Method for manufacturing fluorine-based piezoelectric film

Abstract

To provide a method for manufacturing a piezoelectric film having high piezoelectricity and high transparency. [Solution] A piezoelectric constant d is used to polarize the fluororesin film, comprising: a first stretching step of stretching a fluororesin film to 3.0 to 5.0 times its original size at a temperature of 110°C or higher but less than 150°C (T1); a second stretching step, after the first stretching step, of stretching the fluororesin film to 1.1 to 2.0 times its original size at a temperature of T1+5°C or higher but less than 186°C (T2) in the same direction as the stretching in the first stretching step; and a polarization step, simultaneously with or after the first stretching step, of applying a voltage of 5kV to 30kV at a temperature of 50°C or higher but less than 150°C. 31 A method for manufacturing a fluororesin piezoelectric film having a density of 20 pC / N or more and 50 pC / N or less, and a retardation of 100 nm or more and 3000 nm or less.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a fluororesin piezoelectric film.

Background Art

[0002] Display and input devices with a touch panel installed on the front surface of display devices such as liquid crystal displays are widely used and are used in operation panels of portable devices such as mobile phones and operation panels of household appliances. In a display and input device using a touch panel, a user operates a device by pressing a display on a screen. Therefore, the piezoelectric film used for the touch panel is required to have high piezoelectricity for enhancing detection sensitivity and high transparency for accurately visualizing an image of a display.

[0003] A film mainly composed of a fluororesin such as polyvinylidene fluoride (PVDF) can be made into a piezoelectric film having a high piezoelectric constant and pyroelectric constant by polarization treatment. In Patent Document 1, a film of a copolymer of PVDF or vinylidene fluoride (VDF) and trifluoroethylene (TFE) is subjected to polarization treatment while being stretched at 60°C to 110°C, and the piezoelectric constant d 31 is described as producing a piezoelectric film of 40 to 60 pC / N.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As described in Patent Document 1, a piezoelectric film can be manufactured by simultaneously performing stretching and polarization treatment while heating a fluororesin film. However, according to the findings of the present inventors, the piezoelectric film obtained in this way has excellent piezoelectric properties, but has a low transmittance in the visible light region and has a problem with transparency. Since a high transparency is required for a piezoelectric film used in a touch panel or the like, there is a demand for the development of a fluororesin piezoelectric film having high piezoelectricity and high transparency.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a fluororesin piezoelectric film having high piezoelectricity and high transparency.

Means for Solving the Problems

[0007] One embodiment of the present invention for solving the above problems relates to a method for manufacturing a fluororesin piezoelectric film according to the following [1] to [9]. [1] A first stretching step of stretching a fluororesin film at a temperature (T1) of 110 ° C or higher and lower than 150 ° C by 3.0 times or more and 5.0 times or less, and after the first stretching step, the fluororesin film is heated at a temperature (T2) of T1 + 5 ° C or higher and lower than 186 ° C. A second stretching step of stretching in the same direction as the stretching direction in the first stretching step by 1.1 times or more and 2.0 times or less, and simultaneously with the first stretching step or after the first stretching step, at a temperature of 50 ° C or higher and lower than 150 ° C. A polarization step of polarizing the fluororesin film by applying a voltage of 5 kV or more and 30 kV or less, having a piezoelectric constant d 31 A method for manufacturing a fluororesin piezoelectric film having a piezoelectric constant d of 20 pC / N or more and 50 pC / N or less and a retardation of 100 nm or more and 3000 nm or less. [2] The method for manufacturing a fluororesin piezoelectric film according to [1], wherein the polarization step is performed after the second stretching step. [3] The method for manufacturing a fluororesin piezoelectric film according to [1], wherein the polarization step is performed before the second stretching step. [4] The method for manufacturing a fluororesin piezoelectric film according to [1], wherein the polarization step is performed simultaneously with the second stretching step. [5] The method for manufacturing a fluororesin piezoelectric film according to [1], wherein the polarization step is performed simultaneously with the first stretching step. [6] A method for manufacturing a fluororesin piezoelectric film according to any one of [1] to [5], wherein the first stretching step, the second stretching step, and the polarization step are all performed while conveying the fluororesin film. [7] The fluororesin film is mainly composed of vinylidene fluoride resin, a method for producing a fluororesin piezoelectric film according to any one of [1] to [6]. [8] A method for producing a fluororesin piezoelectric film according to any one of [1] to [7], comprising the steps of heating and melting a resin composition containing a fluororesin before the first stretching step, and forming a film from the heated and melted resin composition. [9] The resin composition was measured at a temperature of 260°C and a shear rate of 50 s² during measurement. -1 A method for producing a fluororesin piezoelectric film according to [8], wherein the melt viscosity η measured is 600 Pa·s or more and 4000 Pa·s or less.

[10] A method for manufacturing a fluororesin piezoelectric film according to [1], wherein at least one of the first stretching step, the second stretching step, and the polarization step is performed in a roll-to-roll manner. [Effects of the Invention]

[0008] The present invention provides a method for manufacturing a fluororesin piezoelectric film having high piezoelectricity and high transparency. [Modes for carrying out the invention]

[0009] One embodiment of the present invention relates to a method for manufacturing a fluororesin piezoelectric film, comprising stretching and polarization treatment of a fluororesin film while heating it. In this embodiment, the fluororesin film is subjected to multiple stretching treatments.

[0010] The above multiple stretching process includes a first stretching step in which the fluororesin film is stretched to 3.0 to 5.0 times its original size at a temperature of 110°C or higher but less than 150°C (T1), and a second stretching step in which, after the first stretching step, the film is stretched to 1.1 to 2.0 times its original size in the same direction as the stretching in the first stretching step at a temperature of T1+5°C or higher but less than 186°C (T2). The above polarization process includes a polarization step in which a voltage of 5kV to 30kV is applied to the fluororesin film at a temperature of 50°C or higher but less than 150°C, either simultaneously with or after the first stretching step.

[0011] In the first and second stretching steps, the stretching direction is preferably the MD direction (film transport direction) when the stretching process is performed continuously while the film is being transported. When both the first and second stretching steps are performed by batch processing, the stretching direction only needs to be the same for the first and second stretching steps, and the stretching direction can be any direction. Continuous processing while transporting the film and batch processing may be appropriately combined in the stretching steps.

[0012] Patent Document 1 describes a method in which stretching and polarization are performed simultaneously in the range of 25°C to 110°C. However, high-magnification stretching in such a temperature range tends to cause film whitening and an increase in haze value. In contrast, by performing the first stretching at a temperature of 110°C to less than 150°C (T1) and then performing multiple stretching processes including a second stretching step at a temperature of T1+5°C to less than 186°C, film whitening and an increase in haze value can be suppressed. This is thought to be because performing the first stretching at a temperature of 110°C or higher softens the polymer, suppressing the generation of craze and whitening due to stress concentration. Furthermore, by performing the second stretching at a temperature higher than the first stretching step, the stretching ratio can be further increased while suppressing whitening. Increasing the stretching ratio increases the degree of orientation of the molecular chains, resulting in a higher storage modulus and an electromechanical coupling coefficient k. 31 A high piezoelectric film can also be obtained.

