検出装置。
- 前記高分子圧電材料が、カルボジイミド基、エポキシ基、及びイソシアネート基からなる群から選ばれる1種類以上の官能基を有する重量平均分子量が200~60000の安定化剤をさらに含み、前記ヘリカルキラル高分子100質量部に対して前記安定化剤が0.01質量部~10質量部含まれる、請求項9に記載の押圧検出装置。
- 前記安定化剤として、カルボジイミド基、エポキシ基、及びイソシアネート基からなる群から選ばれる官能基を1分子内に1つ有する安定化剤を含む、請求項15に記載の押圧検出装置。
- 請求項1または請求項2に記載の押圧検出装置と、表示装置と、を有する、タッチパネル。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018513362A (ja) * | 2015-03-25 | 2018-05-24 | ユニベルシテ ドゥ ロレーヌ | 圧電センサ及び圧電センサを含む装置 |
| US10854807B2 (en) | 2015-03-25 | 2020-12-01 | Université De Lorraine | Piezoelectric sensor and instrument including such a sensor |
| EP3275024B1 (fr) * | 2015-03-25 | 2021-02-17 | Université de Lorraine | Capteur piézoélectrique et instrument comportant un tel capteur |
| KR20180016962A (ko) * | 2016-08-08 | 2018-02-20 | 한양대학교 산학협력단 | 터치 센서 소자 및 그 제조 방법 |
| JP2019134070A (ja) * | 2018-01-31 | 2019-08-08 | 住友理工株式会社 | トランスデューサおよびそれを用いた発電システム |
| WO2019150850A1 (ja) * | 2018-01-31 | 2019-08-08 | 住友理工株式会社 | トランスデューサおよびそれを用いた発電システム |
| JP7045777B2 (ja) | 2018-01-31 | 2022-04-01 | 住友理工株式会社 | トランスデューサおよびそれを用いた発電システム |
| WO2021024567A1 (ja) * | 2019-08-07 | 2021-02-11 | 株式会社村田製作所 | 面方向型振動構造 |
| WO2022220144A1 (ja) * | 2021-04-15 | 2022-10-20 | 株式会社クレハ | 透明導電性圧電積層フィルム |
| JPWO2022220144A1 (ja) * | 2021-04-15 | 2022-10-20 | ||
| JP7629986B2 (ja) | 2021-04-15 | 2025-02-14 | 株式会社クレハ | 透明導電性圧電積層フィルム |
| WO2025182634A1 (ja) * | 2024-02-27 | 2025-09-04 | 株式会社村田製作所 | センサユニット、触覚提示装置及び電子機器 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2998716B1 (en) | 2018-07-04 |
| US10031606B2 (en) | 2018-07-24 |
| US20160092016A1 (en) | 2016-03-31 |
| CN105229436A (zh) | 2016-01-06 |
| JP5985744B2 (ja) | 2016-09-06 |
| EP2998716A4 (en) | 2017-01-18 |
| EP2998716A1 (en) | 2016-03-23 |
| CN105229436B (zh) | 2019-06-28 |
| JPWO2014185530A1 (ja) | 2017-02-23 |
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