WO2022071231A1 - 生体信号センシング電極 - Google Patents

生体信号センシング電極 Download PDF

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Publication number
WO2022071231A1
WO2022071231A1 PCT/JP2021/035414 JP2021035414W WO2022071231A1 WO 2022071231 A1 WO2022071231 A1 WO 2022071231A1 JP 2021035414 W JP2021035414 W JP 2021035414W WO 2022071231 A1 WO2022071231 A1 WO 2022071231A1
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Prior art keywords
mxene
sensing electrode
film
biological signal
signal sensing
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PCT/JP2021/035414
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English (en)
French (fr)
Japanese (ja)
Inventor
一存 佐々木
武志 部田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202180066123.3A priority Critical patent/CN116249484B/zh
Priority to JP2022553957A priority patent/JP7452684B2/ja
Publication of WO2022071231A1 publication Critical patent/WO2022071231A1/ja
Priority to US18/127,249 priority patent/US20230233127A1/en
Anticipated expiration legal-status Critical
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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
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/28—Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
    • 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
    • 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
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/296—Bioelectric electrodes therefor specially adapted for particular uses for electromyography [EMG]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a biological signal sensing electrode.
  • Patent Document 1 discloses a biological electrode coating pad using a hydrophilic gel containing water and an electrolyte.
  • Patent Document 2 describes (a) an electrical conductor, (b) a thin film having selective permeability for ionic conduction to present a dry surface to the subject, and (c) the electrical conduction.
  • a biopotential electrode comprising a conductive medium arranged to communicate with a part of the body and a part of the thin film is shown.
  • MXene has been attracting attention as a new material having conductivity.
  • MXene is a kind of so-called two-dimensional material, and is a layered material having the form of one or a plurality of layers as described later.
  • MXene has the form of particles of such layered material, which may include powders, flakes, nanosheets, and the like.
  • Patent Document 3 shows a bioelectrode formed of a contact material containing this MXene.
  • An object of the present invention is a biological signal sensing electrode that exhibits high conductivity (low impedance), suppresses peeling of a predetermined layered material (also referred to as "MXene" in the present specification), and does not cause discomfort when worn. Is to provide.
  • the present invention comprises a laminate of a porous membrane and a conductive membrane containing particles of a layered material comprising one or more layers.
  • the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, and X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5)
  • the layer body represented by and the modification or termination T existing on the surface of the layer body (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom).
  • T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom).
  • T is at least one selected from the group consisting of a hydroxyl group, a fluorine
  • the biological signal sensing electrode includes a laminate of a conductive membrane containing particles of a predetermined layered material and a porous membrane, and the porous membrane is provided on a contact surface with a subject. This provides a biological signal sensing electrode that exhibits high conductivity (low impedance), suppresses peeling of MXene, and does not cause discomfort when worn.
  • FIG. 6 is a schematic schematic cross-sectional view showing MXene, which is a layered material that can be used for a conductive film in one embodiment of the biological signal sensing electrode of the present invention, in which (a) shows a single-layer MXene and (b) shows a multilayer. (Illustrated two layers) MXene is shown. It is a schematic schematic cross-sectional view which shows the conductive film in another embodiment of this invention.
  • FIG. 1 It is a figure which illustrates the pore shape of the porous membrane in the biological signal sensing electrode of this invention. It is a schematic schematic cross-sectional view which shows the biological signal sensing electrode in one Embodiment of this invention. It is a schematic schematic cross-sectional view which shows the biological signal sensing electrode in another embodiment of this invention. It is a schematic schematic schematic perspective view which shows the biological signal sensing electrode in another embodiment of this invention. It is a schematic schematic cross-sectional view which shows the biological signal sensing electrode in another embodiment of this invention. It is a schematic schematic cross-sectional view which shows the biological signal sensing electrode in another embodiment of this invention. It is a schematic schematic cross-sectional view which shows the biological signal sensing electrode in another embodiment of this invention.
  • the biological signal sensing electrode according to the embodiment of the present invention has a laminate of a conductive film containing particles of a layered material including one or a plurality of layers and a porous film. First, each of the conductive film and the porous film will be described.
