WO2016148249A1 - Procédé de production d'un élément d'électrode, procédé de production d'électrode et fabrication d'un système de mesure utilisant ladite électrode - Google Patents

Procédé de production d'un élément d'électrode, procédé de production d'électrode et fabrication d'un système de mesure utilisant ladite électrode Download PDF

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Publication number
WO2016148249A1
WO2016148249A1 PCT/JP2016/058557 JP2016058557W WO2016148249A1 WO 2016148249 A1 WO2016148249 A1 WO 2016148249A1 JP 2016058557 W JP2016058557 W JP 2016058557W WO 2016148249 A1 WO2016148249 A1 WO 2016148249A1
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electrode
production method
electrode element
producing
pts
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PCT/JP2016/058557
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English (en)
Japanese (ja)
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鳥光　慶一
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国立大学法人東北大学
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Priority to JP2017506201A priority Critical patent/JP6686244B2/ja
Publication of WO2016148249A1 publication Critical patent/WO2016148249A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/268—Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/251—Means for maintaining electrode contact with the body
    • A61B5/257—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/262—Needle electrodes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
    • A61B5/293—Invasive
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/296—Bioelectric electrodes therefor specially adapted for particular uses for electromyography [EMG]

Definitions

  • the present invention relates to a method for producing an electrode element that can be used as an electrode using a specific material, and more specifically, relates to a method for producing an electrode element that can be used as a silk electrode. Furthermore, the present invention is an invention relating to a body electrode used in the body surface or in the body using a conductive material having excellent biocompatibility, and more specifically, an electromyography measurement system such as an electromyograph, an electroencephalograph, etc. And a myoelectric measurement system or an electroencephalogram measurement system using the bioelectrode.
  • conductive polymers are used as materials that are more conductive and hydrophilic and more compatible with living organisms. It is attracting attention. This is because metals, carbon, and the like are hydrophobic and hard, and problems with compatibility with living bodies are recognized. For example, when used on a body surface as a bioelectrode, a conductive paste must be used between the bioelectrode and the body surface in order to ensure electrical continuity between the bioelectrode and the body surface. In addition, problems such as unpleasantness and pruritus caused by stuffiness, contact dermatitis and bacterial infection have been pointed out by users.
  • PEDOT-PSS Poly (3,4-ethlenedioxythiophene) -polystyrenesulfonate
  • bioelectrodes using conductive polymers include electromyographs and electroencephalographs using the bioelectrodes.
  • EMG electromyography
  • the former needle electromyogram is increasingly required in modern society where complex neuromuscular diseases are increasing.
  • the muscle action potential is derived through the surface electrode of the living body and visualized as an electromyogram. I can know.
  • the electromyogram measurement system that provides an electromyogram has improved the performance and cost of the apparatus, and has improved usability including software, so that the myoelectric potential measurement itself is becoming easier. Also, by using general-purpose signal processing software, various signal processing can be easily executed using a personal computer.
  • Electroencephalogram measurement is starting to occupy an important position not only in medical institutions but also in home testing, telemedicine, psychological research, nursing care welfare field, ubiquitous health care system, BCI (Brain Computer Interface), etc.
  • a composite system capable of synchronizing the action potential of the electroencephalogram and the eye movement is also provided.
  • PEDOT-pTS poly (3,4-ethylene-dioxythiophene) -p-toluenesulfonate
  • PEDOT-pTS is an essential component of an electrode element based on silk or the like instead of the PEDOT-PSS.
  • PEDOT-pTS is different in chemical characteristics from PEDOT-PSS, and there are problems unique to PEDOT-PSS in its practical use.
  • the first problem of the present invention is that when the PEDOT-pTS is used as a conductive polymer, the conductive polymer can be directly and efficiently applied to a substrate, which can be used as an electrode element while suppressing bleeding. It is to provide application means.
  • the second problem of the present invention is that the surface bioelectrode of the same use that overcomes the drawbacks associated with the metal surface bioelectrode of the above-described myoelectric measurement system, that is, does not use a conductive gel, and is in a use mode. Accordingly, it is possible to reduce the surface area of the electrode body with excellent conductivity performance, and it is possible to make it close to the skin, and with a little movement, it does not cause blurring between the electrode and the skin. It is to provide a surface electrode applicable to an electromyography measurement system and an electroencephalogram measurement system used in various living situations.
  • pTS solution organic solvent solution containing an oxidizing component and pTS (p-toluenesulfonate).
  • pTS-EDOT mixed liquid EDOT (3,4-ethylenedioxythiophene) mixed liquid
  • the solution is applied to the contact portion with a polymerization acceleration treatment synchronized with the contact, and the solution in the substrate
  • the polymerization reaction of EDOT immediately proceeds in the pTS-EDOT mixed solution, and PEDOT-pTS which is a high molecular polymer is formed.
  • This polymerization reaction follows the following formula. Fe 3+ is exemplified as the oxidizing component, but it is not limited to this as described later.
  • “synchronous” means that the polymerization promotion treatment is performed at a timing related to the timing at which the pTS-EDOT mixed solution contacts the substrate. Specifically, both timings may be the same, or the polymerization promotion treatment may be performed with a time lag from the timing at which the pTS-EDOT mixed solution contacts the substrate. In principle, the time lag is preferably within one minute.
  • the synchronized polymerization promotion treatment is preferably started within 1 minute from the contact of the pTS-EDOT mixed solution with the base material. It is. Further, for example, the production method of the present invention may be configured such that the pTS-EDOT mixed solution is contacted on the surface of the base material while maintaining the state in which the polymerization promotion treatment is continuously performed, and the time lag is not substantially provided. Included in “Synchronization”.
  • the time lag of the above synchronization can be extended by including a binder in the pTS solution.
  • the synchronized polymerization promotion treatment using this binder is preferably started within 24 hours from the contact of the pTS-EDOT mixed solution with the substrate, and more preferably 45 minutes. And most preferably within 10 minutes.
  • the adhesion of the pTS-EDOT mixed solution to the base material in this case is characterized not by impregnation but mainly by superficial adhesion due to the adhesive strength of the binder.
  • the polymerization promotion treatment in the production method of the present invention is not particularly limited as long as it is one or more selected from treatments for promoting the polymerization reaction to PEDOT-pTS in the pTS-EDOT mixed solution of the above formula.
  • the local heat treatment is set so that (a) the direct or indirect contact of the radiator at 50 to 90 ° C. and / or (b) the relevant portion is 50 to 90 ° C. Contact with hot air.
  • “local heat treatment” means, for example, that the heat treatment is not performed by placing the base material in the “heating atmosphere”, but is limited to the contact between the heat radiator and the corresponding part or the vicinity of the corresponding part.
