JP2019033778A - Conductive polymer electrode, and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer electrode having excellent adhesion to skin or the like, excellent breathability, and a good texture, and a method for manufacturing the conductive polymer electrode. SOLUTION: The conductive polymer is immobilized in a state where the fiber sheet 10 is impregnated with the conductive polymer, and the conductive polymer is gradually or gradually gradually or gradually from the first surface 1a to the second surface 1b in the thickness direction. Conductive polymer electrode 1 having a smaller density. The fiber sheet 10 is impregnated with the conductive polymer, and the conductive polymer is applied to the fiber sheet 10 so that the density gradually or gradually decreases from the first surface 1a to the second surface 1b in the thickness direction. A method for manufacturing a conductive polymer electrode 1 to be immobilized. [Selection diagram] Fig. 1

Description

  The present invention relates to a conductive polymer electrode and a method for producing a conductive polymer electrode.

  The biological electrode is used for the purpose of acquiring a weak biological signal in the body stably and efficiently. In order to acquire a biological signal efficiently, it is necessary to reduce the combined resistance of the living body and the biological electrode. Synthetic resistance is greatly influenced by the resistance component of the skin, particularly the stratum corneum of the epidermis. Since the stratum corneum of the epidermis exhibits an insulating property particularly in a dry state, the reduction of the stratum corneum resistance is extremely important for the bioelectrode. Also, the skin usually has irregularities on the surface, and deformation and vibration occur with body movement. Therefore, in order to reduce the combined resistance, it is also important to stabilize the contact state between the skin and the biological electrode by bringing the electrode surface into contact with the skin at as many points as possible and over a wide area.

  As a method for lowering the combined resistance between the living body and the living body electrode, a method of filling the space between the electrode and the skin with a liquid or cream electrolyte solution, a conductive gel or the like, or bringing the electrode into close contact with the adhesive material There is. However, these methods tend to cause itching, redness, contact dermatitis, skin infections such as bacteria, and the like.

  As a bioelectrode, a fabric-like bioelectrode made of a conductive metal-coated yarn such as silver yarn is known, and is mainly used for heart rate measurement in the sports field. However, since the metal-coated yarn is hard, the contact with the skin that is flexible, deformed, and vibrates tends to be unstable due to point contact. Further, since the metal-coated yarn is hydrophobic, the skin is liable to dry and the synthetic resistance between the bioelectrode and the skin is likely to increase due to the increase in impedance of the stratum corneum. For this reason, generation of noise, attenuation of the biological signal, and reduction of the signal-to-noise ratio are likely to occur, which is a great obstacle in long-term measurement of the biological signal.

  Patent Document 1 discloses a conductive polymer electrode obtained by impregnating and immobilizing PEDOT-PSS as a conductive polymer on a fiber sheet made of ultrafine fibers such as polyester nanofibers as a bioelectrode. The conductive polymer electrode is excellent in moisture retention and can easily retain moisture in the stratum corneum. Moreover, since it is excellent in a softness | flexibility, an electrode and skin become multipoint contact and it is excellent in adhesiveness, and the synthetic resistance of an electrode and skin is reduced.

International Publication No. 2013/073673

  However, the conductive polymer electrode as in Patent Document 1 tends to be inferior in air permeability and texture as compared with a biological electrode using a general fiber. Especially in the long-term measurement of biological signals, in addition to excellent adhesion to the skin, excellent breathability to prevent sweating and moisture transpiration, which are physiological phenomena of the skin, and uncomfortable feeling when wearing electrodes Good texture to reduce is important.

