Bio-electrode composition, bio-electrode, method for manufacturing bio-electrode

Abstract

To provide: a bio-electrode composition capable of forming a living body contact layer for a bio-electrode which is excellent in electric conductivity and biocompatibility, light-weight, manufacturable at low cost, capable of preventing a significant reduction in electric conductivity even when wetted with water or dried, and excellent in softness, stretchability and adhesiveness; a bio-electrode including a living body contact layer formed from the bio-electrode composition; and a method for manufacturing the bio-electrode.SOLUTION: A bio-electrode composition includes an (A) ionic resin, wherein the component (A) contains a resin having a structure selected from the group consisting of an ammonium salt, a lithium salt, a sodium salt, a potassium salt, and a silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a bioelectrode that can be brought into contact with the skin of a living body and detect a bodily condition such as heart rate by an electrical signal from the skin, a method for producing the same, and a bioelectrode composition that is suitably used for the bioelectrode. [Background technology]

[0002] In recent years, the development of wearable devices has progressed with the spread of IoT (Internet of Things). Typical examples are watches and glasses that can connect to the Internet. In addition, wearable devices that can constantly monitor the condition of the body are needed in the medical and sports fields, and these are expected to be growth fields in the future.

[0003] In the medical field, wearable devices that monitor the state of the body's organs by sensing weak currents, such as in electrocardiograms, which detect the movement of the heart through electrical signals, are being considered. In electrocardiograms, electrodes coated with conductive paste are attached to the body to perform the measurement, but this is a one-time, short-term measurement. In contrast, the aim of developing medical wearable devices such as those mentioned above is to develop devices that constantly monitor the health state for several weeks in a row. Therefore, the bioelectrodes used in medical wearable devices are required to have no change in conductivity even when used for long periods of time and to be free of skin allergies. In addition to these, they are also required to be lightweight and to be able to be manufactured at low cost.

[0004] Wearable medical devices include those that are attached to the body and those that are incorporated into clothing. As a type that is attached to the body, a bioelectrode that uses 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 that holds water, and converts changes in ion concentration from the skin into electricity. On the other hand, as a type that is incorporated into clothing, a method has been proposed in which a conductive polymer such as PEDOT-PSS (Poly-3,4-ethylenedioxythiophene-Polystyrenesulfonate) or cloth with silver paste incorporated into the fibers is used as an electrode (Patent Document 2).

[0005] However, when using the above-mentioned water-soluble gel containing water and electrolytes, there is a problem that the conductivity is lost when the water dries out. On the other hand, when using metals with a high ionization tendency such as copper, there is a problem that some people may develop skin allergies, and when using conductive polymers such as PEDOT-PSS, there is a problem that the conductive polymer is highly acidic and therefore may develop skin allergies, and the conductive polymer may peel off from the fibers during washing.

[0006] In addition, because of their excellent electrical conductivity, the use of metal nanowires, carbon black, carbon nanotubes, and the like as electrode materials has also been considered (Patent Documents 3, 4, 5). Metal nanowires have a high probability of contact between wires, so they can conduct electricity with a small amount of additive. However, metal nanowires are thin materials with sharp tips, which can cause skin allergies. Thus, even if the material itself does not cause an allergic reaction, the shape and irritation of the material can cause the material to have poor biocompatibility, making it difficult to achieve both electrical conductivity and biocompatibility.

[0007] Metal films are highly conductive and one would think they would function as excellent bioelectrodes, but this is not necessarily the case. When the heart beats, not only a weak current is released from the skin, but also sodium ions, potassium ions, and calcium ions. For this reason, it is necessary to convert the change in ion concentration into an electric current, but precious metals, which are difficult to ionize, are inefficient at converting ions from the skin into an electric current. Therefore, bioelectrodes using precious metals have a high impedance, and there is a high resistance to electrical current passing through the skin.

[0008] On the other hand, batteries to which ionic liquids have been added are being considered (Patent Document 6). Ionic liquids are characterized by high thermal and chemical stability and excellent electrical conductivity, and are being widely used in batteries. However, since ionic liquids with small molecular weights as shown in Patent Document 6 dissolve in water, when a bioelectrode to which this has been added is used, the ionic liquid is extracted by sweat from the skin, which not only reduces electrical conductivity but also penetrates the skin and causes rough skin.

[0009] In addition, a battery using a lithium salt of a polymer-type sulfonimide is being studied (Non-Patent Document 1). However, although lithium is applied to batteries because of its high ion mobility, it is not a biocompatible material. Furthermore, a lithium salt of fluorosulfonic acid pendant on silicone is also being studied (Non-Patent Document 2).

[0010] Bioelectrode materials in which ionic polymers are mixed with silicone adhesives have been proposed (Patent Documents 7 and 8). These materials not only have high ionic conductivity, but also have high electronic conductivity when conductive powders such as carbon and silver are added, so they function as excellent bioelectrodes. By combining silicone adhesives, which have low skin allergies, high water repellency, and the effect of suppressing itching and redness of the skin after removal, with ionic polymers that have high ionic conductivity and do not pass through the skin, it is possible to obtain stable biosignals without peeling off even when attached for a long period of time, including daily bathing and exercise, but there is a demand for further improvement in comfort when attached for a long period of time.