  • an organic solvent solution containing an oxidizing component and pTS, and (2) an adhering portion of the mixed solution of EDOT by contacting the substrate is a part on the substrate plane.
  • Drawing design is different from simple one-sided attachment, and includes simple drawings such as circles and triangles, various drawings such as animal and plant drawings, portraits, characters, patterns, and the like.
  • This mask processing mode is the production method according to the present invention, in which (1) an organic solvent solution containing an oxidative component and pTS and (2) EDOT are adhered to each other by contact with a substrate.
  • contact with the mixed solution at least at the planned adhesion location, and further performing a polymerization promoting treatment, and then removing the mask Is.
  • the mask treatment include, for example, application of anti-staining paste or beeswax as a masking agent.
  • the anti-resisting paste include starch paste such as regular candy paste, corn starch paste and sweet potato starch paste; rubber paste; seaweed paste such as paste; and other various types of paste.
  • starch paste is suitable.
  • concentration of the antifouling paste at the time of use is not particularly limited, but is generally 3 to 5 mass%.
  • the removal of the stain-proofing paste can be performed by washing with water.
  • beeswax a wax derived from beehives. In use, it is usually heated and melted directly. The beeswax is removed by melting again by heating.
  • the base material used in the production method of the present invention is preferably a base material made of silk fiber or a base material coated with sericin or fibroin. Furthermore, it is preferable that the silk fiber has been subjected to soap scouring, alkali scouring, soap / alkali scouring, enzyme scouring, high temperature / high pressure scouring, or acid scouring.
  • the shape of the base material is not particularly limited, such as a fiber-like, string-like, cloth or ribbon-like fiber bundle, film-like, cloth-like, film-like, sheet-like, or gel-like, but as described above, the production method of the present invention
  • it is a substrate with a plane having a certain width, that is, a film shape, a film shape, or a sheet shape. Is preferred.
  • production efficiency can be remarkably improved by performing the production method of the present invention.
  • the content of pTS in the pTS solution is preferably 0.1 to 10% by mass with respect to the organic solvent solution.
  • EDOT may be appropriately diluted in an aqueous solvent such as water.
  • the oxidizing component in the pTS solution is not particularly limited as long as it has a predetermined oxidizing ability, and examples thereof include transition metals and halogens, and transition metals are particularly preferable.
  • the adhesion by contact in the production method of the present invention is preferably performed by dripping, spraying, dipping, transferring, or coating.
  • the mixed solution in order to eliminate waste of the EDOT-pTS mixed solution, the mixed solution is applied, dropped or sprayed so that the mixed solution is attached only in the vicinity of the target portion. It is preferable to apply or drop.
  • the dipping treatment is not impossible.
  • the electrode element of the present invention is an electrode element produced by the production method of the present invention described above, and the electrode of the present invention is characterized by using the electrode element of the present invention. Electrode.
  • the electrode of the present invention can be produced by an electrode production method, characterized in that an electrode element is produced by the production method of the invention, and then an electrode is produced using the electrode element. In the production method of the present invention, it is possible to easily provide two or more regions of different conductivity in the produced electrode element.
  • the electrode element of the present invention has a low resistance value and uses a fiber such as silk as a base material, it has a good touch, is excellent in durability and water resistance, and has flexibility. It can be used as a part or an electrode itself, and moreover, it can be produced as an electrode element having a variety of designs compared to the prior art in order to efficiently produce by the production method of the present invention that allows drawing.
  • the present inventors apply a bioelectrode using an electrode element produced using the production method of the present invention to an electromyography measurement system or an electroencephalogram measurement system, A surface or puncture bioelectrode (hereinafter referred to as a living body according to the present invention), characterized in that the second problem relating to an electroencephalogram measurement system can be solved and the electrode element according to the present invention is used. And also a production method thereof.
  • the biological electrode of the present invention is roughly classified into (a) a surface electrode or (b) a puncture electrode.
  • the area of the electrode element that can contact the skin is 0.25 to 100 cm 2 because the “small and high performance” characteristics of the electrode element of the present invention are apparent.
  • the shape of the electrode element is preferably “linear” or “planar”.
  • “linear” means a thread, string, cloth or ribbon-like fiber bundle, etc.
  • “planar” means a cloth, film, film, or sheet. And so on.
  • a “gel” base material can be used.
  • the shape of the bioelectrode of the present invention is typically linear or needle-like, which substantially coincides with the shape of the electrode element, and puncture the living body from the tip of these shapes. It can be carried out.
  • an electrode element and an auxiliary mechanism for inserting the electrode element into a living body are provided.
  • the mechanism is exemplified by an injection needle-like instrument and the like, and after this is inserted into the living body, only the electrode element portion is left in the living body, and the auxiliary mechanism is removed to remove the bioelectrode.
  • the element part can be left in the body.
  • the contactable surface area of the electrode element of the puncture electrode with the living tissue is preferably 0.0004 to 0.02 cm 2 .
  • the above-described biological electrode of the present invention can be suitably used for a myoelectric measurement system or an electroencephalogram measurement system.
  • the electrical resistance value of the conductive portion in the electrode element or the like in the present invention is calculated as follows.
  • the “conductive portion” means a region where a conductive treatment, specifically, PEDOT-pTS is attached on the base material.
  • PEDOT-pTS is attached to only a part of the base material
  • the PEDOT-pTS attached region corresponds to the “conductive portion”.
  • the electrical resistance value of the linear electrode element or the like is a value obtained by detecting the electrical resistance value per 1 cm of the linear length with a cross-sectional area of about 2.5 ⁇ 10 ⁇ 4 cm 2 by a tester.
  • the cross-sectional area of about 2.5 ⁇ 10 ⁇ 4 cm 2 is the cross-sectional area of a standard thickness silk thread. “About” means that the number after the second decimal place of “2.5” is rounded off. Since the cross-sectional area is inversely proportional to the resistance value, the resistance value corresponding to the cross-sectional area can be easily calculated.
  • the cross-sectional area of the linear base material increases, the cross-sectional area of PEDOT-pTS is also expected to increase accordingly, making it possible to easily compare the electrode elements of the present invention with each other or with other electrode elements. It is a parameter of an appropriate electrical resistance value in the present invention. When the length of 1 cm cannot be secured, the electrical resistance value in the entire conductive region of the linear electrode element is measured, and the comparison can be made by converting the electrical resistance value into the 1 cm length and the cross-sectional area. it can.
  • an electrode element that can efficiently produce an electrode element using a fiber such as silk that is suitable for use in an electrode, particularly a biological electrode, without bleeding into the base material.
  • a production method is provided.