[0013] In this process, any one or all of the first stretching step, the second stretching step, and the polarization step may be performed in batch or continuous processing, or a combination of batch and continuous processing may be performed. From the viewpoint of productivity, it is preferable to perform the process continuously while conveying the film. As a continuous processing method, for example, a roll-to-roll method may be used in which the fluororesin film supplied from a supply roll is conveyed by multiple guide rolls while the first stretching step, the second stretching step, and the polarization step are performed in continuous processing, and the film is wound onto a winding roll for storage. Alternatively, the first stretching step, the second stretching step, and the polarization step may be divided into multiple lines and the fluororesin piezoelectric film may be manufactured by performing multiple roll-to-roll processes corresponding to each line.

[0014] By performing the first stretching process, the second stretching process, and the polarization process while the film is being transported, these processes, which all involve heating, can be completed in a short time of a few seconds. When stretching and polarization are performed over a long period of time using batch processing, the film is prone to haze and discoloration due to the prolonged heating and polarization process. However, by performing the processes in a short time, it is possible to reduce the likelihood of haze and discoloration in the film. From the viewpoint of mass production, it is preferable to perform the stretching and polarization processes continuously using a roll-to-roll method.

[0015] The polarization treatment time is preferably 0.001 seconds to 60 minutes, more preferably 0.01 seconds to 30 minutes, even more preferably 0.1 seconds to 15 minutes, particularly preferably 1 second to 10 minutes, very preferably 1 second to 1 minute, extremely preferably 1 second to 30 seconds, and most preferably 1 second to 10 seconds. By setting the time to 0.001 seconds or more, sufficient polarization treatment can be performed, and the piezoelectric constant can be increased. Furthermore, by setting it to 60 minutes or less, good productivity can be achieved. Here, the polarization treatment time refers to the time during which the film passes through the region sandwiched between the electrode to which a high voltage is applied and the roll when polarization treatment is performed on the roll while the film is being transported. In the case of batch processing, it refers to the time during which the film is subjected to polarization treatment at a predetermined voltage, and when polarization treatment is performed multiple times, the sum of the individual polarization treatment times is considered the polarization time.

[0016] The stretching process in the first and second stretching steps can be performed using a stretching apparatus having multiple rolls and pinch rolls for holding the fluororesin film. In this case, the stretching ratio can be controlled by controlling the ratio of the rotational speed of the feed-side roll in the preceding stage to the rotational speed of the take-up-side roll in the subsequent stage. For example, when performing the first and second stretching processes with four rolls, the stretching can be performed by changing the rotational speed ratio of the feed-side and take-up-side rolls and the temperature of each roll in each of the first and second stretching processes. In the roll-to-roll method, the stretching temperature is the higher of the surface temperatures of the feed-side roll in the preceding stage and the take-up-side roll in the subsequent stage. Specifically, in the first stretching step, the surface temperature of the roll with the higher temperature among the surface temperatures of the preceding and subsequent rolls is set to T1. Also, in the second stretching step, the surface temperature of the roll with the higher temperature among the surface temperatures of the preceding and subsequent rolls is set to T2. In batch processing, the stretching temperature is defined as the temperature at which the film temperature reaches its highest point within the stretching process. When the film is heated and stretched by other methods, the stretching temperature is defined as the temperature at which the film surface temperature reaches its highest point within the stretching process. The film temperature can be measured using either a contact or non-contact method.

[0017] The temperature (T1) during the first stretching step is 110°C or higher and less than 150°C, preferably 115°C or higher and less than 150°C, more preferably 120°C or higher and less than 150°C, even more preferably 125°C or higher and less than 150°C, particularly preferably 125°C or higher and 145°C or lower, and most preferably 130°C or higher and 145°C or lower. By increasing the temperature T1 of the fluororesin film during the first stretching step, the temperature inside the film is increased during stretching, making it easier to deform in the stretching direction (MD direction), and thus reducing the haze value of the film. By moderately lowering the surface temperature of the roll during stretching, the stretching stress of the fluororesin film is increased, and highly piezoelectric β-phase crystals can be efficiently formed. Furthermore, by stretching while heating, the film is stretched uniformly, localized crystallization is suppressed, and molecular chains are uniformly arranged throughout the film, which suppresses light scattering caused by differences in the degree of crystallinity within the film, and thus reduces internal haze. By keeping the surface temperature of the roll during stretching below 150°C, the efficiency of molecular chain alignment during film stretching can be increased, the proportion of β-phase structures that contribute to piezoelectricity can be increased, and deformation of the film due to melting of the fluororesin can be suppressed.

[0018] The stretching ratio in the first stretching step is 3.0 times or more and 5.0 times or less, preferably 3.5 times or more and 5.0 times or less, more preferably 3.5 times or more and 4.7 times or less, even more preferably 3.5 times or more and 4.5 times or less, and particularly preferably 3.5 times or more and 4.3 times or less. By setting the stretching ratio in the first stretching step to 3.0 times or more, the crystal ratio of the β phase in the film increases, making it easier to obtain a fluororesin piezoelectric film with high piezoelectricity through polarization treatment. By setting the stretching ratio in the first stretching step to 5.0 times or less, it is possible to suppress the increase in haze due to the generation of excessive stretching stress.

[0019] The temperature (T2) during the second stretching step is between T1+5°C and less than 186°C, preferably between T1+10°C and less than 186°C, more preferably between T1+15°C and less than 186°C, even more preferably between T1+15°C and 172°C, and particularly preferably between T1+15°C and 165°C. By making the temperature T2 of the fluororesin film in the second stretching step higher than the temperature T1 in the first stretching step, the film can be softened, suppressing the occurrence of crazing and whitening due to stress concentration. Furthermore, by keeping the temperature T2 of the fluororesin film in the second stretching step below 186°C, the stretching stress of the fluororesin can be appropriately increased, allowing for the efficient formation of highly piezoelectric β-phase crystals.

[0020] The stretching ratio in the second stretching step is 1.1 times or more and 2.0 times or less, preferably 1.18 times or more and 2.0 times or less, more preferably 1.18 times or more and 1.7 times or less, even more preferably 1.25 times or more and 1.7 times or less, and most preferably 1.25 times or more and 1.5 times or less. By setting the stretching ratio in the second stretching step to 1.1 times or more, a film with a higher proportion of piezoelectric β-phase crystals and a higher elastic modulus can be obtained. By setting the stretching ratio in the second stretching step to 2.0 times or less, the occurrence of crazes and whitening due to stress concentration can be suppressed, and a highly transparent film can be obtained.