  • the conductive film 30 included in the electrode of the present embodiment contains particles 10 of a predetermined layered material.
  • the particles of the predetermined layered material contained in the conductive film in the present embodiment are defined as follows.
  • a layered material comprising one or more layers, wherein the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, so-called early transition metals such as Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and It may contain at least one selected from the group consisting of Mn.
  • the layer body represented by may have a crystal lattice in which each X is located in an octahedral array of M) and the surface of the layer body (more specifically, facing each other of the layer body).
  • a layered material containing a modification or termination T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on at least one of the two surfaces thereof.
  • n can be 1, 2, 3 or 4, but is not limited to this.
  • M is preferably at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn, preferably from Ti, V, Cr and Mo. More preferably, it is at least one selected from the group.
  • Such MXene can be synthesized by selectively etching (removing and optionally layering) A atoms (and optionally a portion of M atoms) from the MAX phase.
  • the MAX phase is as follows: M m AX n (In the formula, M, X, n and m are as described above, A is at least one group 12th, 13th, 14th, 15th and 16th element, usually a group A element, representatively.
  • Is a group IIIA and a group IVA and more particularly may include at least one selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S and Cd.
  • a layer composed of A atoms is located between two layers represented by and represented by Mm Xn (each X may have a crystal lattice located in an octahedral array of M ). It has a crystal structure.
  • Mm Xn a layer of X atoms
  • MM X n layer a layer of A atoms
  • a atom layer is arranged as a layer next to the n + 1th layer of M atoms, but is not limited to this.
  • the A atom layer (and possibly part of the M atom) is removed by selectively etching (removing and possibly layering) the A atom (and possibly part of the M atom) from the MAX phase.
  • etching solution usually, but not limited to, an aqueous solution of fluoroacid is used
  • Etching can be carried out using an etching solution containing F- , for example, a method that combines etching and intercalation using a mixed solution of lithium fluoride and hydrochloric acid, which is also an intercalator, or hydrofluoric acid. It may be a method or the like. Then, as appropriate, by any appropriate post-treatment (eg, intercalation using an intercalator as one of the delamination treatments, sonication, handshaking or automatic shaker, etc.), the MXene layer separation (delamination, etc.) Separation of multi-layer MXene into single-layer MXene) may be promoted.
  • any appropriate post-treatment eg, intercalation using an intercalator as one of the delamination treatments, sonication, handshaking or automatic shaker, etc.
  • the shearing force of the ultrasonic treatment is too large and the MXene can be destroyed, if it is desired to obtain a two-dimensional shape MXene (preferably a single-layer MXene) having a larger aspect ratio, a hand shake or a hand shake or It is preferable to apply an appropriate shearing force by an automatic shaker or the like.
  • a centrifuge may be used to separate the supernatant containing a single layer MXene and / or a small layer MXene having about 2 to 5 layers into a supernatant containing a multilayer MXene.
  • MXene contained in the supernatant and / or the supernatant can be used as particles of the layered material. It is preferable to use MXene contained in the supernatant containing single-layer / small-layer MXene as particles of the layered material because low impedance can be easily realized.
  • M can be titanium or vanadium and X can be a carbon atom or a nitrogen atom.
  • the MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 T s (in other words, M is Ti, X is C, n is 2 and m is 3). Is).
  • MXene may contain a relatively small amount of residual A atom, for example, 10% by mass or less with respect to the original A atom.
  • the residual amount of A atom can be preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of A atom exceeds 10% by mass, there may be no problem depending on the use and conditions of use of the conductive film.
  • the MXene (particles) 10 synthesized in this way is, as schematically shown in FIG. 2, a layered material containing one or more MXene layers 7a, 7b (as an example of the MXene (particles) 10), FIG. (A) shows one layer of MXene10a and FIG. 2B shows two layers of MXenes10b, but is not limited to these examples). More specifically, the MXene layers 7a and 7b are formed on the surfaces of the layer bodies ( MmXn layer) 1a and 1b represented by MmXn and the layer bodies 1a and 1b (more specifically, in each layer).
