Patent Description:
Conventionally, thin plates of highly conductive metals such as gold, silver, platinum and copper have been used as materials for biological electrode. The material for biological electrode made of these highly conductive metals has poor adhesion to skin and insufficient detection of an electrical signal from the skin. Therefore, when the material for biological electrode made of these highly conductive metals is used, it is necessary to apply gel, cream, paste, or the like to the skin in order to improve detection of electric signals from the skin. In this case, since the applied material used remains on hair or the like and causes discomfort, aftertreatment such as hair washing has been required.

Therefore, in recent years, there has been proposed a conductive silicone rubber electrode or the like in which conductive carbon particles are blended into a silicone rubber as an electrode which does not require application of cream, paste, or the like (see Patent Document <NUM>). Further, there has also been proposed a technique for imparting stretchability to a wiring substrate which can be mounted on a human body or the like in which a substrate and a coating layer constituting the wiring substrate include an elastomer, and the elastomer includes silicone rubber (see Patent Document <NUM>).

The Patent Document <NUM> discloses a bioelectrode including a conductive rubber electrode and a silver coating layer. The silver coating layer is provided on the conductive rubber electrode, contains a silicone rubber and silver particles, and contains modified silicone and, between the silver particles, ions for ionic conduction.

Since the biological electrode described in Patent Document <NUM> is an electrode using a rubber material, it can be used repeatedly, and since it has flexibility, it has good adhesion to the skin. Further, since it combines electronic conduction and ionic conduction, it has high conductivity and strain resistance, and since the surface in contact with the skin is conductive by silver, the contact impedance is low, and it is possible to stably measure even in measurement under dry conditions without using paste or the like.

However, while the biological electrode described in Patent Document <NUM> can be repeatedly used because it is a rubber electrode, the repeated use causes strain and increases the resistance value of the rubber electrode. In addition, depending on the silver powder used for the rubber electrode, the cohesive force is strong, and it is difficult to uniformly disperse the silicone rubber in a liquid silicone rubber because it becomes lumpy state at the time of manufacturing. Therefore, for example, at the time of manufacturing biological electrode, there has been a problem that it is necessary to perform an operation such as sieving and blending silver powder to be used immediately before preparation of a material and thus, the manufacturing process becomes complicated.

The present invention has been made in view of such circumstances, and provides a manufacturing method capable of easily manufacturing a biological electrode in which an increase in resistance value over time due to strain is suppressed.

According to the present invention, there is provided a method for manufacturing a biological electrode shown below.

According to the method for manufacturing a biological electrode of the present invention, it is possible to conveniently manufacture a biological electrode in which an increase in resistance value over time due to strain is suppressed.

The biological electrode obtained by the method for manufacturing the biological electrode in the embodiment of the present invention has a conductive rubber body containing a silicone rubber and a silver powder. The biological electrode may further have a conductive substrate if needed. When the biological electrode has a conductive substrate, it has a conductive rubber body on the conductive substrate. Since the silver powder is uniformly dispersed in the conductive rubber body constituting the biological electrode, an increase in resistance value over time due to strain is suppressed. The shape of the conductive rubber body constituting the biological electrode is not particularly limited, and the conductive rubber body can have a desired shape, such as a layered shape, a brushed shape, or an uneven shape, depending on the type and the surface shape of the object to be measured. Such a biological electrode has good adhesion to the subject's body, is soft to the touch, does not cause discomfort even if it is in close contact for a long time, and can maintain stable contact with the subject's body. Further, even in a three-dimensional shape such as a brushed shape, it expresses high conductivity and it is possible to stably measure with little noise. Further, since it is not necessary to use a gel or the like, it can be stably measured even in measurement under dry conditions, and the method of use is also simple.

Hereinafter, the biological electrode obtained by the method for manufacturing in the embodiment of the present invention (hereinafter, also referred to as "the manufacturing method according to the present embodiment") will be described in detail by referring to the attached drawings. The present invention is not limited in any way by the following embodiments.

<FIG> is a cross-sectional schematic view showing an example of the biological electrode obtained by the manufacturing method according to the present embodiment. The biological electrode <NUM> according to the present embodiment is suitably used for at least one of sensing an electric signal from a living body and transmitting an electric stimulus to a living body. As shown in <FIG>, the biological electrode <NUM> includes a conductive substrate <NUM> containing conductive silicone rubber, and a conductive rubber body <NUM> provided on the conductive substrate <NUM>. In the example of <FIG>, the conductive rubber body <NUM> has a layered shape. That is, in the biological electrode <NUM>, the conductive rubber body <NUM> is provided as a conductive rubber layer covering the conductive substrate <NUM> containing conductive silicone rubber. Thus, adhesion of the conductive rubber body <NUM> to the living body can be further improved.

<FIG> is an explanatory drawing showing the use status of the biological electrode obtained by the manufacturing method of the biological electrode according to the present embodiment. As shown in <FIG>, the biological electrode <NUM> contacts the surface of the conductive rubber body <NUM> and the living body <NUM> with, for example, a signal transmitting member <NUM> connected to a measuring instrument (not shown) connected to the surface of the conductive substrate <NUM>. As a result, since the electric signal from the living body <NUM> is transmitted to the measuring instrument via the conductive rubber body <NUM>, the conductive substrate <NUM>, and the signal transmitting member <NUM>, it is possible to measure the electric signal from the living body <NUM>. Since the biological electrode <NUM> is used in direct contact with the living body, the conductive rubber body <NUM> has a predetermined contact area (area of the outermost surface). The contact area of the conductive rubber body <NUM> with the living body is preferably <NUM><NUM> or more and <NUM><NUM> or less, more preferably <NUM><NUM> or more and <NUM><NUM> or less, and still more preferably <NUM><NUM> or more and <NUM><NUM> or less. When the contact area of the conductive rubber body <NUM> is within the above range, the impedance can be lowered to effectively prevent the mixing of noise. In addition, the measured result is not affected by body movement, and the biological electrode <NUM> can be contacted even at a small site of the living body.