[0011] The health effects of perfluoroalkyl substances (PFAS) have been pointed out, and there are moves to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH regulation. There is an urgent need to develop materials that do not contain PFAS structures. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. WO2013-039151 Brochure [Patent Document 2] JP 2015-100673 A [Patent Document 3] Japanese Patent Application Publication No. 5-095924 [Patent Document 4] JP 2003-225217 A [Patent Document 5] JP 2015-019806 A [Patent Document 6] Special Publication No. 2004-527902 [Patent Document 7] JP 2018-126496 A [Patent Document 8] JP 2018-130533 A [Non-patent literature]

[0013] [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) Summary of the Invention [Problem to be solved by the invention]

[0014] 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 electrical conductivity and biocompatibility, lightweight, can be manufactured at low cost, does not significantly decrease in electrical conductivity whether wetted with water or dried, and is soft, stretchable, and adhesive; a bioelectrode in which a biocontact layer is formed from the bioelectrode composition; and a method for manufacturing the same. [Means for solving the problem]

[0015] In order to solve the above problems, the present invention provides (A) a bioelectrode composition containing an ionic resin, The present invention provides a bioelectrode composition, in which the component (A) contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0016] The bioelectrode composition of the present invention is a bioelectrode composition that has excellent electrical conductivity and biocompatibility, is lightweight, can be produced at low cost, does not significantly decrease in electrical conductivity whether wetted with water or dried, and can form a biocontact layer for a bioelectrode that is soft, stretchable, and adhesive.

[0017] In addition, the resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide preferably has a chemical structure represented by the following general formula (1). [ka] (In the formula, R 1 R is a trifluoromethyl group or a difluoromethyl group. 2 is a hydrogen atom, a linear, branched or cyclic alkyl or alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, or a halogen atom. m is an integer of 1 to 5, and n is an integer of 0 to 4. M+ is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0018] In this case, it is preferable that the chemical structure represented by the general formula (1) is bonded to a resin selected from the group consisting of a resin obtained by polymerizing a monomer having a double bond, a silicone resin, and a polyurethane resin.

[0019] Furthermore, in this case, the resin having the chemical structure represented by general formula (1) bonded thereto is preferably any one of a resin obtained by polymerizing a monomer having a double bond including a repeating unit represented by the following general formula (2)-1, a silicone resin including a repeating unit represented by the following general formula (2)-2-1, a silicone resin including a repeating unit represented by the following general formula (2)-2-2, a silicone resin including a repeating unit represented by the following general formula (2)-2-3, and a silicone resin including a repeating unit represented by the following general formula (2)-2-4, a polyurethane resin including a repeating unit represented by the following general formula (2)-3-1, and a urethane resin including a terminal structure represented by the following general formula (2)-3-2. [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, R 1 , R 2 , m, n, and M + As mentioned above. R 3is a hydrogen atom or a methyl group. 4 X is a single bond, or a linear, branched or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms, which may have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group or a sulfonate ester group. 1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate ester group; X 2 R is a linear, branched or cyclic alkylene group having 1 to 14 carbon atoms, an arylene group having 6 to 12 carbon atoms or a combination thereof, and may have an ether group, an ester group, a carbonyl group, a nitrogen atom, a sulfide group, a sulfonyl group or a sulfonate ester group. 5 ~R 8 R is a linear, branched or cyclic alkyl group having 1 to 66 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 9 R is a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an ether group or an ester group. 10 , and R 12 is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, which may have an oxygen atom; R 10 and R 12 Both of R cannot be single bonds. 11 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a hydroxyl group or an ether group. 10 ~R 12 and the carbon atom to which they are bonded may combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may contain an aromatic ring and / or a heteroatom. 3 is a single bond, a carbonyl group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, which may have an aromatic group; R 11It may combine to form a ring, and the ring may be an aromatic ring. a1 represents the ratio of repeating units, and 0 < a1 ≤ 1.0. a2-1 and a2-3 represent the ratio of repeating units, and 0 < a2-1 ≤ 1.0 and 0 < a2-3 ≤ 1.0. a2-2 represents the number of repetitions and is a number of 0 or more. a3 represents the number of repetitions and is a number greater than 0.)

[0020] Specifically, such an ionic resin can be used as the component (A) in the present invention.

[0021] Further, when the component (A) is the M + It preferably contains an ammonium ion represented by the following general formula (3).

Chemical formula

[0022] (When the component (A) contains a resin having an ammonium salt structure, the ammonium ion can be such.)

[0023] Moreover, it is preferable that the bioelectrode composition of the present invention further contains a resin as a component (B) which is different from the ionic resin as the component (A).

[0024] By including such a component (B), it is possible to prevent the elution of the salt of the component (A) and to further improve the adhesiveness.

[0025] The component (B) is preferably at least one selected from a silicone resin, a (meth)acrylate resin, and a urethane resin.

[0026] In addition, it is preferable that the resin as the component (B) has adhesive properties.

[0027] The component (B) further includes R x SiO (4-x) / 2 units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.5) and SiO 2 The silicone resin may contain a silicone resin having a unit.

[0028] Specifically, such resins can be used as the component (B).

[0029] Moreover, the bioelectrode composition of the present invention preferably further contains carbon powder and / or metal powder as component (C).

[0030] By including such a component (C), the electrical conductivity can be further improved.

