Bioelectrode composition, bioelectrode, and method for manufacturing the same

Abstract

To provide: a bio-electrode composition capable of forming a living body contact layer for a bio-electrode that is excellent in electric conductivity and biocompatibility, is light in weight, can be manufactured at low cost, can avoid significant reduction in conductivity either when the bio-electrode is soaked in water or dried, and has excellent softness, stretchability and adhesiveness; a bio-electrode including a living body contact layer formed of the bio-electrode composition; and a method for manufacturing the bio-electrode.SOLUTION: The present invention relates to a bio-electrode composition containing an ionic polymer material as a component (A), where the component (A) includes a polymer having: a repeating unit (a) having a structure selected from the group consisting of salts of ammonium, sodium, potassium, and silver formed with any of fluorosulfonic acid, fluorosulfonimide, and N-carbonyl-fluorosulfonamide; and a repeating unit (b) having a nitro group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a bioelectrode, a method for manufacturing the same, and a bioelectrode composition suitably used in a bioelectrode. [Background technology]

[0002] In recent years, the development of wearable devices has progressed alongside the spread of IoT (Internet of Things). Watches and glasses that can connect to the internet are prime examples. Furthermore, wearable devices that can continuously monitor the body's condition are needed in the medical and sports fields, making these areas significant growth prospects.

[0003] In the medical field, wearable devices that monitor the state of organs by sensing weak electrical currents are being considered, such as electrocardiograms (ECGs) that detect heart activity using electrical signals. ECG measurements are performed by attaching electrodes coated with conductive paste to the body, but this is a one-time, short-duration measurement. In contrast, the development of the aforementioned medical wearable devices aims to create devices that continuously monitor health status for several weeks. Therefore, bioelectrodes used in medical wearable devices must maintain their conductivity even after prolonged use and must not cause skin allergies. In addition, they must also be lightweight and low-cost to manufacture.

[0004] Medical wearable devices include types that are attached to the body and types that are incorporated into clothing. For the type that is attached to the body, a bioelectrode using a water-soluble gel containing water and electrolytes, which are the materials for the conductive paste mentioned above, has been proposed (Patent Document 1). The water-soluble gel contains sodium, potassium, and calcium as electrolytes in a water-soluble polymer to retain water, and converts changes in ion concentration from the skin into electricity. On the other hand, for the type that is incorporated into clothing, a method has been proposed in which a fabric in which a conductive polymer such as PEDOT-PSS (Poly-3,4-ethylenedioxythiophene-Polystyrenesulfonate) or silver paste is incorporated into the fibers is used as an electrode (Patent Document 2).

[0005] However, when using the water-soluble gel containing water and electrolytes mentioned above, there was a problem that conductivity was lost when the water evaporated due to drying. On the other hand, when using metals with a high ionization tendency such as copper, there was a problem that some people were at risk of developing skin allergies. Similarly, when using conductive polymers such as PEDOT-PSS, there was a problem that the strong acidity of the conductive polymer was at risk of causing skin allergies, and that the conductive polymer would peel off the fibers during washing.

[0006] Furthermore, due to their excellent conductivity, metal nanowires, carbon black, and carbon nanotubes are also being considered as electrode materials (Patent Documents 3, 4, and 5). Metal nanowires have a high probability of contact between wires, allowing current to flow with a small amount of additive. However, because metal nanowires are thin materials with pointed tips, they can cause skin allergies. Thus, even if the material itself does not cause an allergic reaction, its shape and irritancy can worsen biocompatibility, making it difficult to achieve both conductivity and biocompatibility.

[0007] While metal films might seem like excellent bioelectrodes due to their high conductivity, this isn't always the case. The heartbeat releases not only weak electric currents from the skin, but also sodium, potassium, and calcium ions. Therefore, it's necessary to convert changes in ion concentration into electric current, but precious metals, which are difficult to ionize, are inefficient at converting ions from the skin into electric current. Consequently, bioelectrodes using precious metals have high impedance, resulting in high resistance when conducting electricity with the skin.

[0008] On the other hand, batteries with added ionic liquids are being considered (Patent Document 6). Ionic liquids have high thermal and chemical stability and excellent conductivity, and their applications in batteries are expanding. However, since ionic liquids with small molecular weights, as shown in Patent Document 6, dissolve in water, if they are used in bioelectrodes, the ionic liquid is extracted by sweat from the skin, which not only reduces conductivity but also causes skin irritation as it penetrates the skin.

[0009] Furthermore, batteries using lithium salts of polymer-type sulfonimides are being investigated (Non-Patent Literature 1). However, although lithium is used in batteries due to its high ion mobility, it is not a biocompatible material. Moreover, lithium salts of fluorosulfonic acid pendanted to silicone are also being investigated (Non-Patent Literature 2).

[0010] A material for biosensing devices based on a polymer copolymerized of repeating units of betaine-type ammonium salts and repeating units having nitro groups has been proposed (Patent Document 7). Betaine, which utilizes the polarization of nitro groups, has high ionic conductivity and can be an excellent biosensor, but because it is a water-soluble polymer, it cannot be used as a dry bioelectrode.

[0011] When bioelectrodes are separated from the skin, they lose the ability to receive information from the body. Furthermore, even a slight change in the contact area can cause fluctuations in the amount of electricity conducted, resulting in a change in the baseline of the electrocardiogram (electrical signal). Therefore, in order to obtain a stable electrical signal from the body, bioelectrodes must always be in contact with the skin, and their contact area must not change. For this reason, it is preferable that bioelectrodes have adhesive properties. In addition, elasticity and flexibility that can follow changes in skin stretching and bending are also necessary.

[0012] A bioelectrode is being considered in which the part that comes into contact with the skin is made of silver chloride, and silver is layered on the part that conducts to the device. Solid silver chloride has no adhesive properties to the skin and is not flexible, so its ability to collect biosignals decreases, especially when the human body moves. For this reason, a layered film of silver chloride and silver is used as a bioelectrode with a water-soluble gel layered between it and the skin. In this case, degradation occurs due to the drying of the aforementioned gel. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] International Publication No. 2013 / 039151 [Patent Document 2] Japanese Patent Publication No. 2015-100673 [Patent Document 3] Japanese Patent Application Publication No. 05-095924 [Patent Document 4] Japanese Patent Publication No. 2003-225217 [Patent Document 5] Japanese Patent Publication No. 2015-019806 [Patent Document 6] Special Publication No. 2004-527902 [Patent Document 7] Japanese Patent Publication No. 2007-298373 [Non-patent literature]

[0014] [Non-Patent Document 1] J.Mater.Chem.A,2016,4,p10038-10069 [Non-Patent Document 2] J. of the Electrochemical Society, 150(8) A1090-A1094 (2003) [Overview of the Initiative] [Problems that the invention aims to solve]

[0015] The present invention has been made to solve the above problems, and aims to provide a bioelectrode composition that can form a biocontact layer for a bioelectrode that is excellent in conductivity and biocompatibility, is lightweight, can be manufactured at low cost, does not experience a significant decrease in conductivity whether wet or dry, and is soft, stretchable, and has excellent adhesive properties; a bioelectrode in which a biocontact layer has been formed with the bioelectrode composition; and a method for manufacturing the same. [Means for solving the problem]

[0016] To solve the above problems, the present invention provides a bioelectrode composition containing an ionic polymer material as component (A), The present invention provides a bioelectrode composition in which component (A) contains a polymer having a repeating unit a having a structure selected from ammonium salts, sodium salts, potassium salts, and silver salts of fluorosulfonic acid, fluorosulfonimide, and N-carbonylfluorosulfonamide, and a repeating unit b having a nitro group.

[0017] Such a bioelectrode composition would be excellent in conductivity and biocompatibility, lightweight, and could be manufactured at low cost. Furthermore, its conductivity would not significantly decrease whether wet or dry, and it would be able to form a biocontact layer for bioelectrodes that is soft, stretchable, and highly adhesive.

[0018] Furthermore, in the present invention, it is preferable that the repeating unit a has a structure represented by the following general formulas (1)-1 to (1)-4. [ka] (In General Formula (1)-1, Rf1 and Rf2 are a hydrogen atom, a fluorine atom, an oxygen atom, a methyl group, or a trifluoromethyl group. When Rf1 and Rf2 are oxygen atoms, Rf1 and Rf2 are one oxygen atom bonded to one carbon atom to form a carbonyl group. Rf3 and Rf4 are a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group. In General Formula (1)-2, General Formula (1)-3, and General Formula (1)-4, Rf5, Rf6, and Rf7 are each a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, and have at least one fluorine atom. In General Formula (1)-1 to General Formula (1)-4, M 13 , 10 , 14 , 9 , 4 , 2 , 11 , 8 , 12 , 6 is an ion selected from an ammonium ion, a sodium ion, a potassium ion, and a silver ion. In General Formula (1)-2, m is an integer from 1 to 4.)

[0019] If the repeating unit a has such a structure, it can be made into a bioelectrode composition capable of forming a bio-contact layer for a bioelectrode that is excellent in conductivity and biocompatibility.

[0020] In addition, in the present invention, it is preferable that the repeating unit a has one or more selected from the repeating units a1 to a7 described in the following General Formula (2).

Chemical Formula

[0021] If the repeating unit a has such a structure, it is possible to create a bioelectrode composition that can form a biocontact layer for bioelectrodes with even better conductivity and biocompatibility.

[0022] In this case, it is preferable that the polymer contains one or more repeating units a1 to a7 described in the general formula (2) above, in addition to repeating unit b1 having a nitro group as described in the general formula (4) below. [ka] (In general formula (4), R20 is a hydrogen atom or a methyl group, X8 is one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, R 21 n is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or a phenylene group, and the alkylene group may have a hydroxyl group, carboxyl group, ether group, ester group, urethane group, thiourethane group, carbonate group, amide group, or urea bond, and the phenylene group may be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, or a cyano group. n is 1 or 2, 0 <b1<1.0である。)

[0023] If the repeating unit b1 has such a structure, the polarity can be further improved.

[0024] Furthermore, in the present invention, it is preferable that component (A) contains an ammonium ion represented by the following general formula (3) as the ammonium ion constituting the ammonium salt. [ka] (In general formula (3), R 101d , R 101e , R 101f , and R 101g Each of these is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have one or more selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d and R 101e , or R 101d , R 101e and R 101f These may form a ring with the nitrogen atom to which they are bonded, and if a ring is formed, R 101d and R 101e , or R 101d , R101e and R 101f (This is either an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring containing the nitrogen atom in general formula (3) within the ring.)

[0025] If the material contains such a polymer compound (A) containing ammonium ions, it can be used to create a bioelectrode composition that can form a biocontact layer for bioelectrodes with even better conductivity and biocompatibility.

