JP6467217B2 - Piezoelectric vibration sensor - Google Patents

Description

  The present invention relates to a piezoelectric vibration sensor for measuring biological signals.

  In recent years, with the aging of society and heightened health consciousness, in daily life, the biomedical signal such as pulse wave and respiration is measured with a sensor and digitized, and the health condition is grasped by the numerical value. Has been done.

For example, among the biological signals, the pulse wave is one of the biological signals indicating the propagation of the wave generated by the cardiac contraction, and reflects the heart beat interval and the blood vessel state.
As a method for detecting this pulse wave, a method using a piezoelectric element, a method for optical detection, and the like have been put into practical use. As a method of using a piezoelectric element, a piezo-type piezoelectric element is placed on an artery as a sensor, and a pulse wave or a pulse rate is detected from the pressure change of the epidermis (displacement of the epidermis due to pressure) accompanying the pressure change inside the artery. ing.

  However, with the conventional method of detecting pulse waves, measurement is not possible unless the sensor is pressed strongly against the subject, and accurate measurement is not possible due to fluctuations in body temperature and outside air temperature. It was.

  With regard to the above problem, Patent Document 1 discloses a specific piezoelectric element including a piezoelectric sensor, a foam sheet laminated and integrated on one surface of the piezoelectric sensor, and a shape retaining plate laminated and integrated on the other surface of the piezoelectric sensor. A vibration sensor is disclosed.

JP 2014-147571 A

However, the conventional piezoelectric vibration sensor has a room for further improvement in that it easily detects noise due to the influence of electromagnetic waves emitted from an external environment or a living body and measures a biological signal with high sensitivity.
The present invention has been made in view of such problems, and an object of the present invention is to provide a piezoelectric vibration sensor that is difficult to detect noise and can measure a biological signal with high sensitivity.

Under such circumstances, the present inventors have intensively studied to solve the above-mentioned problems. As a result, the inventors have found that the object can be achieved by the piezoelectric vibration sensor having the following configuration, thereby completing the present invention. It came.
A configuration example of the present invention is as follows.

[1] A shield layer A, an electrode layer, a piezoelectric layer including a porous fluororesin layer, an electrode layer, and a shield layer B are laminated in this order,
The shield layers A and B each include an insulating layer and a conductive layer, and the insulating layer exists on the electrode layer side of the conductive layer.
Piezoelectric vibration sensor for measuring biological signals.

  [2] The compressive strength of the shield layer A is greater than the compressive strength of the shield layer A (note that the compressive strength is measured in accordance with JIS K 7181 (2011)), [1] The piezoelectric vibration sensor as described.

[3] The piezoelectric device according to [1] or [2], wherein the capacitance of the shield layer A and the capacitance of the shield layer B measured by the Faraday gauge method satisfy the following requirement (I): Vibration sensor.
Requirement (I): Among the electrostatic capacities of the shield layers A and B, when one of the capacities is Ci and the other is Cii, Ci and Cii satisfy Ci ≧ Cii. If there is a relationship, the difference rate of the capacitance calculated by the following formula (1) is 50% or less. The difference rate of the capacitance = | Ci−Cii | / Ci × 100 (%) (1) )

  [4] The piezoelectric vibration sensor according to any one of [1] to [3], further including an insulating layer on at least a part of the shield layer A and / or the shield layer B opposite to the electrode layer side.

[5] The piezoelectric vibration sensor according to any one of [1] to [4], wherein the porous fluororesin layer is made of a resin having no dipole due to a molecule and a crystal structure.
[6] The piezoelectric vibration sensor according to any one of [1] to [5], wherein the porous fluororesin layer includes a nonwoven fabric or a woven fabric formed from a fiber made of a fluororesin.
[7] The piezoelectric vibration sensor according to any one of [1] to [6], wherein the fluororesin is polytetrafluoroethylene.

  [8] The piezoelectric vibration sensor according to any one of [1] to [7], wherein the porous fluororesin layer or the piezoelectric layer is polarized.

[9] A shield layer A, an electrode layer, a piezoelectric layer including a porous fluororesin layer, an electrode layer, and a shield layer B are laminated in this order,
The capacitance of the shield layer A and the capacitance of the shield layer B measured by the Faraday gauge method satisfy the following requirement (I):
Piezoelectric vibration sensor for measuring biological signals.
Requirement (I): Among the electrostatic capacities of the shield layers A and B, when one of the capacities is Ci and the other is Cii, Ci and Cii satisfy Ci ≧ Cii. If there is a relationship, the difference rate of the capacitance calculated by the following formula (1) is 50% or less. The difference rate of the capacitance = | Ci−Cii | / Ci × 100 (%) (1) )

According to the present invention, it is possible to provide a piezoelectric vibration sensor that is difficult to detect noise and can measure a biological signal with high sensitivity.
In particular, according to the present invention, it is excellent in shape followability according to the measurement site, noise from the measurement target such as the human body and the external environment, noise due to the sensor configuration is reduced, and a weak biological body such as a pulse wave is reduced. Piezoelectric vibration sensor that can detect signals with high accuracy, is portable, and can easily measure biological signals without having to press the sensor strongly against the measurement target, regardless of the measurement location. Can be provided.

FIG. 1 shows an oscilloscope waveform (pulse wave form) in which vibration generated by pulsation of a wrist artery is detected as an electrical signal using the piezoelectric vibration sensor manufactured in Example 1. FIG. 2 is an oscilloscope waveform in which vibration generated by pulsation of the wrist artery is detected as an electrical signal using the piezoelectric vibration sensor manufactured in Comparative Example 1.