  • MXene layers 7a and 7b are also expressed as "MM X n T s ", and s is an arbitrary number.
  • MXene10 even if the MXene layers are individually separated and exist in one layer (single-layer structure shown in FIG. 2A, so-called single-layer MXene10a), a plurality of MXene layers are separated from each other. It may be a laminated body (multilayer structure shown in FIG. 2B, so-called multi-layer MXene10b) or a mixture thereof.
  • MXene 10 can be particles (also referred to as powder or flakes) as an aggregate composed of single layer MXene 10a and / or multilayer MXene 10b.
  • MXene 10a and / or multilayer MXene 10b In the case of a multilayer MXene, two adjacent MXene layers (for example, 7a and 7b) do not necessarily have to be completely separated, and may be partially in contact with each other.
  • each layer of MXene is, for example, 0.8 nm or more and 5 nm or less, particularly 0.8 nm or more and 3 nm or less (mainly).
  • the maximum dimension in a plane parallel to the layer (two-dimensional sheet surface) is, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less.
  • the interlayer distance or void size, indicated by ⁇ d in FIG. 2B
  • the interlayer distance is, for example, 0.8 nm or more and 10 nm or less, particularly 0.
  • the multilayer MXene that can be contained is a MXene with a small number of layers obtained through a delamination treatment.
  • the above-mentioned "small number of layers” means, for example, that the number of layers of MXene is 6 or less.
  • the thickness of the multilayer MXene having a small number of layers in the stacking direction is preferably 10 nm or less.
  • this "multilayer MXene with a small number of layers” may be referred to as "small layer MXene”.
  • the single layer MXene and the small layer MXene may be collectively referred to as "single layer / small layer MXene”.
  • the MXene (particles) of the present embodiment preferably includes a single layer MXene and a small layer MXene, that is, a single layer / small layer MXene.
  • the ratio of the single layer / small layer MXene having a thickness of 10 nm or less is preferably 90% by volume or more, and more preferably 95% by volume or more.
  • the total number of layers may be 2 or more, but may be, for example, 50 or more and 100,000 or less, particularly 1,000 or more and 20,000 or less.
  • the thickness of the conductive film in the stacking direction may be, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less.
  • the maximum dimension in the plane (two-dimensional sheet surface) perpendicular to the stacking direction is, for example, 0.1 ⁇ m or more and 100 ⁇ m or less, particularly 1 ⁇ m or more and 20 ⁇ m or less.
  • these dimensions are number average dimensions (for example, at least 40 number averages) or X-ray diffraction (for example, number averages of at least 40 pieces) based on photographs of a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an atomic force microscope (AFM). It is obtained as the distance in the real space calculated from the position on the reciprocal lattice space of the (002) plane measured by the XRD) method.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • the film thickness of the conductive film containing the layered particles is preferably 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the film thickness is more preferably 1.0 ⁇ m or more. From the viewpoint of conductivity, a thicker film thickness is preferable, but when flexibility or the like is required, the film thickness is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the film thickness of the conductive film can be measured by, for example, measurement with a micrometer, cross-sectional observation by a method such as a scanning electron microscope (SEM), a microscope, or a laser microscope.
  • SEM scanning electron microscope
  • a conductive film 30 obtained by laminating only conductive two-dimensional particles 10 is shown, but the present invention is not limited thereto.
  • the conductive film may be a conductive composite material film (conductive composite material film) further containing a polymer.
  • the polymer may be contained, for example, as an additive such as a binder added at the time of film formation, or may be added to provide strength or flexibility.
  • the polymer may be more than 0% by volume, preferably 30% by volume or less, in proportion to the conductive composite material film (when dried).
  • the proportion of the polymer may be further 10% by volume or less, further 5% by volume or less.
  • the proportion of the particles of the layered material in the conductive composite material film (when dried) is preferably 70% by volume or more, further 90% by volume or more, and further may be 95% by volume or more.