  Fire resistance, heat resistance, and especially clothing for special environments such as fire fighting, blast furnace work, and automobile racing are required to have fire resistance. In addition to these clothing items, durability is also important in work clothes, exercise clothes and underwear. In particular, in machine washing in a factory, strong mechanical stress is applied to the fiber due to high temperature and high speed washing, so that it is easily damaged and damaged, and excellent durability is required. Ultrafine fibers such as polyester nanofibers have low melting points and ignition points, and it is difficult to obtain excellent flame retardancy and durability. In applications where flame retardancy is required, polyimide fibers having a relatively high melting point and ignition point, and, in some cases, natural fibers such as cotton are used. However, a flame-retardant fiber material is not suitable for making ultrafine fibers because of restrictions on processability and strength, and is also a fiber having a fiber diameter of about several tens of μm in terms of durability. In particular, when using a fiber having such a normal fiber diameter, it is difficult to obtain a bioelectrode having adhesion to the skin, air permeability, texture, and the like.

  An object of the present invention is to provide a conductive polymer electrode that has excellent adhesion to skin and the like, has excellent breathability, and has a good texture, and a method for producing the conductive polymer electrode. .

  The conductive polymer electrode of the present invention is fixed in a state where a conductive polymer is impregnated in a fiber sheet, and the conductive polymer electrode is gradually or gradually increased in the direction from the first surface to the second surface in the thickness direction. The density of the conductive polymer is reduced. Thereby, the outstanding air permeability and a favorable texture can be obtained, ensuring the outstanding adhesiveness to skin etc.

  In the conductive polymer electrode of the present invention, the conductive polymer is preferably fixed to the fiber sheet with a binder resin. Thereby, it becomes easy to firmly fix the conductive polymer in a state of being unevenly distributed in the thickness direction of the fiber sheet.

  In the conductive polymer electrode of the present invention, the binder resin is preferably a thermosetting resin or a photocurable resin. By using a thermosetting resin or a photocurable resin as the binder resin, it becomes easy to immobilize and immobilize the conductive polymer in the thickness direction of the fiber sheet.

  In the method for producing a conductive polymer electrode according to the present invention, a fiber sheet is impregnated with a conductive polymer, and the density gradually decreases gradually from the first surface to the second surface in the thickness direction. In this method, the conductive polymer is fixed to the fiber sheet. As a result, it is possible to obtain a conductive polymer electrode having excellent adhesion to the skin and the like, excellent air permeability, and good texture.

  In the method for producing a conductive polymer electrode of the present invention, the fiber sheet is impregnated with a conductive composition containing the conductive polymer and a thermosetting resin, and heated from one direction on the first surface side. It is preferable to cure the thermosetting resin. Thereby, the conductive polymer electrode in which the conductive polymer is unevenly distributed in the thickness direction of the fiber sheet can be easily obtained.

  In the method for producing a conductive polymer electrode of the present invention, the fiber sheet is impregnated with a conductive composition containing the conductive polymer and a photocurable resin, and light is irradiated from one direction on the first surface side. It is preferable to cure the photocurable resin. Thereby, the conductive polymer electrode in which the conductive polymer is unevenly distributed in the thickness direction of the fiber sheet can be easily obtained.

The conductive polymer electrode of the present invention has excellent adhesion to the skin and the like, is excellent in air permeability, and has a good texture.
According to the method for producing a conductive polymer electrode of the present invention, it is possible to obtain a conductive polymer electrode having excellent adhesion to skin and the like, excellent air permeability, and good texture.

It is sectional drawing which showed an example of the conductive polymer electrode of this invention. It is sectional drawing which showed 1 process of the manufacturing method of the conductive polymer electrode of this invention. It is sectional drawing which showed 1 process of the manufacturing method of the conductive polymer electrode of this invention.

[Conductive polymer electrode]
Hereinafter, an example of the conductive polymer electrode of the present invention will be described. In addition, the dimension of the figure illustrated in the following description is an example, Comprising: This invention is not necessarily limited to them, It is possible to implement suitably changing in the range which does not change the summary. .