[0021] The total stretching ratio (product of the stretching ratios in each stretching step) obtained by the stretching process including the first and second stretching steps is preferably 4.0 to 10.0 times, more preferably 4.5 to 8.0 times, even more preferably 4.7 to 7.0 times, and particularly preferably 5.0 to 7.0 times. The total stretching ratio can be determined as the product of the stretching ratios in each stretching step. By setting the total stretching ratio to 4.0 times or more, the proportion of β phase in the film increases, making it easier to obtain a fluororesin piezoelectric film with high piezoelectricity through polarization treatment. By setting the total stretching ratio to 10.0 times or less, it is possible to reduce the occurrence of crazes and whitening due to stress concentration, as well as film breakage during the stretching process.

[0022] The polarization process is performed simultaneously with the first stretching process or after the first stretching process. By performing a polarization treatment on a fluororesin film whose β-phase proportion has been increased by the first stretching process, a fluororesin piezoelectric film with high piezoelectricity can be manufactured. The polarization process can be performed in batches or continuously while the film is being transported, and from the viewpoint of productivity, continuous processing while the film is being transported is preferred. As a method of performing the process while the film is being transported, for example, a roll-to-roll method is preferred, and the polarization treatment can be performed by discharging DC current from a needle-shaped electrode onto the metal roll performing the first stretching process, the metal roll performing the second stretching process, or a different metal roll. The fluororesin film, which is transported in close contact with the surface of the metal roll, is polarized as it passes between the needle-shaped electrode discharging DC current and the metal roll. At this time, the metal roll from which the DC current is being discharged is grounded.

[0023] When performing polarization in a batch process, the film can be heated by a heating plate method, where the film is placed on a heating plate; a hot air circulation method, where the film is placed in a heating chamber and heated by circulating hot air; or an infrared heating method, where the film is heated non-contact using an infrared heater. Here, the polarization temperature when polarization is performed in a batch process is the highest temperature of the film within the range where a DC electric field is applied. When polarization is performed continuously while the film is being transported, the hot air circulation method or infrared heating method can be applied to heat the film, but from the viewpoint of simplifying the apparatus and facilitating temperature control, it is preferable to heat the film to be polarized by heating a metal roll that discharges DC current from the electrode. When heating with the metal roll, the polarization temperature is the surface temperature of the metal roll, and when the film is heated by other methods, the polarization temperature is the highest temperature of the film within the range where a DC electric field is applied. Here, the film temperature can be measured by either a contact method or a non-contact method.

[0024] In the polarization process, a voltage of 5kV to 30kV is applied to the fluororesin film at a temperature of 50°C to less than 170°C. The temperature in the polarization process is preferably 80°C to 160°C, more preferably 100°C to 150°C, even more preferably 115°C to 150°C, and particularly preferably 130°C to 150°C. The DC voltage applied in the polarization process is preferably 3kV to 30kV, more preferably 5kV to 30kV, even more preferably 5kV to 25kV, particularly preferably 5kV to 20kV, and most preferably 10kV to 17kV.

[0025] The polarization process may be performed simultaneously with the first stretching process, between the first and second stretching processes, simultaneously with the second stretching process, or after the second stretching process. Performing the polarization process after the second stretching process is preferable from the viewpoint of manufacturing stability because it reduces the likelihood of film breakage during flashover compared to performing stretching and polarization simultaneously. The same applies when the polarization process is performed between the first and second stretching processes. Furthermore, performing the polarization process simultaneously with the first stretching process makes it easier to obtain a piezoelectric film with high piezoelectric properties because the orientation of molecular chains due to stretching and the orientation of dipoles due to the electric field proceed simultaneously. The same applies when the polarization process is performed simultaneously with the second stretching process.

[0026] The fluororesin film used in the processing steps described above can be any film containing a fluororesin, and it is preferable that the film has a fluororesin as its main component. A fluororesin is a resin obtained by polymerizing monomers containing fluororesins. Having a fluororesin as its main component means that the proportion of fluororesin to the total mass of the film is 50% by mass or more. The proportion of fluororesin content to the total mass of the film is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less. Since the fluororesin piezoelectric film is made by stretching and polarization treatment of a fluororesin film, the composition of the fluororesin piezoelectric film and the fluororesin film are basically the same.

[0027] Fluorine-based resins can be homopolymers or copolymers obtained by polymerizing TFE, VDF, etc. Examples of fluorine-based resins obtained by polymerizing TFE include copolymers of TFE with ethylene, perfluoroalkyl vinyl ether, VDF, 1-chloro-1-fluoroethylene, chlorotrifluoroethylene (CTFE), and hexafluoropropylene (HFP). Examples of fluorine-based resins obtained by polymerizing VDF include homopolymers of VDF, as well as copolymers of VDF with 1-chloro-1-fluoroethylene, 1-chloro-2-fluoroethylene, trifluoroethylene (TrFE), CTFE, TFE, tetrafluoropropene, HFP, and perfluoroalkyl vinyl ether.

[0028] Of these, from the viewpoint of facilitating polarization of the fluororesin film, fluororesins obtained by polymerizing VDF are preferred, with homopolymers of VDF, copolymers of VDF and TrFE, copolymers of VDF and HFP, copolymers of VDF and TFE, copolymers of VDF, TrFE and TFE, copolymers of VDF, TrFE, TFE and CTFE, and copolymers of VDF, TrFE and TFE and 1-chloro-1-fluoroethylene being more preferred, and homopolymers of VDF being even more preferred. These fluororesins may be used individually or in combination of multiple types.

[0029] The fluororesin included as a component of the fluororesin film is preferably a fluororesin mainly composed of VDF, and more preferably a homopolymer of VDF, because high piezoelectricity is expected. A fluororesin mainly composed of VDF means that the VDF content relative to the total mass of the fluororesin is 50% by mass or more. The VDF content is the ratio of the mass of constituent units derived from VDF to the total mass of the fluororesin. The content of constituent units derived from VDF relative to the total mass of the fluororesin is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

[0030] In particular, fluororesin films are expected to have high piezoelectric properties, so a higher content of the VDF homopolymer is preferable. The content of the homopolymer relative to the total mass of the fluororesin film is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

[0031] The content of resins with VDF as a constituent unit in fluororesin films is: 19 It can be measured by quantitative analysis using an internal standard with F-NMR.