[0031] The carbon powder is preferably either or both of carbon black and carbon nanotubes.

[0032] It is also preferable that the metal powder is a metal powder selected from the group consisting of gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

[0033] In this case, it is more preferable that the metal powder is silver powder.

[0034] Specifically, such electrical conductivity improvers can be used as the component (C).

[0035] It is also preferable that the bioelectrode composition further contains an organic solvent as component (D).

[0036] By including such a component (D), the coatability can be further improved.

[0037] The present invention also 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 above-mentioned bioelectrode composition.

[0038] The bioelectrode of the present invention is a bioelectrode having a biocontact layer formed from a bioelectrode composition that is excellent in electrical conductivity and biocompatibility, lightweight, and can be manufactured at low cost, and the electrical conductivity does not decrease significantly whether it is wetted with water or dried, and which can form a biocontact layer for a bioelectrode that is soft, stretchable, and adhesive.

[0039] 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 a conductive polymer.

[0040] In the bioelectrode of the present invention, such a conductive substrate can be used.

[0041] The present invention also provides a method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, in which the bioelectrode composition described above is applied to the conductive substrate and cured to form the biocontact layer.

[0042] The bioelectrode of the present invention can be produced in this manner.

[0043] In this case, it is preferable to use, as the conductive substrate, 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.

[0044] In the method for producing a bioelectrode of the present invention, such a conductive substrate can be used. Effect of the Invention

[0045] As described above, the bioelectrode composition of the present invention has excellent electrical conductivity and biocompatibility, is lightweight, can be produced at low cost, and does not significantly decrease in electrical conductivity whether wetted with water or dried, and can form a biocontact layer for a bioelectrode that is soft, stretchable, and adhesive; and it is possible to provide a bioelectrode having a biocontact layer formed from the bioelectrode composition, and a method for producing the same. [Brief description of the drawings]

[0046] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a bioelectrode of the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing an example of the bioelectrode of the present invention attached to a living body. [Diagram 3] FIG. 2 is a schematic diagram of a bioelectrode produced in an example of the present invention after printing. [Figure 4] FIG. 2 is a schematic diagram of one of the bioelectrodes produced in the examples of the present invention, cut out and with an adhesive layer and an electric wire attached. [Diagram 5]FIG. 2 is a diagram showing the locations where electrodes and a ground are attached to the human body when measuring a biosignal in an embodiment of the present invention. [Figure 6] 1 is an electrocardiogram waveform obtained using a bioelectrode according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] As described above, there has been a need to develop a bioelectrode composition capable of forming a biocontact layer for a bioelectrode that is excellent in electrical conductivity and biocompatibility, lightweight, can be manufactured at low cost, is soft, stretchable, and adhesive, can be attached to the skin for a long period of time to stably collect biosignals even when wetted with water such as during a bath or dried, and leaves no residue on the skin after being removed from the skin; a bioelectrode in which a biocontact layer is formed from the bioelectrode composition; and a method for manufacturing the same.

[0048] Sodium, potassium, and calcium ions are released from the skin surface in tandem with the heartbeat. Bioelectrodes need to convert the increase or decrease in the ions released from the skin into an electrical signal. To do this, materials with excellent ionic conductivity are required to transmit the increase or decrease in ions.

[0049] To stably obtain biosignals when attached to the skin, the bioelectrode film must be soft, stretchable, and adhesive. The keratin of the epidermis is regenerated daily, and old keratin (dirt) accumulates between the attached bioelectrode film and the skin. Since old keratin is easily peeled off from the epidermis, peeling off the bioelectrode makes it impossible to collect biosignals. For this reason, the adhesiveness of the bioelectrode must not decrease even when it is attached for a long period of time. On the other hand, if any residue remains on the skin after it is removed after being attached for a long period of time, it may cause rashes or rough skin.

[0050] When the acidity of the acid that forms the neutralized salt is high, the ions are strongly polarized, improving ionic conductivity. This is why lithium salts of bis(trifluoromethanesulfonyl)imide acid and tris(trifluoromethanesulfonyl)methide acid show high ionic conductivity in lithium-ion batteries. On the other hand, the higher the acid strength of the acid before it becomes a neutralized salt, the stronger the bioirritation of the salt becomes. In other words, there is a trade-off between ionic conductivity and bioirritation. However, salts to be applied to bioelectrodes must have both high ionic conductivity and low bioirritation.

[0051] The larger the molecular weight of an ionic compound, the less the skin permeability and the less irritation to the skin. For this reason, the ionic compound is preferably a polymer type with a high molecular weight. Therefore, the present inventors have avoided the problem of skin irritation by polymerizing the ionic compound into a form having a polymerizable double bond, or by bonding the ionic compound with silicone, polyurethane, polyether, polyester, etc.

[0052] Furthermore, the inventors have discovered that by mixing this salt with, for example, a silicone-, acrylic-, or urethane-based adhesive (resin), the adhesive can be in constant contact with the skin and a stable electrical signal can be obtained for a long period of time.

[0053] That is, the present invention is a bioelectrode composition containing an ionic resin (A), wherein the component (A) contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0054] The present invention will be described in detail below, but the present invention is not limited thereto.

[0055] <Bioelectrode composition> The bioelectrode composition of the present invention is a bioelectrode composition containing (A) an ionic resin, The bioelectrode composition contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide. Each component will be described in more detail below.

