Conductive Fiber

Abstract

To provide a conductive polymer fiber excellent in conductivity, strength in a dry state and a wet state and flexibility, and a bioelectrode having the same.SOLUTION: In a conductive polymer fiber 40, a base material fiber 41 is impregnated with and / or subjected to adhesion of a conductive material 42 containing a conductive polymer. The conductive polymer fiber 40 is characterized in that the conductive material is arranged in the state of adhering tightly to the base material fiber, among the plurality of base material fibers.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer fiber, a method and apparatus for manufacturing a conductive polymer fiber, a bioelectrode, a biosignal measuring device, an implantable electrode, and a biosignal measuring device. This application claims priority based on Japanese Patent Application No. 2011-251524 filed on November 17, 2011, Japanese Patent Application No. 2012-185343 filed on August 24, 2012, Japanese Patent Application No. 2012-189102 filed on August 29, 2012, and Japanese Patent Application No. 2012-212998 filed on September 26, 2012, the contents of which are incorporated herein by reference. [Background technology]

[0002] Conventional conductive fibers include those coated with metals such as copper, those woven with carbon or thin metal wires, and those made of conductive polymers formed into strings. These conductive fibers are widely used in bioelectrodes, biointerfaces, anti-static clothing, and other applications. However, conventional conductive materials such as metals and carbon are hydrophobic and hard. This makes them less suitable for applications that require contact with the body surface or internal tissues, which are rich in moisture and flexible. For example, when placing a bioelectrode on the body surface, bioelectrodes made of hard, hydrophobic materials are difficult to adhere to the body surface and achieve direct electrical conduction. This necessitates the use of a separately prepared conductive paste (jelly) to electrically connect the bioelectrode to the body surface. In recent years, there has been progress in the development of conductive fibers, which are made by extruding an aqueous solution of PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid))—a conductive polymer with particularly excellent conductivity and hydrophilicity—through a nozzle into a coagulating bath of acetone, thereby forming them into threads. Their practical application is also being considered (see, for example, Non-Patent Document 1).

[0003] However, when the conductive fibers made of PEDOT-PSS are used in a high-humidity environment, the PEDOT-PSS absorbs moisture, resulting in a decrease in strength (especially tensile strength). Furthermore, the conductive fibers made of PEDOT-PSS expand when they absorb moisture, and conversely, shrink when they dry. This can lead to cracks inside the fibers or breakage, resulting in a decrease or loss of the conductivity of the fibers. Clothing can become wet from rain or sweat during use. Bioelectrodes and biointerfaces are used in environments with high humidity. Therefore, solving the above problems was required to utilize PEDOT-PSS, which has excellent conductivity and hydrophilicity, for a wide range of applications.

[0004] In addition to the above-mentioned problem that the strength of conductive fibers made of PEDOT-PSS significantly decreases when wet, there are also the following problems. Specifically, the fibers produced by the wet-spinning method described in Non-Patent Document 1 are thin fibers with a diameter of approximately 10 microns. This makes them difficult to handle and causes problems such as insufficient strength even when dry. Furthermore, the fibers are highly rigid and feel rough to the touch. This also poses a problem in that they do not provide the flexibility required for applications such as clothing.

[0005] On the other hand, body-surface-mounted bioelectrodes are widely used for recording bioelectric signals such as electroencephalograms, event-related potentials, evoked potentials, electromyograms, and electrocardiograms, as well as for providing electrical stimulation to living organisms. (Hereinafter, body-surface-mounted bioelectrodes may be simply referred to as bioelectrodes.)

[0006] Conventionally widely used bioelectrodes consist of a metal electrode plate and a gel or paste containing an electrolyte solution. The basic structure of these bioelectrodes is to fix the metal electrode plate to the skin surface by using (applying) a gel or paste between the electrode plate and the skin surface. Wearing a bioelectrode constantly seals a specific location on the skin surface. For this reason, particularly with long-term continuous use, discomfort or itching due to sweating can occur, and contact dermatitis or bacterial infections can also occur. There is a need to solve these problems in the prior art.

[0007] Furthermore, in countries where the population is aging, there are an increasing number of cases where biosignal monitoring, such as electrocardiograms, is performed for long periods of time, either at medical institutions or at home. Because various skin functions decline in elderly people, highly adhesive electrodes using conventional adhesive tape, etc., are prone to causing skin irritation and discomfort such as itching. Furthermore, there are many cases where wearers, who suffer from dementia or nocturnal delirium, remove the bioelectrodes themselves, and a solution to this problem is needed.

[0008] Conventional bioelectrodes, which are prone to the above-mentioned problems, use a gel or paste containing an electrolyte solution between the skin and a metal electrode plate. When placing a bioelectrode on the skin surface via a gel or paste, it is necessary to increase the electrode contact area. This is because the gel or paste has low conductivity, and therefore it is necessary to increase the contact area with the skin to reduce the electrode resistance. However, increasing the electrode contact area is also a major cause of the above-mentioned problems. Thus, existing bioelectrode configurations that rely on electrolyte gels or pastes are uncomfortable to wear and make it difficult to further miniaturize and increase the density of electrodes.

[0009] On the other hand, implantable bioelectrodes are required to accurately and efficiently receive electrical signals from within the body using external devices, and conversely, to transmit electrical signals from external devices to the body. Signals such as action potentials and synaptic potentials of nerve cells are particularly weak. Therefore, many signals are difficult to measure or input unless electrodes are placed very close to the cells. Implantable bioelectrodes are also widely used outside the nervous system, for example in cardiac pacemakers and cochlear implants. Development of implantable bioelectrodes, such as brain-machine interfaces, is also underway as a future human interface.

[0010] The body is made of flexible tissue rich in water and electrolytes. In contrast, conventional implantable bioelectrodes are made of hard, hydrophobic, conductive materials such as metal or carbon. This has led to problems with mechanical and electrochemical compatibility between conventional bioelectrodes and biological tissue. In particular, mechanical stress at the interface between the bioelectrode and the biological tissue can cause inflammation and damage (invasiveness) to the tissue, which is a problem.

[0011] The following problems can occur when electrodes are implanted into biological tissue, particularly the neural tissue of the cerebrospinal cord. Microscopic damage to the neural tissue can cause inflammation to gradually spread, resulting in degeneration and loss of nerve cells around the electrode, making measurement and stimulation (signal input) difficult. Permanent implantation of electrodes into neural tissue can lead to the loss of nerve cells and the formation of glial scars, resulting in reduced efficiency of electrical stimulation and the degradation or loss of measured waveforms. Furthermore, the loss of nerve cells can lead to neural dysfunction. For these reasons, a solution is needed. [Prior art documents] [Non-patent literature]

[0012] [Non-Patent Document 1] “Spinning and Characterization of Conducting Microfibers” Macromol. Rapid Commun. (2003) 24, pp261-264 Summary of the Invention [Problem to be solved by the invention]

[0013] In order to overcome the problems of the conductive fibers made of PEDOT-PSS, this invention proposes a composite material in which the conductive polymer PEDOT-PSS is fixed to the inside or outside of fibers or fiber bundles (yarn) such as silk. Such conductive fibers made of a PEDOT-PSS composite material are expected to be particularly useful as materials for bioelectrodes because they have conductivity, hydrophilicity, tensile strength, and water resistance.

[0014] Until now, commercially available PEDOT-PSS materials (e.g., Clevios P ​​Heareus) have been supplied as a PEDOT-PSS solution and are generally used by immobilizing them on a substrate. Thus, methods for immobilizing PEDOT-PSS can be broadly divided into two categories: chemical and electrochemical. The chemical method is a relatively simple immobilization method that can immobilize PEDOT-PSS on a variety of substrates, but its conductivity and strength are not as high as those of the electrochemical method described below. The electrochemical method involves electrically polymerizing and immobilizing PEDOT-PSS on the electrode surface, which provides better conductivity and strength than the chemical method. However, since an electric current must be passed between the substrate and the solution, a conductive material must be used for the substrate.

[0015] When manufacturing composite fibers of PEDOT-PSS and fiber bundles as described above, electrochemical methods cannot usually be used because the fiber bundles used as the base material are insulators (non-conductive), and chemical fixation methods must be used. Specifically, fiber bundles impregnated with PEDOT-PSS can be manufactured by spraying them with organic solvents such as acetone, ethanol, or methanol, or electrolyte solutions such as magnesium oxide solution, or by immersing them in the liquid.

[0016] However, conductive polymer fibers made from PEDOT-PSS fiber bundles produced by the chemical fixation method only have a conductivity of about 40 to 50 MΩ / cm when using, for example, No. 9 silk thread (fiber bundle diameter approximately 280 microns), and furthermore, the adhesive strength between the PEDOT-PSS and the fiber bundle is low. This has the drawback of making PEDOT-PSS prone to peeling and reducing its conductivity, so further improvement was necessary.

[0017] In addition to the above, other techniques for fabricating PEDOT-PSS fibers include spinning methods (wet spinning and electrospinning). However, it is technically difficult to produce PEDOT-PSS blended with long fiber bundles (threads) by spinning.

[0018] Another possible method for producing composite fibers of PEDOT-PSS and fiber bundles is to first impart conductivity to the fiber bundles by applying a metal coating to them, or to electrochemically immobilize PEDOT-PSS to the fiber bundles by chemical immobilization, thereby making them conductive, and then use this conductivity as an electrode to electrochemically immobilize PEDOT-PSS. However, this method requires a two-step immobilization process, which can be less productive and more costly.

[0019] The composite fibers of PEDOT-PSS and silk or other fibers, as described above, are conductive materials with excellent biocompatibility and are expected to be applied to bioelectrodes. Although such composite fibers can be produced using the chemical fixation method described above, further improvements in conductivity and durability, as well as more efficient manufacturing, are required.

[0020] Furthermore, a wide range of fields, including medicine, health promotion, information technology, and wearable computers, are demanding surface-mounted bioelectrodes that can be used continuously for long periods of time. Not only are there demands for stable and reliable measurement of bioelectric signals, but there is also a demand for comfortable wear. There is also a demand for implantable electrodes that are minimally invasive to biological tissue.

[0021] The inventors of the present invention focused on the fact that conductive polymers, typified by PEDOT-PSS, which have been developed recently, are highly hydrophilic and flexible, and believed that the stress on biological tissues when conductive polymers are implanted in the body as electrodes could be reduced. As a result of extensive research, they completed the present invention. The first to fourth aspects of the present invention were made in consideration of the above-mentioned conventional problems and through various investigations by the present inventors. In the present invention, the conductive polymer fiber of the first aspect can be preferably produced by the device and production method of the second aspect. Furthermore, the conductive polymer fiber of the first aspect can be preferably used for the electrodes and devices of the third and fourth aspects.

[0022] A first aspect of the present invention aims to provide a conductive polymer fiber that is excellent in conductivity, strength in dry and wet states, and flexibility, and a bioelectrode including the same.

[0023] The second aspect of the present invention aims to provide a method and apparatus for producing conductive polymer fibers, which can impregnate or attach a conductor containing PEDOT-PSS as a conductive polymer to an insulating fiber (fiber bundle) and electrochemically polymerize and fix it continuously, thereby enabling the productive production of conductive polymer fibers that are highly biocompatible, have good homogeneity, and are excellent in conductivity and durability.

[0024] A third aspect of the present invention aims to provide a bioelectrode that has stability and reliability when measuring bioelectrical signals and that is more comfortable to wear than conventional bioelectrodes, and a biosignal measuring device equipped with such a bioelectrode.

[0025] A fourth aspect of the present invention aims to provide an implantable electrode that is capable of detecting weak electrical signals within a living body, has excellent biocompatibility, and is minimally invasive to biological tissue, and a biosignal measuring device equipped with such an implantable electrode. [Means for solving the problem]

[0026] The present invention relates to a bioelectrode using a conductive fiber containing a conductive polymer, characterized in that the conductive fiber is a base fiber impregnated with and / or attached to a conductor containing a conductive polymer, and the conductive polymer is hydrophilic. (First aspect) A first aspect related to the present invention provides the following conductive polymer fiber. I-(A): A conductive polymer fiber in which a conductor containing a conductive polymer is impregnated and / or attached to a base fiber, and the conductor is held and fixed between a plurality of the base fibers. I-(B): A conductive polymer fiber obtained by impregnating and / or attaching a conductor containing a conductive polymer to a base fiber, characterized in that the conductor is arranged between multiple base fibers in close contact with the base fiber.

[0027] Conductive polymer fibers related to the conductive polymer fibers of the first embodiment described above include conductive polymer fibers having the following characteristics. I-(1): The conductive polymer fiber related to the first aspect described above is characterized in that a conductor containing a conductive polymer is impregnated and / or attached to a base fiber containing an animal fiber, and the conductive polymer is PEDOT-PSS. I-(2): In the conductive polymer fiber, the conductor contains glycerol, polyethylene glycol-polypropylene glycol copolymer, ethylene glycol, sorbitol, sphingosine, or phosphatidylcholine as an additive.

[0028] I-(3): In the conductive polymer fiber of I-(1) or (2), the conductor is coated around the base fiber.

[0029] I-(4): In the conductive polymer fiber of any one of I-(1) to I-(3), the conductor is impregnated into the base fiber.

[0030] I-(5): In the conductive polymer fiber of any of I-(1) to (4), the conductor is impregnated into the base fiber, the base fiber is coated with metal or carbon, and the coated metal or carbon is further coated with the conductor.

[0031] I-(6): In the conductive polymer fiber of any one of I-(1) to (5), the conductor is disposed between a plurality of the base fibers in close contact with the base fibers.

[0032] I-(7): In any one of the above I-(1) to (5), the conductive polymer fiber is further coated with an insulating layer around the conductive polymer fiber.

[0033] I-(8): A bioelectrode related to the present invention is characterized by comprising, as an electrode, the conductive polymer fiber described in any one of I-(1) to I-(7).

[0034] (Second aspect) A second aspect related to the present invention provides the following method and apparatus for producing conductive polymer fibers. II-(1): The method for producing the conductive polymer fiber described above is characterized by comprising: a dipping step in which an insulating base fiber consisting of a thread-, string-, cloth-, or ribbon-shaped fiber bundle is immersed in a conductor solution containing PEDOT-PSS {poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)} as a conductive polymer, thereby impregnating and / or adhering the conductor to the base fiber; and a fixing step in which the base fiber is pulled vertically out of the conductor solution while running between electrodes and applying an electric current, thereby electrochemically polymerizing and fixing the conductor impregnated and / or adhered to the base fiber. The above manufacturing method may sequentially include the immersion step, the fixing step, and a drying step of blowing air to dry the base fiber to which the conductor has been polymerized and fixed, and may further be characterized in that each of the immersion step, the fixing step, and the drying step is performed while controlling the atmospheric humidity. The term "electrode" as used herein includes not only a single (unipolar) electrode but also a configuration of multiple electrodes. It is also preferable that the second aspect II-(1) above has the following features.

[0035] II-(2): In the second embodiment of the method for producing conductive polymer fibers, not only a single electrode but also an array of multiple electrodes can be used in the fixing step. Specifically, with regard to the fixing process, multiple electrodes are used as the electrodes, and the multiple electrodes are comb-tooth electrodes having multiple comb teeth arranged in the longitudinal direction of the base fiber, and the comb-tooth electrodes are arranged so as to sandwich the base fiber from both radial sides of the base fiber, and the multiple comb teeth are arranged so as to be alternately combined in the longitudinal direction of the base fiber from both radial sides of the base fiber, and the method may also be such that the base fiber is run while the multiple comb teeth provided on the comb-tooth electrodes are pressed against and guided against the base fiber from both radial sides, and electricity is passed through the base fiber.

[0036] II-(3): In the second aspect of the method for producing conductive polymer fibers, in the fixing step, a plurality of electrodes are used as the electrodes, and the plurality of electrodes are arranged in the longitudinal direction of the base fiber and are rotor electrodes arranged so as to sandwich the base fiber from both radial sides of the base fiber, the rotor electrode arranged on one side of the radial direction of the base fiber is roller-shaped, and the rotor electrode arranged on the other side is pulley-shaped, and the rotor electrodes arranged on both sides of the base fiber are arranged alternately in the longitudinal direction of the base fiber, and it is preferable that the roller-shaped rotor electrode is pressed against the base fiber and the base fiber is guided by a groove formed in the pulley-shaped rotor electrode while the base fiber is run between the plurality of electrodes to pass current through it.

[0037] II-(4): In the second embodiment of the method for producing a conductive polymer fiber, it is more preferable that, in the fixing step, the substrate fiber is pressed against the roller-shaped rotor electrode while being guided by the groove of the pulley-shaped rotor electrode, thereby adjusting the arrangement shape of the fiber bundle, and thereby applying electricity while adjusting the amount of the conductor impregnated into and / or attached to the substrate fiber.

[0038] The second aspect also provides the following manufacturing device for conductive polymer fibers. II-(5): The manufacturing apparatus for conductive polymer fibers of the second aspect described above is characterized by comprising: an immersion container that contains a conductive solution containing PEDOT-PSS {poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)} as a conductive polymer, and that immerses an insulating base fiber consisting of a thread-, string-, cloth-, or ribbon-shaped fiber bundle in the conductive solution to impregnate and / or adhere the conductor to the base fiber; a winding unit that vertically pulls the base fiber out of the conductive solution contained in the immersion container; electrodes that electrochemically polymerize and fix the conductor impregnated and / or adhered to the base fiber by passing an electric current through the base fiber that is pulled vertically while it is running; a drying unit that blows air toward the base fiber to dry it to which the conductor has been polymerized; and a humidity control unit that adjusts the atmospheric humidity in the vicinity of the base fiber.

[0039] The above device also preferably has the following features: II-(6): It is also preferable to adopt a configuration in which the electrode is composed of a plurality of electrodes, and the plurality of electrodes are comb-tooth electrodes having a plurality of comb teeth arranged in the longitudinal direction of the base fiber, the comb-tooth electrodes are arranged so as to sandwich the base fiber from both radial sides of the base fiber, and the plurality of comb teeth are arranged so as to be alternately combined in the longitudinal direction of the base fiber from both radial sides of the base fiber, and the plurality of comb teeth provided on the comb-tooth electrodes are pressed against and guided from both radial sides of the base fiber, while the base fiber is run to pass electricity through it.

[0040] II-(7): In the manufacturing apparatus for conductive polymer fibers of the second aspect described above, it is preferable that the electrode consists of a plurality of electrodes, and the plurality of electrodes are arranged in the longitudinal direction of the base fiber and are rotor electrodes arranged so as to sandwich the base fiber from both radial sides of the base fiber, the rotor electrode arranged on one side of the radial direction of the base fiber is roller-shaped, and the rotor electrode arranged on the other side is pulley-shaped, the rotor electrodes arranged on both sides of the base fiber are arranged alternately in the longitudinal direction of the base fiber, and the base fiber is made to run between the plurality of electrodes while being guided by grooves formed in the pulley-shaped rotor electrode while being pressed against the base fiber, and current is passed through the base fiber.

[0041] II-(8): In the manufacturing device for conductive polymer fibers of the second aspect described above, it is more preferable that the plurality of electrodes are configured such that the roller-shaped rotor electrode is pressed against the base fiber while being guided by the groove of the pulley-shaped rotor electrode to adjust the arrangement shape of the fiber bundle, thereby applying current while adjusting the amount of the conductor impregnated into and / or attached to the base fiber.

[0042] (Third Aspect) A third aspect related to the present invention is the following bioelectrode. III-(1): A bioelectrode characterized by using a conductive composite fiber containing a conductive polymer. The bioelectrode preferably has the following features.

[0043] III-(2): A bioelectrode according to III-(1), characterized in that it is provided with a string-, band- or cloth-shaped contactor made of the conductive composite fiber.

[0044] III-(3): The bioelectrode described in III-(2) is characterized in that the contactor is formed by bundling multiple conductive composite fibers or by wrapping the conductive composite fibers around a metal wire.

[0045] III-(4): The bioelectrode according to any one of III-(1) to (3), wherein the conductive composite fiber has adsorptivity or hydrophilicity to the skin.

[0046] III-(5): A bioelectrode according to any one of III-(2) to (4), characterized in that the contacts are supported by a bow-shaped or hairpin-shaped frame.

[0047] III-(6) The bioelectrode according to any one of III-(2) to (4), wherein the contacts are disposed on the surface of a sheet-like substrate.

[0048] III-(7): A bioelectrode according to III-(6), characterized in that an elastic holder is provided on the back surface of the sheet-like substrate, and the holder is arranged to be slidable along the back surface.

[0049] A third aspect related to the present invention includes the following biological signal measuring device. III-(8): A biosignal measuring device characterized by comprising the bioelectrode according to any one of III-(1) to (7).

[0050] (Fourth aspect) A fourth aspect related to the present invention is the following electrode. IV-(1): An implantable electrode characterized by comprising a conductive composite fiber containing a conductive polymer. The implantable electrode according to the present invention preferably also has the following features.

[0051] IV-(2) The implantable electrode according to IV-(1), wherein the conductive composite fiber is formed into a rod or coil shape.

[0052] IV-(3): An implantable electrode according to IV-(1) or (2), characterized in that the conductive composite fiber is bonded to the tip of a needle.

[0053] IV-(4): An implantable electrode according to IV-(3), characterized in that the conductive composite fiber is adhered to the needle via a water-soluble adhesive material.

[0054] IV-(5): The implantable electrode according to any one of IV-(1) to (4), wherein the conductive composite fiber is in a dried and shrunk state.

[0055] IV-(6): An implantable electrode according to any one of IV-(1) to (5), characterized in that a metal, silicon, or carbon wire is connected to the conductive composite fiber.

[0056] IV-(7): The implantable electrode according to any one of IV-(1) to IV-(6), characterized in that the conductive composite fiber formed into a rod or string shape is used as a core, and at least a portion of the core is coated with a water-resistant polymer, thereby forming a flow path for liquid to permeate from one end of the coated core to the other end.

[0057] IV-(8): The implantable electrode according to IV-(7), wherein the flow path contains a solution containing a drug.

[0058] IV-(9): A biological signal measuring device characterized by being equipped with the implantable electrode according to any one of IV-(1) to (8).

[0059] The conductive composite fibers described in IV-(1) to (8) above may contain one or more of glycerol, sorbitol, ethylene glycol, squalane, silicone, mineral oil, and MPC (2-methacryloyloxyethyl phosphorylcholine). By containing these, the rate at which the conductive composite fiber absorbs water in biological tissue can be slowed, and the rate at which the conductive composite fiber swells can be slowed. As a result, the conductive composite fiber can be prevented from swelling and reducing its mechanical strength during the process of embedding the conductive composite fiber in biological tissue.

[0060] The conductive composite fiber described in IV-(7) above may have a reservoir or chamber connected to one end thereof that can hold a drug solution. By filling the reservoir or chamber with a solution containing one or more drugs, such as glycerol, sorbitol, mannitol, fructose, NGF (nerve growth factor), BDNF (brain-derived neurotrophic factor), SKF96365, cilostazol, gadolinium, NT3 (neurotrophin-3), GSNO (S-nitrosoglutathione), magnesium, TRIM (1-(2-trifluoromethylphenyl)imidazole), EGTA (ethylene glycol tetraacetic acid), or Ruthenium Red, the solution can be permeated from the one end to the other end of the coated conductive composite fiber. In other words, the solution can be released from the other end within biological tissue, allowing the drug or other substance contained in the solution to be administered locally around the conductive composite fiber.

[0061] One or more of the drugs may be impregnated into or coated on the conductive composite fiber described in any one of IV-(1) to (8). In this case, the drug is gradually released from the conductive composite fiber placed in biological tissue, and the drug can be administered locally around the conductive composite fiber.

[0062] A thread may be connected to the conductive composite fiber described in IV-(1), (2), (5), (6), or (7). Furthermore, a surgical needle may be tied to the thread. By first introducing the thread into a living body and then pulling the thread, the thread connected to the thread can be smoothly introduced into the living tissue. [Effects of the Invention]

[0063] The present invention can provide the following excellent effects. (Effect of the first aspect) According to a first aspect of the present invention, it is possible to provide a conductive polymer fiber that is excellent in conductivity, strength in both dry and wet states, and flexibility, and a bioelectrode including the same. According to the conductive polymer fiber described in I-(1) of the present invention, a fiber can be obtained that combines the high strength and flexibility of the base fiber with the electrical conductivity and hydrophilicity of the conductive polymer PEDOT-PSS. According to the configuration of I-(2), the additive suppresses the water absorption of PEDOT-PSS, preventing a decrease in strength due to the wet state, resulting in a conductive polymer fiber with higher strength. According to the configuration of I-(3), the conductor covers the base fiber, thereby further increasing the conductivity of the conductive polymer fiber and making it easier to bring multiple conductive polymer fibers into contact with each other and establish electrical conductivity. According to the configuration of I-(4), since the conductor is impregnated into the base fiber, there is no risk of the conductor and the base fiber separating, resulting in a fiber with excellent long-term reliability. According to the configuration of I-(5), the metal or carbon is disposed inside the conductive polymer fiber and sandwiched between the surrounding conductors, resulting in a fiber with even higher conductivity. Furthermore, since the metal or carbon is not exposed on the fiber surface, corrosion and deterioration of the metal or carbon are prevented. According to the configuration of I-(6), the conductor covers the base fiber, thereby further increasing the conductivity of the conductive polymer fiber and making it easier to bring multiple conductive polymer fibers into contact with each other and establish electrical conductivity. According to the configuration of I-(7), the conductive polymer fiber is protected by the insulating layer, resulting in a fiber with excellent durability. The bioelectrode I-(8) of the present invention is provided with conductive polymer fibers that are excellent in conductivity, strength in both dry and wet states, and flexibility. This allows for a high degree of freedom in the location where it can be placed on the body surface or inside the body, provides excellent workability during placement, enables sufficient electrical measurements, and enables measurements over a relatively long period of time.

[0064] (Effect of the second aspect) According to the second aspect of the present invention, the following effects can be obtained. According to a second aspect of the present invention, the method for producing conductive polymer fibers employs a method in which a base fiber impregnated with and / or attached to a conductor containing PEDOT-PSS is vertically lifted from a conductor solution while being transported between one or more electrodes and an electric current is applied. This allows the process of electrochemically polymerizing and fixing the conductor to the base fiber to be carried out continuously in a single step, thereby improving productivity. Furthermore, by vertically lifting the base fiber while transporting it between electrodes, the conductor to be polymerized and fixed to the base fiber can be evenly dispersed, preventing uneven distribution. Therefore, it is possible to produce conductive polymer fibers with high biocompatibility, good homogeneity, and excellent conductivity and durability with high productivity.

