WO2019130833A1

WO2019130833A1 - Conductive material, conductive member, electrode leg, and biological information measurement electrode

Info

Publication number: WO2019130833A1
Application number: PCT/JP2018/041220
Authority: WO
Inventors: 三森　健一
Original assignee: アルプスアルパイン株式会社
Priority date: 2017-12-27
Filing date: 2018-11-06
Publication date: 2019-07-04
Also published as: JPWO2019130833A1; JP6821058B2

Abstract

This conductive material is provided on at least the surface of a part of a biological information measurement electrode where a contact can be made with a living organism. The conductive material includes fibers and a conductive polymer. In addition, this conductive member uses the conductive material, is formed by including fibers and a binder that have a conductive polymer for binding the fibers, and has a large number of pores. Further, this biological information measurement electrode has an part that can come into contact with a living organism. A conductive layer that uses the conductive material is formed on a surface of the part, and the conductive layer includes fibers that are dispersed in a matrix of a synthetic resin containing the conductive polymer.

Description

Conductive material, conductive material, electrode leg, and electrode for measuring biological information

The present invention relates to a conductive material, a conductive material, an electrode leg, and an electrode for measuring biological information.

For example, an electrode (electrode for measuring biological information) for measuring biological information is used for measuring biological information such as brain waves, pulse waves, electrocardiograms, electromyography and body fat. When measuring biological information, an electrode for measuring biological information is attached to a living body (skin), an electrical signal related to biological information is obtained by the electrode for measuring biological information, and biological information (for example, an electroencephalogram or the like) is measured. .

When measuring biological information, it is important that the biological information measuring electrode is in stable contact with the living body. Therefore, various electrodes for measuring biological information have been proposed in order to enhance the stability of contact with a living body.

As one of such biological information measurement electrodes, for example, an electrode is proposed which forms a conductive polymer film on the surface of a protrusion of the electrode to impart conductivity, and detects a biological signal (for example, , Patent Document 1).

Japanese Patent Application Laid-Open No. 2016-36642

The contact resistance (contact impedance) generated between the conductive polymer film and the living body is lower in the case where the conductive polymer film is wet with water than in the case where the conductive polymer film is not wet with water. Tend to Therefore, by previously wetting the conductive polymer film with an aqueous solution such as water, the electrical connection between the conductive polymer film and the living body can be stabilized more stably, and the electrical signal of the living body can be detected with higher sensitivity.

However, the conductive polymer film used for the electrode of Patent Document 1 has low hydrophilicity and poor wettability to water. Therefore, the conductive polymer membrane tends not to be in stable contact with the living body, and the conduction between the conductive polymer membrane and the living body tends to be difficult to stabilize. If the conduction between the conductive polymer film and the living body is not stable, it may not be possible to stably measure the biological information.

In addition, since the biological information measurement electrode is used in contact with a living body, it is necessary to be clean at the time of use. Therefore, every time the biological information measurement electrode is used, generally, cleaning liquid such as alcohol is used to wipe off the moisture, dirt, etc. remaining on the surface of the electrode for the purpose of cleaning the biological information measurement electrode in advance. ing.

However, the conductive polymer film used for the electrode of Patent Document 1 is easily worn. Therefore, if you wipe the surface of the protrusion repeatedly when wiping off the water droplets or dirt remaining on the surface of the protrusion of the electrode, the conductive polymer film may be worn away and part of the conductive polymer film may be peeled off There is sex. As a result, since the conductive polymer film remaining on the surface of the protrusion and the living body do not contact stably, it becomes difficult for the conductive polymer film and the living body to conduct. On the other hand, when a part of the conductive polymer film peels off, the surface of the exposed protrusion comes in contact with the living body. The contact impedance generated between the projection of the electrode and the skin tends to be higher than the contact impedance generated between the conductive polymer film and the skin. Therefore, when contact of the conductive polymer film with the living body is slight, it may not be possible to stably measure biological information.

An aspect of the present invention aims to provide a conductive material capable of stably measuring biological information.

One aspect of a conductive material according to the present invention is a conductive material provided on at least the surface of a biological information measuring electrode having a region capable of being in contact with a living body, which includes a fiber and a conductive polymer. .

Another aspect of the conductive material according to the present invention is a conductive material using the above-described conductive material, and is formed by including the fiber and a binder having the conductive polymer that bonds the fibers. And have a large number of pores.

Another aspect of the biological information measuring electrode according to the present invention is a biological information measuring electrode having a region capable of being in contact with a living body, and a conductive layer using the above-described conductive material is formed on the surface of the region. The conductive layer includes the fibers dispersed in a matrix of a synthetic resin containing the conductive polymer.

One aspect of the conductive member according to the present invention can stably measure biological information. One aspect of the conductive material according to the present invention can stably measure biological information. One aspect of the biological information measuring electrode according to the present invention can improve the wear resistance of the conductive layer formed on the surface of the area that can be in contact with the living body. Thereby, biological information can be measured stably.

It is a perspective view of the electrically-conductive material which concerns on 1st Embodiment. FIG. 2 is a cross-sectional view taken along line II of FIG. It is an optical microscope photograph which shows the state which installed the electrically conductive material on the carbon base material. It is the SEM photograph which expanded and looked at the electrically conductive material. It is a flowchart which shows the manufacturing method of the electrically-conductive material which concerns on 1st Embodiment. It is a perspective view of the electrode leg concerning 2nd Embodiment. It is II-II sectional drawing of FIG. It is a fragmentary sectional view which shows an example of the other structure of an electrode leg. It is a flowchart which shows the manufacturing method of the electrode leg concerning 2nd Embodiment. It is another flowchart which shows the manufacturing method of an electrode leg. It is another flowchart which shows the manufacturing method of an electrode leg. It is another flowchart which shows the manufacturing method of an electrode leg. It is another perspective view which shows the external appearance of the electrode leg concerning 3rd Embodiment. It is a front view of an electrode leg. FIG. 14 is a cross-sectional view taken along the line III-III in FIG. It is explanatory drawing which shows an example of the cross section of the front end groove part of a front-end | tip part. It is explanatory drawing which shows an example of the cross section of the auxiliary | assistant groove part of the side of an electrode leg. It is an explanatory view showing the state where a part of electric conduction layer of a tip part wears. It is explanatory drawing which shows the state which the liquid hold | maintained by the front end groove part spreads. It is a perspective view which shows another example of the groove part formed in the one end part of an electrode leg. It is a perspective view which shows another example of the groove part formed in the one end part of an electrode leg. It is a flowchart which shows the manufacturing method of the electrode leg concerning 3rd Embodiment. It is another flowchart which shows the manufacturing method of an electrode leg. It is another flowchart which shows the manufacturing method of an electrode leg. It is a perspective view showing the appearance of the living body information measurement electrode concerning a 4th embodiment. It is another perspective view which shows the external appearance of the electrode for biological information measurement. FIG. 26 is a cross-sectional view taken along line IV-IV of FIG. It is a figure which shows an example which measures a test subject's brain waves using the test | inspection apparatus provided with the electrode for biological information measurement. It is a perspective view which shows an example of the other structure of the electrode for biological information measurement. FIG. 30 is a VV cross-sectional view of FIG. 29. It is a fragmentary sectional view of the electrode leg in which the base conductive layer was formed. It is a flowchart which shows the manufacturing method of the electrode for biological information measurement which concerns on 4th Embodiment. It is a figure which shows an example of the state by which the raw material supply channel | path is being fixed to the terminal part. It is another flowchart which shows the manufacturing method of the electrode for biological information measurement. It is another flowchart which shows the manufacturing method of the electrode for biological information measurement. It is another flowchart which shows the manufacturing method of the electrode for biological information measurement. It is a perspective view which shows the external appearance of the electrode for biometric information measurement which concerns on 5th Embodiment. It is another perspective view which shows the external appearance of the electrode for biological information measurement. It is another perspective view which shows the external appearance of the electrode for biological information measurement. FIG. 37 is a cross-sectional view taken along the line VI-VI of FIG. It is explanatory drawing which shows an example of the state which made the front-end | tip part of a base | substrate part contact the scalp via a conductive layer. It is a flowchart which shows the manufacturing method of the electrode for biometric information measurement which concerns on 5th this embodiment. It is another flowchart which shows the manufacturing method of the electrode for biological information measurement. It is a perspective view showing the appearance of the living body information measurement electrode concerning a 6th embodiment. It is another perspective view which shows the external appearance of the biological information measurement electrode which concerns on 6th Embodiment. FIG. 45 is a cross-sectional view taken along line VII-VII of FIG. It is a fragmentary sectional view of the electrode leg in which the base conductive layer was formed. It is a flowchart which shows the manufacturing method of the electrode for biometric information measurement which concerns on 6th Embodiment. It is a flowchart which shows another example of the manufacturing method of the electrode for biological information measurement. It is a flowchart which shows another example of the manufacturing method of the electrode for biological information measurement. It is a perspective view which shows the external appearance of the electrode for biometric information measurement which concerns on 7th Embodiment. It is another perspective view which shows the external appearance of the electrode for biometric information measurement which concerns on 7th Embodiment. It is another perspective view which shows the external appearance of the electrode for biometric information measurement which concerns on 7th Embodiment. It is a VIII-VIII sectional view of FIG. It is a flowchart which shows the manufacturing method of the electrode for biometric information measurement which concerns on 7th Embodiment. It is a flowchart which shows another example of the manufacturing method of the electrode for biological information measurement. It is a figure which shows the test result of the abrasion resistance of the electrode for biological information measurement. It is a figure which shows the test result of the measurement precision of the electrode for biological information measurement.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in order to make an understanding of description easy, the same code | symbol is attached | subjected with respect to the same component in each drawing, and the overlapping description is abbreviate | omitted. In addition, the scale of each member in the drawings may be different from the actual one. In this specification, using a three-dimensional orthogonal coordinate system in three axial directions (X-axis direction, Y-axis direction, Z-axis direction), the direction parallel to the central axis J of the biological information measurement electrode is taken as the Z-axis direction. In the plane orthogonal to the axis J, one of two directions orthogonal to each other is taken as an X-axis direction, and the other as a Y-axis direction. In the following description, the + Z axis direction may be referred to as the upper side, and the −Z axis direction may be referred to as the lower side.

The conductive material according to the embodiment of the present invention is provided on the surface of at least a region of a biological information measurement electrode having a region capable of being in contact with a living body, and includes a fiber and a conductive polymer. According to the conductive member according to one embodiment, biological information can be stably measured. The conductive material is used as a conductive material in the first embodiment, and is used as a conductive layer in the second to seventh embodiments. Each embodiment will be described below.

First Embodiment
<Conductive material>
The conductive material according to the first embodiment will be described. In the present embodiment, as an example, the case of being attached to the tip of the electrode leg of the electrode for measuring biological information which is brought into contact with a living body to measure biological information will be described. Here, a living body refers to a human body or a living body other than the human body, and the tip of the electrode leg is brought into contact with the scalp, forehead, skin, and the like.

FIG. 1 is a perspective view of a conductive material according to the present embodiment, and FIG. 2 is a cross-sectional view taken along the line II of FIG. FIG. 3 is an optical micrograph showing a state in which the conductive material is placed on the carbon base CF, and FIG. 4 is an SEM photograph showing the conductive material in an enlarged manner. In addition, the dashed-dotted line in FIG. 1 and FIG. 2 shows the central axis J of a electrically conductive material. The central axis J is an axis serving as a center when the conductive material is installed in a living body.

As shown to FIG. 1 and FIG. 2, the electrically-conductive material 10 which concerns on this embodiment is formed in the surface of the front-end | tip part 131 which is an area | region which can contact with the biological body of the electrode leg 13 of the electrode for biological information measurement. The tip end portion 131 of the electrode leg 13 is formed in a curved shape having a rounded end, and is formed in a dome shape in FIGS. 1 and 2. The conductive material 10 is formed in a dome shape so as to correspond to the shape of the tip portion 131.

In the present embodiment, the tip means the tip in contact with the living body and the peripheral region of the tip which may come in contact with the living body when the conductive material 10 is inclined, as shown in FIG. In 2, the entire outer surface of the conductive material 10 is obtained. In the present specification, the tip end portion is referred to as “a region A capable of being in contact with a living body (hereinafter, referred to as“ region A ”)”.

The conductive material 10 is formed including a fiber and a binder, and has a large number of pores 11. The conductive material 10 has a large number of pores 11 on its surface and inside, and is formed like a sponge. In FIGS. 1 and 2, the conductive material 10 is schematically illustrated as a film, but as shown in FIG. 3, the conductive material 10 is formed in a sponge shape having elasticity. Further, in FIG. 1 and FIG. 2, the pores 11 are schematically illustrated as black dots, but as shown in FIG. 4, there are innumerable fine gaps.

The conductive material 10 can hold a liquid containing water in the pores 11 by having the pores 11. The liquid contained in the pores 11 may be any liquid other than water as long as it is a liquid that does not harm the living body, such as an electrolytic solution (saline solution).

As a fiber of the conductive material 10, a metal fiber made of metal such as Au, Pt, Ag, Cu, Al, Ni, Si, Co, Zr, Ti, W, or steel; Al ₂ O ₃ , NiO, SiO ₂ metal oxide fibers composed of metal oxides such as TiO ₂ , Ti ₂ O ₃ , ZnO, ZrO ₂ , WO ₃ , or Y ₂ O ₃ ; carbon fibers; SiC, ZrC, Al ₄ C ₃ , CaC _2. Carbide fibers made of carbides such as WC, TiC, HfC, VC, TaC, or NbC; organic fibers such as polyester fibers can be used.

In the present specification, when the fiber thickness is represented by a circle equivalent diameter, a fiber having an average thickness (average diameter) of 1 nm to 100 μm, preferably 1 nm to 30 μm, more preferably 1 nm to 5 μm is generally used. It is. The thickness of the fiber can be determined using a light scattering device, a laser microscope, a scanning electron microscope (SEM) or the like. For example, observe the fiber with an SEM or the like, and measure the length in the direction orthogonal to the longitudinal direction of the predetermined number (for example, 10 to 200) of fibers arbitrarily selected (the length in the radial direction of the fiber) The average diameter is determined by calculating the average value.

The fiber is preferably a nanofiber. In nanofibers, nanofibers are intertwined better than fibers, and finer pores 11 are formed in those bound with a binder. Therefore, the liquid containing water can be retained in the pores 11 more. In the present specification, the term “nanofiber” as used herein refers to the average diameter of 1 nm to 1000 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm when the thickness of the nanofibers is represented by the equivalent circle diameter. . The average diameter of the nanofibers can be obtained by measurement using the same method as in the case of measuring the thickness of the fibers.

The aspect ratio of the nanofibers is preferably 1: 100 to 1: 1000, more preferably 1: 100 to 1: 300. If the aspect ratio of the nanofibers is in the range of 1: 100 to 1: 1000, it is possible to suppress the dispersion failure in the coating layer (see the coating process described later) for forming the conductive material 10. As a result, the nanofibers in the conductive material 10 are uniformly present, and the strength of the conductive material 10 is enhanced.

The nanofibers are, for example, metal nanowires composed of the same kind of metal as the metal used for the above-mentioned metal fiber; metal oxide nanofibers composed of the same kind of metal as the metal used for the above-mentioned metal oxide fiber Carbon nanofibers, carbon nanotubes, carbon nanohorns, cellulose nanofibers, polyester nanofibers, etc. It can be formed using plastic nanofibers. Above all, in the present embodiment, it is preferable to use a cellulose nanofiber.

Cellulose nanofibers are cellulose nanofibers obtained by mechanically disintegrating water-insoluble natural cellulose fibers in the presence of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Cellulose nanofibers (TEMPO oxidized cellulose nanofibers) obtained by allowing an oxidizing agent such as hypochlorous acid to act to advance the oxidation reaction, or cellulose obtained by hydrophobizing the surface of natural cellulose fibers There are nanofibers (surface hydrophobized cellulose nanofibers) and the like. In the present embodiment, a cellulose nanofiber obtained by mechanical disintegration treatment is preferable. For example, in the case of TEMPO oxidized cellulose nanofibers, it is considered that part of hydroxyl groups of cellulose nanofibers is substituted by carboxyl groups, and swelling when touched with water, and the strength of the conductive material 10 can not be maintained. Moreover, in the case of surface-hydrophobicized cellulose nanofibers, if the hydrophobization proceeds too much, the hydrophilicity with water or the electrolyte solution may be lost, and the measurement may be unstable.

As a cellulose nanofiber obtained by mechanical disintegration treatment, a cellulose nanofiber (ACC cellulose nanofiber) obtained by cleaving a natural cellulose fiber by using an aqueous counter collision (ACC) method Is preferred.