≪Piezoelectric vibration sensor≫
The piezoelectric vibration sensor for measuring a biological signal of the present invention is a sensor for detecting a biological signal such as a pulse wave and a breath, particularly a pulse wave,
(1) A shield layer A, an electrode layer, a piezoelectric layer including a porous fluororesin layer, an electrode layer and a shield layer B are laminated in this order, and the shield layers A and B each include an insulating layer and a conductive layer. The insulating layer is present on the electrode layer side of the conductive layer, or
(2) The shield layer A, the electrode layer, the piezoelectric layer including the porous fluororesin layer, the electrode layer, and the shield layer B are laminated in this order, and the capacitance of the shield layer A measured by the Faraday gauge method The electrostatic capacity of the shield layer B satisfies the following requirement (I).
Requirement (I): Among the electrostatic capacities of the shield layers A and B, when one of the capacities is Ci and the other is Cii, Ci and Cii satisfy Ci ≧ Cii. If there is a relationship, the difference rate of the capacitance calculated by the following formula (1) is 50% or less. The difference rate of the capacitance = | Ci−Cii | / Ci × 100 (%) (1) )

  Since the piezoelectric vibration sensor of the present invention has such a configuration, noise derived from the measurement target such as a human body and the external environment, noise due to the sensor configuration is reduced, and weak biological signals such as pulse waves are generated. Piezoelectric vibration sensor that can be detected with high accuracy, can be carried, and can easily measure weak biological signals without having to press the sensor strongly against the object to be measured, regardless of the measurement location. Can be provided.

The piezoelectric vibration sensor of the present invention is not particularly limited as long as it has a shield layer A, an electrode layer, a piezoelectric layer including a porous fluororesin layer, an electrode layer, and a shield layer B in this order. Etc. may exist. For example, in the piezoelectric vibration sensor of the present invention, a known layer conventionally used for a piezoelectric vibration sensor, for example, an insulating layer, is provided between the piezoelectric layer and the electrode layer, on the side opposite to the electrode layer side of the shield layer. A surface smoothing layer, a protective layer, and an adhesive layer may be present.
When two or more of these conventionally known layers are included in the piezoelectric vibration sensor of the present invention, they may be the same layer or different layers.

  The piezoelectric vibration sensor of the present invention is opposite to the electrode layer side of the shield layer A and / or the shield layer B from the point that noise derived from the measurement target such as a human body and the external environment is further reduced. It is preferable to have an insulating layer on at least a part of the side, noise from the measurement target such as a human body and the external environment is further reduced, and weak biological signals such as pulse waves can be detected more accurately. From this point, it is preferable that the insulating layer, the shield layer A, the electrode layer, the piezoelectric layer, the electrode layer, the shield layer B, and the insulating layer are stacked in this order. An adhesive layer may be present between the layers of these laminates, and the insulating layer that is the outermost layer of these laminates also functions as a protective layer or the like.

  Furthermore, the piezoelectric vibration sensor of the present invention includes a conductive wire connected to an electrode layer, an amplification unit such as a charge amplifier that amplifies a signal from the conductive wire, an information processing unit that processes a signal output from the conductive wire or the amplification unit, You may have a display part etc. which display the processed information.

For example, if the piezoelectric vibration sensor of the present invention is attached to a site where a blood vessel of a human body exists, vibration from the measurement target caused by a contraction movement of a blood vessel of the living body as the measurement target is transmitted to the piezoelectric layer, Stress is applied inside the piezoelectric layer. The charge generation amount of the porous fluororesin layer also changes in accordance with the change in stress applied to the piezoelectric layer, and as a result, the potential difference generated between the electrodes existing on the front and back surfaces of the piezoelectric layer changes.
By detecting this change in potential difference through, for example, a conducting wire connected to the electrode, and further amplifying it through a circuit such as a charge amplifier, it becomes possible to output a voltage, and a pulse wave signal can be output. It is also possible to obtain a pulse.

  The thickness of the piezoelectric vibration sensor of the present invention may be appropriately selected according to the desired application, but is preferably such a thickness that has a shape following property corresponding to the measurement site, for example, 20 μm to 20 mm. The thickness is preferably 100 μm to 5 mm. In particular, when the wrist of a human body is the object to be measured, the thickness is preferably flexible enough to allow the wrist to be appropriately pressed without a sense of incongruity, and such thickness is preferably 100 μm to 3 mm. Is mentioned.

<Shield layers A and B>
The piezoelectric vibration sensor of the present invention has shield layers A and B on both sides of the electrode layer.
By having such a shield layer, noise derived from the measurement target such as the human body and the external environment can be reduced, and a biological signal such as a pulse wave can be detected with high accuracy. In this case, a piezoelectric vibration sensor that can measure a weak biological signal without pressing the sensor strongly against the object to be measured can be easily obtained.

  The shield layers A and B may be the same layer or different layers, but are preferably different layers having the following physical properties. In the present invention, the shield layers A and B are collectively referred to simply as a “shield layer”.

In the piezoelectric vibration sensor of the present invention, when the shield layer A is on the measurement target side and the shield layer B is on the external environment side, a biological signal such as a pulse wave is transmitted to the piezoelectric layer without being absorbed or attenuated. It is easy to use, has excellent shape followability according to the measurement site, and can efficiently remove noise such as impact from the external environment, so that the compressive strength of the shield layer B is better than the compressive strength of the shield layer A. It is preferable that it is large, and specifically, it is more preferable that the ratio of the following compression strength is in the following range. The ratio of the compressive strength of the shield layer B to the compressive strength of the shield layer A (compressive strength of the shield layer B / compressive strength of the shield layer A) is preferably 1.2 to 50, more preferably 1 0.5 to 20, more preferably 2 to 10.
The compressive strength of the shield layer can be measured by the method described in the following examples.
Further, the compressive strength of the shield layer can be adjusted by adjusting the material used for each shield layer and the thickness of the layers constituting each shield layer.

It is preferable that the electrostatic capacity of the shield layer A and the electrostatic capacity of the shield layer B satisfy the following requirement (I).
Requirement (I): Among the electrostatic capacities of the shield layers A and B, when one of the capacities is Ci and the other is Cii, Ci and Cii satisfy Ci ≧ Cii. When there is a relationship, the rate of difference in capacitance calculated by the following formula (1) is preferably 50% or less, and more preferably 20% or less.
Dissimilarity ratio of capacitance = | Ci−Cii | / Ci × 100 (%) (1)

The relationship between the electrostatic capacities of the shield layers A and B being in the above range indicates that the electrostatic capacities of the shield layer A and the shield layer B are substantially equal. By using A and B, noise caused by the sensor configuration, specifically, noise caused by charge movement caused by a difference in the ease of holding charges between the shield layers is reduced, and weak waves such as pulse waves are reduced. Biological signals can be detected with higher accuracy. If the absolute value of the difference in capacitance is out of the above range, charge transfer may occur between the shield layers A and B, and noise may be generated. In the conventional piezoelectric vibration sensor, the configuration on both sides of the electrode layer, specifically, the electrostatic capacitance based on the configuration is asymmetrical. Therefore, charge movement inside the piezoelectric vibration sensor due to the non-target causes noise. It was.
The capacitance of the shield layer can be measured by the method described in the following examples.
Moreover, the electrostatic capacitance of a shield layer can be adjusted by adjusting the material which comprises each shield layer, the area of a laminated surface, and the thickness of a layer.