[0032] The fluoropolymer film was measured at a temperature of 260°C and a shear rate of 50s during measurement. -1The melt viscosity measured (hereinafter, unless otherwise specified, the melt viscosity measured under the above conditions will be referred to as "melt viscosity") is preferably 600 Pa·s or more and 4000 Pa·s or less, more preferably 1000 Pa·s or more and 3500 Pa·s or less, and even more preferably 1000 Pa·s or more and 2400 Pa·s or less. Since the melt viscosity of the fluororesin does not change even after going through the processes of film formation, stretching, and polarization, the melt viscosity of the piezoelectric film serves as an indicator of the melt viscosity of the resin composition containing the fluororesin that is the raw material (hereinafter, the resin composition containing the fluororesin will be referred to as "resin composition") and the fluororesin film. Since the fluororesin film is made by forming the resin composition, a resin composition with a melt viscosity of 4000 Pa·s or less can be formed by extrusion at a relatively low temperature. Furthermore, since the resin composition has short molecular chains and little entanglement of molecular chains, the film made from the resin composition can be stretched at high magnification without breaking. Furthermore, the short molecular chains improve the mobility of the molecular chains due to heat, leading to selective alignment of the molecular chains during cooling, and consequently, an improvement in crystallinity. Stretching the film with high crystallinity promotes molecular chain orientation, increasing the proportion of β-phase crystals. Polarization treatment of the film with well-developed β-phase crystals causes the molecular dipoles to align in one direction, resulting in high piezoelectricity. Therefore, resin films with lower melt viscosity are advantageous as raw materials for piezoelectric films with high piezoelectricity.

[0033] Furthermore, to obtain a piezoelectric film with fewer impurities, it is preferable to filter the heat-melted resin composition during film manufacturing to remove impurities and then form a film using the resulting resin composition. Resin compositions with a melt viscosity of 4000 Pa·s or less readily decrease in viscosity upon heating, making it less likely for the filter to clog and thus easier to filter. Therefore, it is not necessary to raise the melting temperature to enable filtration, and it is less likely for the resin to change due to heat and generate impurities, resulting in mottled irregularities on the film surface. On the other hand, resin compositions with a melt viscosity exceeding 4000 Pa·s have a large molecular weight, and the movement of molecular chains is suppressed, making crystallization difficult. Therefore, films made from such resin compositions have a uniform structure, are less prone to light scattering due to differences in refractive index between crystalline and amorphous parts, exhibit excellent transparency, and have stable various physical properties. However, these resin compositions require relatively high temperatures to achieve the viscosity necessary for filtration, which can easily lead to deterioration and decomposition of the resin composition. Resin compositions with a melt viscosity of less than 600 Pa·s contain many molecular chains with small molecular weights, which makes it difficult to maintain the stability of various physical properties in the resulting films.

[0034] The melt viscosity is measured in accordance with ASTM D 3835:2016 (ISO 11443:2021, JIS K 7199:1999). Specifically, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used, with a capillary die of φ1 mm inner diameter x 10 mm tube length, measured at a temperature of 260°C and a shear rate of 50 s. -1 This is the viscosity measured using [the specified method].

[0035] The fluoropolymer film may be produced by melt extrusion of the resin composition or by solvent casting.

[0036] In the melt extrusion method, a molten resin composition is extruded to form a film, thereby producing a fluoropolymer resin film. In the solvent casting method, a liquid composition in which the resin composition is dissolved in a solvent is cast (coated) onto a substrate, and the solvent is vaporized by heating and drying to produce a fluoropolymer resin film.

[0037] In the melt extrusion method, a fluororesin film can be produced by performing a step of heating and melting the above-mentioned resin composition (melting step) and a step of forming the molten resin composition into a film (film formation step). At this time, a step of filtering the molten resin composition (filtration step) may be further performed between the melting step and the film formation step.

[0038] In the melting step, the resin composition is melted. This step can be carried out, for example, by melting and kneading the resin composition using an extruder.

[0039] The resin composition melted in the melting process may be any resin composition mainly composed of the fluororesin described above. However, if the resin composition contains solvent components, the residual solvent components that do not volatilize may hinder polarization in subsequent processes. Therefore, it is preferable that the content of the above solvent components in the resin composition be small, preferably 1.0% by mass or less, and more preferably 0.1% by mass or less, relative to the total mass of the resin composition. In particular, the solvent content is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less, relative to the total mass of the resin composition.

[0040] The melting temperature shall be the highest temperature in the conduit from the extruder to the filtration device.

[0041] The melting temperature of the resin composition is preferably 20°C (mp+20°C) to 130°C (mp+130°C) above the melting point (mp) of the resin composition, more preferably (mp+50°C) to (mp+100°C), even more preferably (mp+80°C) to (mp+100°C), and particularly preferably (mp+85°C) to (mp+95°C). By setting the melting temperature to 20°C (mp+20°C) or higher above the melting point of the resin composition, the viscosity of the resin composition can be reduced to a degree that allows for extrusion. By setting the melting temperature to 130°C (mp+130°C) or lower above the melting point of the resin composition, decomposition and condensation of the resin due to heating can be suppressed, and the generation of decomposition products can be suppressed. By suppressing the generation of the above-mentioned decomposition products, the amount of foreign matter in the fluororesin piezoelectric film can be reduced, and the transparency and smoothness of the fluororesin piezoelectric film can be improved.

[0042] The melting point of the resin composition shall be the value measured in accordance with JIS K 7121:1987. Specifically, 5 mg of the sample shall be sealed in an aluminum pan and placed in a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Under a nitrogen atmosphere, the temperature shall be raised from room temperature to 230°C at a heating rate of 10°C / min, and the maximum melting peak temperature in the DSC curve shall be defined as the melting point of the resin composition.

[0043] (Filtration process) In the filtration step, the resin composition, which has been melted and reduced in viscosity in the melting step, is filtered. The filtration method is not particularly limited; it is sufficient for the molten resin composition to pass through the filter, and known types of filters such as pleated filters and leaf disc filters can be used.

[0044] In the filtration process, the resin composition is filtered using a filter with a filtration accuracy of 10 μm to 40 μm. Using a filter with a filtration accuracy of 10 μm or more facilitates the filtration of the resin composition that has been heated and melted to the above temperature, and also prevents the filtration pressure from becoming too high, thus shortening the filtration time. Using a filter with a filtration accuracy of 40 μm or less allows for sufficient removal of foreign matter from the resin composition, resulting in a fluororesin film with fewer foreign matter particles. The filtration accuracy of the filter is preferably 10 μm to 30 μm, and more preferably 15 μm to 30 μm.

[0045] The filter may be placed between the extruder and the die used in the film formation process. Alternatively, the filter may be placed in a different extruder or melt-kneading device than the one used in the film formation process, and the resin composition filtered through this filter may be introduced into the extruder used in the melting process for film formation.

[0046] In the film formation process, the resin composition, which has been heated and melted in the melting process and filtered in the filtration process as needed, is formed into a film. The film formation method is not particularly limited, and known methods such as extruding the melted and filtered resin composition from a T-die and cooling it by contacting it with a cooling roll can be used.