As shown in FIG. 1, the conductive polymer electrode 1 of the present embodiment is fixed by a fiber sheet 10 made of fibers 12 being impregnated with a conductive composition 14 containing a conductive polymer. Is formed. In the conductive polymer electrode 1, the first surface 1a is a contact surface that is brought into contact with the skin or the like.
The planar view shape and size of the conductive polymer electrode 1 are not particularly limited, and can be appropriately designed according to the application.

  It does not specifically limit as the fiber 12 which comprises the fiber sheet 10, A synthetic fiber, a vegetable fiber, and an animal fiber can be illustrated. 1 type of fiber 12 which forms the fiber sheet 10 may be sufficient, and 2 or more types may be sufficient as it.

Examples of the synthetic fiber include nylon fiber, polyester fiber, acrylic fiber, aramid fiber, polyurethane fiber, and carbon fiber.
Examples of vegetable fibers include cotton, hemp and jute.
Examples of animal fibers include silk, wool, collagen, and elastic fibers constituting animal tissues.

The diameter (thickness) of the fiber 12 is not particularly limited, and can be appropriately selected depending on the application. For example, the diameter can be 0.1 μm to 5 mm. When the conductive polymer electrode 1 is used as a biological electrode, the diameter of the fiber 12 is preferably 1 μm to 1000 μm.
The length of the fiber 12 is not particularly limited and can be appropriately selected depending on the application. For example, the length can be 1 mm to 100 m.

The form of the fiber sheet 10 is not particularly limited, and examples thereof include a fabric and a band. The fabric may be a woven fabric (fabric) or a non-woven fabric.
The thickness in particular of the fiber sheet 10 is not restrict | limited, It can select suitably according to a use, for example, can be 1 micrometer-100 mm.

  The conductive composition 14 of this example includes a conductive polymer and a binder resin. In the conductive polymer electrode 1, the conductive polymer is bonded and fixed to the fiber sheet 10 with a binder resin impregnated in the fiber sheet 10. In the present invention, it is preferable that the conductive polymer is fixed to the fiber sheet with the binder resin as described above. By using the binder resin, it becomes easy to firmly fix the conductive polymer to the fiber sheet. Further, wear resistance, peel resistance, water resistance, chemical resistance and mechanical strength are improved.

  The conductive polymer is not particularly limited, and is a polythiophene polymer such as PEDOT (poly (3,4-ethylenedioxythiophene)), polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyparaphenylene vinylene, A polyfluorene etc. can be illustrated. As the conductive polymer, one kind may be used alone, or two or more kinds may be used in combination.

The conductive polymer may include a dopant agent.
The dopant agent is not particularly limited, and examples of the electron acceptor include halogens such as bromine and iodine, Lewis acids such as PF ₅ , BF ₃ and SO ₃ , and proton acids such as H ₂ SO ₄ and HClO _4. Can do. Examples of the polymer dopant include polystyrene sulfonic acid (PSS). Examples of the electron donor include alkali metals and alkaline earth metals.

  As the conductive polymer, PEDOT-PSS is preferable from the viewpoint of excellent hydrophilicity and flexibility. By using PEDOT-PSS, when used as a bioelectrode, a conductive polymer electrode having excellent moisture retention that stably retains moisture in the stratum corneum on the skin surface and excellent adhesion to the skin, etc. is obtained. It becomes easy to be done.

  The molecular weight of the conductive polymer is not particularly limited, and for example, the molecular weight can be in the range of thousands to hundreds of thousands. The polymerization average molecular weight (Mw) in terms of styrene of the conductive polymer is not particularly limited, and can be, for example, 1000 to 900000, 3000 to 450,000, or 5000 to 50000.

  The binder resin may be any resin that can adhere and fix the conductive polymer to the fibers 12 of the fiber sheet 10 without deactivating the conductivity of the conductive polymer. Is preferred. The thermosetting resin or photocurable resin in the conductive polymer electrode exists in a cured state. As the binder resin, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, and silicon resin.
Examples of the photocurable resin include epoxy acrylate, acrylic epoxy cationic polymerization, and photosensitive polyimide.