[0065] Furthermore, a second aspect of the present invention, in accordance with an apparatus for producing conductive polymer fibers, is configured to include a winding section that vertically pulls up a base fiber impregnated with and / or attached to a conductor, including PEDOT-PSS, from a conductor solution in a dipping vessel, and one or more electrodes that apply a current while the base fiber is running. This, as with the above, enables the process of electrochemically polymerizing and fixing a conductor to the base fiber to be carried out continuously in a single step, thereby improving productivity. Furthermore, by providing an electrode that applies a current while the base fiber is being pulled up vertically, the conductor that is polymerized and fixed to the base fiber can be evenly dispersed, preventing uneven distribution. Therefore, conductive polymer fibers with high biocompatibility, good homogeneity, and excellent conductivity and durability can be obtained with high productivity. More specifically, the following effects can be obtained. According to II-(1) to (8) of the second aspect, the following effects can be obtained.

[0066] According to the method for producing conductive polymer fibers having the configuration of II-(1), a base fiber impregnated with and / or attached to a conductor including PEDOT-PSS is pulled vertically from a conductor solution while running between electrodes and applying electricity, thereby electrochemically polymerizing and fixing the conductor to the base fiber. Furthermore, with this configuration, by pulling the base fiber vertically while running it between the electrodes, the conductor polymerized and fixed to the base fiber can be evenly dispersed, preventing uneven distribution, thereby obtaining conductive polymer fibers with excellent conductivity and durability.

[0067] In the case of II-(2), the process of electrochemically polymerizing and fixing the conductor to the base fiber can be carried out continuously in a single step, thereby improving productivity. In addition, according to this configuration, a comb-tooth electrode having multiple comb teeth arranged in the longitudinal direction of the base fiber is used, and the multiple comb teeth are arranged so that they are alternately combined in the longitudinal direction of the base fiber from both radial sides of the base fiber.As a result, the base fiber repeatedly comes into contact with the multiple comb teeth and electricity is passed through, thereby increasing the efficiency of polymerization fixation of the conductor to the base fiber.

[0068] According to the configuration of II-(4), the base fiber is pressed against the roller-shaped rotor electrode, and the base fiber is guided by grooves formed in the pulley-shaped rotor electrode while running between the electrodes and applying current. This reduces friction caused by contact between the base fiber and the electrodes and prevents the conductor fixed to the base fiber from peeling off. Furthermore, by adjusting the arrangement of the fiber bundles, the amount of conductor impregnated into and / or attached to the base fiber can be adjusted while applying current, allowing any amount of PEDOT-PSS to be retained and polymerized and fixed.

[0069] The conductive polymer fiber manufacturing apparatus of II-(5) includes a winding section that vertically lifts a base fiber impregnated with and / or attached to a conductor, including PEDOT-PSS, from a conductor solution in an immersion vessel, and an electrode that applies current while the base fiber is running, thereby electrochemically polymerizing and fixing the conductor to the base fiber. Furthermore, this configuration includes an electrode that applies current while the base fiber is vertically lifted, which allows the conductor to be evenly dispersed and fixed to the base fiber, preventing uneven distribution, thereby enabling the production of conductive polymer fibers with excellent conductivity and durability. The conductive polymer fiber manufacturing apparatus of the present invention can employ a configuration in which a single electrode is used as the electrode, or an arrangement of multiple electrodes. In this case, the electrochemical polymerizing and fixing of the conductor to the base fiber can be performed continuously in a single step, thereby improving productivity.

[0070] According to the configuration of II-(6), the electrodes are provided with comb-tooth electrodes, and the comb teeth are arranged so that they are alternately combined in the longitudinal direction of the base fiber from both radial sides of the base fiber.Therefore, by repeatedly contacting the base fiber with the comb teeth and passing electricity through them, it is possible to increase the efficiency of polymerization fixation of the conductor to the base fiber.

[0071] According to the configuration of II-(8), the multiple electrodes are composed of a roller-shaped rotor electrode arranged on one radial side of the base fiber and a pulley-shaped rotor electrode arranged on the other radial side. Therefore, by pressing the roller-shaped rotor electrode against the base fiber and guiding it using the grooves formed in the pulley-shaped rotor electrode, the base fiber is run between the multiple electrodes and an electric current is applied. This reduces friction caused by contact between the base fiber and the electrodes and prevents the conductor fixed to the base fiber from peeling off. Furthermore, by adjusting the arrangement of the thread-like fiber bundles with the above-mentioned rotor electrode, the amount of conductor impregnated into and / or attached to the base fiber can be adjusted while applying an electric current, thereby enabling the retention and polymerization of any amount of PEDOT-PSS.

[0072] (Effect of the third aspect) According to the third aspect of the present invention, the following effects can be obtained. The body-surface-mounted bioelectrode of the third aspect of the present invention comprises a composite fiber made by combining a conductive polymer and a flexible fiber material. This improves the ease of attachment to the body surface compared to conventional methods, allowing for a smaller electrode and a smaller contact area with the skin. Furthermore, because the bioelectrode of the present invention is made of a flexible fiber material, it causes less irritation to the skin when worn and is less likely to cause discomfort during wear. Furthermore, because the composite fiber constituting the bioelectrode of the present invention has appropriate adhesive properties to the skin, it is not necessary to seal the skin and the electrode with a highly adhesive gel or tape, as is the case with conventional bioelectrodes. In other words, the bioelectrode of the present invention reduces the burden on the subject (wearer) and provides a comfortable fit. More specifically, the following effects can be obtained.

[0073] The bioelectrode and device according to the third aspect can provide the following effects. The III-(1) bioelectrode uses a conductive composite fiber that is conductive, flexible, and has excellent tensile strength. Compared to conventional bioelectrodes, it causes less discomfort and damage to the wearer when worn, has low electrode resistance per unit area, enables precise transmission of biosignals, and is suitable for miniaturization and lightweight design. In III-(2), the shape of the contact is suitable for contact with the skin or the surface of a living body, allowing for more precise transmission of biological signals. In addition, discomfort and damage to the wearer are further reduced. In III-(3), the bioelectrode is provided with a contactor having the above-described configuration, thereby increasing the structural strength of the contactor and the bioelectrode and further reducing the electrode resistance. In III-(4), the conductive composite fiber has adhesiveness or hydrophilicity to the skin, so that the bioelectrode can be placed independently on the skin surface or the surface of a living body, and it is easier to transmit high-precision biosignals with reduced noise. Furthermore, the bioelectrode can be placed without using adhesive and conductive paste or gel, which was previously required to place a conventional bioelectrode on the skin surface.

[0074] According to the bioelectrode of III-(5), it is possible to more easily insert the bioelectrode between the hairs and bring the electrode surface into contact with the scalp. According to the bioelectrode of III-(6), the contacts can be brought into stable contact with a wide area of ​​the skin surface or the surface of the living body. According to the bioelectrode of III-(7), the elasticity of the holder allows the contacts arranged on the surface of the sheet-like substrate to be pressed against the skin surface, thereby stably placing the contacts. Furthermore, while maintaining this stable state, the holder slides along the back surface of the sheet-like substrate, moving independently of the sheet-like substrate and changing the relative position between the holder and the skin surface. Therefore, biosignals can be transmitted stably even when the wearer of the bioelectrode moves their body. In III-(8), examples of the biosignal measuring device include an electrocardiogram measuring device, a heart rate monitor, an electroencephalogram measuring device, etc. In the biosignal measuring device, the bioelectrode may have not only a function of receiving a signal from the surface of the living body but also a function of transmitting an electrical signal (electrical stimulation).

[0075] The sheet-like substrates described in III-(6) and (7) above and the sheet-like substrates that may be included in the bioelectrodes constituting the biosignal measuring device described in III-(8) above are preferably provided with openings, which improve the breathability between the sheet-like substrate and the skin and reduce stuffiness of the skin.

[0076] (Effects of the fourth aspect) According to the fourth aspect of the present invention, the following effects can be obtained. According to the implantable electrode of the fourth aspect of the present invention, the conductive composite fiber constituting the electrode is flexible and has excellent biocompatibility, thereby reducing invasiveness to the biological tissue it is implanted in. Furthermore, the conductive polymer contained in the conductive composite fiber can detect weak electrical signals within the body, allowing highly accurate signal transmission and reception between an external device and the implanted electrode. Furthermore, since the mechanical strength is increased by the fiber material that constitutes the conductive composite fiber, the electrode will not be damaged by external forces when implanted in the body, and it has excellent durability after implantation in the body. The implantable electrodes provided in the biosignal measuring device of the present invention are less invasive to biological tissue, and therefore high-precision signal transmission and reception can be performed between an externally installed measuring device and the implanted electrode portion without impairing the inherent functions of the biological tissue. More specifically, the following effects can be obtained.

[0077] According to the electrode and device of the fourth aspect, the following effects can be obtained. According to the implantable electrode of IV-(1), the conductive composite fiber that constitutes the electrode has excellent flexibility and biocompatibility, thereby reducing invasiveness to the biological tissue it is implanted in. Furthermore, the conductive polymer contained in the conductive composite fiber can transmit weak electrical signals within the body, allowing for highly accurate signal transmission and reception between an external device and the implanted electrode. Furthermore, since the mechanical strength is increased by the fiber material that constitutes the conductive composite fiber, the electrode will not be damaged by external forces when implanted in the body, and it has excellent durability after implantation in the body. According to IV-(2), rod-shaped conductive composite fibers can be inserted like needles when implanted in the body, thereby reducing invasiveness to biological tissue. Conductive composite fibers formed into a coil (spiral) shape hardly shift in position within the implanted biological tissue, enabling highly accurate transmission and reception of signals between an external device and the implanted electrode. According to IV-(3), the conductive composite fiber can be placed in biological tissue easily and minimally invasively by the simple operation of inserting (piercing) the needle with the conductive composite fiber attached to its tip into biological tissue. Furthermore, by the simple operation of removing the needle while leaving the placed conductive composite fiber inside the living body, the needle, which is not necessary for transmitting and receiving signals, can be removed from the living body easily and minimally invasively, completing the placement of the conductive composite fiber. According to IV-(4), when the needle is inserted into biological tissue, the adhesive material dissolves by absorbing moisture such as body fluids, and the adhesion between the needle and the conductive composite fiber can be easily released. After the adhesion is released, the needle can be removed from the body, and the conductive composite fiber can be left in the biological tissue.

[0078] According to IV-(5), the conductive fiber in the dry and shrunk state is flexible but has a relatively high mechanical strength, which prevents the conductive fiber from breaking (fracturing) when it is placed (inserted) into biological tissue. In addition, the physical volume of the conductive fiber in the dry and shrunk state is relatively small, which reduces the invasiveness when it is placed (inserted) into biological tissue. According to IV-(6), the conductive composite fiber embedded in biological tissue can be electrically connected to an external device by the electric wire. According to IV-(7), by connecting one end of the core to a reservoir containing a drug solution or the like or a chamber equipped with a tube connector, and placing the other end of the core at a predetermined position within the biological tissue, the drug solution or the like can pass through (penetrate) the conductive composite fiber that constitutes the core, and transport the drug solution into the biological tissue where the other end is located. According to IV-(8), the drug (medicine) can be administered to the site where the electrode is embedded via the flow path. The drug is preferably a drug that has a pharmacological action of suppressing or promoting a biological reaction. Examples of the drug include drugs that reduce damage to biological tissue, drugs that promote the repair of biological tissue, and drugs that promote the growth of biological tissue. According to IV-(9), the implantable electrode is minimally invasive to biological tissue, and therefore signals can be sent and received with high accuracy between an externally installed measuring device and the implanted electrode portion without impairing the inherent functions of the biological tissue.

[0079] The base fiber described in the present invention includes not only a single filament-like fiber but also, for example, a fiber obtained by twisting together a plurality of base fibers to form a twisted thread of a desired thickness. The shape of the base fiber in the present invention is not limited to the above-mentioned filament-like shape, but also includes, for example, a string-like shape, a cloth-like shape, a ribbon-like shape, etc. [Brief explanation of the drawings]

[0080] [Figure 1] 1 is a schematic diagram showing a longitudinal cross section of an example of a conductive polymer fiber of the present invention. FIG. [Figure 2] 1 is a schematic diagram showing a longitudinal cross section of an example of a conductive polymer fiber of the present invention. FIG. [Figure 3] 1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 4] 1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 5]1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 6] 1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 7] 1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 8] 1 is a schematic diagram showing a cross section in a direction perpendicular to the longitudinal direction of an example of a conductive polymer fiber of the present invention. FIG. [Figure 9A] 1 is a graph showing the results of Comparative Example 1-1. [Figure 9B] 1 is a graph showing the results of Example 1-1. [Figure 10] 1 is a graph showing the results of Example 1-2. [Figure 11A] 1 is a schematic diagram showing an example of the present invention, illustrating a state in which a bioelectrode is placed on the body surface. FIG. [Figure 11B] This is a measured human electrocardiogram (leads I, II, and III from top to bottom). [Figure 12A] 10 is a photograph of the fabricated thread-shaped implantable bioelectrode observed with a stereomicroscope. [Figure 12B] These are the action potentials measured in a rat sciatic nerve (from top to bottom: at rest, during muscle contraction, and during muscle relaxation).

[0081] [Figure 13] 1 is a diagram schematically illustrating an embodiment of a method and apparatus for producing conductive polymer fibers according to the present invention, and is a schematic diagram illustrating an example of the configuration of an apparatus for producing conductive polymer fibers. FIG. [Figure 14] This is an enlarged view of a main part that schematically shows an example of an embodiment of the method and manufacturing apparatus for producing conductive polymer fibers of the present invention, and shows the state in which comb-shaped electrodes are arranged on both sides of the base material fiber. [Figure 15A] FIG. 1 is an enlarged view of a main part that schematically illustrates an example of an embodiment of a method and apparatus for producing conductive polymer fibers of the present invention, and shows an example of a roller-shaped rotor electrode. [Figure 15B] FIG. 10 is a diagram showing an example of a pulley-shaped rotor electrode. [Figure 15C] FIG. 10 is a diagram showing an example of a state in which roller-shaped rotor electrodes and pulley-shaped rotor electrodes are alternately combined in the longitudinal direction of the base fiber. [Figure 16] FIG. 10 is a schematic diagram showing another example of an embodiment of the method and apparatus for producing conductive polymer fibers of the present invention, illustrating the case where a single electrode is used. [Figure 17A] FIG. 2 is a diagram for explaining an example of a method and apparatus for producing conductive polymer fibers according to the present invention, and is a photograph showing conductive polymer fibers obtained in Example 2-1 by passing current through a rotor electrode according to the present invention. [Figure 17B] FIG. 1 is a photograph showing conductive polymer fibers obtained by applying current using a comb-shaped electrode in Example 2-2. [Figure 18A] FIG. 2 is a diagram illustrating an example of a method and apparatus for producing conductive polymer fibers according to the present invention, and is a photograph showing the state of conductive polymer fibers obtained in Example 2-1 by electrochemical polymerization and fixation using the method and apparatus of the present invention after a water resistance test. [Figure 18B] FIG. 10 is a photograph showing the state of the conductive polymer fiber obtained by conventional chemical fixation in Comparative Example 2-2 after a water resistance test.

[0082] [Figure 19A] This is a schematic diagram of a comb electrode according to the first embodiment of the third aspect of the present invention, and is a side view of a comb-shaped bioelectrode 310 showing how contactors 311 are fixed like strings to a bow-shaped first frame 312. [Figure 19B] FIG. 3 is a perspective view of the bioelectrode 310. [Figure 19C] 10 is a perspective view showing a state in which the bioelectrode 310 is inserted into the gaps in the hair H and fixed at a position in contact with the scalp S. FIG. [Figure 19D] 10 is a photograph showing the area where the bioelectrode 310 contacts the skin. [Figure 20A]This is a schematic diagram of a hairpin-shaped electrode according to the first embodiment of the third aspect of the present invention, and is a side view of a bioelectrode 320 showing how two contacts 321 are fixed in parallel like strings to a hairpin-shaped hair clip via fixing posts 322. [Figure 20B] FIG. 3 is a perspective view of the bioelectrode 320. [Figure 20C] 10 is a perspective view showing a state in which the hairpin-shaped bioelectrode 320 pinches the hair H at a position close to the scalp S, and the contactor 21 is in contact with the scalp S. FIG. [Figure 20D] The upper photograph shows the upper surface of the hairpin-shaped bioelectrode 320, and the lower photograph shows the lower surface that comes into contact with the skin.

[0083] [Figure 21A] 1 is a schematic diagram showing an example of a cross-sectional structure of a contact, the left part of which shows a cross section of the right part taken along line XX. [Figure 21B] FIG. 10 is a schematic diagram showing a cross-sectional structure of a contact 321 of a second embodiment of the third aspect, in which the left part shows a cross section of the right part taken along line XX. [Figure 21C] 19C is a photograph of a string-like contact 321 having the structure of FIG. 19B. [Figure 22A] 1 is a schematic diagram showing a state in which a comb-shaped bioelectrode 310 is inserted between the hair and an elastic net-shaped holder N is placed over it to hold the bioelectrode 310. FIG. [Figure 22B] FIG. 10 is a top view showing an example in which a bioelectrode 310 is placed on an elastic net N in accordance with the international 10-20 system. [Figure 23A] 1 is a graph showing human electroencephalograms (C3 C4 50 μV 400 msec / div) measured using hairpin-shaped EEG electrodes. [Figure 23B] 1 is a graph showing a human auditory brainstem response (0.2 μV, 1 ms / div 90 dB, click sound, 1000 averagings, showing peaks of IV-VII evoked potentials) measured with a hairpin-shaped EEG electrode.

[0084] [Figure 24A] FIG. 2 is a plan view showing the contact surface of an electrocardiogram electrode 330 with the skin. [Figure 24B] 10 is a side view showing the electrocardiogram electrode 330 placed on the skin surface S. FIG. [Figure 25A] 1 shows an example of a side view and a front view (skin contact surface, i.e., surface) of an electrode pad. [Figure 25B] 1 shows another example of a side view and a front view (skin contact surface, i.e., front surface) of the electrode pad. [Figure 26A] 10 is a cross-sectional view showing the arrangement of electrode pads 338 and holders 335 relative to the trunk B. FIG. [Figure 26B] FIG. [Figure 27] 3 is a graph showing the recorded waveforms of electrocardiograms measured using the bioelectrode 1 according to the present invention and conventional bioelectrodes 2 and 3 in Example 3-3, where the scale bar represents one second and 50 mV. [Figure 28] 10 is a graph showing the results of measuring the moisture content of the skin where bioelectrodes B and C according to the present invention or conventional bioelectrodes D and E are placed, and comparing the degree of sweatiness of the skin caused by each electrode.

[0085] [Figure 29A] FIG. 1 is a side view of a first embodiment of an implantable electrode according to the fourth aspect of the present invention. [Figure 29B] 29B is a side view showing how the conductive composite fiber bundle shown in FIG. 29A swells due to water absorption. FIG. [Figure 29C] FIG. 10 is a side view showing the needle being removed from the swollen conductive composite fiber bundle. [Figure 30A] 10A and 10B are a side view and a bottom view showing an example of an electrode according to a fourth embodiment of the present invention, in which a guide needle is provided with one conductive composite fiber bundle. [Figure 30B] 10A and 10B are a side view and a bottom view showing an example of an electrode according to a fourth embodiment of the present invention, in which two conductive composite fiber bundles are provided in a guide needle. [Figure 30C] 10A and 10B are side and bottom views showing an example of an electrode according to a fourth embodiment of the present invention, in which four conductive composite fiber bundles are provided in a guide needle. [Figure 31A] FIG. 10 is a side view of a second embodiment of the implantable electrode according to the fourth aspect of the present invention. [Figure 31B] FIG. 4 is a side view showing the state in which the conductive composite fiber bundle of the electrode swells due to water absorption. [Figure 31C] FIG. 10 is a side view showing the needle being removed from the swollen conductive composite fiber bundle of the electrode.

[0086] [Figure 32A] FIG. 10 is a schematic diagram showing the introduction of a third embodiment of the implantable electrode of the fourth aspect of the present invention into a nerve cord N'. [Figure 32B] FIG. 10 is a schematic diagram showing the introduction of a third embodiment of an implantable electrode into a nerve cord N′. [Figure 32C] FIG. 10 is a schematic diagram showing the introduction of a third embodiment of an implantable electrode into a nerve cord N′. [Figure 32D] FIG. 10 is a schematic diagram showing the introduction of a third embodiment of an implantable electrode into a nerve cord N′. [Figure 33A] 10A and 10B are side and bottom views of a fourth embodiment of an implantable electrode with a flow channel and a reservoir. [Figure 33B] 4 is a fourth embodiment with a chamber and a tube connector.

[0087] [Figure 34A] (A) Waveforms of the population action potential of the rat brain measured using the fourth embodiment of the implantable electrode (PEDOT-PSS) and a conventional metal electrode (Scale bar 250 ms 40 mV). [Figure 34B] This shows an immunostained image of glial cells (astrocytes) in the rat cerebral cortex using an anti-GFAP antibody, without any electrodes implanted. [Figure 34C] 1 shows an immunostained image of glial cells (astrocytes) in the rat cerebral cortex using an anti-GFAP antibody, and also shows the position (dotted line) where an electrode according to a fourth embodiment of the present invention is embedded and the surrounding area. [Figure 34D]The figure shows an immunostained image of glial cells (astrocytes) in the rat cerebral cortex using an anti-GFAP antibody, and also shows the location where a conventional metal electrode was implanted (dotted line) and the surrounding area. [Figure 35A] 1 is a waveform showing an action potential of the cerebral cortex (barrel cortex) of a rat recorded by the implantable electrode of the first embodiment of the present invention. [Figure 35B] 10 is a waveform showing the collective action potential of the sciatic nerve of a rat recorded using an implantable electrode according to a third embodiment of the present invention (Scale bar 1 second 50 μV). [Figure 35C] 10 is a waveform showing an electrocardiogram of a rat recorded using an implantable electrode according to a third embodiment of the present invention (Scale bar 1 second 50 mV). [Figure 36] 1 is a graph showing the rate of drug transport in a conductive composite fiber bundle coated with PDMS. DETAILED DESCRIPTION OF THE INVENTION

[0088] Preferred examples and embodiments of the present invention will be described below with reference to the drawings for the first to fourth aspects of the present invention. However, the present invention is not limited to the following examples and embodiments. For example, the components and conditions of these preferred examples and embodiments may be combined as appropriate. Preferred examples may also be used interchangeably between aspects. Furthermore, they may be combined with other components as long as no problems arise. Various changes can be made to the position, number, size, quantity, etc., without departing from the spirit of the present invention. For example, the examples that are preferred in the description of FIG. 1 can also be preferably used in other examples of this embodiment unless otherwise specified. Regarding the first aspect Hereinafter, an embodiment of the first aspect of the present invention will be described with reference to the drawings, but the present invention is not limited to such an embodiment. A first aspect of the present invention relates to a conductive polymer fiber and a bioelectrode. More specifically, the present invention relates to a conductive polymer fiber in which a conductive polymer is impregnated or attached to a base fiber, and a bioelectrode including the conductive polymer fiber. <First embodiment of the first aspect> The conductive polymer fiber 10 (first embodiment) of the present invention shown in FIG. 1 is a fiber in which a base fiber 11 is coated with a conductor 12 containing PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)) as a conductive polymer. FIG. 1 is a longitudinal cross-sectional view of the conductive polymer fiber 10, and FIG. 3 is a cross-sectional view perpendicular to the longitudinal direction. The conductive polymer fiber 10 has a base fiber 11 as a core, which is surrounded by a conductor 12. This increases the contact area between the two fibers, resulting in a composite fiber in which they are sufficiently bonded to each other. With this configuration, the conductor 12 is reinforced by the base fiber 11, resulting in increased strength compared to a fiber consisting only of the conductor 12. This fiber exhibits excellent strength, particularly in dry and wet conditions. Furthermore, the flexibility of the base fiber 11, which serves as the core, is imparted to the conductive polymer fiber 10.

[0089] The type of base fiber 11 is not particularly limited as long as it is made of a polymer. For example, synthetic fibers, plant fibers, animal fibers, etc. may be used. The material may be a single material or a mixture thereof. Examples of the synthetic fibers include nylon, polyester, acrylic, aramid, polyurethane, and carbon fiber. Examples of the plant fibers include cotton, hemp, and jute. Examples of the animal fibers include silk, wool, collagen, and elastic fibers that constitute animal tissue.

[0090] Among the exemplified base fiber materials, animal fibers (protein-containing fibers) are preferred, as they have excellent adhesion to the conductor 12, high strength in both dry and wet states, and flexibility suitable for use in clothing, etc. Silk fibers are even more preferred, as they have particularly excellent adhesion to and hydrophilicity with PEDOT-PSS, which will be described later. The base fiber is preferably silk alone. A mixture is also preferable if necessary. In the case of a silk mixture, the silk content may be 0.1% or more and less than 100%, 1% or more and less than 95%, 3% or more and less than 90%, 10% or more and less than 80%, 30% or more and less than 70%, or 40% or more and less than 60%. It is also preferable to mix it with other materials as appropriate depending on the purpose.

[0091] Examples of silk fibers that can be used as the base fiber 11 include natural silk fibers from silkworm moths, spiders, and bees, as well as artificial silk fibers produced using genetic engineering technology. Silk contains a protein called fibroin and is a fiber with excellent hydrophilicity, biocompatibility, and dyeability, which has led to its use in clothing and surgical threads. It is one of the fibers that has been used by humans for a long time. For this reason, it is ideally suited for use as the base fiber 11.

[0092] The silk fiber used for the base fiber 11 may be either unprocessed raw silk from which the gelatin component sericin has not been removed, or degummed silk from which some or all of the sericin has been removed. Degummed silk is more preferred from the viewpoints of improving adhesion to the conductor 12 and fiber strength.

[0093] The diameter (thickness) of the base fiber 11 is not particularly limited and can be appropriately selected depending on the application. For example, ranges such as 0.1 μm to 1 mm, 1 μm to 1 mm, and 1 μm to 0.5 mm are possible diameters. When used in clothing, bioelectrodes, biointerfaces, etc., a diameter of 1 μm to 100 μm is preferred. The length of the base fiber 11 is not particularly limited and can be selected appropriately depending on the application. For example, it can be 10 μm to 10 cm for an electrode to be implanted in biological tissue, 1 mm to 50 cm for use in a biointerface on the body surface, and 1 cm to 100 m as a fiber material for weaving or knitting into clothing. However, it is not limited to these lengths and can be selected as needed.