[0047] The film formation method is not particularly limited, and known methods such as extruding the molten and filtered resin composition from a T-die and cooling it in contact with a cooling roll can be used. The surface temperature of the cooling roll is preferably 125°C or lower. By rapidly cooling the film of the resin composition extruded by a cooling roll with a low surface temperature, crystal growth can be suppressed, and the internal haze of the resulting fluororesin film and the fluororesin piezoelectric film produced therefrom can be reduced. The surface temperature of the cooling roll is preferably 5°C to 115°C, more preferably 20°C to 80°C, and even more preferably 30°C to 60°C. By setting the surface temperature of the cooling roll to 5°C or higher, the film does not become too hard, and a decrease in the stretchability and transportability of the film due to a decrease in adhesion between the guide roll or stretching roll and the film is less likely to occur.

[0048] The fluororesin film thus obtained may be wound up once and stored, or may be continuously used in the first stretching step, the second stretching step, and the polarization step as it is.

[0049] [Fluororesin piezoelectric film] Thus, the fluororesin piezoelectric film according to this embodiment can be obtained.

[0050] The fluororesin piezoelectric film has a retardation of 100 nm or more and 3000 nm or less, preferably 500 nm or more and 3000 nm or less, and more preferably 750 nm or more and 3000 nm or less. The larger the retardation, the higher the degree of orientation of the molecular chains of the fluororesin, the sufficiently high crystal ratio of the β phase, and the easier it is to obtain high piezoelectricity.

[0051] The retardation is measured by using a light source having a wavelength of 589.1 nm and by the parallel Nicol rotation method. The retardation of a film cut out to 20 mm × 20 mm from a range including the intersection of the diagonals of the fluororesin piezoelectric film is measured, and the value is taken as the representative value of the retardation of the fluororesin piezoelectric film. When the length of one side of the fluororesin piezoelectric film is 300 mm or more, a rectangular area with an arbitrary side of 300 mm is assumed, and the retardation of a film cut out to 20 mm × 20 mm from a range including the intersection of the diagonals of the rectangular area is measured. When both sides of the fluororesin piezoelectric film are 300 mm or more, a square with an arbitrary side of 300 m is set in the piezoelectric film, and the measurement range is set according to the above method.

[0052] The fluororesin piezoelectric film has a piezoelectric constant d 31 of 20 pC / N or more and 50 pC / N or less, preferably 30 pC / N or more and 50 pC / N or less, more preferably 32 pC / N or more and 50 pC / N or less, further preferably 35 pC / N or more and 50 pC / N or less, and particularly preferably 35 pC / N or more and 45 pC / N or less.

[0053] <神仙道 The piezoelectric constant d of the fluororesin piezoelectric film 31The measurement is performed using a static method. Specifically, Al-deposited electrodes are formed on both sides of a piezoelectric film, and a rectangular sample with a length of 60 mm parallel to the slow phase axis detected by in-plane birefringence of the film during retardation measurement and a width of 10 mm perpendicular to the slow phase axis is cut out as a test piece from near the center of the planar portion of the piezoelectric film with electrodes. Next, the test piece is placed on a tensile testing machine with a chuck distance of 50 mm, and the amount of induced charge Q (pC) is measured using an electrometer when the test piece is stretched in the longitudinal direction (slow phase axis direction) with a force F (N) at a tensile speed of 10 mm / min at room temperature. The relationship between different forces F (N) and the amount of induced charge Q (pC) for each is measured at 128 points using the above method, and the relationship between force F (N) and the amount of induced charge Q (pC) is plotted with force F (N) on the horizontal axis and the amount of induced charge Q (pC) on the vertical axis, and the slope (pC / N) of the generated charge Q (pC) with respect to force F (N) is determined by the least squares method. The charge quantity is measured by the method described above, within the range including the intersection of the diagonals of the polarization surface of the fluororesin piezoelectric film, and the absolute value of this measurement is taken as the representative value Q(pC) of the charge quantity of the fluororesin piezoelectric film. In this case, if the length of one side of the fluororesin piezoelectric film is 300 mm or more, a rectangular area with sides of 300 mm is arbitrarily set, and the range including the intersection of the diagonals of the rectangular area is measured. Furthermore, if both sides of the fluororesin piezoelectric film are 300 mm or more, a square with sides of 300 mm is arbitrarily set on the piezoelectric film, and the measurement range is set according to the method described above. Piezoelectric constant d 31 (pC / N) can be calculated using Equation 1.

[0054]

number

[0055] The internal haze of the fluororesin piezoelectric film is preferably 0.01% to 1.50%, more preferably 0.01% to 1.20%, even more preferably 0.01% to 1.00%, and particularly preferably 0.01% to 0.80%. The lower the internal haze, the better the transparency of the piezoelectric film.

[0056] The internal haze of a fluororesin piezoelectric film is determined by filling in any scratches or other irregularities that cause external haze with silicone oil to eliminate the influence of external haze, and then measuring the haze in the area including the center of the piezoelectric film in accordance with ISO 14782:1999. Specifically, silicone oil (Nikon, MXA22179) is placed between two glass plates (thickness: 0.15 mm, flatness: 0.01 mm or less), and the haze (H2) caused by the glass plates and silicone oil is measured using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000). Next, a 50 mm x 50 mm rectangular film is cut out so as to include the intersection of the diagonals of the fluororesin piezoelectric film. If the length of one side of the piezoelectric film is 300 mm or more, a rectangle with sides of 300 mm is arbitrarily assumed, and the rectangular film is cut out from the area including the intersection of the diagonals of the rectangular film. Furthermore, if both sides of the piezoelectric film are 300 mm or longer, a square with sides of 300 mm is arbitrarily set on the piezoelectric film, the measurement range is set according to the method described above, and the rectangular film is cut out. Both sides of the cut piezoelectric film are uniformly wet with the silicone oil described above, and the haze (H3) is measured using the haze meter while sandwiched between the two glass plates. H2 is subtracted from H3 to obtain the internal haze (H1) of the piezoelectric film. The internal haze (H1) of the piezoelectric film is calculated using the following formula. H1 = H3 - H2

[0057] The storage modulus of the piezoelectric film is preferably 1.0 GPa or more and 10.0 GPa or less, more preferably 1.5 GPa or more and 8.8 GPa or less, even more preferably 2.0 GPa or more and 6.0 GPa or less, and particularly preferably 2.7 GPa or more and 5.0 GPa or less. As shown in the formula described later, the larger the storage modulus, the higher the elastic compliance s 11The electromechanical coupling coefficient k becomes smaller. 31 This increases. Therefore, the higher the storage modulus, the higher the conversion efficiency between electrical energy and mechanical energy. On the other hand, if the storage modulus is 10.0 GPa or less, the sensitivity to load when using a fluororesin piezoelectric film as a sensor does not decrease easily.