The amount of the conductive composition 14 impregnated in the fiber sheet 10 is preferably 0.01 ml to 10 ml, more preferably 0.1 ml to 1 ml, per unit area of 1 cm ^{2 of the} fiber sheet 10. If the amount of impregnation of the conductive composition 14 is not less than the lower limit of the above range, excellent conductivity is easily obtained. If the amount of impregnation of the conductive composition 14 is less than or equal to the upper limit of the above range, excellent air permeability and texture can be easily obtained.

  0.1-10 mass% is preferable with respect to the total mass of a conductive composition, and, as for content of the conductive polymer in a conductive composition, 0.5-2 mass% is more preferable. If the content of the conductive polymer is not less than the lower limit of the above range, sufficient conductivity can be easily obtained. If the content of the conductive polymer is less than or equal to the upper limit of the above range, the content of the resin binder can be relatively increased, and the dropping of the conductive polymer is easily suppressed, and the durability is improved. .

  0.1-10 mass% is preferable with respect to the total mass of a conductive composition, and, as for content of the resin binder in an electroconductive composition, 1-4 mass% is more preferable. When the content of the resin binder is equal to or higher than the lower limit of the above range, the dropping of the conductive polymer is easily suppressed, and the durability is improved. If content of the resin binder is below the upper limit of the said range, content of a conductive polymer can be increased relatively and electroconductivity will improve.

  The total content of the conductive polymer and the binder resin in the conductive composition is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 25 to 25% with respect to the total mass of the conductive composition. 100 mass% is more preferable. If the total content of the conductive polymer and the binder resin is greater than or equal to the lower limit of the above range, durability and conductivity are improved.

  The mass ratio of the binder resin to the conductive polymer in the conductive composition is preferably 1: 0.5 to 1: 5, and more preferably 1: 1 to 1: 2. When the mass ratio is within the above range, it is easy to achieve both excellent durability and conductivity.

  The conductive composition 14 may contain components other than the conductive polymer and the binder resin as necessary. Examples of other components include additives such as glycerol, sorbitol, polyethylene glycol-polypropylene glycol copolymer, ethylene glycol, sphingosine, and phosphatidylcholine. Use of these additives improves wettability, flexibility, affinity with the skin when used as a bioelectrode, and the like. As an additive, 1 type may be used independently and 2 or more types may be used in combination.

As additives, surfactants, alcohols, natural polysaccharides, sugar alcohols, acrylic resins, and the like can be used.
Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. As the surfactant, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the cationic surfactant include quaternary alkyl ammonium salts and halogenated alkyl pyridiniums.
Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, and fatty acid salts.
Examples of nonionic surfactants include polyoxyethylene and polyoxyethylene alkyl ether.

The alcohol may be a monohydric alcohol or a polyhydric alcohol. As alcohol, 1 type may be used independently and 2 or more types may be used in combination.
Examples of monohydric alcohols include methanol, ethanol, propyl alcohol, isopropyl alcohol, and butanol.
Examples of the polyhydric alcohol include glycols such as ethylene glycol, chain polyhydric alcohols such as glycerin, cyclic polyhydric alcohols such as glucose and sucrose, and polymeric polyhydric alcohols such as polyethylene glycol, polyvinyl alcohol, polyethylene glycol, and polypropylene glycol copolymers. Alcohol can be illustrated.

Examples of natural polysaccharides include chitosan, chitin, glucose, and aminoglycan.
Examples of sugar alcohols include sorbitol, xylitol, and erythritol.
Examples of the acrylic resin include polyacrylate and polymethyl methacrylate.

  In the conductive polymer electrode 1, the conductive composition 14 is unevenly distributed in the thickness direction, and the density of the conductive composition 14 is gradually or gradually increased from the first surface 1a toward the second surface 1b. It is getting smaller. Thereby, in the conductive polymer electrode 1, the conductive polymer is unevenly distributed in the thickness direction, and the density of the conductive polymer gradually or gradually increases from the first surface 1a toward the second surface 1b. It is getting smaller. Thus, in the conductive polymer electrode 1, the conductive polymer is unevenly distributed in the portion on the first surface 1a side which is a contact surface to be brought into contact with the skin or the like.