[0094] The base fiber 11 (41) is not particularly limited and can be selected as needed. For example, a plurality of base fibers may be twisted together to form a twisted yarn of a desired thickness (see the example shown in FIG. 6), or a blended yarn made by blending different types of base fibers may be used. The shape of the base fiber is not limited to the thread-like shape described above; for example, string-like, cloth-like, ribbon-like, or other base fiber shapes may be used. Furthermore, in order to improve the hydrophilicity of the base fiber 11, it is also possible to use base fiber that has been subjected to plasma treatment, pore treatment, or chemical coating.

[0095] The conductor 12 contains a conductive macromolecule (conductive polymer), and may consist of only a conductive macromolecule, or may contain other additives.

[0096] The conductive polymer used in the present invention is PEDOT-PSS {poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)}, which has excellent conductivity and hydrophilicity. PEDOT-PSS is a conductive polymer obtained by polymerizing the monomer 3,4-ethylenedioxythiophene in the presence of poly(4-styrenesulfonic acid). PSS functions as a dopant that imparts a negative charge to PEDOT. In the present invention, from the viewpoint of increasing the conductivity of the conductive polymer fiber, it is preferable that the conductive polymer contains a dopant.

[0097] The present inventors have found that the adhesiveness between PEDOT-PSS and protein-containing fibers such as silk is particularly excellent, and the adhesive surfaces of the two do not easily peel off. Based on this finding, in the present invention, it is more preferable to use silk fibers as the base fiber 11 and PEDOT-PSS as the conductive polymer contained in the conductor 12.

[0098] Other examples of conductive polymers that can be used include polyaniline sulfonic acid and polypyrrole. The conductive polymer contained in the conductor 12 may be one type, or two or more types may be used in combination. The molecular weight of the conductive polymer used in the present invention is not particularly limited. For example, a molecular weight in the range of several thousand to several hundred thousand can be used. It may be selected arbitrarily as needed. To give a specific example, the weight average molecular weight (Mw) in terms of polystyrene may be in the range of 1,000 to 900,000, 3,000 to 450,000, or 5,000 to 50,000. However, it is not limited to these ranges.

[0099] An example of a method for forming the conductor 12 is to coat the base fiber 11 with a solvent containing a conductive polymer such as PEDOT-PSS and a dilution solvent, and then dry the solvent to form the conductor 12 consisting only of the conductive polymer. However, the conductor 12 may contain additives other than the conductive polymer.

[0100] Examples of the additives include glycerol, sorbitol, polyethylene glycol-polypropylene glycol copolymer, ethylene glycol, sphingosine, phosphatidylcholine, etc. The additive contained in the conductor 12 may be one type, or two or more types may be used in combination.

[0101] The additives in the above examples can be used to adjust the wettability of conductive polymer fibers such as PEDOT-PSS, or to impart flexibility, thereby improving affinity with biological tissues (skin and tissues) when used as a bioelectrode. Specific examples of the adjustment of the wettability include adjustment of water absorption and prevention of excessive expansion and contraction when wetted and dried.

[0102] The use of a combination of PEDOT-PSS and the additive is preferred because it makes it easier to adjust the wettability of the conductor 12, and in particular makes it easier to prevent excessive expansion and contraction. One reason for this is thought to be that by incorporating PEDOT-PSS, which has high water absorption, together with the additive in advance, there is less room for moisture to penetrate later. Among the above examples, glycerol, sorbitol, polyethylene glycol, and polyethylene glycol-polypropylene glycol copolymer are particularly preferred as additives used to adjust the wettability of PEDOT-PSS and further impart flexibility.

[0103] The conductive polymer fiber 10 having the conductor 12 containing the additive and PEDOT-PSS does not absorb excessive water, has high fiber strength, and is excellent in conductivity even when used in a high-humidity environment. Furthermore, because it also has excellent flexibility, the stiffness (rigidity) of PEDOT-PSS is alleviated, and it has excellent contact and affinity with biological tissue, making it possible to form a bioelectrode that can measure biological signals with little noise.

[0104] The additives contained in the conductor 12 are not limited to the above examples, and may also be, for example, surfactants, alcohols, natural polysaccharides, sugar alcohols, acrylic resins, known organic solvents such as dimethyl sulfoxide, etc.

[0105] The surfactant may be a cationic surfactant, an anionic surfactant, or a nonionic surfactant, which may be used alone or in combination of two or more.

[0106] Examples of the cationic surfactant include quaternary alkyl ammonium salts and alkylpyridinium halides. Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, and fatty acid salts. Examples of the nonionic surfactant include polyoxyethylene and polyoxyethylene alkyl ether.

[0107] As the alcohol, a wide variety of known monohydric alcohols and polyhydric alcohols can be used, and these alcohols may be used alone or in combination of two or more.

[0108] Examples of monohydric alcohols include methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, etc. The carbon skeleton constituting these alcohols may be linear, branched, or cyclic. Examples of polyhydric alcohols include glycols such as ethylene glycol, linear 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.

[0109] 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 polyacrylic acid, polymethyl methacrylate, and polymethyl methacrylate resin.

[0110] The thickness h of the conductor 12 coated around the base fiber 11 is not particularly limited and can be selected arbitrarily. Any thickness is acceptable as long as the effects of the present application are obtained. For example, the thickness may be 0.001 to 2 times the diameter L of the base fiber 11. The thickness h can be selected as needed, for example, 0.01 to 1 times, 0.001 to 0.1 times, 1 to 2 times, or 0.1 to 1 times the diameter L of the base fiber 11. More specifically, when a core is made of silkworm silk fibers with a diameter of 2 to 3 denier (D), i.e., silk fibers with a fiber diameter of approximately 10 to 15 microns, the thickness should be 0.01 microns to 10 microns. The fiber diameter can be measured by any method, but can also be confirmed using, for example, electron microscope photographs. If necessary, the base fiber may not be completely covered by the conductor. In the present invention, the thickness may be the length of the line from the center of the base fiber to the surface that is covered by the conductor.

[0111] By covering the periphery of the base fiber 11 with the conductor 12, the conductivity of the conductive polymer fiber 10 is further increased, and it becomes easier to contact and conduct electricity between multiple conductive polymer fibers 10. Furthermore, within the above thickness range, the conductive polymer fiber 10 can be made into a fiber with better conductivity without impairing its flexibility. Within the above range, the thicker the fiber, the higher the conductivity of the fiber. In other words, by adjusting the thickness of the conductor 12, the conductivity or electrical resistance of the conductive polymer fiber 1 can be adjusted.

[0112] <Method for producing conductive polymer fibers (1a)> As in the conductive polymer fiber 10 shown in FIG. 1, examples of a method for attaching or covering the surface of the base fiber 11 with the conductor 12 include the following methods. First, an aqueous solution containing a conductive polymer (e.g., a commercially available PEDOT-PSS solution (Heraeus: CLEVIOS P)) is applied to the surface of the base fiber 11 in a solution bath. After this, or after the solution is uniformly applied to the surface of the base fiber 11 using a roller or brush, some of the water contained in the solution is dried and removed. Next, an organic solvent such as acetone, methanol, or ethanol, or a fixing solution such as a magnesium chloride solution, is applied to gel the conductive polymer such as PEDOT-PSS. This provides an example of a method (hereinafter sometimes referred to as "preparation method 1a") for fixing a conductor 12 containing a conductive polymer such as PEDOT-PSS to the surface of the base fiber 11. One example of the aqueous solution is an aqueous solution containing a conductive polymer such as PEDOT-PSS at a concentration of 0.1 to 50 (v / v)%. This concentration can be selected as needed. For example, the concentration may be 1 to 30%, 30 to 50%, or 0.5 to 15%. The aqueous solution may contain the additives described above as needed. Furthermore, in the present invention, in addition to the example of CLEVIOS P, any solution containing PEDOT-PSS can be used as the aqueous solution containing a conductive polymer.

[0113] <Method of adding additives> Examples of methods for incorporating an additive into the conductor 12 include a method in which the conductor 12 coated on the base fiber 11 by preparation method 1a is dried, and then the resulting conductive polymer fiber 10 is used to coat the surface with the additive, or a method in which the conductive polymer fiber 10 is immersed in a solution containing the additive for a predetermined time, and then the excess additive solution remaining on the surface is removed. Another method that can be applied is a method in which a mixed solution in which the additive is mixed into a solution containing a conductive polymer to be coated on the surface of the base fiber 11 is used, and the conductive polymer and the additive are coated or immersed together.

[0114] An example of the mixed liquid is an aqueous solution containing a conductive polymer such as PEDOT-PSS at a concentration of 0.1 to 50 (v / v) % and an additive such as glycerol at a concentration of 0.1 to 50 (v / v) %. The concentration of the additive in the conductor 12 in the present invention is not particularly limited and can be, for example, 0.1 to 50 wt %. This concentration can be selected as needed and may be, for example, 0.1 to 20 wt %, 20 to 50 wt %, or 0.1 to 5 wt %.

[0115] <Second embodiment of the first aspect> The conductive polymer fiber 20 (second embodiment) of the present invention shown in Fig. 2 is a fiber in which a base fiber 21 is impregnated with a conductor 22 containing a conductive polymer. Fig. 2 is a longitudinal cross-sectional view of the conductive polymer fiber 20, and Fig. 4 is a cross-sectional view in a direction perpendicular to the longitudinal direction. The conductor 22 permeates the interior of the base fiber 21, forming a composite fiber in which the two are integrated. With this configuration, there is no risk of the conductor 22 falling off the base fiber 21. Furthermore, since the conductor 22 is reinforced by the base fiber 21, the strength can be increased compared to a fiber consisting only of the conductor 22. The flexibility of the base fiber 21 is also maintained. In the present invention, the entire internal space of the base fiber may be filled with the conductor, but some spaces may be unfilled. It is also preferable that the conductor reaches the center of the base fiber, but if necessary, some parts may not reach the center.

[0116] The materials constituting the base fiber 21 and the conductor 22 can be the same as those constituting the base fiber 11 and the conductor 12 described in the first embodiment. As in the first embodiment, it is preferable that the conductor 22 contains the additive.

[0117] <Method for producing conductive polymer fibers (1b)> An example of a method for immersing a conductor 22 inside a base fiber 21, as in the conductive polymer fiber 20 shown in Figure 2, is to place the base fiber 21 in a solution bath and immerse the base fiber 21 in an aqueous solution containing a conductive polymer (for example, a commercially available PEDOT-PSS solution (Heraeus CLEVIOS P)) for a predetermined period of time, then dry and remove some of the water contained in the solution, and then apply an organic solvent such as acetone, methanol, or ethanol, or a fixing solution such as a magnesium chloride solution, to gel the PEDOT-PSS, thereby fixing the conductor 22 containing PEDOT-PSS to the surface of the base fiber 21 (hereinafter sometimes referred to as preparation method 1b). The aqueous solution may contain the additives as required.

[0118] Examples of methods for promoting penetration of the solution containing the conductive polymer into the base fiber 21 include adjusting the pH of the solution before immersion, applying mechanical manipulation such as tension or compression to the base fiber 21 during immersion, heating the solution during immersion, and applying a treatment such as reduced pressure or increased pressure during immersion. Specifically, when base fiber 21 such as silk is immersed in a PEDOT-PSS solution, it is preferable to adjust the pH of the solution to 1 to 6.

[0119] <Third embodiment of the first aspect> The conductive polymer fiber 30 (third embodiment) of the present invention shown in Fig. 5 is formed by impregnating a base fiber 31 with a conductor 32 containing a conductive polymer, coating the base fiber 31 with a metal 33, and further coating the coated metal or carbon 33 with a conductor 34. Fig. 5 is a cross-sectional view of the conductive polymer fiber 30 in a direction perpendicular to the longitudinal direction. Hereinafter, unless otherwise specified, "metal or carbon" will be referred to as metals.

[0120] The third embodiment combines the advantages of the first and second embodiments. In addition, the coated metals 33 themselves contribute to improving the conductivity of the conductive polymer fiber 30. Because the metals 33 are sandwiched between the conductors 32 and 34, the metals 33 are not exposed on the fiber surface. This prevents corrosion and deterioration of the metals 33. If necessary, a portion of the metals 33 may be exposed on the fiber surface.

[0121] The materials constituting the base fiber 31 and the conductors 32, 34 can be the same as those constituting the base fiber and conductors described in the first and second embodiments. As in the first and second embodiments, it is preferable that the conductors 32, 34 contain the additive. The materials constituting the conductors 32 and 34 may be the same or different.

[0122] There are no particular limitations on the type of metal 33, and examples include titanium, gold, silver, copper, carbon, etc. Among these metals, gold is preferred because it has excellent corrosion resistance, conductivity, and ductility. The carbon is preferably one containing carbon atoms as a main raw material, and examples thereof include carbon materials containing carbon black, glassy carbon, graphene, carbon nanotubes, fullerene, etc. The carbon content in these carbon materials is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and even more preferably 95 to 100 mass%. The metals 33 may be one type of metal used alone or two or more types of metals used in combination.

[0123] The thickness of the metal 33 (metal layer or carbon layer) coated around the base fiber 31 is not particularly limited and can be changed appropriately depending on the type of metal. For example, it can be in the range of 0.1 nm to 1 mm. For example, when gold is used, the thickness can be 1 nm to 2 μm. The metal layer 33 can be formed by a known film formation method such as sputtering or electroless plating. The carbon layer can be formed by a known film formation method such as carbon vapor deposition.

[0124] <Method for producing conductive polymer fibers (2a)> The conductive polymer fibers 30 can be produced by the following method, for example. First, the conductive polymer fiber 20 obtained by Preparation Method 1b is coated with a metal 33 by a known film-forming method. The obtained fiber is immersed in an aqueous solution containing a conductive polymer (for example, a commercially available PEDOT-PSS solution (Heraeus CLEVIOS P)), and the metal 33 is used as an electrode. By applying a DC voltage of +0.5 V to 20 V, a conductive polymer fiber 30 can be produced in which a conductive polymer such as PEDOT-PSS is electrochemically fixed to the surface of the metal 33. This method will be referred to as Preparation Method 2a below. Here, a method of forming a metal layer around the conductive polymer fiber 20 has been exemplified, but it is also possible to adopt a method of simply forming a metal layer on a base fiber and similarly electrically fixing the conductive polymer around the metal layer.

[0125] By adding ethylenedioxythiophene (EDOT) to the solution, conductive polymer fibers 30 with even better conductivity can be obtained. The amount of ethylenedioxythiophene can be selected arbitrarily. For example, a 0.1 w / v % solution of ethylenedioxythiophene (Heraeus CLEVIOS M V2) may be added to the solution.

[0126] <Method for producing conductive polymer fibers (2b)> Another example is a method of electrochemically immobilizing a conductive polymer without forming a metal 33. That is, the conductive polymer fiber 20 obtained by Preparation Method 1b already has conductivity. Utilizing this conductivity, the conductive polymer fiber 20 obtained by Preparation Method 1b is added to a solution containing a conductive polymer (for example, a commercially available PEDOT-PSS solution (Heraeus CLEVIOS P)), and a DC voltage of +0.5 V to 20 V is applied thereto, thereby producing a conductive polymer fiber in which a conductive polymer such as PEDOT-PSS is electrochemically immobilized on the surface surrounding the conductive polymer fiber 20. This method will be referred to as Preparation Method 2b below. The aqueous solution may contain the additives described above, if necessary.

[0127] Although the structure of the conductive polymer fiber obtained by preparation method 2b is not shown, it has a structure in which the metal 33 is removed from the conductive polymer fiber 30 shown in FIG. 5 and the metal 33 is replaced with a conductor 34.

[0128] <Fourth embodiment> A conductive polymer fiber 40 (fourth embodiment) of the present invention shown in FIG. 6 is formed by disposing a conductor 42 containing a conductive polymer between multiple base fibers 41 in close contact with the base fibers 41. FIG. 6 is a cross-sectional view of the conductive polymer fiber 40 in a direction perpendicular to the longitudinal direction. The number of base fibers can be selected arbitrarily and is an integer of 2 or greater. For example, it may be 2, 3, 4, 5, 6, 7, or 8. It may also be a number in the range of 1 to 1,000 or 1 to 30. The conductive polymer fiber 40 may be formed by twisting or knitting multiple base fibers 41 to form a higher-order structure such as a twisted string, woven fabric, or nonwoven fabric. As shown in the example shown in FIG. 6, a conductor 42 containing the conductive polymer PEDOT-PSS is disposed between multiple base fibers 41 in close contact with the base fibers 41, and the conductive polymer fiber 40 can be configured into a higher-order structure such as a twisted string, woven fabric, or nonwoven fabric by twisting or knitting multiple base fibers 41. The conductor 42 serves to bond the multiple base fiber 41 together, thereby increasing the strength of the higher-order structure. Furthermore, a relatively large amount of conductor 42 can be disposed between the multiple base fiber 41, resulting in a conductive polymer fiber with superior conductivity. Note that the amounts compared here are the amounts of conductor disposed on the surface of a single base fiber.

[0129] The method for producing the conductive polymer fibers 40 is not particularly limited, and for example, a method of immersing the higher-order structure in a solution containing a conductive polymer and then drying it can be mentioned. The fiber spacing between the multiple base fibers 41 can be selected arbitrarily. For example, the fiber spacing between the base fibers 41 may be approximately 0.01 to 3 times the diameter of the base fiber. For example, when base fibers 41 with a diameter of 10 μm to 15 μm are used, the fiber spacing can be set to 0.01 μm to 50 μm. With a fiber spacing in this range, the conductors 42 can be sufficiently distributed between the fibers.

[0130] The materials constituting the base fiber 41 and the conductor 42 can be the same as those constituting the base fiber and the conductor described in the first embodiment. As in the first embodiment, it is preferable that the conductor 42 contains the additive.

[0131] Fifth embodiment of the first aspect The conductive polymer fiber 50 (fifth embodiment) of the present invention shown in Fig. 7 is formed by arranging a conductor 54 containing a conductive polymer between a plurality of base fibers 51 impregnated with a conductor 52 containing a conductive polymer and in close contact with the base fibers 51. Fig. 7 is a cross-sectional view of the conductive polymer fiber 50 in a direction perpendicular to the longitudinal direction.

[0132] The configuration of the fifth embodiment is the same as that of the fourth embodiment, except that the base fiber 51 is impregnated with a conductor 52. In this embodiment, the conductor 52 further improves the conductivity.

[0133] The material constituting the conductor 52 may be the same as or different from the material constituting the conductor 54. The manufacturing method of the fifth embodiment can be the same as or different from the manufacturing methods of the first to fourth embodiments.

[0134] Sixth embodiment of the first aspect A conductive polymer fiber 60 (sixth embodiment) of the present invention shown in Fig. 8 is formed by coating a base fiber 61 with a conductor 62 containing a conductive polymer, and coating the periphery of the conductor 62 with an insulating layer 63. Fig. 8 is a cross-sectional view of the conductive polymer fiber 60 in a direction perpendicular to the longitudinal direction. The fiber has excellent durability because the base fiber 61 and the conductor 62 are protected by the insulating layer 63. If necessary, part of the insulating layer 63 can be removed to expose part of the conductor 62 on the surface of the fiber.

[0135] Known insulating materials can be used as the material for the insulating layer 63. From the viewpoints of biocompatibility and flexibility, polytetrafluoroethylene (PTFE) and silicone resin (silicone rubber) are preferred. The thickness of the insulating layer 63 is not particularly limited. It can be selected as desired and can be in the range of, for example, 0.1 μm to 3 mm, 0.1 μm to 2 mm, 1 μm to 2000 μm, or 10 μm to 500 μm. Furthermore, the base fiber 61 and the conductor 62 can be coated with the insulating layer 63 by a known resin coating method.

[0136] <Bioelectrode> The conductive polymer fiber according to the present invention has sufficient strength, conductivity and flexibility even under high humidity conditions, and is therefore suitable for use in clothing as well as bioelectrodes and biointerfaces. By bundling multiple conductive polymer fibers according to the present invention into a thread or string, sufficient conductivity for measuring biosignals can be achieved. Because the conductive polymer PEDOT-PSS is disposed in the fiber, electrical continuity can be immediately established by contacting the fiber with the object to be measured. Therefore, by contacting, ligating, wrapping, sewing, or folding the fiber (thread) with the object to be measured, it is possible to stably record biosignals for a long period of time. When a bioelectrode is made using the conductive polymer fiber of the present invention as an electrode, the fibers can be bound together into a thread and then knotted, knitted, sewn, or bundled to provide a variety of bioelectrodes, such as cloth, belts, straps, etc. Furthermore, by combining the conductive polymer fibers and forming them into a nonwoven fabric, etc., a patch-shaped (cloth-shaped) bioelectrode can also be made.

[0137] Regarding the second aspect A second aspect of the present invention relates to a method and apparatus for producing conductive polymer fibers, and in particular to a method and apparatus for producing conductive polymer fibers, in which a conductor containing a conductive polymer is impregnated into or attached to insulating fibers (fiber bundles). Hereinafter, embodiments of a method and apparatus for producing conductive polymer fibers according to the second aspect of the present invention will be described with reference mainly to Figures 13 to 18 as appropriate, but the second aspect of the present invention is not limited to the following embodiments. Here, Figures 13 to 16 are schematic diagrams showing the apparatus for producing conductive polymer fibers described in this embodiment. Figures 1, 3, 6, etc. are schematic diagrams showing examples of conductive polymer fibers obtained by the method and apparatus for producing conductive polymer fibers according to this embodiment.

[0138] [Conductive polymer fiber] The manufacturing method and manufacturing apparatus according to the second aspect of the present invention can preferably form the conductive polymer fibers described in the first aspect above. The preferred conditions described in the first aspect can also be used here. For example, the conductive polymer fibers shown in Figures 1, 3, and 6 can be easily formed. In this aspect, it is more preferable to use PEDOT-PSS as the conductive polymer contained in the conductor 12, but the base fiber used in this embodiment is not limited to silk fiber, and other general fiber materials can be used without any restrictions. It is only necessary that PEDOT-PSS is included as the conductive polymer.

[0139] In this embodiment, when producing the conductive polymer fiber 10 using the manufacturing method and manufacturing apparatus described below, first, the base fiber 11 is immersed in a solution of the conductor 12, thereby impregnating and / or attaching the conductor 12 to the base fiber 11. In this case, the solution of the conductor 12 contains a dilution solvent in addition to the conductive polymer PEDOT-PSS, and may further contain additives other than the conductive polymer as necessary.

[0140] [Method and apparatus for manufacturing conductive polymer fibers] An embodiment of a method and apparatus for producing conductive polymer fibers according to the present invention will be described in detail below, mainly with reference to FIGS.

[0141] "Manufacturing equipment" First, the manufacturing apparatus used in this embodiment will be described in detail. The conductive polymer fiber manufacturing apparatus (hereinafter sometimes abbreviated as manufacturing apparatus) 210 shown in Figure 13 includes an immersion container 205. The immersion container 205 is an immersion container that contains a conductive solution 204 containing PEDOT-PSS {poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)} as a conductive polymer, and is used to impregnate and / or adhere a conductor (see also conductor 212 shown in Figures 17A, 17B, etc.) to the base fiber 211 by immersing an insulating base fiber 211 made of a thread-, string-, cloth-, or ribbon-like fiber bundle in the conductive solution 204. The manufacturing apparatus 210 also includes a winding section 209 for vertically pulling up the base fiber 211 from the conductor solution 204 contained in the immersion container 205, and a plurality of electrodes 202, 203 for electrochemically polymerizing and fixing the conductor 212 impregnated in and / or attached to the base fiber 211 by passing an electric current through the base fiber 211 while the base fiber 211 is being pulled up vertically. The manufacturing apparatus 210 described in this embodiment is generally configured to include a drying section 208 for drying the base fiber 211 to which the conductor 212 has been polymerized and fixed by blowing air toward it, and a chamber (including a humidity control section) 207 capable of adjusting the atmospheric humidity in the vicinity of the base fiber 211.

[0142] The immersion container 205 is a container that contains a conductor solution 204 containing PEDOT-PSS as a conductive polymer, as described above, and any conventionally known container can be used. A spool 206 is also contained in the immersion container 205 so that it is immersed in the conductor solution 204. An insulating base fiber 211 made of a thread-like, string-like, cloth-like, or ribbon-like fiber bundle wound around the spool 206 is immersed in the conductor solution 204, thereby impregnating and / or attaching a conductor 212 to the base fiber 211.

[0143] In this embodiment, a conventionally known spool 206 can also be used. For example, a bobbin-like shape is used, which can be rotated by a motor or the like to wind the base fiber 211. The base fiber 211 before being impregnated with and / or attached to the conductor 212 is wound around this spool 204, and as the treated base fiber 211, i.e., the conductive polymer fiber 201, is wound by a winding unit 209 described below, the base fiber 211 wound around the spool 204 is unwound. Note that the shape of the spool 204 is not limited to the above-mentioned bobbin. For example, when a cloth-like or string-like base fiber is used, a winding shaft suitable for that shape may be used.

[0144] The winding unit 209 vertically pulls up the base fiber 211 from the conductor solution 204 contained in the immersion container 205 at a constant speed, and winds and rolls up the base fiber 211. As with the spool 204 described above, a rotatable device such as a roll bobbin can be used for this purpose. Furthermore, as will be described in detail below, the winding unit 209 is configured to be able to adjust the amount of conductor 212 electrochemically polymerized and fixed to the base fiber 211 by adjusting the running speed of the base fiber 211.

[0145] In this embodiment, the base fiber 211 is vertically pulled up from the conductor solution 204 by the winding section 209, so that the amount of conductor 212 impregnated into and / or attached to the base fiber 211 is constant, and therefore electrochemical polymerization fixation by passing current is uniform.

[0146] As shown in Figure 13, manufacturing apparatus 210 is provided with alternating electrodes 202, 203 that pass electricity through base fiber 211, which is pulled up vertically by winding section 209, while it travels, electrochemically polymerizing and fixing conductor 212 impregnated in and / or attached to base fiber 211. These electrodes 202, 203 are provided in the longitudinal direction of base fiber 211 and are arranged on both sides of the base fiber 211 in the lateral diameter direction, so that base fiber 211 is sandwiched between the electrodes 202, 203. A constant current or constant voltage is applied to these electrodes 202, 203 from a DC regulated power supply (not shown). As long as the effects of the present invention can be obtained, the multiple electrodes 202, 203 do not have to be arranged perpendicularly. It is preferable that the electrodes are spaced apart and not in contact with each other, but the distance can be selected arbitrarily. The number of electrodes can also be selected arbitrarily, as long as there is at least one combination of anode and cathode. For example, the number of combinations can be in the range of 1 to 10, 2 to 8, or 3 to 5.