[0056] [(A) Ionic resin] (A) The ionic resin contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0057] The resin (ionic resin) having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide preferably has a chemical structure (partial structure) represented by the following general formula (1).

[0058] [ka] (In the formula, R 1 R is a trifluoromethyl group or a difluoromethyl group. 2 is a hydrogen atom, a linear, branched or cyclic alkyl or alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, or a halogen atom. m is an integer of 1 to 5, and n is an integer of 0 to 4. M + is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0059] In this case, it is preferable that the chemical structure represented by the general formula (1) is bonded to a resin selected from a resin obtained by polymerizing a monomer having a double bond, a silicone resin, and a polyurethane resin.

[0060] The resin having the chemical structure represented by the above general formula (1) bonded thereto is preferably any one of a resin obtained by polymerizing a monomer having a double bond including a repeating unit represented by the following general formula (2)-1, a silicone resin including a repeating unit represented by the following general formula (2)-2-1, a silicone resin including a repeating unit represented by the following general formula (2)-2-2, a silicone resin including a repeating unit represented by the following general formula (2)-2-3, and a silicone resin including a repeating unit represented by the following general formula (2)-2-4, a polyurethane resin including a repeating unit represented by the following general formula (2)-3-1, and a urethane resin including a terminal structure represented by the following general formula (2)-3-2.

[0061] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, R 1 , R 2 , m, n, and M + As mentioned above. R 3 is a hydrogen atom or a methyl group. 4 X is a single bond, or a linear, branched or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms, which may have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group or a sulfonate ester group. 1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate ester group; X 2is a linear, branched or cyclic alkylene group having 1 to 14 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a combination thereof, and may have an ether group, an ester group, a carbonyl group, a nitrogen atom, a sulfide group, a sulfonyl group or a sulfonic acid ester group. R 5 ~R 8 is a linear, branched or cyclic alkyl group having 1 to 66 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 9 is a linear or branched alkyl group having 1 to 20 carbon atoms and may have an ether group or an ester group. R 10 , and R 12 is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and the alkylene group may have an oxygen atom. R 10 and R 12 will not both be single bonds. R 11 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and may have a hydroxyl group or an ether group. Or, R 10 ~R 12 and the carbon atom in the formula to which these are attached may combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may contain an aromatic ring and / or a hetero atom. X 3 is a single bond, a carbonyl group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may have an aromatic group, and R 11 may combine to form a ring, and the ring may be an aromatic ring. a1 represents the ratio of the repeating unit and 0 < a1 ≤ 1.0. a2-1 and a2-3 represent the ratio of the repeating unit and 0 < a2-1 ≤ 1.0 and 0 < a2-3 ≤ 1.0. a2-2 represents the number of repetitions and is a number of 0 or more. a3 represents the number of repetitions and is a number greater than 0.)

[0062] [Resin obtained by polymerizing a monomer having a double bond] As the monomer for obtaining the repeating unit a1 represented by the above general formula (2)-1, it is represented by the following general formula (2)-1-1.

[0063] [Chemical formula] (In the general formula, R 1 ~R 4 , X 1 , M + , m, and n are as described above.)

[0064] Specific examples of the monomer represented by the above general formula (2)-1-1 include the following.

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka] (In the formula, R 3 , M is as above.)

[0075] In addition, the component (A) is M in the repeating unit a (repeating unit a1). + It is preferable that the ammonium ion (ammonium cation) is contained in the following general formula (3).

[0076] [ka] (In the formula, R 101d , R 101e , R 101f , R 101g R is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 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 groups selected from an ether group, a carbonyl group, an ester group, a hydroxy group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d and R 101e , R 101d and R 101e and R 101f may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R 101d and R 101e and R 101d and R 101e and R 101f is an alkylene group having 3 to 10 carbon atoms, or forms a heteroaromatic ring having the nitrogen atom in the ring.

[0077] Specific examples of the ammonium ion represented by the above general formula (3) include the following.

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] As the ammonium ion represented by the above general formula (3), a tertiary or quaternary ammonium ion is particularly preferred.

[0095] (Repeating unit b1) In the component (A) of the bioelectrode composition of the present invention, in addition to the repeating unit a1 obtained by polymerizing a monomer having a polymerizable double bond, a repeating unit b1 having a glyme chain can also be copolymerized to improve electrical conductivity. Specific examples of monomers for obtaining the repeating unit b1 having a glyme chain are shown below. By copolymerizing a repeating unit having a glyme chain, the movement of ions released from the skin in the dry electrode film can be promoted, and the sensitivity of the dry electrode can be increased.

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka] (R is a hydrogen atom or a methyl group.)

[0100] (Repeating unit c1) In addition to the repeating units a1 and b1, the component (A) of the bioelectrode composition of the present invention can also be copolymerized with a hydrophilic repeating unit c1 having a hydroxyl group, a carboxyl group, an ammonium salt, a betaine, an amide group, a pyrrolidone, a lactone ring, a lactam ring, a sultone ring, a sodium salt of sulfonic acid, or a potassium salt of sulfonic acid in order to improve electrical conductivity. Specific examples of monomers for obtaining the hydrophilic repeating unit c1 are shown below. By copolymerizing repeating units containing these hydrophilic groups, the sensitivity of the ions released from the skin can be increased, and the sensitivity of the dry electrode can be increased.