[0026] Furthermore, in the present invention, it is preferable that the (B) component further contains a resin.

[0027] Such a bioelectrode composition is compatible with component (A) and can prevent the elution of salt.

[0028] In this case, it is preferable that component (B) is one or more selected from silicone resin, (meth)acrylate resin, and urethane resin.

[0029] The component (B) to be included in the bioelectrode composition can be selected according to the characteristics to be imparted to the biological contact layer.

[0030] In this case, it is preferable that component (B) has adhesive properties.

[0031] Such a (B) component can further improve the adhesiveness of the bioelectrode composition.

[0032] At this time, component (B) is R x SiO (4-x) / 2 The units (R is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, x is in the range of 2.5 to 3.5) and SiO 4 / 2 It is preferable that the material contains a silicone resin having units.

[0033] Such component (B) is compatible with component (A) to prevent salt elution and can also impart high tackiness to the bioelectrode composition.

[0034] Furthermore, in the present invention, it is preferable that the (C) component further contains carbon material and / or metal powder.

[0035] Carbon materials and metal powders act as conductivity enhancers, providing superior conductivity to the biocontact layer formed from the bioelectrode composition.

[0036] In this case, it is preferable that the carbon material is carbon black, carbon nanotubes, or both.

[0037] By incorporating such carbon materials, higher conductivity can be achieved.

[0038] In this case, it is preferable that the metal powder is one or more metal powders selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

[0039] Thus, various metal powders can be used in the bioelectrode composition of the present invention.

[0040] In this case, it is preferable that the metal powder is silver powder.

[0041] In the bioelectrode composition of the present invention, silver powder is most preferred overall from the viewpoint of conductivity, cost, and biocompatibility.

[0042] Furthermore, in the present invention, it is preferable that the (D) component further contains an organic solvent.

[0043] Bioelectrode compositions containing organic solvents can exhibit high coatability.

[0044] Furthermore, the present invention provides a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is a cured product of the bioelectrode composition described above.

[0045] The bioelectrode of the present invention has a biocontact layer containing a cured product of the bioelectrode composition described above, and therefore has excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, does not experience a significant decrease in conductivity whether wet or dry, and is soft, stretchable, and adhesive.

[0046] In this case, it is preferable that the conductive substrate contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0047] Thus, various conductive substrates can be used in the bioelectrode of the present invention.

[0048] Furthermore, the present invention provides a method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is formed by applying the bioelectrode composition described above onto the conductive substrate and curing it.

[0049] This manufacturing method allows for the easy and low-cost production of bioelectrodes that are highly conductive and biocompatible, lightweight, maintain their conductivity even when wet or dry, and possess excellent flexibility and adhesive properties.

[0050] In this case, it is preferable to use a conductive substrate that contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0051] Thus, the method for manufacturing bioelectrodes of the present invention can utilize a variety of conductive substrates. [Effects of the Invention]

[0052] As described above, the present invention provides a bioelectrode composition, a bioelectrode having a biocontact layer formed with the bioelectrode composition, and a method for manufacturing the same, which are excellent in conductivity and biocompatibility, lightweight, and can be manufactured at low cost, and can stably collect biological signals without a significant decrease in conductivity even when attached to the skin for a long period of time and wet with water during bathing or drying, and can form a biocontact layer for a bioelectrode that is soft, has excellent elasticity and adhesion, and leaves no residue on the skin after being peeled off, a bioelectrode having a biocontact layer formed with the bioelectrode composition, and a method for manufacturing the same. [Brief explanation of the drawing]

[0053] [Figure 1] This is a schematic cross-sectional view showing an example of a bioelectrode of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of how the bioelectrode of the present invention is attached to a living body. [Figure 3] This is a schematic diagram of a bioelectrode after printing, fabricated according to an embodiment of the present invention. [Figure 4] This is a schematic diagram showing one of the bioelectrodes fabricated in an embodiment of the present invention cut out and with an adhesive layer and wire attached. [Figure 5] This figure shows the locations where electrodes and grounds are attached to the human body when measuring biological signals in an embodiment of the present invention. [Figure 6] This is one electrocardiogram waveform obtained using the bioelectrode of an embodiment of the present invention. [Modes for carrying out the invention]

[0054] As described above, there has been a need for the development of a bioelectrode composition that is excellent in conductivity and biocompatibility, lightweight, can be manufactured at low cost, is soft, stretchable and adhesive, and can form a biocontact layer for bioelectrodes that does not experience a significant decrease in conductivity even when attached to the skin for a long period of time and wet or dried by bathing, a bioelectrode with a biocontact layer formed using the bioelectrode composition, and a method for manufacturing the same.

[0055] Sodium, potassium, and calcium ions are released from the skin surface in conjunction with the heartbeat. Bioelectrodes need to convert the increase or decrease in ions released from the skin into electrical signals. For this purpose, a material with excellent ion conductivity is required to transmit the increase or decrease in ions.

[0056] To reliably obtain biological signals when attached to the skin, the bioelectrode membrane needs to be soft, elastic, and adhesive. The stratum corneum of the epidermis regenerates daily, and old keratin (dead skin cells) accumulates between the attached bioelectrode membrane and the skin. Since old keratin is easily detached from the epidermis, the bioelectrode may detach, making it impossible to collect biological signals. Therefore, the bioelectrode must maintain its adhesiveness even when attached for a long period of time. On the other hand, if there is any residue on the skin after being attached for a long time and then removed, it may cause rashes or skin irritation.

[0057] When the acid that forms the neutralization salt is highly acidic, the ions are strongly polarized, improving ionic conductivity. This is why lithium salts of bis(trifluoromethanesulfonyl)imide acid and tris(trifluoromethanesulfonyl)methidic acid exhibit high ionic conductivity when used in lithium-ion batteries. On the other hand, the higher the acidity of the acid before it forms the neutralization salt, the more bioirritating the resulting salt becomes. In other words, there is a trade-off between ionic conductivity and bioirritation. However, salts applied to bioelectrodes must achieve both high ionic conductivity and low bioirritation.

[0058] As the molecular weight of an ionic compound increases, its penetration into the skin decreases, and its skin irritation also decreases. For this reason, high molecular weight polymer forms of ionic compounds are preferred. Therefore, the inventors avoided the problem of skin irritation by polymerizing this ionic compound as a polymer in a form having polymerizable double bonds.

[0059] While polymerizing ions helped avoid skin irritation, it resulted in a decrease in ionic conductivity. To increase ionic conductivity, it is effective to increase the polarization of the polymer itself. According to the aforementioned published patents related to biosensing devices, polymers containing nitro groups are effective in increasing polarity, which led to the idea of ​​the present invention to introduce highly polarizing nitro groups into the ionic polymer of a bioelectrode.

[0060] In other words, the present invention relates to a bioelectrode composition containing an ionic polymer material as component (A), The bioelectrode composition is one in which component (A) contains a polymer having a repeating unit a having a structure selected from ammonium salts, sodium salts, potassium salts, and silver salts of fluorosulfonic acid, fluorosulfonimide, and N-carbonylfluorosulfonamide, and a repeating unit b having a nitro group.

[0061] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0062] <Bioelectrode composition> The bioelectrode composition of the present invention contains an ionic polymer material as component (A). It may also contain a resin or the like as component (B). Each component will be described in further detail below.

[0063] [(A) Ionic polymer materials] The bioelectrode composition of the present invention is characterized by containing an ionic polymer material as component (A). Component (A) contains a polymer having a repeating unit a having a structure selected from ammonium salts, sodium salts, potassium salts, and silver salts of fluorosulfonic acid, fluorosulfonimide, and N-carbonylfluorosulfonamide, and a repeating unit b having a nitro group.

[0064] The repeating unit a is preferably having a structure represented by the following general formulas (1)-1 to (1)-4. [ka] (In general formula (1)-1, Rf1 and Rf2 are a hydrogen atom, a fluorine atom, an oxygen atom, a methyl group, or a trifluoromethyl group. When Rf1 and Rf2 are oxygen atoms, Rf1 and Rf2 are one oxygen atom bonded to one carbon atom to form a carbonyl group. Rf3 and Rf4 are a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and one or more of Rf1 to Rf4 are fluorine atoms or trifluoromethyl groups. In general formulas (1)-2, (1)-3, and (1)-4, Rf5, Rf6, and Rf7 are each a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and each has at least one fluorine atom. In general formulas (1)-1 to (1)-4, M + m is an ion selected from ammonium ions, sodium ions, potassium ions, and silver ions. In general formula (1)-2, m is an integer between 1 and 4.

[0065] It is preferable that the repeating unit a has one or more repeating units a1 to a7 described in the following general formula (2). [ka] (In general formula (2), R 1 , R 3 , R 5 , R 8 , R 10 , R 11 , and R 13 Each is independently either a hydrogen atom or a methyl group, and R 2 , R 4 , R 6 , R 9 , R 12 , and R 14Each of these is independently a single bond or a linear, branched, or cyclic hydrocarbon group having 1 to 13 carbon atoms. The hydrocarbon group may have an ester group, an ether group, or both. 7 R is a linear or branched alkylene group having 1 to 4 carbon atoms. 7 One or two of the hydrogen atoms in the molecule may be substituted with fluorine atoms. X1, X2, X3, X4, X6, and X7 are each independently one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, and X5 is one of a single bond, an ether group, and an ester group. Y is an oxygen atom or -NR 19 - is a base, R 19 R is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. 4 They may form a ring together. Rf1' and Rf5' are a fluorine atom, a trifluoromethyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms, and have at least one fluorine atom. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are such that 0≦a1<1.0, 0≦a2<1.0, 0≦a3<1.0, 0≦a4<1.0, 0≦a5<1.0, 0≦a6<1.0, 0≦a7<1.0, and 0 <a1+a2+a3+a4+a5+a6+a7<1.0である。M + (This is an ion selected from ammonium ions, sodium ions, potassium ions, and silver ions.)

[0066] Of the repeating units a1 to a7 shown in the general formula (2) above, the following are examples of fluorosulfonate monomers used to obtain repeating units a1 to a5.

[0067] [ka]

[0068] [ka]

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] Specific examples of fluorosulfonimide salt monomers for obtaining the repeating unit a6 shown in the general formula (2) above are shown below.

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] The N-carbonylfluorosulfonamide salt monomers used to obtain the repeating unit a7 shown in the general formula (2) above can be specifically exemplified below.

[0095] [ka]

[0096] [ka] (In the formula, R 1 , R 3 , R 5 , R 8 , R 10 , R 11 , and R 13 As mentioned above.