[0147] In the example shown in Fig. 13, the plurality of electrodes 202 are anodes, and the plurality of electrodes 203 are cathodes. As a result, in Fig. 13, the base material fiber 211 impregnated with and / or attached with the conductor 212 travels vertically and passes through each electrode in the order of "positive electrode (+)" - "negative electrode (-)" - "positive electrode (+)" - "negative electrode (-)". In this way, the positive and negative electrodes are applied alternately.

[0148] The multiple electrodes 202, 203 are made of, for example, a conductive metal material or a carbon material, and while in contact with the vertically running base fiber 211, conduct electricity in the longitudinal direction of the base fiber 211. In this way, by conducting electricity between the electrodes to the running base fiber 211, the PEDOT-PSS contained in the conductor 212 impregnated into and / or attached to the base fiber 211 is polymerized and electrochemically polymerized and fixed.

[0149] As the multiple electrodes 202, 203, known electrodes of various shapes conventionally used in the field of electrodes, such as smooth-surfaced metal rods and metal plates, can be used without any restrictions. In particular, when a comb-shaped electrode having multiple comb teeth (electrodes) is used, it is possible to further increase the efficiency of electrochemical polymerization fixation of the conductor 212 to the base fiber 211.

[0150] Figure 14 shows an enlarged view of a main part of an example in which the multiple electrodes (reference numerals 202 and 203) shown in Figure 13 are configured with comb-tooth electrodes 221 and 231 having multiple comb teeth. The number of comb teeth may be selected as desired. The comb-tooth electrodes 221 and 231 shown in Figure 14 have multiple comb teeth 221a and 231a arranged in the longitudinal direction of the base fiber 211, and are arranged so as to sandwich the base fiber 211 from both radial sides of the base fiber 211, and the multiple comb teeth 221a and 231a are arranged so as to alternately interdigitate with each other in the longitudinal direction of the base fiber 211 from both radial sides of the base fiber 211. The comb-tooth electrodes 221 and 231 press and guide the multiple comb teeth 221a and 231a against the base fiber 211 from both radial sides, and energize the base fiber 211 by running it in the direction of the arrow in Figure 14. At this time, a constant current or a constant voltage is supplied to the comb-shaped electrodes 221 and 231 by connecting a DC stabilized power supply (not shown) to terminals 221b and 231b.

[0151] As described above, the comb-shaped electrodes 221, 231 have anodes (comb teeth 221a) and cathodes (comb teeth 231a) arranged alternately along the running direction of the base fiber 211, and by coming into contact with the base fiber 211, electricity can be repeatedly passed through the base fiber 211 in a short period of time, thereby polymerizing and immobilizing PEDOT-PSS.

[0152] In this embodiment, first, the base fiber 211 is made to run in the vertical direction, thereby distributing the fixed conductors 212 evenly inside and outside the fiber bundle made of the base fiber 211, and preventing uneven distribution. Furthermore, by using comb-shaped electrodes 221, 231 as multiple electrodes and arranging comb teeth (anode) 221a and comb teeth (cathode) 231a alternately and continuously, it is possible to polymerize and fix the conductors 12 to the base fiber (fiber bundle) 211 multiple times in a single run.

[0153] Furthermore, because the multiple comb teeth (electrodes) 221a, 231a are connected in parallel, the combined resistance between the electrodes is reduced, allowing the applied voltage to be set low. Generally, when the applied voltage to each electrode is set high, problems such as water electrolysis and polymer degradation due to heating are likely to occur. Therefore, it is preferable to set the applied voltage as low as possible within a range that allows for polymerization and fixation. Thus, when the applied voltage to the electrodes is set low, it is necessary to efficiently pass the current required for polymer polymerization. From this perspective, too, it is preferable to use the comb-shaped electrodes 221, 231 configured as described above. In this case, the applied voltage to the comb-shaped electrodes 221, 231 can be selected arbitrarily. For example, it can be set in the range of 0.1 to 18 (V).

[0154] In this embodiment, the configuration using the comb-like electrodes 221, 231, which are multipolar electrodes having multiple comb teeth 221a, 231a, utilizes the property that PEDOT-PSS (conductor 212), which has already been electrochemically polymerized, does not normally decompose even when a reverse current is passed through it after polymerization. Therefore, as the base fiber 211 travels between the comb-like electrodes 221, 231, polymerization and fixation occur when the base fiber 211 approaches the anode (positive electrode). Electrochemical polymerization is repeated as the base fiber travels between the comb-like electrodes 221, 231, which are multipolar electrodes, and the conductor 212 containing PEDOT-PSS is superposed on the base fiber 211.

[0155] The size of the comb-tooth electrodes 221, 231 is not particularly limited, but the distance between the multiple comb teeth 221a (231a) (distance between the electrodes) is preferably in the range of 1 to 50 mm, and from the viewpoint of the processing efficiency of electrochemical polymerization fixation, it is preferably about 10 mm.

[0156] The multiple electrodes (reference numerals 202 and 203) shown in FIG. 13 are not limited to the comb-shaped electrodes 221 and 231 described above. For example, as shown in the detailed enlarged views of the main parts in FIGS. 15A to 15C, the multiple electrodes may be composed of rotor electrodes 222 and 232 arranged in the longitudinal direction of the base fiber 211 and positioned so as to sandwich the base fiber 211 from both radial sides of the base fiber 211. In the example shown in FIGS. 15A to 15C, the rotor electrode 232 arranged on one radial side of the base fiber 211 is roller-shaped, and the rotor electrode 222 arranged on the other radial side is pulley-shaped. These rotor electrodes 222 and 232 are alternately arranged in the longitudinal direction of the base fiber 211.

[0157] As shown in Figure 15C, when rotor electrodes 222, 232 are used as multiple electrodes, the roller-shaped rotor electrode 232 is pressed against the base fiber 211, and the base fiber 211 is guided by the groove portion 222b formed in the pulley-shaped rotor electrode 222, while running between each of the multiple electrodes 222, 232 to pass electricity.

[0158] 15A, the roller-shaped rotor electrode 232 is a negative electrode (-) in this embodiment, and is configured by assembling a roller 232a to a metal shaft portion 232c. The metal shaft portion 232c is connected to the negative side of a DC stabilized power supply (not shown), and therefore, a conductive metal material is used for this metal shaft portion 232c. The roller 232a is also made of, for example, stainless steel, and is a small metal roller with a built-in ball bearing for rotation.

[0159] 15C, the base fiber 211 running vertically contacts the outer peripheral surface 232b of the roller-shaped rotor electrode 232. For this reason, the size of the roller 232a can be selected as needed, but taking into consideration the running speed of the base fiber 211, for example, a diameter of about 6 mm and a width of about 3 mm can be used.

[0160] 15B, the pulley-shaped rotor electrode 222 is an anode (+) in this embodiment, and is configured by assembling a pulley 222a having a groove 222b formed on its outer circumferential surface to a metal shaft portion 222c. The metal shaft portion 222c is connected to the (+) side of a DC stabilized power supply (not shown), and therefore, a conductive metal material is used for this metal shaft portion 222c, as in the case of the roller-shaped rotor electrode 232. The pulley 222a is also made of, for example, stainless steel, and is a small metal pulley with a built-in ball bearing for rotation.

[0161] 15C, the pulley-shaped rotor electrode 222 is guided by the vertically running base fiber 211 in contact with grooves 222b formed on its outer circumferential surface. For this reason, the size of the pulley 222a can be selected as needed, as in the case of the roller-shaped rotor electrode 232, but taking into account the running speed of the base fiber 11, for example, a pulley with a diameter of about 8 mm and a width of about 4 mm can be used.

[0162] Also, as shown in Figure 15C, in this embodiment, pulley-shaped rotor electrodes 222 and roller-shaped rotor electrodes 232 are arranged alternately along the vertical running direction of the base fiber 211, i.e., anodes (+) and cathodes (-) are arranged alternately (see also symbols 202 and 203 in Figures 15A to 15C).

[0163] Then, the base fiber (fiber bundle) 211 impregnated with and / or attached with the conductor 212 comes into contact with a pulley-shaped rotor electrode (anode) 222 and a roller-shaped rotor electrode (cathode) 32, which are made of metal and have built-in bearings, and are fixed to metal shafts 222c and 232c, respectively. A constant current or low voltage is supplied to each of these rotor electrodes 222 and 232 from a stabilized DC power supply (not shown), thereby electrochemically polymerizing and fixing the conductor 212 containing PEDOT-PSS to the base fiber 211.

[0164] When using rotor electrodes 222, 232 as described above, the amount of electricity required for polymerizing and fixing the conductor 212 containing PEDOT-PSS can be selected arbitrarily. For example, when a silk thread (No. 9: silk thread: manufactured by Fujix Co., Ltd.) with a diameter of approximately 280 μm is used as the base fiber, the amount of electricity is 0.1 to 6 mC per 10 mm, and particularly, good polymerizing and fixing is possible at around 3 mC.

[0165] The rotor electrodes 222, 232 as described above rotate together with the traveling base fiber 211. This reduces friction due to contact, and prevents the conductor 212 containing PEDOT-PSS electrochemically fixed to the base fiber 211 from peeling off due to friction. That is, it is possible to prevent the surface destruction of the polymer in the conductive polymer fiber 201 from occurring.

[0166] Furthermore, in the manufacturing apparatus 210 of this embodiment, the arrangement shape of the thread-like fiber bundles is adjusted by pressing the roller-shaped rotor electrode 232 against the base fiber 211 and guiding it through the groove 222b of the pulley-shaped rotor electrode 222. This makes it possible to adopt a configuration in which current can be applied while adjusting the amount of conductor 212 impregnated into and / or attached to the base fiber 211. In this case, for example, the shapes and arrangement of the pulley-shaped rotor electrode 222 and the roller-shaped rotor electrode 232, as well as the tension, running speed, and rotation state of the base fiber (fiber bundle) 201, can be adjusted. This makes it possible to adjust the spreading and bundling function of the base fiber (fiber bundle), the fiber spacing, the arrangement (shape) of the fiber bundle, and the like.

[0167] By adjusting the gaps between the base fibers as described above, it becomes possible to hold and fix any amount of conductor 212 (42) between the base fibers, as shown in the example of Fig. 6. In particular, by setting the shape of base fiber (fiber bundle) 211 using pulley-shaped rotor electrode 422 and roller-shaped rotor electrode 232, it becomes possible to adjust it to various shapes as described above.

[0168] Here, the set shape of the fiber bundle may be various shapes, such as whether or not the fiber bundle is twisted, the cross-sectional shape of the fiber bundle (flat, circular, elliptical, rectangular, etc.), or the convolution of the fiber bundle (reversing the twist to straighten the fiber bundle, or adding further twist), and the shape may be set by appropriately selecting and adjusting the shape. In this embodiment, by setting the shape of the fiber bundle as described above, a composite fiber bundle of conductive polymer fibers 201 set (molded) into a predetermined shape is obtained. When forming such a composite fiber bundle, as shown in the example of Figure 6, a conductor 212 (42) containing the conductive polymer PEDOT-PSS is arranged between multiple base fibers 211 (41) in close contact with the base fibers 211 (41), and the multiple base fibers 211 (41) are twisted or knitted to form a higher-order structure such as a twisted string, woven fabric, or nonwoven fabric.

[0169] As shown in Figure 13, in addition to the above configuration, the manufacturing apparatus 210 of this embodiment can further include a drying section 208 that blows air toward the base fiber 211 to which the conductor 212 has been polymerized and fixed, and a chamber (including a humidity control section) 207 that adjusts the atmospheric humidity in the vicinity of the base fiber 211.

[0170] The chamber 207 has a humidity and temperature control function (humidity control section) and maintains a high humidity level inside the chamber to maintain a constant concentration (PEDOT-PSS concentration) of the conductor 212. As the chamber 207, a thermo-hygrostat tank or the like that has been conventionally used in this field and is sized to accommodate the immersion container 205 and the plurality of electrodes 202 and 203 can be used without any restrictions.

[0171] The drying section 208 dries the base fiber 211 (conductive polymer fiber 201) to which the conductor 212 is polymerized and fixed by blowing low-humidity dry air. For example, any conventionally known air-blowing drying means consisting of a motor, a fan, etc. can be used without any restrictions.

[0172] Furthermore, in this embodiment, by adding the above-mentioned chamber and adjusting the humidity near the multiple electrodes 202, 203, it becomes possible to adjust the moisture content of the PEDOT-PSS solution (conductor 212) impregnated into the base fiber (fiber bundle) 211. Furthermore, when the chamber is configured with three compartments and the humidity of each compartment is adjusted independently, the following settings (A) to (C) can be used. (A) Immersion container: To prevent evaporation of water from the conductive solution containing PEDOT-PSS and to maintain a constant concentration of PEDOT-PSS, the humidity setting is adjusted to be in the range of 50 to 100%, for example. (B) Multiple electrodes: The moisture content of the conductive solution containing PEDOT-PSS impregnated into the fiber is adjusted by setting the humidity to a range from high to low, for example, 99 to 10%. (C) Drying section: A function for blowing dry air has been added to circulate low-humidity dry air to promote drying of the base fiber (conductive polymer fiber) to which the conductor has been polymerized and fixed (for example, humidity setting in the range of 0 to 40%).

[0173] Furthermore, although not shown in the drawings, the manufacturing apparatus of this embodiment may further be provided with a container-shaped disinfecting and cleaning unit that fixes and sterilizes residual monomers using, for example, an ethanol or acetone bath, in addition to the above-mentioned components. Furthermore, the disinfecting and cleaning unit may be provided with a configuration that enables removal of residual monomers using a cleaning bath of physiological saline or the like.

[0174] Furthermore, the electrodes used in the present invention are not limited to a plurality of electrodes as shown in FIGS. 13 to 15, but may also be, for example, a manufacturing apparatus 250 equipped with unipolar (single) electrodes 252, 253 as shown in FIG. This manufacturing apparatus 250 includes an immersion container 255 that contains a PEDOT-PSS solution 204, an electrode (negative electrode) 253 made of a metal plate or the like that is placed in the PEDOT-PSS solution inside the immersion container 255, an electrode (anode) 252 made of a metal rod or the like that is placed outside the immersion container 255 and that comes into contact with the base fiber 211, a spool 256 that is placed in the immersion container 255 and around which the base fiber 211 is wound, a chamber 257 that contains the immersion container 255, the spool 256, and each of the electrodes 252, 253 and controls the humidity inside, a DC stabilized power supply 251 that supplies current to the electrodes 252, 253, a drying section 258 that blows air to dry the base fiber 201 (conductive polymer fiber 201), and a winding section 259 that winds up the completed conductive polymer fiber 201.

[0175] Even when using such a manufacturing apparatus 250 equipped with single (monopolar) electrodes 252, 253, by vertically pulling up the base fiber 211 and running it between the electrodes, the conductor 212 polymerized and fixed to the base fiber 211 can be evenly dispersed, preventing uneven distribution, making it possible to manufacture conductive polymer fiber 201 with excellent conductivity and durability.

[0176] "Manufacturing method" The procedure for producing conductive polymer fibers 201 using the above-mentioned production apparatus 210 will be described below with reference to the same drawings (FIGS. 13 to 15) as those used to explain the above-mentioned production apparatus. The manufacturing method of the conductive polymer fiber 201 described in this embodiment comprises the following steps (1) to (3) in order, and each of these steps (1) to (3) is carried out while controlling the atmospheric humidity. (1) A dipping process in which an insulating base fiber 211 consisting of a thread-like fiber bundle is immersed in a solution of a conductor containing PEDOT-PSS as a conductive polymer, thereby impregnating and / or attaching a conductor 212 to the base fiber 211. (2) A fixation process in which the base fiber 211 is pulled vertically from a conductive solution, runs between multiple electrodes 202, 203, and electricity is applied, thereby electrochemically polymerizing and fixing the conductive material 212 impregnated and / or attached to the base fiber 211. (3) A drying step of blowing air to dry the base fiber 211 to which the conductor 212 has been polymerized and fixed.

[0177] (Soaking process) In the immersion process, as described above, the base fiber 211 is immersed in a solution of a conductor containing PEDOT-PSS as a conductive polymer, thereby impregnating and / or attaching the conductor 212 to the base fiber 211. Specifically, a conductor solution containing PEDOT-PSS, a conductive polymer, is placed in an immersion container 205 as shown in Fig. 13, and a base fiber (fiber bundle) 211 is immersed in this solution. As a result, conductive conductor 212 is impregnated into and / or attached to the base fiber 211, and the base fiber 211 becomes conductive.

[0178] When preparing a solution of a conductor containing the above-mentioned conductive polymer, additives can be added as needed to a commercially available PEDOT-PSS solution (e.g., CLEVIOS P from Heraeus). That is, a method can be used in which an additive is mixed into a solution of a conductor containing PEDOT-PSS to prepare a mixed solution, and the conductive polymer and additive are simultaneously applied to or immersed in the base fiber 211. Such a mixed solution can be selected arbitrarily. One example is an aqueous solution containing a conductive polymer such as PEDOT-PSS at a concentration of 0.1 to 50 (V / V) % and an additive such as glycerol at a concentration of 0.1 to 50 (V / V) %. The concentration of the additive in the conductor solution is not particularly limited and can be, for example, in the range of 0.1 to 50 wt %.

[0179] (Fixed process) Next, in the fixing step, the base fiber 211 is pulled vertically out of the solution while being transported between multiple electrodes 202, 203 and an electric current is applied, thereby electrochemically polymerizing and fixing the conductor 212 impregnated in and / or attached to the base fiber 211.

[0180] Specifically, for example, base fiber (fiber bundle) 211 impregnated with and / or attached with conductor 212 is pulled up vertically from the solution and run by a winding unit 209 as shown in Fig. 13. By pulling up and running base fiber 211 vertically in this manner, the conductor 212 is not eccentric due to gravity, and is evenly distributed and impregnated with and / or attached to base fiber 211.

[0181] 13, a plurality of electrodes 202, 203 are used to apply current while sandwiching and contacting the base fiber 211 from both radial sides. By bringing the base fiber (fiber bundle) 211 impregnated and / or attached with the conductor 212 containing PEDOT-PSS into contact with the electrodes 202, 203 and passing a current through it, the conductor 212 containing PEDOT-PSS attached to the inside and outside of the fiber bundle is electrochemically polymerized and fixed, and a conductive polymer fiber 201 is obtained, which is a composite fiber of the conductor 212 containing PEDOT-PSS and the base fiber (fiber bundle) 211.

[0182] In the fixing process, the multiple electrodes can be comb-tooth electrodes 221, 231 having multiple comb teeth 221a, 231a as shown in Fig. 14, as described above. In this case, the comb-tooth electrodes 221, 231 are arranged so as to sandwich the base fiber 211 from both radial sides of the base fiber 211, and the multiple comb teeth 221a, 231a are arranged so as to be alternately combined in the longitudinal direction of the base fiber 211 from both radial sides of the base fiber 211. Then, a method can be employed in which the base fiber 211 is run vertically while the multiple comb teeth 221a, 231a of the comb-tooth electrodes 221, 231 are pressed against and guided against the base fiber (fiber bundle) 211 from both radial sides, and electricity is applied to the base fiber 211.

[0183] In addition, in the fixing process, it is also possible to use rotor electrodes 222, 232 as multiple electrodes, which are arranged in the longitudinal direction of the base fiber 211 and are arranged so as to sandwich the base fiber 211 from both radial sides of the base fiber 211, as shown in Figures 15A to 15C. That is, a roller-shaped rotor electrode 232 is arranged on one radial side of the base fiber 211, and a pulley-shaped rotor electrode 222 is arranged on the other radial side, and the rotor electrodes 222, 232 arranged on both sides of the base fiber 211 are arranged alternately in the longitudinal direction of the base fiber 211. Then, a method can be adopted in which the roller-shaped rotor electrode 232 is pressed against the base fiber (fiber bundle) 211, and the base fiber 211 is guided by the groove 222b formed in the pulley-shaped rotor electrode 222, while the base fiber 211 is made to run between the multiple electrodes to pass current.

[0184] Furthermore, in the fixing process, as described in the configuration of the manufacturing apparatus above, it is also possible to adopt a method in which the base fiber 211 is pressed against the roller-shaped rotor electrode 232 and guided by the groove portion 222b of the pulley-shaped rotor electrode 222, thereby adjusting the arrangement shape of the thread-like fiber bundle, thereby passing electricity while adjusting the amount of conductor 212 impregnated into and / or attached to the base fiber 211.

[0185] (drying process) Next, in the drying step, low-humidity dry air is blown toward the base fiber 211 to which the conductor 212 has been polymerized and fixed, that is, the conductive polymer fiber 201, to dry the conductive polymer fiber 201.

[0186] 13, for example, dry air is blown onto the base fiber (fiber bundle) 211 to which the conductor 212 has been electrochemically polymerized and fixed in the fixing step using a drying unit 208 equipped with a humidity adjusting means and a blowing means (not shown).This dries and removes the water (solvent) contained in the solution of the conductor 212 containing PEDOT-PSS.

[0187] In the manufacturing method of this embodiment, it is preferable to then wash the conductive polymer fiber 201 with an electrolyte solution such as physiological saline to remove unpolymerized PEDOT-PSS and the solvent. Furthermore, in this embodiment, it is preferable to clean and disinfect the conductive polymer fiber 201 using an ethanol solution, and then dry it.

[0188] Although detailed explanation will be omitted, in the manufacturing method of this embodiment, it is also possible to manufacture conductive polymer fibers 201 using a manufacturing apparatus 250 equipped with monopolar (single) electrodes 252, 253 as shown in Figure 16.

[0189] The method for producing the conductive polymer fiber 201 according to the present invention, as described above, employs a method in which a base fiber 11 impregnated with and / or attached with a conductor 212 containing PEDOT-PSS is vertically lifted from a conductor solution while running between multiple electrodes 202, 203 and applying current. This allows the process of electrochemically polymerizing and fixing the conductor 212 to the base fiber 211 to be performed continuously in a single step, thereby improving productivity. Furthermore, by vertically lifting the base fiber 211 while running it between multiple electrodes 202, 203, the conductor 212 polymerized and fixed to the base fiber 211 can be evenly dispersed, preventing uneven distribution. This makes it possible to produce conductive polymer fibers 201 with high biocompatibility, good homogeneity, and excellent conductivity and durability with high productivity.

[0190] Furthermore, the conductive polymer fiber manufacturing apparatus 210 according to the present invention is configured to include a winding section 209 that vertically pulls up the base fiber 211, impregnated with and / or attached with a conductor 212 containing PEDOT-PSS, from the conductor solution in the immersion container 5, and multiple electrodes 202, 203 that apply current while the base fiber 211 is running. This allows the process of electrochemically polymerizing and fixing the conductor 212 to the base fiber 211 to be performed continuously in a single step, thereby improving productivity. Furthermore, by providing multiple electrodes 202, 203 that apply current while the base fiber 211 is pulled up vertically, the conductor 212 polymerized and fixed to the base fiber 211 can be evenly dispersed, preventing uneven distribution. Therefore, conductive polymer fibers 201 with high biocompatibility, good homogeneity, and excellent conductivity and durability can be obtained with high productivity.

[0191] Regarding the third aspect The third aspect of the present invention relates to a bioelectrode and a biosignal measuring device. More specifically, the present invention relates to a body surface-mounted bioelectrode using a composite material of a conductive polymer and a fiber (hereinafter referred to as a conductive composite fiber), and a biosignal measuring device equipped with the bioelectrode. In this aspect, the fiber described in the first aspect of the present invention can be preferably used. Hereinafter, an embodiment of the third aspect of the present invention will be described with reference to the drawings, but the present invention is not limited to such an embodiment.

[0192] <<Example of using bioelectrodes as electrodes for measuring electroencephalograms>> In recent years, EEG measurement has been applied not only to testing within medical institutions, but also to home EEG testing, telemedicine, health information, and ubiquitous healthcare systems. In addition to the medical field, it is also expected to be applied to psychological research using event-related potential measurements, engineering such as BCI (brain-computer interface), and the nursing care and welfare fields.

[0193] When measuring electroencephalograms, it is necessary to place electrodes on the scalp, avoiding the presence of hair. In conventional EEG measurements using bioelectrodes, electrodes are stabilized and fixed by using adhesives to secure them to the skin, by using a head cap that covers the entire head to compress the electrodes, or by increasing the amount of paste or gel between the electrode and the scalp to prevent the electrodes from floating up. However, these measures are inconvenient to wear and place a significant burden on the subject, which is particularly problematic when performing continuous EEG measurements over long periods of time. Furthermore, the appearance of the electrodes can be somewhat uncomfortable for the wearer or others, preventing the use of EEG beyond medical applications.

[0194] The bioelectrode of the first embodiment of the third aspect of the present invention described below utilizes the conductivity of a conductive polymer, allowing for miniaturization of the electrode and a reduction in the contact area with the skin. Furthermore, this electrode, which is made of a flexible fiber material, causes less irritation to the skin when worn and is less likely to cause discomfort while wearing it. Furthermore, unlike conventional bioelectrodes, there is no need to seal the skin with highly adhesive gels or tape. The bioelectrode of the first embodiment of the third aspect of the present invention is comfortable to wear, can be used continuously, and has a natural appearance when worn, making it suitable for use in, for example, electroencephalography (EEG) measurement.

[0195] [First embodiment of the third aspect] The bioelectrode of the first embodiment has string-like contacts made of conductive composite fibers. Brain waves can be measured by placing the contacts in close contact with the scalp through gaps in the hair (see Figures 19A to 19D and Figures 20A to 20D).

[0196] The bioelectrode 310 shown in FIGS. 19A to 19D includes at least a string-like contactor 311 made of conductive composite fiber, a first frame 312, and a second frame 313 (connecting portion). Both ends of the contactor 311 are fastened to both ends of the arch-shaped first frame 312. The shape of the flexible contactor 311 is adjusted by the first frame 312. Tension may be applied to the contactor 311 by the first frame 312. The second frame 313, which spans multiple first frames 312, functions as a beam that fixes each first frame 312. The end of each contactor 311 is connected to a signal cable 314. Electrical signals are transmitted and received between each contactor 311 and an electroencephalogram (EEG) analysis device (not shown) connected to the end of the signal cable 314. The direction of the electrical signal may be unidirectional or bidirectional.