The ACC method is a method of preparing a translucent aqueous dispersion by rapidly dispersing and dispersing natural cellulose fibers in water from the nano level to the molecular level. In the ACC method, dispersions of natural cellulose fibers are simultaneously sprayed from one pair of opposing nozzles toward one point under high pressure (for example, about 70 to 250 MPa) to cause jet streams to collide at high speed. As a result, the surface of the natural cellulose fiber is peeled off to be nanofibrillated (nano-refined), and the affinity with water, which is the carrier, is improved to finally bring about a state close to dissolution. By using ACC method, only the interaction between the fibers of natural cellulose fiber is broken to perform nano-refining, there is no structural change of the cellulose molecule, and the state where the polymerization degree accompanied by the cleavage is minimized Thus, cellulose nanofibers are obtained. In ACC cellulose nanofibers, the hydroxyl groups on the fiber surface exhibit hydrophilicity, and the oxygen binding between cellulose molecules exhibits hydrophobicity. Thus, ACC cellulose nanofibers have both hydrophilic and hydrophobic sites exposed on the fiber surface and have amphiphilic properties. Since ACC cellulose nanofibers have the above-mentioned properties, they can be dispersed more uniformly in an aqueous dispersion. As a result, it is possible to obtain the conductive material 10 in which the ACC cellulose nanofibers are uniformly present, and to obtain the stable conductive material 10 that does not absorb moisture and swell excessively. Therefore, the conductive material 10 containing ACC cellulose nanofibers can exhibit conductivity more stably and can have strength.

As natural cellulose fibers, pulp fibers such as bamboo, rattan or hemp, and wood pulp fibers such as softwood and hardwood can be used. In the case of ACC cellulose nanofibers, the ratio of the hydrophilic site to the hydrophobic site exposed on the fiber surface differs depending on the type of natural cellulose fiber used. Among natural cellulose fibers, in the case of natural cellulose fibers derived from bamboo, the proportion of hydrophobic sites exposed on the fiber surface is higher than that of hydrophilic sites, and it is thought that amphipathic characteristics appear strongly. Therefore, as natural cellulose fiber used as a raw material of ACC cellulose nanofiber, it is preferable to use natural cellulose fiber derived from bamboo.

The cellulose nanofibers may be used in the state of being dispersed in a solution or may be used in the form of powder.

The binder of the conductive material 10 functions as a binder for binding the fibers together, and includes a conductive polymer and a synthetic resin (binder resin). The binder resin may not be contained when the binder is sufficient to bond the fibers with each other and the shape of the conductive material 10 can be maintained.

As the conductive polymer of the binder, for example, PEDOT / PSS, polyacetylene, polyaniline, polythiophene in which polystyrenesulfonic acid (poly 4-styrene sulfonate; PSS) is doped to poly3,4-ethylenedioxythiophene (PEDOT) , Polyphenylene vinylene, or polypyrrole can be used. Among them, it is preferable to use PEDOT / PSS in view of lower contact impedance with a living body and high conductivity.

As binder resin of a binder, various resin, such as a thermoplastic resin, a thermosetting resin, and a photocurable resin, can be used. In the present embodiment, a thermosetting resin is used. As a thermoplastic resin, for example, polycarbonate resin, polyarylate resin, styrene-butadiene resin, styrene-acrylonitrile resin, styrene-maleic acid resin, acrylic acid resin, styrene-acrylic acid resin, polyethylene resin, ethylene-vinyl acetate resin , Chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate resin, alkyd resin, polyamide resin, urethane resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyester resin, Or polyether resin. As a thermosetting resin, a silicone resin, an epoxy resin, a phenol resin, a urea resin, or a melamine resin is mentioned, for example. As a photocurable resin, for example, an epoxy-acrylic acid resin (more specifically, an acrylic acid derivative adduct of an epoxy compound, etc.) or a urethane-acrylic acid resin (more specifically, a urethane compound) Acrylic acid derivative adducts) and the like. Among these resins, resins with small curing shrinkage are preferable, and, for example, silicone resins are preferable. One of these binder resins may be used alone, or two or more thereof may be used in combination.

In this embodiment, it is assumed that a cellulose nanofiber is used as a fiber, PEDOT / PSS is used as a conductive polymer, and a silicone resin is used as a binder resin. In this case, the conductive material 10 can be used as a cellulose sponge body formed to include cellulose nanofibers and PEDOT / PSS.

The mixing ratio of binder to fiber is preferably in the range of 3: 7 to 9: 1. Within this range, the conductive material 10 can maintain conductivity and can reduce the amount of conductive polymer used.

When the fiber is a cellulose nanofiber, the mixing ratio of the binder and the cellulose nanofiber is preferably in the range of 3: 7 to 9: 1, and in the range of 5: 5 to 8: 2 More preferable. Within this range, the conductive material 10 can maintain conductivity and can reduce the amount of conductive polymer used. When the conductive polymer is PEDOT / PSS, the cost of cellulose nanofibers is 1/10 or less of the cost of PEDOT / PSS, so the ratio of PEDOT / PSS used in the unit thickness of the conductive material 10 is It is lowered.

The average thickness of the conductive material 10 is preferably 1 μm to 30 μm. Within this range, conductivity can be provided, and when the conductive material 10 is provided at the tip end portion 131 of the electrode leg 13, an electrical signal transmitted from a living body can be stably energized. Moreover, since the conductive material 10 contains a fiber, the average thickness of the conductive material 10 can be easily made 10 μm or more. The thicker the average thickness of the conductive material 10, the higher the conductivity and the more durable the wear resistance. On the other hand, the thicker the average thickness of the conductive material 10, the more expensive the material cost and the process cost, and the balance should be taken into consideration to determine the upper limit average thickness. For example, the average thickness is more preferably 5 μm to 27 μm, still more preferably 10 μm to 25 μm, and most preferably about 20 μm. The average thickness of the conductive material 10 refers to the average value of the thickness of the conductive material 10. For example, in the cross section of the conductive material 10, when several places (for example, six places) are measured in arbitrary places, the average value of the thickness of these measurement points is said. Further, in the present embodiment, the thickness refers to the length of the layer in the direction perpendicular to the contact surface of the conductive material 10.

The conductive material 10 configured as described above is formed of a fiber and a binder containing a binder resin and a conductive polymer. A large number of fibers are fixed by a binder and connected in a network, and a plurality of pores 11 are formed on the surface and inside of the conductive material 10, and the conductive material 10 is formed in a so-called sponge shape. Therefore, the conductive material 10 can contain a solution in the pores 11.

Further, when the conductive material 10 is provided on the surface of the tip portion 131 of the electrode leg 13 of the biological information measurement electrode and the solution is contained in the pores 11, the conductive material 10 is brought into contact with the surface of the living body. The solution held in the pores 11 of the material 10 flows and spreads on the surface of the living body in contact with the conductive material 10. Then, by bringing the conductive material 10 and the surface of the living body into conduction through the solution, the contact impedance between the living body and the conductive material 10 can be lowered, so that an electrical signal from the living body can be easily obtained. Therefore, the conductive material 10 can maintain electrical connection with the living body. Therefore, biological information can be stably measured by using the conductive material 10 for the electrode leg 13 of the biological information measurement electrode.

In particular, when the conductive material 10 is brought into contact with the scalp or forehead as a living body, the conductive material 10 includes a solution, so that even if the surface of the scalp or forehead is dry, the conductive material 10 can measure the contact impedance by electroencephalogram. (E.g., less than 200 k.OMEGA.). Therefore, if the conductive material 10 is used for the electrode leg 13 of the biological information measurement electrode, an electroencephalogram can be stably obtained, and thus the electroconductive material 10 can be suitably used for electroencephalogram measurement.

In addition, the fiber has higher strength than the binder and has high abrasion resistance. Therefore, when the conductive material 10 is attached to the tip end portion 131 of the electrode leg 13 of the biological information measurement electrode and used, even if the surface of the conductive material 10 is repeatedly rubbed during use or washing, the surface of the conductive material 10 is used. Can be suppressed.

Furthermore, in the conductive material 10, a large number of fibers are connected in a mesh shape, and a plurality of pores 11 are formed on the surface and inside of the conductive material 10. Therefore, the conductive material 10 has high elasticity. When the conductive material 10 is attached to the tip end portion 131 of the electrode leg 13 of the biological information measurement electrode and used, when the conductive material 10 comes in contact with a living body, the conductive material 10 elastically deforms. Thereby, since the pressing force on the living body is alleviated, the conductive material 10 can be brought into soft contact with the living body, and pain in the subject can be alleviated. In addition, when the conductive material 10 contacts the living body, the conductive material 10 can be reliably contacted with the living body by being elastically deformed.

The conductive material 10 has a large number of pores 11 and is formed like a sponge. The fibers contained in the conductive material 10 are auxiliaryly bonded with a cured product of a binder resin in addition to the conductive polymer. Therefore, the conductive material 10 can be made stronger than the case where the binder resin is not included. Therefore, the conductive material 10 can be made into an elastic body having an appropriate hardness while improving the wear resistance.

The conductive material 10 contains a fiber. The conductive material 10 can reduce the amount of conductive polymer per unit thickness as compared to the case where the conductive material 10 does not include fiber, thereby reducing the necessary cost per unit layer. Therefore, the manufacturing cost of the conductive material 10 can be suppressed.

In addition, a biological information measurement electrode including a conductive material formed of metal can not be used for a subject having metal allergy. In the present embodiment, since the conductive material 10 is formed to include the binder, the user can receive the conductive material 10 even if the conductive material 10 is attached to the tip end portion 131 of the electrode leg 13 of the biological information measurement electrode and brought into contact with the living body. It does not cause metal allergy and is safe. Therefore, the conductive material 10 can be used safely for the subject.

When the fibers included in the conductive material 10 are nanofibers, the nanofibers are closely connected to each other at a shorter distance, so that a smaller gap is likely to be formed between the nanofibers. Therefore, the conductive material 10 can have many smaller pores. As a result, the conductive material 10 can more easily contain the solution therein, so that the electrical connection with the living body can be stably maintained.

Also, nanofibers can be more finely and uniformly present in the conductive material 10 than fibers. Therefore, since many nanofibers can be connected in more detail (entangled) in the conductive material 10 than fibers, the strength of the conductive material 10 can be increased. Therefore, the wear resistance of the conductive material 10 can be further improved.

When the fiber contained in the conductive material 10 is a cellulose nanofiber, even if the conductive material 10 is attached to the tip portion 131 of the electrode leg 13 of the electrode for measuring biological information, the cellulose nanofiber has high hydrophilicity, The solution can be more easily contained inside the material 10. Therefore, by using cellulose nanofibers as the fibers, the electrical connection with the living body can be maintained more stably. Moreover, since cellulose nanofibers have high resistance to alcohol, alcohol can be washed when washing the conductive material 10.

<Method of Manufacturing Conductive Material According to First Embodiment>
Next, a method of manufacturing the conductive material according to the first embodiment will be described. FIG. 5 is a flowchart showing a method of manufacturing a conductive material according to the present embodiment. As shown in FIG. 5, the method of manufacturing a conductive material according to the present embodiment includes a mixing step (step S11), a solidifying step (step S12), and a curing step (step S13). Each step will be described below.

First, in the mixing step (step S11), mixing including a fiber, a binder (a conductive polymer and a thermosetting resin which is a binder resin) for bonding the fibers, and a solvent as a solvent for dispersing the fiber Make a solution. The mixed solution is prepared by adding fibers, a conductive polymer, and a thermosetting resin to a solvent and mixing them, and dispersing the fiber, the conductive polymer, and the thermosetting resin in the solvent. For preparation of the mixed solution, for example, a bead mill, a roll mill, a ball mill, or an ultrasonic disperser can be used.

As the solvent, a dispersion medium consisting only of water, or a dispersion medium consisting of water and an organic solvent can be used. Examples of the organic solvent include alcohols such as benzene and methanol. Further, in the dispersion medium, only one of the above-mentioned organic solvents may be contained, or two or more may be contained.

The content of the solvent in the mixed solution is preferably in the range of 80 to 95% by mass. By adjusting the content of the solvent in the mixture within the above range, the distribution of the size (pore diameter) of the pores 11 in the obtained porous body can be adjusted.

The mixing time of the fiber, conductive polymer, thermosetting resin, and solvent is preferably long to ensure the dispersibility of the fiber, conductive polymer, and thermosetting resin in the solvent, but production is preferable. It is set appropriately in consideration of the balance with the sex.

Next, in the solidifying step (step S12), the mixed solution is dried using a lyophilization method to obtain a porous body having a large number of pores. The solidification step (step S12) includes a freezing step (step S121) and a dehydration step (step S122). In addition, lyophilization is a method of freezing a mixed solution and drying the mixed solution by reducing the pressure in the frozen state to sublime the solvent in the mixed solution.

In the freezing step (step S121) of the solidification step (step S12), after flowing the mixed solution into the mold, the mixed solution is frozen in a state of being put into the mold to freeze water contained in the mixed solution (cooling ). The mold containing the mixed solution is placed under reduced pressure and under a cold atmosphere to freeze the solvent.

The freezing temperature of the mixed solution should be below the freezing point of the solvent in the mixed solution, preferably below -40.degree. C. and more preferably below -80.degree.

The pressure is preferably 100 Pa or less, more preferably 10 Pa or less, and still more preferably in a vacuum state. When the pressure exceeds 100 Pa, the solvent in the frozen mixed solution may be melted.

The freezing time of the mixed solution is preferably about 12 to 48 hours in order to ensure that the water contained in the mixed solution is cooled and to achieve the productivity of the porous body.

In the dehydration step (step S122) of the solidification step (step S12), the solvent in the frozen mixed solution is sublimed under reduced pressure. As a result, the solvent is removed in a state in which the fibers are bound by the conductive polymer, and the portion from which the solvent is removed becomes a large number of fine spaces. Thus, a porous body having a large number of pores and containing an uncured binder resin is obtained.

In the curing step (step S13), the porous body is heated to cure the uncured binder resin contained in the porous body. The temperature at which the porous body is heated may be any temperature at which the thermosetting resin which is the binder resin can be cured. For example, the temperature is preferably 80 to 200 ° C., and more preferably 100 to 150 ° C. More preferably, the temperature is 130 ° C.

As described above, the conductive material 10 having a large number of pores 11 is obtained.

In the present embodiment, by drying the mixed solution using a lyophilization method, it is possible to easily obtain the conductive material 10 having a large number of pores 11 inside and on the surface.

[Modification of manufacturing method of conductive material according to the first embodiment]
In the present embodiment, since the binder resin is a thermosetting resin, the porous body is heated in the curing step (step S13). However, when the binder resin is a photocurable resin, curing is performed. In the step (step S13), the porous body is irradiated with ultraviolet light. When the binder resin is a thermoplastic resin, the binder resin is cured at the same time as the porous body is obtained in the solidification step (step S12), and thus the curing step (step S13) is omitted.

Second Embodiment
<Electrode leg>
An electrode leg 20A according to a second embodiment will be described. The electrode leg 20A according to the present embodiment is obtained by attaching the conductive material 10 according to the first embodiment as the conductive layer (first conductive layer) 22 to the tip of the electrode leg 20A. 6 is a perspective view of an electrode leg 20A according to a second embodiment, and FIG. 7 is a cross-sectional view taken along the line II-II of FIG.

The electrode leg 20A according to the present embodiment, as shown in FIGS. 6 and 7, has an electrode base (base body) 21A and a conductive layer 22 on the surface of the tip portion 211 which is the region A of the electrode base 21A. .

The electrode base 21A of the electrode leg 20A is detachably attached to the biological information measurement electrode.

The electrode base 21A is formed in a cylindrical shape, and has a tip 211 capable of contacting the scalp at its tip. The tip end portion 211 of the electrode base 21A is formed in a curved shape having a rounded end, and in the present embodiment, is formed in a dome shape. The shape of the tip end portion 211 may be a conical shape having a rounded shape as another curved surface shape, or may be a flat shape having an end face which can be in contact with a living body.

As described above, the tip end portion 312a means the tip end in contact with the scalp which is a living body and the peripheral region of the tip which may come in contact with the living body when the electrode leg 20A is inclined.

The electrode substrate 21A can be formed using a conductive elastomer or an insulating material. Note that the insulating material refers to a material which does not have conductivity or which has extremely low conductivity. In the present embodiment, the electrode base 21A is integrally formed of a conductive elastomer.