The shape of the shield layer may be appropriately selected according to the application to be used, but is preferably a sheet from the viewpoint of ease of production, biosignal detection, and the like.
When the shield layers A and B are in the form of a sheet, the thickness of each layer may be adjusted as appropriate according to the application to be used, and is not particularly limited, but has shape followability according to the measurement site. The thickness is preferably, for example, 5 μm to 10 mm, and preferably 10 μm to 3 mm.

  When the shield layer is in the form of a sheet, the area (the area on the side laminated with the electrode layer, or the area in the direction substantially perpendicular to the lamination direction when the shield layer is the following laminate) is larger than that of the piezoelectric layer. It is preferable. When the shield layer has such an area, it prevents leakage of electric charges generated in the piezoelectric layer and prevents the piezoelectric layer from coming into contact with the object to be measured. A piezoelectric vibration sensor can be obtained in which noise from the external environment hardly affects the piezoelectric layer.

The shield layer includes an insulating layer and a conductive layer in that noise from a measurement target such as a human body and the external environment is reduced, and weak biological signals such as pulse waves can be detected with high accuracy. Preferably, each of the insulating layers and the conductive layer is more preferably composed of only one insulating layer and a conductive layer, and more preferably a laminated body including the insulating layer on the electrode layer side of the conductive layer.
The piezoelectric vibration sensor of the present invention may include an insulating layer and a conductive layer other than the insulating layer and the conductive layer that constitute the shield layer. In this case, from the insulating layer and the conductive layer closest to the electrode layer. This layer is called a shield layer.

<Insulation layer>
The insulating layer is not particularly limited as long as it has insulating properties.
The insulating layer may be formed on the conductive layer or the electrode layer by a conventionally known method, or a pre-formed film may be used.

The shape, size, and thickness of the insulating layer are not particularly limited, and are preferably layers having a shape, size, and thickness so that the electrode layer and the conductive layer do not contact each other.
In the piezoelectric vibration sensor of the present invention, when the shield layer includes an insulating layer, the shield layer A is the measurement target side, and the shield layer B is the external environment side, the insulating layer included in the shield layer A is It is preferable that the thickness does not hinder the transmission of a biological signal such as a pulse wave from the measurement target.

  Examples of the material for forming the insulating layer include synthetic resin, synthetic fiber, and synthetic rubber, and preferably include polypropylene, polyethylene, polyethylene terephthalate, and fluororesin.

<Conductive layer>
The shield layer preferably includes a conductive layer. By including such a conductive layer together with an insulating layer, the piezoelectric layer is affected by noise such as electromagnetic waves derived from the measurement target such as a human body and the external environment. Therefore, it is possible to obtain a piezoelectric vibration sensor that can reduce noise and accurately detect a biological signal such as a pulse wave.
The shape, size, and thickness of the conductive layer may be appropriately selected according to a desired application, and are not particularly limited.
The conductive layer may be formed by a conventionally known method.

  The material constituting the conductive layer is not particularly limited as long as it has electrical conductivity, and examples thereof include the same materials as those exemplified as the material constituting the following electrode layer.

<Electrode layer>
The electrode layer is not particularly limited as long as it has electrical conductivity.
The shape, size, and thickness of the electrode layer may be appropriately selected according to a desired application, and are not particularly limited.
The piezoelectric vibration sensor of the present invention has an electrode layer between the piezoelectric layer and the shield layer A and between the piezoelectric layer and the shield layer B, thereby obtaining a sensor that can easily convert a biological signal into an electrical signal. it can.
What is necessary is just to form the said electrode layer on the insulating layer which may be contained in a piezoelectric layer and a shield layer by a conventionally well-known method.

The material constituting the electrode layer is not particularly limited, and examples thereof include metals (alloys), metal oxides, metal sulfides, conductive carbides, conductive polymers, and combinations thereof.
Metals (alloys), metal oxides, and metal sulfides include lithium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, antimony, tin, silver, gold, copper, nickel, palladium, platinum , Chromium, molybdenum, tungsten, manganese, cobalt, alloys thereof, oxides thereof, composite oxides thereof, and sulfides thereof. Particularly preferred are indium tin oxide (ITO), zinc oxide (ZnO), silver and the like.
Examples of the conductive carbide include carbon black, graphite, activated carbon, carbon fiber, single wall carbon nanotube (SWCNT), double wall carbon nanotube (DWCNT), multi-wall carbon nanotube (MWCNT), and carbon nanosheet (graphene sheet). .
Examples of the conductive polymer include poly (ethylene-3,4-dioxythiophene), polyaniline derivatives, polypyrrole derivatives, and the like.

<Piezoelectric layer>
The piezoelectric layer is not particularly limited as long as it includes a porous fluororesin layer, and may include a conventionally known layer. The piezoelectric layer may include one porous fluororesin layer. The piezoelectric layer may include two or more porous fluororesin layers having different layers, porous shape, porosity, thickness, and the like in the layer. May be included. The porous fluororesin layer to be used may have voids other than the porous pores inside or on the surface, and when two or more porous fluororesin layers are included, voids between these layers You may have.
In addition, the porous fluororesin layer in the present invention is not only a layer obtained by using a porous fluororesin layer, but also two or more non-porous fluororesin layers (inside or on the surface of the porous fluororesin layer) It may be a laminate obtained by laminating a void other than the pores that may be formed) so as to have a void between layers.