[0197] The shape of the contactor 311 is not particularly limited as long as it can be brought into contact with the scalp S, and may be any shape such as string, thread, strip, cloth, or net. The size and length of the contactor 11 are adjusted as appropriate.

[0198] The shape, number, and size of the first frame 312 and the second frame 313 are not particularly limited. For example, a shape capable of applying an appropriate tension to the contacts 311 or a shape capable of fixing the contacts 311 without loosening can be adopted. The materials constituting the first frame 312 and the second frame 313 are not particularly limited as long as they do not disrupt the electrical signals in the contacts 311, and conventionally known resin materials can be used. Examples of the number of first frames 312 include 1 to 20, 2 to 8, and 2 to 4. Examples of the number of second frames 313 include 1 to 6, 1 to 3, and 1 to 2. The shapes of the first frames 312 and the second frames 313 may be, for example, a partial loop shape or a plate shape. The thickness is preferably constant, but may vary partially. In the figure, one second frame 313 is arranged perpendicular to four first frames 312. Multiple second frames 313 may be arranged, or they may be arranged diagonally as necessary. Furthermore, as long as it does not interfere with electroencephalogram (EEG) measurement (signal measurement), at least one of the first frame 312 and the second frame 313 may be made of metal. For example, by making the first frame 312 and the second frame 313 out of a metal material, the signal cable 314 may be connected to the first frame 312 or the second frame 313 without being connected to the contactor 311, and transmission and reception of electrical signals to and from the contactor 311 may be performed via the first frame 312 or the second frame 313.

[0199] The method of connecting the conductive composite fiber constituting the contact 311 to the signal cable 314 is not particularly limited as long as it is a method that allows electrical connection. For example, any of the following methods can be applied: crimping using metal, wrapping or ligating the conductive composite fiber around the signal cable 314, or bonding with a conductive adhesive.

[0200] In the present invention, one to multiple string-like contactors 311 can be used per electrode. As illustrated in Figures 19A to 19D, a comb-shaped bioelectrode 310 is configured using a first frame 312 and a second frame 313, thereby achieving stable contact between the contactors 311 and the skin. In the comb-shaped bioelectrode 310 shown in Figures 19A to 19D, multiple string-like contactors 311 are arranged in parallel. The comb-shaped bioelectrode 310, in which multiple contactors 311 are arranged in parallel, can be inserted between hair or at the hairline like a comb, and can be fixed by covering the comb with a net-like holder (Figures 22A to 22B).

[0201] (Modification of the first embodiment of the third aspect) As a further miniaturized bioelectrode configuration, a hairpin-shaped bioelectrode 320 with two contacts 321 fixed to a hairpin-shaped hair clip (metal leaf spring) is shown in Figures 20A to 20D. This hairpin-shaped bioelectrode 320 can be used by inserting it near the root of the hair. The hairpin-shaped hair clip can grip the hair. In the illustrated example, the two contacts 321 are fixed on the scalp S.

[0202] The hairpin-shaped bioelectrode 320 shown in FIGS. 20A to 20D includes at least a string-like contactor 321 made of conductive composite fiber, a third frame 322, and a fourth frame 323. Both ends of the contactor 321 are fastened between two cylindrical third frames 322. The tension applied to the contactor 321 can be adjusted by adjusting the distance between the two third frames 322. The two third frames 322 are fixed to the tip and bent portion of a fourth frame 324 using a hairpin, respectively. In the example shown in FIGS. 20A to 20D, two string-like contactors 321 are provided on the hairpin. The ends of each contactor 321 are connected to a signal cable 324. Electrical signals are transmitted and received between each contactor 321 and an electroencephalogram (EEG) analysis device (not shown) connected to the end of the signal cable 324. The direction of the electrical signal may be unidirectional or bidirectional.

[0203] The shape of the contactor 321 is not particularly limited as long as it can be brought into contact with the scalp S, and may be any shape such as string, thread, strip, cloth, or net. The size and length of the contactor 321 are adjusted as appropriate.

[0204] The shape of the third frame 322 is not particularly limited, and may be, for example, a cylindrical shape, a polygonal prism such as a triangular prism or a square prism, or a spherical shape. In this configuration, the fourth frame 323 has a hairpin structure and functions as a hairpin, so that the fourth frame 323 can be fixed to the hair H. As a result, the contactor 321 can be easily brought into contact with the skin (scalp) S and fixed at a desired position.

[0205] The material constituting the third frame 322 and the fourth frame 323 is not particularly limited as long as it does not disrupt the electrical signal in the contactor 321, and for example, a conventionally known resin material can be used. Furthermore, at least one of the third frame 322 and the fourth frame 323 may be made of metal as long as it does not interfere with the electroencephalogram (EEG) measurement (signal measurement). In this modification, for example, the third frame 322 may be made of insulating resin, and the hairpin serving as the fourth frame 323 may be made of metal. As long as it does not interfere with the electroencephalogram (EEG) measurement, the contactor 321 may be electrically connected to the metallic fourth frame 323.

[0206] One to multiple string-like contacts 321 can be used per electrode. As illustrated in FIGS. 20A to 20D, a hairpin-shaped 320 electrode is formed using a third frame 322 and a fourth frame 323, thereby achieving stable contact between the contacts 321 and the skin. In the hairpin electrode 320 shown in FIGS. 20A to 20D, multiple string-like contacts 321 are arranged in parallel. The hairpin electrode 320, in which multiple contacts 321 are arranged in parallel, can be fixed in place in the same way as hair is fixed with a hairpin.

[0207] The conductive composite fiber that forms the string-like contact 321 may be the same as that of the contact 311 described above.

[0208] (Conductive composite fiber) A composite fiber of a conductive polymer and a conventionally known fiber material can be used as the conductive composite fiber that constitutes the string-like contacts 311, 321. The form (method) of the composite is not particularly limited, and for example, the conductive polymer may be coated on the surface of the string-like (thread-like) fiber material, the conductive polymer may be impregnated into the string-like fiber material, or the string-like conductive polymer and the string-like fiber material may be twisted or spun together. The materials and conductive polymer fibers described in the first embodiment can be preferably used, and the device and method described in the second embodiment may also be used.

[0209] The type of the conductive polymer is not particularly limited, and known conductive polymers can be used. Examples include the aforementioned PEDOT-PSS, as well as hydrophilic conductive polymers such as PEDOT-S (poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2yl-methoxy-1-butanesulfonic acid, potassium salt)). By using a composite fiber containing a hydrophilic conductive polymer as the material for the contacts 11 and 21, the contacts 11 and 21 themselves can easily be made to have adhesive properties (stickiness) to the skin.

[0210] As the fiber material, conventionally known fiber materials such as silk, cotton, linen, rayon, and chemical fibers can be used. Among these, silk is preferred. When silk is used, the strength and hydrophilicity of the composite fiber can be further improved. Furthermore, when silk is used, the wearing comfort when it comes into contact with the skin is superior. The type of the conductive polymer to be combined with silk is not particularly limited, but the above-mentioned hydrophilic conductive polymer such as PEDOT-PSS or PEDOT-S is preferred.

[0211] As the conductive composite fiber constituting the contact of each embodiment of the present invention, a conductive polymer fiber, which will be described in more detail later, can be used.

[0212] (Contact structure) Two types of structures are exemplified as the structure of the string-like contacts constituting each embodiment of the present invention. The first structure of the string-like contactor is a structure in which the conductive composite fiber bundle is used alone. An example of the first structure is the contactor 311 shown in Figures 19A to 19D. The contactor 311 is made by weaving a thread (string) made of a bundle of multiple conductive composite fibers, and therefore has appropriate thickness and strength. The first structure, which is made up of only conductive composite fibers, is flexible, and is therefore suitable for applications in which flexibility and a comfortable fit are required for the bioelectrode. The conductive composite fiber is preferably in the form of a thread or string.

[0213] The second structure of the string-like contactor is a structure in which the conductive composite fiber bundle is combined with a metal cable or a metal thin wire. Examples of the second structure include the structures shown schematically in Figures 21A and 21B. The contactor 321 in Figure 20 has the structure shown in Figure 21B. Because the conductivity of the second structure is increased by the metal cable or metal thin wire, it is suitable for applications in which the electrode resistance per contact area of ​​the bioelectrode must be reduced.

[0214] In the second structure shown in Figure 21A, a thin metal wire 321f is wound around a bundle of multiple core materials 321g, and a conductive composite fiber 321e is wound around the thin metal wire 321f. The material constituting the core material 321g may be conductive or insulating. In the illustrated example, the core material 311 is a core made of insulating fiber. The number and thickness of the core material 311 are adjusted as appropriate. In the figure, the number of turns of the thin metal wire and the number of turns of the conductive composite fiber 321e are depicted as being approximately the same, but this relative relationship in number of turns is not limited to this. For example, the number of turns of the thin metal wire 321f may be fewer than the number of turns of the conductive composite fiber. Furthermore, if necessary, a portion of the string-like contact may be covered with an insulating cover 321z. An example of an insulating cover is a cover made of silicone resin.

[0215] In the second structure shown in FIG. 21B, conductive composite fiber 321a is wound around a bundle of multiple metal cables 321b. There are no particular restrictions on the type of metal constituting the metal cables, and copper wires with high conductivity are preferred. In the illustrated example, metal cables 321b are copper wires. There are no particular restrictions on the number or thickness of metal cables 321b, and these can be adjusted as appropriate. Using multiple thin metal cables or thin metal wires may sometimes increase flexibility for the same diameter, rather than using a few thick metal cables. If necessary, the string-like contactor may be partially covered with an insulating cover 321c. Examples of insulating covers include covers made of silicone resin. FIG. 21C is a photograph of string-like contactor 321 having the structure of FIG. 21B.

[0216] Comparing the first and second structures, in the first structure, electrical connection between contactor 311 and metallic (conductive) signal cable 314 is made at one point at the end of contactor 311, whereas in the second structure, electrical connection between contactor 321 and signal cable 324 is made over the entire contactor 321. Therefore, in the second structure, the distance between the skin and the metallic cable is shorter than in the first structure, and therefore the electrode resistance is lower.

[0217] The thickness of the contact is not particularly limited, but is preferably a thickness that provides structural strength that makes it difficult to break when it comes into contact with the skin. For example, a thickness of 0.1 mm to 5 mm makes it easy to obtain structural strength that makes it difficult to break. Usually, the second structure having a metal wire tends to have greater structural strength than the first structure. Other examples of thickness ranges include a thickness of 0.1 mm to 3 mm and a thickness of 0.5 mm to 1 mm.

[0218] Because the contacts with conductive composite fibers are adhesive (adsorbent) to the skin, the bioelectrode of the first embodiment can be installed independently without using paste or adhesive for electrode installation. However, there is a possibility that the bioelectrode may come off (peel off) from the skin surface when an external force is applied, such as the subject's movement or pulling on the signal cable. To prevent this, a means for pressing the bioelectrode against the skin surface can be used. For example, a net-shaped holder (cap) N as shown in Figure 22A can be used as such a means.

[0219] (Electroencephalogram electrode holder; stretchable net cap) The bioelectrode of the first embodiment of the third aspect, for example, the comb-shaped electrode 310 shown in Fig. 22A, can be fixed by covering it with the stretchable net cap N shown in Fig. 22A. The net N can be used as a holder that lightly presses down on the comb-shaped electrode 310 from above and stably holds it in place. Because the comb-shaped electrode 310 is inserted into the gaps between hair strands, it is unlikely to lift up. Therefore, unlike conventional electrodes, the comb-shaped electrode 310 does not require strong pressure and fixation with a head cap or the like. Instead, a cover such as a low-tension stretchable net can be used to achieve stable fixation. Examples of the low-tension stretchable net include commercially available net bandages (manufactured by Nihon Eisai Co., Ltd.). The bioelectrode of the first embodiment can easily be designed to fit under the hair. Furthermore, when using a stretchable net, hair can be pulled out of the net. Therefore, the use of the bioelectrode of the first embodiment improves both the comfort and appearance of the device while worn. Figure 22A shows the comb-shaped electrode 310 and a cap made of a stretchable net N. Figure 22B shows an example (top view) of the comb-shaped electrode 310 placed on a stretchable lattice net N. In Figure 22B, the triangle represents the nose, and the two ellipses represent the left and right ears, respectively. The hatched areas within the grid indicate where the comb-shaped electrode 310 is placed. In this configuration, by adjusting the spacing between the strings of the stretchable net N, the placement site of the bioelectrode 310 can be made to conform to the International 10-20 system.

[0220] <Example of using bioelectrodes as electrodes for electrocardiogram measurement> Conventionally, bioelectrodes for Holter electrocardiogram testing and bioelectrodes for monitoring heart rate or myoelectric potential have been widely used. Electrodes for Holter electrocardiogram testing are often used in a state where they are fixed to the skin using highly adhesive tape or adhesive pads. Fixing the bioelectrodes to the skin prevents noise generation. Furthermore, adhesive pads made of conductive gel are often used to fix monitor electrodes to the skin, which are often used continuously for long periods of time. Measurement data using these electrodes is less likely to be contaminated by artifacts such as noise, and the measurement waveform is highly stable.

[0221] However, there is a problem of attenuation of high-frequency components of biosignals. This problem is thought to be caused by the effect of the capacitance of the electrolyte solution, which is used in conventional bioelectrodes because electrolyte paste or gel is used between the metal electrode plate and the skin. Therefore, electrolyte paste and electrolyte gel are one of the factors that make it difficult to analyze biosignals containing high-frequency components and to achieve high-speed communication between the living body and external devices in BCI and other applications. Furthermore, conventional bioelectrodes, which have high adhesiveness and are attached to the skin, tend to cause sweating, which causes discomfort for the subject (wearer). Furthermore, to obtain the full effect of the adhesive, the skin surface must be degreased with alcohol swabs or similar pretreatment. However, degreasing with alcohol is highly irritating to the skin, which can cause itching and contact dermatitis, and improvements are needed.

[0222] As described above, the effects on frequency characteristics and the problem of stuffiness caused by using metal electrode plates are problems that must be solved not only in electrocardiogram measurement but also in the transmission of electrical signals or electrical stimuli between a living body and electrodes, including the above-mentioned electroencephalogram measurement. Attempts to improve these problems have been made in the past, but have not yet been sufficient.

[0223] For example, in order to reduce the effect of electrolyte paste on frequency characteristics, conventional bioelectrodes for EEG measurement have been attempted by placing small sintered metal electrodes directly on the skin. However, this method poses problems with the stability of the measured waveform. Specifically, when placing metal electrodes directly on the skin, the resistance between the skin and the electrode is prone to fluctuations due to mechanical compliance and electrochemical mismatch between the metal electrode and the skin. Furthermore, vibrations such as body movement and breathing can easily destabilize the measured signal, often resulting in noise contamination. Furthermore, rigid metal electrodes can easily cause discomfort or discomfort when placed in direct contact with the skin, leaving other issues to be resolved.

[0224] To alleviate the problems associated with rigid metal electrodes, textile electrodes using conductive fibers have been developed in recent years and are becoming increasingly popular, particularly in the fields of sports and health. Textile electrodes are cloth-like bioelectrodes incorporating conductive fibers, and are used by compressing and securing them to the skin using elastic bands or similar. Most textile electrodes do not use electrolyte paste; instead, the electrodes are placed in direct contact with the skin or the cloth that makes up the electrode is moistened with water. Pasteless types are the most common. Measurements using textile electrodes can obtain relatively good biosignals if stable contact with the skin is maintained. However, even slight instability in contact with the skin can cause significant fluctuations in the resistance between the skin and the electrode, leading to artifacts such as distortion of the recorded waveform and the introduction of hum noise, which can reduce the reliability of the measured waveform.

[0225] The bioelectrode of the second embodiment of the third aspect of the present invention, described below, utilizes the conductivity of a conductive polymer, similar to the bioelectrode of the first embodiment, allowing for miniaturization of the electrode and a reduced contact area with the skin. Furthermore, this electrode, made of a flexible fiber material, causes less irritation to the skin when worn and is less likely to cause discomfort during wear. Furthermore, unlike conventional bioelectrodes, there is no need to seal the skin with highly adhesive gels or tape. The bioelectrode of the second embodiment of the present invention is comfortable to wear, can be used continuously, and has a natural appearance when worn, making it suitable for use in, for example, medical or sports textiles.

[0226] [Second embodiment of the third aspect] 24A and 24B show a bioelectrode 330 of a second embodiment. The bioelectrode 330 includes a contact portion (electrode surface) 332 in which a plurality of string-like contacts 331 made of conductive composite fiber are arranged in a plane, and a sheet-like substrate 333 that supports the contact portions 332. The combination of the contact portions 332 and the substrate 333 is called an electrode pad. A signal cable 334 electrically connected to each contact 331 is provided. Furthermore, a holder 335 made of a stretchable material is provided as means for pressing the contact portions 332 of the electrode pad against the skin S.

[0227] The shapes of the planar contact portion 332 and substrate 333, in which a plurality of contactors 331 made of conductive composite fiber bundles are arranged, are not particularly limited as long as they are shaped to ensure surface contact between the contact portion 332 and the skin, and do not necessarily have to be flat. In other words, the contact portion 332 or substrate 333 may have a curved surface, concave or convex, to fit the curved surface of the skin. The shape of the electrode pad does not need to be rigidly fixed, and may flexibly deform to fit contact with the skin.

[0228] The use of a sheet-like substrate 332 ensures the flatness of the skin contact surface of the bioelectrode and promotes stable adhesion to the skin. The material, size, and shape of the substrate can be selected arbitrarily. For example, the substrate may be a 0.2 mm thick PVC (polyvinyl chloride) sheet or a flat silicone sheet (1 mm thick). The substrate material is not limited to these, and a flexible film-like (sheet-like) material that easily maintains the flatness of the substrate and has good adhesion to the skin is preferably used.

[0229] Contacts 331 made of conductive composite fibers are arranged and fixed on the substrate to form contact portions 332 (electrode pads) with the skin. One side of the sheet-like substrate (the side on which contact portions 332 are provided) may be given a mild adhesive force to allow the substrate surface to adhere to the skin. The size of the sheet that forms substrate 333 is not particularly limited, and for example, in the case of a square electrode for electrocardiograms, each side can be set to about 30 mm (for example, in the range of 5 mm to 75 mm).

[0230] 25A and 25B show a specific example of the bioelectrode 30. The upper diagram is a side view, and the lower diagram is a front view. The holder 335 is omitted and not shown. 25A to 25B, a plurality of contacts 331 are arranged in parallel in the horizontal direction of the paper, and both ends of each contact 331 are connected to a signal cable 334 arranged in the vertical direction of the paper. Both ends of the contact 331 pass through a substrate 333 and are connected to the signal cable 334. In the example shown, the signal cable 334 is arranged on the surface (back side) of the substrate 333, which is the base material, opposite to the surface (front side) on which the contacts 331 are arranged and fixed. With this configuration, the signal cable 334 can draw the contact 331 toward the substrate surface. The surface on which the signal cable 334 is arranged may be the front surface of the substrate 333 instead of the back surface.

[0231] An opening 336 is provided in the substrate 333 at the overlapping position between the substrate 333 and the contact portion 332. The opening 336 functions as a ventilation hole (air vent). In other words, when an electrode pad consisting of the contact portion 332 and the substrate 333 is pressed against the skin, steam or sweat from the skin can be discharged to the outside of the electrode pad through the opening 336. The shape of the opening 336 is not particularly limited as long as it allows gas to pass through the substrate 333, and may be any shape such as circular or rectangular. The contactor 331 arranged on the front surface of the substrate 333 may be exposed to the back surface of the substrate 333 through the opening 336.

[0232] The position of the openings 336 on the substrate 333 is not particularly limited, but it is preferable that the multiple openings 336 are arranged symmetrically with respect to the center of the substrate 333. Furthermore, it is preferable that the multiple openings 336 are provided at positions overlapping the contact portions 332. The total opening area of ​​the openings 336 provided on the substrate 333 is not particularly limited. It is preferable to avoid an opening area that is so large that it impairs the structural strength of the substrate 333. Typically, the opening area is preferably about 1 to 40% of the area of ​​the substrate 333. It is preferable to select this range depending on the purpose, for example, 1 to 20%, 20 to 40%, or 10 to 30%. Within the above range, the structural strength of the substrate 333 is sufficiently maintained, while improving the breathability between the substrate 333 and the skin and reducing stuffiness of the skin. Furthermore, it is preferable that the total opening area of ​​the openings 336 provided at positions overlapping the contact portions 332 is about 2 to 60% of the area of ​​the contact portions 332. It is preferable to select from this range depending on the purpose, and it may be, for example, 2 to 40%, 40 to 60%, 10 to 30%, or 5 to 45%. Within the above range, the structural strength of the contact portion 332 is sufficiently maintained, while the breathability between the contact portion 332 and the skin is improved and stuffiness of the skin can be reduced.

[0233] 25B, a humidity control pad 337 may be provided on the surface (back surface) of substrate 333 opposite contact portion 332. Moisture control pad 337 can absorb steam or sweat that has passed through opening 336. There are no particular limitations on the material of humidity control pad 337 as long as it is a water-absorbent material. A humidity control cover 338 for covering or fixing the humidity control pad 337 may also be provided.

[0234] Humidity conditioning pad 337 not only absorbs sweat and the like from the skin, but can also be used to supply moisture or a moisturizer such as glycerol to the skin or contacts by pre-impregnating humidity conditioning pad 337 with moisture or a moisturizer such as glycerol. In Figures 25A and 25B, contactor 331 arranged on the front surface of substrate 333 may be exposed to the back surface of substrate 333 through opening 336, and contactor 331 may come into contact with humidity conditioning pad 337. This contact makes it possible to supply moisture and the like to contactor 331.

[0235] By providing openings 336 in substrate 333, it is possible to accommodate various skin conditions, from situations where sweating is high and humidity is likely to occur, such as in summer, for young people, or during exercise, to dry situations, such as in winter, for the elderly, or when at rest. Openings 336 are not provided solely for the purpose of releasing the skin closed (covered) by the electrode pads to dissipate moisture, but may also be provided for the purpose of actively supplying moisture to the skin. In other words, by placing a water-absorbent pad (sponge, etc.) 337 on opening 336, sweat can be removed and humidity can be regulated. In dry environments, moisture-regulating pad 337 can contain water, glycerol, and moisturizing ingredients, allowing the pad 337 to replenish the ingredients to contacts 331 and the skin. For the purpose of moisturizing during dry conditions, it is preferable to further cover the outside of moisture-regulating pad 37 with a cover such as PVC. The conductive composite fiber that makes up the contactor 331 has moderate moisture absorption properties, and moisture moves and diffuses due to capillary action caused by the fine fibers that make up the contactor 331. Therefore, by installing the opening 336 and pad 337, it is possible to smoothly adjust the humidity around the contactor 332.

[0236] The size (area) of opening 336 can be adjusted appropriately depending on the conditions of use, such as room temperature, humidity, exercise, and whether or not heat is generated. The total area of ​​the single or multiple openings 336 provided in substrate 333 is not particularly limited as long as it is within a range that maintains an appropriate structural strength of substrate 333, and can be adjusted, for example, within a range of 0.1 to 50% of the area of ​​sheet-like substrate 333 that constitutes the electrode pad. It is preferable to select within this range depending on the purpose, and it may be, for example, 0.1 to 30%, 30 to 50%, 5 to 40%, 15 to 50%, or 0.1 to 5%, etc.

[0237] The description of the conductive composite fiber that constitutes the contact 331 is the same as the description of the conductive composite fiber in the first embodiment described above. The description of the structure of the contact 331 is the same as the description of the contact in the first embodiment described above.

[0238] The density of the contacts 331 in the contact portion 332, the number of contacts 331 per unit area of ​​the contact portion 332, and the area of ​​the contact portion 332 are not particularly limited and may be adjusted appropriately depending on the application. The density of the contacts 331 in the contact section 332 is, for example, when contacts 331 (fiber bundles) with a diameter of 280 microns are arranged in parallel, usually about 30 pieces are used per 10 mm of electrode width, but is not limited to this. For example, it can be adjusted in the range of 1 to 200 pieces. More specifically, when conductive composite fiber bundles (contacts made of composite fibers of PEDOT-PSS and silk fibers impregnated with glycerol) similar to those in Example 3-1 described below are arranged in parallel without gaps and fixed to a substrate for use as a bioelectrode for electrocardiogram measurement, the contact area with the skin (area of ​​contact portion 332) is 1 cm x 1 cm (100 mm 2 ) and is usually set to 10 to 50,000 mm 2 When the bioelectrode for electrocardiogram measurement is used as a skin surface electrode for electrical stimulation, the contact area of ​​the electrode can be set to, for example, 10 to 50,000 mm 2 can be set to.

[0239] The arrangement of the contacts 331 in the contact portion 332 is not particularly limited and may be adjusted appropriately depending on the application. For example, in addition to arranging the multiple contacts 331 (conductive composite fiber bundles) in parallel with no gaps, it is also possible to adopt a configuration in which the multiple contacts 331 are laid out in multiple layers, a configuration in which the multiple contacts 331 are woven or knitted into a cloth-like structure, or a towel-like configuration in which the multiple contacts 331 are made of a raised fabric. In a configuration in which the multiple contacts 331 overlap each other, the contacts 331 are in contact with each other and electrically connected (conductivity is obtained), so no problems arise in use. Furthermore, it is also possible to adopt a configuration in which the multiple contacts 331 are sparsely arranged by widening the spacing between the multiple contacts 331 in the contact portion 332. In this configuration, the surface of the substrate 333 is exposed from the gaps between the contacts 331, and the exposed surface can come into direct contact with the skin between the contacts 331. Therefore, by making the exposed surface of the substrate 333 adhesive, it is possible to adjust the adhesive strength of the electrode pad to the skin, the current density, and the contact area between the electrode contact portion 332 and the skin.

[0240] By impregnating the conductive composite fiber that makes up the contactor 331 with a moisturizing ingredient such as glycerol and by having the moisture (sweating) from the skin where the bioelectrode is placed absorbed by the conductive composite fiber, the conductive composite fiber is maintained in a moderately moist (wet) state. When the conductive composite fiber has an appropriate amount of moisture, the conductive composite fiber becomes slightly sticky.