[0101] [ka]

[0102] [ka]

[0103] [ka] (R is a hydrogen atom or a methyl group.)

[0104] The component (A) of the bioelectrode composition of the present invention can have a repeating unit d1 that imparts adhesive properties.

[0105] Specific examples of monomers from which the repeating unit d1 is obtained include the following.

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] Furthermore, a crosslinkable repeating unit e1 can be copolymerized. Examples of the crosslinkable repeating unit include a repeating unit having an oxirane ring or an oxetane ring.

[0112] Specific examples of monomers for obtaining the repeating unit e1 having an oxirane ring or oxetane ring include those shown below.

[0113] [ka]

[0114] [ka] (wherein R is a methyl group or a hydrogen atom).

[0115] The component (A) of the bioelectrode composition of the present invention can have a repeating unit f1 having silicon in addition to the repeating units selected from the above a1, b1, c1, d1, and e1. Specifically, the following can be exemplified.

[0116] [ka]

[0117] [ka]

[0118] The repeating units having the above alkoxysilyl groups may be copolymerized and the alkoxysilyl groups may be hydrolyzed to form a silsesquioxane structure as shown in JP 2022-164579 A, ​​or may be reacted with silanols on the silica surface to form a composite with silica as shown in JP 2022-64291 A.

[0119] The component (A) of the bioelectrode composition of the present invention can have a fluorine-containing repeating unit g1 in addition to the repeating units selected from the above a1 and b1 to f1.

[0120] Specific examples of monomers for obtaining the fluorine-containing repeating unit g1 include the following.

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka] (where R is a hydrogen atom or a methyl group.)

[0128] The component (A) of the bioelectrode composition of the present invention can have a repeating unit h1 having a cyano group in addition to the repeating units selected from the above a1 and b1 to g1.

[0129] Specific examples of monomers for obtaining the repeating unit h1 having a cyano group include the following.

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka] (where R is a hydrogen atom or a methyl group.)

[0134] The component (A) of the bioelectrode composition of the present invention can have a repeating unit i1 having a nitro group in addition to the repeating units selected from the above a1 and b1 to h1.

[0135] Specific examples of monomers for obtaining the repeating unit i1 having a nitro group include the following.

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka] (where R is a hydrogen atom or a methyl group.)

[0142] One method for synthesizing an ionic resin (polymer compound) containing a1 having a polymerizable double bond as component (A) can be a method in which a desired monomer from among monomers that give repeating units a1, b1, c1, d1, e1, f1, g1, h1, and i1 is heated and polymerized in an organic solvent with the addition of a radical polymerization initiator to obtain a copolymer polymer compound.

[0143] Examples of the organic solvent used during polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, etc. Examples of the 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.

[0144] Here, the ratios of the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 in the ionic resin of component (A) are 0 < a1 ≤ 1.0, 0 ≤ b1 < 1.0, 0 ≤ c1 < 1.0, 0 ≤ d1 < 1.0, 0 ≤ e1 < 0.9, 0 ≤ f1 < 0.9, 0 ≤ g1 < 0.9, 0 ≤ h1 < 0.9, 0 ≤ i1 < 0.9, preferably 0.1 ≤ a1 ≤ 0.9, 0.01 ≤ b1 ≤ 0.9, 0 ≤ c1 ≤ 0.8, 0 ≤ d1 ≤ 0.8, 0 ≤ e1 < 0.8, 0 ≤ f1 < 0.8, 0 ≤ g1 < 0.8, 0 ≤ h1 < 0.8, 0 ≤ i1 < 0.8, more preferably 0.15 ≤ a1 ≤ 0.8, 0.05 ≤ b1 ≤ 0.8, 0 ≤ c1 ≤ 0.7, 0 ≤ d1 ≤ 0.5, 0 ≤ e1 < 0.3, 0 ≤ f1 < 0.7, 0 ≤ g1 < 0.7, 0 ≤ h1 < 0.7, 0 ≤ i1 < 0.7.

[0145] Note that, for example, a1 + b1 + c1 + d1 + e1 + f1 + g1 + h1 + i1 = 1 indicates that in the polymer compound containing the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1, the total amount of the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 is 100 mol% with respect to the total amount of all repeating units. And a1 + b1 + c1 + d1 + e1 + f1 + g1 + h1 + i1 < 1 indicates that the total amount of the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 is less than 100 mol% with respect to the total amount of all repeating units and that there are other repeating units in addition to a1, b1, c1, d1, e1, f1, g1, h1, i1.

[0146] The molecular weight of the ionic resin containing a1 having a polymerizable double bond of the component (A) is preferably 500 or more as 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. In addition, if the amount of ionic monomer (residual monomer) that is not incorporated in the ionic resin of the component (A) after polymerization is small, there is no risk of this monomer penetrating into the skin and causing allergies in a biocompatibility test, so it is preferable to reduce the amount of the residual monomer. The amount of the residual monomer is preferably 10 parts by mass or less relative to 100 parts by mass of the entire ionic resin of the component (A) before the condensation reaction. In addition, the component (A) may be used alone or in a mixture of two or more types having different molecular weights, dispersities, and polymerizable monomers.

[0147] [Silicone resin] Specific examples of the repeating unit a2-1 represented by the above general formula (2)-2-1 include the following.