The type of the conductive elastomer is not particularly limited. The conductive elastomer is obtained, for example, by melt mixing the conductive filler and the nonconductive elastomer. The electrode base 21A has a low elastic modulus by being molded including a nonconductive elastomer having rubber elasticity. Therefore, when the electrode leg 20A is used as an electrode for measuring biological information, the electrode base 21A is easily deformed according to the uneven shape of the surface of the living body, so that contact with the living body can be ensured and the pressing force to the living body is alleviated. it can.

The type of the conductive filler described above is not particularly limited as long as it has conductivity. For example, as the conductive filler, carbon materials such as graphite, carbon black, carbon nanotubes, carbon nanohorns or carbon fibers (carbon fibers); aluminum, gold, silver, copper, iron, platinum, chromium, tin, indium, antimony, Examples thereof include metals such as titanium and nickel; and conductive ceramics such as a so-called ABO ₃ type perovskite-type composite oxide, but the present invention is not limited thereto. These conductive fillers may be used alone or in combination of two or more. From the viewpoint of durability, it is preferable to use a carbon material.

Examples of the above-mentioned non-conductive elastomers include silicone rubber, ethylene propylene rubber, ethylene propylene diene rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, chloroprene rubber, acrylonitrile nitrile butadiene rubber, butyl rubber, urethane rubber, or Fluororubber etc. are mentioned. These may be used alone or in combination of two or more. Among these, in terms of durability and the like, it is preferable to use silicone rubber.

Moreover, as the insulating material which is not a conductive elastomer, the above non-conductive elastomer, polypropylene (PP), polycarbonate (PC), ABS resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide (PA), Alternatively, liquid crystal polymer (LCP) or the like can be used.

The conductive layer 22 is provided on the surface of the tip end portion 211 of the electrode base 21A. As long as the conductive layer 22 is provided on the surface of the tip portion 211 which is the region A, the region to be formed is not limited. When the electrode base 21A is formed using a conductive elastomer, since the electrode base 21A can ensure conduction, the conductive layer 22 may be formed only on the surface of the tip end portion 211. When the electrode base 21A is formed of an insulating material, the conductive layer 22 may be provided on the entire surface of the electrode base 21A in order to ensure conduction of the electrode base 21A.

The conductive layer 22 is formed of the conductive material 10 according to the above-described first embodiment, and has a plurality of pores 221 on the surface and inside thereof.

In the electrode leg 20A having the above configuration, the conductive layer 22 is formed on the tip end portion 211 of the electrode base 21A, and the solution is contained in the pores 221 of the conductive layer 22. When the conductive layer 22 is in contact with the surface of the living body, the solution held in the pores 221 of the conductive layer 22 flows to the surface of the living body. Conduction of the conductive layer 22 and the surface of the living body through the solution can significantly lower the contact impedance between the living body and the electrode leg 20A, so that it becomes easy to obtain an electrical signal from the living body, and the living body can be obtained. Can detect electrical signals of higher sensitivity. Therefore, since the electrode leg 20A can stably maintain the electrical connection with the living body, the biological information can be stably measured.

Moreover, since the conductive layer 22 is formed of the conductive material 10 according to the first embodiment described above, it has high wear resistance. Therefore, even when the conductive layer 22 on the surface of the tip end portion 211 of the electrode leg 20A is rubbed, the conductive layer 22 can be prevented from being scraped off during use or cleaning of the electrode leg 20A. Therefore, even when the electrode leg 20A is used for a biological information measurement electrode, the conductive layer 22 can stably contact with the living body at the contact portion with the living body, so that the conduction between the conductive layer 22 and the living body is stably maintained. be able to. Therefore, if the electrode leg 20A is used, the electrical connection between the tip end portion 211 of the electrode leg 20A and the living body can be maintained, so that an electrical signal from the living body can be stably obtained.

[Modification of electrode leg according to the second embodiment]
The conductive layer 22 is formed on the tip end portion 211 of the electrode base 21A, but may be formed on another portion of the electrode base 21A as long as it is formed on at least the tip end portion 211. It may be formed on the entire surface of For example, when the electrode base 21A is formed of an insulating material, the conductive layer 22 is formed on the entire surface of the electrode base 21A.

In addition, when the electrode base 21A is formed of an insulating material, other configurations can be considered. FIG. 8 is a view for explaining a modification of the electrode leg 20A according to the second embodiment, and is a partial cross-sectional view of the electrode leg corresponding to the II-II cross-sectional view of FIG. As shown in FIG. 8, it is preferable to form a base conductive layer (second conductive layer) 23 electrically connected to the conductive layer 22 on the entire surface of the electrode base 21A. Thus, the entire surface of the electrode base 21A can be electrically connected. A conductive polymer similar to the conductive layer 22 can be used as the conductive polymer contained in the base conductive layer 23. The thickness of the base conductive layer 23 only needs to be conductive, and may be, for example, about 200 nm to 1 μm. In FIG. 8, the base conductive layer 23 may be electrically connected to the electrode for biological measurement to which the electrode base 21A is connected, and may not be formed on the end face of the electrode base 21A opposite to the tip end portion 211.

<Method of Manufacturing Electrode Leg According to Second Embodiment>
Next, a method of manufacturing the electrode leg 20A according to the second embodiment will be described. FIG. 9 is a flowchart showing a method of manufacturing the electrode leg 20A according to the present embodiment.

In the method of manufacturing the electrode leg 20A according to the present embodiment, as shown in FIG. 9, a leg base manufacturing step (step S21A) of manufacturing the electrode base 21A having conductivity and a conductive layer at the tip portion 211 of the electrode base 21A. And 22 forming a conductive layer (step S22A).
Each step will be described below.

In the leg base producing step (step S21A), the electrode base 21A is formed using a material for forming the electrode base 21A. When the molding method is used, a mold corresponding to the shape of the electrode base 21A is used. The electrode base 21A can be formed by using the mold.

The conductive layer forming step (step S22A) includes a coating step (step S221) and a solidification step (step S222).

In the coating step (step S221) of the conductive layer forming step (step S22A), a fiber, a conductive polymer that bonds the fibers with one another, a thermosetting resin that is a binder resin, and a solvent as a solvent in which the fiber is dispersed The mixed solution containing it is apply | coated to the front-end | tip part 211, and a coating layer is formed.

The solidifying step (step S222) of the conductive layer forming step (step S22A) can be performed in the same manner as the solidifying step (step S12) of the method of manufacturing the conductive material of the first embodiment shown in FIG. In the solidification step (step S222), the conductive layer 22 having a large number of pores 221 can be formed on the tip end portion 211 of the electrode base 21A.

As described above, the electrode leg 20A in which the conductive layer 22 is formed at the tip end portion 211 of the electrode base 21A is obtained.

In the present embodiment, the electrode leg 20A provided with the conductive layer 22 having a large number of pores 221 inside and on the surface is obtained by drying the coating layer formed on the tip end portion 211 of the electrode base 21A using the freeze-drying method. It can be easily obtained.

Further, in the present embodiment, in the coating step (step S221) of the conductive layer forming step (step S22A), the film thickness of the coating layer formed when the mixed solution is applied once to the tip end portion 211 does not include a fiber. It can be thicker than the thickness of the coating layer formed when the solution is applied once. Since the desired thickness of the conductive layer 22 can be obtained with a small number of application times of the mixed solution, the cost required for forming the application layer in the application step (step S221) can be reduced. In addition, by thickening the thickness of the conductive layer 22, the conductive layer 22 is worn even when the surface of the conductive layer 22 is abraded and worn when the electrode leg 20A is used for a biological information measurement electrode or when the electrode leg 20A is cleaned. It is possible to delay the time until it wears off from the surface of the tip portion 211. As a result, the life of the conductive layer 22 can be further extended.

When the fibers contained in the conductive layer 22 are cellulose nanofibers, the mixed solution containing cellulose nanofibers and a conductive polymer has good wettability to the electrode substrate 21A and high thixotropy. Therefore, when the conductive layer 22 is formed using a mixed solution containing cellulose nanofibers and a conductive polymer, the thickness of the coated layer formed when the mixed solution is applied to the tip portion 211 once is made thicker. be able to. The film thickness of the coating layer formed in one application of the mixed solution is, for example, about 1.3 to 4 times the film thickness of the coating layer formed by coating a solution not containing cellulose nanofibers. It can be thickened.

[Modified Example of Method of Manufacturing Electrode Leg According to Second Embodiment]
In the present embodiment, in the conductive layer forming step (step S22A), the conductive layer 22 is formed only at the tip end portion 211 of the electrode base 21A, but in addition to the tip end portion 211, a part of the side surface of the electrode base 21A. Alternatively, the conductive layer 22 may be formed entirely.

Further, in the present embodiment, the conductive layer 22 is formed by freeze-drying the coating layer applied to the tip end portion 211 of the electrode base 21A in the conductive layer forming step (step S22A), but the present invention is not limited thereto. In the conductive layer forming step (step S22A), for example, the conductive layer 22 prepared in advance may be attached to the tip end portion 211 of the electrode base 21A. An example of a method of manufacturing the electrode leg in this case is shown in FIG. FIG. 10 is another flowchart showing the method of manufacturing the electrode leg according to the present embodiment. As shown in FIG. 10, the method of manufacturing the electrode leg according to the present embodiment includes a leg base producing step (step S21A) and a conductive layer forming step (step S22B). In the conductive layer forming step (step S22B), the conductive layer 22 made of the conductive material 10 according to the first embodiment is attached to the tip end portion 211 of the electrode base 21A. The conductive layer 22 is obtained by the method of manufacturing a conductive material according to the first embodiment. For example, the conductive layer 22 may be attached to the tip end portion 211 using an adhesive, or may be fitted and fixed to the tip end portion 211. The electrode leg 20A is obtained by attaching the conductive layer 22 to the tip end portion 211 of the electrode base 21A.

In addition, although the electrode base 21A is manufactured using a conductive material, when the electrode base 21A is manufactured using an insulating material, the surface of the electrode base 21A manufactured using an insulating material is surface treated Thereafter, the conductive layer 22 is formed. An example of the manufacturing method of the electrode leg in this case is shown in FIG. FIG. 11 is another flowchart showing the method of manufacturing the electrode leg according to the present embodiment. As shown in FIG. 11, the method of manufacturing the electrode leg according to the present embodiment includes a leg base manufacturing step (step S21B) and a conductive layer forming step (step S22A). The leg base producing step (step S21B) includes a leg base forming step (step S211) for forming the electrode base 21A, and a surface treatment step (step S212) for activating the surface of the tip end portion 211 of the electrode base 21A. . In the leg base forming step (step S211), the electrode base 21A is formed using a material for forming the electrode base 21A. In the surface treatment step (step S212), the surface of the tip end portion 211 is subjected to activation treatment to improve the adhesion to the conductive layer 22. Details of the surface treatment step (step S212) will be described later in the surface treatment step (step S32) of the method for manufacturing the electrode leg 20B according to the third embodiment shown in FIG. The conductive layer 22 is stably formed on the tip end portion 211 of the electrode base 21A by surface treating the tip end portion 211 of the electrode base 21A in advance before forming the conductive layer 22 on the tip end portion 211 of the electrode base 21A. it can.

In addition, although the electrode base 21A is manufactured using a conductive material, when the electrode base 21A is manufactured using an insulating material, as shown in FIG. 8, the electrode base 21A and the conductive layer 22 are manufactured. Preferably, the underlying conductive layer 23 is formed between them. In this case, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the base conductive layer 23 containing a conductive polymer is formed on the surface of the electrode base 21A. As shown in FIG. 12, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the base conductive layer 23 containing a conductive polymer on the surface of the electrode base 21A and the surface of the electrode base 21A is a leg base producing step (step S21A). And a conductive layer forming step (step S23). The conductive layer formation step (step S23) includes a coating step (step S231) and a solidification step (step S232). The conductive layer forming step (step S23) is the same as the conductive layer forming step (step S22A) shown in FIG. 9 described above. The applying step (step S231) and the solidifying step (step S232) are similar to the applying step (step S221) and the solidifying step (step S222) of the conductive layer forming step (step S22A) shown in FIG. 9 described above. is there. Even if the electrode base 21A is formed of an insulating material, the electrode base 21A ensures conduction between the conductive layer 22 and the base conductive layer 23 by forming the base conductive layer 23 on the surface of the electrode base 21A. be able to.

Third Embodiment
<Electrode leg>
An electrode leg according to a third embodiment will be described with reference to the drawings. The electrode leg according to the present embodiment includes the groove (tip groove portion) 24A provided in the tip end portion 211 which is the region A in the electrode base 21A of the electrode leg 20A according to the second embodiment, and the tip portion 211 other than An auxiliary groove (side groove) 25 provided on the side surface 212 of the electrode leg 20B which is a portion is formed.

FIG. 13 is a perspective view showing the appearance of the electrode leg according to the third embodiment, FIG. 14 is a front view of the electrode leg according to the third embodiment, and FIG. It is III sectional drawing. As shown in FIGS. 13 to 15, the electrode leg 20B according to the present embodiment includes an electrode base 21B in place of the electrode base 21A shown in FIGS. The electrode base 21B is provided on the electrode base 21A shown in FIGS. 6 and 7 with a groove (tip groove) 24A provided in the tip end portion 211 which is the region A and a side surface 212 of the electrode leg 20B which is a portion other An auxiliary groove (side groove) 25 to be provided is formed. The conductive layer 22 is formed on the surface of the distal end portion 211, and therefore is also formed on the surface of the distal end groove portion 24A. The electrode leg 20B can hold the liquid in the tip groove 24A and the side groove 25 by providing the tip groove 24A and the side groove 25.

The liquid contained in the tip groove 24A and the side groove 25 may be the same liquid as the liquid contained in the pore 11.

The tip groove portion 24A is formed on the surface of the tip portion 211 of the electrode base 21B. In the present embodiment, the tip groove portion 24A is formed in a cross shape when the tip portion 211 of the electrode leg 20B is viewed from the tip portion 211 in the + Z-axis direction.

As shown in FIG. 16, the cross-sectional shape of the tip groove portion 24A is formed substantially in a U-shape in a cross-sectional view. In addition, the cross-sectional shape of tip groove part 24A may be formed in the substantially V shape in the cross sectional view.

The width W1 (see FIG. 16) of the end groove 24A is preferably 10 μm to 120 μm. If the width W1 of the end groove 24A is in the above range, the liquid can be held in the end groove 24A even after the conductive layer 22 is formed in the end groove 24A. Further, if the conductive layer 22 is formed in the end groove 24A, for example, even if the end portion 211 of the electrode leg 20B is strongly wiped with a Kimwipe containing alcohol, the Kimwipe fibers enter the end groove 24A. Can be reduced. In addition, if the width W1 is within the above range, since the width is smaller than the average thickness of the hair, the penetration of the hair into the tip groove 24A can be reduced. The width W1 of the tip groove 24A is more preferably 20 μm to 70 μm, and still more preferably 30 μm to 50 μm.

In the present embodiment, the width W1 (see FIG. 16) refers to the maximum value (maximum width) of the width from the bottom of the tip groove 24A to the surface side. Even when the cross-sectional shape of the tip groove 24A is formed in a substantially V-shape in a cross-sectional view, the width W1 refers to the maximum width, that is, the value of the width on the surface of the tip 211.

The maximum depth H1 (see FIG. 16) of the tip groove 24A is preferably 10 μm to 500 μm. If the maximum depth H1 of the end groove 24A is within the above range, the end groove 24A can have a predetermined depth even if the conductive layer 22 is formed on the end 211 of the electrode leg 20B. The maximum depth H1 of the tip groove 24A is 20 μm to 300 μm, and more preferably 30 to 150 μm.

As shown in FIGS. 13 to 15, a plurality of side grooves 25 are formed on the surface of the side 212 of the electrode leg 20B, which is a portion other than the tip 211, and communicate with at least a part of the tip groove 24A. There is.

The width W2 (see FIG. 17) of the side surface groove 25 is preferably 10 μm to 120 μm, similarly to the width W1 of the tip groove 24A. If the width W2 of the side groove 25 is 10 μm to 120 μm, the liquid can be held in the side groove 25 even if the conductive layer 22 is formed in the side groove 25 as shown in FIG. Also, if the conductive layer 22 is formed in the side groove 25, for example, even if the side 212 of the electrode leg 20B is strongly wiped with a Kimwipe containing alcohol, the Kimwipe fibers enter into the side groove 25. It can be reduced. In addition, when the width W2 is in the above range, the hair does not exceed the thickness of the hair, so that the penetration of the hair into the side groove 25 can be reduced. The width W2 of the side groove 25 is more preferably 20 μm to 70 μm, and still more preferably 30 to 50 μm. In addition, since the definition of the width W2 of the side surface groove part 25 is the same as the above-mentioned width W1, description is abbreviate | omitted.

