JP6821058B2 - Electrodes for measuring biological information - Google Patents

Description

The present invention relates to a raw body information measuring electrode.

For example, an electrode for measuring biological information (electrode for measuring biological information) is used for measuring biological information such as electroencephalogram, pulse wave, electrocardiogram, electromyography, and body fat. When measuring biological information, an electrode for measuring biological information is attached to the living body (skin), an electrical signal related to the biological information is acquired by the electrode for measuring biological information, and biological information (for example, brain wave) is measured. ..

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

As one of such electrodes for measuring biological information, for example, an electrode has been proposed in which a conductive polymer film is formed on the surface of a protrusion of the electrode to impart conductivity and detect a biological signal (for example). , Patent Document 1).

Japanese Patent Application Laid-Open No. 2016-366442

The contact resistance (contact impedance) generated between the conductive polymer film and the living body is lower when the conductive polymer film is wetted with water than when the conductive polymer film is not wetted with water. It tends to be. Therefore, by pre-wetting the conductive polymer film with an aqueous solution such as water, the electrical connection between the conductive polymer film and the living body is more stable, 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 with water. Therefore, the conductive polymer film tends to be difficult to come into stable contact with the living body, and the conduction between the conductive polymer film and the living body tends to be difficult to be stable. 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.

Further, since the electrode for measuring biological information is used in contact with the living body, it needs to be clean at the time of use. Therefore, every time the biometric information measuring electrode is used, the moisture and dirt remaining on the surface of the electrode are generally wiped off with a cleaning solution such as alcohol for the purpose of cleaning the biometric information measuring electrode in advance. ing.

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

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

One aspect of the biological information measuring electrode according to the present invention includes an electrode legs having a region contactable with the raw body one side and a conductive material including a fiber and a conductive polymer, on the surface of the region It was provided with a formed conductive layer .

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 electrode for measuring biological information according to the present invention can improve the wear resistance of the conductive layer formed on the surface of the region in contact with the living body. As a result, biological information can be measured in a stable manner.

It is a perspective view of the conductive material which concerns on 1st Embodiment. FIG. 1 is a cross-sectional view taken along the line I-I of FIG. It is an optical micrograph which shows the state which put the conductive material on the carbon base material. It is an SEM photograph which saw the conductive material enlarged. It is a flowchart which shows the manufacturing method of the conductive material which concerns on 1st Embodiment. It is a perspective view of the electrode leg which concerns on 2nd Embodiment. FIG. 6 is a sectional view taken along line II-II of FIG. It is a partial cross-sectional view which shows an example of another structure of an electrode leg. It is a flowchart which shows the manufacturing method of the electrode leg which concerns on 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 appearance of the electrode leg which concerns on 3rd Embodiment. It is a front view of the electrode leg. 13 is a sectional view taken along line III-III of FIG. It is explanatory drawing which shows an example of the cross section of the tip groove part of the tip part. It is explanatory drawing which shows an example of the cross section of the auxiliary groove part of the side surface of an electrode leg. It is explanatory drawing which shows the state which a part of the conductive layer of the tip part was worn. It is explanatory drawing which shows the state which the liquid held in the tip groove part spreads. It is a perspective view which shows another example of the groove part formed in one end part of an electrode leg. It is a perspective view which shows another example of the groove part formed in one end part of an electrode leg. It is a flowchart which shows the manufacturing method of the electrode leg which concerns on 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 which shows the appearance of the electrode for measuring biological information which concerns on 4th Embodiment. It is another perspective view which shows the appearance of the electrode for measuring biological information. FIG. 5 is a sectional view taken along line IV-IV of FIG. It is a figure which shows an example of measuring the electroencephalogram of a subject using the inspection apparatus provided with the electrode for measuring biological information. It is a perspective view which shows an example of another structure of the electrode for measuring biological information. It is a VV cross-sectional view of FIG. It is a partial cross-sectional view of the electrode leg which formed the base conductive layer. It is a flowchart which shows the manufacturing method of the electrode for measuring biological information which concerns on 4th Embodiment. It is a figure which shows an example of the state which the raw material supply passage is fixed to a terminal part. It is another flowchart which shows the manufacturing method of the electrode for measuring biological information. It is another flowchart which shows the manufacturing method of the electrode for measuring biological information. It is another flowchart which shows the manufacturing method of the electrode for measuring biological information. It is a perspective view which shows the appearance of the electrode for measuring biological information which concerns on 5th Embodiment. It is another perspective view which shows the appearance of the electrode for measuring biological information. It is another perspective view which shows the appearance of the electrode for measuring biological information. FIG. 7 is a sectional view taken along line VI-VI of FIG. It is explanatory drawing which shows an example of the state which the tip part of the base part was brought into contact with the scalp through a conductive layer. It is a flowchart which shows the manufacturing method of the electrode for measuring biological information which concerns on 5th Embodiment. It is another flowchart which shows the manufacturing method of the electrode for measuring biological information. It is a perspective view which shows the appearance of the electrode for measuring biological information which concerns on 6th Embodiment. It is another perspective view which shows the appearance of the electrode for measuring biological information which concerns on 6th Embodiment. FIG. 4 is a sectional view taken along line VII-VII of FIG. 44. It is a partial cross-sectional view of the electrode leg which formed the base conductive layer. It is a flowchart which shows the manufacturing method of the electrode for measuring biological information which concerns on 6th Embodiment. It is a flowchart which shows another example of the manufacturing method of the electrode for measuring biological information. It is a flowchart which shows another example of the manufacturing method of the electrode for measuring biological information. It is a perspective view which shows the appearance of the electrode for measuring biological information which concerns on 7th Embodiment. It is another perspective view which shows the appearance of the electrode for measuring biological information which concerns on 7th Embodiment. It is another perspective view which shows the appearance of the electrode for measuring biological information which concerns on 7th Embodiment. FIG. 5 is a cross-sectional view taken along the line VIII-VIII of FIG. It is a flowchart which shows the manufacturing method of the electrode for measuring biological information which concerns on 7th Embodiment. It is a flowchart which shows another example of the manufacturing method of the electrode for measuring biological information. It is a figure which shows the test result of the wear resistance of the electrode for measuring biological information. It is a figure which shows the test result of the measurement accuracy of the electrode for measuring biological information.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in order to facilitate understanding of the description, the same components are designated by the same reference numerals in each drawing, and duplicate description will be omitted. In addition, the scale of each member in the drawing may differ from the actual scale. In the present specification, a three-dimensional Cartesian coordinate system in three axial directions (X-axis direction, Y-axis direction, Z-axis direction) is used, and the direction parallel to the central axis J of the biometric information measurement electrode is defined as the Z-axis direction. On the plane orthogonal to the axis J, one of the two directions orthogonal to each other is the X-axis direction, and the other is the Y-axis direction. In the following description, the + Z-axis direction may be referred to as up, and the −Z-axis direction may be referred to as down.

The conductive material according to the embodiment of the present invention is provided on the surface of at least the region of the electrode for measuring biological information having a region 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 the conductive material in the first embodiment and as the conductive layer in the second to seventh embodiments. Hereinafter, each embodiment will be described.

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

FIG. 1 is a perspective view of the 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 material CF, and FIG. 4 is an SEM photograph of the conductive material as viewed in an enlarged manner. The alternate long and short dash line in FIGS. 1 and 2 indicates the central axis J of the conductive material. The central axis J is an axis that becomes the center when the conductive material is installed in the living body.

As shown in FIGS. 1 and 2, the conductive material 10 according to the present embodiment is formed on the surface of the tip portion 131, which is a region of the electrode leg 13 of the electrode for measuring biological information that can come into contact with the living body. The tip 131 of the electrode leg 13 is formed in a curved shape with a rounded tip, 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 portion means a tip that comes into contact with a living body and a peripheral region of the tip that may come into contact with a living body when the conductive material 10 is tilted. In 2, it is the whole outer surface of the conductive material 10. In the present specification, the tip portion is referred to as "region A in contact with a living body (hereinafter referred to as" region A ")".

The conductive material 10 is formed by 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 in a sponge shape. In addition, in FIG. 1 and FIG. 2, the conductive material 10 is schematically shown in a film shape, but as shown in FIG. 3, the conductive material 10 is formed in an elastic sponge shape. Further, in FIGS. 1 and 2, the pores 11 are schematically shown by black dots, but as shown in FIG. 4, they are innumerable fine voids.

By having the pores 11, the conductive material 10 can hold a liquid containing water in the pores 11. In addition to water, the liquid contained in the pores 11 can be used as long as it is a liquid that does not harm the living body, such as an electrolytic solution (saline solution).

The fiber of the conductive material 10 is a metal fiber composed of a metal such as Au, Pt, Ag, Cu, Al, Ni, Si, Co, Zr, Ti, W, or steel; Al ₂ O ₃ , NiO, SiO. Metal oxide fiber composed of metal oxides such as ₂ , TiO ₂ , Ti ₂ O ₃ , ZnO, ZrO ₂ , WO ₃ , or Y ₂ O ₃ ; carbon fiber; SiC, ZrC, Al ₄ C ₃ , CaC _2. Carbide-based fibers composed 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 thickness of the fiber is expressed by the diameter equivalent to a circle, the fiber generally has an average thickness (average diameter) of 1 nm to 100 μm, preferably 1 nm to 30 μm, and more preferably 1 nm to 5 μm. 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, the fibers are observed by SEM or the like, and the length in the direction orthogonal to the longitudinal direction of an arbitrarily selected predetermined number (for example, 10 to 200) fibers (length in the radial direction of the fibers) is measured. Then, the average diameter can be obtained by calculating the average value.

The fiber is preferably a nanofiber. In nanofibers, nanofibers are more entangled with each other than fibers, and finer pores 11 are formed in those bound by a binder. Therefore, more liquid containing water can be retained in the pores 11. In the present specification, when the thickness of the nanofiber is expressed by the diameter equivalent to a circle, the nanofiber generally has an average diameter of 1 nm to 1000 nm, preferably 5 nm to 100 nm, and more preferably 10 nm to 50 nm. .. The average diameter of the nanofibers can be determined by measuring using the same method as when measuring the thickness of the fibers.

The aspect ratio of the nanofiber is preferably 1: 100 to 1: 1000, more preferably 1: 100 to 1: 300. When the aspect ratio of the nanofibers is in the range of 1: 100 to 1: 1000, it is possible to suppress dispersion defects in the coating layer (see the coating process described later) 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 increased.

The nanofiber is, for example, a metal nanowire composed of the same type of metal as the metal used in the above-mentioned metal fiber; a metal oxide nanofiber composed of the same type of metal as the metal used in the above-mentioned metal oxide fiber. It can be formed by using a plastic nanofiber composed of carbon nanofibers, carbon nanotubes, carbon nanohorns; cellulose nanofibers; polyester nanofibers and the like. Above all, in this embodiment, it is preferable to use cellulose nanofibers.

Cellulose nanofibers are obtained by mechanically defibrating natural cellulose fibers that are insoluble in water, in the presence of 2,2,6,6-tetramethylpiperidin-N-oxyl (TEMPO). Cellulose nanofibers (TEMPO oxidized cellulose nanofibers) obtained by allowing an oxidizing agent such as hypochlorous acid to act to promote the oxidation reaction, or cellulose obtained by hydrophobizing the surface of natural cellulose fibers. There are nanofibers (surface hydrophobic cellulose nanofibers) and the like. In the present embodiment, cellulose nanofibers obtained by mechanically defibrating are preferable. For example, in the case of TEMPO-oxidized cellulose nanofibers, it is considered that some of the hydroxyl groups of the cellulose nanofibers are substituted with carboxyl groups and swell when they come into contact with water, and the strength of the conductive material 10 cannot be maintained. Further, in the case of surface-hydrophobicized cellulose nanofibers, if the hydrophobization progresses too much, the hydrophilicity with water or the electrolytic solution may be lost, and the measurement may become unstable.

As the cellulose nanofibers obtained by mechanically defibrating, the cellulose nanofibers (ACC cellulose nanofibers) obtained by crushing the natural cellulose fibers by using the underwater opposed collision (ACC) method. ) Is preferable.