<FIG> and <FIG> are explanatory drawings of the signal transmitting member of the biological electrode obtained by the manufacturing method of the biological electrode according to the present embodiment. The example shown in <FIG> shows an example using a covering wire <NUM> as the signal transmitting member <NUM>. The covering wire <NUM> includes a conductive metal core wire <NUM> and a resin covering material <NUM> covering the core wire <NUM>. In the covering wire <NUM>, the distal end portion of the core wire <NUM> is exposed from the covering material <NUM>. The exposed distal end portion of the core wire <NUM> is fixed to the surface of the conductive substrate <NUM> by an adhesive tape <NUM> or the like. With such a configuration, since the electric signal flowing through the conductive substrate <NUM> is transmitted to the outside by the covering wire <NUM> via the core wire <NUM>, it is possible to transmit the electric signal from the living body <NUM> to the outside.

The example shown in <FIG> shows an example using a flexible printed substrate <NUM> as the signal transmitting member <NUM>. The flexible printed substrate <NUM> includes a resin base film <NUM> and a metal conductive foil <NUM> provided on the base film <NUM>. The conductive foil <NUM> is a copper or a copper plated with gold. With such a configuration, since the electrical signal flowing through the conductive substrate <NUM> is transmitted to the outside by the flexible printed substrate <NUM> via the conductive foil <NUM>, it is possible to transmit the electrical signal from the living body <NUM> to the outside.

In the example shown in <FIG>, the covering wire <NUM> having a predetermined thickness, which is a signal-transmitting member <NUM>, is disposed on the upper surface side of the conductive substrate <NUM>. Therefore, when the biological electrode <NUM> is mounted to the living body <NUM>, there is a case where an uneven load based on the thickness of the covering wire <NUM> is applied to the conductive rubber body <NUM> that is in direct contact with the living body <NUM> (see <FIG>, hereinafter, the same) and the living body <NUM> feels unevenness on the mounting portion. In contrast, in the example shown in <FIG>, the surface of the thin plate-shaped flexible printed substrate <NUM>, which is a signal-transmitting member <NUM>, is substantially flush with the surface of the conductive substrate <NUM>. Thus, since the load based on the thickness of the flexible printed substrate <NUM> is less likely to be applied to the conductive rubber body <NUM>, even if the biological electrode <NUM> is mounted for a long period of time, the living body hardly feels the unevenness in the mounting portion, the discomfort is reduced, and the biological electrode <NUM> can realize weight reduction and miniaturization.

<FIG> is a diagram showing another configuration example of the biological electrode obtained by the method for manufacturing the biological electrode according to an embodiment of the present invention. In the example shown in <FIG>, the biological electrode <NUM> comprises an insulating layer <NUM> provided on the conductive substrate <NUM>. The insulating layer <NUM> contains insulating rubber. In the biological electrode <NUM>, even if the insulating layer <NUM> is provided on the conductive substrate <NUM>, the surface of the conductive substrate <NUM> is not in direct contact with the living body <NUM>, so that the transmission of electric signals from the living body <NUM> is not hindered by the insulating layer <NUM>. Then, when the insulating layer <NUM> is provided, as shown in <FIG>, by providing the flexible printed substrate <NUM> as the signal transmitting member <NUM>, the surface of the flexible printed substrate <NUM> is substantially flush with the surface of the conductive substrate <NUM>, so that it is possible to stably hold the insulating layer <NUM> and prevent the curvature of the biological electrode <NUM>. Hereinafter, various components of the biological electrode will be described in detail.

The conductive rubber body <NUM> contains an additive such as silicone rubber, silver powder, and, if necessary, a dispersant. Examples of the silicone rubber contained in the conductive rubber body <NUM> include a room temperature-curable liquid silicone rubber. The room temperature-curable liquid silicone rubber is a silicone rubber which is in a liquid state or a paste state before curing, and usually undergoes a curing reaction at <NUM> to <NUM> to become a rubber elastic body. The curing reaction may proceed gradually by moisture in air or immediately by adding a curing agent to the main agent, and any type of the curing reaction may be used in the present invention. In some cases, the reaction of curing by moisture is classified as <NUM>-component type, and the reaction of curing by adding the curing agent is classified as <NUM>-components type.

As the room temperature-curable liquid silicone rubber, a commercially available product can be used. For example, as the liquid silicone rubber, a trade name "KE-<NUM>" (manufactured by Shin-Etsu Chemical Co. ), a trade name "CAT-RG" (manufactured by Shin-Etsu Chemical Co. ), or the like can be used. In addition, as the liquid silicone rubber, a kind of silicone rubber may be used alone, or a plurality of kinds may be mixed and used.

The conductive rubber body <NUM> preferably contains <NUM> to <NUM> parts by mass, preferably <NUM> to <NUM> parts by mass, of silver powder with respect to <NUM> parts by mass of silicone rubber from the viewpoint of improving conductivity.

The silver powder contained in the conductive rubber body <NUM> may contain at least one selected from aggregated silver powder, flaked silver powder, and the like. As the silver powder contained in the conductive rubber body <NUM>, a mixed silver powder composed of silver powder and fumed silica, which is obtained by adding fumed silica to an aggregated silver powder and mixing, is at least used. In the mixed silver powder, the aggregated silver powder and the fumed silica are mixed and dispersed by a disperser, and a part of the aggregated silver powder may be crushed and finely divided. For example, a part of the aggregated silver powder used for the preparation of the mixed silver powder may become primary particles or finer particles in the vicinity of the primary particles by crushing and dispersing, and may be dispersed in the conductive rubber body <NUM> in the state of such finer particles. Further, the fumed silica is mixed with the silver powder to effectively suppress reaggregation of the silver powder, and to improve the fluidity of the silver powder.