[0241] The method for placing the electrode pad of the bioelectrode 330 on the skin surface is not particularly limited as long as it can stably fix the bioelectrode. For example, the electrode pad can be attached to the skin independently by utilizing the adhesiveness of the conductive composite fiber described above or the adhesiveness of the sheet-like substrate 333. When the contact section 332 on which the contacts 331 are arranged is brought into contact with the body surface (skin surface), the contacts 331 quickly adhere to the skin surface, establishing electrical continuity between the contacts 331 and the skin surface, and allowing the biosignal to be acquired. The biosignal is sent to an external device such as a bioamplifier via a signal cable 334 (metal conductor) connected to the contacts 331.

[0242] In this way, the electrode pad's adhesiveness can be utilized to fix (place) it independently on the skin surface. In this fixing method, the electrode pad is attached to the skin using the weakly adhesive substrate 333 and the adhesiveness generated by wetting the conductive composite fiber of the contactor 331, so the fixing strength to the skin is not strong. Therefore, there is a possibility that the electrode pad may shift or fall off due to traction by the signal cable 334 or large body movements. Therefore, a holder 335 may be used to press the electrode pad against the skin surface S in order to stably hold the electrode pad and prevent it from shifting or falling off.

[0243] There are no particular limitations on the shape, size, and other configuration of holder 335. For example, as shown in Figures 25A and 25B, a strip-shaped stretchable cloth (curtain) may be used to place electrode pad 338 on the skin surface S of body B, and stretchable holder 335 may be wrapped around the waist of body B from above electrode pad 338. In this configuration, electrode pad 338 will not easily fall off even if body B moves significantly, and electrode pad 338 can be more stably fixed.

[0244] For example, as shown in FIGS. 26A and 26B , the holder 335 can be placed inside underwear (shirt) T. The electrode pad 338 and a portion of the holder 335 are fixed to the inside of the underwear T. The holder 335 and the electrode pad 338 are structurally independent, and the holder 335 is movable laterally over the electrode pad 338, i.e., movable (shiftable) in a direction along the surface of the body B. Therefore, it is preferable that the electrode pad 338 and the holder 335 are arranged so that they can be separated from each other, and it is preferable that the electrode pad 338 and the holder 335 are not completely fixed. Because the electrode pad 338 and the holder 335 are structurally independent in this way, and the contact portion between the electrode pad 338 and the holder 335 is not fixed, and the holder 335 is slidable over the electrode pad 338 at this contact portion, it is possible to prevent the electrode pad 338 from falling off due to misalignment between the body B and the underwear T, loss of biological signals, and noise due to electrode misalignment. Furthermore, if necessary, the electrode pad 338 can be removed or replaced by actively moving the holder 335 away from the body B. The holder 335 not only serves to stably hold the electrode pad 338, but is also used to hold accessories of the bioelectrode (such as a cable, connector, and amplifier 339).

[0245] The fabric (material) from which the holder 335 is made is not particularly limited. For example, it is preferable to use a stretchable fabric, such as cloth, sheet, mesh, or rubber band. Specifically, a strip of two-way stretchable fabric, Lycra (registered trademark) (generic name: Spandex) (manufactured by Toray Industries, Inc.), can be sewn to the inside of an undershirt in a width (vertical length) of 15 cm, aligned with the height of the heart (see Figures 25A and 25B). This holder is suitable, for example, as a holder for electrodes for a Holter electrocardiogram (for CC5 lead). In the case of CC5, a configuration can be adopted in which electrode pads 338 are placed on the left and right sides of the anterior chest, and these are covered by the electrode holder 335.

[0246] The holder 335 is not limited to being placed inside the upper body underwear as described above, but may also be placed by wrapping it around the limbs, head, neck, or fingers in a band shape, depending on the application of the bioelectrode 330. The material of the holder 335 is not limited to the spandex described above, and various types of cloth, sheet, mesh, band, etc. can be used as long as they are a stretchy, flat material (fabric).

[0247] Effects achieved by the bioelectrodes of the first and second embodiments of the third aspect of the present invention Examples of effects obtained by the materials and structures of the bioelectrodes of each embodiment are listed below.

[0248] When placing the bioelectrode of the present invention at the measurement site, there is no need to use a conductive gel (electrolyte gel) or a conductive paste (electrolyte paste). By not using a conductive gel or paste, the following effects (A) to (E) can be obtained. (A) Improved wearing comfort. The discomfort caused by attaching electrodes to the skin is reduced. Because no gel or paste is used, there is no need to seal the skin with a liquid or gel, and the electrodes can be placed in an open state to the outside air. In other words, measurements can be made with string-like electrodes lightly in contact with the skin, or with soft cloth-like electrodes in contact with the skin. (B) Problems caused by electrolyte paste are avoided. There is no risk of leakage of the electrolyte solution, or of poor contact or noise occurring when the water in the gel or paste dries. (C) The electrical properties of the electrode are improved. It is possible to reduce the electrode resistance per unit area compared to conventional bioelectrodes, which is advantageous for measuring weak signals such as electroencephalograms and evoked potentials. Furthermore, because the electrodes of the present invention have low capacitance, they have excellent high-frequency propagation characteristics and are advantageous for recording biosignals containing high-frequency components such as electroencephalograms and electromyograms. (D) The electrodes are highly convenient to use. Since no paste or gel is used, there is no need to remove the paste or gel after measurement (test). For example, washing hair after EEG measurement, which was previously required when using electrodes, can be omitted. (E) The electrodes can be made smaller and lighter. Since the electrode resistance per unit area is smaller than that of conventional electrodes, the electrode can be made smaller, lighter, and denser than conventional bioelectrodes.

[0249] By providing the bioelectrode according to the present invention with the conductive composite fiber, the following effects (F) to (K) can be obtained. (F) Improved installation stability. The electrodes can be placed stably using light pressure or weak adhesive materials, and there is no need for strong adhesives or strong compression fixation using bands, headgear, etc. as with conventional bioelectrodes. (G) A low-noise signal is obtained. The adhesive, flexible, thin and lightweight properties of the conductive composite fiber reduce unnecessary vibration of the electrode when the wearer (subject) moves, thereby reducing noise. (H) A natural appearance is achieved. In particular, when used as an EEG electrode, the electrodes are small and flat, and designed to be hidden under the hair, making them unnoticeable even when worn. This means that EEG measurements can be taken at any time during daily life. (I) It can reduce the sweating of the skin caused by wearing bioelectrodes for long periods of time. Generally, when electrodes are worn continuously for a long period of time, sweating can easily cause the skin to become stuffy. However, when the bioelectrode of the present invention uses a hydrophilic conductive composite fiber as the electrode material and has ventilation openings in the substrate as described above, it is possible to further reduce stuffiness of the skin during long-term use. (J) The range of applications of bioelectrodes can be expanded. The overall shape (basic shape) of the bioelectrode can be processed into a thin, flat shape (cloth-like) or a linear shape (string-like). Because it is lighter, flatter, and more flexible than conventional electrodes, it is also possible to fabricate linear electrodes that are thinner than strings. It is also comfortable to wear. These properties allow the bioelectrode of the present invention to be used as a wearable electrode, broadening its range of application. (K) Measurements can be made as stable as or more stable than conventional bioelectrodes. The bioelectrode of the present invention overcomes the drawbacks of conventional pasteless electrodes, such as noise contamination and instability of the measurement signal, even when it does not use electrolyte paste (pasteless). In other words, it can achieve a measurement signal stability equal to or greater than that of conventional medical bioelectrodes that use electrolyte paste.

[0250] Hereinafter, conductive polymer fibers that can be used as the conductive composite fibers that constitute the bioelectrode of the present invention will be described in detail, but the conductive composite fibers are not limited to these conductive polymer fibers.

[0251] Regarding the fourth aspect A fourth aspect of the present invention relates to an implantable electrode and a biosignal measuring device. More specifically, the present invention relates to an implantable bioelectrode using a composite material of a conductive polymer and fiber (hereinafter referred to as conductive composite fiber), and a biosignal measuring device equipped with the bioelectrode. Hereinafter, an embodiment of the fourth aspect of the present invention will be described with reference to the drawings, but the present invention is not limited to such an embodiment.

[0252] As mentioned above, PEDOT-PSS, a conventionally known conductive polymer, gels in biological tissue due to its high water absorption, resulting in a significant decrease in mechanical strength. For this reason, it is difficult to place needle- or rod-shaped PEDOT-PSS alone inside the body, as with conventional metal or carbon bioelectrodes. Even if PEDOT-PSS could be embedded in biological tissue, the connection between the electrode made entirely of PEDOT-PSS and the metal conductor (cable) connecting it to an external device becomes brittle due to PEDOT-PSS absorbing water, making it prone to breakage (disconnection).

[0253] In a fourth aspect of the present invention, by using a conductive composite fiber in which a conductive polymer is combined with a fiber as an implantable electrode, the problems of the electrode itself disintegrating due to the conductive polymer absorbing water and the weakening of the connection between the conductive polymer and the metal conductor are solved.

[0254] First Embodiment of the Fourth Aspect The implantable electrode 410 of the first embodiment of the fourth aspect of the present invention shown in Figures 29A to 29C includes a conductive composite fiber bundle 401 formed by bundling a plurality of conductive composite fibers containing a conductive polymer and forming them into a rod (needle) shape. A metal conductor 402 is wound around a portion of the conductive composite fiber bundle 401 to form a connection part 403. The connection part 403 is coated with an insulating and water-resistant polymer 404 (resin). The conductive composite fiber bundle 401 has superior mechanical strength, both before and after water absorption, to a conductor formed by forming a single conductive polymer into a rod shape of the same diameter. This prevents the conductive composite fiber bundle 401 from being damaged when embedded in biological tissue or from being disintegrated within the biological tissue after implantation.

[0255] The conductive composite fiber bundle 401 is preferably in a dry state before use. The conductive composite fiber bundle 401 in the dry state has high mechanical strength and, since it has shrunk compared to when it is wet, has a relatively small volume. Therefore, by using the conductive composite fiber bundle 1 in a dry and shrunk state, it is possible to reduce the invasiveness when inserting it into biological tissue.

[0256] (Conductive composite fiber) The conductive composite fibers constituting the conductive composite fiber bundle 401 can be composite fibers of a conductive polymer and a conventionally known fiber material. The form (method) of the composite is not particularly limited, and for example, the conductive polymer may be coated on the surface of the thread-like (string-like) fiber material, the conductive polymer may be impregnated into the thread-like fiber material, or the thread-like conductive polymer and the thread-like fiber material may be twisted or spun together. The fibers described in the first aspect of the present invention can be preferably used.

[0257] The type of conductive polymer is not particularly limited, and known conductive polymers can be used. Examples include the aforementioned PEDOT-PSS, as well as hydrophilic conductive polymers such as PEDOT-S (poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2yl-methoxy-1-butanesulfonic acid, potassium salt)). By using a composite fiber containing a hydrophilic conductive polymer as the material for the conductive composite fiber bundle 1, the conductive composite fiber bundle 1 itself can be easily imparted with adhesiveness (stickiness) to the needles 5.

[0258] As the fiber material, conventionally known fiber materials such as silk, cotton, hemp, rayon, and chemical fibers can be used. Among these, silk is preferred. When silk is used, the strength and hydrophilicity of the composite fiber can be further improved. Silk is also preferred because it is almost non-toxic to biological tissues, does not easily induce inflammation due to immune reactions, and has excellent compatibility with biological tissues. The type of the conductive polymer to be combined with silk is not particularly limited, but the above-mentioned hydrophilic conductive polymer such as PEDOT-PSS or PEDOT-S is preferred.

[0259] The length and thickness of the conductive composite fiber constituting the implantable electrode of the present invention are not particularly limited and can be adjusted appropriately depending on the length and thickness of the fiber material to be combined. Furthermore, the length and thickness of the conductive composite fiber bundle formed by twisting or bonding multiple conductive composite fibers are not particularly limited and can be adjusted appropriately depending on the purpose and application. For example, the thickness may be in the range of 0.01 μm to 5 mm, and the length may be in the range of 0.1 μm to 1 m. In another example, the thickness may be in the range of 0.1 μm to 1 mm, and the length may be in the range of 0.1 μm to 50 cm. As a specific example, the rod-shaped conductive composite fiber bundle 401 shown in FIGS. 29A to 29C can have a thickness of 0.1 μm to 500 μm and a length of 1 μm to 10 mm. Furthermore, the coil-shaped conductive composite fiber bundle 401 shown in FIGS. 31A to 31C can have a thickness of 10 μm to 500 μm and a length of 100 μm to 50 cm. Here, the thickness and length refer to the thickness and total length of the coiled conductive composite fiber bundle 1 in an unrolled state. The coiled coil shown in FIGS. 301A to 301C can have an outer diameter of 10 μm to 5 mm and a length in the direction of the central axis of the coil, for example, 100 μm to 50 mm. Furthermore, the conductive composite fiber bundle 401 connected to a surgical suture shown in FIGS. 32A to 32D can have a thickness of 0.1 μm to 500 μm and a length of 1 μm to 10 cm. The conductive composite fiber bundle 401 constituting the core shown in FIG. 33B can have a thickness of, for example, 10 μm to 10 mm and a length of 10 μm to 50 cm.

[0260] As the conductive composite fiber constituting the implantable electrode of each embodiment of the present invention, a conductive polymer fiber, which will be described in more detail later, can be used.

[0261] (Adhesion between needle and conductive composite fiber bundle) The conductive composite fiber bundle 401 of the first embodiment of the fourth aspect is adhered to the tip of a needle 405 (guide needle). When the conductive composite fiber bundle 401 is moistened with water, alcohol, or the like, the conductive polymer on its surface becomes adhesive (sticky), and when it is dried again, it shrinks and hardens. Utilizing this property, the conductive composite fiber bundle 401 can be adhered (fixed) to the tip of a needle 405 (FIG. 29A). When an implantable electrode 410 having this configuration is inserted into biological tissue, the conductive composite fiber bundle 401 absorbs bodily fluids (extracellular fluid, cerebrospinal fluid, etc.) and swells (FIG. 29B). Furthermore, the adhesive force (fixing force) between the swollen conductive composite fiber bundle 401 and the needle 405 decreases, so the needle 405 can be removed while leaving the conductive composite fiber bundle 1 in the biological tissue (Fig. 29C). The conductive composite fiber bundle 401 placed in the biological tissue is connected to an external device via an electric wire 402 (metal conductor wire 402), and signals (electrical signals or electrical stimuli) are sent and received.

[0262] The material of which needle 405 is made is not particularly limited, and examples thereof include metals such as gold, platinum, and copper, carbon, and resin (plastic).

[0263] The electric wire 402 is preferably a wire material capable of electrically conducting the conductive composite fiber bundle and an external device. The constituent material of the electric wire 402 is not particularly limited, and examples thereof include metal, silicon, and carbon. The type of metal is not particularly limited, and any metal used in conventionally known electric wires may be used. To prevent the electric wire 402 embedded in biological tissue from picking up electrical noise and to ensure stable function for a long period of time, the electric wire 402 is preferably coated with an insulating and water-resistant polymer. The type of polymer is not particularly limited, and examples of applicable materials include the water-resistant polymer used to coat the conductive composite fiber bundle of the fourth embodiment of the present invention described below. The thickness and length of the electric wire 402 are not particularly limited, and can be adjusted appropriately depending on the application.

[0264] The conductive composite fiber bundle 401 can be bonded to the needle 5 using the adhesive properties of the conductive polymer when wet, as described above, or by using a hydrophilic adhesive material (adhesive). The adhesive material is not particularly limited, and is preferably a material that can bond the conductive composite fiber bundle 1 to the needle 5 (exhibits adhesive properties) in a dry state and whose adhesive strength (adhesive strength) decreases when it absorbs water. Examples of such materials include PEG (polyethylene glycol), PEDOT-PSS, polylactic acid, sorbitol, fibrin glue, starch glue, etc.

[0265] The type of PEG is not particularly limited, and for example, a relatively high molecular weight PEG that is solid at room temperature (e.g., about 20°C) to body temperature (e.g., about 40°C) and becomes liquid when heated can be used. The PEG is heated and melted and applied to a needle, and then a conductive composite fiber bundle is brought into contact with the needle. The PEG solidifies when the temperature is returned to room temperature, allowing the needle and fiber bundle to bond together. When this is placed in an environment with body fluids, such as in tissue, the PEG gradually dissolves, allowing the conductive composite fiber bundle to naturally separate from the needle.

[0266] In addition, as a method of adhering the conductive composite fiber bundle 401 to the needle 405, the conductive composite fiber bundle 1 and the needle 5 may be indirectly adhered via the adhesive material applied to the polymer 404 covering the wire connection portion 403.

[0267] (Protection of wiring connections) The connection part 403 is coated with a polymer 404. Because the conductive composite fiber bundle 401 that constitutes the connection part 403 is coated with the polymer 404 in biological tissue, swelling and a decrease in mechanical strength due to water absorption hardly occur. Furthermore, because the mechanical strength of the conductive composite fiber bundle 401 is increased by combining it with a fiber material, the connection between the conductive composite fiber bundle 401 and the metal conductor 403 does not break (disconnect) even after water absorption, and the electrical connection can be sufficiently maintained.

[0268] The method for connecting the metal conductor wire 402 to the conductive composite fiber bundle 401 at the connection portion 403 is not particularly limited, and examples thereof include winding, ligating, crimping, and bonding with a conductive adhesive (silver paste, silver epoxy, etc.). The type of polymer 404 that covers the connection portion 403 is not particularly limited, and examples thereof include silicone, PTFE (polytetrafluoroethylene), and PVC (polyvinyl chloride). By covering the connection portion 403 with the polymer 404, electrical short circuits can be prevented and the connection portion 403 can be protected.

[0269] (Electrode placement inside the body) A method for placing the implantable electrode 410 of the first embodiment of the fourth aspect in biological tissue includes, for example, using a manipulator capable of high-speed operation to insert the needle 405 into the living body at high speed (in a short time). The needle 405 leads the way to a predetermined position in the living body, and the conductive composite fiber bundle 401 attached to the needle 405 and the connected metal conductor wire 402 are both introduced into the predetermined position in the living body. This insertion is preferably completed at high speed and before the conductive composite fiber bundle 401 begins to swell in the living body. The insertion speed is not particularly limited, but can be, for example, about 100 to 1000 mm / sec. As a specific example, using an electroconductive actuator capable of high-speed operation, the conductive composite fiber bundle 401 of the implantable electrode 410 can be inserted at a speed of 10 to 20 msec so that it is placed 2 mm deep under the cerebral cortex of the animal. Thereafter, the conductive composite fiber bundle 401 is caused to swell with body fluid, dissolving the adhesive material bonding the conductive composite fiber bundle 401 to the needle 405, and once the adhesive strength has weakened, it is possible to remove only the needle 405. The conductive composite fiber bundle 401 placed in the biological tissue swells and adheres closely to the surrounding biological tissue.

[0270] (Multiple electrode placement) The implantable electrode 10 of the first embodiment may have one conductive composite fiber bundle 401 at the tip of the needle 405 as shown in Figure 30A, or may have multiple conductive composite fiber bundles 401 at the needle 405 as shown in Figures 30B and 30C.

[0271] In the configuration of Figure 30B, the heights of the adhesive points of the two conductive composite fiber bundles 401 on the needle 405 are offset (the positions are offset in the length direction of the needle 405). With this configuration, when inserted into the body, each conductive composite fiber bundle 401 is placed at a different height (depth), and each can function as an independent electrode (2-channel electrode). In the configuration example of Figure 30B, when viewed from the side and bottom, the conductive composite fiber bundles 401 are fixed on both sides of the needle 405, but two electrodes may be fixed to one side of the needle 405. In this case, when viewed from the bottom, the two conductive composite fiber bundles 401 appear to overlap in the depth direction (height direction). In other words, the cross-sectional area is reduced. By fixing in this manner, it is possible to further reduce the invasiveness to living tissue when the catheter is inserted into the body.

[0272] 30C, the four conductive composite fiber bundles 401 are arranged so that the heights of the bonding points of the four conductive composite fiber bundles 401 on the needle 405 are the same and the four conductive composite fiber bundles 401 surround the needle 405. In this case, the four conductive composite fibers 401 (four-channel electrodes) can be placed in the biological tissue with the position where the needle 405 is inserted as the center.

[0273] Second Embodiment of the Fourth Aspect An implantable electrode 420 according to a second embodiment of the fourth aspect of the present invention, shown in Figures 31A to 31C, is similar to the first embodiment, except that a conductive composite fiber bundle 401 is wound in a coil shape around the tip of a needle 405. In Figures 31A to 31C, the same components as those in the first embodiment of the fourth aspect are denoted by the same reference numerals.

[0274] The coil-shaped conductive composite fiber bundle 401 may be adhered to the tip of the needle 405, or may simply be wrapped around it. Because the coil-shaped conductive composite fiber bundle 401 is tightly wrapped around the tip of the needle 405, the conductive composite fiber bundle 401 is prevented from falling off the needle 405 when the tip of the needle 405 is inserted into biological tissue (FIG. 31A). Furthermore, the outer diameter of the coil (the diameter of the circle that the coil describes when it is wound around) after drying and shrinking is small, reducing invasiveness to biological tissue. When the implantable electrode 420 is inserted into biological tissue, the conductive composite fiber bundle 1 absorbs body fluids and swells to become a swollen fiber bundle 401' (FIG. 31B). In other words, the coil spontaneously unfolds, increasing its outer diameter and bringing the conductive composite fiber bundle 401 into close contact with the biological tissue. The adhesive force between the conductive composite fiber bundle 401 and the needle 405 weakens due to water absorption, so the needle 405 can be removed while leaving the conductive composite fiber bundle 401 in the biological tissue (FIG. 31C).

[0275] The second embodiment of the implantable electrode 420 having a coil-shaped conductive composite fiber bundle 401 is suitable for cases where the installation of the electrode (conductive composite fiber bundle 401) may cause atrophy or the formation of dead space in the biological tissue, or where the cells or nerve fibers to be measured are scattered throughout the biological tissue.

[0276] Third Embodiment of the Fourth Aspect 32A to 32D show an implantable electrode 430 according to a third embodiment of the fourth aspect of the present invention. A metal conductor 402 is connected to one end of a conductive composite fiber bundle 401, and a surgical nylon monofilament thread 406 is attached to the other end by the method described above. A curved needle 405 for surgical suturing is attached to the nylon thread 406.

[0277] The following shows an example of a method for placing an implantable electrode 430 in a nerve cord (bundle). Using a microsurgery technique used for neurovascular suturing, a needle 405 is pierced (pierced) through a nerve cord N' in the same manner as suturing a nerve cord N (FIG. 32A). The nylon thread 406 is then pulled up, and the conductive composite fiber bundle 401 is pulled by the nylon thread 406 and introduced into the nerve cord N' (FIG. 32B). Thereafter, the conductive composite fiber bundle 401 absorbs bodily fluids at a predetermined position within the nerve cord N, causing the nylon thread 406 to peel off from the conductive composite fiber bundle 401 and be removed from the nerve cord N'. The conductive composite fiber bundle 401 placed within the nerve cord N' swells due to water absorption and adheres tightly to the inside of the nerve cord N' (FIG. 32C). FIG. 32D shows the placement of multiple implantable electrodes on multiple nerve cords N within a nerve bundle.

[0278] Peripheral nerves are often a mixture of motor, sensory, and autonomic nerves, forming nerve cords (bundles). Nerve cords run three-dimensionally within nerve fascicles, and the distribution of nerve cords varies greatly from person to person. Therefore, it is difficult to identify nerve cords using brain coordinates like the central nervous system. However, clinically, major nerve fibers can be identified by observation under a microscope and measurement of neural activity. The implantable electrode of the third embodiment utilizes this clinical technology to enable selective signal recording and stimulation of motor, sensory, and autonomic nerves.

[0279] The implantable electrode of the third embodiment can be installed not only by surgical procedures but also by mechanical insertion using an automatic anastomosis instrument, a micromanipulator, or the like.

[0280] (Adjustment of water absorption speed) The rate at which the conductive composite fibers and conductive composite fiber bundles constituting the implantable electrode of the present invention absorb body fluids in the body can be delayed. One method for delaying this is to pre-impregnate or pre-apply the conductive composite fibers (bundles) with one or more of glycerol, sorbitol, ethylene glycol, squalane, silicone, mineral oil, or MPC (2-methacryloyloxyethyl phosphorylcholine). For example, by pre-impregnating the conductive composite fiber bundle 401 of the third embodiment with glycerol, even if the introduction of the electrode into the living body is difficult and the surgery takes a long time, swelling of the conductive composite fiber bundle 401 due to water absorption and peeling of the nylon thread 406 during the surgery can be prevented. Maintaining a small diameter for the conductive composite fiber bundle 401 reduces the invasiveness to biological tissue during electrode introduction.

[0281] Fourth embodiment of the fourth aspect 33A and 33B, an implantable electrode 440 according to a fourth embodiment of the present invention has a core made of a conductive composite fiber (bundle) 401 formed into a rod (needle) or string (cable) shape, and at least a portion of the core is covered with a water-resistant polymer 404, forming a flow path for a liquid to permeate (transmit) from one end 1a (401a) of the core to the other end 1b. The one end 1a and the other end 1b are not covered with the polymer 404 and are exposed.

[0282] The term "channel" does not refer to a hollow tube, but rather to a configuration in which a tube is formed by a water-resistant polymer 404 and a conductive composite fiber bundle 1 is disposed within the tube. The conductive composite fiber bundle 401 is water-absorbent and permeable to substances, allowing liquid to permeate from one end 1a to the other end 1b and move spontaneously. Methods for transporting liquid or substances through the channel are not limited to spontaneous movement such as permeation, capillary action, and diffusion. Other methods that may be used include electrophoresis of substances using one of the one end 1a and the other end 1b as a positive electrode and the other as a negative electrode, or a method of connecting a pump (e.g., an osmotic pump) to one end 1a to pressurize the liquid and send it. Either method allows for stable drug transport and liquid delivery at a constant rate.

[0283] A reservoir 407 (FIG. 33A) or a chamber 408 (FIG. 33B) capable of containing a drug solution is connected to one end 1a of the core formed by the conductive composite fiber bundle 401. A pump for supplying the liquid may be connected to a tube connector 409 provided in the chamber 408. By storing a drug-containing solution in reservoir 407 or chamber 408, the solution can permeate the flow path and flow from one end 1a of the core to the other end 1b. Therefore, by placing the other end 1b at a desired position in the living tissue, the drug can be administered locally around the other end 1b.