  • the present invention provides a small and high-performance electrode element produced by the production method, an electrode such as a biological electrode using the electrode element, and a production method of the electrode.
  • the bioelectrode can be suitably used as a bioelectrode of an electromyography measurement system or an electroencephalogram measurement system, and a production method thereof is also provided.
  • FIG. 2 (a) shows a part of a flat electrode produced by drawing a plurality of dumbbells on a plain weave silk fabric. The silk fabric is sufficiently impregnated with PEDOT-pTS and is in contact with the brain. An electrode having PEDOT-pTS attached to the surface is also shown.
  • FIG. 2 (b) shows an electrode having PEDOT-pTS attached only to the contact surface with the brain.
  • FIG. 7B shows an electromyogram obtained by the measurement shown in FIG. 7B among the drawings showing the measurement of the muscle action potential using the surface electrode of the present invention. It is drawing which showed the electroencephalogram obtained using the electrode for puncture (needle electrode) of this invention.
  • FIG. 8A is a schematic view showing the state of this measurement
  • FIG. 8B shows an electroencephalogram obtained by this measurement. It is drawing which showed the result of having measured the muscle action potential using the electrode for puncture (needle electrode) of this invention.
  • FIG. 9A is a schematic view showing the state
  • FIG. 9B is a needle electromyogram obtained by this measurement.
  • the pTS-EDOT mixed solution is a mixed solution of pTS solution and EDOT.
  • the pTS solution is an organic solvent solution containing pTS (p-toluenesulfonate) and an oxidizing component.
  • PTS is known as a p-toluenesulfonic acid compound (a salt or ester with p-toluenesulfonic acid (tosylic acid)) and is also commercially available.
  • An organic solvent that can serve as a solvent for the pTS solution is capable of dissolving pTS and an oxidizing component, and preferably has good compatibility with an aqueous solvent.
  • Specific examples include monovalent lower alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, pentanol, or hexanol.
  • the skeleton of carbon atoms constituting these monovalent lower alcohols may be linear, branched or cyclic, and may be used alone or in combination of two or more. Moreover, you may dilute and use with water suitably.
  • monovalent lower alcohols having 1 to 4 carbon atoms specifically, methanol, ethanol, propyl alcohol, isopropyl alcohol, or butanol are suitable as the organic solvent for the pTS solution.
  • the oxidizing component contained in the pTS solution is not particularly limited as long as it can activate the polymerization reaction to PEDOT-pTS in the pTS-EDOT mixed solution, and examples thereof include transition elements and halogens.
  • Transition elements include first transition elements such as iron, titanium, chromium, manganese, cobalt, nickel, and zinc; second transition elements such as molybdenum, silver, zirconium, and cadmium; third transition elements such as cerium, platinum, and gold Is exemplified. These transition elements may be used as a single metal or as a metal salt. Among these, it is preferable to use a first transition element such as iron or zinc.
  • the content of the oxidizing component in the pTS solution varies depending on the type of the oxidizing component used, and is not particularly limited as long as it is an amount that can activate the polymerization reaction.
  • the ferric chloride is 1 to 10% by mass with respect to the solution, and particularly preferable. Is 3 to 7% by mass. If the amount is too large, the polymerization reaction proceeds rapidly, but it is difficult to remove iron in the subsequent step, and if it is small, the polymerization reaction proceeds slowly.
  • the content of pTS acting as a dopant in the pTS solution is preferably 0.1 to 10% by mass, more preferably 0.15 to 7% by mass, and particularly preferably 1 to 6% by mass with respect to the solution. %, Most preferably 2-5% by weight.
  • EDOT is known as 3,4-ethylenedioxythiophene and is also commercially available. It is liquid at room temperature and water-soluble, and can be appropriately diluted in an aqueous solvent such as water.
  • the pTS solution can contain a binder. As described above, it is possible to delay the timing at which the polymerization acceleration treatment is applied to the pTS-EDOT mixed solution in synchronism with the binder. However, the adhesion of PEDOT-pTS to the substrate has a larger factor of superficial adhesion due to the adhesive force of the binder itself than the impregnation.
  • the binder used here is not particularly limited, and can be selected according to, for example, the characteristics of dissolution thereof, and examples thereof include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, Nafion, polycarbonate, polyacrylonitrile, polyethylene, polypropylene, polybutene, polyether, polyester, polystyrene, poly-p-xylene, polyvinyl acetate, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl Thermoplastic resins including thermoplastic elastomers such as ether, polyvinyl ketone, polyamide, butadiene resin, and fluorine resin; polyurethane resin, urea resin, melamine resin, modified silicone resin, phthalic acid resin, phenol resin, furan resin, aniline Thermosetting resins such as resin, unsaturated polyester resin, xylene / formaldehyde resin, epoxy resin; light such as epoxy
  • the content of the binder in the above solution is not particularly limited as long as the conductivity of the electrode element of the present invention is maintained.
  • 10 to 30% by mass of the total amount of the pTS solution and EDOT is preferably 10%.
  • -40% by weight or 1-30% by weight is second preferred, 1-40% is third preferred, 1-50% by weight or 0.1-40% by weight fourth preferred, 0.1-50 5% by mass is preferred.
  • 0.1 to 1% by mass, 0.1 to 10% by mass, 1 to 10% by mass, 40 to 50% by mass, 30 to 50% by mass, and 30 to 40% by mass of the total amount of the pTS solution are also preferable.
  • the other components include glycerol, polyethylene glycol-polyprene glycol polymer, ethylene glycol, sorbitol, sphingosine, and phosphatidylcholine, preferably glycerol, polyethylene glycol-polyprene glycol polymer, and sorbitol. 1 type, or 2 or more types.
  • cationic surfactants such as quaternary alkyl ammonium salts and alkylpyridinium halides; anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, fatty acid salts; polyoxyethylene, poly Nonionic surfactants such as oxyethylene alkyl ethers; natural polysaccharides such as chitosan, chitin, glucose and aminoglycan; sugar alcohols, dimethyl sulfoxide and the like.
  • the pTS-EDOT mixed solution is a mixed solution obtained by mixing the pTS solution and EDOT, and the polymerization reaction to PEDOT-pTS starts immediately by the above mixing.
  • the polymerization accelerating treatment is particularly limited as long as it is one or more selected from treatments that promote the polymerization reaction to PEDOT-pTS in the pTS-EDOT mixed solution.
  • heat processing etc. are mentioned.
  • As the heat treatment (a) direct or indirect contact with a radiator at 50 to 90 ° C. or (b) contact with hot air set so that the corresponding portion reaches 50 to 90 ° C. , Etc.
