Piezoelectric film and method for producing same

Abstract

An object of the present invention is to improve the piezoelectricity of a PVT having the VDF ratio of 82 to 90% represented by a copolymer, in which copolymerization of vinylidene fluoride VDF and trifluoroethylene TrFe is 85 versus 15 (this is written as PVT85/15, and which is excellent in resistance to deformation, and heat resistance, etc. And therefore, it is also to obtain a piezoelectric film having piezoelectricity exceeding a PVT of less than 82 mol % of VDF represented by a PVT75/25, which conventionally shows the highest piezoelectricity, and a method of producing the same. A piezoelectric film is made of a mixture of two kinds (for example, a first copolymer is PVT85/15 and a second copolymer is PVT75/25) having different polymerization ratios of vinylidene fluoride VDF and trifluoroethylene TrFE.

Claims

1. A piezoelectric film formed from a copolymer mixture wherein the copolymer mixture comprises at least a first copolymer (PVT1) and a second copolymer (PVT2) wherein both PVT1 and PVT2 are copolymers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE), wherein PVT1 comprises from 82 to 90 mol % of VDF and from 10 to 18 mol % of TrFE, and wherein PVT2 comprises from 60 to 82 mol % of VDF and from 18 to 40 mol % of TrFE, and wherein a residual polarization and an electromechanical coupling coefficient of the piezoelectric film comprising the copolymer mixture are higher than each of PVT1 and PVT2 alone.

2. The piezoelectric film according to claim 1, wherein PVT1 comprises 85 mol % of VDF and 15 mol % of TrFE, and wherein PVT2 comprises 75 mol % of VDF and 25 mol % of TrFE.

3. The piezoelectric film according to claim 2, wherein an amount of PVT1 relative to the total weight of the film is in the range of 50 wt % to 80 wt %.

4. The piezoelectric film according to claim 1, wherein PVT1 comprises 85 mol % of VDF and 15 mol % of TrFe, and wherein PVT2 comprises 81 mol % of VDF and 19 mol % of TrFe.

5. The piezoelectric film according to claim 4, wherein an amount of PVT1 relative to the total weight of the film is in the range of 30 wt % to 70 wt %.

6. A producing method of a piezoelectric film formed from a copolymer mixture wherein the copolymer mixture comprises at least a first copolymer (PVT1) and a second copolymer (PVT2) wherein both PVT1 and PVT2 are copolymers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE), wherein PVT1 comprises from 82 to 90 mol % of VDF and from 10 to 18 mol % of TrFE, and wherein PVT2 comprises from 60 to 82 mol % of VDF and from 18 to 40 mol % of TrFE, and a solution of a mixture of the two kinds of copolymers and a solvent is applied to a substrate and dried, and a film of the copolymer mixture formed by drying is heat treated at a temperature range between 140° C. and a melting point.

7. The producing method of the piezoelectric film according to claim 6, wherein PVT1 comprises 85 mol % of VDF and 15 mol % of TrFE, and wherein PVT2 comprises 75 mol % of VDF and 25 mol % of TrFE, and wherein an amount of PVT1 relative to the total weight of the film is in the range of 50 wt % to 80 wt %.

8. The producing method of the piezoelectric film according to claim 6, wherein PVT1 comprises 85 mol % of VDF and 15 mol % of TrFE, and wherein PVT2 comprises 81 mol % of VDF and 19 mol % of TrFE, and wherein an amount of PVT1 relative to the total weight of the film is in the range of 30 wt % to 70 wt %.

9. A producing method of a piezoelectric film formed from a copolymer mixture wherein the copolymer mixture comprises at wo a first copolymer (PVT1) and a second copolymer (PVT2) wherein both PVT1 and PVT2 are copolymers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE), wherein PVT1 comprises from 82 to 90 mol % of VDF and from 10 to 18 mol % of TrFE, and wherein PVT2 comprises from 60 to 82 mol % of VDF and from 18 to 40 mol % of TrFE, and a solution of a mixture of the two kinds of copolymers and a solvent is applied to a substrate and dried, a film of the copolymer mixture formed by drying is stretched, and the film is heat treated at a temperature range between 140° C. and a melting point.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a process flow diagram of a method for producing a blended lamella crystal piezoelectric film of Example 1-1.