The piezoelectric layer is a laminate in which a surface coating layer is laminated on at least one surface of the porous fluororesin layer in order to obtain a piezoelectric layer that retains electric charge for a long time and retains a high piezoelectric rate. The body is preferred.
The piezoelectric layer may have an intermediate layer between the porous fluororesin layer and the surface coating layer.
Each of the surface coating layer, the intermediate layer, and the conventionally known layer may be included in the piezoelectric layer, or two or more layers having different components and thickness may be included. .

The shape of the piezoelectric layer may be appropriately selected according to the application to be used, but is preferably a sheet from the viewpoints of manufacturability and biosignal detection.
In the case where the piezoelectric layer is in the form of a sheet, the thickness thereof may be appropriately adjusted according to the application to be used, and is not particularly limited, but is, for example, 10 μm to 10 mm, and preferably 50 μm to 5 mm.

When the piezoelectric layer is in the form of a sheet, if the area (the area on the side laminated with the shield layer) is small, the sensitivity of the piezoelectric vibration sensor may easily vary. Since voltage may fall and it may become difficult to detect a weak biological signal, 1 to 3000 cm ² is preferable, and 4 to 1000 cm ² is more preferable.

<Porous fluororesin layer>
In the piezoelectric vibration sensor of the present invention, the porous fluororesin layer is used as a piezoelectric material and plays a role of detecting a biological signal by converting a biological signal such as a pulse wave into electric power.
The porous fluororesin layer has high charge responsiveness to minute stress and high biosignal detection ability. By using this porous fluororesin layer, it has excellent biosignal detection ability and high flexibility. It is possible to obtain a piezoelectric vibration sensor that is excellent in shape followability according to a part, excellent in impact resistance, and lightweight. Furthermore, since the porous fluororesin layer can be easily formed into an arbitrary shape such as a thin film or a large area, a piezoelectric vibration sensor having an arbitrary shape can be manufactured according to a desired application. For example, it is considered that the sensitivity to micro-stress such as a biological signal is increased by increasing the micro-stress transmissibility in the porous fluororesin layer by the thinning.

  The fluororesin is not particularly limited, but polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene. -Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc. are mentioned.

  The fluororesin is preferably a resin capable of holding a charge, and particularly has no dipole due to the molecular and crystal structure from the viewpoint of being hardly affected by fluctuations in body temperature, outside temperature, and the like. A resin is preferred.

  The resin having no dipole due to the molecule and crystal structure is not particularly limited as long as the molecule and crystal structure are not polar resins, and examples thereof include PTFE, PFA, and FEP.

  In particular, when PTFE is used as the resin, it is possible to obtain a piezoelectric vibration sensor that is excellent in balance in biosignal detection ability, water resistance and durability, and is hardly affected by fluctuations in body temperature, outside air temperature, and the like.

The porous fluororesin layer may contain conventionally known additives in addition to the fluororesin as long as the effects of the present invention are not impaired.
For example, as the porous fluororesin layer, a matrix resin and charge-induced hollow particles (particles in which a conductive substance is attached to at least a part of the surface of the hollow particles are used from the viewpoint that a high piezoelectricity can be maintained for a long time. ).

The porosity calculated by the following formula is preferably 20% or more, more preferably 60% or more, and further preferably 80 to 99%. A porous fluororesin layer having a porosity in the above range is preferable because of a high charge retention amount.
Porosity = (true resin density−apparent density) × 100 / true resin density

The shape of the porous fluororesin layer may be appropriately selected according to the application to be used, but is preferably a sheet from the viewpoint of ease of production, biosignal detection and the like.
When the porous fluororesin layer is in the form of a sheet, the thickness is not particularly limited, but is, for example, 1 μm to 1 mm, preferably 10 μm to 500 μm.

  The porous fluororesin layer can be obtained by various conventionally known methods. For example, a method of forming a molded body having pores by utilizing the phase change of the solution containing the fluororesin (phase separation method), an additive for pore formation is mixed and dispersed in the fluororesin, and molding is performed. A method of removing pores later (extraction method), a method of forming pores by molding the fluororesin and then chemically cleaving a part of the molded body or conversely performing a binding reaction (chemical treatment method) ), Preparing a plurality of fluororesin sheets and laminating them so that there are gaps between the sheets (lamination method), stretching the fluororesin and forming micropores in the microfibril structure, or mixing additives Dispersing and forming pores at the time of stretching (stretching method), neutron beam, laser, etc. to form pores (irradiation etching method), fluororesin fine pieces fused by heating, etc. A method for forming a material (melt Method), a method of forming pores using a foaming agent (foaming method), a method of forming pores by combining the above methods (composite method), dry spinning, wet spinning, dry-wet spinning, melt spinning, Examples thereof include a method of forming a fiber (fiber) from the fluororesin by electrospinning or the like, and forming a woven fabric or a non-woven fabric using the fiber.

  The porous fluororesin layer is preferably a structure including a nonwoven fabric or a woven fabric formed from fibers made of a fluororesin from the viewpoint of durability and the ability to maintain deformation performance over a long period of time. The structure may include the non-woven fabric or woven fabric, or may be a structure made of only the non-woven fabric or woven fabric, or a laminate in which a conventionally known layer is laminated on the surface of the non-woven fabric or woven fabric. Also good.

  The average fiber diameter of the fiber is preferably 0.05 to 50 μm, more preferably 0.1 to 20 μm, and still more preferably 0.5 μm to 5 μm. The porous fluororesin layer containing fibers having an average fiber diameter within the above range can form a sufficient space for holding electric charges by increasing the fiber surface area, and even if it is made into a thin film, the fiber distribution uniformity is increased. It is preferable in that it can be used.

  The average fiber diameter can be adjusted by appropriately selecting the conditions for forming the fiber.For example, when the fiber is formed by electrospinning, the humidity is reduced during electrospinning, and the nozzle diameter is adjusted. There is a tendency that the average fiber diameter of the obtained fiber can be reduced by decreasing the voltage, increasing the applied voltage, or increasing the voltage density.

  The average fiber diameter was determined by observing the fiber (group) to be measured with a scanning electron microscope (SEM) (magnification: 10000 times), and randomly selecting 20 fibers from the obtained SEM image. The fiber diameter (major diameter) of each fiber is measured, and is an average value calculated based on the measurement result.