The ACC method is a method for preparing a translucent aqueous dispersion by rapidly finely dividing and nanodispersing natural cellulose fibers from the nano level to the molecular level in water. In the ACC method, dispersions of natural cellulose fibers are simultaneously jetted from a pair of opposing nozzles toward one point at a high pressure (for example, about 70 to 250 MPa), and the jet streams collide with each other at high speed. As a result, the surface of the natural cellulose fiber is peeled off to make it nanofibrillated (nano-miniaturized), and the affinity with water, which is a carrier, is improved, so that the state is finally close to dissolution. By using the ACC method, only the interaction between the fibers of natural cellulose fibers is ruptured to perform nanominiaturization, so that there is no structural change in the cellulose molecules and the decrease in degree of polymerization due to rupture is minimized. Then, cellulose nanofibers can be obtained. In the ACC cellulose nanofiber, the hydroxyl group on the fiber surface is hydrophilic, and the oxygen bonded between the cellulose molecules is hydrophobic. Therefore, in the ACC cellulose nanofiber, both the hydrophilic part and the hydrophobic part are exposed on the fiber surface, and the ACC cellulose nanofiber has an amphoteric property. Since the ACC cellulose nanofibers have the above-mentioned characteristics, they can be more uniformly dispersed in the aqueous dispersion. As a result, the conductive material 10 in which the ACC cellulose nanofibers are uniformly present can be obtained, and the stable conductive material 10 that does not swell by excessively absorbing water can be obtained. Therefore, the conductive material 10 containing the ACC cellulose nanofibers can exhibit more stable conductivity and have strength.

As the natural cellulose fiber, pulp fiber such as bamboo, straw, or hemp, or woody pulp fiber such as softwood or hardwood can be used. In the case of ACC cellulose nanofibers, the ratio of the hydrophilic part and the hydrophobic part exposed on the fiber surface differs depending on the type of natural cellulose fiber used. Among the natural cellulose fibers, the bamboo-derived natural cellulose fibers have a higher proportion of hydrophobic parts exposed on the fiber surface than the hydrophilic parts, and it is considered that the amphipathic characteristics are strongly exhibited. Therefore, it is preferable to use bamboo-derived natural cellulose fibers as the natural cellulose fibers used as a raw material for the ACC cellulose nanofibers.

The cellulose nanofibers may be used in a state of being dispersed in a solution, or may be used in a state of being powdered.

The binder of the conductive material 10 functions as a binder for binding the fibers to each other, and includes a conductive polymer and a synthetic resin (binder resin). The binder resin may not be contained in the case where the fibers can be sufficiently bonded to each other even if the binder is only a conductive polymer 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 obtained by doping poly 3,4-ethylenedioxythiophene (PEDOT) with polystyrene sulfonic acid (poly 4-styrene sulfonate; PSS). , Polyphenylene vinylene, polypyrrole and the like can be used. Above all, it is preferable to use PEDOT / PSS because the contact impedance with the living body is lower and the conductivity is high.

As the binder resin of the binder, various resins such as a thermoplastic resin, a thermosetting resin, and a photocurable resin can be used. In this embodiment, a thermosetting resin is used. Examples of the thermoplastic resin include polycarbonate resin, polyarylate resin, styrene-butadiene resin, styrene-acrylonitrile resin, styrene-maleic acid resin, acrylic acid resin, styrene-acrylic acid resin, polyethylene resin, and 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, Alternatively, a polyether resin or the like can be mentioned. Examples of the thermosetting resin include silicone resin, epoxy resin, phenol resin, urea resin, and melamine resin. Examples of the photocurable resin include an epoxy-acrylic acid resin (more specifically, an adduct of an acrylic acid derivative of an epoxy compound) or a urethane-acrylic acid resin (more specifically, a urethane compound). Acrylic acid derivative adduct) and the like. Among these resins, a resin having a small curing shrinkage is preferable, and for example, a silicone resin is preferable. One type of these binder resins may be used alone, or two or more types may be used in combination.

In this embodiment, cellulose nanofibers are used as the fibers, PEDOT / PSS is used as the conductive polymer, and a silicone resin is used as the binder resin. In this case, the conductive material 10 can be used as a cellulose sponge body formed by containing cellulose nanofibers and PEDOT / PSS.

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

The average thickness of the conductive material 10 is preferably 1 μm to 30 μm. Within this range, it is possible to have conductivity, and when the conductive material 10 is provided at the tip portion 131 of the electrode leg 13, the electric signal transmitted from the living body can be stably energized. Further, since the conductive material 10 contains fibers, the average thickness of the conductive material 10 can be easily set to 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 higher the material cost and the process cost, and it is better to determine the upper limit average thickness in consideration of the balance. For example, the average thickness is more preferably 5 μm to 27 μm, further preferably 10 μm to 25 μm, and most preferably about 20 μm. The average thickness of the conductive material 10 means an average value of the thickness of the conductive material 10. For example, in the cross section of the conductive material 10, when several points (for example, 6 points) are measured at arbitrary places, it means the average value of the thicknesses of these measurement points. Further, in the present embodiment, the thickness means 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 mesh shape, 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 electrode for measuring biological information and the conductive material 10 is brought into contact with the surface of the living body in a state where the solution is contained in the pores 11, the conductive material 10 is conductive. 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 conducting the conductive material 10 and the surface of the living body through the solution, the contact impedance between the living body and the conductive material 10 can be lowered, so that an electric signal from the living body can be easily acquired. Therefore, the conductive material 10 can maintain an electrical connection with the living body. Therefore, by using the conductive material 10 for the electrode legs 13 of the electrode for measuring biological information, biological information can be measured stably.

In particular, when the conductive material 10 is brought into contact with the scalp or forehead as a living body, the conductive material 10 can measure the contact impedance by brain waves even if the surface of the scalp or forehead is dry because the conductive material 10 contains a solution. It can be reduced to a value (for example, less than 200 kΩ). Therefore, if the conductive material 10 is used for the electrode legs 13 of the electrode for measuring biological information, brain waves can be stably obtained, and therefore, it can be suitably used for measuring brain waves.

In addition, the fiber has higher strength than the binder and has high wear resistance. Therefore, when the conductive material 10 is attached to the tip 131 of the electrode leg 13 of the electrode for measuring biological information and used, even if the surface of the conductive material 10 is repeatedly rubbed during use or cleaning, the surface of the conductive material 10 Can be suppressed from being scraped.

Further, 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, so that the conductive material 10 has high elasticity. When the conductive material 10 is attached to the tip 131 of the electrode leg 13 of the electrode for measuring biological information and used, the conductive material 10 elastically deforms when the conductive material 10 comes into contact with the living body. As a result, the pressing force on the living body is relaxed, so that the conductive material 10 can come into soft contact with the living body, and it is possible to alleviate the pain caused to the subject. Further, when the conductive material 10 comes into contact with the living body, the conductive material 10 is elastically deformed so that the conductive material 10 can surely come into contact with the living body.

The conductive material 10 has a large number of pores 11 and is formed in a sponge shape. The fibers contained in the conductive material 10 are auxiliary bonded to each other 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 contained. Therefore, the conductive material 10 can be an elastic body having an appropriate hardness while improving the wear resistance.

The conductive material 10 contains a fiber. By including the fiber in the conductive material 10, the amount of the conductive polymer per unit thickness can be reduced as compared with the case where the conductive material 10 does not contain the fiber, so that the required cost per unit layer can be reduced. Therefore, the manufacturing cost of the conductive material 10 can be suppressed.

Further, an electrode for measuring biological information including a conductive material made of metal cannot be used for a subject having a metal allergy. In the present embodiment, since the conductive material 10 is formed including a binder, even if the conductive material 10 is attached to the tip 131 of the electrode leg 13 of the electrode for measuring biological information and brought into contact with the living body, the user can use it. It does not cause metal allergies and is safe. Therefore, the conductive material 10 can be used safely by the subject.

When the fibers contained in the conductive material 10 are nanofibers, a large number of nanofibers are finely connected to each other at a shorter distance, so that smaller gaps are 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 inside, so that the electrical connection with the living body can be stably maintained.

Further, the nanofibers can be more finely and uniformly present in the conductive material 10 than the fibers. Therefore, the nanofibers can be more finely connected (entangled) in the conductive material 10 than the fibers, so that the strength of the conductive material 10 can be further 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 131 of the electrode leg 13 of the electrode for measuring biological information, the cellulose nanofiber has high hydrophilicity and is therefore conductive. The solution can be more easily contained inside the material 10. Therefore, by using cellulose nanofibers as fibers, it is possible to maintain a more stable electrical connection with the living body. Further, since the cellulose nanofibers have high resistance to alcohol, they can be washed with alcohol when the conductive material 10 is washed.

<Method for manufacturing conductive material according to the first embodiment>
Next, the method for producing the conductive material according to the first embodiment will be described. FIG. 5 is a flowchart showing a method for manufacturing a conductive material according to the present embodiment. As shown in FIG. 5, the method for producing a conductive material according to the present embodiment includes a mixing step (step S11), a solidification step (step S12), and a curing step (step S13). Hereinafter, each step will be described.

First, in the mixing step (step S11), the fiber is mixed with a binder (a conductive polymer and a thermosetting resin which is a binder resin) for binding the fibers and a solvent as a solvent for dispersing the fibers. Make a solution. The mixed solution is prepared by adding a fiber, 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 the preparation of the mixed solution, for example, a bead mill, a roll mill, a ball mill, an ultrasonic disperser, or the like 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, the dispersion medium may contain only one of the above-mentioned organic solvents, or may contain two or more of them.

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, the conductive polymer, the thermosetting resin, and the solvent is preferably long from the viewpoint of ensuring the dispersibility of the fiber, the conductive polymer, and the thermosetting resin in the solvent. It is set appropriately in consideration of the balance with sex.

Next, in the solidification step (step S12), the mixed solution is dried by using a freeze-drying 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). The freeze-drying is a method of drying the mixed solution by freezing the mixed solution and reducing the pressure in the frozen state to sublimate the solvent in the mixed solution.

In the freezing step (step S121) of the solidification step (step S12), after the mixed solution is poured into a mold, the mixed solution is frozen in a mold and the water contained in the mixed solution is frozen (cooling). Let). The mold containing the mixed solution is placed under reduced pressure and in a low temperature atmosphere to freeze the solvent.

The freezing temperature of the mixed solution must be equal to or lower than the freezing point of the solvent in the mixed solution, preferably −40 ° C. or lower, and more preferably −80 ° C. or lower.

The pressure is preferably 100 Pa or less, more preferably 10 Pa or less, and even more preferably in a vacuum state. If the pressure exceeds 100 Pa, the solvent in the frozen mixed solution may melt.

The freezing time of the mixed solution is preferably about 12 to 48 hours from the viewpoint of surely cooling the water contained in the mixed solution and improving 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 sublimated under reduced pressure. As a result, the solvent is removed in a state where the fibers are bound to each other by the conductive polymer, and the places where the solvent is released become a large number of fine spaces. As a result, a porous body having a large number of pores and containing an uncured binder resin can be 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 for heating the porous body may be any temperature as long as the thermosetting resin which is a binder resin can be cured, for example, 80 to 200 ° C., more preferably 100 to 150 ° C., and 120 to 120 ° C. It is more preferably 130 ° C.

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

In the present embodiment, the conductive material 10 having a large number of pores 11 inside and on the surface can be easily obtained by drying the mixed solution using a freeze-drying method.

[Modified example of the method for manufacturing a 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), but when the binder resin is a photocurable resin, it is cured. In the step (step S13), the porous body is irradiated with ultraviolet rays. When the binder resin is a thermoplastic resin, the curing step (step S13) is omitted because the binder resin is cured at the same time as the porous body is obtained in the solidification step (step S12).

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

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

The electrode base 21A of the electrode legs 20A is detachably attached to the electrode for measuring biological information.

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

As described above, the tip portion 312a means the tip that comes into contact with the scalp, which is a living body, and the peripheral region of the tip that may come into contact with the living body when the electrode legs 20A are tilted.

The electrode substrate 21A can be formed by using a conductive elastomer or an insulating material. The insulating material is a material having no conductivity or extremely low conductivity. In the present embodiment, the electrode substrate 21A is integrally formed of a conductive elastomer.

The type of the conductive elastomer is not particularly limited. The conductive elastomer can be obtained, for example, by melting and mixing a conductive filler and a non-conductive elastomer. The electrode substrate 21A has a low elastic modulus because it is molded by containing a non-conductive elastomer having rubber elasticity. Therefore, when the electrode leg 20A is used as the 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 the contact with the living body can be ensured and the pressing force on the living body is relaxed. it can.

The type of the above-mentioned conductive filler is not particularly limited as long as it has conductivity. For example, conductive fillers include carbon materials such as graphite, carbon black, carbon nanotubes, carbon nanohorns or carbon fiber (carbon fiber); aluminum, gold, silver, copper, iron, platinum, chromium, tin, indium, antimony, Metals such as titanium or nickel; conductive ceramics such as so-called ABO ₃ type perovskite type composite oxides, and the like, but are 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 non-conductive elastomer described above include silicone rubber, ethylene propylene rubber, ethylene propylene diene rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, chloroprene rubber, acrylonitrile butadiene rubber, butyl rubber, urethane rubber, or Fluorine rubber and the like can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, it is preferable to use silicone rubber from the viewpoint of durability and the like.