  The first surface 1a of the conductive polymer electrode 1 is smoothed by filling the gaps between the fibers 12 due to the uneven distribution of the conductive composition 14, and therefore has a lot of contact with the skin and the like. It becomes point contact and excellent adhesion to the skin and the like is ensured. Further, excellent conductivity is ensured by the uneven distribution of the conductive polymer, and even a weak biological signal can be acquired efficiently. Moreover, since the density of the conductive composition 14 is low in the portion on the second surface 1b side of the conductive polymer electrode 1, the air permeability is excellent and the texture is also good.

  The conductive polymer may be unevenly distributed so that the density decreases stepwise from the first surface a of the conductive polymer electrode 1 toward the second surface 1b. You may be unevenly distributed so that a density may become small gradually as it goes to the surface 1b. Especially, from the point which maintains a texture, reducing the contact resistance of a bioelectrode, a conductive polymer so that a density may become small rapidly as it goes to the 2nd surface 1b from the 1st surface a of the conductive polymer electrode 1. FIG. Is preferably unevenly distributed.

In the conventional conductive polymer electrode, since the conductive polymer is uniformly impregnated and fixed in the thickness direction with respect to the fiber sheet, it is difficult to obtain sufficient air permeability and the texture tends to be inferior. It was.
In contrast, as described above, in the present invention, in the thickness direction of the conductive polymer electrode, the density of the conductive polymer decreases stepwise or gradually as it goes from the first surface to the second surface. In addition, the conductive polymer is unevenly distributed. Since the portion of the conductive polymer electrode on the second surface side has a low density of the conductive composition, excellent air permeability is obtained and the texture is also good. Moreover, since the 1st surface is smooth | blunted moderately because the space | gap between fibers is fully filled with an electroconductive composition, a contact state with skin etc. becomes a multipoint contact, and becomes stable. Thereby, when used as a biological electrode, the combined resistance of the electrode and the skin can be reduced, and the signal to noise ratio is improved.

  Examples of the use of the conductive polymer electrode of the present invention include bioelectrodes, drug delivery system electrodes, antistatic coatings, touch panel operating tools, and various sensor electrodes. The conductive polymer electrode of the present invention can ensure a stable contact state even with skin where deformation or vibration occurs, and can reduce the combined resistance of the skin and the electrode. It is particularly effective as a biological electrode used for long-term measurement of biological signals, because it does not hinder transpiration and can reduce discomfort during electrode mounting with a good texture.

  The conductive polymer electrode of the present invention is not limited to the conductive polymer electrode 1 described above. For example, the conductive polymer electrode of the present invention may be obtained by fixing a conductive polymer to a fiber sheet without using a binder resin.

[Method for producing conductive polymer electrode]
In the method for producing a conductive polymer electrode according to the present invention, the conductive polymer is impregnated with a conductive polymer in a fiber sheet, and the conductive polymer electrode has a density that decreases from the first surface to the second surface in the thickness direction. Is fixed to the fiber sheet. The conductive polymer electrode of the present invention described above can be obtained by the method for producing a conductive polymer electrode of the present invention.
Hereinafter, the manufacturing method of the above-described conductive polymer electrode 1 will be described as an example of the method of manufacturing the conductive polymer electrode of the present invention.

In the production of the conductive polymer electrode 1, the fiber sheet 10 is first impregnated with the conductive composition 14.
The method for impregnating the conductive composition 14 is not particularly limited, and examples thereof include a method of impregnating the conductive composition 14 into the fiber sheet 10 by a method such as coating, printing, dipping, spraying, and dropping.