[0097] Furthermore, it is preferable that component (A) contains an ammonium ion (ammonium cation) represented by the following general formula (3) as the ammonium ion constituting the ammonium salt. [ka] (In general formula (3), R 101d , R 101e , R 101f, and R 101g Each of these is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have one or more selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d and R 101e , or R 101d , R 101e and R 101f These may form a ring with the nitrogen atom to which they are bonded, and if a ring is formed, R 101d and R 101e , or R 101d , R 101e and R 101f (This is either an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring containing the nitrogen atom in general formula (3) within the ring.)

[0098] The following are specific examples of ammonium ions represented by the general formula (3) above.

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104]

change

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

change

[0114] [ka]

[0115] As the ammonium ion represented by the above general formula (3), tertiary or quaternary ammonium ions are particularly preferred.

[0116] (Repeat unit b1) The bioelectrode composition of the present invention contains a polymer having repeating unit a and repeating unit b having a nitro group. The repeating unit b is preferably the repeating unit b1 having a nitro group as described in the following general formula (4). [ka] (In general formula (4), R 20 is a hydrogen atom or a methyl group, X8 is one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, R 21 n is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or a phenylene group, and the alkylene group may have a hydroxyl group, carboxyl group, ether group, ester group, urethane group, thiourethane group, carbonate group, amide group, or urea bond, and the phenylene group may be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, or a cyano group. n is 1 or 2, 0 <b1<1.0である。)

[0117] The monomers used to obtain the repeating unit b1 described in general formula (4) can be specifically exemplified below.

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka] (In the formula, R 20 As mentioned above.

[0124] (Repeat unit c) In addition to the repeating units a1 to a7 and b1 described above, component (A) of the bioelectrode composition of the present invention may also contain copolymerized repeating unit c having a glyme chain to improve conductivity. Specific examples of monomers for obtaining repeating unit c having a glyme chain are shown below. By copolymerizing repeating unit c having a glyme chain, the movement of ions released from the skin within the dry electrode film is promoted, thereby increasing the sensitivity of the dry electrode.

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka] (In the formula, R is a hydrogen atom or a methyl group.)

[0129] (Repeating unit d) In addition to the repeating units a1 to a7, b1, and c of the biological electrode composition of the present invention, in order to improve conductivity, a hydrophilic repeating unit d having a hydroxy group, a carboxyl group, an ammonium salt, betaine, an amide group, pyrrolidone, a lactone ring, a lactam ring, a sultone ring, a sodium salt of sulfonic acid, or a potassium salt of sulfonic acid can also be copolymerized. Monomers for obtaining the hydrophilic repeating unit d can be specifically exemplified as follows. By copolymerizing the repeating unit d containing these hydrophilic groups, the sensitivity to ions released from the skin can be enhanced, and the sensitivity of the dry electrode can be enhanced.

[0130] [Chemical formula]

[0131] [Chemical formula]

[0132] [Chemical formula] (In the formula, R is a hydrogen atom or a methyl group.)

[0133] (Repeating unit e) The (A) component of the biological electrode composition of the present invention can have a repeating unit e that imparts adhesiveness in addition to the repeating units a1 to a7, b1, c, and d described above. Monomers for obtaining the repeating unit e can be specifically exemplified as follows.

[0134] [Chemical formula]

[0135] [Chemical formula]

[0136] [Chemical formula]

[0137] [Chemical formula]

[0138] [Chemical formula] T

[0139] (Repeating unit f) In addition to the repeating units a1 to a7, b1, c, d, and e of the biocompatible electrode composition of the present invention, the component (A) can also copolymerize the crosslinkable repeating unit f. Examples of the crosslinkable repeating unit f include repeating units having an oxirane ring or an oxetane ring. Specific examples of the monomers for obtaining the crosslinkable repeating unit f having an oxirane ring or an oxetane ring are as follows.

[0140] [Chemical formula]

[0141] [Chemical formula] (In the formula, R is a hydrogen atom or a methyl group.)

[0142] (Repeating unit g) In addition to the repeating units selected from a1 to a, b1, c to f above, the component (A) of the biocompatible electrode composition of the present invention can have a repeating unit g having silicon. Specifically, the following can be exemplified.

[0143] [Chemical formula]

[0144] [Chemical formula]

[0145] (Repeating unit h) Component (A) of the biocompatible electrode composition of the present invention can have a repeating unit h having fluorine in addition to the repeating units selected from a1 to a7, b1, c to g described above. Specific examples of the monomer for obtaining the repeating unit h having fluorine include the following.

[0146] [Chemical formula] [[ID=2??5]]

[0147] [Chemical formula] <000098??>

[0148] [Chemical formula]

[0149] [Chemical formula]

[0150] [Chemical formula]

[0151] [Chemical formula]

[0152] [Chemical formula] (In the formula, R is a hydrogen atom or a methyl group.)

[0153] As one of the methods for synthesizing an ionic polymer material of component (A), a desired monomer among the monomers giving repeating units a1 to a7, b1, c, d, e, f, g, h can be heated and polymerized by adding a radical polymerization initiator in an organic solvent to obtain an ionic polymer material of a copolymer.

[0154] Examples of the organic solvent used during polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, etc. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. The heating temperature is preferably 50 to 80°C, and the reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

[0155] Here, the ratios of the repeating units a1 to a7, b1, c, d, e, f, g, h in the ionic polymer material of component (A) are 0≦a1<1.0, 0≦a2<1.0, 0≦a3<1.0, 0≦a4<1.0, 0≦a5<1.0, 0≦a6<1.0, 0≦a7<1.0, 0<a1+a2+a3+a4+a5+a6+a7<1.0, 0<b1<1.0, 0≦c<1.0, 0≦d<1.0, 0≦e<0.9, 0≦f<0.9, 0≦g<0.9, 0≦h<0.9, preferably 0≦a1≦0.9, 0≦a2≦0.9, 0≦a3≦0.9, 0≦a4≦0.9, 0≦a5≦0.9, 0≦a6≦0.9, 0≦a7≦0.9, 0.01≦a1+a2+a3+a4+a5+a6+a7≦0.99, 0.01≦b1≦0.9, 0≦c≦0.8, 0≦d≦0.8, 0≦e<0.8, 0≦f<0.8, 0≦g<0.8, 0≦h<0.8, more preferably 0≦a1≦0.8, 0≦a2≦0.8, 0≦a3≦0.8, 0≦a4≦0.8, 0≦a5≦0.8, 0≦a6≦0.8, 0≦a7≦0.8, 0.02≦a1+a2+a3+a4+a5+a6+a7≦0.95, 0.05≦b1≦0.8, 0≦c≦0.7, 0≦d≦0.5, 0≦e<0.3, 0≦f<0.7, 0≦g<0.7, 0≦h<0.7.

[0156] For example, a1+a2+a3+a4+a5+a6+a7+b1+c+d+e+f+g+h=1 means that in a polymer compound containing repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h, the total amount of repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h is 100 mol% of the total amount of all repeating units. The statement a1+a2+a3+a4+a5+a6+a7+b1+c+d+e+f+g+h<1 indicates that the total amount of repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h is less than 100 mol% of the total amount of all repeating units, and that there are other repeating units besides a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h.

[0157] The molecular weight of the ionic polymer material of component (A) is preferably 500 or more as a weight-average molecular weight, more preferably 1,000 or more and 1,000,000 or less, and even more preferably 2,000 or more and 500,000 or less. Furthermore, if there is a small amount of ionic monomer that is not incorporated into the ionic polymer material of component (A) after polymerization (residual monomer), the risk of it penetrating the skin and causing allergies in biocompatibility tests is eliminated, so it is preferable to reduce the amount of residual monomer. The amount of residual monomer is preferably 10 parts by mass or less per 100 parts by mass of the total ionic polymer material of component (A). In addition, component (A) may be used alone, or two or more types with different molecular weights, dispersibility, and polymerization monomers may be used in mixture form. The molecular weight (Mw) was confirmed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0158] (A) The ionic polymer material of component (A) preferably contains a polymer obtained by copolymerizing one or more repeating units a1 to a7 described in the following general formula (2)' with a repeating unit b1 having a nitro group.

[0159] [Chemical formula] (In the formula, R 1~14 , R 20 , R 21 , X 1~8 , a1 to a7, b1, Rf1’, Rf5’, m, n, M + are the same as above.)

[0160] In the biocompatible electrode composition of the present invention, the blending amount of component (A) is preferably 0.1 to 300 parts by mass, more preferably 1 to 200 parts by mass, based on 100 parts by mass of component (B) described later. Component (A) may be used alone or in combination of two or more.

[0161] [(B) Resin] The biocompatible electrode composition of the present invention may further contain a resin as component (B). The (B) resin blended in the biocompatible electrode composition of the present invention is compatible with the above (A) ionic polymer material (salt) to prevent elution of the salt, retains conductivity improvers such as metal powder, carbon powder, silicon powder, lithium titanate powder, etc., and is a component for further improving adhesiveness. When the ionic polymer material of (A) has sufficient adhesiveness, the (B) resin is not necessarily required. The resin may be any resin other than the above component (A), and is preferably either a thermosetting resin and / or a photocurable resin, particularly preferably one or more selected from silicone-based, acrylic-based, and urethane-based resins, i.e., silicone resin, (meth)acrylate resin, and urethane resin. It is also preferably adhesive, and preferably contains a silicone resin having R x SiO (4-x) / 2 units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, x is in the range of 2.5 to 3.5) and SiO 4 / 2 units.

[0162] Examples of adhesive silicone-based resins include those of the addition reaction curing type or the radical crosslinking reaction curing type. Examples of the addition reaction curing type include the diorganosiloxane having an alkenyl group, R3SiO, as described in Japanese Patent Publication No. 2015-193803. 1 / 2 and SiO 4 / 2 A solution containing MQ resin having units, organohydrogenpolysiloxane having multiple SiH groups, platinum catalyst, addition reaction control agent, and organic solvent can be used. Furthermore, as a radical crosslinking reaction curing type, for example, a diorganopolysiloxane having or not having alkenyl groups, as described in Japanese Patent Application Publication No. 2015-193803, and R3SiO 1 / 2 and SiO 4 / 2 A solution containing MQ resin having units, organic peroxides, and organic solvents can be used. Here, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0163] Furthermore, a polysiloxane-resin integrated compound can be used, which is formed by a condensation reaction between a polysiloxane having silanols at its polymer ends or side chains and MQ resin. MQ resin contains a large amount of silanol, and adding it improves adhesion, but it does not crosslink and therefore does not molecularly bond with the polysiloxane. As described above, by integrating the polysiloxane and resin, adhesion can be increased.