Examples of the insulating material other than the conductive elastomer include the above-mentioned non-conductive elastomer, polypropylene (PP), polycarbonate (PC), ABS resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamide (PA). Alternatively, a liquid crystal polymer (LCP) or the like can be used.

The conductive layer 22 is provided on the surface of the tip portion 211 of the electrode substrate 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 in which the conductive layer 22 is formed is not limited. When the electrode base 21A is formed by using a conductive elastomer, the electrode base 21A can ensure conductivity, so that the conductive layer 22 need only be formed on the surface of the tip portion 211. When the electrode base 21A is made of an insulating material, the conductive layer 22 may be provided on the entire surface of the electrode base 21A in order to ensure the continuity of the electrode base 21A.

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

In the electrode leg 20A having the above-described configuration, the conductive layer 22 is formed at the tip portion 211 of the electrode substrate 21A, and the solution is contained in the pores 221 of the conductive layer 22. When the conductive layer 22 is brought into contact with the surface of the living body, the solution retained in the pores 221 of the conductive layer 22 flows to the surface of the living body. By conducting the conductive layer 22 and the surface of the living body through the solution, the contact impedance between the living body and the electrode legs 20A can be significantly reduced, so that it becomes easy to acquire an electric signal from the living body and the living body. The electrical signal of is more sensitive. Therefore, since the electrode legs 20A can stably maintain the electrical connection with the living body, the biological information can be measured stably.

Further, 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 if the conductive layer 22 on the surface of the tip portion 211 of the electrode leg 20A is rubbed during use or cleaning of the electrode leg 20A, it is possible to prevent the conductive layer 22 from being scraped. Therefore, even if the electrode legs 20A are used as the electrode for measuring biological information, the conductive layer 22 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 is stably maintained. be able to. Therefore, if the electrode leg 20A is used, the electrical connection between the tip portion 211 of the electrode leg 20A and the living body can be maintained, so that an electric signal from the living body can be stably obtained.

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

Further, when the electrode substrate 21A is made of an insulating material, other configurations are also conceivable. FIG. 8 is a diagram illustrating a modified example 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 sectional view of FIG. As shown in FIG. 8, it is preferable to form the underlying conductive layer (second conductive layer) 23 electrically connected to the conductive layer 22 on the entire surface of the electrode substrate 21A. As a result, conduction can be taken over the entire surface of the electrode substrate 21A. As the conductive polymer contained in the underlying conductive layer 23, the same conductive polymer as the conductive layer 22 can be used. The thickness of the base conductive layer 23 may be about 200 nm to 1 μm, as long as it is conductive. In FIG. 8, the base conductive layer 23 may be conductive with the biometric electrode to which the electrode base 21A is connected, and may not be formed on the end surface of the electrode base 21A opposite to the tip portion 211.

<Manufacturing method of electrode legs according to the second embodiment>
Next, a method of manufacturing the electrode legs 20A according to the second embodiment will be described. FIG. 9 is a flowchart showing a method of manufacturing the electrode legs 20A according to the present embodiment.

As shown in FIG. 9, the method for manufacturing the electrode legs 20A according to the present embodiment includes a leg substrate manufacturing step (step S21A) for producing the electrode substrate 21A having conductivity, and a conductive layer on the tip portion 211 of the electrode substrate 21A. A step of forming a conductive layer (step S22A) for forming 22 is included.
Hereinafter, each step will be described.

In the leg substrate manufacturing step (step S21A), the electrode substrate 21A is molded using the material forming the electrode substrate 21A. When using the molding method, a mold corresponding to the shape of the electrode substrate 21A is used. By using the mold, the electrode substrate 21A can be molded.

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), the fiber, the thermosetting resin which is a conductive polymer and binder resin that binds the fibers to each other, and a solvent as a solvent in which the fibers are dispersed are used. The mixed solution containing the mixture is applied to the tip portion 211 to form a coating layer.

The solidification step (step S222) of the conductive layer forming step (step S22A) can be performed in the same manner as the solidification step (step S12) of the method for producing a conductive material according to 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 portion 211 of the electrode substrate 21A.

As described above, the electrode leg 20A in which the conductive layer 22 is formed on the tip portion 211 of the electrode substrate 21A can be obtained.

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

Further, in the present embodiment, the film thickness of the coating layer formed when the mixed solution is applied once to the tip portion 211 in the coating step (step S221) of the conductive layer forming step (step S22A) does not include fibers. The film thickness of the coating layer formed when the solution is applied once can be made thicker. Since the desired thickness of the conductive layer 22 can be obtained with a small number of coatings of the mixed solution, the cost required for forming the coating layer in the coating step (step S221) can be reduced. Further, by increasing the thickness of the conductive layer 22, even if the surface of the conductive layer 22 is rubbed and worn when the electrode legs 20A are used as electrodes for measuring biological information or when the electrode legs 20A are cleaned, the conductive layer 22 is thickened. It is possible to delay the time until the 22 is worn away and peeled 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 fiber contained in the conductive layer 22 is a cellulose nanofiber, the mixed solution containing the cellulose nanofiber and the conductive polymer has good wettability to the electrode substrate 21A and has high thixophilicity. Therefore, when the conductive layer 22 is formed by using a mixed solution containing cellulose nanofibers and a conductive polymer, the thickness of the coating layer formed when the mixed solution is applied once to the tip portion 211 is made thicker. be able to. The film thickness of the coating layer formed by one coating of the mixed solution is, for example, about 1.3 to 4 times the film thickness of the coating layer formed by coating the solution containing no cellulose nanofibers. Can be thickened.

[Modified example of the method for manufacturing the electrode legs according to the second embodiment]
In the present embodiment, in the conductive layer forming step (step S22A), the conductive layer 22 is formed only on the tip portion 211 of the electrode base 21A, but a part of the side surface of the electrode base 21A in addition to the tip portion 211. Alternatively, the conductive layer 22 may be formed on the entire surface.

Further, in the present embodiment, the conductive layer forming step (step S22A) is not limited to this, although the coating layer applied to the tip portion 211 of the electrode substrate 21A is freeze-dried to form the conductive layer 22. In the conductive layer forming step (step S22A), for example, the conductive layer 22 prepared in advance may be attached to the tip portion 211 of the electrode substrate 21A. FIG. 10 shows an example of a method for manufacturing the electrode legs in this case. FIG. 10 is another flowchart showing a method of manufacturing the electrode legs according to the present embodiment. As shown in FIG. 10, the method for manufacturing an electrode leg according to the present embodiment includes a leg substrate manufacturing 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 portion 211 of the electrode substrate 21A. The conductive layer 22 is obtained by the method for manufacturing a conductive material according to the first embodiment. The conductive layer 22 may be attached to the tip portion 211 using an adhesive, or may be fitted and fixed to the tip portion 211. By attaching the conductive layer 22 to the tip portion 211 of the electrode substrate 21A, the electrode legs 20A can be obtained.

Further, the electrode base 21A is manufactured using a conductive material, but when the electrode base 21A is manufactured using an insulating material, the surface of the electrode base 21A prepared using the insulating material is surface-treated. After that, the conductive layer 22 is formed. FIG. 11 shows an example of a method for manufacturing the electrode legs in this case. FIG. 11 is another flowchart showing a method of manufacturing the electrode legs according to the present embodiment. As shown in FIG. 11, the method for manufacturing an electrode leg according to the present embodiment includes a leg substrate manufacturing step (step S21B) and a conductive layer forming step (step S22A). The leg substrate manufacturing step (step S21B) includes a leg substrate molding step (step S211) for molding the electrode substrate 21A and a surface treatment step (step S212) for activating the surface of the tip portion 211 of the electrode substrate 21A. .. In the leg substrate molding step (step S211), the electrode substrate 21A is formed by using the material for forming the electrode substrate 21A. In the surface treatment step (step S212), the surface of the tip portion 211 is activated to improve the adhesion to the conductive layer 22. The details of the surface treatment step (step S212) will be described in the surface treatment step (step S32) of the method for manufacturing the electrode legs 20B according to the third embodiment shown in FIG. 24, which will be described later. By surface-treating the tip portion 211 of the electrode base 21A before forming the conductive layer 22 on the tip portion 211 of the electrode base 21A, the conductive layer 22 is stably formed on the tip portion 211 of the electrode base 21A. it can.

Further, the electrode base 21A is made of a conductive material, but when the electrode base 21A is made of an insulating material, the electrode base 21A and the conductive layer 22 are as shown in FIG. It is preferable to form the underlying conductive layer 23 between the two. In this case, in the method for manufacturing an electrode for measuring biological information according to the present embodiment, a base conductive layer 23 containing a conductive polymer is formed on the surface of the electrode substrate 21A. As shown in FIG. 12, the method for manufacturing the electrode for measuring biological information according to the present embodiment includes a leg substrate manufacturing step (step S21A) and a base conductive layer 23 containing a conductive polymer on the surface of the electrode substrate 21A. The base conductive layer forming step (step S22C) and the conductive layer forming step (step S23) are included. The conductive layer forming 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 coating step (step S231) and the solidification step (step S232) are the same as the coating step (step S221) and the solidification 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 made of an insulating material, the electrode base 21A secures continuity 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 legs>
The electrode legs according to the third embodiment will be described with reference to the drawings. The electrode legs according to the present embodiment are the electrode base 21A of the electrode legs 20A according to the second embodiment, other than the groove portion (tip groove portion) 24A provided in the tip portion 211 which is the region A and the tip portion 211. An auxiliary groove portion (side surface groove portion) 25 provided on the side surface 212 of the electrode leg 20B, which is a portion, is formed.

13 is a perspective view showing the appearance of the electrode legs according to the third embodiment, FIG. 14 is a front view of the electrode legs according to the third embodiment, and FIG. 15 is III- of FIG. III is a cross-sectional view. As shown in FIGS. 13 to 15, the electrode legs 20B according to the present embodiment include the electrode base 21B instead of the electrode base 21A shown in FIGS. 6 and 7. The electrode base 21B is formed on the electrode base 21A shown in FIGS. 6 and 7 on the groove portion (tip groove portion) 24A provided in the tip portion 211 which is the region A and the side surface 212 of the electrode leg 20B which is a portion other than the tip portion 211. An auxiliary groove portion (side groove portion) 25 to be provided is formed. Since the conductive layer 22 is formed on the surface of the tip portion 211, it is also formed on the surface of the tip groove portion 24A. By providing the tip groove portion 24A and the side surface groove portion 25, the electrode leg 20B can hold the liquid in the tip groove portion 24A and the side surface groove portion 25.

As the liquid contained in the tip groove portion 24A and the side groove portion 25, the same liquid as the liquid contained in the pore 11 can be used.

The tip groove portion 24A is formed on the surface of the tip portion 211 of the electrode substrate 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 in a substantially U shape in cross-sectional view. The cross-sectional shape of the tip groove portion 24A may be formed in a substantially V shape in cross-sectional view.

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

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

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

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

The width W2 of the side groove portion 25 (see FIG. 17) is preferably 10 μm to 120 μm, similar to the width W1 of the tip groove portion 24A. When the width W2 of the side groove portion 25 is 10 μm to 120 μm, as shown in FIG. 17, even if the conductive layer 22 is formed in the side groove portion 25, the liquid can be held in the side groove portion 25. Further, if the conductive layer 22 is formed in the side groove portion 25, for example, even if the side surface 212 of the electrode leg 20B is strongly wiped with a Kimwipe containing alcohol, the fibers of the Kimwipe will not penetrate into the side groove portion 25. Can be reduced. Further, when the width W2 is within the above range, the thickness of the hair is not exceeded, so that it is possible to reduce the invasion of the hair into the side groove portion 25. The width W2 of the side groove portion 25 is more preferably 20 μm to 70 μm, and further preferably 30 to 50 μm. Since the definition of the width W2 of the side groove portion 25 is the same as the width W1 described above, the description thereof will be omitted.

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

The electrode leg 20B configured as described above has a plurality of tip groove portions 24A on the surface of the tip portion 211 which is the region A, and has a conductive layer 22 on the surface of the tip portion 211. When the electrode legs 20B are attached to the biometric information measuring electrode and the biometric information measuring electrode is repeatedly used for a long period of time, for example, as shown in FIG. 18, a part of the conductive layer 22 on the surface of the tip portion 211 is gradually rubbed. There is a possibility that a part of the conductive layer 22 will be peeled off until the tip 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 portion 24A remains. Therefore, the continuity 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 portion 24A and the living body, so that the continuity between the conductive layer 22 and the living body can be stably maintained. Therefore, according to the electrode legs 20B, since the electrical connection between the tip portion 211 of the electrode substrate 21B and the living body can be maintained, an electric signal from the living body can be stably obtained, and the biological information can be stably measured. be able to.