  • a laminated film of two or more conductive composite material films having different proportions of particles of the layered material may be provided on one electrode.
  • the polymer for example, a hydrophilic polymer having a polar group, wherein the polar group is a group that forms a hydrogen bond with the modification or termination T of the layer is preferable.
  • the polymer for example, one or more kinds of polymers selected from the group consisting of water-soluble polyurethane, polyvinyl alcohol, sodium alginate, acrylic acid-based water-soluble polymer, polyacrylamide, polyaniline sulfonic acid, and nylon are preferably used.
  • one or more kinds of polymers selected from the group consisting of water-soluble polyurethane, polyvinyl alcohol, and sodium alginate are more preferable.
  • the polymer a polymer having a urethane bond having both hydrogen bond donor property and hydrogen bond acceptor property is preferable, and from this viewpoint, the water-soluble polyurethane is particularly preferable.
  • the conductive film of the present embodiment preferably maintains a conductivity of 500 S / cm or more when it is in the form of a sheet having a film thickness of 5 ⁇ m, for example.
  • the conductivity is preferably 1000 S / cm or more, more preferably 1800 S / cm or more, still more preferably 2400 S / cm or more, still more preferably 2900 S / cm or more.
  • There is no particular upper limit to the conductivity of the conductive film but it can be, for example, 10000 S / cm or less.
  • the conductivity can be determined as follows. That is, the surface resistivity is measured by the 4-probe method, and the value obtained by multiplying the thickness [cm] by the surface resistivity [ ⁇ / ⁇ ] is the volume resistivity [ ⁇ . cm], and the reciprocal of the reciprocal can be the conductivity [S / cm].
  • porous membrane means "a membrane having fine pores, which selectively permeates ions and molecules having a size smaller than the diameter of the pores”.
  • the porous membrane preferably has an average pore diameter of 1 nm or more and 1 ⁇ m or less. Ions derived from the subject, that is, the human body, pass through the porous membrane in contact with the subject and reach the conductive membrane, so that electrodes such as myoelectricity of the subject can be measured. That is, the porous membrane has a role of preventing direct contact between the subject and the conductive membrane and a role of a permeable membrane for the above-mentioned ions and the like.
  • the porous membrane preferably has an average pore diameter of 1 nm or more from the viewpoint of easily transmitting the ions and the like, which are carriers of electric current, and easily reducing the impedance. The average pore diameter is more preferably 10 nm or more.
  • the average pore size of the porous membrane is preferably 1 ⁇ m or less, more preferably 500 nm or less. be.
  • the average pore size is determined as a number average dimension (for example, at least 40 number averages) by image analysis based on a photograph of a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
  • the pore shape of the porous membrane is not limited, and for example, as schematically shown in FIG. 4, (a) aggregated particulate porous membrane, (b) mesh-like porous membrane, and (c) fibrous, having a plurality of pores 26.
  • the porous membrane may be insulating or conductive.
  • the porous membrane preferably has a conductivity smaller than that of the conductive membrane.
  • the conductivity of the conductive membrane is 500 S / cm or more as described above, and the porous membrane has a conductivity smaller than the conductivity of the conductive membrane, so that ions from the subject can be transferred to the conductive membrane. It is considered that it can be moved more easily to, and as a result, biological signals such as myoelectricity can be measured more accurately.
  • the material of the porous membrane is not particularly limited, and a material formed of an organic material, an inorganic material, or a mixture thereof can be used.
  • examples of the organic material having a conductivity lower than the conductivity of the conductive film include polymers, and examples of the inorganic material having a conductivity lower than the conductivity of the conductive film include ceramics or a combination thereof.
  • the porous membrane preferably contains a hydrophilic polymer.
  • the hydrophilic polymer includes a hydrophobic polymer in which a hydrophilic auxiliary agent is blended to exhibit hydrophilicity, and a hydrophobic polymer whose surface is hydrophilized.
  • the porous membrane contains a hydrophilic polymer, as described above, the adhesion to the hydrophilic conductive membrane (MXene membrane) can be further enhanced.