[0164] Furthermore, modified siloxanes having groups selected from amino groups, oxirane groups, oxetane groups, polyether groups, hydroxyl groups, carboxyl groups, mercapto groups, methacrylic groups, acrylic groups, phenolic groups, silanol groups, carboxylic acid anhydride groups, aryl groups, aralkyl groups, amide groups, ester groups, and lactone rings can also be added to silicone-based resins. Adding modified siloxanes improves the dispersibility of component (A) in ionic polymer materials. Modified siloxanes may be those in which one end, both ends, or side chains of the siloxane are modified.

[0165] As the adhesive acrylic resin, for example, those described in Japanese Patent Publication No. 2016-011338, which have hydrophilic (meth)acrylic acid esters and long-chain hydrophobic (meth)acrylic acid esters as repeating units, can be used. In some cases, (meth)acrylic acid esters having functional groups or (meth)acrylic acid esters having siloxane bonds may be copolymerized.

[0166] As an adhesive urethane-based resin, for example, one having urethane bonds and polyether or polyester bonds, polycarbonate bonds, or siloxane bonds, as described in Japanese Patent Publication No. 2016-065238, can be used.

[0167] Furthermore, in order to prevent a decrease in conductivity due to the shedding of component (A) from the biocontact layer, it is preferable that the resin (B) in the bioelectrode composition of the present invention has high compatibility with the above-mentioned component (A). Also, in order to prevent the biocontact layer from peeling off from the conductive substrate, it is preferable that the resin (B) in the bioelectrode composition of the present invention has high adhesion to the conductive substrate. To make the resin highly compatible with the conductive substrate and salt, it is effective to use a resin with high polarity. Examples of such resins include resins having one or more selected from ether bonds, ester bonds, amide bonds, imide bonds, urethane bonds, thiourethane bonds, and thiol groups, or polyacrylic resins, polyamide resins, polyimide resins, polyurethane resins, and polythiourethane resins. On the other hand, since the biocontact layer is in contact with the body, it is susceptible to the effects of sweat from the body. Therefore, in the bioelectrode composition of the present invention, it is preferable that the resin (B) has high water repellency and is resistant to hydrolysis. To make the resin highly water repellent and resistant to hydrolysis, it is effective to use a resin containing silicon.

[0168] Polyacrylic resins containing silicon atoms include polymers with silicone as the main chain and polymers with silicon atoms as side chains, and both can be suitably used. As polymers with silicone as the main chain, siloxanes or silsesquioxanes having (meth)acrylpropyl groups can be used. In this case, the (meth)acrylic portion can be polymerized and cured by adding a photoradical generator.

[0169] As polyamide resins containing silicon atoms, for example, polyamide silicone resins described in Japanese Patent Publication No. 2011-079946 and U.S. Patent No. 5981680 can be suitably used. Such polyamide silicone resins can be synthesized, for example, by combining a silicone or non-silicone compound having amino groups at both ends with a non-silicone or silicone having carboxyl groups at both ends.

[0170] Alternatively, polyamic acid obtained by reacting a carboxylic acid anhydride with an amine, before cyclization, may be used. For crosslinking the carboxyl groups of the polyamic acid, epoxy or oxetane crosslinking agents may be used, or the carboxyl groups may be esterified with hydroxyethyl (meth)acrylate to perform photoradical crosslinking of the (meth)acrylate portion.

[0171] As a polyimide resin containing silicon atoms, for example, the polyimide silicone resin described in Japanese Patent Publication No. 2002-332305 can be suitably used. Although polyimide resins have very high viscosity, their viscosity can be reduced by incorporating (meth)acrylic monomers as a solvent and crosslinking agent.

[0172] Examples of the polyurethane resin containing a silicon atom include a polyurethane silicone resin. In such a polyurethane silicone resin, crosslinking by urethane bonds can be achieved by blending a compound having isocyanate groups at both ends and a compound having hydroxy groups at the ends and heating. In this case, it is necessary for either the compound having isocyanate groups at both ends or the compound having hydroxy groups at the ends or both to contain a silicon atom (siloxane bond). Alternatively, as described in JP-A-2005-320418, a urethane (meth)acrylate monomer can be blended with a polysiloxane and photocrosslinked. Further, a polymer having both a siloxane bond and a urethane bond and having a (meth)acrylate group at the end can also be photocrosslinked. In particular, materials described in JP-A-2018-123304 and JP-A-2019-070109, which have a silicone chain in the side chain and a polyurethane main chain, are preferable because they have high strength and high stretchability characteristics.

[0173] The polythiourethane resin containing a silicon atom can be obtained by the reaction of a compound having a thiol group and a compound having an isocyanate group, and either of these may contain a silicon atom. Further, if it has a (meth)acrylate group at the end, it can also be photocured.

[0174] In the silicone-based resin, in addition to the above-described diorganosiloxane having an alkenyl group, R3SiO 1 / 2 and the MQ resin having a unit of SiO 4 / 2 and the organohydrogenpolysiloxane having a plurality of SiH groups, the compatibility with the above-described salt is enhanced by adding a modified siloxane having a group selected from an amino group, an oxirane group, an oxetane group, a polyether group, a hydroxy group, a carboxyl group, a mercapto group, a methacryl group, an acrylic group, a phenol group, a silanol group, a carboxylic anhydride group, an aryl group, an aralkyl group, an amide group, an ester group, and a lactone ring.

[0175] Diorganosiloxanes having alkenyl groups and organohydrogenpolysiloxanes having multiple SiH groups can be crosslinked by a platinum-catalyzed addition reaction.

[0176] Examples of platinum catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, reaction products of chloroplatinic acid and vinyl group-containing siloxanes, platinum-olefin complexes, platinum-vinyl group-containing siloxane complexes, and other platinum-based catalysts, as well as platinum group metal catalysts such as rhodium complexes and ruthenium complexes. Alternatively, these catalysts may be dissolved or dispersed in alcohol-based, hydrocarbon-based, or siloxane-based solvents.

[0177] Furthermore, the amount of platinum catalyst added is preferably in the range of 5 to 2,000 ppm, and more preferably 10 to 500 ppm, per 100 parts by mass of the resin combined from component (A) and component (B).

[0178] In the bioelectrode composition of the present invention, the amount of component (B) is preferably 0 to 2000 parts by mass, and more preferably 10 to 1000 parts by mass, per 100 parts by mass of the ionic polymer material of component (A). Furthermore, component (A) and component (B) may be used individually or as a mixture of two or more.

[0179] Furthermore, when using an addition-curing type silicone resin, an addition reaction control agent may be added. This addition reaction control agent is added as a quencher to prevent the platinum catalyst from acting in the solution and in the low-temperature environment before heat curing after film formation. Specifically, examples include 3-methyl-1-butynate-3-ol, 3-methyl-1-pentin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butynate, 3-methyl-3-trimethylsiloxy-1-pentine, 3,5-dimethyl-3-trimethylsiloxy-1-hexyn, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butinoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0180] The amount of addition reaction control agent added is preferably in the range of 0 to 10 parts by mass, particularly 0.05 to 3 parts by mass, per 100 parts by mass of the resin of component (B).

[0181] If component (B) has a double bond that can be radical-crosslinked, the addition of a radical generator is effective. Radical generators include photoradical generators and thermal radical generators.

[0182] Examples of photoradical generators include acetophenone, 4,4'-dimethoxybenzyl, benzyl, benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether, 4-benzoylbenzoic acid, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzyl Examples include 2-(dimethylamino)-4'-morpholinobtyrophenone, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthioxantheno-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-isonitrosopropiophenone, and 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone.

[0183] The material can also be cured by adding a thermal radical generator. Examples of thermal radical generators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methylpropionamidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(cyclohexane-1-carbonitride), 1[(1-cyano-1-methylethyl)azo]formamide, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl] Examples include )propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), dimethyl-2,2'-azobis(isobutyrate), 4,4'-azobis(4-cyanopentanoic acid), dimethyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, di-n-butyl peroxide, dicumyl peroxide, etc.

[0184] Furthermore, the amount of radical generator added is preferably in the range of 0.1 to 50 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0185] As described later, the biocontact layer is a cured product of the bioelectrode composition. By curing it, the biocontact layer exhibits good adhesion to both the skin and the conductive substrate. The curing method is not particularly limited and general methods can be used, such as heat and / or light, or a crosslinking reaction catalyzed by an acid or base. For the crosslinking reaction, for example, the method described in Chapter 2, pp. 51-371 of the Crosslinking Reaction Handbook by Yasuharu Nakayama, Maruzen Publishing (2013) can be appropriately selected.

[0186] [Ionic polymer] In addition to component (A), an ionic polymer may be added to the bioelectrode composition of the present invention. The repeating units of the ionic polymer may be those described in the general formula (2) above. The amount of ionic polymer added is preferably in the range of 0.1 to 100 parts by mass per 100 parts by mass of the resin combined of components (A) and (B).

[0187] [(C) Carbon materials and / or metal powders] The bioelectrode composition of the present invention may further contain a carbon material and / or metal powder as component (C).

[0188] [Metal powder] The bioelectrode composition of the present invention may also contain metal powder to enhance its electronic conductivity. The metal powder may be one or more selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium. The amount of metal powder added is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0189] From the viewpoint of conductivity, gold, silver, and platinum are preferred as metal powders, while from the viewpoint of price, silver, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, and chromium are preferred. From the viewpoint of biocompatibility, precious metals are preferred, and overall, silver is the most preferred from all these viewpoints.

[0190] The metal powder can take the form of a sphere, disc, flake, or needle, but flake-shaped powder is preferred as it provides the highest conductivity. The metal powder size should be 100 μm or less, and the tap density should be 5 g / cm³. 3 Below, the specific surface area is 0.5 m². 2 Flakes with a relatively low density and large specific surface area, with a density of 1 / g or more, are preferred. The size of the metal powder was determined using a scanning microscope (SEM). The tap density was determined using the method described in JIS Z 2512:2012. The specific surface area was determined using the method described in JIS Z 8830:2013.

[0191] [Carbon materials] Carbon materials can be added as conductivity enhancers. Examples of carbon materials include carbon black, graphite, carbon nanotubes, carbon fibers, and graphene. Carbon nanotubes may be single-layered or multi-layered, and their surfaces may be modified with organic groups. It is preferable that the carbon material is carbon black, carbon nanotubes, or both. The amount of carbon material added is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0192] [Silicon powder] The bioelectrode composition of the present invention may contain silicon powder to enhance ion acceptance sensitivity. Examples of silicon powder include powders composed of silicon, silicon monoxide, and silicon carbide. The particle size of the powder is preferably smaller than 100 μm, and more preferably 1 μm or less. Finer particles have a larger surface area, allowing them to receive more ions and resulting in a highly sensitive bioelectrode. The amount of silicon powder added is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the resin combined from components (A) and (B). The particle size of the powder was determined using SEM.