The fiber diameter variation coefficient calculated by the following formula of the fiber is preferably 0.7 or less, more preferably 0.01 to 0.5. When the fiber diameter variation coefficient is within the above range, the fiber has a uniform fiber diameter, and the nonwoven fabric obtained by using the fiber has a higher porosity, and has a porous fluorine resin layer with high charge retention. Is preferable.
Fiber diameter variation coefficient = standard deviation / average fiber diameter

  The fiber length of the fiber is preferably 0.1 to 1000 mm, more preferably 0.5 to 100 mm, and still more preferably 1 to 50 mm.

  The method for forming the fiber is not particularly limited, but the fiber obtained by the electrospinning method has a small fiber diameter, and the nonwoven fabric obtained by using the fiber has a high hollow ratio and a high specific surface area. In view of obtaining a porous fluororesin layer having piezoelectric characteristics, the electrospinning method is preferable.

  A porous fluororesin layer can be produced by accumulating the obtained fibers into a nonwoven fabric or weaving them into a woven fabric and molding them.

Basis weight of the nonwoven fabric and woven fabric, preferably 100 g / m ² or less, more preferably 0.1 to 20 g / m ^2.
The thickness of the nonwoven fabric and the woven fabric is usually 1 μm to 1 mm, preferably 10 μm to 500 μm.
The basis weight and thickness tend to increase by increasing the spinning time or increasing the number of spinning nozzles.

  The non-woven fabric and woven fabric are obtained by accumulating or weaving the fibers in a sheet shape. Such non-woven fabric and woven fabric are composed of a single layer, or composed of two or more layers having different materials and fiber diameters. Any of these may be used.

[Electrospinning method]
When forming a fiber made of a fluororesin using the electrospinning method, for example, a spinning solution containing the fluororesin and, if necessary, a solvent is used.

  The solvent is not particularly limited as long as it can dissolve or disperse the fluororesin. For example, water, dimethylacetamide, dimethylformamide, tetrahydrofuran, methylpyrrolidone, xylene, acetone, chloroform, ethylbenzene, cyclohexane, benzene, Examples include sulfolane, methanol, ethanol, phenol, pyridine, propylene carbonate, acetonitrile, trichloroethane, hexafluoroisopropanol, and diethyl ether. These solvents may be used alone or in combination of two or more.

  In addition to the fluororesin and the solvent, the spinning solution may further contain additives such as a surfactant, a dispersant, a charge adjusting agent, functional particles, an adhesive, a viscosity adjusting agent, and a fiber forming agent. . When the spinning solution contains a resin having low solubility in a solvent and the solvent (for example, when the resin is PTFE and the solvent is water), fiber formation is further performed from the viewpoint of forming the resin into a fiber shape during spinning. It is preferable that an agent is included.

  The fiber forming agent is preferably a polymer having high solubility in a solvent, such as polyethylene oxide, polyethylene glycol, dextran, alginic acid, chitosan, starch, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, Examples thereof include cellulose and polyvinyl alcohol.

As a method for producing the fiber, a method for producing a fiber made of PTFE by an electrospinning method will be specifically described. As a method for producing the PTFE fiber, a conventionally known production method can be employed, and examples thereof include the following methods described in JP-T-2012-515850.
Providing a spinning solution comprising PTFE, a fiber forming agent and a solvent and having a viscosity of at least 50,000 cP;
Spinning the spinning solution from a nozzle and forming a fiber by electrostatic traction;
Collecting the fibers on a collector (eg, a take-up spool) to form a precursor;
Calcining the precursor to remove the solvent and the fiber former to form PTFE fibers.

[Production method of non-woven fabric or woven fabric]
In order to form a nonwoven fabric using the fiber, the step of forming the fiber and the step of collecting the obtained fibers into a sheet to form the nonwoven fabric may be performed separately or simultaneously. . Specifically, for example, a step of forming a fiber by using an electrospinning method and a step of collecting the obtained fibers into a sheet to form a nonwoven fabric may be simultaneously performed, or a step of forming a fiber. After performing, you may perform the process of accumulating the fiber obtained by the wet method in a sheet form, and forming a nonwoven fabric.

  Examples of a method for forming a nonwoven fabric by the wet method include a method of forming (paper making) a sheet by depositing (accumulating) the fibers on a mesh using an aqueous dispersion containing the fibers. .

  In order to improve the dispersion state, the aqueous dispersion is added with a dispersant or an oil agent composed of a cationic, anionic, or nonionic surfactant, or an antifoaming agent that suppresses the generation of bubbles. May be.

The woven fabric formed from the fiber can be manufactured by a method including a step of forming a fiber and a step of weaving the obtained fiber into a sheet to form a woven fabric.
As a method of weaving the fiber into a sheet, a conventionally known weaving method can be used, and methods such as a water jet room, an air jet room, and a rapier room can be used.

[Polarization treatment]
The porous fluororesin layer is preferably subjected to polarization treatment.
As the method for the polarization treatment, a conventionally known method can be used, and is not particularly limited, and examples thereof include voltage application processing such as DC voltage application processing and AC voltage application processing, and corona discharge processing.

  For example, the corona discharge treatment can be performed using a commercially available device composed of a high voltage power source and electrodes.

  In the polarization treatment, the porous fluororesin layer alone may be polarized. However, when a laminate of a porous fluororesin layer and a conventionally known layer such as the surface coating layer is used as the piezoelectric layer, It is preferable to perform polarization treatment after forming the laminate. This is because a conventionally known layer such as a surface coating layer serves to prevent the electric charge held in the porous fluororesin layer from being attenuated by being electrically connected to the external environment. It is considered that a sensor can be obtained, and a new interface capable of holding an electric charge can be formed between the porous fluororesin layer and the surface coating layer. This is because it is considered that the piezoelectricity of the fluororesin layer is improved.

<Surface coating layer>
The piezoelectric layer is a laminate in which a surface coating layer is laminated on at least one surface of the porous fluororesin layer in view of obtaining a piezoelectric layer that retains electric charge for a long time and retains a high piezoelectric rate. Is preferred. Such a surface coating layer works to prevent the electric charge held in the porous fluororesin layer from being attenuated by being electrically connected to the external environment, and is thus effective in maintaining the piezoelectricity of the piezoelectric layer. It seems to function.