  • a hydrophilic polymer that can further enhance the adhesion to the conductive film (MXene film) (a hydrophobic polymer mixed with a hydrophilic auxiliary agent to exhibit hydrophilicity, and the surface of the hydrophobic polymer or the like are hydrophilized.
  • a hydrophobic polymer mixed with a hydrophilic auxiliary agent to exhibit hydrophilicity, and the surface of the hydrophobic polymer or the like are hydrophilized.
  • a hydrophilic polymer selected from the group consisting of polysulfone, cellulose acetate, regenerated cellulose, polyethersulfone, water-soluble polyurethane, polyvinyl alcohol, sodium alginate, acrylic acid-based water-soluble polymer, polyacrylamide, polyaniline sulfonic acid, and nylon. More preferably, it contains 1 or more. More preferably, 50% by mass or more of the porous membrane is occupied by the hydrophilic polymer, and particularly preferably one or more of the hydrophilic polymer.
  • a hydrophobic polymer for example, olefin resin such as polyethylene and polypropylene, vinyl resin such as polystyrene and polyvinyl chloride, fluororesin such as polyvinylidene fluoride and polytetrafluoroethylene, polyester and the like
  • plasma for example.
  • examples thereof include those that have been hydrophilized by various known methods such as graft polymerization treatment.
  • the hydrophobic polymer one or more selected from the group consisting of polypropylene, polyethylene, polyvinylidene fluoride, and polytetrafluoroethylene is more preferable.
  • the hydrophobic polymer may be a laminated structure of a plurality of different hydrophobic polymers such as polypropylene and polyethylene.
  • the surface of ceramics such as alumina, aluminum nitride, silicon nitride, and zirconium oxide may be hydrophilized.
  • the film thickness of the porous membrane is preferably 0.1 ⁇ m or more and 300 ⁇ m or less.
  • the film thickness of the porous membrane is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the film thickness of the porous membrane is preferably 0.1 ⁇ m or more.
  • the film thickness of the porous film can be measured by, for example, measurement with a micrometer, cross-sectional observation by a method such as a scanning electron microscope (SEM), a microscope, or a laser microscope.
  • the contact area between the conductive film and the porous film is not particularly limited as long as the electrode exhibits high conductivity, the peeling of MXene is suppressed, and further, there is no discomfort during mounting.
  • the entire surfaces of both the conductive membrane and the porous membrane may be in contact with each other, (a) the porous membrane is in contact with a part of the conductive membrane, or (b) the conductive membrane is in contact with a part of the porous membrane. You may be doing it.
  • FIG. 5 is a diagram showing an example of the above (a), in which a porous film 22 and, for example, an insulating film 25 are provided on the surface of the conductive film 21 on the subject side.
  • FIG. 6 is a diagram showing an example of the above (b), in which a porous film 22 is provided on a surface formed of a conductive film 21 and, for example, an insulating film 25.
  • the contact area ratio of the conductive film with the porous film on the surface of the subject side is preferably 60% or more, more preferably 80% or more. Most preferably 100%.
  • the porous film a commercially available product may be used, or the porous film may be obtained by a method such as a phase conversion method, a melt quenching method, an extraction method, or an electron beam irradiation method.
  • a phase conversion method a film-forming solution (cast solution) prepared by dissolving an organic polymer in an organic solvent is cast on a glass plate or the like, and then an appropriate gelling solution (organic polymer) is used. This is a method of forming micropores by utilizing the two-phase separation phenomenon that occurs when the polymer is immersed in an insoluble organic solvent, water, etc., or dried.
  • the melt quenching method is a method of forming a film using a varnish in which a solvent and a polymer are combined so that the solubility greatly differs depending on the temperature, and then quenching and solidifying.
  • extraction method replica method
  • an additive that can be easily extracted in a subsequent step is added to a polymer solution or a dispersion liquid, the additive is formed into a film, and then the additive is extracted by an appropriate method. How to do it.