Further, when the electrode legs 20B are immersed in the liquid, the liquid can be held in the tip groove portion 24A provided on the surface of the tip portion 211 by a capillary phenomenon. Therefore, when the tip portion 211 is brought into contact with the living body when measuring biological information, as shown in FIG. 19, the liquid held in the tip groove portion 24A flows to the surface of the living body 26 in contact with the tip portion 211. spread. By conducting the living body 26 with the conductive layer 22 via the liquid, the area of conducting from the living body 26 to the conductive layer 22 becomes large, so that the contact impedance between the living body 26 and the electrode legs 20B can be further lowered. As a result, the biological information measuring electrode provided with the electrode legs 20B can measure the biological information more stably.

Further, the electrode leg 20B has a plurality of side surface groove portions 25 on the side surface of the electrode substrate 21B, and the side surface groove portion 25 communicates with at least a part of the tip groove portion 24A. Therefore, at the time of measuring the biological information, the liquid held in the tip groove portion 24A flows to the surface of the living body in contact with the tip portion 211, and the liquid held in the tip groove portion 24A is consumed. At that time, the liquid held in the side groove portion 25 flows to the tip groove portion 24A and is supplied to the surface of the living body. As a result, 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 as the electrode for measuring biological information, the biological information can be measured more stably and continuously.

[Modification example of electrode legs according to the third embodiment]
An example of the electrode leg 20B is shown, but the present invention is not limited to this. Some modifications of the electrode legs 20B are shown below.

In the present embodiment, the tip groove portion 24A is formed in a cross shape when the tip portion 211 of the electrode substrate 21B is viewed in the + Z axis direction, but the tip groove portion 24A holds a liquid in the groove. Any shape that can be used is sufficient. For example, as shown in FIG. 20, the tip portion 211 of the electrode substrate 21B may be provided with the tip groove portion 24B formed in a mesh shape, or the tip portion formed in a dendritic shape as shown in FIG. 21. The groove portion 24C may be provided. As shown in FIGS. 20 and 21, by providing the tip groove portion 24B formed in a mesh shape or the tip groove portion 24C formed in a dendritic shape in the tip portion 211, the tip groove portions 24B and 24C on the surface of the tip portion 211 are provided. The liquid can be held more efficiently. Therefore, the continuity between the conductive layer 22 and the living body can be maintained more stably. Further, when the tip portion 211 comes into contact with the living body, the tip portion 211 can stably maintain the continuity between the conductive layer 22 on the surface of the tip groove portions 24B and 24C and the living body in all directions. Therefore, even if the tip portion 211 is moved along the living body in all directions, the biological information can be measured more stably.

In the present embodiment, the side groove portion 25 is formed on the surface of the side surface 212 of the electrode substrate 21B, but the side groove portion 25 is not formed when the tip groove portion 24A is sufficient to hold the liquid. You may. This makes it possible to manufacture an electrode leg in which a plurality of tip groove portions 24A are formed in the tip portion 211.

<Manufacturing method of electrode legs according to the third embodiment>
Next, a method of manufacturing the electrode legs 20B according to the third embodiment will be described. FIG. 22 is a flowchart showing a method of manufacturing the electrode legs 20B according to the present embodiment. As shown in FIG. 22, in the method for manufacturing the electrode legs 20B according to the present embodiment, a conductive electrode substrate is formed, and a plurality of tip groove portions 24A are formed on the surface of the tip portion 211 which is a region A. A leg substrate manufacturing step (step S31A) in which a side groove portion 25 is formed on the side surface 212 to fabricate the electrode substrate 21B, a surface treatment step (step S32) in which the surface of the tip portion 211 of the electrode substrate 21B is activated, and an electrode It includes a conductive layer forming step (step S33) of forming the conductive layer 22 on the tip portion 211 of the substrate 21B. Hereinafter, each step will be described.

In the leg substrate manufacturing step (step S31A), the electrode substrate 21B is molded using the material forming the electrode substrate 21B, and a plurality of tip groove portions 24A are formed on the surface of the tip portion 211 which is the region A, and the side surface 212 A side groove portion 25 is formed in the surface.

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

In the surface treatment step (step S32), the surface of the tip portion 211 is activated by using a method of irradiating with vacuum ultraviolet light (excimer UV light) by excimer or a method of plasma treatment in a mixed gas containing Ar and oxygen. To process. By activating the surface of the tip portion 211, the adhesion between the tip portion 211 and the conductive layer 22 can be improved in the conductive layer forming step (step S33) described later. As a result, it is possible to prevent the conductive layer 22 from being easily peeled off from the electrode substrate 21B (mainly the tip portion 211) when a physical force is applied by cleaning or wiping the tip portion 211.

When the method of irradiating the excimer UV light is used, the surface of the tip portion 211 is irradiated with the excimer UV light. The excimer UV light is UV light having a wavelength of 240 nm or less in the atmosphere, and has a predetermined wavelength (center wavelength) depending on the type of the discharge gas. As the discharge 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) and the like can be used. .. It is assumed that the irradiation lamp that emits excimer UV light is, for example, a dielectric barrier discharge lamp filled 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 when the excimer state is dissociated into Xe atoms again, light having a wavelength of about 172 nm is generated. By irradiating oxygen with light having a wavelength of 172 nm, high-concentration ozone is generated. By the action of this ozone, the surface of the portion of the electrode substrate 21B to be irradiated with Exima UV light is modified, and a highly hydrophilic group (for example, a hydroxyl group (OH group), an aldehyde group (CHO group), a carboxyl group (for example) A COOH group) is formed. As a result, the surface of the tip portion 211 of the electrode substrate 21B can be activated, and the surface of the tip portion 211 can be changed to hydrophilic. As a result, the tip portion 211 can be changed. Since the wettability of the surface of the electrode base 21B to water can be enhanced, only the tip portion 211 can be easily activated, and therefore, it can be effectively used when the electrode substrate 21B is made of a conductive material. It is possible to irradiate at least the surface of the tip portion 211 with an activation treatment, and the portion other than the tip portion 211 of the electrode base 21B or the entire electrode base 21B may be irradiated with Exima UV light.

When the method of plasma treatment in a mixed gas containing Ar and oxygen is used, the entire surface of the electrode substrate 21B is activated by plasma. As a result, the entire surface of the electrode substrate 21B can be changed to be hydrophilic in addition to the surface of the tip portion 211. As a result, the wettability of the entire surface of the electrode substrate 21B including the tip portion 211 to water can be improved. Therefore, the electrode substrate 21B can be effectively used regardless of whether it is made of a conductive material or an insulating material.

The conductive layer forming 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, and the coating step (step S331) and the solidification step (step S332) are both described above. , The same as the coating step (step S221) and the solidification 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 portion 211.

As described above, the electrode leg 20B having the conductive layer 22 formed on the surface of the tip portion 211 can be obtained.

[Modified example of the method for manufacturing the electrode legs according to the third embodiment]
In the present embodiment, in the leg substrate manufacturing step (step S31A), the electrode substrate 21B is simultaneously formed by using a mold provided with protrusions corresponding to the tip groove portion 24A and the side groove portion 25. Not limited. For example, after molding the electrode substrate 21B, the tip groove portion 24A and the side groove portion 25 may be formed simultaneously or separately. When the tip groove portion 24A and the side groove portion 25 are formed separately, the methods for manufacturing the electrode legs 20B according to the present embodiment are a leg substrate manufacturing step (step S31B) and a surface treatment step (step S32), as shown in FIG. ) And the conductive layer forming step (step S33). The leg substrate manufacturing step (step S31B) includes a preparatory step of preparing the electrode substrate (step S311) and a groove forming step (step S312) of forming a plurality of tip groove portions 24A and side groove portions 25 on the electrode substrate. In the preparation step (step S311), the electrode substrate is produced by using a molding method or the like, and the electrode substrate is prepared. In the groove forming step (step S312), the tip groove portion 24A and the side groove portion 25 are formed on the prepared electrode substrate. As a result, the electrode substrate, the tip groove portion 24A, and the side groove portion 25 can be formed separately.

Further, the tip groove portion 24A and the side groove portion 25 may be formed separately. In this case, as shown in FIG. 24, the method for manufacturing the electrode legs 20B according to the present embodiment is a leg substrate manufacturing step (step S31C), a surface treatment step (step S32), and a conductive layer forming step (step S33). And include. The leg substrate manufacturing step (step S31C) includes a preparatory step of preparing an electrode substrate (step S311), a tip groove forming step of forming a plurality of tip groove 24A (step S312), and a side groove forming of the side groove 25. It includes a step (step S313). As a result, the tip groove portion 24A and the side groove portion 25 can be separately formed on the electrode substrate.

[Fourth Embodiment]
<Electrodes for measuring biological information>
The electrode for measuring biological information according to the fourth embodiment will be described. The electrode for measuring biological information according to the present embodiment measures biological information by contacting a part of the living body. The electrode for measuring biological information according to the present embodiment has the electrode leg 20A according to the second embodiment described above.

FIG. 25 is a perspective view showing the appearance of the biometric information measuring electrode according to the fourth embodiment, and FIG. 26 is another perspective view showing the appearance of the biometric information measuring electrode according to the fourth embodiment. Yes, FIG. 27 is a sectional view taken along line IV-IV of FIG. As shown in FIGS. 25 to 27, the biometric information measuring 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 and the like), and this central axis J also includes the central axis of the electrode 30A for measuring biological information. This means that it serves as a central axis when the biological information measuring electrode 30A is installed in the living body.

The base portion 31 and the terminal portion 33 can be formed by using the conductive elastomer or the insulating material used for forming the electrode base 21A of the electrode legs 20A according to the second embodiment described above. The base portion 31 and the terminal portion 33 may be made of the same material or may be made 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, it conducts from the tip end portion 312a (described later) side of the electrode leg 20A to the terminal portion 33.

When the base portion 31 and the terminal portion 33 are formed by using a conductive elastomer, the conductive elastomer can be obtained, for example, by melting and mixing a conductive filler and a non-conductive elastomer. The base portion 31 and the terminal portion 33 have a low elastic modulus because they are molded by containing a non-conductive elastomer having rubber elasticity. Therefore, when the electrode 30A for measuring biological information is used, the base portion 31 and the terminal portion 33 are easily deformed according to the uneven shape of the surface of the living body, so that the contact with the living body can be ensured and the pressing force on the living body is applied. Can be relaxed.

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

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

The electrode legs 312A extend 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 second embodiment described above is used. The electrode legs 312A are separable from the base 311.

[Terminal part]
As shown in FIGS. 25 to 27, the terminal portion 33 is the upper surface of the base portion 311 of the base portion 31, and projects in the + Z axis direction from the substantially central portion (position through which the central axis J passes) of the base portion 311 in a plan view. It is provided. A metal layer 35 is provided at the center of the terminal portion 33. As the metal layer 35, a metal such as gold, silver, or copper is used. The wiring 42 (see FIG. 28) of the inspection device 40 (see FIG. 28), which will be described later, is connected to the portion where the metal layer 35 is provided. The terminal portion 33 is electrically connected to the base portion 31 in which the electrode legs 312A are integrally formed. Therefore, the terminal portion 33 is electrically connected to the tip portion 312a, which is the region A of the electrode leg 312A, and the information signal from the region A can be taken out. A layer formed of a conductive material other than metal may be provided in the central portion of the terminal portion 33.

The terminal unit 33 is connected to the measuring unit 43 (see FIG. 28). Specifically, the terminal unit 33 is connected to a wiring 42 (see FIG. 28) or the like, and the wiring 42 (see FIG. 28) and the measuring unit 43 (see FIG. 28) are connected to each other. The terminal portion 33 transmits an electric signal from a living body (for example, the scalp or the forehead) obtained from the tip portion 211 of the electrode leg 312A to the measuring unit 43 (see FIG. 28) via the base portion 31, and provides biological information (for example, FIG. , Brain wave).

Next, an example will be described in which an electroencephalogram is measured as biological information of a subject using an inspection device provided with a biological information measuring electrode 30A according to the present embodiment. FIG. 28 is a diagram showing an example of measuring an electroencephalogram of a subject using an inspection device provided with an electrode 30A for measuring biological information. As shown in FIG. 28, the inspection device 40 includes an electrode 30A for measuring biological information, a cap 41 that covers the head of a subject, a wiring 42, a measuring unit 43, and a display unit 44. The cap 41 has the shape of a hat or a helmet so as to cover the head of the subject, and is made of synthetic resin, cloth, or the like. Electrodes 30A for measuring biological information are provided on the cap 41 at a plurality of locations (for example, 21 locations) at predetermined intervals, and are attached to arbitrary locations on the scalp 45 of the subject. The wiring 42 is, for example, a lead wire, one end of which is connected to the terminal portion 33 and the other end of which is connected to the measurement portion 43. The measuring unit 43 includes a power supply unit 431 and a signal analysis unit 432 that analyzes an electric signal and measures an electroencephalogram as biological information. The display unit 44 is a monitor and displays the brain waves analyzed by the signal analysis unit 432. EEG is 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 electrode 30A for measuring biological information is fixed to the cap 41, and the tip 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 the measurement is started, an electric signal from the scalp 45 is transmitted from the scalp 45 to the tip portion 312a of the electrode legs 312A via the conductive layer 22. The transmitted electric signal is transmitted from the tip portion 312a to the terminal portion 33, the wiring 42, and the measuring portion 43 in this order via the base portion 31. The signal analysis unit 432 analyzes the transmitted electric signal and displays an electroencephalogram (for example, α wave, β wave, θ wave, etc.) 441 on the display unit 44.