[0193] [Lithium titanate powder] The bioelectrode composition of the present invention may be enriched with lithium titanate powder to enhance the sensitivity of ion receptors. Examples of lithium titanate powder include Li2TiO3, LiTiO2, and Li4Ti5O2 with a spinel structure. 12The molecular formula can be listed, and spinel structures are preferred. Alternatively, lithium titanate particles composited with carbon can be used. The particle size of the powder is preferably smaller than 100 μm, and more preferably 1 μm or less. Finer particles have a larger surface area, allowing them to receive more ions and thus become highly sensitive bioelectrodes. These may also be composite powders with carbon. The amount of lithium titanate powder added is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0194] [Crosslinking agent] An epoxy-based crosslinking agent may also be added to the bioelectrode composition of the present invention. In this case, the crosslinking agent is a compound having multiple epoxy groups or oxetane groups in a single molecule. The amount added is 1 to 30 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0195] [Crosslinking catalyst] The bioelectrode composition of the present invention may also be supplemented with a catalyst for crosslinking epoxy groups or oxetane groups. In this case, the catalyst can be the one described in paragraphs

[0027] to

[0029] of Japanese Patent Publication No. 2019-503406. The amount to be added is 0.01 to 10 parts by mass per 100 parts by mass of the resin combined of components (A) and (B).

[0196] [Ionic additives] The bioelectrode composition of the present invention may be to which ionic additives can be added to increase ionic conductivity. Considering biocompatibility, examples of such additives include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium saccharin salt, acesulfame potassium, sodium carboxylate, potassium carboxylate, calcium carboxylate, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, betaine, and salts of Japanese Patent Publication Nos. 2018-044147, 2018-059050, 2018-059052, and 2018-130534. The amount to be added is 0 to 10 parts by mass per 100 parts by mass of the resin combined of components (A) and (B).

[0197] [(D) Organic solvents] Furthermore, an organic solvent may be added as component (D) to the bioelectrode composition of the present invention. Specifically, the organic solvents include toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, butylbenzene, sec-butylbenzene, isobutylbenzene, cymene, diethylbenzene, 2-ethyl-p-xylene, 2-propyltoluene, 3-propyltoluene, 4-propyltoluene, 1,2,3,5-tetramethyltoluene, 1,2,4,5-tetramethyltoluene, and tetrahydro Ronaphthalene, 4-phenyl-1-butene, tert-amylbenzene, amylbenzene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-di Aromatic hydrocarbon solvents such as isopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, 1,3,5-triethylbenzene, n-heptane, isoheptane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexine, norbornane, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, 1-heptin, 2-heptin, cycloheptane, cyclohex Butene, 1,3-dimethylcyclopentane, ethylcyclopentane, methylcyclohexane, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, methylenecyclohexane, 4-methyl-1-cyclohexene, 2-methyl-1-hexene, 2-methyl-2-hexene, 1-heptene, 2-heptene, 3-heptene, n-octane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclooctane, cyclooctene, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, vinylcyclohexane, isopropylcyclopentane, 2,2-dimethyl-3-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1- Hexene, 2,5-dimethyl-2-hexene, 3,3-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 2-ethyl-1-hexene, 2-methyl-1-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1,7-octadiene, 1-octin, 2-octin, 3-octin, 4-octin, n-nonane, 2,3-dimethylheptane, 2,4-dimethylheptane, 2,5-dimethylheptane, 3,3-dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4-E Tylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,2,4,4-tetramethylpentane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane, 2,2-dimethyl-3-heptene, 2,3-dimethyl-3-heptene, 2,4-dimethyl-1-heptene, 2,6-dimethyl-1-heptene, 2,6-dimethyl-3-heptene, 3,5-dimethyl-3-heptene, 2,4,4-trimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, 1-ethyl-2-methylcyclohexane, 1-ethyl-3 -Methylcyclohexane, 1-ethyl-4-methylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,1,3-trimethylcyclohexane, 1,1,4-trimethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, allylcyclohexane, hydrindan, 1,8-nonadien, 1-nonine, 2-nonine, 3-nonine, 4-nonine, 1-nonene, 2-nonene, 3-nonene, 4-nonene, n-decane, 3,3-dimethyloctane, 3,5-dimethyloctane, 4,4-dimethyloctane, 3-ethyl-3-methylheptane, 2-methylnonane, 3-methylnonane, 4-methylnonane, tert-butylcyclohexane, butylcyclohexane, isobutylcyclohexane, 4-isopropyl-1-methylcyclohexane, pentylcyclopentane, 1,1,3,5-tetramethylcyclohexane, cyclododecane, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, 1,9-decadien, decahydronaphthalene, 1-decine, 2-decine, 3-decine, 4-decine, 5-decine, 1, 5,9-Decatriene, 2,6-Dimethyl-2,4,6-Octatriene, Limonene, Myrcene, 1,2,3,4,5-Pentamethylcyclopentadiene, α-Phellandrene, Pinene, Terpinene, Tetrahydrodicyclopentadiene, 5,6-Dihydrodicyclopentadiene, 1,4-Decadiin, 1,5-Decadiin, 1,9-Decadiin, 2,8-Decadiin, 4,6-Decadiin, n-Undecane, Amylcyclohexane, 1-Undecene, 1,10-Undecadien, 1-Undecine, 3-Undecine, 5-Undecine, Tricyclo[6.2.1.0, 2,7Undeca-4-ene, n-dodecane, n-tridecane, n-pentadecane, n-hexadecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 2,2,4,6,6-pentamethylheptane, 1,3-dimethyladamantane, 1-ethyladamantane, 1,5,9-cyclododecatriene, 1,2,Aliphatic hydrocarbon solvents such as 4-trivinylcyclohexane and isoparaffins; ketone solvents such as cyclohexanone, cyclopentanone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, and methyl n-pentyl ketone; alcohol solvents such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, and diethylene glycol Examples of ether-based solvents include monoheptyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, di-sec-pentyl ether, di-tert-amyl ether, di-n-hexyl ether, anisole, ester-based solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, and lactone-based solvents such as γ-butyrolactone.

[0198] Furthermore, the amount of organic solvent added is preferably in the range of 10 to 50,000 parts by mass per 100 parts by mass of the resin combined from component (A) and component (B).

[0199] Furthermore, water can be added to the bioelectrode composition of the present invention. Preferably, the amount of water added is in the range of 10 to 50,000 parts by mass per 100 parts by mass of the resin combined of components (A) and (B).

[0200] [Other additives] The bioelectrode composition of the present invention may also contain a mixture of silica particles, polyether silicone, and polyglycerin silicone. Silica particles have a hydrophilic surface and readily blend with hydrophilic ionic polymers, polyether silicones, and polyglycerin silicones, improving the dispersibility of ionic polymers, polyether silicones, and polyglycerin silicones in hydrophobic silicone adhesives. Silica particles can be used in both dry and wet applications.

[0201] [Silicone compounds having a polyglycerin structure] In the bioelectrode composition of the present invention, a silicone compound having a polyglycerin structure may be added to improve the moisturizing properties of the membrane and enhance the sensitivity and ionic conductivity of ions released from the skin. The amount of the silicone compound having a polyglycerin structure is preferably 0.01 to 100 parts by mass, and more preferably 0.5 to 60 parts by mass, per 100 parts by mass of the total of components (A) and (B). Furthermore, one type of silicone compound having a polyglycerin structure may be used alone, or two or more types may be used in mixture.

[0202] The silicone compound having a polyglycerin structure is preferably represented by the following general formulas (4)' and (5)'. [ka] (In the formula, R 1Each of the elements is independent and may be the same or different from one another, and is a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, or a phenyl group, which may contain an ether group, and may also be a silicone chain represented by general formula (6)', R 2 ' is a group having a polyglycerin group structure represented by general formula (4)'-1 or general formula (4)'-2, R 3 ' are independent of each other and may be the same or different from each other, the R 1 'Base or the R 2 'It is a base, R 4 ' are independent of each other and may be the same or different from each other, the R 1 'Base, the R 2 It is a group or an oxygen atom. 4 If ' is an oxygen atom, then the two R 4 The groups may combine to form a single ether group, which may form a ring with the silicon atom. a' may be the same or different and range from 0 to 100, b' may be from 0 to 100, and a'+b' may be from 0 to 200. However, when b' is 0, R 3 ' at least one of the R 2 It is the basis. 5 ' is an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms, R 6 ', R 7 ', R 8 ' is an alkylene group having 2 to 6 carbon atoms, R 7 ' may be an ether group, c' is 0-20, and d' is 1-20.

[0203] Examples of silicone compounds having such a polyglycerin structure include the following:

[0204] [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] [ka] (In the formula, a', b', c', and d' are as described above.)

[0214] A silicone compound having such a polyglycerin structure can be used to create a bioelectrode composition that exhibits superior moisturizing properties and, as a result, forms a biocontact layer that exhibits superior sensitivity to ions released from the skin.

[0215] As described above, the bioelectrode composition of the present invention has high adhesiveness, maintains sufficient adhesiveness even after being peeled off the skin and reattached, can efficiently transmit electrical signals from the skin to the device (i.e., has excellent conductivity), does not cause allergies even when worn on the skin for a long period of time (i.e., has excellent biocompatibility), is lightweight, can be manufactured at low cost, and can form a biocontact layer for bioelectrodes that does not experience a significant decrease in conductivity whether wet or dry. Furthermore, conductivity can be further improved by adding carbon material, and by combining it with a resin that has adhesiveness and elasticity, a bioelectrode with particularly high adhesiveness and high elasticity can be manufactured. In addition, elasticity and adhesiveness to the skin can be improved by adding additives, and elasticity and adhesiveness can be adjusted by appropriately adjusting the composition of the resin and the thickness of the biocontact layer.

[0216] <Bioelectrodes> Furthermore, the present invention provides a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is a cured product of the bioelectrode composition of the present invention described above.

[0217] The bioelectrodes of the present invention will be described in detail below with reference to the drawings, but the present invention is not limited to these.

[0218] Figure 1 is a schematic cross-sectional view showing an example of a bioelectrode of the present invention. The bioelectrode 1 in Figure 1 has a conductive substrate 2 and a biocontact layer 3 formed on the conductive substrate 2. The biocontact layer 3 is made of a cured product of the bioelectrode composition of the present invention. The biocontact layer 3 is, for example, a composite material of an ionic polymer material 5 and silicone having T units and Q units. The biocontact layer 3 may further include a resin 6 other than the ionic polymer material 5 and the silicone composite material having T units and Q units, and a conductive powder 4. The following description will refer to Figures 1 and 2 and will explain the case in which the biocontact layer 3 is a layer in which the ionic polymer material 5, the silicone composite material having T units and Q units, and the conductive powder 4 are dispersed in the resin 6, but the bioelectrode of the present invention is not limited to this embodiment.