[0058] The storage modulus is measured in accordance with JIS K7244-4:1999 (ISO 6721-4:1994), using a sample cut parallel to the slow axis in the in-plane birefringence of the piezoelectric film, with a length of 25 mm and a width of 3 mm, as the test specimen. If one side of the fluororesin piezoelectric film is 300 mm or longer, a rectangular area with sides of 300 mm is arbitrarily defined, and the test specimen is cut from the area including the intersection of the diagonals of this rectangular area. If both sides of the fluororesin piezoelectric film are 300 mm or longer, a square with sides of 300 mm is arbitrarily defined on the piezoelectric film, and the test specimen is cut according to the above method. Specifically, the storage modulus of the test specimen is measured using a TA Instruments RSA-III with a chuck distance of 15 mm, an initial load of 1.5 N, a frequency of 10 Hz, a strain of 0.1%, and a temperature of 23 °C, and the obtained value is defined as the storage modulus of the piezoelectric film.

[0059] Dielectric constant ε of fluororesin piezoelectric film 33 Preferably, the pressure is 60 pF / m to 150 pF / m, more preferably 80 pF / m to 140 pF / m, even more preferably 90 pF / m to 130 pF / m, particularly preferably 100 pF / m to 130 pF / m, and most preferably 110 pF / m to 130 pF / m.

[0060] Dielectric constant ε 33 The measurement is performed in accordance with JIS C2138:2007. Specifically, electrodes with a diameter of 19.5 mm are formed on both sides of a piezoelectric film by aluminum vapor deposition, and the relative permittivity is measured at room temperature, voltage of 1 V, and frequency of 1 kHz using an LCR meter manufactured by HIOKI Corporation. The obtained relative permittivity is then multiplied by the permittivity of vacuum (8.854 × 10⁻¹⁴). -12It is calculated by multiplying by F / m. Dielectric constant ε in the range including the center of the polarization surface of the fluororesin piezoelectric film (in the case of a rectangular piezoelectric material, the range including the intersection of the diagonals). 33 The dielectric constant ε of the fluororesin piezoelectric film is measured using the method described above, and the absolute value of that value is taken as the dielectric constant ε of the fluororesin piezoelectric film. 33 This shall be a representative value. If the length of one side of the fluororesin piezoelectric film is 300 mm or more, a rectangular area with sides of 300 mm shall be arbitrarily set, and the range including the intersection of the diagonals of the above rectangular area shall be measured. If both sides of the fluororesin piezoelectric film are 300 mm or more, a square with sides of 300 mm shall be arbitrarily set on the piezoelectric film, and the measurement range shall be set according to the above method.

[0061] Furthermore, the electromechanical coupling coefficient k of fluororesin piezoelectric films. 31 k is preferably 0.14 or higher, more preferably 0.16 to 0.40, even more preferably 0.17 to 0.35, and particularly preferably 0.18 to 0.30. 31 The higher the value of k, the higher the conversion efficiency between electrical and mechanical energy. On the other hand, the electromechanical coupling coefficient k 31 By setting this value to 0.40 or less, it becomes unnecessary to increase the stretching ratio and polarization voltage during the manufacturing of fluorine-based piezoelectric films, and the haze of the film is less likely to increase during film formation.

[0062] Electromechanical coupling coefficient k 31 The piezoelectric constant d 31 , dielectric constant ε 33 , and elastic compliances 11 The elastic compliance s is calculated using the following formula. 11 Let be the reciprocal of the storage modulus.

[0063]

number

[0064] The thickness of the fluororesin piezoelectric film is not particularly limited, but is preferably 10 μm to 200 μm, more preferably 20 μm to 80 μm, and even more preferably 30 μm to 80 μm. The thicker the film, the more advantageous it is in terms of insulation and mechanical properties. The thinner the film, the more advantageous it is in terms of optical properties such as transparency and cost.

[0065] The thickness of fluororesin piezoelectric films is generally measured using a micrometer (JIS C 2151:2019), but it can also be measured using known methods such as a laser displacement meter, a capacitance displacement meter, or infrared light. Specifically, the thickness of a 20mm x 20mm section of film cut from the area including the intersection of the diagonals of the fluororesin piezoelectric film is measured, and this value is taken as a representative value of the thickness of the fluororesin piezoelectric film. If the length of one side of the piezoelectric film is 300mm or more, a rectangle with sides of 300mm is arbitrarily assumed, and the thickness of a 20mm x 20mm section of film cut from the area including the intersection of the diagonals of the rectangular film is measured. If both sides of the piezoelectric film are 300mm or more, a square with sides of 300mm is arbitrarily set on the piezoelectric film, and the measurement range is set according to the method described above.

[0066] Fluorine-based piezoelectric film has a minimum size of 100 μm, and the number of foreign objects is 7 per 0.25 m when viewed from above. 2 The following is the result: 0 pieces / 0.25m 2 More than 5 pieces / 0.25m 2 The following is preferable: 0 pieces / 0.25m 2 More than 3 pieces / 0.25m 2 The following are more preferable: 0 pieces / 0.25m 2 More than 1 piece / 0.25m 2 The following are even more preferable.

[0067] The fluororesin piezoelectric film has zero foreign particles larger than 200 μm in size when viewed from above. 2 More than 3 pieces / 0.25m 2 The following is preferable: 0 pieces / 0.25m 2More than 2 pieces / 0.25m 2 The following are more preferable: 0 pieces / 0.25m 2 More than 1 piece / 0.25m 2 The following is even more preferable: 0 pieces / 0.25m 2 That is particularly preferable.

[0068] Fluorine-based piezoelectric film has a minimum number of foreign particles (less than 100 μm in size) per 0.25 m² when viewed from above. 2 More than 50 pieces / 0.25m 2 The following is preferable: 0 pieces / 0.25m 2 More than 25 pieces / 0.25m 2 The following are more preferable: 0 pieces / 0.25m 2 More than 16 pieces / 0.25m 2 The following are even more preferable.

[0069] The fewer these impurities there are, the better the transparency of the fluororesin piezoelectric film can be, and the more uniform the stretching and polarization processes can be during the manufacturing process of the fluororesin piezoelectric film. The number of impurities can be reduced by filtering the molten fluororesin during film manufacturing.

[0070] The number of these foreign objects is determined by cutting out four rectangular pieces of film (observation pieces) from the fluororesin piezoelectric film so that they are adjacent to each other, and then summing the number of foreign objects measured from each of these observation pieces. Specifically, the pieces are cut out in a position that is adjacent to each other from the fluororesin piezoelectric film, with a length of 0.010 m. 2 Four observation pieces measuring (100mm x 100mm) are cut out. Then, the sum of the number of foreign objects measured from each observation piece is calculated, and this sum of foreign object counts is multiplied by 25 / 4 and rounded to the first decimal place to obtain 0.25m. 2 This is the number of foreign objects per sample. At this time, the foreign objects are observed using transmitted light and marked, and the size of the foreign object is determined by observing the marked area under a microscope. The size of the foreign object is the arithmetic mean of the maximum and minimum widths of the foreign object.