The biological information measuring electrode 30A configured as described above has a conductive layer 22 on the surface of the tip portion 312a, which is a region A of the electrode legs 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 contain the solution in the pores 221 (see FIG. 6). The conductive layer 22 can be provided on the surface of the tip portion 312a of the electrode legs 312A of the biometric information measuring electrode 30A. When the conductive layer 22 comes into contact with 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, by conducting the conductive layer 22 and the surface of the living body through the solution, the contact impedance between the living body and the conductive layer 22 can be lowered, so that an electric signal from the living body can be easily acquired. Therefore, since the electrode 30A for measuring biological information can maintain an electrical connection with the living body, the biological information can be easily and stably measured.

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

Since the electrode legs 312A are separable from the base 311 so that the electrode legs 312A to which the conductive layer 22 is attached can be easily replaced. As a result, even if the conductive layer 22 of the tip portion 312a of the electrode leg 312A becomes unstable due to wear or the like, it can be replaced with the electrode leg 312A capable of normally acquiring the measurement of biological information.

[Modification of the electrode for measuring biological information according to the fourth embodiment]
An example of the electrode 30A for measuring biological information is shown, but the present invention is not limited to this. A modified example of the biological information measuring electrode 30A will be described below.

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 formed of separate members. 29 and 30 show an example of the biometric information measuring electrode 30A when the base portion 31 and the terminal portion 33 are made of separate members. FIG. 29 is a perspective view showing an example of another configuration of the electrode 30A for measuring biological information, and FIG. 30 is a sectional view taken along line VV of FIG. 29. 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 fixedly connected to the end portion 311b on the side opposite to the side where the base portion 311 of the base portion 31 is continuous with the electrode legs 312A by, for example, a conductive adhesive or a conductive paste (not shown). Has been done. As a result, the terminal portion 33 is electrically connected to the base portion 31 formed integrally with the electrode legs 312A. Therefore, the tip portion 312a of the electrode leg 312A 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 a projecting portion 311a on its back surface (-Z axis direction side), but the projecting portion 311a is not provided, and the electrode legs 312A are continuously formed on the base portion 311 of the disk portion. May be done.

In the present embodiment, the base portion 31 is integrally formed with the base portion 311 and the electrode legs 312A, but the base portion 311 and the electrode legs 312A may be formed of separate members. At this time, the base portion 311 and the electrode legs 312A are bound by a binding member made of synthetic resin. The binding member is a cured synthetic resin such as epoxy resin or urethane resin. Further, as the binding member, in addition to the synthetic resin, a synthetic resin having elasticity such as rubber may be used.

The conductive layer 22 is formed at the tip portion 312a of the electrode leg 312A which is the region A, but may be formed at least at the tip portion 211 and may be formed at another portion of the base portion 31. , The base portion 31 and the terminal portion 33 may be formed on the entire surface. For example, when the base portion 31 and the terminal portion 33 are made of an insulating material, they 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 the 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. As a result, continuity can be taken between the tip portion 211 and the terminal portion 33. As the conductive polymer contained in the underlying 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 will be omitted. The thickness of the base conductive layer 51 may be about 200 nm to 1 μm, as long as it is conductive.

<Manufacturing method of electrode for measuring biological information according to the fourth embodiment>
Next, a method for manufacturing the electrode for measuring biological information according to the fourth embodiment will be described. FIG. 32 is a flowchart showing a method of manufacturing an electrode for measuring biological information according to the present embodiment. As shown in FIG. 32, in the method for manufacturing an electrode for measuring biological information according to the present embodiment, a molding step (step S41A) for molding the base portion 31 and the terminal portion 33 and the surface of the tip portion 312a are activated. The surface treatment step (step S42) and the conductive layer forming step (step S43A) of forming the conductive layer 22 on the surface of the tip portion 312a are included. Hereinafter, each step will be described.

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

The base portion 31 and the terminal portion 33 are formed by a known molding method such as compression molding (compression molding), injection molding (injection molding), or extrusion molding (transfer molding) to form the base portion 31 and the terminal portion 33 having a desired shape. 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 molded at the same time.

When an injection molding method or the like is used, after injection molding, the raw material supply passage (for example, spool, runner, etc.) to which the raw material (resin, metal, etc.) for molding the base portion 31 and the terminal portion 33 is supplied is the base portion 31 or the terminal. It is connected to the unit 33. For example, as shown in FIG. 33, when 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 the terminal portion 33 even after the base portion 31 and the terminal portion 33 are molded. It is preferable to connect to. In the conductive layer forming step (step S13) described later, when at least a part of the base portion 31 and the terminal portion 33 is immersed in the solution containing the conductive polymer, the raw material supply passage 52 is a gripper of the base portion 31. Can be used as. The raw material supply passage 52 determines the position of the product in order to perform suitable molding, and may be connected to the base portion 311 of the base portion 31 or the like in addition to the terminal portion 33 shown in FIG. 33. ..

The surface treatment step (step S42) can be performed in the same manner as the surface treatment step (step S32) of the electrode leg manufacturing method according to the third embodiment shown in FIG. 22.

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

In the conductive layer forming step (step S43A), the fibers are formed on the surface of the tip portion 312a in a state where the fibers are bonded to each other by the conductive polymer and the thermosetting resin, and the conductive layer 22 having a large number of pores is formed. To do. The conductive layer forming 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 applied to at least the tip portion 312a to form a coating layer. As a method of applying the mixed solution to at least the tip portion 211, a dipping method in which at least the tip portion 312a is immersed in the mixed solution, a spray method in which the mixed solution is sprayed on 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 heated and dried at, for example, 120 to 130 ° C., and the coating layer is cured. As a result, the conductive layer 22 is formed on the surfaces of the tip portion 312a and the tip groove portion 24A. In the present embodiment, since the base portion 31 and the terminal portion 33 are formed of the conductive elastomer, the conductive layer 22 may be formed on the surface of the tip portion 312a.

As described above, the biometric information measuring electrode 30A having the conductive layer 22 formed on the surface of the tip portion 312a can be 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 portion 211 is only the conductive polymer. The film thickness of the coating layer formed when the containing solution is applied once can be made thicker. Therefore, the cost required to prepare the coating layer in the coating step (step S131) can be reduced. Further, since the conductive layer 22 becomes thicker, the life of the conductive layer 22 can be further extended.

When the fiber contained in the conductive layer 22 is a cellulose nanofiber, the mixed solution containing the cellulose nanofiber and the conductive polymer has good wettability to the base portion 31 and the terminal portion 33 and has high thixophilicity. Therefore, when the conductive layer 22 is formed by using a mixed solution containing cellulose nanofibers and a conductive polymer, the thickness of the coating layer formed by one coating of the mixed solution includes cellulose nanofibers. It can be, for example, about 1.3 to 4 times thicker than the thickness of the coating layer formed by applying a non-cellulose solution.

[Modified example of the method for manufacturing the electrode for measuring biological information according to the fourth embodiment]
In the present embodiment, in the molding step (step S41A), the base portion 31 and the terminal portion 33 are integrally formed at the same time, 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, the method for manufacturing the electrode for measuring biological information according to the present embodiment includes a molding step (step S41B), a surface treatment step (step S42), and a conductive layer forming step (step S43A). And include. The molding step (step S41B) includes a leg base molding step (step S411) for molding the base portion 31 and the terminal portion 33 and a binding step (step S412) for binding and integrating the base portion 31 and the terminal portion 33. And include. In the binding step (step S412), a known binding member can be used as the binding member used for binding the base portion 31 and the terminal portion 33. For example, an epoxy resin, a synthetic resin such as urethane resin, a synthetic resin having elasticity such as rubber, or the like can be used.

In the present embodiment, since the base portion 31 and the terminal portion 33 are formed of the 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. As a result, the electric signal obtained from the living body is transmitted from the tip portion 312a of the electrode leg 312A to the terminal portion 33 via the conductive layer 22.

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

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

In the present embodiment, the conductive layer forming step (step S43A) is not limited to this, although the coating layer applied to the tip portion 211 of the electrode substrate 21A is freeze-dried to form the conductive layer 22. For example, the electrode legs 312A prepared in advance may be attached to the projecting portion 311a of the base portion 311. FIG. 36 shows an example of a method for manufacturing an electrode for measuring biological information in this case. FIG. 36 is another flowchart showing a method of manufacturing an electrode for measuring biological information according to the present embodiment. As shown in FIG. 36, the method for manufacturing an electrode for measuring biological information according to the present embodiment includes an electrode body manufacturing step (step S51) for manufacturing an electrode body including a base portion 311 of a base portion 31 and a terminal portion 33. , A connecting step (step S52) of connecting the electrode legs 312A to the base 311 is included.

In the electrode body manufacturing step (step S51), the base portion 311 and the terminal portion 33 of the base portion 31 are formed by the same method as in the case of molding the base portion 31 and the terminal portion 33 in the molding step (step S41A). The electrode body can be manufactured by integrally molding. Further, after molding the base portion 311 of the base portion 31 and the terminal portion 33 as separate bodies, the end portion 311b (see FIG. 30) of the base portion 311 and the terminal portion 33 are formed of, for example, a conductive adhesive (not shown). The electrode body may be manufactured by connecting with a conductive paste or the like.

In the connecting step (step S52), the electrode legs 312A having the conductive layer 22 formed on the tip portion 312a of the electrode substrate are produced in advance. As the electrode leg 312A, the electrode leg 20A according to the second embodiment described above can be used. By connecting the electrode legs 312A to the projecting portion 311a of the base portion 311, the electrode 30A for measuring biological information can be obtained.

[Fifth Embodiment]
<Electrodes for measuring biological information>
The electrode for measuring biological information according to the fifth embodiment will be described with reference to the drawings. The biometric information measuring electrode according to the present embodiment is the electrode leg 312A of the base portion 31 of the biometric information measuring electrode 30A according to the fourth embodiment shown in FIGS. 25 to 27, and is shown in FIGS. 13 to 15. The electrode leg 20B according to the third embodiment is used.

FIG. 37 is a perspective view showing the appearance of the biometric information measuring electrode according to the fifth embodiment, and FIGS. 38 and 39 are other views showing the appearance of the biometric information measuring electrode according to the fifth embodiment. It is a perspective view, and FIG. 40 is a sectional view taken along line VI-VI of FIG. 37. As shown in FIGS. 37 to 40, the biometric information measuring electrode 30B according to the present embodiment is replaced with the electrode leg 312A of the base portion 31 of the biometric information measuring electrode 30A shown in FIGS. 25 to 27. -The electrode leg 312B according to the third embodiment shown in FIG. 15 is provided. That is, the biological information measuring electrode 30B has an electrode leg 312B having a tip groove portion 24A on the tip portion 312a and a side groove portion 25 on the side surface 312b.

An example of the case where the brain wave of the subject is measured by using the inspection device 40 (see FIG. 28) provided with the electrode 30B for measuring biological information according to the present embodiment will be described. In the present embodiment, in the biometric information measuring electrode 30B, at least the tip portion 312a of the electrode legs 312B is immersed in the liquid in the container in advance, and the tip groove portion 24A and the side groove portion 25 of the conductive layer 22 contain the liquid. After pulling up the electrode legs 312B from the state of being immersed in the liquid, the biometric information measurement electrode 30B is fixed to the cap 41 (see FIG. 28) with the liquid contained in the tip groove portion 24A and the side groove portion 25. As shown in FIG. 41, the tip portion 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 electric signal from the scalp 45 is transmitted from the scalp 45 to the tip portion 312a of the electrode legs 312B via the conductive layer 22. The transmitted electric signal is transmitted from the tip portion 312a via the base portion 31 to the terminal portion 33, the wiring 42 (see FIG. 28), and the measuring portion 43 (see FIG. 28) in this order. The signal analysis unit 432 (see FIG. 28) analyzes the transmitted electrical signal and displays brain waves (for example, α wave, β wave, θ wave, etc.) 441 (see FIG. 28) on the display unit 44 (see FIG. 28). Is displayed.