[0219] When using the bioelectrode 1 shown in Figure 1, as shown in Figure 2, the biocontact layer 3 (i.e., a layer in which an ionic polymer material 5, a silicone composite material having T units and Q units, and conductive powder 4 dispersed in resin 6) is brought into contact with the living body 7. The ionic polymer material 5, the silicone composite material having T units and Q units, and the conductive powder 4 extract an electrical signal from the living body 7, which is then transmitted to a sensor device (not shown) via a conductive substrate 2. Thus, with the bioelectrode of the present invention, both conductivity and biocompatibility can be achieved by the aforementioned ionic polymer material and silicone composite material having T units and Q units, and because it also has adhesive properties, the contact area with the skin is constant, and electrical signals from the skin can be obtained stably and with high sensitivity.

[0220] The constituent materials of the bioelectrode of the present invention will be described in more detail below.

[0221] [Conductive base material] The bioelectrode of the present invention has a conductive substrate. This conductive substrate is usually electrically connected to a sensor device or the like, and conducts electrical signals extracted from the body via a biocontact layer to the sensor device or the like.

[0222] The conductive substrate is not particularly limited as long as it is conductive, but it is preferable that it contains one or more selected from, for example, gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0223] Furthermore, the conductive substrate is not particularly limited and may be a rigid conductive substrate, a flexible conductive film, a fabric coated with a conductive paste, or a fabric kneaded with a conductive polymer. The conductive substrate may be flat, uneven, or a mesh made of woven metal wires, and can be appropriately selected depending on the application of the bioelectrode.

[0224] [Bio-contact layer] The bioelectrode of the present invention has a biocontact layer formed on a conductive substrate. This biocontact layer is the part that actually comes into contact with the living body when the bioelectrode is used, and is conductive and adhesive. The biocontact layer is a cured product of the bioelectrode composition of the present invention described above, that is, an adhesive resin layer consisting of a cured product of a composition containing component (A) described above, and optionally components (B), (C), (D), and other components.

[0225] Furthermore, the adhesive strength of the bio-contact layer is preferably in the range of 0.01 N / 25 mm to 20 N / 25 mm. The method for measuring adhesive strength is generally as shown in JIS Z 0237, and while metal substrates such as SUS (stainless steel) or PET (polyethylene terephthalate) substrates can be used as base materials, it is also possible to measure using human skin. The surface energy of human skin is lower than that of metals and various plastics, and is close to that of Teflon (registered trademark), making it difficult to adhere.

[0226] The thickness of the biocontact layer of the bioelectrode is preferably 1 μm to 5 mm, and more preferably 2 μm to 3 mm. As the biocontact layer becomes thinner, the adhesive strength decreases, but flexibility improves, and it becomes lighter and more comfortable against the skin. The thickness of the biocontact layer can be selected by balancing adhesiveness and feel against the skin.

[0227] Furthermore, in the bioelectrode of the present invention, similar to conventional bioelectrodes (for example, the bioelectrode described in Japanese Patent Publication No. 2004-033468), an adhesive film may be provided separately on the biocontact layer to prevent the bioelectrode from peeling off the body during use. If an adhesive film is provided separately, it can be formed using an adhesive film material such as acrylic, urethane, or silicone. Silicone is particularly suitable because it has high oxygen permeability, allowing skin respiration while attached, and also has high water repellency, resulting in less reduction of adhesiveness due to sweat, and furthermore, it is less irritating to the skin. However, in the bioelectrode of the present invention, as described above, peeling off from the body can be prevented by adding an adhesive-adding agent to the bioelectrode composition or by using a resin with good adhesion to the body, so it is not necessarily required to provide the above-mentioned separately provided adhesive film.

[0228] When using the bioelectrode of the present invention as a wearable device, the wiring between the bioelectrode and the sensor device, as well as other components, are not particularly limited, and for example, those described in Japanese Patent Application Publication No. 2004-033468 can be applied.

[0229] As described above, with the bioelectrode of the present invention, since the biocontact layer is formed by the cured product of the bioelectrode composition of the present invention, electrical signals from the skin can be efficiently transmitted to the device (i.e., it has excellent conductivity), there is no risk of allergies even when worn on the skin for a long period of time (i.e., it has excellent biocompatibility), it is lightweight, can be manufactured at low cost, and the conductivity does not decrease significantly whether it is wet or dry. Furthermore, conductivity can be further improved by adding conductive powder, and by combining it with a resin that has adhesive and elastic properties, a bioelectrode with particularly high adhesive strength and high elasticity can be manufactured. In addition, elasticity and adhesiveness to the skin can be improved by additives, and elasticity and adhesiveness can be adjusted by appropriately adjusting the composition of the resin and the thickness of the biocontact layer.Therefore, such a bioelectrode of the present invention is particularly suitable as a bioelectrode used in medical wearable devices.

[0230] <Method for manufacturing bioelectrodes> Furthermore, the present invention provides a method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is formed by applying the bioelectrode composition of the present invention described above onto the conductive substrate and curing it.

[0231] The conductive substrate and the like used in the method for manufacturing the bioelectrode of the present invention may be the same as those described above.

[0232] The method for applying the bioelectrode composition onto a conductive substrate is not particularly limited, but preferred methods include dip coating, spray coating, spin coating, roll coating, flow coating, doctor coating, screen printing, flexographic printing, gravure printing, and inkjet printing.

[0233] The method for curing the resin is not particularly limited and can be appropriately selected depending on the components (A) and (B) used in the bioelectrode composition. However, it is preferable to cure it using either heat and / or light, or both. Alternatively, a catalyst that generates an acid or base can be added to the bioelectrode composition to induce a crosslinking reaction and cure it.

[0234] The heating temperature is not particularly limited and can be appropriately selected depending on the components (A) and (B) used in the bioelectrode composition, but for example, around 50 to 250°C is preferred.

[0235] Furthermore, when combining heating and light irradiation, heating and light irradiation may be performed simultaneously, heating may be performed after light irradiation, or light irradiation may be performed after heating. In addition, air drying may be performed before heating after coating in order to evaporate the solvent.

[0236] Applying water droplets to the surface of the hardened film, or spraying it with water vapor or mist, improves its affinity with the skin and allows for quicker acquisition of biosignals. Water mixed with alcohol can also be used to create finer water droplets for the water vapor or mist. The film surface can also be moistened by contacting it with water-soaked cotton wool or cloth.

[0237] The water used to wet the surface of the cured film may contain salt. The water-soluble salt to be mixed with the water can be selected from sodium salts, potassium salts, calcium salts, magnesium salts, and betaine.

[0238] Specifically, the water-soluble salt can be a salt selected from sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium saccharin salt, acesulfame potassium, sodium carboxylate, potassium carboxylate, calcium carboxylate, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, and betaine. Note that component (A) mentioned above is not included in the water-soluble salt.

[0239] More specifically, in addition to the above, sodium acetate, sodium propionate, sodium pivalate, sodium glycolate, sodium butyrate, sodium valerate, sodium caproate, sodium enanthate, sodium caprylate, sodium pelargonate, sodium caprate, sodium undecylate, sodium laurate, sodium tridecylate, sodium myristate, sodium pentadecylate, sodium palmitate, sodium margarate, sodium stearate, sodium benzoate, disodium adipate, disodium maleate, disodium phthalate, sodium 2-hydroxybutyrate, sodium 3-hydroxybutyrate, sodium 2-oxobutyrate, sodium gluconate, methane Examples include sodium sulfonate, sodium 1-nonanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-undecanesulfonate, sodium cocoyl cethionate, sodium lauroyl methylalanine, sodium cocoyl methyltaurate, sodium cocoyl glutamate, sodium cocoyl sarcosinate, sodium lauroyl methyltaurate, laumidopropyl betaine, potassium isobutyrate, potassium propionate, potassium pivalate, potassium glycolate, potassium gluconate, potassium methanesulfonate, calcium stearate, calcium glycolate, calcium gluconate, calcium 3-methyl-2-oxobutyrate, and calcium methanesulfonate. Betaine is a general term for intramolecular salts, specifically compounds in which three methyl groups are added to the amino group of an amino acid, but more specifically, trimethylglycine, carnitine, and proline betaine can be cited.

[0240] The water-soluble salt may further contain a monohydric alcohol or polyhydric alcohol having 1 to 4 carbon atoms, and it is preferable that the alcohol is selected from ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, polyethylene glycol, polypropylene glycol, polyglycerin, diglycerin, and silicone compounds having a polyglycerin structure, and it is more preferable that the silicone compound having a polyglycerin structure is represented by the above general formulas (4)' to (5)'.

[0241] The pretreatment method using a water-soluble salt-containing aqueous solution allows the bioelectrode membrane to be wetted after curing by methods such as spraying or droplet dispensing. It can also be wetted in a high-temperature, high-humidity environment like a sauna. After wetting, to prevent drying, a protective film can be laminated on top of the permeable layer. Since the protective film needs to be peeled off immediately before application to the skin, it can be coated with a release agent or made of a releaseable fluororesin film. For long-term storage, dry electrodes covered with a release film are preferably sealed in a bag covered with aluminum or similar material. To prevent drying inside the aluminum-covered bag, it is preferable to seal moisture inside.

[0242] Before attaching the bioelectrode of the present invention to the skin, the skin side may be moistened with water or alcohol, or the skin may be wiped with a cloth or cotton ball containing water or alcohol. The aforementioned salt may also be included in the water or alcohol.

[0243] As described above, the method for manufacturing bioelectrodes of the present invention allows for the easy and low-cost production of bioelectrodes that are highly conductive and biocompatible, lightweight, and whose conductivity does not significantly decrease whether wet or dry. [Examples]

[0244] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these.

[0245] Ionic polymers 1-22, which were incorporated into the bioelectrode solution as ionic materials (conductive materials), were synthesized as follows. A 30% by mass cyclopentanone solution of each monomer was placed in a reaction vessel and mixed. The reaction vessel was cooled to -70°C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 0.02 moles of azobisisobutyronitrile (AIBN) were added as a polymerization initiator per mole of total monomer, and the temperature was raised to 60°C and the reaction was carried out for 15 hours. The composition of the obtained polymer after drying the solvent was as follows: 1 The results were confirmed by 1H-NMR. Furthermore, the molecular weight (Mw) and dispersion (Mw / Mn) of the obtained polymers were confirmed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent. The ionic polymers 1-22 containing nitro groups synthesized in this manner are shown below.

[0246] Ionic polymer 1 Mw = 16,200 Mw / Mn = 1.66 [ka]

[0247] Ionic polymer 2 Mw = 26,700 Mw / Mn = 1.79 [ka]

[0248] Ionic polymer 3 Mw = 32,300 Mw / Mn = 1.94 [ka]

[0249] Ionic polymer 4 Mw = 36,400 Mw / Mn = 2.01 [ka] (The number of repetitions in the formula represents the average value.)