When the conductive composition 14 is impregnated into the fiber sheet 10, water, a mixed solution of water and alcohol (ethanol, methanol, etc.), a solvent such as dimethyl sulfoxide, acetone, or the like may be used as necessary. As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
The conductivity, air permeability, and texture of the conductive polymer electrode 1 to be manufactured can also be adjusted by the amount of solvent used and the amount of the conductive composition 14 that is impregnated into the fiber sheet 10.

  When using a solvent, 50 mass%-99 mass% are preferable with respect to the total solution mass of the reagent containing the electroconductive composition 14, and the usage-amount of a solvent has more preferable 80 mass%-90 mass%. When the amount of the solvent used is not less than the lower limit of the above range, aggregation of the conductive polymer is suppressed. If the usage-amount of a solvent is below the upper limit of the said range, content of a conductive polymer can be made to increase relatively and electroconductivity will improve.

The amount of the conductive composition 14 to be impregnated into the fiber sheet 10 is preferably 0.01 ml to 10 ml, more preferably 0.1 ml to 1 ml, per unit area of 1 cm ^{2 of the} fiber sheet 10. If the input amount of the conductive composition 14 is not less than the lower limit of the above range, excellent conductivity is easily obtained. If the input amount of the conductive composition 14 is less than or equal to the upper limit of the above range, excellent air permeability and texture can be easily obtained.

  After the fiber sheet 10 is impregnated with the conductive composition 14, the conductive composition 14 is fixed to the fiber sheet 10 so that the density decreases from the first surface to the second surface in the thickness direction.

  When a thermosetting resin is used as the binder resin, for example, the thermosetting resin is cured by heating from one direction on the surface side that becomes the first surface 1 a of the conductive polymer electrode 1. The method for heating the fiber sheet 10 impregnated with the conductive composition 14 is not particularly limited, and examples thereof include a method using a heating press.

  For example, as shown in FIG. 2, a heating roller 30 having a heating mechanism 31 and a cooling roller having a cooling mechanism 41 while a long impregnated sheet 20 impregnated with a conductive composition in a fiber sheet travels in one direction. 40 is continuously sandwiched and pressed in the thickness direction. A heating roller 30 is disposed on the surface side of the impregnated sheet 20 that becomes the first surface 1a of the conductive polymer electrode 1, and a cooling roller is disposed on the opposite surface side.

  As a result, a thermal gradient is formed in the thickness direction of the fiber sheet 10, and the thermal gradient cures more thermosetting resin faster on the heating roller 30 side (heating side), resulting in faster electrical conductivity. The polymer is immobilized. Therefore, on the first surface 1a side of the obtained conductive polymer electrode 1, the gap between the fibers 12 is filled with the conductive composition 14 and smoothed. On the other hand, on the cooling roller 40 side (non-heated side), the thermosetting resin cures slower than the heating side, the fixing of the conductive polymer is delayed, and the gaps between the fibers 12 are not sufficiently filled and remain. Therefore, the density of the conductive polymer is reduced in the portion of the obtained conductive polymer electrode 1 on the second surface 1b side. Thus, it fixes to the fiber sheet 10 in the state where the electroconductive composition 14 was unevenly distributed so that a density might become small as it goes to the 2nd surface from the 1st surface in thickness direction.

The heating mechanism 31 is not particularly limited, and a known heater can be used.
The cooling mechanism 41 is not particularly limited, and examples thereof include a mechanism that circulates and cools cooling water, a radiator that dissipates heat, and a mechanism that cools by blowing air.

As shown in FIG. 3, separator films 50 may be inserted between the press surface of the heating roller 30 and the impregnated sheet 20 and between the press surface of the cooling roller 40 and the impregnated sheet 20. By inserting the separator film 50, it is easy to suppress the conductive composition from adhering to the press surface of the heating roller 30 and the press surface of the cooling roller 40.
The separator film 50 only needs to have heat resistance and peelability, and examples thereof include a polyimide sheet, a paper or a cloth whose surface is siliconized.
Instead of the cooling roller 40, a natural heat may be radiated using a roller having no cooling mechanism.