(2) FIG. 2 shows a process flow diagram of a method for producing a blended single crystalline piezoelectric film of Example 1-2.

(3) FIG. 3 shows a graph indicating the relationship between weight ratio (%) of PVT85/15 and residual polarization (mC/m.sup.2) of a blended piezoelectric film comprising PVT85/15 and PVT75/25.

(4) FIG. 4 shows a graph indicating the relationship between weight ratio (%) of PVT85/15 and electromechanical coupling coefficient kt of a blended piezoelectric film comprising PVT85/15 and PVT75/25.

(5) FIG. 5 shows a process flow diagram of a method for producing a blended lamella crystal piezoelectric film of Example 3.

(6) FIG. 6 shows a graph indicating the relationship between weight ratio (%) of PVT85/15 and residual polarization (mC/m2) of a blended piezoelectric film comprising PVT85/15 and PVT81/19.

(7) FIG. 7 shows a graph indicating the relationship between weight ratio (%) of PVT85/15 and electromechanical coupling coefficient kt of a blended piezoelectric film comprising PVT85/15 and PVT81/19.

MODE FOR CARRYING OUT THE INVENTION

(8) A piezoelectric film according to the embodiment of the present invention uses a copolymer of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) {This copolymer is written as P(VDF/TrFe), or written exclusively as PVT by simplifying below.}. This piezoelectric film comprises a mixture of at least two kinds of copolymers (a first copolymer is written as PVT1 and a second copolymer is written as PVT2), the first copolymer PVT1 is selected from a copolymerization ratio of VDF: 82 to 90% versus TrFE: 18 to 10% in molar ratio, and the second copolymer PVT2 is selected from a copolymerization ratio of VDF: 60 to 82% versus TrFE: 40 to 18% in molar ratio.

(9) In the piezoelectric film, the first copolymer PVT1 is a copolymer PVT85/15, which has a VDF polymerization ratio of 85 mol % and a TrFE polymerization ratio of 15 mol %, and the second copolymer PVT2 is a copolymer PVT75/25, which has a VDF polymerization ratio of 75 mol % and a TrFE polymerization ratio of 25 mol %. The piezoelectric film is characterized in that a mixing ratio of PVT1 (PVT85/15) is in the range of 50 wt % to 80 wt %.

(10) Following content is appear from FIG. 3. When the mixing ratio of the first copolymer PVT 85/15 is 50 weight % or more by weight ratio, it enters a region, where the numerical value of the residual polarization of the piezoelectric film begins to rise, and is 80 weight % or less, the numerical value of the residual polarization of the piezoelectric film is in the region, where the increase is held.

(11) As another example, in the piezoelectric film, the first copolymer PVT1 is a copolymer PVT85/15, which has a VDF polymerization ratio of 85 mol % and a TrFE polymerization ratio of 15 mol %, and the second copolymer PVT2 is a copolymer PVT81/19, which has a VDF polymerization ratio of 81 mol % and a TrFE polymerization ratio of 19 mol %. The piezoelectric film is characterized in that the mixing ratio of PVT1 (PVT85/15) is in the range of 30 wt % to 70 wt %.

(12) Following content is appear from FIG. 6. When the mixing ratio of the first copolymer PVT 85/15 is 30 weight % or more by weight ratio, it enters a region, where the numerical value of the residual polarization of the piezoelectric film begins to rise, and is 70 weight % or less, The numerical value of the residual polarization of the piezoelectric film is in the region, where the increase is held.

(13) A method of producing a piezoelectric film according to the embodiment of the present invention uses a copolymer of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) {This copolymer is written as P(VDF/TrFe), or written exclusively as PVT by simplifying below.}. This piezoelectric film comprises a mixture of at least two kinds of copolymers (a first copolymer is written as PVT1 and a second copolymer is written as PVT2), the first copolymer PVT1 is selected from a copolymerization ratio of VDF: 82 to 90% versus TrFE: 18 to 10% in molar ratio, and the second copolymer PVT2 is selected from a copolymerization ratio of VDF: 60 to 82% versus TrFE: 40 to 18% in molar ratio. A solution of a mixture of the two kinds of copolymers and a solvent is applied to a substrate and dried, and a film of the copolymer mixture formed by drying is heat treated at a temperature range between 140° C. and a melting point. At this point, a piezoelectric film of a lamella crystal film is produced by the method of producing the piezoelectric film.