  In addition, the piezoelectric layer including the laminate can form a new interface capable of holding electric charge between the porous fluororesin layer and the surface coating layer, so that the piezoelectricity is improved and the interface is held at such an interface. It is considered that there is an effect that the amount of charge that can be held synergistically increases by moving the generated charge to the hollow structure of the porous fluororesin layer and contributes to improvement of the piezoelectricity.

  As the laminate, a piezoelectric vibration sensor including a porous fluororesin layer that retains a high piezoelectric rate is obtained. From the viewpoint of manufacturability and cost of the sensor, the front and back surfaces of the porous fluororesin layer (mostly From the standpoint of obtaining a piezoelectric vibration sensor including a porous fluororesin layer that retains a higher piezoelectric rate, a laminate in which a surface coating layer is laminated on two surfaces having a large area) is preferable. A laminate in which a surface coating layer is laminated on the entire surface (front and back surfaces and end surfaces) of the layer is preferable.

  Although the material which forms the said surface coating layer is not specifically limited, A thermosetting resin or a thermoplastic resin is mentioned. Examples of thermosetting resins include polyimide, epoxy resin, thermosetting fluororubber (eg, vinylidene fluoride rubber), polyurethane, phenolic resin, imide resin (eg, polyimide, polyamideimide, bismaleimide), silicone resin Is mentioned. Examples of thermoplastic resins include acrylic resin, methacrylic resin, polypropylene, polyamide, vinyl chloride resin, silicone resin, fluororesin (eg PTFE, PCTFE, ETFE, PVDF, PFA, FEP), nylon, polystyrene, high density polyethylene , Silicone rubber, low density polyethylene, polyphenylene sulfide, polyethylene oxide, polysulfone, and vinylidene chloride.

The volume resistivity of the surface coating layer is preferably 1 × 10 ¹³ Ω · cm or more, more preferably 1 × 10 ¹⁴ from the viewpoint of improving long-term charge retention in the porous fluororesin layer or the piezoelectric layer. Ω · cm or more.
The volume resistivity is measured based on the double ring electrode method using a single surface coating layer (film) to be measured.

The elastic modulus of the surface coating layer is likely to be nonlinearly deformed with respect to the compressive strain at the time of charge extraction, and can exhibit a high piezoelectricity of about 100 to 500 (unit: d ₃₃ (pC / N)). It is preferable that the elastic modulus of the porous fluororesin layer is different from the point that a layer is obtained. In this case, the elastic modulus of the surface coating layer may be higher or lower than the elastic modulus of the porous fluororesin sheet. In this case, the difference in elastic modulus between the surface coating layer and the porous fluororesin layer is preferably 10 MPa or more, more preferably 50 MPa or more. If the difference in elastic modulus is within this range, it is preferable in that nonlinear deformation is likely to occur when the piezoelectric layer is compressed.

The surface coating layer preferably has a relative dielectric constant of 2 to 100.
If the relative permittivity is within this range, when charge is applied by corona discharge, the charge is concentrated inside the surface coating layer having a high dielectric constant, and the surface coating layer and porous fluorine are also collected. There is a tendency that electric charges are easily held at the interface with the resin layer. Further, since the held charges move to the hollow structure in the porous fluororesin layer, it is considered that the amount of charges held as the whole piezoelectric layer is increased and the initial value of the piezoelectricity is improved.

  The thickness of the surface coating layer is usually 1 μm or more, preferably 30% or less of the thickness of the porous fluororesin layer. When the thickness is less than 1 μm, for example, when a surface coating layer is formed using a film for the surface coating layer, the handleability of the film is poor and the insulation due to film defects (pinholes) is reduced. This may cause problems and is not preferable. Further, when the thickness of the surface coating layer exceeds 30% of the thickness of the porous fluororesin layer, it is necessary to set a high corona discharge voltage when injecting charges into the porous fluororesin layer. In particular, it tends to be difficult to put into practical use.

  When the surface coating layer is formed on the front and back surfaces of the porous fluororesin layer, if the thicknesses of the respective surface coating layers are made different from each other, the resulting piezoelectric laminate will have the compressive strain of the laminate. On the other hand, it is preferable because non-linear deformation is likely to occur and the piezoelectric characteristic tends to be high.

  The surface coating layer can be formed by a conventionally known method. For example, when a thermosetting resin is used, a thermosetting resin, a curing agent (crosslinking agent), and a solvent are formed on at least one surface of the porous fluororesin layer. It can form by apply | coating and drying the liquid containing these. Moreover, it can also form by apply | coating a photocurable resin and making it harden | cure.

  As the curing agent, a conventionally known curing agent can be used. For example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Perhexa 25B (NOF Corporation) Product)), triallyl isocyanurate (trade name: TAIC (manufactured by NOF Corporation)) and the like.

  Examples of the solvent include tetrahydrofuran (THF), toluene, benzene, acetone, ethylbenzene, and the like.

  Examples of the method for forming (laminating) the surface coating layer include, in addition to the above-described method, a method in which a surface coating layer (film for use) is formed in advance and then laminated by thermocompression bonding with the porous fluororesin layer. It is done.

  When the surface coating layer (film for) is formed in advance, the thermoplastic resin, the thermosetting resin, or the photocurable resin can be obtained by a conventionally known molding method, for example, a molding machine such as a single-screw or twin-screw extruder. For example, there may be mentioned a method in which a curing agent and a solvent are mixed as necessary, and then molded into a sheet or the like with a pressure molding machine or a T-die. In the case of a thermoplastic resin, the molding temperature is usually about the same as the melting temperature of the resin, and in the case of a thermosetting resin, it is usually about the same as the curing temperature of the resin.

<Intermediate layer>
The piezoelectric layer may have an intermediate layer between the porous fluororesin layer and the surface coating layer. Further, when the piezoelectric layer has two or more porous fluororesin layers, an intermediate layer may be provided between these layers.