The maximum depth H2 (see FIG. 17) of the side groove 25 is preferably 10 μm to 500 μm, as in the case of the tip groove 24A. If the maximum depth H2 of the side groove 25 is within the above range, the tip groove 24A can have a predetermined depth even if the conductive layer 22 is formed on the side 212 of the electrode leg 20B. The maximum depth H2 of the tip groove 24A is more preferably 20 μm to 300 μm, and still more preferably 30 μm to 150 μm.

The electrode leg 20B configured as described above has a plurality of tip grooves 24A on the surface of the tip portion 211 which is the region A, and the conductive layer 22 on the surface of the tip portion 211. When the electrode leg 20B is attached to a biological information measurement electrode and the biological information measurement electrode is repeatedly used for a long time, for example, as shown in FIG. 18, a part of the conductive layer 22 on the surface of the tip end portion 211 is gradually rubbed As a result, part of the conductive layer 22 may be peeled off until the tip end portion 211 is partially exposed. Even in such a case, in the electrode leg 20B, the conductive layer 22 formed on the surface of the tip groove 24A remains. Therefore, since the conduction of the conductive layer 22 can be maintained at the contact portion between the conductive layer 22 formed on the surface of the tip groove 24A and the living body, the conduction between the conductive layer 22 and the living body can be stably maintained. Therefore, according to the electrode leg 20B, since the electrical connection between the tip portion 211 of the electrode base 21B and the living body can be maintained, the electrical signal from the living body can be stably obtained, and the living body information can be stably measured. be able to.

Further, when the electrode leg 20B is immersed in the liquid, the liquid can be held by the capillary phenomenon in the tip groove 24A provided on the surface of the tip portion 211. Therefore, when measuring the biological information, when the tip end portion 211 is brought into contact with the living body, the liquid held in the tip groove portion 24A flows on the surface of the living body 26 in contact with the tip end portion 211 as shown in FIG. spread. By bringing the living body 26 into conduction with the conductive layer 22 via the liquid, the area of conduction from the living body 26 to the conductive layer 22 is increased, so the contact impedance between the living body 26 and the electrode leg 20B can be further lowered. Thereby, the biological information measurement electrode provided with the electrode leg 20B can measure biological information more stably.

Furthermore, the electrode leg 20B has a plurality of side grooves 25 on the side surface of the electrode base 21B, and the side grooves 25 communicate with at least a part of the tip groove 24A. Therefore, at the time of measurement of biological information, the liquid held by the tip groove 24A flows to the surface of the living body in contact with the tip 211, and the liquid held by the tip groove 24A is consumed. At that time, the liquid held in the side groove 25 flows to the tip groove 24A and is supplied to the surface of the living body. Thereby, the contact between the living body and the electrode leg 20B can be maintained while the contact impedance between the living body and the electrode leg 20B is kept low. Therefore, if the electrode leg 20B is used for a biological information measurement electrode, biological information can be measured more stably and continuously.

[Modification of electrode leg according to the third embodiment]
Although an example of electrode leg 20B was shown, it is not limited to this. Below, some modifications of the electrode leg 20B are shown.

In the present embodiment, the front end groove 24A is formed in a cross shape when the front end portion 211 of the electrode base 21B is viewed in the + Z axial direction, but the front end groove 24A holds the liquid in the groove. It is sufficient that the shape can be For example, as shown in FIG. 20, the distal end portion 211 of the electrode base 21B may be provided with a distal end groove portion 24B formed in a mesh shape, or the distal end formed in a dendritic shape as shown in FIG. The groove 24C may be provided. As shown in FIGS. 20 and 21, by providing the distal end groove portion 24B formed in a mesh shape at the distal end portion 211 or the distal end groove portion 24C formed in a dendritic shape, the distal

end groove portions

24B and 24C on the surface of the distal end portion 211 The liquid can be held more efficiently. Therefore, conduction between the conductive layer 22 and the living body can be maintained more stably. Further, when the tip end portion 211 comes in contact with a living body, the tip end portion 211 can stably maintain conduction between the conductive layer 22 on the surface of the tip

end groove portions

24B and 24C and the living body in all directions. Therefore, biological information can be measured more stably even if the tip end portion 211 is moved in any direction along the living body.

In the present embodiment, the side surface groove 25 is formed on the surface of the side surface 212 of the electrode base 21B, but the side surface groove 25 is not formed if the tip groove 24A can sufficiently hold the liquid. May be Thereby, the electrode leg in which the some front end groove part 24A was formed in the front-end | tip part 211 can be manufactured.

<Method of Manufacturing Electrode Leg According to Third Embodiment>
Next, a method of manufacturing the electrode leg 20B according to the third embodiment will be described. FIG. 22 is a flowchart showing a method of manufacturing the electrode leg 20B according to the present embodiment. As shown in FIG. 22, in the method of manufacturing the electrode leg 20B according to the present embodiment, the electrode base having conductivity is formed, and a plurality of tip grooves 24A are formed on the surface of the tip portion 211 which is the region A. A side surface groove portion 25 is formed on the side surface 212, a leg base producing step (step S31A) for producing the electrode base 21B, a surface treatment step for activating the surface of the tip portion 211 of the electrode base 21B (step S32) And a conductive layer forming step (step S33) of forming the conductive layer 22 on the tip end portion 211 of the base 21B. Each step will be described below.

In the leg base producing step (step S31A), the electrode base 21B is formed using a material for forming the electrode base 21B, and a plurality of tip grooves 24A are formed on the surface of the tip end portion 211 which is the region A. The side grooves 25 are formed in the

The electrode base 21B can be formed in the same manner as the forming step (step S21A) in the method of manufacturing the electrode leg 20A according to the second embodiment shown in FIG. When the molding method is used, a mold corresponding to the shape of the electrode base 21B is used. The mold is provided with a protrusion corresponding to the end groove 24A and the side groove 25. By using the mold, the electrode base 21B can be formed, and the tip groove 24A and the side groove 25 can be simultaneously formed.

In the surface treatment step (step S32), the surface of the tip portion 211 is activated using a method of irradiating vacuum ultraviolet light (excimer UV light) by excimer or a method of plasma processing in a mixed gas containing Ar and oxygen. To process. By performing the activation process on the surface of the tip end portion 211, the adhesion between the tip end portion 211 and the conductive layer 22 can be improved in the later-described conductive layer forming step (step S33). Thereby, when physical force is applied by washing | cleaning of the tip part 211, wiping off, etc., it can prevent that the conductive layer 22 peels easily from electrode base 21B (mainly, tip part 211).

In the case of using a method of irradiating excimer UV light, the surface of the tip portion 211 is irradiated with excimer UV light. Excimer UV light is UV light having a wavelength of 240 nm or less in the atmosphere, and has a predetermined wavelength (central wavelength) depending on the type of discharge gas. As the dischargeable gas, Ar ₂ (wavelength 126 nm), Kr ₂ (wavelength 146 nm), ArBr (wavelength 165 nm), Xe ₂ (wavelength 172 nm), KrI (wavelength 191 nm), KrCl (wavelength 222 nm) or the like can be used. . A radiation lamp emitting excimer UV light is, for example, a dielectric barrier discharge lamp sealed with Xe gas. In this case, the dielectric barrier discharge lamp is in an excimer state (Xe ₂ ^* ) in which Xe atoms are excited, and generates light with a wavelength of about 172 nm when it dissociates again into Xe atoms from this excimer state. By irradiating the light of wavelength 172 nm to oxygen, high concentration ozone is generated. By the action of the ozone, the surface of the portion of the electrode substrate 21B to which the excimer UV light is irradiated is modified to have a highly hydrophilic group (for example, a hydroxyl group (OH group), an aldehyde group (CHO group), a carboxyl group As a result, the surface of the tip end portion 211 of the electrode base 21B can be activated, and the surface of the tip end portion 211 can be made hydrophilic. Since the wettability to the water of the surface of the surface can be enhanced, only the tip end portion 211 can be activated easily, so that it can be effectively used when the electrode base 21B is formed of a conductive material. In addition, it is sufficient if at least the surface of the tip end portion 211 can be activated, and the entire electrode base body 21B or the portion other than the tip end portion 211 of the electrode base body 21B may be exposed. It may be irradiated with UV light.

When using a method of plasma treatment in a mixed gas containing Ar and oxygen, the entire surface of the electrode substrate 21B is plasma activated. Thus, the entire surface of the electrode base 21B can be changed to hydrophilicity in addition to the surface of the tip end portion 211. As a result, the wettability to the water of the whole surface of electrode base 21B including tip part 211 can be improved. Therefore, even when the electrode base 21B is formed of either a conductive material or an insulating material, it can be effectively used.

The conductive layer formation step (step S33) includes a coating step (step S331) and a solidification step (step S332). The conductive layer forming step (step S33) is the same as the conductive layer forming step (step S22A) shown in FIG. 9 described above, and the coating step (step S331) and the solidifying step (step S332) are both described above. The same as the coating step (step S221) and the solidifying step (step S222) of the conductive layer forming step (step S22A) shown in FIG. Therefore, in the conductive layer forming step (step S33), the conductive layer 22 is formed on the surface of the tip end portion 211.

As described above, the electrode leg 20B in which the conductive layer 22 is formed on the surface of the tip end portion 211 is obtained.

[Modified Example of Method of Manufacturing Electrode Leg According to Third Embodiment]
In the present embodiment, in the leg base manufacturing step (step S31A), the electrode base 21B is simultaneously formed using a mold provided with a protrusion corresponding to the end groove 24A and the side groove 25. It is not limited. For example, after the electrode base 21B is formed, the tip grooves 24A and the side grooves 25 may be formed simultaneously or separately. When the tip groove 24A and the side groove 25 are formed separately, the method of manufacturing the electrode leg 20B according to the present embodiment is, as shown in FIG. 23, a leg base producing step (step S31B) and a surface treatment step (step S32). And a conductive layer forming step (step S33). The leg base manufacturing step (step S31B) includes a preparation step (step S311) of preparing an electrode base, and a groove forming step (step S312) of forming a plurality of tip grooves 24A and side grooves 25 in the electrode base. In the preparation step (step S311), the electrode substrate is manufactured using a molding method or the like to prepare the electrode substrate. In the groove forming step (step S312), the tip groove 24A and the side groove 25 are formed in the prepared electrode base. Thus, the electrode base, the tip groove 24A and the side groove 25 can be formed separately.

Further, the tip groove 24A and the side groove 25 may be formed separately. In this case, as shown in FIG. 24, in the method of manufacturing the electrode leg 20B according to the present embodiment, the leg base producing step (step S31C), the surface treatment step (step S32), and the conductive layer forming step (step S33) And. The leg base manufacturing step (step S31C) includes a preparation step (step S311) of preparing an electrode base, a tip groove forming step (step S312) of forming a plurality of tip grooves 24A, and a side groove forming of side grooves 25. And (step S313). Thereby, the tip groove 24A and the side groove 25 can be separately formed in the electrode base.

Fourth Embodiment
<Electrode for measuring biological information>
A biological information measurement electrode according to a fourth embodiment will be described. The electrode for measuring biological information according to the present embodiment is for measuring biological information by bringing it into contact with a part of a living body. The biological information measurement electrode according to the present embodiment includes the electrode leg 20A according to the second embodiment.

FIG. 25 is a perspective view showing the appearance of the biological information measurement electrode according to the fourth embodiment, and FIG. 26 is another perspective view showing the appearance of the biological information measurement electrode according to the fourth embodiment. FIG. 27 is a cross-sectional view taken along the line IV-IV of FIG. As shown in FIGS. 25 to 27, the biological information measurement electrode 30A according to the present embodiment has a base portion 31 and a terminal portion 33. As described above, the alternate long and short dash line in FIGS. 25 to 27 is the central axis J of the conductive material 10 (see FIG. 1 etc.), and the central axis J corresponds to the central axis of the biological information measurement electrode 30A. It means an axis that is the center when the biological information measurement electrode 30A is installed on a living body.

The base portion 31 and the terminal portion 33 can be formed using a conductive elastomer or an insulating material used for forming the electrode base 21A of the electrode leg 20A according to the second embodiment described above. The base portion 31 and the terminal portion 33 may be formed of the same material, or may be formed of different materials. In the present embodiment, the base portion 31 and the terminal portion 33 are integrally formed of the same conductive elastomer. Therefore, the terminal portion 33 is conducted from the tip end portion 312a (described later) side of the electrode leg 20A.

When the base portion 31 and the terminal portion 33 are formed using a conductive elastomer, the conductive elastomer can be obtained, for example, by melt mixing the conductive filler and the nonconductive elastomer. The base portion 31 and the terminal portion 33 have a low elastic modulus by being molded including a nonconductive elastomer having rubber elasticity. Therefore, at the time of use of the electrode 30A for measuring biological information, the base 31 and the terminal 33 are easily deformed according to the uneven shape of the surface of the living body, so that the contact to the living body can be ensured and the pressing force to the living body is It can be relaxed.

[Substrate]
The base portion 31 has a base portion 311 and a plurality of electrode legs 312A.

The base 311 is provided on the other side of the electrode leg 312A. The base 311 is formed in a substantially circular shape in a plan view (when viewed from the + Z axis direction). The base 311 has a projecting portion 311 a on the back surface (in the −Z axis direction) of the base 311. Plural (eight in FIG. 25 to FIG. 27) protruding portions 311 a are annularly provided on the back surface of the base portion 311. An electrode leg 312A is integrally formed at an end of the protruding portion 311a. The number of projecting portions 311a is designed to match the number of electrode legs 312A.

The electrode leg 312A is extended from the projecting portion 311a of the base portion 311 in the −Z axis direction. As the electrode leg 312A, the electrode leg 20A according to the above-described second embodiment is used. The electrode leg 312A is separable from the base 311.

[Terminal]
The terminal portion 33 is an upper surface of the base portion 311 of the base portion 31 and protrudes in the + Z-axis direction from a substantially central portion of the base portion 311 (a position through which the central axis J passes) in plan view, as shown in FIGS. Is provided. A metal layer 35 is provided at the central portion of the terminal portion 33. As the metal layer 35, a metal such as gold, silver or copper is used. Wirings 42 (see FIG. 28) of an inspection device 40 (see FIG. 28) described later are connected to the portions where the metal layer 35 is provided. The terminal portion 33 is electrically connected to the base portion 31 on which the electrode leg 312A is integrally formed. Therefore, the terminal portion 33 is electrically connected to the tip end portion 312a which is the region A of the electrode leg 312A, and the information signal from the region A can be extracted. In the middle portion of the terminal portion 33, a layer formed of a conductive material other than metal may be provided.

The terminal unit 33 is connected to the measurement unit 43 (see FIG. 28). Specifically, the terminal portion 33 is connected to a wire 42 (see FIG. 28) or the like, and the wire 42 (see FIG. 28) and the measurement unit 43 (see FIG. 28) are connected. The terminal unit 33 transmits an electrical signal from a living body (for example, scalp or forehead) obtained from the tip end portion 211 of the electrode leg 312A through the base portion 31 to the measurement unit 43 (see FIG. 28). , As an electroencephalogram).

Next, an example of measuring an electroencephalogram as biological information of a subject using the inspection apparatus provided with the biological information measurement electrode 30A according to the present embodiment will be described. FIG. 28 is a view showing an example of measuring an electroencephalogram of a subject using an inspection apparatus provided with a biological information measurement electrode 30A. As shown in FIG. 28, the inspection apparatus 40 includes a biological information measurement electrode 30A, a cap 41 that covers the head of the subject, a wire 42, a measurement unit 43, and a display unit 44. The cap 41 has a hat or helmet shape so as to cover the subject's head, and is formed of synthetic resin, cloth or the like. The biological information measurement electrodes 30A are provided at a plurality of locations (for example, 21 locations) on the cap 41 at predetermined intervals, and are attached to an arbitrary location of the subject's scalp 45. The wire 42 is, for example, a lead wire, and one end thereof is connected to the terminal portion 33 and the other end is connected to the measurement portion 43. The measurement unit 43 includes a power supply unit 431 and a signal analysis unit 432 that analyzes an electrical signal and measures an electroencephalogram as biological information. The display unit 44 is a monitor and displays the electroencephalogram analyzed by the signal analysis unit 432. The brain waves are classified into, for example, α wave (8 to 13 Hz), β wave (14 to 30 Hz), θ wave (4 to 7 Hz), and δ wave (0.5 to 3 Hz) according to the frequency.