[0071] The fluororesin piezoelectric film preferably has a melt viscosity of 600 Pa·s to 4000 Pa·s, more preferably 600 Pa·s to 3500 Pa·s, even more preferably 600 Pa·s to 2400 Pa·s, particularly preferably 600 Pa·s to 2000 Pa·s, and very preferably 600 Pa·s to 1500 Pa·s.

[0072] [Application] The fluororesin piezoelectric film described above can be used in various applications such as piezoelectric films for touch sensors and touch panels, actuators, protective films, and phase difference films.

[0073] [Other embodiments] It should be noted that the embodiments described above are exemplary embodiments of the present invention, and it goes without saying that the present invention may include embodiments other than those described above within the scope of its core technical concept. [Examples]

[0074] The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

[0075] 1. Fabrication of piezoelectric film Piezoelectric films 1 to 8 were fabricated using the following procedure.

[0076] The melt viscosity of the resin composition used as raw material was measured in accordance with ASTM D 3835:2016 (ISO 11443:2021, JIS K 7199:1999). Specifically, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and a capillary die with an inner diameter of 1 mmφ and a tube length of 10 mm was used, at a measurement temperature of 260°C and a shear rate of 50 s. -1 The viscosity was measured using [a specific method / tool].

[0077] The melting point of the resin composition was measured in accordance with JIS K 7121:1987. Specifically, the melting point of the resin composition was determined by placing a 5 mg sample in an aluminum pan and setting it in a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Under a nitrogen atmosphere, the temperature was raised from room temperature to 230°C at a heating rate of 10°C / min. The maximum melting peak temperature in the resulting DSC curve was defined as the melting point of the resin composition.

[0078] The melting temperature was defined as the highest temperature in the conduit from the extruder to the filtration device.

[0079] 1-1. Piezoelectric film 1 A PVDF with a melt viscosity of 2500 Pa·s and a melting point (mp) of 173°C was melted using a single-screw extruder with a diameter of φ35 mm to a melting temperature of 270°C (mp + 97°C). The molten resin was then extruded into a film using a T-die and brought into contact with a cooling roll at 110°C to obtain a fluoropolymer resin film with a thickness of 150 μm, a width of 240 mm, and a length exceeding 10,000 mm.

[0080] The fluororesin film was stretched to a predetermined magnification by adjusting the rotation speed of the take-up metal roll relative to the rotation speed of the feed-side metal roll using a multi-stage uniaxial stretching apparatus equipped with multiple metal rolls and pinch rolls. In the first stage of stretching, the film was stretched to a magnification of 4.0 times at a stretching temperature of 130°C, and in the second stage of stretching, it was stretched to a magnification of 1.25 times at a stretching temperature of 145°C. The total magnification (product of the magnification of the first stage and the magnification of the second stage) was 5.0 times. Polarization treatment was performed on the feed-side metal roll during the first stage of stretching. The feed-side metal roll was heated to 130°C, and a DC voltage of 13.5kV was applied to multiple needle electrodes positioned 10 mm away from the surface of the metal roll. By discharging from the needle electrodes towards the metal roll, the fluororesin film passing between the metal roll and the needle electrodes was polarized. The polarization time, determined from the time it took for the film to pass through the space between the needle electrode and the metal roll, was 5 seconds. In this way, a piezoelectric film 1 with a thickness of 40 μm and a length of over 5000 mm was obtained.

[0081] 1-2. Piezoelectric film 2 Piezoelectric film 2 was obtained in the same manner as the preparation of piezoelectric film 1, except that the applied voltage during polarization treatment was set to 15.0 kV.

[0082] 1-3. Piezoelectric film 3 Piezoelectric film 3 was obtained in the same manner as the preparation of piezoelectric film 1, except that the applied voltage during the polarization treatment was set to 17.0 kV.

[0083] 1-4. Piezoelectric film 4 Piezoelectric film 4 was obtained in the same manner as the preparation of piezoelectric film 3, except that the second stage of stretching was performed at a stretching temperature of 140°C and the stretching ratio was 1.18 times.

[0084] 1-5. Piezoelectric film 5 A fluororesin film that had been stretched and prepared in the same manner as the piezoelectric film 1, except for the polarization treatment, was subjected to the following polarization treatment. A polarization metal roll was placed behind the second stage take-up metal roll of the uniaxial stretching apparatus used to prepare piezoelectric film 1, and multiple needle electrodes were placed 10 mm away from the surface of the polarization metal roll. The surface temperature of the polarization metal roll was heated to 90°C, a DC voltage of 13.5 kV was applied to the needle electrodes, and the stretched fluororesin film was passed between the metal roll and the needle electrodes while a discharge was performed from the needle electrodes toward the polarization metal roll, thereby performing the polarization treatment. The polarization time, determined from the time it took for the film to pass through the space between the needle electrodes and the metal roll, was 5 seconds. In this way, a piezoelectric film 5 with a thickness of 39 μm and a length of over 5000 mm was obtained.

[0085] 1-6. Piezoelectric film 6 Piezoelectric film 6 was obtained in the same manner as the preparation of piezoelectric film 1, except that the temperature of the first-stage feed metal roll was heated to 90°C, the first-stage stretching process was performed at a stretching temperature of 90°C and a stretching ratio of 4.0 times, the second-stage stretching process was omitted, and the polarization temperature was set to 90°C.

[0086] 1-7. Piezoelectric film 7 Piezoelectric film 7 was obtained in the same manner as the preparation of piezoelectric film 1, except that the second stretching process was omitted.

[0087] 1-8. Piezoelectric film 8 PVDF with a melt viscosity of 2500 Pa·s and a melting point (mp) of 173°C was melted to a melting temperature of 270°C (mp + 97°C) using a single-screw extruder with a diameter of φ35 mm. The molten resin was then extruded into a film using a T-die and brought into contact with a cooling roll at 110°C to obtain a fluororesin film with a thickness of 40 μm, a width of 240 mm, and a length of 5000 mm. The obtained film was cut into a square with sides of 120 mm and placed on a grounded 120 mm × 120 mm metal plate electrode. Multiple needle electrodes were positioned 10 mm away from the surface of the metal plate electrode. A DC voltage of 10 kV was applied to the needle electrodes at 25°C for 5 minutes to perform polarization treatment and obtain a piezoelectric film 8 with a width of 120 mm, a length of 120 mm, and a thickness of 40 μm.