  • the “corresponding portion” specifically means a portion where the pTS-EDOT mixed solution is brought into contact with the substrate.
  • the time for performing these polymerization promotion treatments is preferably as short as possible while the polymerization is performed without impairing the conductivity of PEDOT-pTS.
  • the electrical resistance that is a measure of conductivity in the electrode element of the present invention is preferably as small as possible, the upper limit of the electrical resistance is 15.0 ⁇ 10 4 ⁇ / cm at most. It is preferably 2.0 ⁇ 10 4 ⁇ / cm or less.
  • the electrical resistance increases according to the length of the treatment time, that is, 2.0 ⁇ 10 4 ⁇ .
  • An electrode element having an electric resistance value exceeding / cm can be obtained, and the electric resistance of the electrode element can be freely adjusted by controlling the processing time.
  • the mask to be selected is made of a material that can be easily removed and that the mask removing means such as water washing is accurately performed. is there.
  • the heating time is preferably 3 to 10 minutes, particularly preferably 3 to 6 minutes, and most preferably 4 to 6 minutes. . If the heating time is other than the preferred time, it is difficult to set the value of the electrical resistance of the electrode element within an assumed condition. However, as described above, this is not the case when the electric resistance value is intentionally increased.
  • the heat treatment under such conditions can be performed, for example, by setting the heat source to 1000 W, the distance from the corresponding part to about 7 to 20 cm, and the air volume to 1 to 2 m 3 / min.
  • the contact with the hot air includes a mode in which air is blown toward the corresponding part in the atmosphere maintained at 50 to 90 ° C. as described above.
  • PEDOT-pTS in the corresponding part of the base material can be generated quickly and in a good conductive state.
  • [A] -3 Substrate
  • the substrate used in the production method of the present invention is not limited as long as sericin or fibroin is contained, and even if it is silk that originally contains these proteins, It is possible to add these proteins afterwards.
  • Base materials for coating sericin or fibroin include polyamide fibers such as nylon, polyester fibers such as PET, synthetic fibers such as acrylic fibers, aramid fibers, polyurethane fibers, and carbon fibers; plant materials such as cotton, hemp, and jute In addition to the above-mentioned silk, animal fibers such as wool and collagen fibers; or mixed fibers thereof can be widely used. It may be a dyed fiber.
  • “covering” is an action of covering the surface of an object with a covering component in appearance, and its specific mode is not limited. For example, any form of “attachment”, “containing”, and “penetration” of the coating component to the object to be coated may be used.
  • Both sericin and fibroline can be obtained from silk (raw silk) by a known method, and are also commercially available.
  • Sericin is a protein component that forms the outside of raw silk, and can be recovered from raw silk by, for example, the method disclosed in JP-A-11-131318, and is also commercially available (for example, stocks) Company plateau company).
  • Fibroin is a protein component that forms the core of raw silk, and can be obtained, for example, by dissolving silk fiber with an alkaline solution and dialyzing it by the method disclosed in JP-A-6-70702, Commercially available (Silkgen G Solvel KE: Ichimaru Falcos Co., Ltd.).
  • sericin or fibroin can be produced basically by immersing the object to be coated (including yarn and fabric) in aqueous sericin or fibroin, drying, and washing to form a film. Yes (Patent Document 3). It is also possible to outsource such coating work to obtain a desired sericin coated substrate [for example, Art Co., Ltd. (Kiryu City, Gunma Prefecture): http://art-silk.jp/ ].
  • the above “silk fiber” means “silk or a fiber mainly composed thereof”.
  • the silk fiber may be a single silk, but if necessary, a mixed fiber with other fibers can be used.
  • the “other fibers” include synthetic fibers, plant fibers, and animal fibers other than silk, which are exemplified as the objects to be coated with sericin or fibroin.
  • silk is obtained from ordinary silkworm silk, wild silk thread, natural silk derived from silkworms and bees, and silk obtained using genetic recombination technology, such as silkworms obtained by incorporating a gene encoding a fluorescent protein. It is also possible to use “silk” or the like.
  • silk that originally contains sericin and fibroline, is excellent in affinity and adhesion with PEDOT-pTS, and is excellent in biocompatibility and strength, or a fiber mainly composed of this, that is, It is preferable to select “silk fiber”.
  • scouring is a process of removing sericin and other impurities from raw silk and the like.
  • scouring include soap scouring, alkali scouring, soap / alkali scouring, enzyme scouring, high temperature / high pressure scouring, acid scouring, and any scouring method can be used. These scouring can be performed on a yarn basis or on a fabric basis. That is, the silk cloth-like substrate may be a raw silk fabric or a kneaded silk fabric.
  • the shape of the substrate is a fiber-like, string-like, cloth- or ribbon-like fiber bundle, film-like, film-like, sheet-like, or gel-like, and is cloth-like, membrane-like, film-like, or sheet-like (
  • a planar substrate which is suitable as an application target of the production method of the present invention, and is a fiber bundle in the form of a thread, string, cloth, or ribbon (hereinafter, these are linear substrates)
  • the production method of the present invention has a great significance in terms of production efficiency.
  • the contact of the pTS-EDOT mixed solution with the substrate is accompanied by a drawing design on a part of the substrate plane. It is suitable for exhibiting the difficulty.
  • the thickness of the linear base material is not particularly limited, and can usually be selected as necessary within a range of about 0.1 ⁇ m to 1 mm. When used for electrodes such as biological electrodes, the thickness is usually about 1 ⁇ m to 100 ⁇ m. The length of the linear substrate can also be selected as necessary.
  • linear base material may be subjected to treatment as necessary, for example, plasma treatment for improving hydrophilicity, pore treatment, chemical coating treatment and the like.
  • the texture of the woven fabric is not particularly limited.
  • it can be used as a three-layer structure of plain weave, twill weave, and satin weave.
  • it may be a changed organization in which the Mihara organization is changed or combined, or may be a single special organization or a pattern weave organization with an aggressive pattern.
  • multiple woven fabrics such as a warp double fabric, a weft double fabric, a warp double fabric, a pile fabric, a towel fabric, and a kneading fabric may be used.
  • [A] -4 Mode of Synchronization Processing
  • “synchronization processing” is performed in which the above-described polymerization promotion processing is performed in synchronization with the contact of the pTS-EDOT mixed solution with the substrate.
  • the time from the above contact to the start of the polymerization accelerating treatment in the synchronous treatment is preferably as short as possible especially in the pTS-EDOT mixed solution not containing the above-mentioned binder, and preferably within 1 minute. More preferably, it is within 30 seconds. By managing this time short, it is possible to prevent the pTS-EDOT mixed solution from spreading on the base material and to increase the production efficiency of the electrode elements.