  • the electron beam irradiation method a polymer thin film of about 10 ⁇ m is irradiated with an electron beam (charged particles) to form a trajectory of the particles on the film, and then an etching treatment with a solvent is performed to expand the trajectory. It is a manufacturing method that makes fine holes.
  • the biological signal sensing electrode of the present embodiment includes a laminate in which the conductive film and the porous film are in direct contact with each other, and the porous film may be provided on the contact surface with the subject, and is not limited to a specific embodiment. ..
  • the electrodes can be considered from a solid state to a flexible and soft state. However, it is preferable to have flexibility as much as possible from the viewpoint of followability to the living body (skin) and suppression of electrode cracking.
  • FIG. 7 illustrates a schematic perspective view of the snap type electrode.
  • FIG. 7 illustrates a schematic perspective view of a snap-type electrode in which a lead wire 32 is connected to a snap portion 31 of an electrode 30 whose contact surface with a subject is flat.
  • An example of a cross-sectional view of the electrode 30 of FIG. 7 is schematically shown in FIG.
  • the conductive film 21 is formed on a base material 23 made of a conductive material.
  • the conductive film 21 is formed, and the porous film 22 is formed as a contact surface with the subject, so that the biological signal sensing electrode having high sensitivity and reduced wearing discomfort can be obtained. Can be provided.
  • the conductive material constituting the base material 23 among metal materials such as gold, silver, copper, platinum, nickel, titanium, tin, iron, zinc, magnesium, aluminum, tungsten and molybdenum, and a conductive polymer. , At least one material is mentioned.
  • the base material may be the conventional snap type electrode 24.
  • the conductive material constituting the snap type electrode the same material as the base material 23 formed of the conductive material can be used. According to the above configuration, since a versatile extraction electrode is used, it is possible to provide a biological signal sensing electrode at low cost and with high sensitivity.
  • the conductive film is a conductive composite material film of a MXene film and a polymer
  • an electrode which is a laminated film of a conductive composite material film and a porous film and does not have a base material. can do.
  • the biological signal sensing electrode of the present embodiment does not contain water as in Patent Document 1, there is no discomfort such as getting wet when worn. Further, when water is contained as in Patent Document 1, impedance change may occur due to drying. On the other hand, since the biological signal sensing electrode of the present embodiment is a dry electrode, there is no impedance change due to the drying, and the signal reliability is high.
  • the biological signal sensing electrode of this embodiment contains a low impedance MXene film as an electric conductor, the signal accuracy is high. Further, since the laminating of the conductive film (MXene film) and the porous film is flexible, it is not necessary to provide a layer for following the skin. Therefore, the biological signal sensing electrode of the present embodiment has a small number of layers and can more easily realize low impedance. On the other hand, for example, in Patent Document 2, the electric conductor is hard, and a layer of a conductive medium is indispensable from the viewpoint of followability to the skin, and as a result, the number of layers is large and the impedance is high.
  • the conductive film is protected by the porous film and the contact layer in contact with the subject is the porous film, it is possible to prevent MXene from being detached from the conductive film.
  • the porous membrane has ionic conductivity in which ions from a subject can easily permeate, and has a low impedance.
  • Direct contact between the conductive membrane and the porous membrane enhances the adhesion between the conductive membrane (MXene membrane) exhibiting hydrophilicity and the porous membrane containing preferably a hydrophilic polymer, and the conductive membrane and the porous membrane are enhanced.
  • High adhesion can be ensured without newly providing an intermediate layer containing a pressure-sensitive adhesive or the like.
  • the number of layers is small, the moving distance of ions from the subject to the conductive membrane via the porous membrane is shortened, low impedance can be realized more easily, and the sensitivity of the electrode can be further increased.
  • the method for manufacturing the electrode of the present embodiment using the MXene produced as described above is not particularly limited.
  • an electrode can be formed, for example, as illustrated below.
  • a MXene aqueous dispersion in which the above MXene particles (particles of a layered material) are present in a solvent, or an MXene organic solvent dispersion is prepared.
  • the solvent of the MXene aqueous dispersion is typically water, and in some cases, a relatively small amount of other liquid substances (for example, 30% by mass or less, preferably 20% by mass or less) in addition to water. It may be included.