The aggregated silver powder is one in which a plurality of particulate primary particles are aggregated in a three-dimensional shape. Examples of the aggregated silver powder include a trade name "G-<NUM>" (manufactured by DOWA Electronics Materials Co.

The flaked silver powder refers to one having a scaly shape, and examples thereof include a trade name "FA-D-<NUM>" and a trade name "FA-<NUM>-<NUM>" (both manufactured by DOWA Electronics Materials Co.

The average particle diameter of the silver powder is not particularly limited as long as it can impart conductivity to the conductive rubber body <NUM>. For example, the average particle diameter of the aggregated silver powder is preferably <NUM> or more and <NUM> or less. The average particle diameter of the flaked silver powder is preferably <NUM> or more and <NUM> or less. The average particle diameter described above is the average particle diameter of the silver powder in the primary particles. The average particle diameter of the silver powder is an average diameter measured by an electron micrograph and calculated by an arithmetic average.

The blending ratio of the aggregated silver powder and the flake silver powder is not particularly limited. For example, the blending ratio (mass ratio) of the aggregated silver powder and the flaked silver powder is preferably <NUM>:<NUM> to <NUM>:<NUM>.

Fumed silica is composed of minute nanometer-sized silica particles. The silver powder contained in the conductive rubber body <NUM> is added to the liquid silicone rubber in a state of a mixed silver powder obtained by adding fumed silica to an aggregated silver powder and mixing (that is, a mixed powder composed of silver powder and fumed silica). In the mixed silver powder, silver powder particles and fumed silica are mixed to suppress aggregation of silver powder particles. Therefore, the mixed silver powder composed of silver powder and fumed silica has extremely excellent fluidity in a liquid silicone rubber. The excellent fluidity of the mixed silver powder facilitates the handling of the material for producing the conductive rubber body <NUM>. In addition, the dispersibility inside the rubber when blended into the silicone rubber is improved, the familiarity with the rubber is improved, and the strain resistance of the conductive rubber body <NUM> is improved. As a result, the resistance value of the biological electrode <NUM> is prevented from rising over time due to strain.

Generally, fumed silica is roughly classified into hydrophobic fumed silica and hydrophilic fumed silica. As the fumed silica, hydrophobic fumed silica is preferably used. Examples of the hydrophobic fumed silica include a trade name "AEROSIL R972" (manufactured by Nippon Aerosil Co. ) and the like. Examples of the hydrophilic fumed silica include a trade name "AEROSIL <NUM>" (manufactured by Nippon Aerosil Co. ) and the like.

The blending amount of the silver powder can be appropriately set within a range capable of imparting conductivity. For example, the silver powder is preferably in the range of <NUM> to <NUM> parts by mass, and particularly preferably in the range of <NUM> to <NUM> parts by mass, per <NUM> parts by mass of the liquid silicone rubber. Note that at least a part of the silver powder is blended into the liquid silicone rubber in a state of a mixed silver powder containing fumed silica. Therefore, the blending amount of the mixed silver powder containing the silver powder is determined in consideration of the addition amount of the fumed silica described above.

In addition to the above-described components, the conductive rubber body <NUM> may further include other components as long as the effects of the present invention are not impaired. As other components, for example, a reinforcing agent, a filler such as dry silica, a compounding agent commonly used in the rubber industry such as an antioxidant, a processing aid, and a plasticizer can be appropriately blended.

The conductive rubber body <NUM> may further contain a modified silicone as a dispersant. As the modified silicone, one in which a side chain resulting in modification is introduced into a main chain composed of a siloxane bond (-Si-O-; also referred to as a silicone chain) can be preferably used, and examples thereof include silicones including polyether modification, polyether-alkyl co-modification, polyglycerin modification, and polyglycerin-alkyl co-modification. The side chain resulting in modification preferably includes an ether bond (-C-O-C-).

As the polyether-modified silicone, one in which a side chain composed of a polyether chain is introduced into a main chain composed of a silicone chain can be used. As the polyether-alkyl co-modified silicone, one in which a side chain composed of a polyether chain and a side chain composed of an alkyl chain are introduced into a main chain composed of a silicone chain can be used. As the polyglycerin-modified silicone, one in which a side chain composed of a polyglycerin chain is introduced into a main chain composed of a silicone chain can be used. As the polyglycerin-alkyl co-modified silicone, one in which a side chain composed of a polyglycerin chain and a side chain composed of an alkyl chain are introduced into a main chain composed of a silicone chain can be used. Among the above, the polyether-modified silicone or the polyglycerin-modified silicone is particularly preferable.

The thickness of the conductive rubber body <NUM> is not particularly limited as long as it can impart conductivity to the conductive rubber body <NUM>. The thickness of the conductive rubber body <NUM> is preferably <NUM> or more and <NUM> or less from the viewpoint of improving the conductivity of the biological electrode and ensuring the flexibility of the biological electrode, and more preferably <NUM> or more and <NUM> or less from the viewpoint of improving the adhesion between the conductive substrate <NUM> and the conductive rubber body <NUM> to prevent peeling of the conductive rubber body <NUM> and reducing the contact impedance with the living body.

The conductive substrate <NUM> is an optional component for supporting the conductive rubber body <NUM>. The material of the conductive substrate <NUM> is not particularly limited as long as it has conductivity. For example, the conductive silicone rubber configured in the same manner as the conductive rubber body <NUM> can be used. The details of the conductive silicone rubber configured in the same manner as the conductive rubber body <NUM> have been described above. As the material of the conductive substrate <NUM>, the conductive silicone rubber containing silicone rubber and conductive particles can also be used. The conductive substrate <NUM> contains the conductive silicone rubber, whereby the adhesion between the conductive substrate <NUM> and the conductive rubber body <NUM> can be improved. As the silicone rubber, a liquid silicone rubber is preferable, and for example, an organosilicon polymer is used. As the organosilicon polymer, one having a siloxane bond (-Si-O-) as a main chain and having a hydrocarbon group such as a methyl group, a phenyl group, or a vinyl group or a hydrogen as a side chain is preferable. As the silicone rubber, a silicone rubber of an addition reaction type may be used, and a silicone rubber of a condensation reaction type may be used. The silicone rubber of the addition reaction type is a silicone rubber which is cured by an addition reaction, and examples thereof include a silicone rubber having a hydrogen or a vinyl group as a side chain. In addition, the silicone rubber of the condensation reaction type is a silicone rubber which is cured by a condensation reaction, and examples thereof include a silicone rubber having a hydroxyl group at its terminal. Among the above, the silicone rubber of an addition reaction type is preferable from the viewpoint of more suitably maintaining adhesion to the conductive rubber body <NUM>. One type of these silicone rubbers may be used alone, or two or more types thereof may be used in combination.