  • the time is preferably within 24 hours, more preferably within 45 minutes, and most preferably within 10 minutes.
  • the step of mixing the pTS solution and EDOT, preferably within the range of the volume ratio described above, to produce a pTS-EDOT mixed solution and bringing it into contact with the substrate first step
  • the synchronous process includes a stage (second stage) and a stage (second stage) in which the polymerization promotion treatment is performed within the above-described time and the pTS-PEDOT is adhered to the substrate.
  • the first stage and the second stage can be performed manually, but in reality, it is preferable to perform all or part of the process automatically by using a printing process technique or the like.
  • FIG. 1 shows a schematic diagram of an embodiment of a system for performing this process.
  • FIG. 1 shows a synchronization process.
  • An ink mechanism 3 capable of bringing the pTS-EDOT mixed solution into contact with the pTS-EDOT mixed solution from above in the vertical direction is provided on the conveyor guide belt 2 capable of feeding the planar substrate mounted thereon in the direction of arrow 1.
  • a thermal head 4 is provided as a heat dissipator at the tip of the arrow 1, and a polymerization acceleration processing mechanism 5 is further provided at the tip.
  • the substrate 6 is set between the ink mechanism 3 of the guide belt 2 and the thermal head 4.
  • the step of bringing the pTS-EDOT mixed solution into contact with the base material 6 through the ink mechanism 3 is the first step described above, and the predetermined polymerization is performed in the thermal head 4 or the polymerization promotion processing mechanism 5 while performing time management.
  • the step of performing the promotion process is the second step.
  • the pTS-EDOT mixed solution is supplied to the substrate 6 and a predetermined contact is performed.
  • a mechanism (not shown) for mixing the pTS solution and EDOT at a specific ratio is provided in the ink mechanism 3 or externally from the ink mechanism 3, and the pTS is provided to the ink outlet 31 via the mixing mechanism.
  • -EDOT mixture is supplied. Examples of the contact mode of the pTS-EDOT mixed liquid from the ink outlet 31 to the substrate 6 include dropping using a syringe pipette or the like, spraying using an inkjet nozzle, or the like. In addition, transfer by a silk screen or the like can be performed in a mode different from this figure.
  • the mechanical or automatic setting for performing a desired drawing design on the substrate is performed by, for example, a pressure-sensitive sensor using a piezo element or the like.
  • the periphery of the drawing design is covered or surrounded with a masking agent to suppress the infiltration of the pTS-EDOT mixed solution into the coating part or the surrounding area, thereby making the drawing design clear and clear. Further improvements can be made.
  • drawing is performed in a short time by contacting the base material 6 with the pTS-EDOT mixed liquid, and the drawing portion is immediately transferred to the thermal head 4 by feeding the drawn base material 6 in the direction of arrow 1 by the guide belt 2.
  • the production method of the present invention is carried out by setting the drawing design by this contact and the time until the start of the polymerization accelerating treatment by the thermal head 4 or the like preferably within 1 minute, more preferably within 30 seconds.
  • direct or indirect contact with the thermal head 4, that is, contact with the heat radiating body is one of the polymerization promotion treatments, and the polymerization promotion by the polymerization promotion treatment mechanism 5 without the contact treatment. You may process and you may combine both.
  • the polymerization promotion processing mechanism 5 is provided with equipment for performing the above-described polymerization promotion processing, for example, hot air processing.
  • a first hot air treatment is performed by a hot air blowing device (not shown) provided in the polymerization promotion mechanism 5, and then drying is performed.
  • a step of performing the water washing of the corresponding part and the masking agent removing process may be mentioned, and then performing the second hot air process again and drying.
  • the second stage is the contact with the thermal head 4 and the first hot air treatment.
  • the water washing treatment performed after the first hot air treatment is performed to remove oxidizing components such as unreacted EDOT and transition metal.
  • the process of attaching pTS-PEDOT to the substrate 6 is completed by the synchronous processing through the processes of the first stage and the second stage.
  • FIG. 1 showing this example is only a schematic diagram. Variations in the embodiment of the production method of the present invention are diverse.
  • the pTS solution and EDOT can be ejected separately, and both solutions can be mixed in the air to make contact with the substrate 6 as a pTS-EDOT mixed solution.
  • the transition from the first stage to the second stage is performed by the feeding operation of the drawn base material 6 on the plane by the guide belt 2, but for example, a space where the drawn base material 6 is directed.
  • the angle it is possible to perform hot air treatment, direct or indirect contact treatment with the thermal head, etc. from the direction in which the drawn substrate 6 is directed at the changed angle.
  • the second stage process can be performed in a “hanging” state or a “stretching” state.
  • the electrode element of the present invention can be produced.
  • the electrode of the present invention is characterized by using the electrode element (electrode element of the present invention) obtained by the production method of the present invention.
  • the electrode “Used” means that the electrode element of the present invention is used as all or part of the electrode.
  • the electrode of the present invention can be produced by an electrode production method characterized in that an electrode element is produced by the production method of the present invention, and then an electrode is produced using the electrode element.
  • the electrode of the present invention is all of the electrodes to which the electrode element of the present invention can be applied due to its properties, but the resistance value is low, and since the fibers such as silk are used as the base material, the touch is good and the durability is high. In order to have excellent water resistance and flexibility, it is particularly preferable to use it as a bioelectrode part or the product itself.
  • the aspect in the case of using the electrode of this invention as a bioelectrode biologically.
  • [B] -1 Surface electrode
  • the surface electrode transmits action potential and brain waves transmitted by volume conduction on the skin, directly on the surface of muscles, brain, and other organs (hereinafter referred to as “body tissue”). It is an electrode that is led out without puncturing the electrode from the surface), and is a biological electrode that is attached to the muscle abdomen or head for use. This can also be used as a stimulation electrode for derivation of evoked potentials or treatment.
  • the electrode of the present invention is a surface electrode
  • the use of the electrode of the present invention is particularly suitable.
  • the contactable area of the electrode element with the body tissue surface is preferably 0.0004 to 100 cm 2 , particularly preferably 0.0004 to 25 cm 2 .
  • the feature of the electrode of the present invention that “it can be derived well” is not fully utilized.
  • the contactable area is smaller than 0.0004 cm 2 , it is difficult to sufficiently derive an action potential or an evoked potential, and an electroencephalogram. However, if the performance of the myoelectric measurement system or electroencephalogram measurement system is improved in the future, even if the contactable area is smaller than 0.0004 cm 2 , there is a possibility that it can be used favorably as the surface electrode.
  • the “area that can be contacted with the body tissue surface” is an area that can contact the body tissue surface when a conductive material is used as the electrode element of the surface electrode.