(14) And, as other example, a method of producing a piezoelectric film according to the embodiment of the present invention uses a copolymer of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) {This copolymer is written as P(VDF/TrFe), or written exclusively as PVT by simplifying below.}. This piezoelectric film comprises a mixture of at least two kinds of copolymers (a first copolymer is written as PVT1 and a second copolymer is written as PVT2), the first copolymer PVT1 is selected from a copolymerization ratio of VDF: 82 to 90% versus TrFE: 18 to 10% in molar ratio, and the second copolymer PVT2 is selected from a copolymerization ratio of VDF: 60 to 82% versus TrFE: 40 to 18% in molar ratio. A solution of a mixture of the two kinds of copolymers and a solvent is applied to a substrate and dried, a film of the copolymer mixture formed by drying is stretched, and the film is heat treated at a temperature range between 140° C. and a melting point. At this point, a piezoelectric film of a single crystalline film is produced by the method of producing the piezoelectric film.

(15) In the method for producing a piezoelectric film the copolymer PVT1 having a VDF polymerization ratio of 85 mol % and a TrFE copolymerization ratio of 15 mol % (represented by PVT85/15), the second copolymer PVT2 is a copolymer PVT75/25 with VDF 75% and TrFE 25%, and the mixing ratio of PVT 1 (PVT85/15) is in the range of 50 wt % to 80 wt %.

(16) In the method for producing a piezoelectric film the copolymer PVT 1 having a VDF polymerization ratio of 85 mol % and a TrFE copolymerization ratio of 15 mol % (represented by PVT85/15), the second copolymer PVT 2 is a copolymer PVT81/19 with VDF 81% and TrFE 19%, and the mixing ratio of PVT 1 (PVT85/15) is in the range of 30 wt % to 70 wt %.

EXAMPLE

Example 1-1

(17) FIG. 1 shows a process flow diagram of a method for producing a blended lamella crystal piezoelectric film. The production process of the piezoelectric film is carried out in the order of a solution preparation process, a coating process, a drying process, a heat treatment process, electrodes formation process and a polarization treatment process, and the blended lamella crystal piezoelectric film is produced.

(18) Detailed descriptions of individual processes of Example 1-1 are listed below.

(19) Solutions Preparation Process

(20) PVT85/15 is selected as PVT1 and PVT75/25 is selected as PVT2, and 7 kinds of solutions with different mixing weight ratios of PVT1 and PVT2 in the range of 25:75 to 90:10 are dissolved in N, N-dimethylformamide (DMF), respectively.

(21) Coating Process

(22) A glass base material, which becomes a substrate, is prepared, and the solutions are coated onto the glass base material.

(23) Drying Process

(24) The coated film is dried at 65° C. for 1 hour at 3 hPa by using a vacuum oven. The thickness of the film obtained after the drying process is about 30 μm.

(25) Heat Treatment Process

(26) The film coated on the glass base material is heated at 142° C. for 2 hours in a convection oven to crystallize.

(27) Electrodes Formation Process

(28) Aluminum is heated and evaporated at a pressure of 3×10−3 Pa or less using a resistance heating type vacuum deposition machine to form electrode coatings on both sides of the film.

(29) Polarization Treatment Process

(30) In the polarization treatment process, the film is placed in silicone oil, and a triangular wave alternating current with an amplitude of 140 MV/m and a frequency of 50 mHz is applied directly between the electrodes on both sides of the film for six cycles.

Example 1-2

(31) FIG. 2 shows a process flow diagram of a method for producing a blended single crystalline piezoelectric film. The production process of the piezoelectric film is carried out in the order of a solution preparation process, a coating process, a drying process, a stretching process, a heat treatment process, electrodes formation process and a polarization treatment process, and the blended single crystalline piezoelectric film is produced.