[0284] The type of drug is not particularly limited, but is preferably a drug with a pharmacological effect of suppressing or promoting a biological reaction. Examples of the drug include drugs that reduce damage to biological tissue, drugs that promote the repair of biological tissue, and drugs that promote the growth of biological tissue. Specific examples include soluble drugs such as glycerol, sorbitol, mannitol, fructose, brain-derived neurotrophic factor (BDNF), nerve growth factor (NGF), neurotrophin-3 (NT3), S-nitrosoglutathione (GSNO), SKF96365, cilostazol, 1-(2-trifluoromethylphenyl)imidazole (TRIM), gadolinium, magnesium, ethylene glycol tetraacetic acid (EGTA), and ruthenium red. A liquid containing one or more of these drugs dissolved therein may be stored in reservoir 407 or chamber 408.

[0285] The type of water-resistant polymer 404 that coats the core is not particularly limited as long as it is a polymer that can form a coating layer around the core (that can form a water seal on the outer surface of the core), and for example, polymers (resins) that are conventionally known and used in the field of medical devices such as catheters are applicable. It is preferable that the water-resistant polymer 404 also has insulating properties to prevent the conductive composite fiber 401 that forms the core from being electrically short-circuited with the surrounding area. There are no particular limitations on the thickness of the coating layer formed by the water-resistant polymer 404, and it can be, for example, 0.1 μm to 5 mm.

[0286] Specific examples of the water-resistant polymer 404 include silicone, PTFE (polytetrafluoroethylene), PVC (polyvinyl chloride), ABS (acrylonitrile butadiene styrene), ANS (acrylonitrile styrene), PEN (polyethylene napthalate), PBT (polybutylene terephthalate), polycarbonate, PEI (polyetherimide), PES (polyether sulfone), PET (polyethylene terephthalate), polyamide, aromatic polyamide, polyester, polyether block amide copolymer, polymethylmethacrylate, polyurethane, and EVA (ethylene vinyl acetate). acetate), ethylene vinyl alcohol, polyethylene, latex rubber, PTFE, FEP, PFA, polypropylene, polysiloxane, ionomer, SAN (styrene acrylonitrile), nylon, thermoplastic elastomer, etc.

[0287] The drug may be pre-impregnated or pre-applied to the conductive composite fiber constituting the implantable electrode of the present invention. In this case, too, the drug is gradually released from the conductive composite fiber placed in the biological tissue, and the drug can be administered locally around the conductive composite fiber.

[0288] With the other end 1b of the core embedded in biological tissue, the one end 1a and the reservoir 407 or chamber 408 may be embedded in the biological tissue or placed outside the biological tissue. When the one end 1a is embedded in biological tissue, it is desirable that the reservoir 407 or chamber 408 connected to the one end 1a has as small a volume as possible. For example, a capsule-shaped reservoir 407 may be used. Furthermore, when the chamber 408 is placed inside the biological tissue, it may be connected to the outside of the biological tissue via a tube connector 409 provided on the chamber 408. From the viewpoint of reducing invasiveness to biological tissue, it is preferable that the one end 1a of the core and the reservoir 7 or chamber 408 be placed outside the biological tissue. The core covered with the water-resistant polymer 4 can be produced in a desired length (for example, 100 μm to 10 cm) and thickness (for example, 10 μm to 5 mm) depending on the application.

[0289] The size and constituent materials of reservoir 407 and chamber 408 are not particularly limited and can be changed appropriately depending on the purpose and mode of use. For example, a bag or box (case) made of plastic such as silicone resin can be used as reservoir 407 or chamber 408.

[0290] In the fourth embodiment, it is not necessary for the entire section of the conductive composite fiber bundle 401 from one end 1a to the other end 1b to be covered with the water-resistant polymer 404. Some sections may not be covered. It is preferable that the section where the conductive composite fiber bundle 401 functions as a liquid transport path is covered with the water-resistant polymer 404. In the fourth embodiment shown in Figures 33A and 33B, the section from the vicinity of the other end 1b to the reservoir 407 or chamber 408 in which the one end 1a is provided is covered with the water-resistant polymer 404.

[0291] There are no particular limitations on the method for connecting reservoir 407 and chamber 408 to one end 1a. An example of a connection method is to place one end 1a exposed in the liquid storage section of reservoir 407 or chamber 408, and then adhere water-resistant polymer 404, which covers the central side of one end 1a, to the outer wall of reservoir 407 or chamber 408 with a known adhesive or the like.

[0292] (Application of drug delivery function) Conventionally, when electrodes are implanted into the nervous system (central nervous system tissue), there is a problem that the limited damage caused by the invasiveness of the implantation process can expand, causing permanent damage over an area larger than the size of the electrode, and a solution to this problem is needed.

[0293] The drug transport function (drug delivery function) of the implantable electrode 440 of the fourth embodiment of the present invention can be applied to administering drugs to alleviate damage caused by implantation of the electrode, and is particularly effective in alleviating damage caused by implantation in nervous tissue. By administering a drug that has the effect of alleviating damage to central nervous tissue, such as GSNO (S-Nitrosoglutathione), from the other end 1b of the core, damage caused by the implantable electrode 440 to the central nervous tissue can be significantly reduced. As a result, signal transmission and reception between the electrode and nervous tissue can be performed stably and with high accuracy for a longer period of time than conventionally possible. This will be described in detail with reference to data in Example 4-4 (Figures 34A to 34D) described below.

[0294] When using conventional metal or carbon bioelectrodes in combination with drugs such as GSNO, a separate tube (e.g., a microcapillary or other ultrafine hollow needle) for drug delivery must be installed at the site of the bioelectrode. Alternatively, a bundle structure (bundle structure) must be formed in which the ultrafine hollow needle is housed (tied) in a single sheath (tube) along the bioelectrode. In such a bundle structure, the drug release hole (release port) of the drug transport pathway and the electrode are located separately (built into the sheath), which not only complicates the configuration of the structure to be implanted in biological tissue, but also makes it difficult to distribute the drug uniformly at the interface between the electrode and biological tissue.

[0295] On the other hand, the fourth embodiment of the present invention has a simple structure because the conductive composite fiber bundle 401, which is the electrode, itself also serves as a drug transport path. Furthermore, because the drug permeates from the surface of the electrode, it is possible to administer the drug uniformly to the interface between the electrode and the cellular tissue, i.e., the area where damage is most likely to occur. Furthermore, the drug release rate can be adjusted by adding the aforementioned additives such as glycerol to the conductive composite fiber bundle 401.

[0296] The drug transport function (drug delivery function) of the implantable electrode 440 of the fourth embodiment of the fourth aspect of the present invention is not limited to the use of drug administration to alleviate damage to biological tissues, but can be used for various purposes of stimulating or utilizing the physiological functions of living cells and biological tissues, such as selective binding of nerve fibers by neurotrophic factors (selective formation of neural wiring), recording of electrical signals accompanying selective stimulation of nerve fibers, etc. Furthermore, the liquid flowing through the flow path of the implantable electrode 440 is not limited to a drug solution, and its composition and function are not limited as long as it is a liquid that can permeate and move through the conductive composite fiber bundle 401.

[0297] <<Examples of Effects Produced by the Fourth Aspect of the Present Invention>> The implantable electrode of the present invention provides the following effects, for example. 1. Bioelectrodes made of flexible conductive composite fibers can be placed inside biological tissue. 2. The connection between the conductive composite fiber and the electrical wire (signal cable) can be maintained stably in vivo. 3. Drugs can be transported at a constant rate to the area where the electrode contacts the biological tissue. 4. Damage to biological tissues (especially cranial nerve tissues) caused by the placement (implantation) of electrodes can be reduced. 5. It is possible to record biological signals stably for a long period of time. 6. Electrodes can be placed three-dimensionally to match the three-dimensional structure of neural tissue. [Example]

[0298] Example of the first aspect Next, the first aspect of the present invention will be described in more detail with reference to examples, but the first aspect of the present invention is not limited to the following examples. <Evaluation of tensile strength> [Comparative Example 1-1] A PEDOT-PSS film (cross-sectional area 0.03 mm) was prepared by drying and concentrating Heraeus CLEVIOS P solution (Heraeus) and applying it evenly to a flat plate, allowing it to dry naturally, and then fixing it with ethanol. 2 The tensile strength of a sample (3 cm long) was measured in both a dry state and a wet state (absorbed pure water until saturated), and the results are shown in Figure 9A. The graph clearly shows that the tensile strength of the PEDOT-PSS linear bodies in the wet state (right) is drastically reduced to approximately 10% of the tensile strength in the dry state (left).

[0299] [Example 1-1] The tensile strength of raw silk thread (No. 9 silk thread; Fujix Co., Ltd., twisted thread of 18 21D denier silk fibers, thread diameter approximately 280 μm, length 20 cm) was investigated in both dry and wet states (absorbed pure water until saturated) and the results are shown in Figure 9B. Figure 9B shows the tensile strength of a conductive polymer fiber bundle (hereinafter referred to as PEDOT-PSS silk fiber bundle 1) with a diameter of approximately 280 μm, obtained by the aforementioned method 2b. The bundle was immersed in 20 cc of the CLEVIOS P solution for 1 hour, followed by electrochemical fixation at 3 mC per cm using a multi-electrode comb. The organic solvent used was ethanol, and 60% of the water was removed by blowing dry air over the bundle. The bundle was then subjected to drying using ethanol as the organic solvent. The bundle was then subjected to drying using dry air to remove 60% of the water. The tensile strength of the bundle was then measured in both the dry and wet states (after absorbing pure water to saturation). The vertical axis of the graph represents the maximum tensile strength (CN: centinewtons), and the error bars represent the standard deviation of 10 samples. The tensile strength test was conducted in accordance with JIS L 1013 using a constant-speed extension tester (Orientec Co., Ltd., model RTC-1210A). The fiber grip interval was 20 cm, the tensile speed was 20 cm / min, and the maximum strength was calculated from the average of the measured values ​​for 10 tests.

[0300] The specific measured values ​​(CN) in the graph were as follows: Raw silk dry; mean value = 1350.4, standard deviation = 8.11 Raw silk wet; mean value = 1082.9, standard deviation = 12.28 PEDOT-PSS silk dry; mean value = 1238.8, standard deviation = 16.93 PEDOT-PSS silk wet; mean value = 1031.4, standard deviation = 24.45

[0301] The graph shows that there was no clear difference in strength between the raw silk thread in the dry and wet states and the PEDOT-PSS silk fiber bundle 1 in the dry and wet states. Specifically, the tensile strength of the PEDOT-PSS silk fiber bundle 1 in the wet state was 83% of its dry strength, while the tensile strength of the raw silk thread in the wet state was 80% of its dry strength. This demonstrates that the conductive polymer fiber of the present invention has excellent strength equivalent to that of the raw silk thread in both the dry and wet states, and is resistant to breakage and cracking, thus reducing its conductivity. Furthermore, the difference in strength between the dry and wet states was smaller for the PEDOT-PSS silk fiber bundle 1 (which lost 17% (207 CN) from its dry strength) than for the raw silk thread (which lost 20% (268 CN) from its dry strength). This indicates that the PEDOT-PSS silk fiber bundle 1 exhibits less change in strength upon wetting and has more stable strength characteristics. Furthermore, from the results of Example 1-1 and Comparative Example 1-1, it is clear that the tensile strength of the conductive polymer fiber (dry state) of the present invention is approximately 10 times higher than that of a conductive fiber (dry state) consisting only of PEDOT-PSS.

[0302] <Water resistance evaluation> [Example 1-2] Conductive polymer fibers (PEDOT-PSS silk fiber bundle 1) were produced in the same manner as in Example 1, and sample A was impregnated with glycerol, and sample B was not impregnated with glycerol. Each sample, A and B, was immersed in pure water and subjected to 10 cycles of shaking at 3 Hz and a horizontal amplitude of 5 cm. The washing process was then repeated three times, followed by air drying. The resistance of each sample, A and B, was recorded over time. Resistance was calculated from the current flow at a DC 5 V load using a regulated DC power supply (PAB18-5.5; Kikusui Electronics Co., Ltd.) and a digital multimeter (VOAC7511; Iwasaki Electric Co., Ltd.). Resistance measurements were performed on samples in a dry (water-free) state. The results are shown in Figure 10. The vertical axis of the graph represents the resistance (MΩ / mm) per mm of PEDOT-PSS silk fiber bundle 1 (dry state) with a fiber diameter of approximately 280 microns.

[0303] The graph shows that the resistance of PEDOT-PSS silk fiber bundle 1 without added glycerol (sample B; plots connected by a solid line in the graph, marked with "◇") increased with repeated washing, and the conductivity decreased. On the other hand, the resistance of PEDOT-PSS silk fiber bundle 1 with added glycerol (sample A; plots connected by a dashed double-dashed line in the graph, marked with "△") did not increase, and it is clear that the conductivity was maintained. In other words, water resistance can be improved by impregnating the conductive polymer fiber of the present invention with an additive such as glycerol.

[0304] <Evaluation of bioelectrodes (1)> [Examples 1-3] Using conductive polymer fibers (hereinafter referred to as PEDOT-PSS silk fiber bundle 2) with a diameter of approximately 280 μm and a length of 300 mm, consisting of PEDOT-PSS obtained by the aforementioned Preparation Method 2b and the aforementioned silk thread (No. 9 silk thread), a string-shaped body surface bioelectrode was fabricated as shown in Figure 11A. A rubber band 4 and a metal conductor 5 were attached to a fixed string 3, and the PEDOT-PSS silk fiber bundle 2 was further wound into a coil to serve as an electrode. This bioelectrode was placed on the surface of a human body 6. An example of the results of measuring a human electrocardiogram using this bioelectrode is shown in Figure 11B. When measuring a human electrocardiogram, the PEDOT-PSS silk fiber bundle 2, which is an electrode constituting the bioelectrode, could be brought into contact with the skin and measurement could be performed without using a paste (jelly) containing electrolytes, etc. In other words, it is clear that the bioelectrode comprising the PEDOT-PSS silk fiber bundle 2 according to the present invention has excellent strength, flexibility, and conductivity, and can be worn in close contact with the body surface. The bioelectrodes were placed on the skin (body surface) of the right upper limb, left upper limb, and left lower limb. Each bioelectrode was connected to an electrocardiograph (polygraph, AP1124; manufactured by TEAC) to record the human electrocardiogram at rest using the bipolar limb lead method (setting sensitivity 2000 μV / mm, time scale 1 second, leads I, II, III).

[0305] <Evaluation of Bioelectrodes (2)> [Examples 1-4] Conductive polymer fibers, approximately 280 μm in diameter and 1.5 mm in length, composed of PEDOT-PSS and the silk thread (No. 9 silk thread) obtained by the aforementioned preparation method 1a were coated with silicone resin to partially insulate them. Specifically, the exposed (non-insulated) portion was approximately 500 μm long, and the insulating coating was approximately 1000 μm long. The resulting conductive polymer fibers (hereinafter sometimes referred to as PEDOT-PSS silk fiber bundle 3) had an electrode resistance of approximately 500 kΩ. They were connected to a thin metal wire (Xwire, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) to form a filamentary implantable bioelectrode. A stereomicroscope photograph of the resulting fibers is shown on the left in Figure 12A.

[0306] Next, under a microscope, the fabricated bioelectrode was inserted directly under the epineurium of the rat's sciatic nerve and ligated using microsurgery thread (S&T 10-0) (right panel of Figure 12A). After surgery, the metal lead wire was connected to a preamplifier, and the action potential (collection action potential) of the sciatic nerve was recorded using a biosignal recording device (AP1024, TEAC). An example of the measurement results is shown in Figure 12B. The measurement conditions were a sensitivity setting of 2000 μV / mm, a time scale of 1 second, and (from top to bottom) the conditions were rest, muscle contraction, and muscle relaxation.

[0307] The implantable bioelectrode comprising the PEDOT-PSS silk fiber bundle 3 according to the present invention is thread-like, so it can be surgically sewn into tissue. Therefore, compared to conventional large, inflexible metal electrodes, the bioelectrode according to the present invention has a high degree of freedom in the placement location, can be stably fixed, and is highly durable and capable of long-term recording because only the minimum necessary areas are exposed and the rest is covered.

[0308] <Evaluation of conductivity> [Examples 1-5] Using the silk thread (No. 9 silk thread), conductive polymer fibers with PEDOT-PSS distributed inside and around the silk thread were fabricated using the above-mentioned fabrication method 2b. Specifically, the following samples were prepared: Sample C, which was electrochemically coated once with PEDOT-PSS on the outer periphery and then dried; Sample D, which was sample C further impregnated with glycerol; Sample E, which was sample C electrochemically coated again with PEDOT-PSS (a total of two coats); and Sample F, which was sample E further impregnated with glycerol. The conductivity of each of Samples C, D, E, and F in a dry state (containing no moisture) was measured using the resistance measurement method described in Example 1-2, and the results of measuring each resistance value using the same method as in Example 1-2 are shown in Table 1. From the results obtained, it is clear that in order to improve the conductivity and resistance value, a thicker conductor is preferable (two coatings are preferable to one), and the addition of glycerol is preferable.

[0309] [Table 1]

[0310] Example of the second aspect The second aspect of the present invention will be explained in more detail below with reference to examples, but the second aspect of the present invention is not limited to these examples in any way.

[0311] [Example 2-1] In this example, silk fibers (No. 9 silk thread: diameter approximately 280 μm) were prepared as substrate fibers, and a manufacturing device equipped with the rotor electrode of the present invention, as shown in Figure 13 and Figures 15A-B, was used to produce conductive polymer fibers in which a conductor containing PEDOT-PSS was polymerized and fixed on the outer periphery of the silk fibers and inside the fiber bundles made of the silk fibers. Two types of conductor solutions were prepared: one without additives and one with glycerol added, and electrochemical polymerization and fixation were carried out for each.

[0312] 13A-13B, pulley-shaped rotor electrodes 222 and roller-shaped rotor electrodes 232 were used, and these rotor electrodes 222, 232 were alternately arranged so as to sandwich the silk fibers from both radial sides of the silk fibers. The pulley-shaped rotor electrode 222 had a pulley 222a with a diameter of 8 mm and a width of 4 mm. The roller-shaped rotor electrode 232 had a roller 232a with a diameter of 6 mm and a width of 3 mm.

[0313] Specifically, as explained in the embodiment of the present invention above, silk fibers were immersed in a conductive solution containing PEDOT-PSS contained in an immersion container, and then vertically pulled up using a winding section. A comb-shaped electrode, as shown in FIG. 14, was used, with the silk fibers alternately sandwiched between multiple comb teeth from both sides, and electricity was applied while the silk fibers were being pulled up. A DC stabilized power supply (KIKUSUI ELECTRONICS CO., LTD.: PAB18-5.5) was used to supply a DC power of 20 μA and 18 V to the comb-shaped electrode, and a quantity of electricity of 3 to 6 mC (electric flux density: 5.85 to 9.95 × 10) was used to polymerize and fix the silk fibers over a 10 mm lengthwise direction. 4 Cm 2 To ensure this, a digital multimeter (Iwasaki Electric Co., Ltd.: VOAC7511) was used to monitor and adjust the current and voltage.

[0314] The fiber resistance and conductivity of the obtained conductive polymer fiber were measured using a resistance measuring device "DM2561 (manufactured by NF Circuit Design Block Co., Ltd.)" at a direct current of 350 mA and a fiber length of 10 mm. A Nanoclip manufactured by Stack Electronics Co., Ltd. was used as the fiber gripping jig. The measurements were carried out in a dry state (a state that did not contain moisture), and the results are shown in Table 2 below. In Table 2, Example 1 represents Example 2-1, and Comparative Example 1 represents Comparative Example 1-1.

[0315] The obtained conductive polymer fibers were also observed using a stereomicroscope to visually confirm the state of coating with the conductor containing PEDOT-PSS, and a photograph of this observation is shown in FIG. 17A. Furthermore, the obtained conductive polymer fiber was immersed in physiological saline (0.9% NaCl solution: 20°C) for one month, and then photographed with a stereomicroscope (using a Leica SZ) to evaluate its water resistance. The photographs are shown in Figure 18A.

[0316] [Table 2]

[0317] [Example 2-2] In this example, conductive polymer fibers were produced under the same conditions and procedures as in Example 2-1 above, except that electricity was applied using comb-like electrodes 221, 231 as shown in Figure 14 in the production apparatus shown in Figure 13. In this case, the comb-like electrodes 221, 231 used had multiple comb teeth 221a, 231a with an inter-tooth distance (inter-electrode distance) of 10 mm.

[0318] The obtained conductive polymer fibers were then observed using a stereomicroscope to visually confirm the state of coating with the conductor containing PEDOT-PSS, and a photograph of this observation is shown in FIG. 17B.

[0319] [Comparative Example 2-1] In the comparative example, conductive polymer fibers were prepared in which a conductor containing PEDOT-PSS was fixed to the outer periphery of the silk fiber and inside the fiber bundle made of the silk fiber under the same conditions and procedures as in Example 2-1 above, except that the conductor was fixed to the silk fiber (base fiber) by a conventional chemical fixation method. The fiber resistance and conductivity of the obtained conductive polymer fibers were then measured using the same method as above, and the results are shown in Table 2.

[0320] Furthermore, water resistance was evaluated in the same manner as in Example 2-1 above, and a photograph taken using a stereomicroscope is shown in FIG. 18B.

[0321] [Evaluation results] As shown in the results in Table 2, the conductive polymer fiber of Example 1, in which a conductor containing PEDOT-PSS was electrochemically polymerized and fixed to silk fibers (base fiber) using the manufacturing apparatus of the present invention and the manufacturing method defined in the present invention, has lower fiber resistance and superior conductivity, regardless of the presence or absence of additives, compared to the conductive polymer fiber of the comparative example, which was produced by a chemical fixation method using conventional manufacturing apparatus. Furthermore, as shown in the photograph in Figure 17A, the conductive polymer fiber obtained in Example 2-1 is uniformly coated with a conductor comprising PEDOT-PSS on the surface of the silk fiber and even inside the fiber bundle, and it can be seen that the conductor is fixed without exposing the silk fiber. Furthermore, as shown in the photograph in Figure 18A, it was confirmed that the conductive polymer fiber obtained in Example 2-1 maintained a state in which the surface of the silk fiber and even the inside of the fiber bundle were coated with a conductor (black color on the surface of the silk fiber) even after a one-month water resistance test.

[0322] On the other hand, it was revealed that the conductive polymer fiber produced using the conventional chemical fixation method had higher fiber resistance and lower conductivity than the conductive polymer fiber of Example 2-1, as shown in Table 2. Furthermore, as shown in the photograph in Figure 18B, after one month of water resistance testing, the conductive polymer fiber obtained in Comparative Example 2-1 was found to have exposed silk fibers (white to gray color on the silk fiber surface), and it was confirmed that most of the conductor had peeled off and been lost.

[0323] 17B, ​​it was confirmed that the conductive polymer fiber obtained using the comb-shaped electrode in Example 2-2 had a portion of the silk fiber surface exposed, compared to the conductive polymer fiber produced using the rotor electrode in Example 1. This was because the conductor peeled off due to contact with some of the comb teeth (metal rod electrode) when electricity was passed through the comb-shaped electrode while the fiber was pulled up vertically. However, since the coverage of the silk fiber surface was higher than that of the conductive polymer fiber produced in the comparative example, it is considered that the silk fiber is superior to conventional products in both fiber resistance and conductivity.

[0324] Example of the third aspect Next, the third aspect of the present invention will be described in more detail with reference to examples, but the third aspect of the present invention is not limited to the following examples. (Example 3-1; Interdigitated electrode for electroencephalogram) Silk fiber bundles (Fujix Co., Ltd., tire size No. 9, fiber diameter approximately 280 μm) before composite fiber formation were immersed in a solution of PEDOT-PSS (Clevios P, Heraeus GmbH, Germany) containing 0.1% EDOT (Heraeus GmbH, Germany). Electricity was then applied to the silk fiber bundle, electrochemically immobilizing PEDOT-PSS on the surface and inside of the silk fiber bundle, producing a conductive composite fiber of silk fiber bundle and PEDOT-PSS. Four of these conductive composite fiber bundles were bundled together and fixed in a comb-shaped arched polystyrene frame (four locations, a total of 16 fibers), resulting in a comb-shaped bioelectrode 10, as shown in Figures 19A to 19D. A signal cable for an electroencephalogram measuring device (manufactured by Nihon Kohden Corporation) was used as the signal cable 314 to be joined to the contact 311 made of conductive composite fiber. 1 cm of the coating of this signal cable was stripped off to expose the copper wire, which was then wrapped with conductive composite fiber and ligated. The joint between the conductive composite fiber and the signal cable was insulated with an ethylene vinyl alcohol adhesive. At this time, the joint was fixed to the end of the frame together with the signal cable. Before using the bioelectrode for EEG measurement, the contacts 311 (conductive composite fiber) were impregnated with glycerol. Glycerol impregnation improves the conductivity and water resistance of the conductive composite fiber, as well as the flexibility of the fiber, ensuring good contact between the contacts 311 and the scalp and enabling stable EEG measurement. The bioelectrode 310 fabricated in this example is thin and lightweight, measuring 12 mm wide, 35 mm long, 6 mm thick, with a comb tip thickness of 2 mm, and weighing 1.1 g (electrode portion only, excluding cable weight). Furthermore, its comb-like shape allows the bioelectrode 310 to be worn hidden under the hair.

[0325] (Example 3-2; Hairpin-shaped EEG electrode) The same conductive composite fiber as in Example 1 was used. A 3.5 cm long hairpin-shaped hair clip was used as the frame. The hairpin was made of steel and its surface was coated with a urethane resin. 3 cm of the sheath of an EEG signal cable (manufactured by Nihon Kohden Corporation) was stripped, and the conductive composite fiber was wrapped twice around the exposed copper wire to form a contact with a thickness of approximately 1 mm (Figure 21C). The two contacts were fixed to both ends of the U-shaped frame of the hairpin via an ethylene vinyl support, resulting in the hairpin-shaped bioelectrode 320 shown in Figures 20A to 20D. The bioelectrode 320 fabricated in this example measured 35 mm in length, 2-5 mm in width, and 3 mm in height, and weighed 0.5 g (electrode portion only, excluding the cable weight). When using the bioelectrode 320 for EEG measurement, the electrode itself can grip the hair, allowing for self-supporting fixation; a holder such as an elastic net may or may not be used.