[0250] Ionic polymer 5 Mw = 28,500 Mw / Mn = 2.11 [ka]

[0251] Ionic polymer 6 Mw = 30,300 Mw / Mn = 1.95 [ka]

[0252] Ionic polymer 7 Mw = 22,800 Mw / Mn = 1.84 [ka]

[0253] Ionic polymer 8 Mw = 25,400 Mw / Mn = 1.85 [ka] (The number of repetitions in the formula represents the average value.)

[0254] Ionic polymer 9 Mw = 22,500 Mw / Mn = 1.76 [ka] (The number of repetitions in the formula represents the average value.)

[0255] Ionic polymer 10 Mw = 26,900 Mw / Mn = 1.92 [ka]

[0256] Ionic polymer 11 Mw = 25,800 Mw / Mn = 1.68 [ka]

[0257] Ionic polymer 12 Mw = 25,500 Mw / Mn = 1.89 [ka]

[0258] Ionic polymer 13 Mw = 29,300 Mw / Mn = 1.93 [ka] (The number of repetitions in the formula represents the average value.)

[0259] Ionic polymer 14 Mw = 27,700 Mw / Mn = 1.98 [ka]

[0260] Ionic polymer 15 Mw = 23,200 Mw / Mn = 1.79 [ka] (The number of repetitions in the formula represents the average value.)

[0261] Ionic polymer 16 Mw = 21,800 Mw / Mn = 1.73 [ka] (The number of repetitions in the formula represents the average value.)

[0262] Ionic polymer 17 Mw = 24,400 Mw / Mn = 1.94 [ka] (The number of repetitions in the formula represents the average value.)

[0263] Ionic polymer 18 Mw = 26,600 Mw / Mn = 1.96 [ka] (The number of repetitions in the formula represents the average value.)

[0264] Ionic polymer 19 Mw = 23,700 Mw / Mn = 1.99 [ka] (The number of repetitions in the formula represents the average value.)

[0265] Ionic polymer 20 Mw = 34,500 Mw / Mn = 2.09 [ka] (The number of repetitions in the formula represents the average value.)

[0266] Ionic polymer 21 Mw = 38,100 Mw / Mn = 2.04 [ka] (The number of repetitions in the formula represents the average value.)

[0267] Ionic polymer 22 Mw = 36,000 Mw / Mn = 2.01 [ka] (The number of repetitions in the formula represents the average value.)

[0268] Blended ionic polymer 1, and comparative ionic polymers 1 and 2 for comparative examples are shown below.

[0269] Blended ionic polymer 1 Mw = 39,100 Mw / Mn = 1.91 [ka] (The number of repetitions in the formula represents the average value.)

[0270] Comparative ionic polymer 1 Mw = 26,900 Mw / Mn = 1.99 [ka]

[0271] Comparative ionic polymer 2 Mw = 26,500 Mw / Mn = 1.85 [ka]

[0272] Siloxane compounds 1 to 4, which were incorporated into the bioelectrode solution as silicone-based resins, are shown below. (Siloxane compound 1) Siloxane compound 1 was defined as a vinyl group-containing polydimethylsiloxane with a viscosity of 27,000 mPa·s in a 30% toluene solution, an alkenyl group content of 0.007 mol / 100g, and molecular chain ends sealed with SiMe2Vi groups. (Siloxane compound 2) Me3SiO 1 / 2 Units and SiO 4 / 2 Polysiloxane (Me3SiO) of MQ resins consisting of units 1 / 2 Unit: SiO 4 / 2 A 60% toluene solution (unit = 0.8) was designated as siloxane compound 2. (Siloxane compound 3) The viscosity in a 30% toluene solution is 42,000 mPa·s, the alkenyl group content is 0.007 mol / 100g, and the molecular chain ends are sealed with OH groups containing vinyl groups: 40 parts by mass of polydimethylsiloxane, Me3SiO 1 / 2 Units and SiO 4 / 2 Polysiloxane (Me3SiO) of MQ resins consisting of units 1 / 2 Unit: SiO 4 / 2 A solution consisting of 100 parts by mass of a 60% toluene solution (unit = 0.8) and 26.7 parts by mass of toluene was heated for 4 hours while being dried, and then cooled to bond polydimethylsiloxane to MQ resin, resulting in siloxane compound 3. (Siloxane compound 4) KF-99, manufactured by Shin-Etsu Chemical Co., Ltd., was used as the methyl hydrogen silicone oil.

[0273] The silicone pendant urethane (meth)acrylate 1 blended into the bioelectrode solution is shown below. [ka] (The number of repetitions in the formula represents the average value.)

[0274] The following shows acrylic polymer 1, which was blended as an acrylic resin into the bioelectrode solution.

[0275] Acrylic polymer 1 Mw = 129,000 Mw / Mn = 2.45 [ka] (The number of repetitions in the formula represents the average value.)

[0276] Polyglycerin silicone compound 1 is shown below.

[0277] [ka]

[0278] The organic solvents used in the bioelectrode solution are listed below. EDE: Diethylene glycol diethyl ether Isopar G: Isoparaffin-based solvent, manufactured by Standard Petroleum Co., Ltd. Isopar M: Isoparaffin-based solvent, manufactured by Standard Petroleum Co., Ltd.

[0279] The following are the additives used in the bioelectrode solution: lithium titanate powder, silver flakes, radical generator, platinum catalyst, and conductivity enhancers (carbon black, multi-walled carbon nanotubes, graphite). Lithium titanate powder, spinel: Sigma-Aldrich, size less than 200nm. Silver flakes: Sigma-Aldrich, average size 10 μm Radical generator: BASF Irgacure TPO Platinum catalyst: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd. Carbon Black: Denka Black Li-400 (manufactured by Denka Co., Ltd.) Multiwalled carbon nanotubes: Manufactured by Sigma-Aldrich, with a diameter of 110-170 nm and a length of 5-9 μm. Graphite: Sigma-Aldrich, diameter 20 μm or less.

[0280] [Examples 1-22, Comparative Examples 1 and 2] Bioelectrode solutions (bioelectrode solutions 1-22, comparative bioelectrode solutions 1 and 2) were prepared by blending ionic polymers, resins, organic solvents, and additives (radical generators, platinum catalysts, and conductivity enhancers) according to the compositions shown in Tables 1, 2, and 3.

[0281] [Table 1]

[0282] [Table 2]

[0283] [Table 3]

[0284] (Evaluation of adhesion) Bioelectrode solutions other than bioelectrode solution 7, as well as comparative bioelectrode solutions 1 and 2, were applied to a 100 μm thick PEN (polyethylene naphthalate) substrate using an applicator. After air-drying at room temperature for 30 minutes, the solutions were baked in an oven under a nitrogen atmosphere at 120°C for 10 minutes to produce adhesive films. After application, air-drying, and baking, bioelectrode solution 7 was subjected to a 500 mJ / cm³ treatment using a 1,000 W xenon lamp under a nitrogen atmosphere. 2 The composition coating film was cured by irradiating it with light.

[0285] A 25mm wide tape was cut from this adhesive film and pressed onto a stainless steel plate (SUS304). After being left at room temperature for 20 hours, the force (N / 25mm) required to peel the tape with the bioelectrode attached from the stainless steel plate was measured using a tensile testing machine at an angle of 180 degrees and a speed of 300mm / min. The results are shown in Table 4.

[0286] (Measurement of the thickness of the biological contact layer) In the bioelectrodes fabricated using the adhesion evaluation test described above, the thickness of the biocontact layer was measured using a micrometer. The results are shown in Table 4.

[0287] (Evaluation of biosignals) As shown in Figure 3, a conductive paste, Dotite FA-333, manufactured by Fujikura Chemical Co., Ltd., was screen printed onto Bemis's ST-604 thermoplastic polyurethane (TPU) film 20, and baked in an oven at 120°C for 10 minutes to print a keyhole-shaped conductive pattern with a diameter of 2 cm. The bioelectrode solutions described in Tables 1, 2, and 3 were then screen printed onto the circular portion on top of the bioelectrode, air-dried at room temperature for 10 minutes, and then baked in an oven at 125°C for 10 minutes to evaporate the solvent and cure, thereby fabricating a bioelectrode 1. Each bioelectrode 1 contained a conductive substrate 2 and a biocontact layer 3 formed on top of the circular portion of the conductive substrate 2. Three bioelectrode samples 10 were prepared for each bioelectrode solution by cutting out the thermoplastic polyurethane film 20 with the printed bioelectrode and attaching double-sided tape 21 (Figure 4).

[0288] (Measurement of biological signals) A conductive wiring pattern made of conductive paste on a bioelectrode was connected to an Omron Healthcare HCG-901 portable electrocardiograph with a conductive wire. The positive electrode of the electrocardiograph was attached to the LA location on the human body in Figure 5, the negative electrode to the LL location, and the ground to the RA location. Immediately after attachment, electrocardiogram measurement was started, and the time until the electrocardiogram waveform consisting of P, Q, R, S, and T waves shown in Figure 6 appeared was measured. The results are shown in Table 4.

[0289] [Table 4]

[0290] As shown in Table 4, in Examples 1 to 22, where a bioelectrode composition of the present invention containing an ionic polymer copolymerized with units containing nitro groups was used to form a biocontact layer, excellent adhesion was observed, and a biosignal could be obtained in a short time after application to the body. On the other hand, in Comparative Example 2, which did not contain an ionic component of a specific structure, a biosignal could not be obtained, and in Comparative Example 1, which did not contain a nitro group, the time from application to the skin until a biosignal appeared was long.