  • the electrode element is planar. In this case, it is the area of the sheet surface. In the case of such a planar electrode element, 0.25 to 100 cm 2 is particularly preferable, and 0.25 to 25 cm 2 is more preferable.
  • the electrode element is linear
  • the area of the surface area of the linear electrode element that is expected to be in contact with the body surface is the area that can come into contact with the body tissue surface.
  • 0.0004 to 0.02 cm 2 is particularly preferable, and 0.0004 to 0.005 cm 2 is more preferable.
  • the contactable area is a single electrode element. For example, in the case where a plurality of electrode elements are provided in a single surface electrode without contact with each other, the area of each electrode element.
  • the basic structure of the surface electrode according to the present invention includes (1) an electrode element, and (2) an action potential or evoked potential captured by the electrode element, such as the following signal cable or transmitter chip, and an electroencephalogram, an amplifier, etc. It is a mechanism for transmitting to the main body of the myoelectric measurement system and the electroencephalogram measurement system.
  • the surface electrode of the present invention can be produced by a conventional method.
  • the electrode for the surface of the present invention having this basic structure is attached to the muscle belly or scalp on the skin to be measured, or directly to the surface of the muscle or brain, at least two locations, preferably at least three locations.
  • the action potential or evoked potential in the muscle can be measured, or the electroencephalogram in the brain region can be measured.
  • two or more, preferably three or more surface electrodes of the present invention are applied to the muscle belly or scalp on the skin where electrical stimulation is performed, or directly on the surface of the muscle or brain, and electrical stimulation for the subject is performed. It can be performed.
  • the sticking means to the body tissue surface can be easily performed by using a double-sided tape, a single-sided tape or the like when the body tissue surface is skin, for example.
  • the double-sided tape can be used by adhering the region other than the electrode element in the electrode and the body tissue surface, and the single-sided tape is adhered to the body tissue surface from the upper side of the electrode element placed on the body tissue surface. It is possible to use.
  • the body tissue surface is the brain surface or the organ surface, it is preferable to perform placement depending on the moisture on the surface of the brain or the like without using the above-mentioned adhesive means such as the double-sided tape.
  • the fixing means for the skin surface and the surface electrode provided in the member can be fixed on the body tissue surface.
  • the skin and the electrode can be fixed by the adhesive force of the adhesive part protruding from the electrode element of the adhesive sheet as an adhesive sheet provided with an adhesive part on the side facing the skin.
  • an electrode element is incorporated in the contact part with the skin of daily products such as bracelets, wristbands, wristwatch bands, stomach wraps, supporters, etc. It can be set as the surface electrode of the present invention.
  • the surface electrode of the present invention can be provided with an opening for preventing stuffiness and a humidity control unit incorporating a water-absorbing material that can absorb sweat, water vapor, etc., if necessary. is there.
  • the first feature of the surface electrode of the present invention is that it is possible to freely draw an electrode element on a planar substrate, and therefore, the use location of the electrode can be selected flexibly. Can do.
  • a surface electrode element having a design adapted to the shape of a desired part of the body can be easily created, and the surface of the textile It is possible to diversify the electrodes.
  • the surface electrode of the present invention can be directly mounted on the body tissue.
  • the electrode element is formed by drawing an electrode element of a desired shape on the plane of a planar base material such as silk fabric excellent in biocompatibility based on the first feature.
  • the conductive performance of the electrode element used is superior to that of a product using a conventional conductive polymer. It is possible to transmit an evoked potential and also an electroencephalogram. For example, even if the shape of the electrode element is “linear”, it is possible to accurately transmit action potentials, evoked potentials, and brain waves.
  • multi-channel surface electrodes multi-point electrodes
  • smaller surface electrode elements arranged at higher density, which enables analysis of a wide range of muscle activities and multi-regional electroencephalograms. It becomes possible to carry out precisely.
  • FIG. 2 shows a plurality of dumbbells (both lines bulging at both ends) on a plain-woven silk fabric in accordance with the production process described above (FIG. 2 (a) shows a part of two and FIG. 2 (b) shows a part of each).
  • the drawing shows a state in which a material having the drawn portion as a planar electrode element is placed on a human brain model.
  • the bulging portions at both ends correspond to the electrode elements, and the thin linear portions connecting these correspond to the cords connecting the electrode elements.
  • the black drawing portion by PEDOT-pTS may be on the front side as shown in FIG. Fully impregnated PEDOT-pTS is in direct contact with the brain).
  • FIG. 1 shows a plurality of dumbbells (both lines bulging at both ends) on a plain-woven silk fabric in accordance with the production process described above
  • FIG. 2 (a) shows a part of two
  • FIG. 2 (b) shows a part of each).
  • the drawing shows a state in which a material
  • the unit is an electrode element of about 10 mm square, but the size can be further adjusted. In the case of the surface electrode of the brain, it is assumed that the size is about 3 ⁇ 3 with an interval of about 10 mm if the size is about this example.
  • the drawing unit of individual dumbbells can be made finer, and a lattice-like surface electrode that can be brought into direct contact with a higher density brain can be obtained.
  • the wired cord electrically connected to the external device has an insulating coating.
  • the coating material include natural fibers such as silk, chemical fibers such as polyester, and synthetic resins such as silicone resins.
  • the electrode of the present invention is a surface electrode
  • action potentials, evoked potentials, and brain waves can be measured in every scene of life, and health management, disease diagnosis, elucidation of exercise principles, and the like can be performed more flexibly and widely.
  • Puncture electrode is an electrode that literally brings a desired biological signal into contact with an electrode element in a living body. This can also be used as a stimulation electrode for derivation of evoked potentials or treatment.
  • Accessible surface area of the biological tissue of a living body electrode element of this embodiment is preferably a 0.0004 ⁇ 0.02 cm 2, particularly preferably a 0.0004 ⁇ 0.002 cm 2. This is a very small surface area as compared with the conventional one, but at the same time, an excellent bioelectrode function can be exerted due to good conductive properties.
  • the basic configuration of the puncture electrode according to the present invention includes (1) an electrode element, and (2) an action potential or evoked potential captured by the electrode element, such as the following signal cable or transmission chip, and an electroencephalogram, an amplifier, etc. It is a mechanism for transmitting to the main body of the myoelectric measurement system and the electroencephalogram measurement system.
  • the puncture electrode of the present invention can be produced by a conventional method.
  • the puncture electrode of the present invention having this basic configuration is punctured at one or more locations in a living tissue to be measured, and an action potential or an evoked potential captured by the electrode element, or an electroencephalogram is used as an electromyography measurement system or electroencephalogram measurement.