The intermediate layer is preferably a layer made of an organic material.
Examples of such organic materials include PFA, FEP, PCTFE, ETFE, PVDF, polyvinyl fluoride (PVF), a copolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV), PTFE, ethylene. -Containing resin such as chlorotrifluoroethylene copolymer (ECTFE); polyolefin resin such as polypropylene and polyethylene; polystyrene, polymethyl methacrylate, poly (meth) acrylate, polyvinyl chloride, polyvinylidene chloride Vinyl polymers such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid, polyhydroxyalkanoate, polybutylene succinate, polyethylene succinate, polyethylene Polyester polymers such as lensuccinate adipate; polyamides such as 6-nylon, 6,6-nylon, 11-nylon, 12-nylon and aramid; imides such as polyimide, polyamideimide, polyetherimide and bismaleimide Resins: Thermoplastic resins such as engineering plastics such as polycarbonate and cycloolefins, or unsaturated polyester, vinyl ester resin, diallyl phthalate resin, epoxy resin, polyurethane, silicon-based resin, polyimide, alkyd resin, furan resin, dichroic resin Thermosetting resins such as pentadiene resin, acrylic resin, and allyl carbonate resin can be used, and further, foams, stretched porous membranes, nonwoven fabrics, woven fabrics, gel-like / rubber-like bodies, etc. of the above-mentioned organic polymers can be used. Also Kill.

  Among these materials, polyamides such as aramid, polyamideimide, bismaleimide, polytetrafluoroethylene, polyvinylidene fluoride, PFA, FEP, ETFE, PCTFE, and ECTFE are more preferable from the viewpoints of heat resistance and weather resistance.

The elastic modulus of the intermediate layer is preferably a layer different from the elastic modulus of the porous fluororesin layer and / or the surface coating layer, and from the elastic modulus of the porous fluororesin layer and / or the surface coating layer It may be a high layer or a low layer. The use of an intermediate layer having a different elastic modulus between the porous fluororesin layer and the surface coating layer is likely to cause nonlinear deformation with respect to the compressive strain of the layer, and exhibits high piezoelectricity. preferable.
In this case, the difference in elastic modulus between the intermediate layer and the surface coating layer and / or the porous fluororesin layer is usually 10 MPa or more, preferably 50 MPa or more. If it exists in this range, it is preferable at the point which a nonlinear deformation | transformation tends to occur at the time of compression of the said piezoelectric layer.

<Method for manufacturing piezoelectric vibration sensor>
The piezoelectric vibration sensor of the present invention is not particularly limited in its manufacturing method as long as the shield layer A, the electrode layer, the piezoelectric layer including the porous fluororesin layer, the electrode layer, and the shield layer B are laminated in this order. It may be manufactured by directly forming a shield layer on the layer, or may be manufactured by directly forming an electrode layer, a piezoelectric layer, an electrode layer and a shield layer B on the shield layer A, or prepared in advance. The electrode layer, the piezoelectric layer, and the shield layer may be laminated by a conventionally known method. Moreover, you may manufacture by laminating | stacking layers other than these layers in a desired position as needed.

  Furthermore, if necessary, a conductor is connected to the electrode layer in the obtained laminate, an amplifier such as a charge amplifier that amplifies a signal from the conductor, or a signal output from the charge amplifier is processed. The piezoelectric vibration sensor of the present invention can be obtained by connecting an information processing unit or a display unit for displaying processed information. Furthermore, if necessary, the piezoelectric vibration sensor of the present invention can be applied to a frame having a wristband shape or the like.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by the following Example.

<Measurement of porosity>
The porosity of the porous fluororesin sheet obtained below was measured based on the following method.
The porous fluororesin sheet was calculated using the weight of a test piece cut into a 4 cm square (vertical 4 cm, horizontal 4 cm) and the thickness measured by a micrometer (LITEMATIC VL-50, manufactured by Mitutoyo Corporation). The porosity was calculated by the following formula using the apparent density.
(True density of PTFE−apparent density) × 100 / true density of PTFE

<Measurement of elastic modulus>
The elastic modulus of the porous fluororesin sheet obtained below was measured using an indentation tester (Elionix, ENT-2100).

<Measurement of average fiber diameter and fiber diameter standard deviation>
The average fiber diameter of the PTFE fibers obtained below was measured by randomly selecting an SEM observation region for the following porous fluororesin sheet, and this region was observed by SEM observation (apparatus: S-3400 (Hitachi High Corporation). (Manufactured by Technologies, Inc., 10,000 times), 20 fibers were randomly selected, and the average fiber diameter (arithmetic), fiber diameter standard deviation, and fiber diameter variation coefficient were calculated based on the measurement results of these fibers.
The fiber diameter variation coefficient was calculated from the following equation.
Fiber diameter variation coefficient = fiber diameter standard deviation / average fiber diameter

<Volume resistivity>
The volume resistivity of the surface coating layer obtained below was measured based on the double ring electrode method using the surface coating layer alone.

[Example 1]
<Production of piezoelectric layer>
PTFE fibers are accumulated in a sheet form by electrospinning described in JP-T-2012-515850, and a PTFE nonwoven fabric having a thickness of 60 μm (porosity 80%, elastic modulus 6 MPa, average fiber diameter 1.3 μm, fiber diameter) A porous fluororesin sheet having a standard deviation of 0.4 and a fiber diameter variation coefficient of 0.3) was produced.

On both surfaces (both front and back surfaces) of the obtained porous fluororesin sheet, a fluororesin sheet (PFA film manufactured by Daikin Industries, Ltd. (“AF0012”, thickness 12.5 μm, volume resistivity 1.0 × 10 ¹⁸ Ω) -A laminate (piezoelectric laminate) in which a surface coating layer is laminated on both sides of a porous fluororesin sheet is formed by pressure-bonding by holding for 180 seconds at a pressure of 2 MPa with a hot press at 300 ° C. did.

  Subsequently, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane was prepared by dissolving 100 parts by weight of fluororubber (Daikin Kogyo Co., Ltd., Daiel G912) in 1000 parts by weight of toluene. (Product name: Perhexa 25B (manufactured by NOF Corporation)) and 2 parts by weight of triallyl isocyanurate (trade name: TAIC (manufactured by NOF Corporation)) are added to the end face. As a material, this was applied to four end faces of the piezoelectric laminate and thermally cured at 150 ° C. for 15 minutes to form an end face coating layer, thereby obtaining a piezoelectric layer.