Therefore, the electrode 30B for measuring biological information according to the present embodiment has a plurality of tip groove portions 24A on the surface of the tip portion 312a which is the region A, and has a 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 electrode 30B for measuring biological information, for example, as shown in FIG. 18, the conductive layer provided on the tip portion 312a There is a possibility that a part of 22 is gradually worn away and scraped until the tip portion 312a is partially exposed. Even in such a case, the biometric information measuring electrode 30B can maintain continuity with the living body at the contact portion between the conductive layer 22 formed on the surface of the tip groove portion 24A and the living body (for example, the scalp or the forehead). Therefore, the continuity between the conductive layer 22 and the living body can be stably maintained. Therefore, according to the electrode 30B for measuring biological information, since the electrical connection between the tip portion 312a of the electrode leg 312B and the living body can be maintained, an electric signal from the living body can be stably obtained, and the biological information can be obtained, for example. Brain waves can be measured stably.

Further, as described in the electrode leg 20B according to the third embodiment described above, when the biometric information measuring electrode 30B is immersed in a liquid, a capillary tube is formed in the tip groove portion 24A provided on the surface of the tip portion 312a which is the region A. The liquid can be retained by the phenomenon. Therefore, for example, when the tip portion 312a is brought into contact with the scalp when measuring an electroencephalogram, as shown in FIG. 19, the liquid held by the tip groove portion 24A flows to the surface of the scalp in contact with the tip portion 211. Spreads on the scalp. As a result, the area conducting from the scalp to the conductive layer 22 becomes large, so that the contact impedance between the scalp and the biometric information measuring electrode 30B can be further lowered. This makes it possible to measure brain waves more stably.

Further, the electrode 30B for measuring biological information has a plurality of side groove portions 25 on the side surface of the electrode leg 20B as described in the electrode leg 20B according to the third embodiment described above, and the side groove portion 25 is a tip groove portion. It communicates with at least part of 24A. Therefore, at the time of measuring the 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 that time, the liquid held in the side groove portion 25 flows to the tip groove portion 24A and is supplied to the scalp. As a result, 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 maintained more stably. Can be measured.

[Modification of the electrode for measuring biological information according to the fifth embodiment]
An example of the electrode 30B for measuring biological information is shown, but the present invention is not limited to this. A modified example of the biological information measuring electrode 30B will be described below.

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 is the same as the electrode leg 20B according to the third embodiment described above. Similarly, the tip groove portion 24A may have a shape that can hold the liquid in the groove. For example, as shown in FIG. 20, when the tip portion 312a of the electrode leg 312B is viewed in the + Z axis direction, the tip portion 312a may be provided with the tip groove portion 24B formed in a mesh shape. , As shown in FIG. 21, the tip groove portion 24C formed in a dendritic shape may be provided. As shown in FIGS. 20 and 21, by providing the tip groove portion 24B formed in a mesh shape or the tip groove portion 24C formed in a dendritic shape in the tip portion 312a, the tip groove portions 24B and 24C on the surface of the tip portion 312a are provided. The liquid can be held more efficiently. Therefore, the continuity between the conductive layer 60 and the scalp can be maintained more stably. Further, when the tip portion 312a comes into contact with the scalp, the tip portion 312a can stably maintain the continuity between the conductive layer 60 on the surface of the tip groove portions 24B and 24C and the scalp in all directions. Therefore, even if the tip portion 312a is moved along the scalp in all directions, the biological information can be measured more stably.

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

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

In the molding step (step S61A), the base portion 31 and the terminal portion 33 are formed in the same manner as in the molding step (step S41A) of the method for manufacturing the electrode for measuring biological information according to the fourth embodiment shown in FIG. Mold. Further, in the same manner as in the leg substrate manufacturing step (step S31A) of the electrode leg manufacturing method according to the third embodiment shown in FIG. 22, a plurality of tip groove portions 24A are formed on the surface of the tip portion 312a. A side groove portion 25 can be formed on the side surface 312b.

The surface treatment step (step S62) can be performed in the same manner as the surface treatment step (step S32) of the method for manufacturing an electrode for measuring electrode leg biometric information according to the third embodiment shown in FIG. 22.

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 for manufacturing the electrode for measuring biological information according to the fourth embodiment shown in FIG. 32.

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

Therefore, according to the method for manufacturing an electrode for measuring biological information according to the present embodiment, a living body provided with an 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. The information measurement electrode 30B can be obtained.

[Modified example of the method for manufacturing the electrode legs according to the fifth embodiment]
In the present embodiment, in the molding step (step S61A), the tip groove portion 24A and the side groove portion 25 are simultaneously formed on the base portion 31 by using a mold provided with protrusions corresponding to the tip groove portion 24A and the side groove portion 25. However, it is not limited to this. For example, after molding the base portion 31 and the terminal portion 33, the tip groove portion 24A and the side groove portion 25 may be formed at the same time or separately.

When the tip groove portion 24A and the side groove portion 25 are formed separately, the method for manufacturing the electrode for measuring biological information according to the present embodiment includes a molding step (step S61B) and a surface treatment step (step S62), as shown in FIG. ) And the conductive layer forming step (step S63). The molding step (step S61B) includes a preparatory step (step S611) for preparing the base portion 31 and the terminal portion 33, a tip groove portion forming step (step S612) for forming the tip groove portion 24A on the tip portion 312a of the electrode leg, and an electrode. A side groove forming step (step S613) of forming the side groove 25 on the side surface of the substrate is included.

The molding step (step S61B) can be performed in the same manner as the leg substrate manufacturing step (step S31C) of the electrode leg manufacturing method shown in FIG. 24. The preparatory step (step S611), the tip groove forming step (step S612), and the side groove forming step (step S613) are all preparatory steps (steps) of the leg substrate manufacturing step (step S31C) shown in FIG. 24 described above. S311), the tip groove forming step (step S312), and the side groove forming step (step S313) can be performed in the same manner.

In the conductive layer forming step (step S63), the conductive layer 22 is formed only on the tip portion 312a of the electrode legs, but the conductive layer 22 may be formed at least on the tip portion 312a, and the conductive layer 22 may be formed. , The base portion 31 may be formed on a portion other than the tip portion 312a, or 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 electrodes 30A and 30B for measuring biological information according to the first to fifth embodiments are obtained from the living body while maintaining electrical connection with the living body. It is possible to stably measure the biological information to be obtained. Therefore, these can be suitably used for measuring various biological information such as brain waves, pulse waves, electrocardiograms, myoelectrics, and body fats in contact with the skin. The living body includes a human body, an organism other than the human body, and the like, and the conductive materials 10, the electrode legs 20A and 20B, and the electrodes 30A and 30B for measuring biological information according to each of the above embodiments are for the human body. Can be used particularly preferably.

[Sixth Embodiment]
<Electrodes for measuring biological information>
The electrode for measuring biological information according to the sixth embodiment will be described. The biometric information measuring electrode according to the present embodiment has a conductive layer 22 of the biometric information measuring electrode 30A according to the fourth embodiment shown in FIGS. 25 to 27 in a matrix of synthetic resin containing a conductive polymer. It is changed to a conductive layer in which fibers are dispersed and contained.

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

As shown in FIGS. 44 to 46, the biometric information measuring electrode 30C according to the present embodiment is provided on the base portion 31 having the base portion 311 and the plurality of electrode legs 312A, and on the upper side (+ Z axis direction) of the base portion 311. It is provided with a terminal portion 33 and a conductive layer 60 provided on the surface of the electrode legs 312A. The biometric information measuring electrode 30C according to the present embodiment is described above, except that the configuration of the conductive layer 22A formed on the tip portion 312a of the biometric information measuring electrode 30A according to the fourth embodiment is changed. Since it is the same as the electrode 30A for measuring biological information according to the fourth embodiment, 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 portion 312a of the electrode legs 312A. In the present embodiment, since the base portion 31 and the terminal portion 33 are integrally formed by using the conductive elastomer, the continuity between the base portion 31 and the terminal portion 33 is ensured. Therefore, the conductive layer 60 is formed only on the surface of the tip portion 312a. When the base portion 31 and the terminal portion 33 are made of an insulating material, the conductive layer 60 covers the entire surface of the base portion 31 and the terminal portion 33 in order to ensure continuity between the base portion 31 and the terminal portion 33. It is provided in.

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

As the matrix of the synthetic resin, it is possible to form it only with a conductive polymer, but it is also possible to form it by mixing other synthetic resins as appropriate. As another synthetic resin, the same resin as the binder contained in the conductive material 10 of the first embodiment described above can be used. Therefore, the details of the synthetic resin will be omitted.

Further, 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 described above. Since the details of the average thickness of the conductive layer 60 are the same as those of the conductive material 10 of the first embodiment described above, the details are omitted.

As the conductive polymer, the same conductive polymer as the conductive polymer of the binder contained in the conductive material 10 of the first embodiment can be used. Therefore, the details of the types of conductive polymers will be omitted.

As the fiber, a fiber similar to the fiber contained in the conductive material 10 of the first embodiment described above can be used. Therefore, the details of the fiber type will be omitted.

The mixing ratio of the conductive polymer and 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 the conductive polymer used, and can maintain the layer strength of 40 of the conductive layer.

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

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

The definition of nanofiber is as described above in the first embodiment. Therefore, the description of the definition of nanofibers will be omitted.

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

As the nanofiber, the same nanofiber as the nanofiber contained in the conductive material 10 of the first embodiment described above can be used. Therefore, the details of the nanofiber will be omitted.

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

When the brain wave of the subject is measured using the biological information measuring electrode 30C, the inspection device 40 provided with the biological information measuring electrode 30C (FIG. 28) as described with reference to FIG. 28 in the fourth embodiment described above. By using (see), the subject's brain waves can be measured.

The biological information measurement electrode 30C configured as described above has a conductive layer 60 on the surface of the tip portion 312a which is the region A. The conductive layer 60 contains fibers in a dispersed state in a matrix of synthetic resin containing a conductive polymer. Since the conductive layer 60 includes fibers, the strength can be increased, so that the abrasion resistance can be improved. Therefore, even if the conductive layer 60 on the surface of the tip portion 312a is rubbed by repeatedly using the biometric information measuring electrode 30C, it is possible to prevent the conductive layer 60 on the surface of the tip portion 312a from being scraped. Therefore, since the conductive layer 60 on the surface of the tip portion 312a can stably contact the living body at the contact portion with the living body, the continuity between the conductive layer 60 and the scalp can be stably maintained. Therefore, according to the biometric information measuring electrode 30A, the electrical connection between the tip portion 312a of the electrode leg 312A and the scalp can be maintained as in the biometric information measuring electrode 30A according to the fourth embodiment described above, so that the scalp can be maintained. It is possible to stably obtain an electrical signal from the scalp, and to stably measure brain waves as biological information.

Since the biometric information measuring electrode 30C has the conductive layer 60 on the surface of the tip portion 312a, the tip portion 312a comes into direct contact with the scalp as in the biometric information measuring electrode 30A according to the fourth embodiment described above. It is possible to lower the contact impedance between the scalp and the electrode 30C for measuring biological information as compared with the case where the case is used.

Further, 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 an electric signal from the scalp can be easily obtained. Therefore, the brain wave can be measured more stably.

By including the fiber in the conductive layer 60, the electrode 30C for measuring biological information is a unit as compared with the conductive layer composed of only the conductive polymer, like the conductive material 10 according to the first embodiment described above. Since the amount of the conductive polymer per thickness can be reduced, the cost required per unit layer can be reduced. Therefore, the manufacturing cost of the electrode 30C for measuring biological information can be suppressed.

Further, the electrode for measuring biological information formed of metal cannot be used for a subject having a metal allergy. In the present embodiment, since the electrode 30C for measuring biological information has the conductive layer 60 formed of the conductive layer 60 including the conductive polymer, even if the conductive layer 60 comes into contact with the scalp, it causes a metal allergy to the user. Not safe. Therefore, the electrode 30C for measuring biological information can be safely used by all subjects as in the case of the conductive material 10 according to the first embodiment described above.

When the fiber contained in the conductive layer 60 is a nanofiber, the biometric information measuring electrode 30C has a higher strength of the conductive layer 60 because the nanofiber can be more uniformly dispersed in the conductive layer 60 than the fiber. 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 electrode 30C for measuring biological information has high resistance to alcohol, so that the conductive layer 60 can be washed with alcohol.

[Modification of the electrode for measuring biological information according to the sixth embodiment]
An example of the electrode 30C for measuring biological information is shown, but the present invention is not limited to this. A modified example of the electrode 30C for measuring biological information will be described below.