  The conductivity, air permeability, and texture of the conductive polymer electrode 1 can be adjusted by pressing pressure, heating temperature, and heating amount.

  The heating temperature is preferably 50 to 200 ° C, more preferably 100 to 150 ° C. When the heating temperature is equal to or higher than the lower limit of the above range, the fixing of the conductive polymer is stabilized. If heating temperature is below the upper limit of the said range, deterioration by the heat | fever of a conductive polymer can be prevented.

  When a photocurable resin is used as the binder resin, for example, the photocurable resin is cured by irradiating UV light or the like from one direction on the surface side that is the first surface 1a of the conductive polymer electrode 1. Thereby, more photocurable resin hardens | cures faster on the light irradiation side, and more conductive polymer is unevenly distributed and fixed faster. Therefore, the space between the fibers 12 is filled on the first surface 1a side of the obtained conductive polymer electrode 1 to be appropriately smoothed. On the other hand, on the side opposite to the light irradiation side (non-light irradiation side), the curing of the photocurable resin is slower than the light irradiation side, and the fixing of the conductive polymer is delayed. Therefore, the density of the conductive polymer is reduced on the second surface 1b side of the conductive polymer electrode 1 obtained.

  Alternatively, the conductive polymer may be unevenly distributed and fixed without using the binder resin. For example, the current density on the surface of the fiber sheet can be controlled by electrophoretically collecting a conductive polymer on a specific electrode (for example, the cathode), polymerizing and immobilizing it, and adjusting the electrode shape and conductive composition. Thus, an electrolytic polymerization method that promotes immobilization may be used. Further, an immobilization method using a binder resin may be combined with an electrolytic polymerization or an electrochemical immobilization method.

  According to the manufacturing method of the present invention described above, the conductive polymer is unevenly distributed so that the density decreases from the first surface toward the second surface, so that the skin on the first surface side, etc. It is possible to obtain a conductive polymer electrode that is ensured in adhesion and conductivity and is excellent in air permeability and texture.

  In addition, the manufacturing method of the conductive polymer electrode of this invention is not limited to an above described method. For example, the method of pressing the impregnated sheet is not limited to a method using a roll, and may be a method using a press machine including a pair of plates, for example.

  DESCRIPTION OF SYMBOLS 1 ... Conductive polymer electrode, 1a ... 1st surface, 1b ... 2nd surface, 10 ... Fiber sheet, 12 ... Fiber, 14 ... Conductive composition, 20 ... Impregnation sheet, 30 ... Heating roller, 31 ... Heating mechanism , 40 ... cooling roller, 41 ... cooling mechanism, 50 ... separator film.

Claims (6)

  The fiber sheet is fixed in a state of being impregnated with a conductive polymer, and the density of the conductive polymer decreases stepwise or gradually from the first surface to the second surface in the thickness direction. Polymer electrode.   The conductive polymer electrode according to claim 1, wherein the conductive polymer is fixed to the fiber sheet with a binder resin.   The conductive polymer electrode according to claim 2, wherein the binder resin is a thermosetting resin or a photocurable resin. Impregnating the fiber sheet with conductive polymer,
A method for producing a conductive polymer electrode, comprising fixing the conductive polymer to the fiber sheet so that the density decreases stepwise or gradually from the first surface in the thickness direction toward the second surface.   The conductive composition containing the conductive polymer and a thermosetting resin is impregnated into the fiber sheet, and heated from one direction on the first surface side to cure the thermosetting resin. A method for producing a conductive polymer electrode.   5. The fiber sheet is impregnated with a conductive composition containing the conductive polymer and a photocurable resin, and the photocurable resin is cured by irradiating light from one direction on the first surface side. The manufacturing method of the electroconductive polymer electrode of description.

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