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka] Here, M + is as mentioned above.

[0153] (Repeating unit b2) In addition to the repeating unit a2-1, the component (A) of the bioelectrode composition of the present invention can have a repeating unit b2 having a glyme chain in order to improve conductivity. Specific examples of the repeating unit b2 include those described in paragraphs 0068 and 0069 of JP 2020-851 A.

[0154] (Repeating unit c2) In addition to the repeating units a2-1 and b2, the component (A) of the bioelectrode composition of the present invention can have a repeating unit c2 having a hydrogen atom, an alkyl group, or an aryl group in order to improve the mixability with the resin of the component (B). The alkyl group or aryl group may have a hydroxyl group, a halogen atom, an ester group, an ether group, a carboxyl group, a thiol group, a (meth)acrylic group, a cyano group, or a nitro group. Specific examples of the repeating unit c2 include those described in paragraph 0071 of JP 2020-851 A.

[0155] One method for synthesizing the silicone compound having the a2-1 unit of component (A) is to carry out a hydrosilylation reaction between a sulfonamide salt having a double bond and a silicone compound having a Si-H group in the presence of a platinum catalyst. To obtain the repeating unit b2, a compound having a double bond and an ether group and a silicone compound having a Si-H group can be carried out a hydrosilylation reaction in the presence of a platinum catalyst. The a2-1 unit and the b2 and c2 units may both be present in one silicone molecule, or silicone compounds having the a2-1 unit and the b2 and c2 units, respectively, may be blended. When the a2-1 unit and the b2 and c2 units are copolymerized, the copolymerization ratio is 0. <a2-1≦1.0、0≦b2<1.0、0≦c2<1.0である。

[0156] The silicone compound before hydrosilylation may be any of chain, branched, and cyclic structures, but is preferably a polymeric compound with a molecular weight of 300 to 1,000,000. The sulfonamide salt pendant on the polymeric silicone prevents it from passing through the skin and causing allergies.

[0157] In addition, as component (A), a silicone compound having a sulfonamide salt at the terminal, represented by the above general formula (2)-2-2 or (2)-2-3, can be obtained by hydrosilylation reaction of a sulfonamide salt having a double bond with a silicone compound having a Si-H group at the terminal in the presence of a platinum catalyst. The reaction conditions are as described above.

[0158] The terminal portions of the silicone compounds represented by the above general formulas (2)-2-2 and (2)-2-3 are specifically as follows:

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] [ka] Here, * denotes the bond position with the silicone polymer, M + is as mentioned above.

[0164] The component (A) may be a silsesquioxane having a three-dimensional ladder structure containing the repeating unit a2-3 represented by the general formula (2)-2-4. Specific examples of the structure of the repeating unit a2-3 are shown below.

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka] Here, M + is as mentioned above.

[0170] (Repeating unit b3) In addition to the repeating unit a2-3, the component (A) of the bioelectrode composition of the present invention can have a repeating unit b3 having a glyme chain in order to improve conductivity. Specific examples of the repeating unit b3 include those described in paragraphs 0069 and 0070 of JP 2020-6069 A.

[0171] (Repeating unit c3) In addition to the repeating units a2-3 and b3, the (A) component of the bioelectrode composition of the present invention can have a repeating unit c3 having a hydrogen atom, an alkyl group, or an aryl group in order to improve the mixability with the resin of the (B) component. The alkyl group or aryl group may have a hydroxyl group, a halogen atom, an ester group, an ether group, a carboxyl group, a thiol group, a (meth)acrylic group, a cyano group, or a nitro group. Specific examples of the repeating unit c3 include those described in paragraphs 0072 and 0073 of JP 2020-6069 A.

[0172] [Urethane resin] The polyurethane resin having the repeating unit a3 represented by general formula (2)-3-1 can be obtained by reacting a monomer having a dihydroxy group represented by the following general formula (2)-3-1-1 with a compound having an isocyanate group.

[0173] [ka] (In the formula, R 1 , R 2 , R 4 , R 10 ~R 12 , X 3 , M + , m, and n are as described above.)

[0174] Specific examples of the dihydroxy group-containing monomer of the general formula (2)-3-1-1 include the following.

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] The dihydroxy group-containing sulfonamide salt can be synthesized by synthesizing sulfonamide by the method described in paragraph 177 of JP-A-2022-078861, followed by neutralization or ion exchange with ammonium hydroxide, ammonium chloride, sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride, silver hydroxide, silver chloride, silver nitrate, etc.

[0186] The resin having the repeating unit a3 represented by the general formula (2)-3-1 can be obtained by reacting a monomer having a dihydroxy group represented by (2)-3-1-1 with a compound having an isocyanate group. Examples of the compound having an isocyanate group can be found in paragraphs 0067 and 0068 of JP 2020-55300 A.

[0187] Since isocyanate compounds have high reactivity with hydroxyl group-containing compounds, it may be difficult to control this. In addition, since isocyanate compounds may react with moisture in the air during storage and the isocyanate group may be deactivated, sufficient care must be taken during storage, such as preventing humidity. Therefore, in order to prevent these events, compounds having blocked isocyanate groups in which the isocyanate group is protected by a substituent may be used.