The biological information measuring electrode 30A is fixed to the cap 41, and the tip end portion 211 of the electrode leg 312A is brought into contact with the scalp 45 via the conductive layer 22. When the power supply unit 431 is turned on and measurement is started, an electrical signal from the scalp 45 is transmitted from the scalp 45 through the conductive layer 22 to the tip portion 312a of the electrode leg 312A. The transmitted electric signal is transmitted from the tip end portion 312 a through the base portion 31 in the order of the terminal portion 33, the wiring 42, and the measurement portion 43. The signal analysis unit 432 analyzes the transmitted electric signal, and displays an electroencephalogram (for example, an α wave, a β wave, a θ wave, etc.) 441 on the display unit 44.

The biological information measurement electrode 30A configured as described above has the conductive layer 22 on the surface of the tip end portion 312a which is the region A of the electrode leg 312A. The conductive layer 22 is formed of the conductive material 10 (see FIGS. 1 and 2) according to the first embodiment. Therefore, the conductive layer 22 can include a solution in the pores 221 (see FIG. 6). The conductive layer 22 can be provided on the surface of the tip end portion 312a of the electrode leg 312A of the biological information measurement electrode 30A. When the conductive layer 22 contacts the surface of the living body, the solution held in the pores 221 (see FIGS. 6 and 7) of the conductive layer 22 flows and spreads on the surface of the living body in contact with the conductive layer 22. Then, the conduction impedance between the living body and the conductive layer 22 can be lowered by bringing the conductive layer 22 and the surface of the living body into conduction through the solution, so that an electrical signal from the living body can be easily obtained. Therefore, since the biological information measurement electrode 30A can maintain electrical connection with the living body, biological information can be easily and stably measured.

In addition, the conductive layer 22 has high wear resistance. Therefore, even if the conductive layer 22 on the surface of the tip end portion 211 is rubbed by repeatedly using the biological information measurement electrode 30A, the conductive layer 22 on the surface of the tip end portion 312a can be suppressed from being scraped. Thus, the conductive layer 22 on the surface of the tip end portion 312a can stably contact the living body at the contact portion with the living body, so that the conduction between the conductive layer 22 and the living body can be stably maintained. Therefore, according to the biological information measuring electrode 30A, since the electrical connection between the tip end portion 312a of the electrode leg 312A and the living body can be maintained, an electrical signal from the living body can be stably obtained, and the biological information is stabilized. Can be measured.

Since the electrode leg 312A is separable from the base 311, the electrode leg 312A attached with the conductive layer 22 can be easily replaced. Thereby, even if the measurement becomes unstable due to wear or the like, the conductive layer 22 of the tip end portion 312a of the electrode leg 312A can be replaced with the electrode leg 312A which can obtain the measurement of the biological information normally.

[Modified Example of Electrode for Measuring Biological Information According to Fourth Embodiment]
Although an example of the biological information measurement electrode 30A is shown, the present invention is not limited to this. Below, the modification of the electrode 30A for biometric information measurement is demonstrated.

In the present embodiment, the base portion 31 and the terminal portion 33 are integrally formed, but the base portion 31 and the terminal portion 33 may be configured by separate members. An example of the biological information measuring electrode 30A when the base portion 31 and the terminal portion 33 are constituted by separate members is shown in FIG. 29 and FIG. FIG. 29 is a perspective view showing an example of another configuration of the biological information measurement electrode 30A, and FIG. 30 is a cross-sectional view taken along the line VV of FIG. As shown in FIGS. 29 and 30, the terminal portion 33 has a disk-shaped base portion 331 and a convex portion 332 protruding from the central portion of the base portion 331. The terminal portion 33 is formed of a conductive material such as a metal material. The terminal portion 33 is fixed and connected to the end portion 311b opposite to the side where the base portion 311 of the base portion 31 is continuous with the electrode leg 312A, for example, with a conductive adhesive or conductive paste (not shown). It is done. Thus, the terminal portion 33 is electrically connected to the base portion 31 integrally formed with the electrode leg 312A. Accordingly, the tip end portion 312 a of the electrode leg 312 A is electrically connected to the terminal portion 33 via the base portion 311 of the base portion 31.

In the present embodiment, the base portion 311 has the projecting portion 311a on the back surface side (−Z axis direction side), but the projecting portion 311a is not provided, and the electrode leg 312A is continuously formed on the base portion 311 of the disc portion It may be done.

In the present embodiment, the base portion 31 integrally forms the base portion 311 and the electrode leg 312A, but the base portion 311 and the electrode leg 312A may be configured by separate members. At this time, the base 311 and the electrode leg 312A are bound by a binding member made of a synthetic resin. The binding member is one obtained by curing a synthetic resin such as an epoxy resin or a urethane resin. In addition to the synthetic resin, the binding member may be an elastic synthetic resin such as rubber.

The conductive layer 22 is formed on the tip end portion 312a of the electrode leg 312A which is the region A, but it may be formed on at least the tip end portion 211 and may be formed on other portions of the base portion 31 Alternatively, it may be formed on the entire surface of the base portion 31 and the terminal portion 33. For example, when the base portion 31 and the terminal portion 33 are formed of an insulating material, the base portion 31 and the terminal portion 33 are formed on the entire surface of the base portion 31 and the terminal portion 33.

In this case, as shown in FIG. 31, it is preferable to form a base conductive layer 51 electrically connected to the conductive layer 22 on the entire surface of the base portion 31 and the terminal portion 33. Thereby, conduction between the tip end portion 211 and the terminal portion 33 can be achieved. As the conductive polymer contained in the base conductive layer 51, the same conductive polymer as the conductive layer 22 can be used. Since the same conductive polymer as the conductive layer 22 is used as the conductive polymer, the description of the conductive polymer is omitted. The thickness of the base conductive layer 51 may be any as long as conduction can be obtained, and may be, for example, about 200 nm to 1 μm.

<Manufacturing Method of Biological Information Measuring Electrode According to Fourth Embodiment>
Next, a method of manufacturing the biological information measuring electrode according to the fourth embodiment will be described. FIG. 32 is a flowchart showing a method of manufacturing the biological information measuring electrode according to the present embodiment. As shown in FIG. 32, in the method of manufacturing the biological information measuring electrode according to this embodiment, a forming step (step S41A) of forming the base portion 31 and the terminal portion 33, and activation processing of the surface of the tip portion 312a. It includes a surface treatment step (step S42) and a conductive layer forming step (step S43A) of forming conductive layer 22 on the surface of tip portion 312a. Each step will be described below.

In the molding step (step S41A), the base portion 31 and the terminal portion 33 are integrally molded using a material for forming the base portion 31 and the terminal portion 33. The forming step is also referred to as a leg base producing step.

The base portion 31 and the terminal portion 33 are formed of the base portion 31 and the terminal portion 33 having desired shapes by a known molding method such as compression molding (compression molding), injection molding (injection molding), or extrusion molding (transfer molding). It can be molded. When these molding methods are used, a mold corresponding to the shapes of the base portion 31 and the terminal portion 33 is used. By using the mold, the base portion 31 and the terminal portion 33 can be simultaneously formed.

In the case of using an injection molding method or the like, a raw material supply passage (e.g., a spool, a runner, etc.) to which a raw material (resin or metal) for molding the base portion 31 and the terminal portion 33 is supplied after injection molding is the base portion 31 or terminal It is connected to the part 33. For example, as shown in FIG. 33, in the case where the raw material supply passage 52 is connected to the terminal portion 33, at least a part of the raw material supply passage 52 is also used for the terminal portion 33 It is preferable to connect to When immersing at least a part of the base portion 31 and the terminal portion 33 in a solution containing a conductive polymer in the conductive layer forming step (step S13) described later, the raw material supply passage 52 serves as a grip of the base portion 31. It can be used as The raw material supply passage 52 is determined at which position of the product to perform suitable molding, and may be connected to the base 311 or the like of the base 31 other than the terminal 33 shown in FIG. .

The surface treatment step (step S42) can be performed in the same manner as the surface treatment step (step S32) of the method of manufacturing the electrode leg according to the above-described third embodiment shown in FIG.

The conductive layer forming step (step S43A) can be performed in the same manner as the conductive layer forming step (step S22A) of the method of manufacturing the electrode leg according to the above-described second embodiment shown in FIG.

In the conductive layer forming step (step S43A), the conductive layers 22 are formed on the surface of the tip portion 312a in a state in which the fibers are bound with the conductive polymer and the thermosetting resin, and have many pores. Do. The conductive layer formation step (step S43) includes a coating step (step S431) and a solidification step (step S432).

In the coating step (step S431), a mixed solution containing a fiber and a conductive polymer is coated on at least the tip portion 312a to form a coated layer. As a method of applying the mixed solution to at least the tip portion 211, an immersion method of immersing at least the tip portion 312a in the mixed solution, a spray method of spraying the mixed solution to at least the tip portion 312a, or the like can be used.

In the solidification step (step S432), the coating layer formed on the tip portion 312a is dried by heating at 120 to 130 ° C., for example, to cure the coating layer. Thereby, the conductive layer 22 is formed on the surfaces of the tip end portion 312a and the tip end groove portion 24A. In the present embodiment, since the base portion 31 and the terminal portion 33 are formed of a conductive elastomer, the conductive layer 22 may be formed on the surface of the tip portion 312a.

As described above, the biological information measurement electrode 30A in which the conductive layer 22 is formed on the surface of the tip end portion 312a is obtained.

In the present embodiment, in the coating step (step S431) of the conductive layer forming step (step S43), the film thickness of the coating layer formed when the mixed solution is applied once to the tip end portion 211 is only the conductive polymer. It can be thicker than the film thickness of the coating layer formed when the solution containing it is applied once. Therefore, the cost required to produce a coating layer by a coating process (step S131) can be reduced. In addition, since the conductive layer 22 is thicker, the life of the conductive layer 22 can be further extended.

When the fibers contained in the conductive layer 22 are cellulose nanofibers, a mixed solution containing cellulose nanofibers and a conductive polymer has good wettability to the base portion 31 and the terminal portion 33 and has high thixotropy. Therefore, when the conductive layer 22 is formed using a mixed solution containing cellulose nanofibers and a conductive polymer, the film thickness of the coated layer formed in one application of the mixed solution contains cellulose nanofibers. The thickness can be, for example, about 1.3 to 4 times greater than the thickness of the coating layer formed by applying the solution without the solution.

[Modified Example of Method of Manufacturing Biological Information Measurement Electrode According to Fourth Embodiment]
In the present embodiment, in the molding step (step S41A), the base portion 31 and the terminal portion 33 are simultaneously formed integrally, but the present invention is not limited to this. For example, the base portion 31 and the terminal portion 33 may be separately molded and integrated. In this case, as shown in FIG. 34, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the forming step (step S41B), the surface treatment step (step S42), and the conductive layer forming step (step S43A) And. In the forming step (step S41B), a leg base forming step (step S411) for forming the base portion 31 and the terminal portion 33, and a binding step (step S412) for bonding and integrating the base portion 31 and the terminal portion 33. And. A known binding member can be used as a binding member used to bind the base portion 31 and the terminal portion 33 in the binding step (step S412). For example, synthetic resin such as epoxy resin or urethane resin, or synthetic resin having elasticity such as rubber can be used.

In the present embodiment, since the base portion 31 and the terminal portion 33 are formed of a conductive elastomer, the conductive layer 22 may be formed at least on the surface of the tip portion 312a. However, when the base portion 31 and the terminal portion 33 are formed of an insulating material, the conductive layer 22 is formed on the entire surface of the base portion 31 and the terminal portion 33. Thereby, the electrical signal obtained from the living body is transmitted from the tip end portion 312a of the electrode leg 312A to the terminal portion 33 through the conductive layer 22.

When base portion 31 and terminal portion 33 are formed of an insulating material, as shown in FIG. 31, base conductive layer 51 may be formed between base portion 31 and terminal portion 33 and conductive layer 22. preferable. In this case, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the base conductive layer 51 containing a conductive polymer is formed on the surfaces of the base portion 31 and the terminal portion 33. As shown in FIG. 35, in the method of manufacturing the biological information measuring electrode according to this embodiment, the forming step (step S41A), the surface treatment step (step S42), and the surfaces of the base portion 31 and the terminal portion 33 A base conductive layer forming step (step S43B) of forming base conductive layer 51 containing a conductive polymer, and a conductive layer forming step (step S44) are included.

In the base conductive layer forming step (step S43B), a solution containing a conductive polymer is applied to the surfaces of the base portion 31 and the terminal portion 33 to form a coating layer. The method for forming the base conductive layer 51 can be performed in the same manner as the conductive layer forming step (step S22C) of FIG. 12 described above.

The conductive layer forming step (step S44) includes a coating step (step S441) and a solidification step (step S442). The conductive layer formation step (step S44) is the same as the conductive layer formation step (step S43A) shown in FIG. 34 described above, and the application step (step S441) and the solidification step (step S442) are both described above. The same steps as the coating step (step S431) and the solidifying step (step S432) of the conductive layer forming step (step S43A) shown in FIG.

In the present embodiment, the conductive layer 22 is formed by freeze-drying the coating layer applied to the tip end portion 211 of the electrode substrate 21A in the conductive layer forming step (step S43A), but the present invention is not limited thereto. For example, the electrode leg 312A prepared in advance may be attached to the projecting portion 311a of the base 311. An example of a method of manufacturing the biological information measuring electrode in this case is shown in FIG. FIG. 36 is another flowchart showing the method of manufacturing the biological information measuring electrode according to the present embodiment. As shown in FIG. 36, in the method of manufacturing a biological information measuring electrode according to this embodiment, an electrode main body manufacturing step (step S51) of manufacturing an electrode main body including a base portion 311 of a base portion 31 and a terminal portion 33 Connecting the electrode leg 312A to the base 311 (step S52).

In the electrode main body manufacturing step (step S51), the base 311 of the base portion 31 and the terminal portion 33 are formed using the same method as in the case of molding the base portion 31 and the terminal portion 33 in the molding step (step S41A). By integrally molding, the electrode body can be produced. Further, after the base portion 311 of the base portion 31 and the terminal portion 33 are separately formed, the end portion 311 b (see FIG. 30) of the base portion 311 and the terminal portion 33 are made of, for example, a conductive adhesive or The electrode body may be manufactured by connection using a conductive paste or the like.

In the connection step (step S52), an electrode leg 312A in which the conductive layer 22 is formed on the tip end portion 312a of the electrode base is manufactured in advance. The electrode leg 312A can use the electrode leg 20A according to the second embodiment described above. By connecting the electrode leg 312A to the protruding portion 311a of the base 311, the biological information measurement electrode 30A can be obtained.

Fifth Embodiment
<Electrode for measuring biological information>
An electrode for measuring biological information according to a fifth embodiment will be described with reference to the drawings. The biological information measurement electrode according to the present embodiment is the fourth embodiment shown in FIGS. 13 to 15 as the electrode leg 312A of the base portion 31 of the biological information measurement electrode 30A according to the fourth embodiment shown in FIGS. The electrode leg 20B according to the third embodiment is used.

FIG. 37 is a perspective view showing the appearance of the biological information measurement electrode according to the fifth embodiment, and FIGS. 38 and 39 are other views showing the appearance of the biological information measurement electrode according to the fifth embodiment. FIG. 40 is a perspective view, and FIG. 40 is a cross-sectional view taken along the line VI-VI of FIG. As shown in FIGS. 37 to 40, the biological information measurement electrode 30B according to this embodiment is the same as the one shown in FIGS. 25 to 27, except for the electrode leg 312A of the base 31 of the biological information measurement electrode 30A. An electrode leg 312B according to a third embodiment shown in FIG. 15 is provided. That is, the biological information measurement electrode 30B has an electrode leg 312B having a tip groove 24A at the tip end 312a and a side groove 25 on the side surface 312b.

An example in the case of measuring a brain wave of a subject using an inspection apparatus 40 (see FIG. 28) provided with a biological information measurement electrode 30B according to the present embodiment will be described. In the present embodiment, the biological information measurement electrode 30B immerses at least the tip portion 312a of the electrode leg 312B in the liquid in the container so that the tip groove 24A of the conductive layer 22 and the side groove 25 contain the liquid. By pulling up the electrode leg 312B from the immersion state in the liquid, fixing the biological information measurement electrode 30B to the cap 41 (see FIG. 28) in a state where the liquid is contained in the tip groove 24A and the side groove 25. As shown in FIG. 41, the tip end 312a of the electrode leg 312B is brought into contact with the scalp 45 via the conductive layer 22. At the time of measurement, an electrical signal from the scalp 45 is transmitted from the scalp 45 through the conductive layer 22 to the tip end 312a of the electrode leg 312B. The transmitted electric signal is transmitted from the tip end portion 312a through the base portion 31 in the order of the terminal portion 33, the wiring 42 (see FIG. 28), and the measurement portion 43 (see FIG. 28). The signal analysis unit 432 (see FIG. 28) analyzes the transmitted electric signal, and an electroencephalogram (eg, α wave, β wave, θ wave, etc.) 441 (see FIG. 28) on the display unit 44 (see FIG. 28). Display

Thus, the biological information measurement electrode 30B according to the present embodiment has a plurality of tip grooves 24A on the surface of the tip portion 312a which is the region A, and the conductive layer 22 on the surface of the tip portion 312a. Therefore, as described in the electrode leg 20A according to the second embodiment described above, by repeatedly using the biological information measurement electrode 30B, for example, as shown in FIG. 18, the conductive layer provided on the tip end portion 312a A part of 22 may be worn away gradually and may be scraped off until the tip 312a is partially exposed. Even in such a case, the biological information measurement electrode 30B can maintain the conduction with the living body at the contact portion between the conductive layer 22 formed on the surface of the tip groove 24A and the living body (for example, scalp and forehead) Therefore, the conduction between the conductive layer 22 and the living body can be stably maintained. Therefore, according to the biological information measurement electrode 30B, since the electrical connection between the tip end portion 312a of the electrode leg 312B and the living body can be maintained, an electrical signal from the living body can be stably obtained. EEG can be measured stably.