  • the MXene-containing aqueous mixture obtained by selectively etching the A atom from the MAX phase is subjected to solid-liquid separation (for example, precipitation, centrifugation, etc.), and the mixture is subjected to an aqueous solvent (for example, sedimentation, centrifugation, etc.).
  • the liquid phase) may be partially removed, a fresh aqueous solvent may be added to the mixture, and an operation of applying a shearing force to the mixture may be carried out at any appropriate timing to obtain a MXene-containing aqueous medium. Such an operation may be performed once or may be repeated twice or more depending on the case.
  • a MXene-containing aqueous medium such as a MXene aqueous dispersion or a MXene organic solvent dispersion may be used to form a precursor of a conductive membrane (also referred to as a "precursor membrane").
  • the method for forming the precursor film is not particularly limited, and for example, coating, suction filtration, spray and the like can be used. More specifically, the MXene-containing aqueous medium may be applied to the substrate as it is or after being appropriately adjusted (for example, diluted with an aqueous solvent or added with a binder).
  • a coating method for example, a method of spray coating using a nozzle such as a 1-fluid nozzle, a 2-fluid nozzle, or an airbrush, a table coater, a comma coater, a slit coat using a bar coater, screen printing, metal mask printing, etc. Methods, spin coats, dip coats, drips and the like can be mentioned.
  • a substrate made of a metal material, resin, or the like suitable for the biological signal sensing electrode can be appropriately adopted.
  • a precursor on the substrate by coating on any suitable substrate (which may form a predetermined member together with the conductive film or may be finally separated from the conductive film). Can form a body membrane.
  • the MXene-containing aqueous medium is appropriately adjusted (for example, diluted with an aqueous solvent), and a filter installed in a nutche or the like (even if it constitutes a predetermined member together with the conductive film, is finally separated from the conductive film).
  • a precursor can be formed on the filter by suction filtration through (may be) and at least partially removing the aqueous solvent.
  • the filter is not particularly limited, but a membrane filter or the like may be used. By suction filtration, a conductive film can be produced without using the binder or the like.
  • drying means removing the aqueous solvent that may be present in the precursor.
  • drying Even if the drying is performed under mild conditions such as natural drying (typically placed in an air atmosphere under normal temperature and pressure) or air drying (blowing air), warm air drying (spraying heated air) is performed. ), Heat drying, and / or vacuum drying may be performed under relatively active conditions.
  • the drying may be carried out at a temperature of 400 degrees or less using, for example, a normal pressure oven or a vacuum oven.
  • the formation and drying of the precursor may be repeated as appropriate until the desired conductive film thickness is obtained.
  • the combination of spraying and drying may be repeated a plurality of times.
  • the method for manufacturing the electrode provided with the conductive composite material is not particularly limited.
  • the conductive composite material of the present embodiment has a sheet-like form, for example, as illustrated below, the layered material and the polymer can be mixed to form a coating film.
  • the MXene aqueous dispersion, the MXene organic solvent dispersion, or the MXene powder in which the MXene particles (particles of the layered material) are present in the solvent may be mixed with the polymer.
  • the solvent of the MXene aqueous dispersion is typically water, and in some cases, a relatively small amount of other liquid substances (for example, 30% by mass or less, preferably 20% by mass or less) in addition to water. It may be included.
  • the above MXene particles and polymer can be agitated using a disperser such as a homogenizer, a propeller agitator, a thin film swirl type agitator, a planetary mixer, a mechanical shaker, and a vortex mixer.
  • a disperser such as a homogenizer, a propeller agitator, a thin film swirl type agitator, a planetary mixer, a mechanical shaker, and a vortex mixer.
  • the slurry which is a mixture of the MXene particles and the polymer, may be applied to a base material (for example, a substrate), but the application method is not limited.
  • a method of applying a spray using a nozzle such as a 1-fluid nozzle, a 2-fluid nozzle, or an air brush, a method such as a table coater, a comma coater, a slit coat using a bar coater, screen printing, metal mask printing, and spin coating. , Dip coat, and application method by dropping.