[0188] The blocked isocyanate group is a group in which the blocking group is deprotected by heating to become an isocyanate group. Specific examples of the blocked isocyanate group include isocyanate groups substituted with alcohol, phenol, thioalcohol, imine, ketimine, amine, lactam, pyrazole, oxime, β-diketone, etc.

[0189] A catalyst can be added to lower the deprotection temperature of the blocked isocyanate group. Known examples of such catalysts include organotins such as dibutyltin dilaurate, bismuth salts, and zinc carboxylates such as zinc 2-ethylhexanoate and zinc acetate.

[0190] In particular, JP 2012-152725 A discloses that the deprotection reaction can be carried out at a lower temperature by using an α,β-unsaturated carboxylate zinc salt as a carboxylic acid and a blocked isocyanate dissociation catalyst.

[0191] It is also possible to copolymerize with a compound having a hydroxy group other than the monomer of general formula (2)-3-1-1. Examples of compounds having a hydroxy group other than the monomer of general formula (2)-3-1-1 are exemplified in paragraphs 0054-0064 and 0077-0082 of JP 2020-55300 A.

[0192] In the polyurethane polymerization, it is preferable to add a catalyst as necessary in order to promote the urethane bond forming reaction.

[0193] The urethanization catalyst can be appropriately selected from known catalysts, and examples of such catalysts include amine catalysts, ammonium salt catalysts, potassium salt catalysts, and organometallic catalysts.

[0194] Examples of the amine catalyst include triethylamine, N,N-dimethylcyclohexylamine, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethylhexanolamine, N,N-dimethyl-N'-(2-hydroxyethyl)ethyl Examples of the dimethylaminoethyl ether include dimethylaminoethyl ether, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, N,N,N'-trimethylaminoethylethanolamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methyl-N'-(2-hydroxyethyl)piperazine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, and 1-(2-hydroxypropyl)-2-methylimidazole.

[0195] Examples of the ammonium salt catalyst include quaternary ammonium salts such as tetraethylhydroxylammonium, and ammonium salts of 1,8-diazabicyclo(5,4,0)-undecene-7 or 1,5-diazabicyclo(4,3,0)-nonene-5 with octylic acid, oleic acid, p-toluenesulfonic acid, formic acid, phenolic acid, orthophthalic acid, acetic acid, maleic acid, or boric acid.

[0196] Examples of potassium salt catalysts include potassium carbonate, potassium acetate, and potassium octylate.

[0197] Examples of the organometallic catalyst include organotin compounds such as tin acetate, tin octoate (tin 2-ethylhexanoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organolead compounds such as lead octoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocobalt compounds such as cobalt naphthenate; organocopper compounds such as copper octoate; and organobismuth compounds such as bismuth octoate and bismuth neodecanoate.

[0198] These urethanization catalysts may be used alone or in combination of two or more. The amount of the urethanization catalyst used is preferably in the range of 0 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of the polyurethane constituents.

[0199] The component (A) may also be a resin having a terminal sulfonamide salt bonded to a urethane group represented by the general formula (2)-3-2. This resin can be obtained by reacting a monomer having a hydroxyl group represented by the following general formula (2)-3-2-1 with a compound having an isocyanate group.

[0200] [ka] (R 1 , R 2 , R 4 , X 3 , M + , m, and n are as described above.)

[0201] The compound having an isocyanate group may be the above-mentioned compound or a polyurethane compound having an isocyanate group at the end, which is obtained by reacting a compound having an isocyanate group with a compound having a dihydroxy group. The reaction conditions are as described above.

[0202] The amount of the (A) component in the bioelectrode composition of the present invention is not particularly limited, but for example, the amount of the (A) component is preferably 1 to 95 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the total amount of the composition. In the bioelectrode composition of the present invention, the amount of the (A) component is preferably 0.1 to 300 parts by mass, more preferably 1 to 200 parts by mass, per 100 parts by mass of the (B) component described below. In addition, the (A) component may be used alone or in a mixture of two or more kinds.

[0203] [(B) Resin] The (B) resin blended in the bioelectrode composition of the present invention is a component that is compatible with the ionic resin of the (A) component to prevent the elution of salt, holds a conductivity enhancer such as metal powder, carbon powder, silicon powder, lithium titanate powder, and further improves adhesion. If the ionic resin of the (A) component has sufficient adhesion, the (B) resin is not necessarily required. The resin may be any resin other than the above-mentioned (A) component, and is preferably either a thermosetting resin or a photocurable resin, or both, and is particularly preferably one or more selected from silicone-based, acrylic-based, and urethane-based resins.

[0204] Examples of adhesive silicone-based resins include those that are cured by addition reaction or radical crosslinking reaction. Examples of the addition reaction cured type include diorganosiloxane having an alkenyl group, R 3 SiO 0.5 and SiO 2The resin may contain an MQ resin having a unit, an organohydrogenpolysiloxane having a plurality of SiH groups, a platinum catalyst, an addition reaction inhibitor, and an organic solvent. In addition, the radical crosslinking reaction curing type may contain, for example, a diorganopolysiloxane which may or may not have an alkenyl group, R 3 SiO 0.5 and SiO 2 One containing an MQ resin having units, an organic peroxide, and an organic solvent can be used, where R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0205] It is also possible to use a polysiloxane-resin integrated compound formed by condensing polysiloxane with silanols at the polymer end or side chain with MQ resin. MQ resin contains a lot of silanols, so adding this improves adhesive strength, but since it is not crosslinkable, it is not molecularly bonded to the polysiloxane. By integrating polysiloxane and resin as described above, adhesive strength can be increased.