(32) Detailed descriptions of individual processes of Example 1-2 are listed below.

(33) Solutions Preparation Process

(34) PVT85/15 is selected as PVT1 and PVT75/25 is selected as PVT2, and 7 kinds of solutions with different mixing weight ratios of PVT1 and PVT2 in the range of 25:75 to 90:10 are dissolved in N, N-dimethylformamide (DMF), respectively.

(35) Coating Process

(36) A glass base material, which becomes a substrate, is prepared, and the solutions are coated onto the glass base material.

(37) Drying Process

(38) The coated film is dried at 65° C. for 1 hour at 3 hPa by using a vacuum oven. The thickness of the film obtained after the drying process is about 100 μm.

(39) Stretching Process

(40) The dried film is removed from the glass base material, and the film is deformed to a length of 5 times in a uniaxial direction using a dedicated jig, and held in that state.

(41) Heat Treatment Process

(42) The film fixed to the dedicated jig is heated at 142° C. for 2 hours in a convection oven to crystallize. The thickness of the film obtained after the heat treatment process is about 30 to 45 μm.

(43) Electrodes Formation Process

(44) Aluminum is heated and evaporated at a pressure of 3×10−3 Pa or less using a resistance heating type vacuum deposition machine to form electrode coatings on both sides of the film.

(45) Polarization Treatment Process

(46) In the polarization treatment process, the film is placed in silicone oil, and a triangular wave alternating current with an amplitude of 120 MV/m and a frequency of 50 mHz is applied directly between the electrodes on both sides of the film for six cycles.

Example 2

(47) Table 1 shows the each measurement result of the residual polarization Pr, the coercive electric field Ec, and the electromechanical coupling coefficient kt of the piezoelectric films of Example 1-1 (Invention 1) and Example 1-2 (Invention 2). And, comparison list with measurement results of residual polarizations, coercive electric fields, and an electromechanical coupling coefficients kt of each piezoelectric film of example (1, 2 and 3) is shown.

(48) The residual polarization Pr and the coercive electric field Ec were read from the D (electrical displacement)-E (electric field) hysteresis curve measured during the polarization process. The D-E hysteresis curve is obtained from the waveform of the charge amplifier output at sixth cycle, where E is applied 140 MV/in for the lamellar crystal film and 120 MV/m for the single crystal film with 50 mHz triangular wave AC for 6 cycles. The electromechanical coupling coefficient kt is obtained by washing a polarized sample with hexane, cutting it to a size of 5 mm×5 mm, sampling Cp (electrostatic capacitance)-G (conductance) data in the range of 1 kHz to 110 MHz by using an impedance analyzer, and being calculated by using a free resonance analysis formula.

(49) [Table 1]

(50) TABLE-US-00001 TABLE 1 Piezoelectric properties of blended lamella crystal piezoelectric film and blended single crystalline piezoelectric film PVT1 = PVT2 = Residual Coercive Electromechanical PVT85/15 PVT75/25 Polarization electric field coupling coefficient Kind of film [wt %] [wt %] Pr [mC/m.sup.2] Ec [MV/m] Kt Invention 1 Blended lamella 25 75 79.4 43.9 0.251 crystal film 50 50 94.8 42.8 0.290 60 40 94.8 44.9 0.295 70 30 95.8 45.6 0.301 75 25 97.6 45.2 0.299 80 20 94.5 45.6 0.296 90 10 92.0 44.7 0.286 Invention 2 Blended single 25 75 96.8 45.8 0.315 crystalline film 50 50 99.5 47.7 0.308 60 40 101.3 42.5 0.318 70 30 103.0 42.7 0.317 75 25 102.3 42.9 0.315 80 20 98.4 44.2 0.296 90 10 94.1 38.3 0.284 Comparison Lamella crystal 100 0 87.7 42.9 0.275 item 1 film Comparison Lamella crystal 0 100 72.9 45.5 0.240 item 2 film Comparison Single crystalline 0 100 95.4 49.7 0.311 item 3 film Note: Comparison items 1 and 2 are produced with same producing method of the Example 1-1, and Comparison item 3 are produced with same method of the Example 1-2.