[0326] Figure 23A shows human EEG measured using the hairpin-shaped EEG electrodes of Example 3-2. The hairpin-shaped electrodes of Example 3-2 were placed at C3 and C4 as the relevant electrodes. Silver-silver chloride plate electrodes (NE134A, manufactured by Nihon Kohden Corporation, for collodion electrodes) were placed as indifferent electrodes, secured to the earlobes (ear lobes) on both sides with tape via absorbent cotton soaked in physiological saline. No pretreatment such as degreasing or exfoliation was performed on the skin where the electrodes were to be placed. Figure 23A shows the waveform of the awake EEG of an adult male measured in a conventional laboratory using a Nihon Kohden MEB5504 with a low-cut filter of 1 Hz and a high-cut filter of 20 Hz. Here, the horizontal axis of the figure is 400 ms / div and the vertical axis is 50 μV / div.

[0327] Figure 23B shows the auditory brainstem response (evoked potential) of an adult male measured using the hairpin-shaped EEG electrode of Example 3-2. The measurement equipment used (Nihon Kohden MEB5504) and electrode placement were the same as those used for the EEG measurement in Figure 23A. A 90 dB click sound was input to both ears via headphones, and 1,000 arithmetic averages were taken using the standard settings for the auditory evoked potential. The horizontal axis of the figure is 1 ms / div, and the vertical axis is 0.2 μV / div. The evoked potential waveforms measured with a low-cut filter of 1 Hz and a high-cut filter of 200 Hz demonstrate that the bioelectrode of the present invention can be used to measure evoked potentials.

[0328] (Example 3-3: Electrocardiogram Electrodes) In order to compare the stability and noise generation of the measured biological signals, the following three types of electrodes 1 to 3 were placed on the body surface of the same experimental animal (rat), and the electrocardiogram was measured simultaneously, and the measured waveforms were compared. Electrode 1 (electrode according to the second embodiment of the present invention): A contactor consisting of an array of 30 fibers (12 mm long) made of conductive composite fiber impregnated with glycerol, prepared in the same manner as in Example 3-1, was placed on the surface of the rat's body and fixed in place using the two methods described below. Electrode 2 (conventional type): A silver-silver chloride electrode coated with conductive gel (F120S, manufactured by Nihon Kohden Corporation) was placed on the surface of the rat's body and fixed using the two methods described below. Electrode 3 (conventional textile electrode): A commercially available electrode for sports heart rate monitors (product name: Smart Fabric Sensor, WearLink+ strap electrode, manufactured by Polar) with silver-coated woven fabric was placed on the surface of the rat's body and fixed in place using one of the two methods described below.

[0329] The skin on the rat's thoracic and dorsal regions was shaved and washed with disinfectant ethanol. The three types of bioelectrodes (electrodes 1 to 3) were then placed on the left and right thoracic and dorsal regions, respectively. Electrodes 1 to 3 were placed as close as possible to each other on each region. A medical bioelectrode (F-150S, Nihon Kohden Corporation) was placed on the thoracic and lumbar regions as an indifferent electrode (body earth). The signals obtained from each bioelectrode were analyzed using a measuring device (Polymate AP1124, TEAC Corporation).

[0330] Measurements were performed on the left and right thoracic and dorsal electrodes of the rats, with each electrode fixed using two different methods (elastic band or tape). The measurement results are shown in Figure 27. First, when electrode pads constructed by placing a PVC sheet substrate on each electrode were compressed and fixed with an elastic band, the signals obtained from the three types of electrodes were nearly identical, and signals could be recorded stably. Next, when the bands were removed and the electrodes were fixed with medical adhesive tape (Silkypore®), stable signals were recorded from electrodes 1 and 2 both when the rat was at rest and when it was moving. However, the signal from electrode 3 showed baseline fluctuations due to body movement, and hum noise was observed. From these results, it is clear that the stability of the signal measured with electrode 1 according to the second embodiment of the present invention is similar to that of medical electrode 2 and superior to that of textile electrode 3.

[0331] (Example 3-4: Regulation of skin moisture) The change in skin moisture content due to the sweating of the skin with the bioelectrode attached was measured using a skin moisture measuring device (corneometer), and the skin moisture content was compared between a conventional bioelectrode and the bioelectrode according to the second embodiment of the present invention 6 hours after attachment. The skin of an adult male's forearm was used as the measurement site. The subjects performed desk work using a computer in an environment with a room temperature of 26°C and a humidity of 40%. The skin moisture content at each electrode attachment site was measured using a skin moisture content measuring device (TK59823, Courage + Khazaka Electronics, Germany) before and 6 hours after application of each electrode. The measurement results are shown in Figure 10.

[0332] The measurement results shown in Figure 28 show the skin moisture content of the forearm before electrode application (Result A) and 6 hours after electrode application (Results B to E) (error bars 1 SD standard deviation, n = 10). Result B (+13.7%) was obtained using a bioelectrode according to the second embodiment of the present invention, which has a ventilation opening in the sheet substrate. Result C (+15%) was obtained using the same bioelectrode as Result B except that it did not have an opening. Result D (+32.3%) was obtained using a conventional bioelectrode with an adhesive gel coating. Result E (+54.4%) was obtained using a conventional bioelectrode with a highly adhesive pad as the sheet substrate. The results in parentheses indicate the percentage increase in moisture content at the application site of each electrode, with the moisture content before electrode application being set at 100%.

[0333] The specific configurations of electrodes B to E corresponding to each result are as follows: Electrode B is a bioelectrode in the form shown in Figure 25A, in which conductive composite fibers prepared in the same manner as in Example 3-1 were impregnated with glycerol, and 30 of these fibers were arranged in parallel on a 20 x 30 mm PVC sheet substrate to form a 7 x 12 mm contact. 2 Two openings were provided, and the sheet was fixed to the skin surface with an adhesive applied to the surface of the PVC sheet. Electrode C has the same configuration as electrode B, except that a sheet-like substrate without an opening is used. Electrode D is a silver-silver chloride medical bioelectrode (F120S, 18x35mm, manufactured by Nihon Kohden Corporation) using a conductive adhesive gel. Electrode E is a silver-silver chloride medical bioelectrode (M150, manufactured by Nihon Kohden Corporation, diameter 40 mm) with a highly adhesive foam pad. Bioelectrodes B to D were used while being independently fixed to the subject's forearm.

[0334] The above results showed that the skin moisture content of conventional electrode D, which used adhesive gel, increased by +32.3%, and that of conventional electrode E, which used a highly adhesive foam pad, increased by +54.4%. On the other hand, compared to the conventional types, the skin moisture content of electrode B (with openings), which used conductive composite fiber, increased by +13.7%, and that of electrode C (without openings) increased by only +15.0%. These results indicate that the electrode according to the second embodiment of the present invention is less prone to becoming stuffy than conventional electrodes. Furthermore, electrode B, which had openings in the sheet-like substrate, showed a lower increase in skin moisture content than electrode C, which had no openings, demonstrating the humidity-reducing effect of openings.

[0335] (Example 3-5: Comparison of electrical properties of bioelectrodes) Comparison of combined resistance between bioelectrodes and skin The following three types of bioelectrodes, 4 to 6, were placed on the skin of a human forearm with a 5 cm electrode spacing between them, and the combined resistance of each bioelectrode and the skin was measured using a bioelectrode impedance meter (manufactured by Melon Technos Co., Ltd.) under conditions of 10 Hz and a sine wave. The measurement results are shown in the table below as resistance ratios normalized by electrode area, with the result for electrode 4 set to "1." The contact area and impedance of each electrode are also listed. The above results demonstrate that the bioelectrode 4 according to the second embodiment of the present invention has the lowest impedance per area. Note that the impedance of the sports bioelectrode 6 when the contact surface was dry was extremely high and was not measurable with the measuring equipment used.

[0336] Electrode 4 (the present electrode) is a bioelectrode in which 15 conductive composite fibers impregnated with glycerol are arranged in parallel on a PVC sheet substrate, and a 12 mm x 7 mm contact is fixed by the method of the second embodiment. Electrode 4 was placed on the surface of the skin of a human forearm and fixed with an elastic band. In this case, the contact area between the surface of the human forearm skin and the contact part formed by the contact was 84 mm 2 (7x12mm). Electrode 5 (conventional type): A silver-silver chloride electrode coated with conductive gel (Vitrode F 150S, manufactured by Nihon Kohden Corporation) was placed on the skin surface, covered with the same sheet substrate as used for electrode 4, and secured with an elastic band. In this case, the contact area between the surface of the human forearm skin and electrode 5 was 630 mm 2 It was. Electrode 6 (conventional sports bioelectrode): a commercially available sports heart rate monitor electrode (Smart Fabric Sensor, WearLink+ strap electrode, manufactured by Polar) with silver-coated nylon fiber woven fabric was placed on the skin surface and fixed with an elastic band. At this time, the contact area between the surface of the human forearm skin and electrode 6 was 600 mm 2 It was. The results of measuring the combined resistance of each bioelectrode and the skin are shown below.

[0337] [Table 3]

[0338] Frequency response In order to compare the frequency characteristics of the electrode 7 below, which has conductive composite fibers, with the conventional electrode 8 below, which uses an electrolyte solution, the frequency characteristics of both electrodes were measured using an autolab (PGSTAT, manufactured by Metrohm Autolab). The results are shown in the table below. It was shown that the impedance of the electrode 7 below, which is the second embodiment of the third aspect of the present invention, is lower than the impedance of the electrode 8 below, which is made of silk fibers impregnated with a sodium chloride electrolyte solution, in the range of 10 Hz to 10 KHz.

[0339] The electrode 7 (main electrode) is a contact of a conductive composite fiber with a length of 2 cm that is impregnated with glycerol and is prepared in the same manner as in Example 3-1. The electrode 8 is an electrode (length: 2 cm) obtained by impregnating the silk fiber (fiber diameter: 280 microns) that constitutes the electrode 7 with a 0.9% sodium chloride electrolyte solution. The results of measuring the frequency characteristics of each electrode are shown below.

[0340] [Table 4]

[0341] Example of the fourth aspect Next, the fourth aspect of the present invention will be described in more detail with reference to examples, but the fourth aspect of the present invention is not limited to the following examples.

[0342] [Example 4-1] (Fabrication of implantable electrodes using conductive composite fibers) Before being converted into composite fibers, a silk fiber bundle (manufactured by Fujix Co., Ltd., tire size No. 9, fiber diameter approximately 280 μm) was immersed in a solution of PEDOT-PSS (Clevios P, manufactured by Heraeus GmbH, Germany) containing 0.1% EDOT (manufactured by Heraeus GmbH, Germany). An electric current was then passed through the silk fiber bundle using a comb-shaped electrode, and PEDOT-PSS was electrochemically fixed to the surface and interior of the silk fiber bundle, yielding a conductive composite fiber bundle of silk fiber bundle and PEDOT-PSS.

[0343] The coating at the tip of a polyimide-coated platinum-iridium wire (30 microns in diameter) (California Wire Company, USA) was removed and ligated to the prepared conductive composite fiber bundle (fiber diameter approximately 280 microns). The ligated portion and the surface of the conductive composite fiber bundle were coated with PDMS (Polydimethylsiloxane) (product name: Sylgard 184, Dow Corning Toray Co., Ltd.). A 500-2000 micron portion of the coating at the tip of the conductive composite fiber bundle was peeled off to expose the tip of the conductive composite fiber bundle. The PEDOT-PSS contained in the exposed tip was contacted with a stainless steel guide needle (100 microns in diameter, Seirin Co., Ltd.) and further coated with ethanol for chemical fixation (adhesion), thereby producing an implantable electrode.

[0344] (Placement of implantable electrodes) SD rats were anesthetized with isoflurane, and a skull window was created. The dura mater was removed to expose the cerebral cortex. The implantable electrode was placed into the cerebral cortex using an electric actuator (RCD, IAI Corporation) attached to the micromanipulator of a brain fixation device (SR-6R, Narishige Co., Ltd.). Specifically, the electrode was inserted into the left barrel cortex to a depth of 2 mm subcortically within 0.01–0.02 seconds. The platinum-iridium wire ligated to the conductive composite fiber bundle was connected to the head amplifier of a cranial nerve signal measurement and analysis system (model number: RZ51, TDT, USA). A silver-silver chloride wire was placed on the cortex as a reference electrode, and a silver-silver chloride wire was placed under the skull as a body earth. Measured signals were recorded and analyzed using dedicated software (Open EX, Open Explorer TDT).

[0345] The composite composed of PEDOT-PSS and silk fibers has a slow water absorption. For example, when the conductive composite fiber bundle in a dry state is immersed in 0.9% NaCl physiological saline, fiber expansion is clearly observed approximately 30 seconds after the start of immersion. If the conductive composite fiber bundle is inserted into biological tissue at high speed (in a short time (e.g., within 1 second), the PEDOT-PSS will absorb water and expand, and the implantable electrode comprising the conductive composite fiber bundle can be placed in the body before its strength decreases.

[0346] After the implantable electrode was inserted into the brain, the conductive composite fiber containing PEDOT-PSS that had been placed in the tissue gradually absorbed body fluids (extracellular fluid or cerebrospinal fluid), expanded, and adhered to the surrounding tissue. Further water absorption caused the adhesive between the conductive composite fiber and the guide needle to peel, and the conductive composite fiber electrode was separated from the guide needle. The guide needle was then removed using a micromanipulator, and the conductive composite fiber bundle, the main body of the electrode, was left in the tissue.

[0347] (recording of brain action potentials) Using the above insertion method, the implantable electrodes, each with a fiber diameter of 200 microns and a fiber length of 1 mm, were placed at two locations in the left barrel cortex of a rat brain at a depth of 2 mm. The distance between the electrodes was 2 mm. Figure 35A shows the action potentials recorded in the rat's cerebral cortex (barrel cortex). The upper and lower graphs show the signals detected by the two electrodes, respectively. Mechanical stimulation of the rat's right whiskers resulted in burst-like population action potentials recorded from the two electrodes. Synchronized population potentials (↓: arrows) and asynchronous population potentials (▼) were observed in the waveforms of the two electrodes.

[0348] [Example 4-2] (Fabrication of implantable electrodes) A conductive composite fiber bundle (length 3 mm, wire diameter 50 microns) prepared in the same manner as in Example 4-1 was immersed in glycerol to impregnate the fibers with glycerol. An insertion guide thread was attached to one end of the resulting conductive composite fiber bundle. A nylon monofilament suture thread with a curved needle for microsurgery (thickness: 10-0, manufactured by S&T) was used as the insertion guide thread. A bare gold wire (X-wire, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) with its insulating coating removed was wound around and fixed to the other end of the conductive composite fiber bundle, and the fixed portion was covered with PDMS (product name: Sylgard 184, manufactured by Dow Corning Toray Co., Ltd.).

[0349] (Recording of sciatic nerve mass action potential) Wistar rats were anesthetized with isoflurane, and a skin incision was made in the left hind limb to expose the left sciatic nerve. Under a microscope, a 10-0 guide thread was inserted into the adventitia of the sciatic nerve bundle. The conductive composite fiber bundle, attached to the guide thread, was then pulled along the guide thread and introduced into the sciatic nerve bundle. Because the conductive composite fiber bundle was treated to retard water absorption (i.e., impregnated with glycerol, its water absorption rate was slowed), it did not significantly expand during the surgical procedure and was inserted into the tissue (under the epineurium). The conductive composite fiber bundle expanded and was fixed within the tissue 15 minutes after insertion. Figure 35B shows the collective action potential (scale bar 1 s, 50 μV) of the rat sciatic nerve measured after the electrodes were fixed.

[0350] [Example 4-3] (Electrocardiogram recording of a rat) A rat's electrocardiogram was recorded using a conductive composite fiber bundle (20 mm long, 280 microns in diameter) prepared in the same manner as in Example 4-1. Under isoflurane anesthesia, the rat was placed in the subcutaneous tissue by ligating the conductive composite fiber bundle to the subcutaneous tissue layer at three locations: the right anterior chest, the left anterior chest, and the hypochondrium. The conductive composite fiber bundle constituting the electrode was connected to the signal cable of the preamplifier of a polygraph (AP1124, manufactured by TEAC Corporation) via a metal wire coated with an insulating and water-resistant polymer. The rat's electrocardiogram (bipolar lead) (Scale bar 1 second, 50 mV) recorded at a sampling frequency of 1 kHz is shown in Figure 35C.

[0351] [Example 4-4] (Drug delivery using implantable bioelectrodes) The same method as in Example 1 was used, except that a relatively long conductive composite fiber bundle was prepared. A silicone bag containing a drug solution was connected as a reservoir to one end of the bundle. The outer surface of the conductive composite fiber bundle was coated (sealed) with PDMS (product name: Sylgard 184, manufactured by Dow Corning Toray Co., Ltd.) to form a drug transport path. This coating resulted in an implantable bioelectrode with the conductive composite fiber bundle at its core and a PDMS tube forming the outer shell of the transport path.

[0352] In order to measure the drug transport rate in the conductive composite fiber bundle constituting the core of the electrode, a test conductive composite fiber bundle was prepared and a drug transport test was carried out. First, the central portion of a conductive composite fiber bundle (20 mm long, 280 micron diameter) prepared by the same method as in Example 4-1 was coated with PDMS over a 5 mm length. One end of the conductive composite fiber bundle was immersed in a chamber containing 1 mL of physiological saline containing 100 μM of the fluorescent substance Lucifer Yellow, and the other end was placed in a dish containing 0.5 mL of normal (fluorescent substance-free) physiological saline. The water level in the chamber containing Lucifer Yellow was set 5 mm higher than the water level in the dish containing normal physiological saline. These were placed in a thermostatic chamber at 37°C, and the concentration of Lucifer Yellow in the physiological saline in the dish was measured on days 0, 1, 2, 3, 4, and 7 after placement. Measurements were performed using a fluorescence intensity measurement device (Multilabel Counter, ALVO SX1420, PerkinElmer) using fluorometric methods. The measurement results are shown in Figure 36.

[0353] As Lucifer Yellow was transported from the chamber to the dish through the conductive composite fiber bundle, the concentration of Lucifer Yellow in the dish increased at a rate of 0.17 μM / day. This result indicates that Lucifer Yellow was permeating (permeating) through the conductive composite fiber at a constant rate (Figure 36, ▲ plot and dotted line).

[0354] [Examples 4-5] A conductive composite fiber bundle with a central portion coated with PDMS was prepared in the same manner as in Example 4-4, except that the conductive composite fiber bundle was impregnated with glycerol before being coated with PDMS. When the drug transport rate was measured using this conductive composite fiber bundle in the same manner as in Example 4-4, the concentration of Lucifer Yellow in the dish increased at a rate of 6.7 μM / day (Figure 36, plot and solid line). This result indicated that the drug transport rate increased by adding glycerol to the conductive composite fiber.

[0355] One of the reasons why the drug transport rate improves when the conductive composite fiber bundle is impregnated with glycerol is that when the conductive composite fiber bundle is coated with PDMS, glycerol prevents the PDMS from penetrating (staining) into the interior of the conductive composite fiber bundle, thereby maintaining the state of the flow path formed by the conductive composite fiber bundle in a state suitable for drug transport.

[0356] [Examples 4-6] (Evaluation of invasiveness of electrodes to central nervous tissue) The implantation of a bioelectrode into the tissue of the central nervous system causes permanent damage to the tissue of the central nervous system over an area larger than the size of the electrode, which interferes with measurements, and a solution to this problem has been sought. After inserting the implantable electrode of Example 4-4 according to the present invention into the brain, we investigated whether the damage (invasiveness) caused to the central nervous tissue by implanting the electrode can be reduced by administering a drug (GSNO: S-Nitrosoglutathione) that has the effect of reducing damage to the central nervous tissue through the flow path (drug transport path) of the electrode through animal experiments (Figures 34B to 34D).

[0357] The extent of neural tissue damage caused by electrode insertion (insertion) into rat brains was assessed by immunohistochemical staining of glial cells (astrocytes) in the cerebral cortex and the degree of neural tissue loss. Immunohistochemical staining was performed as follows: 25-micron frozen sections were prepared from cerebral cortex perfusion-fixed in 4% paraformaldehyde, and anti-GFAP antibody (MAB360 Chemicon) was bound to the sections at a 1:1000 dilution at 4°C overnight. Then, the sections were further labeled with a secondary antibody (Alexa 568) and observed under a fluorescence microscope (BX51, Olympus Corporation).

[0358] When a conventional metal needle electrode was implanted in a rat brain and the cerebral cortex was observed one week later under a fluorescence microscope, a significant tissue defect (black area) was observed beyond the implanted area of ​​the metal needle electrode (dotted area), as shown in Figure 34D. GFAP-positive glial cells (astrocytes) proliferated in the neural tissue (▲ in Figure 34D). Glial cells proliferated densely, particularly in the area in contact with the electrode, forming a glial scar (arrow in Figure 34D). Thus, seven days after electrode implantation, significant tissue defect, the formation of a glial scar (arrow), and a cluster of glial cells (▲) were observed.

[0359] Using conventional metal needle electrodes placed in this way, we measured the population action potentials of the rat cerebral cortex. Measurements were taken on days 1 and 7 after electrode implantation. The results are shown in the lower panel of Figure 34A (Conventional) (Scale bar 250 ms 40 mV). The measured signal on day 1 was good, but on day 7, the measured waveform was reduced and spikes were missing (arrows). In Figure 34A, Day 1 is the measurement record from day 1 after electrode implantation, and Day 7 is the measurement record from day 7 after electrode implantation. The arrows indicate missing spikes.

[0360] On the other hand, the implantable electrode prepared in Example 4-4 was inserted into the rat brain, and then an anti-inflammatory agent (GSNO) was administered at 15 μg / day per 250 g body weight via the drug transport pathway of the electrode. The rate of drug delivery was controlled by a miniature osmotic pump (Alzet, USA) connected to the drug delivery channel. In this example, where an anti-inflammatory drug was administered, the tissue defect was smaller than that observed with conventional electrodes, and the tissue defect was limited to the electrode placement area (dotted line area) (Figure 34C). Furthermore, glial cell proliferation in the neural tissue was mild, and no clear glial scar was observed at the electrode contact area (Figure 34C). In Figure 34C, GSNO was administered around the electrode, and even 7 days after electrode implantation, the tissue defect was limited to the electrode placement area (dotted line), and glial cell proliferation in the tissue was also low. For comparison, Figure 34B shows a fluorescent immunostained image of glial cells in a normal cerebral cortex without implanted electrodes.

[0361] Using the electrode of Example 4 of the present invention thus installed, the population action potential of the rat's cerebral cortex was measured. Measurements were performed on the first and seventh days after implantation of the electrode. The results are shown in the upper part of Figure 34A (PEDOT-PSS) (Scale bar 250 ms 40 mV). Good waveforms were observed in both the measurement signals on the first and seventh days.

[0362] The configurations and combinations thereof in the above-described embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible without departing from the spirit of the present invention. Furthermore, the present invention is not limited to the embodiments, but is limited only by the scope of the claims. [Industrial Applicability]

[0363] The present invention can provide a conductive polymer fiber that is excellent in conductivity, strength in both dry and wet states, and flexibility, and a bioelectrode including the same. The present invention provides a method and an apparatus for producing conductive polymer fibers, which can impregnate or adhere a conductor containing PEDOT-PSS to a base fiber and electrochemically polymerize and fix it continuously, thereby enabling the efficient production of conductive polymer fibers with excellent conductivity and durability. The bioelectrode of the present invention can be widely used as a surface-mounted bioelectrode that can be used continuously for long periods of time in a wide range of fields, including medicine, health promotion, information technology, and wearable computers. It is possible to provide a bioelectrode that is more comfortable to wear than conventional bioelectrodes, and a biosignal measuring device equipped with such a bioelectrode. The implantable electrode of the present invention can be widely used as an implantable bioelectrode in a wide range of fields, including medicine, health promotion, information technology, wearable computers, etc. More specifically, it can be used, for example, in electrical stimulation treatments such as deep brain stimulation, implantable electrodes for recording neural activity, brain-machine interfaces, etc. It is possible to provide an implantable electrode that is capable of detecting weak electrical signals within a living body, has excellent biocompatibility, and is minimally invasive to living tissue. [Explanation of symbols]

[0364] 2...Conductive polymer fiber 3...Fixing string 4...Rubber band 5…Metal conductor wire 6...Human body surface 33...Metal or carbon 34...Conductor 54...Conductor 63...insulating layer L: Diameter of the base fiber h: Thickness of the coated conductor 10, 20, 30, 40, 50, 60...Conductive polymer fiber 11, 21, 31, 41, 51, 61...Base fiber 12, 22, 32, 42, 52, 62...Conductors 210, 250...Conductive polymer fiber manufacturing equipment (manufacturing equipment) 202...Multiple electrodes (anodes) 221... Interdigital electrode (multiple electrodes; anode) 221a...Comb tooth (electrode) 221b…Terminal 222...Rotor electrode (pulley-shaped electrode) 222a...pulley 222b…Groove 222c…Metal shaft part 203...Multiple electrodes (cathode) 231... Interdigital electrode (multiple electrodes; cathode) 231a...Comb tooth (electrode) 231b…Terminal 232...Rotor electrode (roller-shaped electrode) 232a... Roller 232b…Outer surface 232c…Metal shaft part 252...Single (unipolar) electrode (anode) 253...Single (unipolar) electrode (cathode) 204...Conductor solution 205, 255...Immersion container 206, 256...Thread spools 207, 257...Chamber (humidity control section) 208, 258...Drying section 209, 259...winding section

[0365] 310...Bioelectrode 311...contact 312...First frame 313...Second frame 314...Signal cable H...Hair (head hair) S…Skin (scalp) 320...Bioelectrode 321...contact 322...Third frame 323...Fourth frame 324...Signal cable 321a...Conductive composite fiber 321b…Metal wire rod 321c...Insulating coating material 321e...Conductive composite fiber 321f…Thin metal wire 321g...Core material 321z...insulating coating material N...Low tension net 330...Bioelectrode 331...contact 332...contact part 333...Substrate (base material) 334...Signal cable 335…Holder 336...Opening 337...Humidity control pad 338...Electrode pad 339...Amplifier (external device) B…Body (trunk) T...underwear (shirt) 401...Conductive composite fiber bundle 402...Electric wire (metal conductor wire) 403...Connection section 404...Polymer 405...Needle (guide needle) 406...Thread 407…Reservoir 408...Chamber 409...Tube connector 410, 420, 430, 440...Implantable electrodes N'... nerve cord

Claims

1. The base fiber is coated with carbon, A conductive fiber characterized in that a conductor is impregnated within the base fiber.

2. 2. The conductive fiber according to claim 1, wherein the carbon is carbon black.

3. 3. The conductive fiber according to claim 1, wherein the substrate fiber is a straight or twisted fiber.

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