  • a substrate made of a metal material, a resin, or the like suitable for the biological signal sensing electrode can be appropriately adopted.
  • the above coating and drying may be repeated a plurality of times as necessary until a film having a desired thickness is obtained. Drying and curing may be performed, for example, using a normal pressure oven or a vacuum oven at a temperature of 400 ° C. or lower.
  • a porous film After forming the MXene film by any of the above methods, before drying and curing the MXene film, for example, a commercially available product is laminated as a porous film as described above, and then the MXene film is dried and cured, or the MXene film is formed. After drying and curing, a porous film may be formed on the surface of the MXene film by the above-mentioned phase conversion method or the like.
  • the biological signal sensing electrode in one embodiment of the present invention has been described in detail above, but various modifications are possible. It should be noted that the biological signal sensing electrode of the present invention may be manufactured by a method different from the manufacturing method in the above-described embodiment.
  • a hydrophilic porous membrane manufactured by Merck Co., Ltd., product number GPWP04700, hydrophilic polyether sulfone (PES) membrane, thickness about 175 ⁇ m, pore diameter 0.22 ⁇ m) so that the area is 196 mm 2 .
  • An aqueous dispersion containing 4.5% by mass of MXene was sprayed on the cut pieces with scissors for 3 seconds, and then temporarily dried with a dryer. After repeating this spraying and temporary drying 5 times, the conductive membrane (MXene membrane) having a thickness of 5 ⁇ m and the hydrophilic porous membrane obtained by main drying in an oven at 80 ° C. for 30 minutes were obtained.
  • the laminated film of the above was used as a biological signal sensing electrode sample.
  • a biological signal sensing electrode sample prepared in the same manner as above was also prepared except that the above-mentioned porous membrane was not provided and only the MXene membrane (MXene membrane having an area of 196 mm 2 and a thickness of 5 ⁇ m) was used.
  • MXene membrane having an area of 196 mm 2 and a thickness of 5 ⁇ m
  • Comparative Example 2 a commercially available bioelectrode, a monitoring electrode manufactured by 3M (Product No. 2228), was also prepared.
  • the impedance of the biological signal sensing electrode sample (MXene film + porous film) according to the present embodiment, the impedance of the biological signal sensing electrode sample (MXene film only) according to Comparative Example 1, and the impedance of the commercially available electrode according to Comparative Example 2 are shown. It was measured by the following method.
  • each of the above electrodes was brought into contact with the chicken skin, which is considered to be equivalent to human skin, and the impedance was measured with an impedance measuring device Autolab (manufactured by Metrohm Autolab).
  • the measurement conditions were a measurement frequency of 1 Hz, 10 Hz or 1000 Hz, and an effective voltage of 10 mV.
  • the level of the commercially available bioelectrode according to Comparative Example 2 was set to a total of 3 levels. Since the measurement was performed with two poles this time, the reference pole was not used. The measurement results are shown in Table 1 below.
  • the biological signal sensing electrode sample (MXene membrane + porous membrane) according to this embodiment has the same impedance as the MXene membrane alone at any frequency, and even if a porous membrane is formed, the impedance is the same. It turned out that the rise of was small. Further, it can be seen that the biological signal sensing electrode sample of the present invention has a lower impedance than the commercially available Ag / AgCl gel electrode, and the resistance is sufficiently low as the biological signal electrode.
  • the MXene membrane and the porous membrane are in direct contact with each other and the adhesion is good, it is not necessary to provide an adhesive layer between the MXene membrane and the porous membrane, and as a result, the layer It keeps the number low and shows low and stable impedance.
  • the MXene film does not come into contact with the subject, it is possible to suppress the peeling of MXene and perform stable measurement over a long period of time. Further, since it does not retain water or the like, it is possible to reduce the discomfort of wearing it.
  • the biological signal sensing electrode of the present invention can be preferably used in a device for extracting and measuring a biological signal such as an electromyogram signal or an electrocardiogram signal.

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