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

In this case, as shown in FIG. 47, it is preferable to form the base conductive layer 61 electrically connected to the conductive layer 60 on the entire surface of the base portion 31 and the terminal portion 33. As a result, continuity can be established between the tip portion 312a and the terminal portion 33. Since the same conductive polymer as the conductive layer 60 is used as the conductive polymer, the description of the conductive polymer will be omitted. The thickness of the base conductive layer 61 may be about 200 nm to 2 μm, as long as it is conductive.

<Manufacturing method of electrode for measuring biological information according to the sixth embodiment>
Next, a method for manufacturing the electrode for measuring biological information according to the sixth embodiment will be described. FIG. 48 is a flowchart showing a method of manufacturing an electrode for measuring biological information according to the present embodiment.

As shown in FIG. 48, the method for manufacturing an electrode for measuring biological information according to the present embodiment includes a molding step (step S71) for molding the base portion 31 and the terminal portion 33, and an activation treatment on the surface of the tip portion 312a. The surface treatment step (step S72) and the conductive layer forming step (step S73) of forming the conductive layer 60 containing the conductive polymer on the surface of the tip portion 312a are included. Hereinafter, each step will be described.

First, in the molding step (step S71), the base portion 31 and the terminal portion 33 are integrally molded using the material 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 in the molding step (step S41A) of the method for manufacturing the electrode for measuring biological information according to the 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 electrode for measuring biological information according to the third embodiment shown in FIG. 22.

In the conductive layer forming step (step S73), a conductive layer 60 is formed on the surface of the tip portion 312a in a state where the fibers are dispersed in a matrix of 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 coating step (step S731) of the conductive layer forming step (step S73) is performed in the same manner as the coating step (step S431) of the method for manufacturing the electrode for measuring biological information according to the fourth embodiment 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 solidification step (step S432) of the method for manufacturing the electrode for measuring biological information according to the fourth embodiment shown in FIG. be able to.

By forming the conductive layer 60 on the surface of the tip portion 312a in this way, the electrode 30C for measuring biological information can be obtained. Since the conductive layer 60 has high wear resistance, even if the electrode 30C for measuring biological information is repeatedly used or washed and the conductive layer 60 on the surface of the tip portion 312a is rubbed, the conductive layer on the surface of the tip portion 312a It is possible to prevent 60 from being scraped. Therefore, since the conduction with the scalp can be stably maintained at the contact portion between the conductive layer 60 and the scalp, an electric signal from the scalp can be stably obtained.

Further, 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 portion 312a is a solution containing only the conductive polymer. It can be made thicker than the film thickness of the coating layer formed when the coating is applied once. Since the desired thickness of the conductive layer 60 can be obtained with a small number of coatings of the mixed solution, the cost required in the coating step (step S731) can be reduced. Further, by increasing the thickness of the conductive layer 60, even if the surface of the conductive layer 60 is rubbed and worn during the use or cleaning of the electrode 30C for measuring biological information, the conductive layer 60 is worn down and the surface of the tip portion 312a is worn. It is possible to delay the time until it peels off. As a result, the life of the conductive layer 60 can be further extended.

When the fiber contained in the conductive layer 60 is a cellulose nanofiber, the mixed solution containing the cellulose nanofiber and the conductive polymer has good wettability to the base portion 31 and the terminal portion 33 and has high thixophilicity. Therefore, when the conductive layer 60 is formed by using a mixed solution containing cellulose nanofibers and a conductive polymer, the thickness of the coating layer formed when the mixed solution is applied once to the tip portion 312a is made thicker. be able to. The film thickness of the coating layer formed by one coating of the mixed solution is, for example, about 1.3 to 4 times the film thickness of the coating layer formed by coating the solution containing no cellulose nanofibers. Can be thickened.

[Modified example of the method for manufacturing the electrode for measuring biological information according to the sixth embodiment]
An example of a method for manufacturing an electrode for measuring biological information according to an embodiment has been shown, but the present invention is not limited thereto. Hereinafter, a modified example of the method for manufacturing the electrode for measuring biological information will be described.

In the present embodiment, the base portion 31 and the terminal portion 33 are formed at the same time 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, the method for manufacturing a modified example of the electrode for measuring biological information according to the present embodiment is a molding step (step S71) and a preparatory step (step) for preparing the base portion 31 and the terminal portion 33. It is composed of S711) and a binding step (step S712) of binding and integrating the base portion 31 and the terminal portion 33. Then, as in the present embodiment, the surface treatment step (step S72) for activating the surface of the tip portion 312a and the conductive layer 60 containing the conductive polymer and the fiber are formed on the surface of the tip portion 312a. The conductive layer forming step (step S73) is performed.

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

Further, in the present embodiment, in the conductive layer forming step (step S73), the conductive layer 60 is formed only on the tip portion 312a of the base portion 31, but if the conductive layer 60 is formed at least on the tip portion 312a. Often, the conductive layer 60 may be formed on a portion other than the tip portion 312a 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 the conductive elastomer, the conductive layer 60 may be formed at least on the surface of the tip portion 312a. When the base portion 31 and the terminal portion 33 are made of an insulating material, the conductive layer 60 is formed on the entire surface of the base portion 31 and the terminal portion 33. As a result, the electric signal obtained from the scalp is transmitted from the tip portion 312a of the electrode leg 312A to the terminal portion 33 via the conductive layer 60.

When the base portion 31 and the terminal portion 33 are made of an insulating material, as shown in FIG. 47, the base conductive layer 61 is formed between the base portion 31 and the terminal portion 33 and the conductive layer 60. Is preferable.

In this case, as shown in FIG. 50, the method for manufacturing a modified example of the electrode for measuring biological information according to the present embodiment is a base conductive layer 61 containing a conductive polymer on the surfaces of the base portion 31 and the terminal portion 33. To form. That is, the method for manufacturing a modified example of the electrode for measuring biological information according to the present embodiment is that the molding step (step S71), the surface treatment step (step S72), and the surfaces of the base portion 31 and the terminal portion 33 are conductive. The process includes a base conductive layer forming step (step S73) for forming the base conductive layer 61 containing a polymer, and a conductive layer forming step (step S74). 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. As a method for forming the underlying conductive layer 61, the same forming method as in the conductive layer forming step (step S74) can be used.

[7th Embodiment]
<Electrodes for measuring biological information>
The electrode for measuring biological information according to the seventh embodiment will be described with reference to the drawings. The biometric information measuring electrode according to the present embodiment is the electrode leg 312A of the base portion 31 of the biometric information measuring electrode 30C according to the sixth embodiment shown in FIGS. 44 to 46, and is shown in FIGS. 37 to 40. The electrode leg 312B according to the fifth embodiment is used.

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

As shown in FIGS. 51 to 54, the biometric information measuring electrode 30D according to the seventh embodiment is replaced with the electrode leg 312A of the base portion 31 of the biometric information measuring electrode 30C shown in FIG. 44. It is provided with the electrode legs 312B according to the sixth embodiment shown in FIG. 40.

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

When the brain wave of the subject is measured by using the electrode 30D for measuring biological information, the inspection device 40 provided with the electrode 30D for measuring biological information (FIG. 28) as described with reference to FIG. 28 in the fourth embodiment described above. By using (see), the subject's brain waves can be measured.

The biological information measuring electrode 30D configured as described above has a plurality of tip groove portions 24A on the surface of the tip portion 312a which is the region A, and has a conductive layer 60 on the surface of the tip portion 312a. By repeatedly using the electrode 30D for measuring biological information for a long period of time, for example, as shown in FIG. 17, a part of the conductive layer 60 on the surface of the tip portion 312a is gradually worn away, and the tip portion 312a is partially exposed. There is a possibility that a part of the conductive layer 60 will be peeled off until the state is reached. Even in such a case, in the biological information measurement electrode 30D, the conductive layer 60 formed on the surface of the tip groove portion 24A remains. Therefore, the continuity 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 portion 24A and the scalp, so that the continuity between the conductive layer 60 and the scalp can be stably maintained. Therefore, according to the biometric information measuring electrode 30D, the electrical connection between the tip portion 312a of the electrode leg 312B and the scalp can be maintained as in the biometric information measuring electrode 30A according to the fourth embodiment described above, so that the scalp can be maintained. The electrical signal from the scalp can be stably obtained, and the brain wave can be stably measured as biological information.

Further, when the biometric information measuring electrode 30D is immersed in a liquid, a capillary tube is formed in the tip groove portion 24A provided on the surface of the tip portion 312a which is the region A, similarly to the biometric information measuring electrode 30B according to the fifth embodiment described above. Water can be retained by the phenomenon. Therefore, when the tip portion 312a is brought into contact with the scalp when measuring the electroencephalogram, as shown in FIG. 18, the water held in the tip groove portion 24A flows to the surface of the scalp in contact with the tip portion 312a and reaches the scalp. spread. As a result, the area conducting from the scalp to the conductive layer 60 becomes large, so that the contact impedance between the scalp and the biometric information measuring electrode 30D can be further lowered. This makes it possible to measure brain waves more stably.

Further, the biological information measuring electrode 30D has a plurality of side groove portions 25 on the side surface of the electrode legs 312B, and the side surface groove portions 25 communicate with at least a part of the tip groove portion 24A. Therefore, as in the case of the biometric information measuring electrode 30B according to the fifth embodiment described above, the water held in the tip groove portion 24A flows to the surface of the scalp in contact with the tip portion 312a at the time of measuring the brain wave, and the tip groove portion 24A The water held in is consumed. At that time, the water held in the side groove portion 25 flows to the tip groove portion 24A and is supplied to the scalp. As a result, 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 maintained more stably. Can be measured.

<Manufacturing method of electrode for measuring biological information according to the seventh embodiment>
Next, a method for manufacturing the electrode for measuring biological information according to the seventh embodiment will be described. FIG. 55 is a flowchart showing a method of manufacturing an electrode for measuring biological information according to the seventh embodiment.

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

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

The base portion 31 and the terminal portion 33 can be molded by using a known molding method as in the molding step (step S71) in the method for manufacturing the electrode for measuring biological information according to the sixth embodiment shown in FIG. 48. .. 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 tip groove portion 24A and the side groove portion 25. By using the mold, the base portion 31 and the terminal portion 33 can be formed at the same time, and the tip groove portion 24A and the side groove portion 25 can be formed at the same time.

Next, in the surface treatment step (step S82), the surface of the tip portion 312a is activated. As the method for activating the surface of the tip portion 312a, the same method as the surface treatment step (step S72) in the method for manufacturing the electrode for measuring biological information according to the sixth embodiment shown in FIG. 48 can be used. , 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 portion 312a. As the method for forming the conductive layer 50, the same method as in the conductive layer forming step (step S73) in the method for manufacturing the electrode for measuring biological information according to the sixth embodiment shown in FIG. 48 can be used, and thus the description thereof is omitted. To do.

By forming the conductive layer 60 on the surface of the tip portion 312a in this way, the electrode 30D for measuring biological information according to the present embodiment can be obtained. The tip groove portion 24A is formed on the surface of the tip portion 312a, and the side surface groove portion 25 is formed on the side surface 312b. Therefore, by repeatedly using the electrode 30D for measuring biological information, even if the conductive layer 60 provided on the tip portion 312a is worn and scraped by long-term use, the conductive layer provided on the surface of the tip groove portion 24A is provided. 60 remains. Therefore, the continuity with the scalp can be maintained at the contact portion between the conductive layer 60 formed on the surface of the tip groove portion 24A and the scalp, so that the continuity between the conductive layer 60 and the scalp can be stably maintained. ..

[Modified example of the method for manufacturing the electrode for measuring biological information according to the seventh embodiment]
An example of a method for manufacturing an electrode for measuring biological information according to an embodiment has been shown, but the present invention is not limited thereto. Hereinafter, some modifications in the method for manufacturing the electrode for measuring biological information will be described with reference to FIG. 56.

In the seventh embodiment, in the molding step (step S21), the base portion 31 and the terminal portion 33 are simultaneously formed by using a mold provided with protrusions corresponding to the tip groove portion 24A and the side groove portion 25. Not limited to this. For example, the base portion 31 and the terminal portion 33 may be separately molded and integrated, and then the tip groove portion 24A and the side groove portion 25 may be formed.

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

The base portion 31 and the terminal portion 33 of the above-mentioned molding step (step S81) are integrated by using a binding member. As the binding member used for this binding, a known binding member can be used. For example, an epoxy resin, a synthetic resin such as urethane resin, a synthetic resin having elasticity such as rubber, or the like can be used.