  Using the obtained piezoelectric layer, a corona discharge device manufactured by Kasuga Electric Co., Ltd. was used to polarize the piezoelectric layer by performing a corona discharge for 3 minutes at an inter-electrode distance of 12.5 mm, an inter-electrode voltage of 3 kV, and room temperature. Processed.

<Formation of electrode layer>
Electrode layers (thickness of about 0.5 μm) made of aluminum were formed on the front and rear surfaces of the polarization-treated piezoelectric layer by sputtering. These electrode layers are electrically insulated from each other.

<Preparation of shield layer A>
A conductive layer (thickness of about 0.5 μm) made of aluminum was formed on the surface of a polyethylene film (thickness: 80 μm) by sputtering to obtain a shield layer A.

<Preparation of shield layer B>
A conductive layer (thickness of about 0.5 μm) made of aluminum was formed on the surface of a polyethylene terephthalate film (thickness of 100 μm) by sputtering to obtain a shield layer B.

<Evaluation of capacitance>
The capacitances of the shield layers A and B were measured by a Faraday cage method using a Faraday cage (manufactured by Kasuga Denki Co., Ltd.). The capacitance of the shield layer A and the shield layer B and C _A and C _B, respectively, were calculated percent difference of the capacitance of the shield layers A and B by the following equation. In the following formulas, C _X has a value of larger absolute value when comparing C _A and C _B. The results are shown in Table 1.
Capacitance difference rate = | C _A −C _B | / C _X × 100 (%)

<Evaluation of compressive strength>
The compressive strength in the stacking direction of the shield layers A and B was measured as follows.
Using a compression tester (manufactured by Minebea Co., Ltd.), the shield layers A and B were compressed in the stacking direction in accordance with JIS K 7181 (2011), and the stress at 10% strain was measured.
The compressive strength of the shield layer B relative to the compressive strength of the shield layer A (compression strength ratio = compressive strength of the shield layer B / compressive strength of the shield layer A) was calculated, and the results are shown in Table 1.

<Production of piezoelectric vibration sensor>
The shield layer A and the shield layer B were adhered to both surfaces of the piezoelectric layer on which the electrode layer was formed so that the polyethylene film and the polyethylene terephthalate film were in contact with the electrode layer, respectively. In this bonding, the electrode layer and the shield layer A are thermally bonded under the conditions of 100 ° C./0.3 MPa / 10 minutes, and the electrode layer and the shield layer B are 180 ° C./0.3 MPa / Thermal bonding was performed for 10 minutes.

  Next, an adhesive tape in which an acrylic adhesive and a polyester film (thickness: 12 μm) are integrated is attached to the side opposite to the electrode layer of the shield layer A, and an acrylic type is applied to the side opposite to the electrode layer of the shield layer B. A piezoelectric vibration sensor was manufactured by attaching an adhesive tape in which an adhesive and a polyester film (thickness: 12 μm) were integrated. Table 1 shows the configuration of the obtained piezoelectric vibration sensor in the order of lamination.

[Comparative Example 1]
In Example 1, a piezoelectric vibration sensor was produced in the same manner as in Example 1 except that the shield layer A and the shield layer B were not produced and laminated. Table 2 shows the structure of the obtained piezoelectric vibration sensor in the order of lamination.

<Measurement of biological signals>
The two electrode layers of each piezoelectric vibration sensor manufactured in Example 1 and Comparative Example 1 and the oscilloscope are connected via a cable, a charge amplifier, and a noise filter, and the conductive layer and shield layer B of shield layer A are connected. Each of the conductive layers was connected to the ground. Next, the piezoelectric vibration sensor was fixed on the wrist artery so that the shield layer A was on the human body side. By standing in this state, the vibration generated by the pulsation was detected by converting it into an electrical signal by the piezoelectric vibration sensor, and the pulse wave pattern was displayed on the oscilloscope screen. The pulse wave shapes obtained at this time are shown in FIG. 1 (Example 1) and FIG. 2 (Comparative Example 1), respectively.
From this result, in the piezoelectric vibration sensor not having the shield layer, noise derived from the human body and the external environment and noise due to the sensor configuration were greatly detected, and a biological signal (pulse wave) could not be observed. On the other hand, according to the piezoelectric vibration sensor of the present invention, it has been found that it is difficult to detect noise, and a biological signal such as a pulse wave (PQRST wave) can be measured with high sensitivity.

Claims (8)

Shield layer A, electrode layer, piezoelectric layer including porous fluororesin layer, electrode layer and shield layer B are laminated in this order,
The shield layers A and B each include an insulating layer and a conductive layer, and the insulating layer exists on the electrode layer side of the conductive layer.
Piezoelectric vibration sensor for measuring biological signals.   2. The piezoelectric device according to claim 1, wherein the compressive strength of the shield layer B is greater than the compressive strength of the shield layer A (note that the compressive strength is measured in accordance with JIS K 7181 (2011)). Vibration sensor. The piezoelectric vibration sensor according to claim 1 or 2, wherein the capacitance of the shield layer A and the capacitance of the shield layer B measured by a Faraday gauge method satisfy the following requirement (I).
Requirement (I): Among the electrostatic capacities of the shield layers A and B, when one of the capacities is Ci and the other is Cii, Ci and Cii satisfy Ci ≧ Cii. If there is a relationship, the difference rate of the capacitance calculated by the following formula (1) is 50% or less. The difference rate of the capacitance = | Ci−Cii | / Ci × 100 (%) (1) )   The piezoelectric vibration sensor according to any one of claims 1 to 3, further comprising an insulating layer on at least a part of the shield layer A and / or the shield layer B opposite to the electrode layer side.   The piezoelectric vibration sensor according to any one of claims 1 to 4, wherein the porous fluororesin layer is made of a resin having no dipole due to a molecule and a crystal structure.   The piezoelectric vibration sensor according to any one of claims 1 to 5, wherein the porous fluororesin layer includes a nonwoven fabric or a woven fabric formed of a fiber made of a fluororesin.   The piezoelectric vibration sensor according to claim 1, wherein the fluororesin is polytetrafluoroethylene.   The piezoelectric vibration sensor according to claim 1, wherein the porous fluororesin layer or the piezoelectric layer is subjected to polarization treatment.

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