As the conductive particles, conductive carbon particles such as various carbon blacks and the like are used. The conductive carbon particles are not limited as long as they can impart conductivity to the conductive substrate <NUM>. Examples of the conductive carbon particles include various carbon particles such as carbon black and graphite. Examples of the carbon black include Ketjen black and acetylene black. One kind of these may be used alone, or two or more kinds thereof may be used in combination. Among the above, Ketjen black is preferable as the carbon black from the viewpoint of improving conductivity of the conductive substrate <NUM>.

The average particle diameter of the conductive particles is not particularly limited as long as it can impart conductivity to the conductive substrate <NUM>. The average particle diameter of the conductive particles is preferably <NUM> or more and <NUM> or less, and more preferably <NUM> or more and <NUM> or less, from the viewpoint of improving the conductivity of the conductive substrate <NUM> and ensuring the flexibility of the conductive substrate <NUM>. The average particle diameter of the conductive particles is an average diameter measured by an electron micrograph and calculated by an arithmetic average.

The content of the conductive particles in the conductive substrate <NUM> is not particularly limited as long as it can impart conductivity to the conductive substrate <NUM>. The content of the conductive particles in the conductive substrate <NUM> is preferably <NUM>% by mass or more and <NUM>% by mass or less, more preferably <NUM>% by mass or more and <NUM>% by mass or less, with respect to the total mass of the conductive substrate <NUM>, from the viewpoint of improving the conductivity of the conductive substrate <NUM> and ensuring the flexibility of the conductive substrate <NUM>.

As the conductive silicone rubber contained in the conductive substrate <NUM>, for example, a commercially available product such as a trade name "KE-<NUM>-U" (manufactured by Shin-Etsu Chemical Co. ) may be used.

In addition, the conductive substrate <NUM> may be obtained by crosslinking the above-described conductive silicone rubber by a crosslinking agent. As the crosslinking agent, for example, a commercially available product such as a trade name "C-8A" (<NUM>,<NUM>-dimethyl-<NUM>,<NUM>-bis(t-butylperoxy)hexane content of <NUM>% by mass, manufactured by Shin-Etsu Chemical Co. ) may be used.

The thickness of the conductive substrate <NUM> is not particularly limited as long as it can ensure the flexibility of the conductive substrate <NUM>, and is preferably <NUM> or more and <NUM> or less, more preferably <NUM> or more and <NUM> or less.

<FIG> are views showing another example of the biological electrode obtained by the method for manufacturing a biological electrode according to the present embodiment; <FIG> is a perspective view of the biological electrode <NUM>, <FIG> is a side view of the biological electrode <NUM>, <FIG> is a top view of the biological electrode <NUM>, and <FIG> is a partially side view showing only the protruding body 22a constituting the biological electrode <NUM>.

As shown in <FIG>, the biological electrode <NUM> is made of a conductive rubber body having a disk <NUM> and a protrusion <NUM> provided on one surface of the disk <NUM>. As such a conductive rubber body, the conductive silicone rubber configured in the same manner as the conductive rubber body <NUM> shown in <FIG> can be used. The protrusion <NUM> has a brushed shape composed of a plurality of protruding bodies 22a. The protrusion <NUM> is composed of a protruding body 22a disposed at the center of the disk <NUM>, and a plurality of protruding bodies 22a disposed on the circumference around the protruding body 22a as the center. On the other main surface of the disk <NUM>, the connecting member <NUM> is provided.

As shown in <FIG>, the protruding body 22a includes a main body 221a and a tip portion 222a provided on the main body 221a. The main body 221a has a substantially cylindrical shape, and one end side thereof is provided on the disk <NUM>. The tip portion 222a has a generally conical shape having a hemispherical shape on the apex side, and the bottom surface is provided on the surface of the other end side of the main body 221a.

In the biological electrode <NUM> shown in <FIG>, a plurality of protruding bodies 22a serve as terminals having a brushed shape and come into contact with the human body. At this time, since the tip portion 222a of the protruding body 22a has a hemispherical shape on the apex side, no discomfort occurs when it comes into contact with the skin, and the adhesion to the skin is also improved due to the flexibility of the protruding body 22a. In addition, since the surface in contact with the skin has conductivity due to silver, the contact impedance is low, and stable measurement can be performed even in measurement under dry conditions in which paste or the like is not used. The present embodiment is also applicable to the biological electrode <NUM> provided with the conductive rubbers having such terminals having a brushed shape.

The method for manufacturing a biological electrode according to the embodiments of the present invention is a manufacturing method of the biological electrode includes a step of adding fumed silica to an aggregated silver powder and mixing to obtain a mixed silver powder in which the silver powder and the fumed silica are dispersed, and a step of forming a conductive rubber body containing silicone rubber and the mixed silver powder.