As described above, the biometric information measuring electrodes 30C and 30D according to the sixth and seventh embodiments maintain an electrical connection with the scalp and stably measure biometric information (brain waves) obtained from the scalp. can do. Therefore, the biometric information measuring electrodes 30C and 30D are suitable as biometric information measuring electrodes for measuring various biological information such as pulse wave, electrocardiogram, myoelectric, and body fat in contact with the skin in addition to brain waves. Can be used for. Further, the living body includes a human body, an organism other than the human body, and the like, and the electrodes for measuring biological information according to each of the above embodiments can be particularly preferably 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 (see FIG. 6 and the like) in 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 binds the fibers to each other. , Which has a large number of pores. The conductive material 10 (see FIG. 1) has electrode legs 20A and 20B (see FIGS. 6 and 13) or electrodes 30A and 30B for measuring biological information (FIGS. 25 and 37, etc.) in the second to fifth embodiments. It is used as each of the conductive layers 22 (see FIG. 6 and the like) of (see). 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 biometric information measuring electrodes 30C and 30D (see FIGS. 44 and 51, etc.). The fibers are dispersed and contained 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 surface of the electrode for measuring biological information having a region capable of contacting a living body.
It is formed by containing a fiber and a binder resin having a conductive polymer that binds the fibers to each other, and has a large number of pores.

The biometric information measuring electrodes according to the sixth and seventh embodiments described above are biometric information measuring electrodes having a region in contact with a living body.
On the surface of the region, a conductive layer is formed in which fibers are dispersed and contained in a matrix of synthetic resin containing a conductive polymer.

The method for producing a conductive material according to the first embodiment described above is a method for producing a conductive material provided on at least the surface of a biometric information measuring electrode having a region in contact with a living body.
A mixing step of preparing a mixed solution containing a fiber, a conductive polymer that binds the fibers to each other, and a solvent in which the fibers are dispersed.
A solidification step of freeze-drying the mixed solution to prepare a porous body having a large number of pores, and
including.

In the above-mentioned method for producing a conductive material, in the mixing step, a binder resin for binding the fibers to each other is mixed with the mixed solution.
It includes 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 solidification step includes a cooling step of cooling the water contained in the mixed solution and a cooling step.
A dehydration process that sublimates the cooled water under vacuum,
including.

The method for manufacturing an electrode leg according to the second embodiment described above is at least a method for manufacturing an electrode leg having the region in contact with a living body.
A leg substrate manufacturing process for manufacturing a conductive electrode substrate, and
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 for manufacturing an electrode leg according to the third embodiment described above is at least a method for manufacturing an electrode leg having a region in contact with a living body.
A leg substrate manufacturing process for manufacturing a conductive electrode substrate, and
Including a conductive layer forming step of forming a conductive layer in the region of the electrode substrate.
The conductive layer forming step is
A coating step of forming a coating layer by applying a mixed solution of a fiber, a conductive polymer that binds the fibers to each other, and a solvent in which the fibers are dispersed to at least the region.
A solidification step of freeze-drying the coating layer to prepare a porous body having a large number of pores, and
including.

In the method for manufacturing an electrode leg according to the second or third embodiment described above, the leg substrate manufacturing step forms a plurality of grooves on the surface of the region.

In the method for manufacturing an electrode leg according to the second or third embodiment described above, in the leg substrate manufacturing step, a plurality of auxiliary groove portions are formed on the surface of a portion other than the region.
The auxiliary groove portion communicates with at least a part of the groove portion.

The method for manufacturing a biometric information measuring electrode according to the fourth or fifth embodiment described above is a method for manufacturing a biometric information measuring electrode having a region in contact with a living body.
A substrate portion having at least an electrode leg having the region on one side and a base portion provided on the other side of the electrode leg,
It has a terminal portion electrically connected to the electrode leg and
A molding process for integrally forming the electrode legs and the base,
Including a conductive layer forming step of forming a conductive layer in the region of the electrode leg.
The conductive layer forming step is
A coating step of forming a coating layer by applying a mixed solution of a fiber, a conductive polymer that binds the fibers to each other, and a solvent in which the fibers are dispersed to at least the region.
A solidification step of freeze-drying the coating layer to prepare a porous body having a large number of pores, and
including.

The method for manufacturing a biometric information measuring electrode according to the fourth or fifth other embodiment described above is a method for manufacturing a biometric information measuring electrode having the region in contact with a living body.
A base portion provided with the electrode leg obtained by using the method for manufacturing an electrode leg according to any one of the above and a base portion provided on the other side of the electrode leg, and
It has a terminal portion electrically connected to the electrode leg and
A connecting step of connecting the electrode legs to the base is included.

The method for manufacturing an electrode for measuring biological information according to the fourth or fifth embodiment described above is a step of forming a base conductive layer that is electrically connected to the conductive layer on the surface of the base portion. including.

The method for manufacturing a biometric information measuring electrode according to the sixth or seventh embodiment described above is a method for manufacturing a biometric information measuring electrode having a region in contact with a living body.
A molding process for molding a substrate portion having the above region, and
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 is included at least on the surface of the region.

The method for manufacturing a biometric information measuring electrode according to the sixth or seventh embodiment further includes a surface treatment step of activating at least the surface of the region after molding 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 for manufacturing an electrode for measuring biological information according to the sixth or seventh embodiment described above, the conductive layer forming step is performed.
A coating step of applying a mixed solution containing the conductive polymer and the fiber to at least the region to form a coating layer.
A drying step of drying the region on which the coating layer is formed and curing the coating layer,
including.

Hereinafter, embodiments will be described in more detail with reference to Examples and Comparative Examples, but the embodiments are not limited to these Examples.

<Example 1>
(Preparation of electrodes for measuring biological information)
After integrally forming the base part and the terminal part by the injection molding method using a resin material (thermoplastic polyester elastomer, trade name: Hytrel (registered trademark), manufactured by Toray DuPont), the tip of the electrode leg is formed. Solution (A) / 6 g containing a conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) and cellulose nanofiber 1 (nanoforest (registered trademark), manufactured by Chuetsu Pulp Industry Co., Ltd.) / A solution mixed with 4 g was applied to form a coating layer, and then the coating layer was dried and cured to form a conductive layer. As a result, an electrode for measuring biological information was produced. The solution (A) contains 1.0% by mass (wt%) of the conductive polymer and 5.0 wt% of the thermosetting resin. Further, the solution (B) contains 1.3 wt% of cellulose nanofiber 1.
(Evaluation of wear resistance)
The impedance of the tip was measured in a state where the tip of the electrode leg of the electrode for measuring biological information was immersed in an electrolytic solution (0.1 M NaCl aqueous solution), and the measurement accuracy of the electrode for measuring biological information was evaluated. After wiping the tip of the electrode leg with a Kimwipe moistened with alcohol, the tip was immersed in an electrolytic solution (0.1 M NaCl aqueous solution), and the impedance of the tip was measured. The frequency was 1 Hz to 1000 Hz. This cycle was set as one time (cycle), and 100,000 cycles were performed. The lower the impedance of the tip portion, the higher the sensitivity of detecting the electric signal obtained from the living body, which indicates that the measurement accuracy of the electrode for measuring biological information is high. The measurement result is shown in FIG. 57.

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

Therefore, if a 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 brain wave can be measured stably. It was confirmed that it could be done.

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

[Example 2-2]
In Example 2-1 the amount of the solution (A) containing the conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) was set to 3 g, and the cellulose nanofiber 1 (nanoforest (registered trademark)), Chuetsu Pulp Industry Co., Ltd. A conductive layer was formed at the tip of the electrode leg in the same manner as in Example 2-1 except that the amount of the solution (B) containing (manufactured by the company) was changed to 7 g, and the electrode for measuring biological information was used. Made.

[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.) was 4 g, and cellulose nanofiber 1 (nanofost (registered trademark)), Chuetsu Pulp Industry Co., Ltd. The amount of the solution (B) containing (manufactured by the company) was 6 g, and the amount of the solution (C) containing the cellulose nanofiber 2 (cellenpia (registered trademark), manufactured by Nippon Paper Co., Ltd.) was changed to 1 g. Except for the above, a conductive layer was formed at the tip of the electrode leg in the same manner as in Example 2-1 to prepare an electrode for measuring biological information. The solution (C) contains 1.2 wt% of cellulose nanofibers 2.

[Comparative Example 2-1]
In Example 2-1 without adding the solution (B) containing the cellulose nanofiber 1 (nanoforest (registered trademark), manufactured by Chuetsu Pulp Industry Co., Ltd.), the conductive polymer (PEDOT / PSS, Shinetsu Polymer Co., Ltd.) In the same manner as in Example 2-1 except that the solution containing only the solution (A) containing (manufactured by) was used, a conductive layer was formed at the tip of the electrode leg to measure biological information. Electrodes for use were prepared.

[Comparative Example 2-2]
In Example 2-1 the amount of the solution (A) containing the conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) was 10 g, and the cellulose nanofiber 2 (cellenpia®, Nippon Paper Co., Ltd.) was added. A conductive layer was formed at the tip of the electrode leg in the same manner as in Example 2-1 except that the amount of the solution (C) containing (manufactured) was changed to 1 g to prepare an electrode for measuring biological information. did.

[Comparative Example 2-3]
In Example 2-1 the amount of the solution (A) containing the conductive polymer (PEDOT / PSS, manufactured by Shin-Etsu Polymer Co., Ltd.) was set to 1 g, and the cellulose nanofiber 1 (nanoforest (registered trademark)), Chuetsu Pulp Industry Co., Ltd. A conductive layer was formed at the tip of the electrode leg in the same manner as in Example 3-1 except that the amount of the solution (B) containing (manufactured by the company) was changed to 9 g, and the electrode for measuring biological information was formed. Made.

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

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

The lower the impedance of the tip portion, the higher the sensitivity of detecting the electric signal obtained from the living body, which indicates that the measurement accuracy of the electrode for measuring biological information is high. Further, if the impedance is lower on the lower frequency side, stable and accurate measurement can be performed at a 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 fiber and Comparative Example 2-2 having extremely few fibers. Impedance equivalent to that of the electrode was obtained. In particular, the biometric information measuring electrodes of Example 2-1 obtained values that were the same as the impedances of the biometric information measuring electrodes of Comparative Examples 2-1 and 2-2. On the other hand, it can be said that the electrode for measuring biological information of Comparative Example 2-3 containing a large amount of fibers is unsuitable for measurement because the conductivity of the conductive layer itself becomes too low and the impedance value becomes high.

Therefore, it was confirmed that even if the conductive layer contains a predetermined amount of cellulose nanofibers on the surface of the tip portion, the impedance of the electrode for measuring biological information becomes small, so that the brain wave can be measured stably.

Although the embodiments have been described above, the above-described embodiments are presented as examples, and the present invention is not limited to the above-described embodiments. The above-described embodiment can be implemented in various other forms, and various combinations, omissions, replacements, changes, etc. can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

This application has priority based on Japanese Patent Application No. 2017-252508 filed with the Japan Patent Office on December 27, 2017 and Japanese Patent Application No. 2017-25209 filed with the Japan Patent Office on December 27, 2017. It is alleged, and the entire contents of Japanese Patent Application No. 2017-252508 and Japanese Patent Application No. 2017-252509 are incorporated in this application.

10 Conductive material 11 Pore 13, 20A, 20B, 312A, 312B Electrode legs 21A, 21B Electrode base 131, 211, 312a Tip part 212, 312b Side surface 22, 60 Conductive layer 23, 51, 61 Underground conductive layer 24A, 24B, 24C groove (tip groove)
25 Auxiliary groove (side groove)
30A, 30B, 30C, 30D Electrodes 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 (11)

An electrode leg having a region that can be contacted with a living body on one side ,
A conductive layer made of a conductive material containing a fiber and a conductive polymer and formed on the surface of the region,
An electrode for measuring biological information, which is characterized by being provided with . The conductive material, said fibers, for binding the fibers to each other, are formed and a binder having a conductive polymer,
The electrode for measuring biological information according to claim 1, wherein the electrode has a large number of pores. The electrode for measuring biological information according to claim 2, wherein the conductive material has elasticity. Before Kishirubedenso, the biological information measuring electrode according to claim 1, characterized in that it comprises by dispersing the fibers in a matrix of synthetic resin containing the conductive polymer. The electrode for measuring biological information according to any one of claims 1 to 4 , wherein the fiber is a nanofiber. The electrode for measuring biological information according to claim 5 , wherein the nanofiber is a cellulose nanofiber. The electrode for measuring biological information according to any one of claims 1 to 6 , wherein an underlying conductive layer electrically connected to the conductive layer is formed on the surface of the electrode legs. The electrode for measuring biological information according to any one of claims 1 to 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 for measuring biological information according to claim 8, wherein the auxiliary groove portion communicates with at least a part of the groove portion. A base portion having a base portion provided on the other side of the electrode legs and said electrode legs,
A terminal portion electrically connected to the electrode leg and
The electrode for measuring biological information according to any one of claims 1 to 9, wherein the electrode is characterized by having. The electrode for measuring biological information according to claim 10, wherein the electrode leg is separable from the base portion.