[0088] 2. Evaluation of piezoelectric films Piezoelectric films 1 to 8 were left to stand at room temperature for 14 days after manufacturing before being subjected to characterization. For piezoelectric films 1 to 7, unless otherwise specified, the following measurements were performed on the area including the intersection of the diagonals of a rectangle cut out of the piezoelectric film, with dimensions of 100 mm in the TD direction and 300 mm in the MD direction, including the center of the manufactured piezoelectric film in the TD direction. The results obtained were used as representative values ​​for that piezoelectric film. For piezoelectric film 8, the following measurements were performed on the area including the intersection of the diagonals of a manufactured film with a width of 120 mm and a length of 120 mm. The results obtained were used as representative values ​​for that piezoelectric film.

[0089] 2-1. Retardation Using a KOBRA-HB measuring instrument manufactured by Oji Instruments, the retardation of a 20mm x 20mm section of film, cut from the area including the intersection of the diagonals of the rectangular film, was measured using the parallel nicol rotation method. The value at a measured wavelength of 589.1nm was defined as the retardation of the film. The lagging axis was determined from the in-plane birefringence of the film.

[0090] 2-2. Piezoelectric constant d 31 Piezoelectric constant d by static method 31 The following measurements were taken. Specifically, Al-deposited electrodes were formed on both sides of each piezoelectric film, and rectangular samples with a length of 60 mm parallel to the slow phase axis detected by in-plane birefringence of the film during retardation measurement and a width of 10 mm perpendicular to the slow phase axis were cut out as test specimens from the area including the intersection of the diagonals of the rectangular film with electrodes. The slow phase axis was identified during retardation measurement. Next, the test specimens were placed on a tensile testing machine with a chuck distance of 50 mm, and the amount of induced charge Q was measured using an electrometer when the test specimens were stretched with a force F in the longitudinal direction (slow phase axis direction) at a tensile speed of 10 mm / min at room temperature. The relationship between different forces F(N) and the amount of induced charge Q(pC) for each was measured at 128 points, and the force F(N) was plotted on the horizontal axis and the amount of induced charge Q(pC) on the vertical axis, and the slope (pC / N) of the generated charge Q(pC) with respect to the force F(N) was determined by the least squares method. Piezoelectric constant d 31 This was obtained using Equation 1.

[0091]

number

[0092] 2-3. Internal haze The internal haze of the piezoelectric film was determined by filling in scratches and other irregularities with silicone oil to eliminate the influence of external haze, and then measuring the haze in the area including the center of the piezoelectric film according to ISO 14782:1999. The haze was measured using a turbidimeter (NDH2000, manufactured by Nippon Denshoku Industries Ltd.) to measure the haze at three different points within the sample, and the arithmetic mean of the three points was calculated as the haze value of the sample. Specifically, silicone oil (Nikon, MXA22179) was placed between two glass plates (thickness: 0.15 mm, flatness: 0.01 mm or less), and the haze (H2) caused by the glass plates and silicone oil was measured. Next, a rectangular film was cut to 50mm x 50mm so as to include the intersection of the diagonals of the above rectangular film. Both sides of the rectangular film were uniformly wet with the above silicone oil, and the haze (H3) was measured by sandwiching it between the two glass plates. The internal haze (H1) of the film was obtained by subtracting H2 from H3 (using the formula below). H1 = H3 - H2

[0093] 2-4. Storage modulus From the area including the intersection of the diagonals of the rectangular film described above, a sample measuring 25 mm in length and 3 mm in width was cut parallel to the slow axis in the in-plane birefringence of the film to serve as a test specimen. The storage modulus of the piezoelectric film was measured using a TA Instruments RSA-III with a chuck distance of 15 mm, an initial load of 1.5 N, a frequency of 10 Hz, a strain of 0.1%, and a temperature of 23 °C.

[0094] 2-5. Dielectric constant ε 33 Electrodes with a diameter of 19.5 mm were formed on both sides of a piezoelectric film by aluminum vapor deposition, and the relative permittivity was measured at room temperature, voltage of 1 V, and frequency of 1 kHz using an LCR meter manufactured by HIOKI Corporation. The obtained relative permittivity was multiplied by the permittivity of vacuum (8.854 × 10⁻⁴). -12 Multiply by F / m to obtain the dielectric constant ε 33 The result was calculated.

[0095] 2-6. Electromechanical coupling coefficient k 31 Piezoelectric constant d 31 , dielectric constant ε 33 , and elastic compliances11 Using the following formula, the electromechanical coupling coefficient k of the film 31 The elastic compliance was calculated. 11 The reciprocal of the storage modulus was used as the value.

[0096]

number

[0097] 3.Results Table 1 shows the production conditions for each film, and Table 2 shows the evaluation results for each.

[0098] [Table 1]

[0099] [Table 2] [Industrial applicability]

[0100] The fluororesin piezoelectric film produced by the manufacturing method of the present invention is useful as a piezoelectric film having high piezoelectricity and high transparency.

Claims

1. A first stretching step in which a fluororesin film is stretched to a length of 3.0 to 5.0 times at a temperature of 110°C or higher but less than 150°C (T1), Following the first stretching step, a second stretching step is performed in which the fluororesin film is stretched to a length of 1.1 to 2.0 times in the same direction as the stretching direction in the first stretching step at a temperature of T1 + 5°C or higher and less than 186°C (T2), The process includes a polarization step, performed simultaneously with or after the first stretching step, in which a voltage of 5 kV to 30 kV is applied at a temperature of 50°C to less than 150°C to polarize the fluororesin film. Piezoelectric constant d ３１ A method for manufacturing a fluororesin piezoelectric film, wherein the density is 20 pC / N or more and 50 pC / N or less, and the retardation is 100 nm or more and 3000 nm or less.

2. The method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein the polarization step is performed after the second stretching step.

3. The method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein the polarization step is performed before the second stretching step.

4. The method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein the polarization step is performed simultaneously with the second stretching step.

5. The method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein the polarization step is performed simultaneously with the first stretching step.

6. A method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein the first stretching step, the second stretching step, and the polarization step are all performed while conveying the fluororesin film.

7. The method for producing a fluororesin piezoelectric film according to claim 1, wherein the fluororesin film mainly consists of vinylidene fluoride resin.

8. Before the first stretching step, A step of heating and melting a resin composition containing a fluororesin, The process includes a step of forming a film from the heated and melted resin composition. A method for producing a fluororesin piezoelectric film according to claim 1.

9. The aforementioned resin composition was measured at a temperature of 260°C and a shear rate of 50 s. －１ A method for producing a fluororesin piezoelectric film according to claim 8, wherein the melt viscosity η measured is 600 Pa·s or more and 4000 Pa·s or less.

10. A method for manufacturing a fluororesin piezoelectric film according to claim 1, wherein at least one of the first stretching step, the second stretching step, and the polarization step is performed using a roll-to-roll method.

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