  • an action potential or an evoked potential captured by the electrode element, or an electroencephalogram is used as an electromyography measurement system or electroencephalogram measurement.
  • the action potential and evoked potential in the muscle, and the electroencephalogram in the brain region can be measured.
  • the electrodes used are all “two or more, preferably three or more” as in the case of the surface electrode described above, but it is not always necessary to use all of them as puncture electrodes. It is also possible to use the part as a surface electrode. If all the electrodes are for puncturing, the number is “two or more, preferably three or more”, as with the surface electrode.
  • the biological electrode of this embodiment is typically in the shape of a needle and is used by inserting it into the living body, and a linear wire electrode element is inserted into the body of an electrode such as an injection needle.
  • a “wire electrode” is used that is inserted into a living body using an auxiliary mechanism for insertion and is used by removing the auxiliary mechanism.
  • the electrode of the present invention is used as a puncture electrode will be described focusing on these two typical examples.
  • a hard linear material for example, a hard silk thread
  • the hard silk thread is provided without removing sericin by scouring, and by applying the PEDOT-pTS through the production process described above, a wire having a hardness close to that of a wire is obtained.
  • Electrode element The needle electrode of the present invention can be produced by adding a basic configuration to the needle electrode element of the present invention by a known means. If the hardness of the electrode element is about this level, it is possible to puncture the body from the outside of the living body if it is a soft part of the skin.
  • the target organ for direct insertion of the needle electrode examples include the brain, but are not limited thereto.
  • the subject's brain is diagnosed in detail and the brain function is elucidated. be able to.
  • [B] -4 Wire electrode
  • a puncture assist mechanism for inserting the electrode element into the living body separately from the electrode element.
  • the most basic puncture assisting mechanism is a hollow needle with a through hole having both ends opened in the length direction. By puncturing from outside the skin with the linear electrode element being passed through the through hole of the hollow needle and then pulling out the hollow needle, only the electrode element can be left in the living body.
  • Such a wire electrode of the present invention can produce a desired electrode by adding the above auxiliary mechanism or the like to the electrode element of the present invention by a known means.
  • wire electrode is the same as that of the needle electrode described above.
  • Puncture electrode PEDOT-pTS utilizing the characteristics of PEDOT-pTS has a characteristic of swelling when it comes into contact with moisture, and it is possible to provide an in-vivo electrode utilizing this characteristic.
  • the basic concept is the same as that of the wire electrode. That is, by the stress accompanying the shrinkage of PEDOT-pTS when moving from the wet state to the dry state, the electrode element to which the PEDOT-pTS is attached adheres to the puncture assisting mechanism, and this is provided as an internal electrode.
  • the moisture in the living body is supplied to the PEDOT-pTS of the electrode element over time to swell and adhere to the puncture assist mechanism of the electrode element The state is released. By pulling out the puncture assist mechanism from the skin in this released state, only the electrode element can be left in the living body.
  • [B] -6 Free adjustment of electric resistance value
  • the electric resistance value in the electrode element using PEDOT-pTS can be adjusted by adjusting the time for heat treatment or the like. it can. That is, it is possible to provide two or more regions having different conductivity in the electrode element. This is one of the major characteristics when the above electrode element production process is used. Normally, the lower the electrical resistance value of the electrode element is, the better. However, for example, the treatment of burning the affected part by applying heat to generate heat is performed using the in vivo electrode of the present invention. In this case, the electrical resistance value on the tip end side of the needle-like electrode element is increased, and the electrical resistance value of the remaining portion is decreased.
  • action potential and evoked potential are measured at low voltage even when voltage is applied.
  • the low electrical resistance region is extracted and only the high electrical resistance part is extracted.
  • an insulating material other than a portion used as an electrode element for example, natural fibers such as silk, chemical fibers such as polyester, synthetic resins such as silicone resin, etc., only a desired portion is obtained. It is possible to create a body electrode in which the electrode element is exposed.
  • [B] -7 Drug Delivery System
  • An injection mechanism for injecting a drug solution into the body is provided in a part of the body electrode of the present invention, and a drug solution corresponding to the muscle action potential or brain wave can be supplied into the body.
  • a tube for drug transport may be provided as an injection mechanism.
  • the electrode element and the drug transport path can be integrated by making the drug transporting means osmotic pressure movement of the base material (silk fiber or the like) of the electrode element.
  • the drug include drugs that alleviate central nervous system disorders such as GSNO (S-Nitrosoglutathione) when the body electrode of the present invention is used as a brain electrode.
  • the myoelectric measurement system and electroencephalogram measurement system of the present invention are characterized by using the bioelectrode (surface electrode or puncture electrode) of the present invention as an electrode.
  • bioelectrode surface electrode or puncture electrode
  • it has other mechanisms necessary as an electromyography measurement system and an electroencephalogram measurement system.
  • amplification unit various stimulation units for obtaining evoked potentials, analysis unit for analysis / recording / addition / calibration, etc.
  • display unit for displaying myoelectric and electroencephalogram movement by voice or video, etc. Is provided as needed.
  • the electric signal transmission means may be wired or wireless.
  • the myoelectric measurement system of the present invention can be produced by producing an electrode by the above production method and then providing the electrode in the myoelectric measurement system as an electrode (biological electrode) for contacting the living body. At this time, a myoelectric measurement system having a desired configuration can be produced by adding the other mechanisms in combination by known means. Furthermore, the electroencephalogram measurement system of the present invention can be produced by producing an electrode by the above production method, and then providing the electrode in the electroencephalogram measurement system as an electrode (biological electrode) for contacting the living body. At this time, an electroencephalogram measurement system having a desired configuration can be produced by adding the above-mentioned other mechanisms in combination by known means.
  • the myoelectric measurement system and the electroencephalogram measurement system can synchronize with other types of biological signals, respectively, so that the state of the muscles and the brain can be grasped further.
  • the blood pressure, electrocardiogram signal, pulse oxy signal, muscle strength, joint angle, etc. can be combined and synchronized.
  • bioelectrode of the present invention is useful as a bioelectrode in the case of a combination of this electroencephalogram and myoelectric signal.
  • a plain-woven silk fabric (thickness of about 0.4 mm) made of silk thread that has been subjected to enzyme scouring (scouring with a proteolytic enzyme); Double (thin silk cloth, thickness of about 0.12 mm), (3) a cloth in which polyester cloth was coated with sericin (consigned production of Art Co., Ltd. (Kiryu City, Gunma Prefecture), thickness of about 0.15 mm) was used.
  • a butanol solution containing iron (III) ions of transition metal and pTS (CLEVIOS CB 40 V2 made by Heraeus Co., Ltd .: about 4% by mass as iron (III) p-toluenesulfonate: “CLEVIOS”) are registered trademarks).