[0291] This specification includes the following embodiments. [1]: A bioelectrode composition containing an ionic polymer material as component (A), A bioelectrode composition characterized in that component (A) contains a polymer having a repeating unit a having a structure selected from ammonium salts, sodium salts, potassium salts, and silver salts of fluorosulfonic acid, fluorosulfonimide, and N-carbonylfluorosulfonamide, and a repeating unit b having a nitro group. [2]: The bioelectrode composition according to [1], characterized in that the repeating unit a has a structure represented by the following general formulas (1)-1 to (1)-4. [ka] (In general formula (1)-1, Rf1 and Rf2 are a hydrogen atom, a fluorine atom, an oxygen atom, a methyl group, or a trifluoromethyl group. When Rf1 and Rf2 are oxygen atoms, Rf1 and Rf2 are one oxygen atom bonded to one carbon atom to form a carbonyl group. Rf3 and Rf4 are a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and one or more of Rf1 to Rf4 are fluorine atoms or trifluoromethyl groups. In general formulas (1)-2, (1)-3, and (1)-4, Rf5, Rf6, and Rf7 are each a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and each has at least one fluorine atom. In general formulas (1)-1 to (1)-4, M + m is an ion selected from ammonium ions, sodium ions, potassium ions, and silver ions. In general formula (1)-2, m is an integer between 1 and 4. [3]: The bioelectrode composition according to [1] or [2] above, characterized in that the repeating unit a has one or more repeating units a1 to a7 described in the following general formula (2). [ka] (In general formula (2), R 1 , R3 , R 5 , R 8 , R 10 , R 11 , and R 13 Each is independently either a hydrogen atom or a methyl group, and R 2 , R 4 , R 6 , R 9 , R 12 , and R 14 Each of these is independently a single bond or a linear, branched, or cyclic hydrocarbon group having 1 to 13 carbon atoms. The hydrocarbon group may have an ester group, an ether group, or both. 7 R is a linear or branched alkylene group having 1 to 4 carbon atoms. 7 One or two of the hydrogen atoms in the molecule may be substituted with fluorine atoms. X1, X2, X3, X4, X6, and X7 are each independently one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, and X5 is one of a single bond, an ether group, and an ester group. Y is an oxygen atom or -NR 19 - is a base, R 19 R is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. 4 They may form a ring together. Rf1' and Rf5' are a fluorine atom, a trifluoromethyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms, and have at least one fluorine atom. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are such that 0≦a1<1.0, 0≦a2<1.0, 0≦a3<1.0, 0≦a4<1.0, 0≦a5<1.0, 0≦a6<1.0, 0≦a7<1.0, and 0 <a1+a2+a3+a4+a5+a6+a7<1.0である。M + (This is an ion selected from ammonium ions, sodium ions, potassium ions, and silver ions.) [4]: The bioelectrode composition according to [3], characterized in that it contains a polymer copolymerized with one or more repeating units a1 to a7 described in general formula (2), in addition to a repeating unit b1 having a nitro group as described in general formula (4) below. [ka] (In general formula (4), R 20 is a hydrogen atom or a methyl group, X8 is one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, R 21 n is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or a phenylene group, and the alkylene group may have a hydroxyl group, carboxyl group, ether group, ester group, urethane group, thiourethane group, carbonate group, amide group, or urea bond, and the phenylene group may be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, or a cyano group. n is 1 or 2, 0 <b1<1.0である。) [5]: Any one of the bioelectrode compositions described in [1] to [4] above, characterized in that the component (A) contains an ammonium ion represented by the following general formula (3) as the ammonium ion constituting the ammonium salt. [ka] (In general formula (3), R 101d , R 101e , R 101f , and R 101g Each of these is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have one or more selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d and R 101e , or R 101d , R 101e and R 101f These may form a ring with the nitrogen atom to which they are bonded, and if a ring is formed, R 101d and R 101e , or R 101d , R 101e and R101f (This is either an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring containing the nitrogen atom in general formula (3) within the ring.) [6]: A bioelectrode composition according to any one of the above [1] to [5], further characterized in that it contains a resin as component (B). [7]: The bioelectrode composition according to [6], characterized in that the component (B) is one or more selected from silicone resin, (meth)acrylate resin, and urethane resin. [8]: The bioelectrode composition according to [6] or [7], characterized in that the component (B) is adhesive. [9]: The above (B) component is R x SiO (4-x) / 2 The units (R is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, x is in the range of 2.5 to 3.5) and SiO 4 / 2 A bioelectrode composition according to any one of the above [6] to [8], characterized in that it contains a silicone resin having units.

[10] : A bioelectrode composition according to any one of the above [1] to [9], further characterized in that it contains a carbon material and / or metal powder as component (C).

[11] : The bioelectrode composition according to

[10] , characterized in that the carbon material is carbon black, carbon nanotubes, or both.

[12] : The bioelectrode composition according to

[10] or

[11] , characterized in that the metal powder is one or more metal powders selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

[13] : The bioelectrode composition according to

[12] , characterized in that the metal powder is silver powder.

[14] : A bioelectrode composition of any one of the above [1] to

[13] , further characterized by containing an organic solvent as component (D).

[15] : A bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is a cured product of any one of the bioelectrode compositions described in [1] to

[14] above.

[16] : The bioelectrode according to

[15] , characterized in that the conductive substrate contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[17] : A method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, characterized in that the biocontact layer is formed by applying any one of the bioelectrode compositions from [1] to

[14] above onto the conductive substrate and curing it.

[18] : A method for producing the bioelectrode according to

[17] , characterized in that the conductive substrate contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0292] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of Symbols]

[0293] 1... Bioelectrode, 2... Conductive substrate, 3... Biocontact layer 4...Conductive powder, 5...Ionic polymer material, 6...Resin 7...Biological tissue, 10...Biometric electrode sample, 20...Thermoplastic polyurethane film, 21…Double-sided tape.

Claims

1. (A) A bioelectrode composition containing an ionic polymer material as component, A bioelectrode composition characterized in that component (A) contains a polymer having a repeating unit a having a structure selected from ammonium salts, sodium salts, potassium salts, and silver salts of fluorosulfonic acid, fluorosulfonimide, and N-carbonylfluorosulfonamide, and a repeating unit b having a nitro group.

2. The bioelectrode composition according to claim 1, characterized in that the repeating unit a has a structure represented by the following general formulas (1)-1 to (1)-4. 【Chemistry 1】 (In general formula (1)-1, Rf １ and Rf ２ are a hydrogen atom, a fluorine atom, an oxygen atom, a methyl group, or a trifluoromethyl group, and when Rf １ and Rf ２ are oxygen atoms, Rf １ and Rf ２ are one oxygen atom bonded to one carbon atom to form a carbonyl group, and Rf ３ and Rf ４ are a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and one or more of Rf １ to Rf ４ are a fluorine atom or a trifluoromethyl group. In general formulas (1)-2, (1)-3, and (1)-4, Rf ５ , Rf ６ and Rf[[ID=??]] ７ are each a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms and having at least one fluorine atom. In general formulas (1)-1 to (1)-4, M ＋ is an ion selected from an ammonium ion, a sodium ion, a potassium ion, and a silver ion. In general formula (1)-2, m is an integer of 1 to 4.) It seems there is a typo in the original text where "Rf ７ " is repeated as "Rf ６ " and then again as "Rf ７ ". I've translated it as best as possible with the given text. If you can correct the original, it would be beneficial for a more accurate translation.

3. The bioelectrode composition according to claim 1, characterized in that the repeating unit a has one or more repeating units a1 to a7 described in the following general formula (2). 【Chemistry 2】 (In general formula (2), R １ , R ３ , R ５ , R ８ , R １０ , R １１ , and R １３ Each is independently either a hydrogen atom or a methyl group, and R ２ , R ４ , R ６ , R ９ , R １２ , and R １４ Each of these is independently a single bond or a linear, branched, or cyclic hydrocarbon group having 1 to 13 carbon atoms. The hydrocarbon group may have an ester group, an ether group, or both. ７ R is a linear or branched alkylene group having 1 to 4 carbon atoms. ７ One or two of the hydrogen atoms inside may be replaced by fluorine atoms. １ , X ２ , X ３ , X ４ , X ６ , and X ７ Each of these is independently one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, X ５ Y is either a single bond, an ether group, or an ester group. Y is an oxygen atom or -NR １９ - It is a group, R １９ R is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. ４ They may form a ring together. Rf １ 'and Rf ５ ' is a fluorine atom, a trifluoromethyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms, and having at least one fluorine atom. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are such that 0 ≤ a1 < 1.0, 0 ≤ a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ a4 < 1.0, 0 ≤ a5 < 1.0, 0 ≤ a6 < 1.0, 0 ≤ a7 < 1.0, and 0 < a1 + a2 + a3 + a4 + a5 + a6 + a7 < 1.

0. M ＋ (This is an ion selected from ammonium ions, sodium ions, potassium ions, and silver ions.)

4. The bioelectrode composition according to claim 3, characterized in that it contains a polymer obtained by copolymerizing one or more repeating units a1 to a7 described in the general formula (2) above with a repeating unit b1 having a nitro group described in the general formula (4) below. 【Transformation 3】 (In general formula (4), R ２０ X is a hydrogen atom or a methyl group. ８ R is one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group. ２１ (n is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or a phenylene group. The alkylene group may have a hydroxyl group, carboxyl group, ether group, ester group, urethane group, thiourethane group, carbonate group, amide group, or urea bond. The phenylene group may be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, or a cyano group. n is 1 or 2, and 0 < b1 < 1.0.)

5. The bioelectrode composition according to claim 1, characterized in that the component (A) contains an ammonium ion represented by the following general formula (3) as the ammonium ion constituting the ammonium salt. 【Chemistry 4】 (In general formula (3), R １０１ｄ , R １０１ｅ , R １０１ｆ , and R １０１ｇ Each of these is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have one or more selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. １０１ｄ and R １０１ｅ , or R １０１ｄ , R １０１ｅ and R １０１ｆ These may form a ring with the nitrogen atom to which they are bonded, and if a ring is formed, R １０１ｄ and R １０１ｅ , or R １０１ｄ , R １０１ｅ and R １０１ｆ (This is either an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having the nitrogen atom in general formula (3) within the ring.)

6. The bioelectrode composition according to claim 1, further characterized in that it contains a resin as component (B).

7. The bioelectrode composition according to claim 6, characterized in that the (B) component is one or more selected from silicone resin, (meth)acrylate resin, and urethane resin.

8. The bioelectrode composition according to claim 6, characterized in that the (B) component has adhesive properties.

9. The aforementioned component (B) is R ｘ SiO （４－ｘ）／２ Units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, x is in the range of 2.5 to 3.5) and SiO ４／２ The bioelectrode composition according to claim 6, characterized in that it contains a silicone resin having units.

10. The bioelectrode composition according to claim 1, further characterized in that it contains a carbon material and / or metal powder as component (C).

11. The bioelectrode composition according to claim 10, characterized in that the carbon material is carbon black, carbon nanotubes, or both.

12. The bioelectrode composition according to claim 10, characterized in that the metal powder is one or more metal powders selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

13. The bioelectrode composition according to claim 12, characterized in that the metal powder is silver powder.

14. The bioelectrode composition according to claim 1, further characterized in that it contains an organic solvent as component (D).

15. A bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, wherein the biocontact layer is a cured product of the bioelectrode composition described in any one of claims 1 to 14.

16. The bioelectrode according to claim 15, characterized in that the conductive substrate contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

17. A method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, characterized in that the biocontact layer is formed by applying the bioelectrode composition according to any one of claims 1 to 14 onto the conductive substrate and curing it.

18. The method for producing a bioelectrode according to claim 17, characterized in that the conductive substrate contains one or more selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

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