In the step of obtaining a mixed silver powder containing silver powder and fumed silica, the aggregated silver powder and the fumed silica are mixed and dispersed by a disperser, for example, and a part of the aggregated silver powder may be crushed and finely divided. For example, a part of the aggregated silver powder used for the preparation of the mixed silver powder may become primary particles or finer particles in the vicinity of the primary particles by crushing and dispersing, and may be contained in the mixed silver powder in the state of such finer particles. Further, the fumed silica is mixed with the silver powder to effectively suppress reaggregation of the silver powder, and to improve the fluidity of the silver powder (in other words, the mixed silver powder). By containing such mixed silver powder in the silicone rubber to form a conductive rubber body, the silver powder is uniformly dispersed in the conductive rubber body constituting the biological electrode, and an increase in resistance value over time due to strain can be effectively suppressed. In addition, the conductive rubber body constituting the biological electrode has good adhesion to the body of a subject for detection, does not easily cause discomfort even if the conductive rubber body is in close contact with the body for a long time with a soft skin touch, and can maintain stable contact with the body of the subject for detection. Further, even in a three-dimensional shape such as a brush, it expresses high conductivity, and it is possible to stably measure with little noise. In addition, since it is not necessary to use a gel or the like, it can be stably measured even in measurement under dry conditions, and the method of use is also simple. Note that, as for the conductivity of the obtained conductive rubber body, there is no effect due to the presence or absence of the addition of fumed silica, and the biological electrode having excellent conductivity can be produced while exhibiting the above-described effects.

The step of obtaining the mixed silver powder is a step of preparing an aggregated silver powder and fumed silica, adding the fumed silica to the aggregated silver powder, and dispersing them in advance by a disperser or the like. As described above, the mixed silver powder is preferably mixed and dispersed by a disperser. Incidentally, the aggregated silver powder and fumed silica may be first mixed by hand or by a kneader or the like, and then the aggregated silver powder may be crushed and dispersed by a disperser. By this step, the aggregated silver powder becomes primary particles or finer particles in the vicinity of the primary particles. There is no particular limitation on the disperser, and for example, a known instrument for pulverizing a powder such as a household mill can be used. The dispersion time by the disperser is not particularly limited, and it is preferable that the dispersion be performed in such a time to form a stable dispersion system. For example, the dispersion time may be from <NUM> to <NUM> minutes.

Examples of the aggregated silver powder include a trade name "G-<NUM>" (manufactured by DOWA Electronics Materials Co. The average particle diameter of the silver powder is not particularly limited as long as it can impart conductivity to the conductive rubber body <NUM>. The average particle diameter of the silver powder is preferably <NUM> or more and <NUM> or less.

As the fumed silica, hydrophobic fumed silica may be used, or hydrophilic fumed silica may be used, but hydrophobic fumed silica is more preferably used. When hydrophobic fumed silica is used, it is considered that the dispersibility of the silver powder is further increased and the handling property is further improved as compared with hydrophilic fumed silica. Examples of the hydrophobic fumed silica include a trade name "AEROSIL R972" (manufactured by Nippon Aerosil Co. ) and the like. Examples of the hydrophilic fumed silica include a trade name "AEROSIL <NUM>" (manufactured by Nippon Aerosil Co. ) and the like.

Although there is no particular limitation on the blending ratio of the aggregated silver powder and the fumed silica, for example, it is preferable that the fumed silica is <NUM> to <NUM> parts by mass per <NUM> parts by mass of the aggregated silver powder.

The step of forming the conductive rubber body containing the silicone rubber and the mixed silver powder is a step of mixing the silicone rubber and the mixed silver powder obtained by the above step to form a conductive rubber body having a desired shape. In the step of forming the conductive rubber body, in addition to the mixed silver powder described above, it is preferable to further add flaked silver powder to form the conductive rubber body. Examples of the flaked silver powder include a trade name "FA-D-<NUM>" and a trade name "FA-<NUM>-<NUM>" (both manufactured by DOWA Electronics Materials Co. The blending ratio (mass ratio) of the aggregated silver powder and the flaked silver powder is preferably <NUM>:<NUM> to <NUM>:<NUM>.

In the step of forming the conductive rubber body, (a) the conductive rubber body may be formed on the conductive substrate, or (b) the conductive rubber body may be formed alone. When (a) the conductive rubber body is formed on the conductive substrate, for example, examples of the method include a method in which a liquid silicone rubber, a mixed silver powder, and, if necessary, a silver powder-containing paste containing a crosslinking agent, a modified silicone, or the like is applied on a conductive substrate, and then the silver powder-containing paste is heated and cured. A material in which the silver powder-containing paste is cured becomes a conductive rubber body. In addition, when (b) the conductive rubber body is formed alone, examples of the method include a method in which the above-described silver powder-containing paste is injected into a forming mold having a predetermined internal shape, and then the silver powder-containing paste is heated and cured in the forming mold. Typically, in the case of (a) above, a layered conductive rubber body can be formed on the conductive substrate, and in the case of (b) above, a conductive rubber body having a desired shape such as a brushed shape can be formed.

Hereinafter, examples of the step of forming the conductive rubber body will be described in detail. When (a) the conductive rubber body is formed on the conductive substrate, a conductive substrate is first prepared. The conductive substrate may be one using a commercially available material or one newly produced. When a conductive substrate is newly produced, for example, a conductive silicone rubber containing a predetermined amount of conductive particles and a crosslinking agent are kneaded by a kneading machine such as a kneader and a roll at room temperature (<NUM> or more and <NUM> or less) for <NUM> minute or more and <NUM> hour or less to obtain a substrate. Thereafter, the kneaded substrate is subjected to primary crosslinking under conditions of <NUM> or more and <NUM> or less and <NUM> minute or more and <NUM> hour or less, and then subjected to secondary crosslinking under conditions of <NUM> or more and <NUM> or less and <NUM> hour or more and <NUM> hours or less to produce a conductive substrate.