  • EDOT an aqueous solution of EDOT (CLEVIOS MV2, manufactured by Heraeus, approximately 98.5% by mass of EDOT: “CLEVIOS” is a registered trademark) was used.
  • Example 1 Examination of heat treatment using thermal head For plain weave silk fabric (4 cm x 4 cm) used as the base material, 6.3 ml of the above pTS solution and 220 ⁇ l of EDOT were prepared. Within 30 seconds after mixing, the mixture was transferred onto the silk fabric used as the substrate using a silk screen cut into two rectangular shapes (1 cm ⁇ 2 cm) adjacent to each other. This operation was performed for 20 minutes in a heated atmosphere at 70 ° C.
  • the mixed liquid is transferred onto the silk fabric used as the base material by using the above-described two silk-shaped silk screens, and 70% from above the entire transfer portion.
  • a metallic thermal head (heat radiating body) at 0 ° C. was immediately brought into direct contact with the transfer portion and maintained in contact with the thermal head for 5 minutes. As a result, there was no blur as described above, and the rectangular PEDOT-pTS could be drawn as intended (FIG. 3).
  • Example 2 Examination of heat treatment using hot air
  • the hot air of a 900 W dryer was set so that the temperature of the two rectangular drawing portions was 70 ° C. Then, local hot air treatment of the drawing portion was performed for 4 minutes.
  • a cloth-like substrate that was drawn in a heated atmosphere at 70 ° C. was used.
  • Example 3 Examination of treatment using a mask
  • the hot air treatment was performed using a mask.
  • FIG. 5B shows a photograph showing the state at that time. Clearly, it is clearly confirmed that black PEDOT-pTS is not observed in the area where the normal glue is applied. When the electric resistance value was measured, it was a slightly high value of 7.0 ⁇ 10 4 ⁇ / cm, which is considered to be due to the fact that a slight amount of regular glue remained.
  • Example 4 Measurement of Muscle Action Potential Using Surface Electrode of the Present Invention
  • a resistance value of 1.5 ⁇ 10 4 prepared by a method using the same material and thermal head as in Example 1 on the subject's upper arm.
  • Three ribbon-shaped surface silk electrodes (width: 1 cm, length: 6 cm) of ⁇ / cm (Fig. 7 (a): one of which is a reference electrode and the other two are measurement electrodes) are arranged at intervals of 2 cm.
  • the time change of the myoelectricity obtained when each was connected to the wireless electromyograph is shown.
  • a substance for reducing impedance, such as gel was not applied between the silk electrode and the skin, but was directly brought into contact with the skin (FIG. 7B).
  • the entire electrode is covered with a transparent adhesive sheet for fixation, and is adhered to the skin surface, but this sheet is for fixing the whole, not for adhering individual electrodes to the surface. No particularly strong force is required for contact of the electrode with the skin.
  • FIG. 8A is a schematic view of the situation. In the measurement, the same puncture silk electrode was used for the reference electrode as well as the measurement electrode. As a result, brain waves (frequency 50 to 70 Hz) including gamma waves (arrows in the figure) could be measured (FIG. 8B).
  • Example 6 Measurement of muscle action potential using puncture electrode (needle electrode) of the present invention
  • Example 5 is the same as Example 5 except that it was prepared by the method using heat treatment by the dryer of Example 2.
  • a puncture electrode made of No. 3 hard silk as a base material was inserted and placed in the muscular tissue of chicken thigh muscle, and the potential change inside the muscle accompanying movement was measured.
  • the reference silk electrode was placed on the surface of the muscle directly under the skin.
  • FIG. 9A is a schematic diagram showing the state.

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Abstract

Le problème de la présente invention concerne : un moyen pour appliquer un polymère électroconducteur sur un matériau de base directement et avec une efficacité élevée, de telle sorte que le polymère électroconducteur peut être utilisé comme élément d'électrode sans être purgé lorsque du PEDOT-pTS est utilisé en tant que polymère électroconducteur ; une électrode de surface qui est produite sans utiliser de gel électroconducteur, qui présente une excellente performance de conduction électrique et qui peut par conséquent présenter une aire de surface réduite, qui peut être collée sur la peau, qui ne subit pas le déplacement sur la peau même lors de l'application d'un faible mouvement d'un corps et qui peut être utilisée dans des systèmes de mesure de signal myoélectrique et des systèmes de mesure d'ondes cérébrales qui ont été utilisés dans différentes situations de la vie. L'invention concerne : un procédé de production d'un élément d'électrode, ledit procédé étant caractérisé en ce qu'une solution mixte (1) d'une solution à base de solvant organique contenant un constituant oxydant et du p-toluènesulfonate (pTS) et (2) du 3,4-éthylènedioxythiophène (EDOT) est mise en contact avec un matériau de base pour faire adhérer la solution mixte sur le matériau de base et ensuite la partie de contact est soumise à un traitement d'accélération de polymérisation en synchronisation avec la mise en contact ; et une électrode de biopotentiel à appliquer sur une surface ou à perforer lors de l'utilisation, ladite électrode de biopotentiel étant caractérisée en ce qu'elle comprend l'élément d'électrode.
PCT/JP2016/058557 2015-03-17 2016-03-17 Procédé de production d'un élément d'électrode, procédé de production d'électrode et fabrication d'un système de mesure utilisant ladite électrode WO2016148249A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018075832A (ja) * 2016-11-01 2018-05-17 エーアイシルク株式会社 導電性高分子導電体の製造方法、及び、基材の製造方法
WO2019240241A1 (fr) * 2018-06-14 2019-12-19 鳥光　慶一 Matériau électroconducteur et élément électrique pourvu de ce dernier, et capteur
JP2019218676A (ja) * 2018-06-14 2019-12-26 鳥光　慶一 導電性材とこれを備える電気的素子、センサ
JP2020143416A (ja) * 2019-03-01 2020-09-10 エーアイシルク株式会社 導電性高分子導電体、及び、その製造方法
JP2021028364A (ja) * 2019-08-09 2021-02-25 エーアイシルク株式会社 導電性高分子導電体、及び、その製造方法
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KR20210134372A (ko) 2019-03-03 2021-11-09 고쿠리츠다이가쿠호진 도호쿠다이가쿠 전자파 차폐재
JP7483856B2 (ja) 2019-03-18 2024-05-15 バイオセンス・ウエブスター・（イスラエル）・リミテッド 不整脈の診断のための装置
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JP7294651B2 (ja) 2019-08-09 2023-06-20 エーアイシルク株式会社 導電性高分子導電体の製造方法

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