Further, as described in the electrode leg 20B according to the third embodiment described above, when the biological information measurement electrode 30B is immersed in the liquid, the capillary tube is formed in the tip groove 24A provided on the surface of the tip portion 312a which is the region A. The phenomenon can hold the liquid. Therefore, for example, when measuring the electroencephalogram, when the tip end portion 312a is brought into contact with the scalp, the liquid held in the tip groove portion 24A flows on the surface of the scalp in contact with the tip end portion 211 as shown in FIG. Spread on the scalp. As a result, the area of conduction from the scalp to the conductive layer 22 is increased, and the contact impedance between the scalp and the biological information measurement electrode 30B can be further lowered. Thereby, the electroencephalogram can be measured more stably.

Furthermore, as described in the electrode leg 20B according to the third embodiment described above, the biological information measurement electrode 30B has a plurality of side groove portions 25 on the side surface of the electrode leg 20B, and the side groove portion 25 is a tip groove portion In communication with at least a portion of 24A. Therefore, at the time of measuring an electroencephalogram, the liquid held in the tip groove 24A flows to the surface of the scalp in contact with the tip 211, and the liquid held in the tip groove 24A is consumed. At this time, the liquid held in the side groove 25 flows to the tip groove 24A and is supplied to the scalp. Thereby, the contact between the scalp and the biological information measuring electrode 30B can be maintained while the contact impedance between the scalp and the biological information measuring electrode 30B is kept low, so that the biological information can be continued more stably. Can be measured.

[Modification of electrode for measuring biological information according to the fifth embodiment]
Although an example of the biological information measurement electrode 30B is shown, the present invention is not limited to this. Below, the modification of the electrode 30B for biological information measurement is demonstrated.

In the present embodiment, the tip groove portion 24A is formed in a cross shape when the tip portion 312a of the electrode leg 312B is viewed in the + Z axis direction, but with the electrode leg 20B according to the third embodiment described above Similarly, the end groove 24A may have a shape that can hold the liquid in the groove. For example, as shown in FIG. 20, when the tip end portion 312a of the electrode leg 312B is viewed in the + Z axial direction, the tip end portion 312a may be provided with a tip end groove portion 24B formed in a mesh shape. As shown in FIG. 21, a distal end groove 24C formed in a dendritic shape may be provided. As shown in FIGS. 20 and 21, by providing the distal end groove portion 24B formed in a mesh shape at the distal end portion 312a or the distal end groove portion 24C formed in a dendritic shape, the distal

end groove portions

24B and 24C on the surface of the distal end portion 312a. The liquid can be held more efficiently. Therefore, the conduction between the conductive layer 60 and the scalp can be maintained more stably. In addition, when the tip end portion 312a contacts the scalp, the tip end portion 312a can stably maintain conduction between the conductive layer 60 on the surface of the tip

end groove portions

24B and 24C and the scalp in any direction. Therefore, biological information can be measured more stably even if the tip end portion 312a is moved in any direction along the scalp.

In the present embodiment, the side surface groove 25 is formed on the surface of the side surface 312b of the electrode leg 312B, but as in the electrode leg 20B according to the third embodiment described above, water is sufficiently retained by the tip groove 24A. The side groove 25 may not be formed, for example.

<Manufacturing method of biological information measuring electrode according to the fifth embodiment>
Next, a method of manufacturing the biological information measuring electrode according to the fifth embodiment will be described. FIG. 42 is a flowchart showing a method of manufacturing the biological information measuring electrode according to the present embodiment. As shown in FIG. 42, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the base portion 31 and the terminal portion 33 are formed, and a plurality of tip grooves 24A are formed on the surface of the tip portion 312a which is the region A. A forming step (step S61A) for forming the side groove portion 25 in the side surface 312b, a surface treatment step (step S62) for activating the surface of the tip end portion 211, and a conductive layer 22 on the surface of the tip end portion 211 And a conductive layer forming step (step S63) to be formed. Each step will be described below.

The forming step (step S61A) is the same as the forming step (step S41A) of the method for manufacturing the biological information measuring electrode according to the fourth embodiment described above shown in FIG. To mold. Further, in the same manner as the leg base manufacturing process (step S31A) of the method of manufacturing the electrode leg according to the above-described third embodiment shown in FIG. The side groove portion 25 can be formed on the side surface 312 b.

The surface treatment step (step S62) can be performed in the same manner as the surface treatment step (step S32) of the method of manufacturing the electrode for measuring the electrode leg biological information according to the above-described third embodiment shown in FIG.

The conductive layer forming step (step S63) can be performed in the same manner as the conductive layer forming step (step S43A) of the method of manufacturing the biological information measuring electrode according to the above-described fourth embodiment shown in FIG.

The conductive layer formation step (step S63) includes a coating step (step S631) and a solidification step (step S632). The conductive layer forming step (step S63) is the same as the conductive layer forming step (step S43A) shown in FIG. 32 described above. The applying step (step S631) and the solidifying step (step S632) are the same as the applying step (step S431) and the solidifying step (step S432) of the conductive layer forming step (step S43A) shown in FIG. It can be carried out.

Therefore, according to the method of manufacturing the biological information measuring electrode according to the present embodiment, the living body provided with the electrode leg 312B in which the tip groove portion 24A is formed on the surface of the tip portion 312a and the side groove portion 25 is formed on the side surface 312b. An information measurement electrode 30B can be obtained.

[Modified Example of Method of Manufacturing Electrode Leg According to Fifth Embodiment]
In the present embodiment, in the molding step (step S61A), the tip groove 24A and the side groove 25 are simultaneously formed in the base portion 31 using a mold provided with a protrusion corresponding to the tip groove 24A and the side groove 25. But it is not limited to this. For example, after the base portion 31 and the terminal portion 33 are formed, the tip groove 24A and the side groove 25 may be formed simultaneously or separately.

When the front end groove 24A and the side groove 25 are formed separately, as shown in FIG. 43, the method of manufacturing the biological information measuring electrode according to this embodiment includes a forming step (step S61B) and a surface treatment step (step S62). And a conductive layer forming step (step S63). In the forming step (step S61B), a preparation step (step S611) of preparing the base portion 31 and the terminal portion 33, a tip groove portion forming step (step S612) of forming the tip groove portion 24A in the tip portion 312a of the electrode leg, And a side surface groove forming step (step S613) of forming the side surface groove 25 on the side surface of the base.

The forming step (step S61B) can be performed in the same manner as the leg base producing step (step S31C) of the method of manufacturing the electrode leg shown in FIG. The preparation step (step S611), the tip groove formation step (step S612), and the side groove formation step (step S613) are all the preparation steps (step S31C) of the leg base production step (step S31C) shown in FIG. It can carry out similarly to S311), a tip slot formation process (Step S312), and a side slot formation process (Step S313).

In the conductive layer forming step (step S63), the conductive layer 22 is formed only at the tip end portion 312a of the electrode leg, but the conductive layer 22 may be formed at least at the tip end portion 312a. Alternatively, it may be formed on a portion other than the tip end portion 312 a of the base portion 31 or on the entire base portion 31 and the terminal portion 33.

As described above, the conductive material 10, the

electrode legs

20A and 20B, and the biological

information measurement electrodes

30A and 30B according to the first to fifth embodiments maintain the electrical connection with the living body and are obtained from the living body. Biological information can be stably measured. Therefore, these can be used suitably for what makes various skin information, such as an electroencephalogram, a pulse wave, an electrocardiogram, an electromyography, a body fat, contact the skin, and measures it. In addition, the living body includes a human body or a living body other than the human body, etc., but the conductive material 10, the

electrode legs

20A and 20B, and the biological

information measuring electrodes

30A and 30B according to the above embodiments are all for the human body. It can be particularly suitably used as

Sixth Embodiment
<Electrode for measuring biological information>
A biological information measurement electrode according to a sixth embodiment will be described. The biological information measuring electrode according to the present embodiment is formed by using the conductive layer 22 of the biological information measuring electrode 30A according to the fourth embodiment shown in FIGS. 25 to 27 in a matrix of a synthetic resin containing a conductive polymer. The fiber is changed to the conductive layer contained in a dispersed manner.

FIG. 44 is a perspective view showing the appearance of the biological information measurement electrode according to the sixth embodiment, and FIG. 44 is another perspective view showing the appearance of the biological information measurement electrode according to the sixth embodiment FIG. 45 is a cross-sectional view taken along the line VII-VII of FIG.

As shown in FIGS. 44 to 46, the biological information measurement electrode 30C according to the present embodiment is provided on the base portion 31 having the base 311 and the plurality of electrode legs 312A, and on the upper side (+ Z axis direction) of the base 311. And a conductive layer 60 provided on the surface of the electrode leg 312A. The biological information measurement electrode 30C according to the present embodiment is the same as the above except that the configuration of the conductive layer 22A formed on the tip portion 312a of the biological information measurement electrode 30A according to the fourth embodiment is changed. The configuration is the same as the biological information measurement electrode 30A according to the fourth embodiment, so only the configuration of the conductive layer 60 will be described.

[Conductive layer]
The conductive layer 60 is provided on the surface of the tip end portion 312a of the electrode leg 312A. In the present embodiment, since the base portion 31 and the terminal portion 33 are integrally formed using a conductive elastomer, the conduction between the base portion 31 and the terminal portion 33 is secured. Therefore, the conductive layer 60 is formed only on the surface of the tip end portion 312a. When base portion 31 and terminal portion 33 are formed of an insulating material, conductive layer 60 ensures the conduction between base portion 31 and terminal portion 33, so that the entire surface of base portion 31 and terminal portion 33 is secured. Provided in

The conductive layer 60 is contained in a state in which fibers are dispersed in a matrix of a synthetic resin containing a conductive polymer. By dispersing the fibers in the synthetic resin matrix, the strength of the conductive layer 60 can be enhanced, and the thickness (layer thickness) of the conductive layer 60 can be increased.

As a matrix of synthetic resin, although it is also possible to form only with a conductive polymer, it is possible to mix and form other synthetic resins as appropriate. As the other synthetic resin, a resin similar to the binder contained in the conductive material 10 of the first embodiment can be used. Therefore, the details of the synthetic resin are omitted.

The average thickness of the conductive layer 60 is preferably 1 to 30 μm, as in the case of the conductive material 10 of the first embodiment. The details of the average thickness of the conductive layer 60 are the same as those of the conductive material 10 according to the first embodiment described above, and thus the details will be omitted.

As the conductive polymer, a conductive polymer similar to the conductive polymer of the binder contained in the conductive material 10 of the first embodiment can be used. Therefore, the details of the type of conductive polymer are omitted.

As the fiber, a fiber similar to the fiber included in the conductive material 10 of the first embodiment can be used. Therefore, the details of the type of fiber are omitted.

The mixing ratio of the conductive polymer to the fiber varies depending on the type of fiber used, but is preferably in the range of 2: 8 to 8: 2. Within this range, the conductive layer 60 can maintain conductivity while reducing the amount of conductive polymer used, and can maintain the layer strength of the conductive layer 40.

The definition of the fiber is as described in the first embodiment. Therefore, the description of the definition of the fiber is omitted.

The fiber is preferably a nanofiber. The strength of the conductive layer 60 is higher because nanofibers can be dispersed more finely and uniformly in a matrix of a synthetic resin containing a conductive polymer than fibers.

In addition, the definition of a nanofiber is as having demonstrated in said 1st Embodiment. Therefore, the description of the definition of nanofibers is omitted.

The aspect ratio of the nanofibers is preferably 1: 100 to 1: 1000, more preferably 1: 100 to 1: 300, as described in the first embodiment above. If the aspect ratio of the nanofibers is in the range of 1: 100 to 1: 1000, dispersion failure in the coated layer can be suppressed. As a result, since the nanofibers are uniformly present in the conductive layer 60, the strength of the conductive layer 60 can be increased.

As the nanofibers, the same nanofibers as the nanofibers included in the conductive material 10 of the first embodiment can be used. Therefore, the details of the nanofibers are omitted.

When using cellulose nanofibers as the nanofibers, the mixing ratio of the conductive polymer to the cellulose nanofibers is preferably in the range of 2: 8 to 7: 3 and in the range of 3: 7 to 6: 4. It is more preferable that Within this range, the conductive layer 60 can maintain conductivity and can reduce the amount of conductive polymer used. When the conductive polymer is PEDOT / PSS, the cost of cellulose nanofibers is 1/10 or less of the cost of PEDOT / PSS, so the ratio of PEDOT / PSS used in the unit thickness of the conductive layer 60 is It is lowered.

When measuring the brain waves of the subject using the biological information measurement electrode 30C, as described with reference to FIG. 28 in the fourth embodiment described above, the inspection apparatus 40 including the biological information measurement electrode 30C (FIG. 28) The subject's EEG can be measured by using the reference).

The biological information measurement electrode 30C configured as described above has the conductive layer 60 on the surface of the tip portion 312a which is the region A. The conductive layer 60 contains fibers dispersed in a matrix of a synthetic resin containing a conductive polymer. Since the conductive layer 60 can have high strength by containing a fiber, the wear resistance can be improved. Therefore, even if the conductive layer 60 on the surface of the tip end portion 312a is rubbed by repeatedly using the biological information measurement electrode 30C, it is possible to suppress scraping of the conductive layer 60 on the surface of the tip end portion 312a. Thus, the conductive layer 60 on the surface of the tip end portion 312a can stably contact the living body at the contact portion with the living body, so that the conduction between the conductive layer 60 and the scalp can be stably maintained. Therefore, according to the biological information measurement electrode 30A, as in the biological information measurement electrode 30A according to the fourth embodiment described above, the electrical connection between the tip end portion 312a of the electrode leg 312A and the scalp can be maintained. It is possible to stably obtain an electrical signal from the above, and to stably measure an electroencephalogram as biological information.

The biological information measurement electrode 30C has the conductive layer 60 on the surface of the tip end portion 312a, so that the tip end portion 312a is in direct contact with the scalp as in the biological information measurement electrode 30A according to the fourth embodiment described above. The contact impedance between the scalp and the biological information measurement electrode 30C can be lowered more than in the case where it is present.

In addition, when a solution containing water is attached to the surface of the conductive layer 60, the contact impedance with the living body can be further lowered, so that the electrical signal from the scalp can be easily obtained. Therefore, the electroencephalogram can be measured more stably.

The biological information measuring electrode 30C includes a fiber in the conductive layer 60, so that it has a unit as compared with a conductive layer made of only a conductive polymer, like the conductive material 10 according to the first embodiment described above. Since the amount of conductive polymer per thickness can be reduced, the cost required per unit layer can be reduced. Therefore, the manufacturing cost of the biological information measurement electrode 30C can be reduced.

Further, the biological information measuring electrode formed of metal can not be used for a subject having metal allergy. In the present embodiment, the biological information measuring electrode 30C is formed to include the conductive polymer in the conductive layer 60, so that even if the conductive layer 60 comes in contact with the scalp, a metal allergy is caused to the user. Not safe. Therefore, the biological information measurement electrode 30C can be used with confidence for all the subjects, as in the case of the conductive material 10 according to the first embodiment described above.

When the fiber including the conductive layer 60 is a nanofiber, the biological information measuring electrode 30C can disperse the nanofibers more uniformly in the conductive layer 60 than the fiber, so the strength of the conductive layer 60 is higher. can do. Therefore, the wear resistance of the conductive layer 60 can be further improved.

When the fiber contained in the conductive layer 60 is a cellulose nanofiber, the biological information measuring electrode 30C has high resistance to alcohol, so that the conductive layer 60 can be washed with alcohol.