Next, a silver powder-containing paste is prepared by stirring a liquid silicone rubber, a mixed silver powder, a crosslinking agent, or the like for a predetermined time by a mixer or the like. The temperature at the time of stirring may be, for example, room temperature (<NUM> or more and <NUM> or less). The stirring time may be, for example, <NUM> minute or more and <NUM> hour or less. Next, the silver powder-containing paste is applied onto the conductive substrate. For example, immersion, spraying, roll coater, flow coater, ink jet, screen printing, or the like are used to apply the silver powder-containing paste onto the conductive substrate. The coating thickness of the silver powder-containing paste is preferably <NUM> or more and <NUM> or less, and more preferably <NUM> or more and <NUM> or less. Thus, since the adhesion of the conductive rubber body to the conductive substrate can be increased, peeling of the conductive rubber body from the conductive substrate can be easily prevented, and the contact impedance can be lowered. Then, curing of the silver powder-containing paste is performed. In this step, for example, curing of the silver powder-containing paste can be performed by heating the silver powder-containing paste to a predetermined temperature for a predetermined time. The heating time of the silver powder-containing paste is preferably <NUM> to <NUM> minutes, more preferably <NUM> to <NUM> minutes, and still more preferably <NUM> to <NUM> minutes. Further, the heating temperature of the silver powder-containing paste is preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, and still more preferably <NUM> to <NUM>. The silver powder-containing paste can be cured by heating, for example, at <NUM> for <NUM> minutes.

When (b) the conductive rubber body is formed alone, a silver powder-containing paste is prepared in the same manner as in the case of (a) above. Next, after injecting the silver powder-containing paste into a mold corresponding to a desired shape such as a brushed shape, primary crosslinking by press crosslinking is performed. This is followed by further secondary cross-linking. Specifically, the kneaded substrate is primary crosslinked under the conditions of <NUM> or more and <NUM> or less and <NUM> minute or more and <NUM> hour or less, and then secondary crosslinked under the conditions of <NUM> or more and <NUM> or less and <NUM> hour or more and <NUM> hours or less to produce a conductive rubber body.

After forming the conductive rubber body as described above (a) or (b), the conductive rubber body may be immersed in an inorganic salt-containing solution having a temperature of <NUM> or more and <NUM> or less. During immersion in the inorganic salt-containing solution, an inorganic salt, an anion derived from the inorganic salt, and a cation effectively penetrate into the conductive rubber body. It is preferable that the inorganic salt-containing solution contains an inorganic salt, a solvent for dissolving the inorganic salt, and, if necessary, other additives.

The inorganic salt contained in the inorganic salt-containing solution is not particularly limited as long as it can penetrate into the conductive rubber body, but at least one inorganic salt selected from the group consisting of chloride salt, sulfide salt, and carbonate is preferably used. As the inorganic salt, it is more preferable to use at least one inorganic salt selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, and magnesium carbonate. One kind of these inorganic salts may be used alone, and two or more kinds thereof may be used in combination. Among the above, as the inorganic salt, a chloride salt is preferable from the viewpoint of solubility in a solvent and ion mobility, and a chloride salt by an alkali metal such as sodium chloride, potassium chloride and lithium chloride is more preferable, and sodium chloride is further preferable from the viewpoint of low cost, safety to the human body, and ion exchange property with salinity contained in sweat of the human body. Further, the conductive rubber body can contain a halide ion, a sulfate ion, and a carbonate ion as an anion derived from an inorganic salt. As the halide ion, chloride ion (Cl-) is preferable. The conductive rubbers may contain Li+, Na+, K+, Mg<NUM>+, Ca<NUM>+ or the like as a cation derived from an inorganic salt. Such an inorganic salt or an anion or a cation derived from an inorganic salt can penetrate into the conductive rubber body to suppress potential fluctuation based on the polarization voltage in the conductive rubber body, thereby effectively reducing the potential fluctuation noise. The concentration of the inorganic salt in the inorganic salt-containing solution is preferably <NUM>. 1mol/L or more, more preferably <NUM>. 5mol/L or more and 20mol/L or less. When the concentration of the inorganic salt in the inorganic salt-containing solution is within these ranges, it is possible to effectively penetrate the inorganic salt and the anion or the cation derived from the inorganic salt into the conductive rubber body.

There is no particular limitation on the solvent contained in the inorganic salt-containing solution as long as it can dissolve the inorganic salt. Examples of the solvent include ketones such as water and acetone, and alcohols such as methanol and ethanol. One kind of these solvents may be used alone, or two or more kinds thereof may be used in combination. Among the above, water, ethanol, or a mixture of water and ethanol is preferable from the viewpoint of safety and low-cost, and water is preferable from the viewpoint of safety and low-cost.

In the step of immersing the conductive rubber body in an inorganic salt-containing solution, it is preferable that the conductive rubber body is immersed in the inorganic salt-containing solution under a pressure condition. More preferably, the conductive rubber body is immersed in the inorganic salt-containing solution under a pressure of <NUM> atm or more and <NUM> atm or less, more preferably under a pressure of <NUM> atm or more and <NUM> atm or less. By immersing the conductive rubber body in the inorganic salt-containing solution under pressure conditions, it is possible to further increase the rate of penetration of an inorganic salt, an anion or a cation derived from an inorganic salt, into the conductive rubber body and to effectively increase the concentration of an inorganic salt, an anion, or a cation in the conductive rubber body. As a result, the potential fluctuation noises of the biological electrode can be effectively reduced. There is no particular limitation on the method of pressurizing, and examples thereof include a method in which a conductive rubber body is placed in a sealed container (e.g., an autoclave) in which an inorganic salt-containing solution is injected, and then a pressure in the sealed container is increased.

The time for immersing the conductive rubber body in the inorganic salt-containing solution can be appropriately changed depending on the temperature of the inorganic salt-containing solution, the concentration of the inorganic salt in the inorganic salt-containing solution, and the pressure at the time of pressurizing. The immersion time of the conductive rubber body in the inorganic salt-containing solution is preferably <NUM> minutes or more and <NUM> minutes or less, more preferably <NUM> minutes or more and <NUM> minutes or less, and still more preferably <NUM> minutes or more and <NUM> minutes or less, from the viewpoint of efficiently dispersing an inorganic salt, an anion or a cation derived from an inorganic salt in the conductive rubber body.