Example 3

(51) FIG. 5 shows a process flow diagram of a method for producing a blended lamella crystal piezoelectric film. The production process of the piezoelectric film is carried out in the order of a solutions preparation process, a coating process, a drying process, a heat treatment process, electrodes formation process and a polarization treatment process, and the blended lamella crystal piezoelectric film is produced.

(52) Detailed descriptions of individual processes of Example 3 are listed below.

(53) Solutions Preparation Process

(54) PVT85/15 is selected as PVT1 and PVT81/19 is selected as PVT2, and 3 kinds of solutions with different mixing weight ratios of PVT1 and PVT2 in the range of 30:75 to 70:30 are dissolved in N, N-dimethylformamide (DMF), respectively.

(55) Coating Process

(56) A glass base material, which becomes a substrate, is prepared, and the solutions are coated onto the glass base material.

(57) Drying Process

(58) The coated film is dried at 65° C. for 1 hour at 3 hPa by using a vacuum oven. The thickness of the film obtained after the drying process is about 30 μm.

(59) Heat Treatment Process

(60) The film coated on the glass base material is heated at 142° C. for 2 hours in a convection oven to crystallize.

(61) Electrodes Formation Process

(62) Aluminum is heated and evaporated at a pressure of 3×10−3 Pa or less using a resistance heating type vacuum deposition machine to form electrode coatings on both sides of the film.

(63) Polarization Treatment Process

(64) In the polarization treatment process, the film is placed in silicone oil, and a triangular wave alternating current with an amplitude of 140 MV/m and a frequency of 50 mHz is applied directly between the electrodes on both sides of the film for six cycles.

Example 4

(65) Table 2 shows the each measurement result of the residual polarization Pr, the coercive electric field Ec, and the electromechanical coupling coefficient kt of the piezoelectric films of Example 3 (Invention 3). And, comparison list with measurement results of residual polarizations, coercive electric fields, and an electromechanical coupling coefficients kt of each piezoelectric film of example (1, 4) is shown.

(66) The residual polarization Pr and the coercive electric field Ec were read from the D (electrical displacement)-E (electric field) hysteresis curve measured during the polarization process. The D-E hysteresis curve is obtained from the waveform of the charge amplifier output at sixth cycle, where E is applied 140 MV/m with 50 mHz triangular wave AC for 6 cycles.

(67) The electromechanical coupling coefficient kt is obtained by washing a polarized sample with hexane, cutting it to a size of 5 mm×5 mm, sampling Cp-G data in the range of 1 kHz to 110 MHz by using an impedance analyzer, and being calculated by using a free resonance analysis formula.

(68) [Table 2]

(69) TABLE-US-00002 TABLE 2 Piezoelectric properties of blended lamella crystal piezoelectric film PVT1 = PVT1 = Residual Coercive Electromechanical PVT85/15 PVT81/19 Polarization electric field coupling coefficient Kind of film [wt %] [wt %] Pr [mC/m.sup.2] Ec [MV/m] Kt Invention 3 Blended lamella 30 70 93.1 48.0 0.297 crystal film 50 50 97.0 46.6 0.302 70 30 91.6 47.0 0.293 Comparison Lamella crystal 100 0 87.7 42.9 0.275 item 1 film Comparison Lamella crystal 0 100 88.5 44.5 0.284 item 4 film Note: Comparison items 1 and 4 are produced with same producing method of Example 3.

INDUSTRIAL APPLICABILITY

(70) According to the present invention, the piezoelectricity of the PVT having the VDF ratio of 82 to 90% represented by the PVT85/15, which is excellent in resistance to deformation, and heat resistance, etc., is improved, and therefore the piezoelectric film having piezoelectricity exceeding the PVT of less than 82 mol % of the VDF represented by the PVT75/25, which conventionally shows the highest piezoelectricity, and the method of manufacturing the piezoelectric film can be obtained. And, they contribute to the development of industries, which use and apply piezoelectric films.