[Modification of Electrode for Measuring Biological Information According to Sixth Embodiment]
Although an example of the biological information measurement electrode 30C is shown, the present invention is not limited to this. Hereinafter, a modification of the biological information measurement electrode 30C will be described.

In the present embodiment, the conductive layer 60 is formed on the tip end portion 312a of the electrode leg 312A which is the region A, but it may be formed on at least the tip end portion 312a. It may be formed on the entire surface of the base portion 31 and the terminal portion 33. For example, when the base portion 31 and the terminal portion 33 are formed of an insulating material, the base portion 31 and the terminal portion 33 are formed on the entire surface of the base portion 31 and the terminal portion 33.

In this case, as shown in FIG. 47, a base conductive layer 61 electrically connected to the conductive layer 60 is preferably formed on the entire surfaces of the base portion 31 and the terminal portion 33. Thereby, conduction between the tip end portion 312 a and the terminal portion 33 can be achieved. Since the same conductive polymer as the conductive layer 60 is used as the conductive polymer, the description of the conductive polymer is omitted. The thickness of the base conductive layer 61 only needs to be conductive, and may be, for example, about 200 nm to 2 μm.

<Manufacturing Method of Biological Information Measuring Electrode According to Sixth Embodiment>
Next, a method of manufacturing the biological information measuring electrode according to the sixth embodiment will be described. FIG. 48 is a flowchart showing a method of manufacturing the biological information measuring electrode according to the present embodiment.

In the method of manufacturing the biological information measuring electrode according to the present embodiment, as shown in FIG. 48, a forming step (step S71) of forming the base portion 31 and the terminal portion 33 and activation processing of the surface of the tip portion 312a A surface treatment step (step S72), and a conductive layer formation step (step S73) of forming a conductive layer 60 containing a conductive polymer on the surface of the tip end portion 312a. Each step will be described below.

First, in the molding step (step S71), the base portion 31 and the terminal portion 33 are integrally molded using a material for forming the base portion 31 and the terminal portion 33.

The base portion 31 and the terminal portion 33 can be performed in the same manner as the forming step (step S41A) of the method for manufacturing the biological information measuring electrode according to the above-described fourth embodiment shown in FIG.

Next, the surface treatment step (step S72) can be performed in the same manner as the surface treatment step (step S32) of the method for manufacturing the biological information measuring electrode according to the third embodiment described above, shown in FIG.

In the conductive layer forming step (step S73), a conductive layer 60 is formed on the surface of the tip portion 312a in which fibers are dispersed in a matrix of a synthetic resin containing a conductive polymer. The conductive layer forming step (step S73) includes a coating step (step S731) and a drying step (step S732).

The application step (step S731) of the conductive layer forming step (step S73) is performed in the same manner as the application step (step S431) of the method of manufacturing the biological information measuring electrode according to the fourth embodiment described above shown in FIG. be able to.

The drying step (step S732) of the conductive layer forming step (step S73) is performed in the same manner as the solidifying step (step S432) of the method of manufacturing the biological information measuring electrode according to the fourth embodiment described above shown in FIG. be able to.

As described above, the conductive layer 60 is formed on the surface of the tip end portion 312a, whereby the biological information measurement electrode 30C is obtained. Since the conductive layer 60 has high abrasion resistance, the conductive layer 60 on the surface of the tip portion 312a is used even if the biological information measurement electrode 30C is repeatedly used or cleaned to rub the conductive layer 60 on the surface of the tip portion 312a. It can suppress that 60 is scraped off. Therefore, since the conduction with the scalp can be stably maintained at the contact portion between the conductive layer 60 and the scalp, the electrical signal from the scalp can be stably obtained.

In the coating step (step S731) of the conductive layer forming step (step S73), the film thickness of the coating layer formed when the mixed solution is applied once to the tip end portion 312a is a solution containing only the conductive polymer. It can be thicker than the thickness of the coating layer formed when it is applied once. The desired thickness of the conductive layer 60 can be obtained with a small number of application times of the mixed solution, so the cost required for the application step (step S731) can be reduced. Further, by thickening the thickness of the conductive layer 60, even if the surface of the conductive layer 60 is abraded and worn during use or cleaning of the biological information measuring electrode 30C, the conductive layer 60 is worn away and the surface of the tip portion 312a It can delay the time until it peels off. As a result, the life of the conductive layer 60 can be further extended.

When the fibers contained in the conductive layer 60 are cellulose nanofibers, a mixed solution containing cellulose nanofibers and a conductive polymer has good wettability to the base portion 31 and the terminal portion 33 and has high thixotropy. Therefore, when the conductive layer 60 is formed using a mixed solution containing cellulose nanofibers and a conductive polymer, the thickness of the coated layer formed when the mixed solution is applied to the tip portion 312 a once is made thicker. be able to. The film thickness of the coating layer formed in one application of the mixed solution is, for example, about 1.3 to 4 times the film thickness of the coating layer formed by coating a solution not containing cellulose nanofibers. It can be thickened.

[Modified Example of Method of Manufacturing Biological Information Measurement Electrode According to Sixth Embodiment]
Although an example of the manufacturing method of the living body information measurement electrode concerning one embodiment was shown, it is not limited to this. Below, the modification in the manufacturing method of the electrode for biological information measurement is explained.

In the present embodiment, the base portion 31 and the terminal portion 33 are simultaneously formed in the molding step (step S71), but the base portion 31 and the terminal portion 33 may be separately molded and integrated. .

In this case, as shown in FIG. 49, in the manufacturing method of the modification of the biological information measuring electrode according to the present embodiment, the forming step (step S71) is a preparing step of preparing the base portion 31 and the terminal portion 33 (step S711), and a bonding step (step S712) for bonding and integrating the base portion 31 and the terminal portion 33 together. Then, as in the present embodiment, a surface treatment step (step S72) for activating the surface of the tip portion 312a and a conductive layer 60 containing a conductive polymer and a fiber are formed on the surface of the tip portion 312a. A conductive layer forming step (step S73) is performed.

In the binding step (step S712) of the above-described forming step (step S71), the base portion 31 and the terminal portion 33 are integrated using a binding member. A known binding member can be used as the binding member used for this binding. For example, synthetic resin such as epoxy resin or urethane resin, or synthetic resin having elasticity such as rubber can be used.

Further, in the present embodiment, the conductive layer 60 is formed only at the tip end portion 312a of the base portion 31 in the conductive layer forming step (step S73), but the conductive layer 60 is formed at least at the tip end portion 312a. The conductive layer 60 may be formed on the portion other than the tip end portion 312 a of the base portion 31 or on the entire base portion 31 and the terminal portion 33.

Further, in the present embodiment, since the base portion 31 and the terminal portion 33 are formed of a conductive elastomer, the conductive layer 60 may be formed at least on the surface of the tip portion 312a. When the base 31 and the terminal 33 are formed of an insulating material, the conductive layer 60 is formed on the entire surface of the base 31 and the terminal 33. Thereby, the electrical signal obtained from the scalp is transmitted from the tip end portion 312 a of the electrode leg 312 A to the terminal portion 33 through the conductive layer 60.

When base 31 and terminal 33 are formed of an insulating material, base conductive layer 61 is formed between base 31 and terminal 33 and conductive layer 60 as shown in FIG. Is preferred.

In this case, as shown in FIG. 50, the manufacturing method of the modification of the biological information measuring electrode according to the present embodiment includes the base conductive layer 61 containing a conductive polymer on the surfaces of the base portion 31 and the terminal portion 33. Form That is, in the manufacturing method of the modification of the biological information measuring electrode according to the present embodiment, the forming step (step S71), the surface treatment step (step S72), and the surfaces of the base portion 31 and the terminal portion 33 are electrically conductive. A base conductive layer forming step (step S73) for forming a base conductive layer 61 containing a polymer, and a conductive layer forming step (step S74) are included. The conductive layer forming step (step S74) is the same as the conductive layer forming step (step S73) of FIG. 48 described above.

In the base conductive layer forming step (step S73), a solution containing a conductive polymer is applied to the surfaces of the base portion 31 and the terminal portion 33 to form a coating layer. The underlying conductive layer 61 can be formed by the same method as the conductive layer forming step (step S74).

Seventh Embodiment
<Electrode for measuring biological information>
A biological information measurement electrode according to a seventh embodiment will be described with reference to the drawings. The biological information measurement electrode according to the present embodiment is the fourth embodiment shown in FIGS. 37 to 40 as the electrode leg 312A of the base 31 of the biological information measurement electrode 30C according to the sixth embodiment shown in FIGS. The electrode leg 312B according to the fifth embodiment is used.

FIG. 51 is a perspective view showing the appearance of the biological information measurement electrode according to the seventh embodiment, and FIGS. 52 and 53 are other views showing the appearance of the biological information measurement electrode according to the seventh embodiment. FIG. 54 is a perspective view, and FIG. 54 is a cross-sectional view taken along the line III-III in FIG.

As shown in FIGS. 51 to 54, the biological information measurement electrode 30D according to the seventh embodiment is replaced with the electrode legs 312A of the base portion 31 of the biological information measurement electrode 30C shown in FIG. An electrode leg 312B according to the sixth embodiment shown in FIG. 40 is provided.

The electrode leg 312B is, as shown in FIG. 51, a groove (tip groove) 24A provided in the tip end portion 312a which is the region A, and an auxiliary groove portion provided in the side surface 312b of the electrode leg 312A which is a portion other than the tip end portion 312a ( Side groove portion 25). As shown in FIG. 52, since the conductive layer 60 is formed on the surface of the tip end portion 312a, the conductive layer 60 is also formed on the surface of the tip groove portion 24A (see FIG. 16). The electrode leg 312B can hold the liquid containing water in the tip groove 24A and the side groove 25 by providing the tip groove 24A and the side groove 25.

When measuring the brain waves of the subject using the biological information measurement electrode 30D, as described with reference to FIG. 28 in the fourth embodiment described above, the inspection apparatus 40 including the biological information measurement electrode 30D (FIG. 28) The subject's EEG can be measured by using the reference).

The biological information measurement electrode 30D configured as described above has a plurality of tip grooves 24A on the surface of the tip portion 312a which is the region A, and a conductive layer 60 on the surface of the tip portion 312a. By repeatedly using the biological information measuring electrode 30D for a long time, for example, as shown in FIG. 17, a part of the conductive layer 60 on the surface of the tip end portion 312a is gradually worn away and the tip end portion 312a is partially exposed. There is a possibility that a part of the conductive layer 60 may be peeled off until it is in the above state. Even in such a case, in the biological information measurement electrode 30D, the conductive layer 60 formed on the surface of the tip groove 24A remains. Therefore, since the conduction of the conductive layer 60 can be maintained at the contact portion between the conductive layer 60 formed on the surface of the tip groove 24A and the scalp, the conduction between the conductive layer 60 and the scalp can be stably maintained. Therefore, according to the biological information measurement electrode 30D, as in the biological information measurement electrode 30A according to the fourth embodiment described above, the electrical connection between the tip end portion 312a of the electrode leg 312B and the scalp can be maintained. It is possible to stably obtain an electrical signal from the above, and to stably measure an electroencephalogram as biological information.

In addition, when the biological information measurement electrode 30D is immersed in the liquid, a capillary is formed in the tip groove 24A provided on the surface of the distal end portion 312a, which is the area A, like the biological information measurement electrode 30B according to the fifth embodiment described above. Water can be retained by the phenomenon. Therefore, when measuring the electroencephalogram, when the tip end portion 312a is brought into contact with the scalp, as shown in FIG. 18, the water held by the tip groove portion 24A flows on the surface of the scalp in contact with the tip end portion 312a spread. As a result, the area of conduction from the scalp to the conductive layer 60 is increased, so the contact impedance between the scalp and the biological information measurement electrode 30D can be further lowered. Thereby, the electroencephalogram can be measured more stably.

Furthermore, the living body information measurement electrode 30D has a plurality of side grooves 25 on the side surface of the electrode leg 312B, and the side grooves 25 communicate with at least a part of the tip groove 24A. Therefore, as with the electrode for measuring biological information 30B according to the fifth embodiment described above, when electroencephalogram is measured, the water held by the tip groove 24A flows to the surface of the scalp in contact with the tip 312a, and the tip groove 24A The water held at is consumed. At this time, the water held in the side groove 25 flows to the tip groove 24A and is supplied to the scalp. Thereby, the contact between the scalp and the biological information measuring electrode 30D can be maintained while the contact impedance between the scalp and the biological information measuring electrode 30D is kept low, so that the biological information can be continued more stably. Can be measured.

<Manufacturing Method of Biological Information Measurement Electrode According to Seventh Embodiment>
Next, a method of manufacturing the biological information measuring electrode according to the seventh embodiment will be described. FIG. 55 is a flowchart showing a method of manufacturing the biological information measuring electrode according to the seventh embodiment.

In the method of manufacturing the biological information measuring electrode according to the present embodiment, as shown in FIG. 55, the base portion 31 and the terminal portion 33 are formed, and a plurality of tip grooves 24A are formed on the surface of the tip portion 312a which is the region A. Forming step (step S81) for forming the side groove portion 25 on the side surface 312b, surface treatment step (step S82) for activating the surface of the tip end portion 312a, conductive polymer on the surface of the tip end portion 312a And a conductive layer forming step (step S83) of forming a conductive layer 60 containing Each step will be described below.

First, in the forming step (step S81), the base portion 31 and the terminal portion 33 are integrally molded using a material for forming the base portion 31 and the terminal portion 33, and a plurality of portions are formed on the surface of the tip portion 312a which is the region A. The end groove 24A is formed, and the side groove 25 is formed on the side surface 312b.

The base portion 31 and the terminal portion 33 can be molded using a known molding method as in the molding step (step S71) in the method of manufacturing the biological information measuring electrode according to the sixth embodiment shown in FIG. . When these molding methods are used, a mold corresponding to the shapes of the base portion 31 and the terminal portion 33 is used. The mold is provided with a protrusion corresponding to the end groove 24A and the side groove 25. By using the mold, the base portion 31 and the terminal portion 33 can be simultaneously formed, and the tip groove portion 24A and the side surface groove portion 25 can be simultaneously formed.

Next, in the surface treatment step (step S82), the surface of the tip end portion 312a is subjected to activation treatment. The method of activating the surface of the distal end portion 312a can be the same method as the surface treatment step (step S72) in the method of manufacturing the biological information measuring electrode according to the sixth embodiment shown in FIG. , The description is omitted.

Finally, in the conductive layer forming step (step S83), the conductive layer 50 is formed on the surface of the tip end portion 312a. The method of forming the conductive layer 50 can be the same as the step of forming the conductive layer (step S73) in the method of manufacturing the biological information measuring electrode according to the sixth embodiment shown in FIG. Do.

As described above, the conductive layer 60 is formed on the surface of the tip end portion 312a, whereby the biological information measurement electrode 30D according to the present embodiment can be obtained. The front end groove portion 24A is formed on the surface of the front end portion 312a, and the side surface groove portion 25 is formed on the side surface 312b. Therefore, even if the conductive layer 60 provided on the tip end portion 312a is worn and scraped for a long time by repeatedly using the biological information measurement electrode 30D, the conductive layer provided on the surface of the tip groove portion 24A 60 remain. Therefore, since the conduction with the scalp can be maintained at the contact portion between the conductive layer 60 formed on the surface of the tip groove 24A and the scalp, the conduction between the conductive layer 60 and the scalp can be stably maintained. .

[Modified Example of Method of Manufacturing Biological Information Measurement Electrode According to Seventh Embodiment]
Although an example of the manufacturing method of the living body information measurement electrode concerning one embodiment was shown, it is not limited to this. Hereinafter, some modified examples of the method of manufacturing the biological information measuring electrode will be described with reference to FIG.

In the seventh embodiment, in the molding step (step S21), the base portion 31 and the terminal portion 33 are simultaneously formed using a mold provided with a protrusion corresponding to the tip groove portion 24A and the side surface groove portion 25. It is not limited to this. For example, the distal end groove 24A and the side groove 25 may be formed after the base portion 31 and the terminal portion 33 are separately molded and integrated.

In this case, as shown in FIG. 56, in the method of manufacturing the biological information measuring electrode according to the present embodiment, the forming step (step S81) is a preparing step (step S811) of preparing the base portion 31 and the terminal portion 33. A bonding step of bonding and integrating the base portion 31 and the terminal portion 33 (step S812), and a groove forming step of forming the plurality of tip grooves 24A and the side grooves 25 on the surface of the tip portion 312a (step S813) And consists of. Then, as in the seventh embodiment, a surface treatment step (step S82) for activating the surface of the tip end portion 312a and a conductive layer 60 containing a conductive polymer is formed on the surface of the tip end portion 312a. A conductive layer forming step (step S83) is performed.