As described above, the method for manufacturing a biological electrode of the present embodiment includes a step of adding fumed silica to an aggregated silver powder and dispersing it in advance by a disperser or the like, and the mixed silver powder obtained by the step is added to the silicone rubber to form a conductive rubber body.

Next, a rubber for the biological electrode according to the embodiment of the present invention will be described. The rubber for the biological electrode according to the present embodiment is a rubber for the biological electrode containing at least silicone rubber, aggregated silver powder, and fumed silica. In addition, the rubber for the biological electrode contains <NUM> to <NUM> parts by mass of fumed silica per <NUM> parts by mass of the aggregated silver powder. The aggregated silver powder does not contain a flaked silver powder having a scaly shape, and examples thereof include silver powder in which a plurality of particulate primary particles are aggregated in a three-dimensional shape. Preferably, the rubber for the biological electrode further contains a flaked silver powder. The blending ratio (mass ratio) of the aggregated silver powder and the flaked silver powder is preferably <NUM>:<NUM> to <NUM>:<NUM>. Examples of the rubber for the biological electrode according to the present embodiment include a conductive rubber body manufactured by the manufacturing method of the biological electrode described above. In the rubber for the biological electrode according to the present embodiment, an increase in resistance value over time due to strain is suppressed. Next, a rubber electrode according to the embodiment of the present invention will be described. The rubber electrode according to the present embodiment is a rubber electrode made of the rubber for the biological electrode described above. Examples of the rubber electrode according to the embodiment include the biological electrode manufactured by the manufacturing method of the biological electrode described above.

Hereinafter, the present invention will be described in more detail based on examples performed in order to clarify the effect of the present invention. Note that the present invention is not limited in any way by the following examples and comparative examples.

A sample mixed in the following blending amount was dispersed with a disperser (household mill) for <NUM> minutes to prepare mixed silver powders <NUM> to <NUM> containing silver powder and fumed silica. Note that the pure silver particles described below ("G-<NUM>" manufactured by DOWA Electronics Materials Co. ) used for preparing the mixed silver powders <NUM> to <NUM> were aggregated silver powders at the time of preparation thereof.

Each of the mixed silver powders <NUM> and <NUM> was sieved using a sieve with a mesh size of <NUM> or <NUM> to calculate a mass ratio of the powder passing through each sieve (hereinafter, referred to as "sieve passage rate"). Incidentally, sieving the respective powder was carried out by beating the side surface of the sieve with a wooden hammer while shaking the sieve by hand. The results of the sieve passage rate test are shown in <FIG>.

<FIG> is a graph showing the results of the sieve passage rate test of the mixed silver powders <NUM> and <NUM>. In <FIG>, the vertical axis represents the sieve passing rate [%], and the horizontal axis represents the mesh size of the sieve. <FIG> shows a test result using a sieve having a mesh size of <NUM> on the right side of the graph, and shows a test result using a sieve having a mesh size of <NUM> on the left side of the graph.

As shown in <FIG>, each of mixed silver powders <NUM> and <NUM> in which fumed silica was blended with pure silver particles exhibited a good sieve passage rate in sieving using a sieve with a mesh size of <NUM> or <NUM>. In particular, the mixed silver powder <NUM> blended with hydrophobic fumed silica had extremely high sieve passage rate in each sieving, and had very good handling property.

The following blended components were mixed for <NUM> seconds with a centrifugal stirrer, press-crosslinked (primary crosslinked) at <NUM> for <NUM> minutes, and then oven-crosslinked (secondary crosslinked) at <NUM> for <NUM> minutes to produce a biological electrode of Example <NUM> consisting of silicone rubber. The biological electrode of Example <NUM> was formed to have a cylindrical shape having a diameter of <NUM> at the end face and a length of <NUM> in the axial direction. Further, the prroduced biological electrode was immersed in a <NUM>%NaCl aqueous solution, and heated and pressurized at <NUM> and <NUM> atm for <NUM> hour. The biological electrode of Example <NUM> is referred to as "conductive rubber body <NUM>". Pure silver particles ("FA-<NUM>-<NUM>" manufactured by DOWA Electronics Materials Co. ) in the blended component described below were flaked silver powder at the time of preparation thereof.

A biological electrode of Example <NUM> was produced in the same manner as in Example <NUM>, except that the following blended components were changed to the following blended components. The biological electrode of Example <NUM> is referred to as "conductive rubber body <NUM> ".

A biological electrode of Comparative Example <NUM> was produced in the same manner as in Example <NUM>, except that the following blended components were changed to the following blended components. The biological electrode of Comparative Example <NUM> is referred to as "conductive rubber body <NUM>".

The volume resistivity [Ω·cm] of the biological electrode in Examples <NUM> and <NUM> and Comparative Example <NUM> was measured by the following measuring method. The measurement result of the volume resistivity is shown in <FIG>. Note that the value of the volume resistivity shown in <FIG> is a value obtained by quickly measuring without applying a load or the like to the respective biological electrode after producing the respective biological electrode.