The base portion 31 and the terminal portion 33 in the above-described forming process (step S81) are integrated using a binding member. A known binding member can be used as the binding member used for this binding. For example, synthetic resin such as epoxy resin or urethane resin, or synthetic resin having elasticity such as rubber can be used.

As described above, the biological

information measurement electrodes

30C and 30D according to the sixth and seventh embodiments maintain electrical connection with the scalp and stably measure biological information (electroencephalograms) obtained from the scalp. can do. Therefore, the electrodes for measuring

biological information

30C and 30D are suitable as electrodes for measuring biological information for measuring information of various living bodies such as pulse waves, electrocardiograms, myoelectric potentials, body fats, etc., in addition to brain waves. It can be used for In addition, although a living body includes a human body or a living body other than the human body, etc., the biological information measuring electrode according to each of the above embodiments can be particularly suitably used for the human body.

As described above, the conductive material is used as the conductive material 10 (see FIG. 1 and the like) in the first embodiment, and the conductive layer 22 (see FIG. 6 and the like) or the conductive layer 60 (the second to seventh embodiments). (See FIG. 44). In each of the above embodiments, in the first embodiment, the conductive material 10 (see FIG. 1 and the like) is formed by including a fiber and a binder having a conductive polymer that bonds the fibers. , And a large number of pores. In the second to fifth embodiments, the conductive material 10 (see FIG. 1) is the

electrode legs

20A and 20B (see FIGS. 6 and 13) or the biological

information measuring electrodes

30A and 30B (see FIGS. 25 and 37). (See FIG. 6 etc.) of each. In the sixth and seventh embodiments, the conductive layer 60 (see FIG. 44) contains a conductive polymer on the surface of the region A of the biological

information measurement electrodes

30C and 30D (see FIG. 44 and FIG. 51). The fibers are contained in a dispersed manner in the matrix of the synthetic resin.

Specifically, the conductive material according to the first embodiment described above is a conductive material provided on the surface of at least the region of the biological information measuring electrode having a region capable of being in contact with a living body,
It is formed to include a fiber and a binder resin having a conductive polymer that bonds the fibers, and has a large number of pores.

The biological information measurement electrode according to the sixth and seventh embodiments described above is a biological information measurement electrode having a region that can be in contact with a living body,
A conductive layer in which fibers are dispersed and contained in a matrix of a synthetic resin containing a conductive polymer is formed on the surface of the region.

The method of manufacturing a conductive material according to the first embodiment is a method of manufacturing a conductive material provided on a surface of at least the region of a biological information measuring electrode having a region capable of being in contact with a living body,
A mixing step of preparing a mixed solution containing a fiber, a conductive polymer bonding the fibers, and a solvent in which the fiber is dispersed;
Solidifying the mixed solution by lyophilization to produce a porous body having a large number of pores;
including.

In the method of manufacturing a conductive material as described above, in the mixing step, a binder resin for binding the fibers to each other is mixed in the mixed solution,
And a curing step of curing the binder resin in the porous body obtained by cooling and drying the mixed solution containing the binder resin.

In the above method for producing a conductive material, the solvent is water containing water,
The solidifying step is a cooling step of cooling water contained in the mixed solution;
A dehydration step of subliming the cooled water under vacuum;
including.

The method of manufacturing an electrode leg according to the second embodiment described above is a method of manufacturing an electrode leg having at least the region capable of being in contact with a living body,
A leg base producing step of producing an electrode base having conductivity;
A conductive layer forming step of forming a conductive layer made of the conductive material obtained by using the method for producing a conductive material according to any one of the above, in the region of the electrode substrate;
including.

The method of manufacturing an electrode leg according to the third embodiment described above is a method of manufacturing an electrode leg having at least a region capable of being in contact with a living body,
A leg base producing step of producing an electrode base having conductivity;
Forming a conductive layer in the region of the electrode substrate;
In the conductive layer forming step,
Applying a mixed solution of a fiber, a conductive polymer for binding the fibers, and a solvent in which the fiber is dispersed to at least the region to form a coating layer;
Solidifying the coated layer by freeze-drying to produce a porous body having a large number of pores;
including.

In the method of manufacturing an electrode leg according to the second or third embodiment, the leg base manufacturing step forms a plurality of grooves in the surface of the region.

In the method of manufacturing an electrode leg according to the second or third embodiment, the leg base manufacturing step forms a plurality of auxiliary groove portions on the surface of a portion other than the region,
The auxiliary groove communicates with at least a part of the groove.

The method of manufacturing a biological information measuring electrode according to the fourth or fifth embodiment is a method of manufacturing a biological information measuring electrode having a region capable of being in contact with a living body,
A base portion comprising an electrode leg having at least the region on one side and a base provided on the other side of the electrode leg;
A terminal portion electrically connected to the electrode leg;
A forming step of integrally forming the electrode leg and the base;
Forming a conductive layer in the area of the electrode leg;
In the conductive layer forming step,
Applying a mixed solution of a fiber, a conductive polymer for binding the fibers, and a solvent in which the fiber is dispersed to at least the region to form a coating layer;
Solidifying the coated layer by freeze-drying to produce a porous body having a large number of pores;
including.

The method of manufacturing a biological information measuring electrode according to the fourth or fifth other embodiment is a method of manufacturing a biological information measuring electrode having the region that can be in contact with a living body,
A base portion comprising the electrode leg obtained by using the method for producing an electrode leg according to any one of the above, and a base provided on the other side of the electrode leg;
A terminal portion electrically connected to the electrode leg;
And connecting the electrode legs to the base.

In the method of manufacturing the biological information measuring electrode according to the fourth or fifth embodiment, a step of forming a base conductive layer which forms a base conductive layer electrically connected to the conductive layer on the surface of the base portion. including.

The method of manufacturing a biological information measuring electrode according to the sixth or seventh embodiment is a method of manufacturing a biological information measuring electrode having a region capable of being in contact with a living body,
A forming step of forming a base portion provided with the region;
A conductive layer forming step of forming a conductive layer in which fibers are dispersed and contained in a matrix of a synthetic resin containing a conductive polymer on at least the surface of the region is included.

The method of manufacturing a biological information measuring electrode according to the sixth or seventh embodiment further includes a surface treatment step of activating the surface of at least the region after forming the base portion,
The surface treatment step is a step of plasma treating at least the surface of the region in a mixed gas containing Ar and oxygen, or a step of irradiating at least the surface of the region with excimer UV light.

In the method of manufacturing a biological information measuring electrode according to the sixth or seventh embodiment, the conductive layer forming step includes:
Applying a mixed solution containing the conductive polymer and the fiber to at least the region to form a coated layer;
Drying the area in which the coating layer is formed to cure the coating layer;
including.

Hereinafter, although an Example and a comparative example are shown and an embodiment is more concretely described, an embodiment is not limited by these examples.

Example 1
(Preparation of electrodes for measuring biological information)
The base portion and the terminal portion are integrally formed by injection molding using a resin material (thermoplastic polyester elastomer, trade name: Hytrel (registered trademark), manufactured by Toray DuPont), and then the tip portion of the electrode leg is Solution (A) containing 6 g of conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) and solution containing cellulose nanofiber 1 (nanoforest (registered trademark), manufactured by Chuetsu Pulp Industries Co., Ltd.) / After applying the solution which mixed 4 g and forming an application layer, the application layer was dried and hardened and the electric conduction layer was formed. Thus, an electrode for measuring biological information was produced. The solution (A) contains 1.0% by mass (wt%) of a conductive polymer and 5.0% by weight of a thermosetting resin. Moreover, 1.3 wt% of the cellulose nanofibers 1 are contained in the solution (B).
(Evaluation of wear resistance)
With the tip of the electrode leg of the biological information measurement electrode immersed in the electrolytic solution (0.1 M NaCl aqueous solution), the impedance of the tip was measured to evaluate the measurement accuracy of the biological information measurement electrode. The tip of the electrode leg was wiped with an alcohol-added Kimwipe, and then the tip was immersed in an electrolytic solution (0.1 M NaCl aqueous solution) to measure the impedance of the tip. The frequency was 1 Hz to 1000 Hz. This cycle was performed once (cycle) for 100,000 cycles. The lower the impedance at the tip, the higher the sensitivity with which an electrical signal obtained from a living body can be detected. This indicates that the measurement accuracy of the biological information measurement electrode is higher. The measurement results are shown in FIG.

As shown in FIG. 57, even when the measurement of the impedance at the tip was repeated 100,000 cycles, the impedance at the tip was 100 Ω or less at a frequency of 5 Hz or more, and hardly changed.

Therefore, if the conductive layer containing a predetermined amount of cellulose nanofibers is formed on the surface of the tip portion, the wear resistance of the conductive layer is improved, and the impedance hardly changes, and the electroencephalogram can be stably measured. It was confirmed that it was possible.

Example 2
(Preparation of electrodes for measuring biological information)
Example 2-1
An electrode for biological information measurement under the same conditions as in Example 1 was produced.

Embodiment 2-2
In Example 2-1, the addition amount of the solution (A) containing a conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) is 3 g, and cellulose nanofiber 1 (nanoforest (registered trademark), Chuetsu Pulp Industrial Co., Ltd.) A conductive layer is formed on the tip of the electrode leg in the same manner as in Example 2-1 except that the amount of the solution (B) containing C.I) is changed to 7 g, and an electrode for measuring biological information is obtained. Made.

Example 2-3
In Example 2-1, the addition amount of a solution (A) containing a conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) is 4 g, and cellulose nanofiber 1 (nanoforest (registered trademark), Chuetsu Pulp Industrial Co., Ltd.) The addition amount of the solution (B) containing a company) was 6 g, and the addition amount of the solution (C) containing cellulose nanofibers 2 (cellenpia (registered trademark), Nippon Paper Industries Co., Ltd.) was changed to 1 g A conductive layer was formed at the tip of the electrode leg in the same manner as in Example 2-1 except for the production of a biological information measuring electrode. In addition, 1.2 wt% of the cellulose nanofibers 2 are contained in the solution (C).

Comparative Example 2-1
In Example 2-1, a conductive polymer (PEDOT / PSS, Shin-Etsu Polymer Co., Ltd.) was added without adding the solution (B) containing cellulose nanofiber 1 (nanoforest (registered trademark), manufactured by Chuetsu Pulp Industries, Ltd.). In the same manner as in Example 2-1, except that the solution (A) containing only the solution (A) containing (addition amount 10 g) was used, a conductive layer was formed on the tip of the electrode leg, and the biological information was measured. An electrode was produced.

Comparative Example 2-2
In Example 2-1, the addition amount of the solution (A) containing a conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) is 10 g, and a cellulose nanofiber 2 (cellenpia (registered trademark), Nippon Paper Industries Co., Ltd.) A conductive layer is formed at the tip of the electrode leg in the same manner as in Example 2-1 except that the addition amount of the solution (C) containing A) is changed to 1 g, and an electrode for biological information measurement is produced. did.

Comparative Example 2-3
In Example 2-1, the addition amount of the solution (A) containing a conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) is 1 g, and cellulose nanofiber 1 (nanoforest (registered trademark), Chuetsu Pulp Industrial Co., Ltd.) A conductive layer is formed on the tip of the electrode leg in the same manner as in Example 3-1 except that the addition amount of the solution (B) containing C.I. Made.

(Evaluation of contact with living body)
The evaluation of the contact of the electrode for measuring biological information with the skin (forehead) was performed by measuring the impedance.

As the evaluation of the contact stability, the tip of the electrode leg of the electrode for measuring biological information is immersed in the electrolyte (0.1 M NaCl aqueous solution), the impedance of the tip in the electrolyte is measured, and the biological information is measured. The measurement accuracy of the measurement electrode was evaluated. The frequency of measurement was 0.5 Hz to 1000 Hz. The measurement results are shown in FIG. In FIG. 58, the horizontal axis represents the measurement frequency (Hz) and the vertical axis represents the impedance (Ω), and the measurement results of Example 2-1 to Example 2-3 and Comparative Example 2-1 to Comparative Example 2-3 are shown. It shows.

The lower the impedance at the tip, the higher the sensitivity with which an electrical signal obtained from a living body can be detected. This indicates that the measurement accuracy of the biological information measurement electrode is higher. Also, if the impedance is lower at the lower frequency side, stable and accurate measurement can be performed at the frequency (10 Hz to 30 Hz) generally used for measurement.

(Evaluation result of contact with living body)
As shown in FIG. 58, the electrodes for measuring biological information of Examples 2-1 to 2-3 are for measuring biological information of Comparative Example 2-1 containing no fibers and Comparative Example 2-2 containing very few fibers. An impedance equivalent to that of the electrode was obtained. In particular, the biological information measuring electrode of Example 2-1 had a value which is not different from the impedance of the biological information measuring electrode of Comparative Example 2-1 and Comparative Example 2-2. On the other hand, in the biological information measurement electrode of Comparative Example 2-3 containing a large amount of fiber, the conductivity of the conductive layer itself becomes too low, and the value of the impedance becomes high, which is considered unsuitable for measurement.

Therefore, it has been confirmed that even if a predetermined amount of cellulose nanofibers is formed on the surface of the tip portion in the conductive layer, the impedance of the biological information measurement electrode is reduced, so that the electroencephalogram can be stably measured.

As mentioned above, although embodiment was described, said each embodiment is shown as an example, and this invention is not limited by the said embodiment. The above embodiments can be implemented in other various forms, and various combinations, omissions, replacements, changes, and the like can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and the gist of the invention, and are included in the invention described in the claims and the equivalent scope thereof.

The present application is based on Japanese Patent Application No. 2017-252508 filed on Dec. 27, 2017, and Japanese Patent Application No. 2017-252509 filed on Dec. 27, 2017. It is claimed that the entire contents of Japanese Patent Application Nos. 2017-252508 and 2017-252509 are incorporated into the present application.

REFERENCE SIGNS LIST 10 conductive material 11

pore

13, 20A, 20B, 312A,

312B electrode leg

21A,

21B electrode base

131, 211,

312a tip

212, 312b

side

22, 60

conductive layer

23, 51, 61 base

conductive layer

24A, 24B, 24C groove (tip groove)
25 Auxiliary groove (side groove)
30A, 30B, 30C, 30D Electrodes 31 for measuring biological information 31

base part

311, 331 base part 311a protruding part 33 terminal part A area H1, H2 maximum depth W1, W2 width

Claims

A conductive material provided on a surface of at least a region of a biological information measuring electrode having a region capable of being in contact with a living body,
A conductive material comprising a fiber and a conductive polymer.
A conductive material using the conductive material according to claim 1, wherein
It is formed to include the fiber and a binder having the conductive polymer that bonds the fibers together,
A conductive material characterized by having a large number of pores.
The conductive material according to claim 2, wherein the conductive material has elasticity.
The conductive material according to claim 2, wherein the fiber is a nanofiber.
The conductive material according to claim 4, wherein the nanofibers are cellulose nanofibers.
An electrode leg having at least the region capable of being in contact with a living body on one side,
An electrode leg, wherein a conductive layer made of the conductive material according to any one of claims 2 to 5 is formed at least in the region.
The electrode leg according to claim 6, wherein a base conductive layer electrically connected to the conductive layer is formed on the surface of the electrode leg.
The electrode leg according to claim 6 or 7, wherein a plurality of grooves are formed on the surface of the region.
A plurality of auxiliary grooves are formed on the surface of the portion other than the region,
The electrode leg according to claim 8, wherein the auxiliary groove communicates with at least a part of the groove.
A base portion comprising the electrode leg according to any one of claims 6 to 9 and a base provided on the other side of the electrode leg,
A terminal portion electrically connected to the electrode leg;
An electrode for biological information measurement characterized by having.
The biological information measuring electrode according to claim 10, wherein the electrode leg is separable from the base.
An electrode for measuring biological information, having a region accessible to a living body,
A conductive layer using the conductive material according to claim 1 is formed on the surface of the region,
The electrode for measuring biological information, wherein the conductive layer includes the fibers dispersed in a matrix of a synthetic resin containing the conductive polymer.
The biological information measuring electrode according to claim 12, wherein the fiber is a nanofiber.
The biological information measuring electrode according to claim 13, wherein the nanofiber is a cellulose nanofiber.
The biological information measuring electrode according to any one of claims 12 to 14, wherein a plurality of grooves are formed on the surface of the region.
A plurality of auxiliary grooves are formed on the surface of the portion other than the region,
The biological information measuring electrode according to claim 15, wherein the auxiliary groove communicates with at least a part of the groove.
A base portion provided with the area;
A terminal portion electrically connected to the region;
The biological information measuring electrode according to any one of claims 12 to 16, which has