The volume resistivity of the biological electrode was measured using plate-shaped resistivity measuring members <NUM> and <NUM> as shown in <FIG> is an explanatory drawing for explaining a method of measuring the volume resistivity of the biological electrode; <FIG> shows a plan view of a resistivity measuring member for measuring the volume resistivity of a biological electrode. <FIG> is a side view for explaining a method of measuring the volume resistivity of a biological electrode. The resistivity measuring members <NUM> and <NUM> are a plate-shaped member as a set by two sheets, and measuring electrodes <NUM> and <NUM> formed by gold plating are disposed on each surface. The measuring electrodes <NUM> and <NUM> were <NUM> in length and <NUM> in width. In <FIG>, the ranges surrounded by dashed lines indicated by reference numerals <NUM> and <NUM> are sample placement positions for placing the biological electrode <NUM> (see <FIG>), which is a sample. As shown in <FIG>, when measuring the volume resistivity of the biological electrode <NUM>, the biological electrode <NUM> was sandwiched between the two plate-shaped resistivity measuring members <NUM> and <NUM>, a constant current of 100mA was applied to the two resistivity measuring members <NUM> and <NUM>, and the potential difference between the measuring electrodes <NUM> and <NUM> placed facing each other with the biological electrode <NUM> therebetween was measured. In <FIG>, reference numeral <NUM> denotes a constant current power supply for applying a constant current, and reference numeral <NUM> denotes a voltmeter for measuring the potential difference. The volume resistivity of the biological electrode <NUM> was calculated based on Ohm's law from the current value applied by the constant current power supply <NUM>, the potential difference measured by the voltmeter <NUM>, and the cross-sectional area and thickness of the biological electrode <NUM>. When measuring the potential difference between the measuring electrodes <NUM> and <NUM> as shown in <FIG>, two plate-shaped resistivity measuring members <NUM> and <NUM> sandwiching the biological electrode <NUM> were horizontally placed, and a weight having a mass of <NUM> was placed on the resistivity measuring member <NUM> of vertically upper side. Considering the electrical resistance of the measuring electrodes <NUM> and <NUM> themselves, the constant current power supply <NUM> and the voltmeter <NUM> were arranged so that their respective electrical contacts with the measuring electrodes <NUM> and <NUM> were sufficiently separated from the sample placement positions <NUM> and <NUM>. Further, the electrical contact of the constant current power supply <NUM> was set to a position <NUM> away from one side edge of the measuring electrodes <NUM> and <NUM>, and the electrical contact of the voltmeter <NUM> was set to a position further <NUM> away in the same direction from the electrical contact of the constant current power supply <NUM>. The size and the like of the measuring electrodes <NUM> and <NUM> were appropriately changed according to the size of the biological electrode <NUM> which is a sample.

<FIG> is a graph showing the measured results of the volume resistivity of the biological electrode (before applying the load) in Examples <NUM> and <NUM> and Comparative Example <NUM>. In <FIG>, the vertical axis represents the volume resistivity [Ω·cm]. As shown in <FIG>, the volume resistivity of each of the biological electrode of Example <NUM> using the mixed silver powder <NUM> and the biological electrode of Example <NUM> using the mixed silver powder <NUM> was not significantly different from the volume resistivity of the biological electrode of Comparative Example <NUM> using the silver powder (pure silver particles) as it is, and it was found that the addition of fumed silica did not significantly affect the conductivity of the biological electrode immediately after producing. Note that, when the volume resistivity of the biological electrodes of Examples <NUM> and <NUM> was compared, it was found that the volume resistivity of the biological electrode of Example <NUM> using hydrophilic fumed silica was higher.

A load was applied to the biological electrodes in Examples <NUM> and <NUM> and Comparative Example <NUM> by the following method, and the volume resistivity [Ω·cm] of each biological electrode was measured over time immediately after the end of the load application. The volume resistivity of the biological electrode is measured as described above. A load of 1kgf was applied <NUM>,<NUM> times to each biological electrode formed to have a cylindrical shape with a diameter of <NUM> at the end face and a length of <NUM> in the axial direction. The load application cycle was <NUM>,<NUM> times/h. The measured results of the volume resistivity shown in <FIG>.

<FIG> is a graph showing the measured results of the volume resistivity of the biological electrode (after applying the load) in Examples <NUM> and <NUM> and Comparative Example <NUM>. In <FIG>, the vertical axis represents the volume resistivity [Ω·cm], the horizontal axis represents the elapsed time [min] from the end of the load application. <FIG> is a semi-logarithmic graph where the horizontal axis is a logarithmic scale. <FIG> shows the change over time of the volume resistivity of each biological electrode from the end of the load application. In the graph shown in <FIG>, the values of the volume resistivities [Ω·cm] of the respective biological electrode before applying the load are plotted at <NUM> minutes, which is the origin of the horizontal axis (see, for example, <FIG>).

As shown in <FIG>, the volume resistivity of the biological electrode in Comparative Example <NUM> using silver powder (pure silver particles) as it is, was increased to about <NUM> times as compared with that before the load application. The volume resistivity of the biological electrode in Comparative Example <NUM> was confirmed to have a tendency to gradually decrease thereafter, but when one day elapsed from the end of the load application, the volume resistivity was <NUM> times or more as compared with that before the load application, and the decrease in the volume resistivity thereafter became extremely slow, and the volume resistivity stagnated at a value substantially <NUM> times or more.

On the other hand, in the biological electrodes of Examples <NUM> and <NUM> in which a mixed silver powder composed of silver powder and fumed silica was used, an increase in the volume resistivity was suppressed to about <NUM> times as compared with that before applying the load. The rate at which the volume resistivity gradually decreased was smaller than that of Comparative Example <NUM>. Therefore, it was found that the biological electrodes of Examples <NUM> and <NUM> exhibited a small change in resistivity with respect to strain. For this reason, for example, when these biological electrodes are used as an electroencephalogram measuring rubber electrode, it is possible to obtain an electrode which is hardly deteriorated in conductivity even in the pressing operation at the time of use or the repeated use of the electroencephalogram measuring rubber electrode. Further, as can be seen from the results of the sieve passage rate test of the mixed silver powder described above, the manufacturing method using the mixed silver powder <NUM> and <NUM> composed of silver powder and fumed silica had extremely good handling property during work.

Claim 1:
A method for manufacturing a biological electrode (<NUM>, <NUM>, <NUM>),
characterized by:
a step of adding fumed silica to an aggregated silver powder and mixing to obtain a mixed silver powder in which the silver powder and the fumed silica are dispersed, and
a step of forming a conductive rubber body (<NUM>) containing a silicone rubber and the mixed silver powder.