[0206] In addition, modified siloxanes having a group selected from amino groups, oxirane groups, oxetane groups, polyether groups, hydroxy groups, carboxyl groups, mercapto groups, methacryl groups, acrylic groups, phenol groups, silanol groups, carboxylic anhydride groups, aryl groups, aralkyl groups, amide groups, ester groups, and lactone rings can be added to silicone resins. By adding modified siloxanes, the dispersibility of component (A) in the silicone resin is improved. The modified siloxanes may be modified at one end, both ends, or the side chains of the siloxane.

[0207] The adhesive acrylic resin may be, for example, one having a hydrophilic (meth)acrylic acid ester or a long-chain hydrophobic (meth)acrylic acid ester as a repeating unit, as described in JP 2016-011338 A. In some cases, a (meth)acrylic acid ester having a functional group or a (meth)acrylic acid ester having a siloxane bond may be copolymerized.

[0208] As the adhesive urethane-based resin, for example, one having a urethane bond and a polyether or polyester bond, a polycarbonate bond, or a siloxane bond, as described in JP 2016-065238 A, can be used.

[0209] In addition, in order to prevent the decrease in conductivity due to the (A) component falling off from the biocontact layer, in the bioelectrode composition of the present invention, it is preferable that the (B) resin has high compatibility with the above-mentioned (A) component. In addition, in order to prevent the biocontact layer from peeling off from the conductive substrate, it is preferable that the (B) resin has high adhesion to the conductive substrate in the bioelectrode composition of the present invention. In order to make the resin highly compatible with the conductive substrate and the 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 contacts the living body, it is easily affected by sweat from the living body. Therefore, in the bioelectrode composition of the present invention, it is preferable that the (B) resin has high water repellency and is not easily hydrolyzed. In order to make the resin highly water repellent and not easily hydrolyzed, it is effective to use a resin containing silicon.

[0210] Silicon-atom-containing polyacrylic resins include polymers having silicone in the main chain and polymers having silicon atoms in the side chain, and both can be used suitably. As the polymer having silicone in the main chain, siloxane or silsesquioxane having a (meth)acrylpropyl group can be used. In this case, the (meth)acryl portion can be polymerized and cured by adding a photoradical generator.

[0211] Suitable examples of polyamide resins containing silicon atoms include polyamide silicone resins described in JP 2011-079946 A and U.S. Patent No. 5,981,680 A. Such polyamide silicone resins can be synthesized by combining, for example, a silicone having amino groups at both ends or a non-silicone compound having amino groups at both ends with a non-silicone having carboxyl groups at both ends or a silicone having carboxyl groups at both ends.

[0212] Alternatively, polyamic acid obtained by reacting a carboxylic anhydride with an amine before cyclization may be used. An epoxy or oxetane crosslinking agent may be used to crosslink the carboxyl groups of the polyamic acid, or the carboxyl groups may be esterified with hydroxyethyl (meth)acrylate to perform photoradical crosslinking of the (meth)acrylate portion.

[0213] As the polyimide resin containing silicon atoms, for example, the polyimide silicone resin described in JP-A-2002-332305 can be suitably used. Polyimide resins have a very high viscosity, but the viscosity can be reduced by blending a (meth)acrylic monomer as a solvent and a crosslinking agent.

[0214] Examples of polyurethane resins containing silicon atoms include polyurethane silicone resins. In such polyurethane silicone resins, crosslinking by urethane bonds can be performed by blending and heating a compound having isocyanate groups at both ends and a compound having hydroxyl groups at the ends. In this case, it is necessary to contain silicon atoms (siloxane bonds) in either or both of the compound having isocyanate groups at both ends and the compound having hydroxyl groups at the ends. Alternatively, as described in JP 2005-320418 A, a urethane (meth)acrylate monomer can be blended with polysiloxane to perform photocrosslinking. In addition, a polymer having both siloxane bonds and urethane bonds and a (meth)acrylate group at the end can also be photocrosslinked. In particular, materials having silicone chains attached to side chains and polyurethane main chains described in JP 2018-123304 A and JP 2019-70109 A are preferred because they have high strength and high elasticity.

[0215] The polythiourethane resin containing silicon atoms can be obtained by reacting a compound having a thiol group with a compound having an isocyanate group, and any one of them may contain a silicon atom. In addition, if the compound has a (meth)acrylate group at the end, it can be photocured.

[0216] In the silicone resin, the diorganosiloxane having the above-mentioned alkenyl group, R 3 SiO 0.5 and SiO 2 In addition to MQ resins having units and organohydrogenpolysiloxanes having multiple SiH groups, the compatibility with the above-mentioned salts is improved by adding modified siloxanes having groups selected from amino groups, oxirane groups, oxetane groups, polyether groups, hydroxyl groups, carboxyl groups, mercapto groups, methacryl groups, acrylic groups, phenol groups, silanol groups, carboxylic anhydride groups, aryl groups, aralkyl groups, amide groups, ester groups, and lactone rings.

[0217] Diorganosiloxanes having alkenyl groups and organohydrogenpolysiloxanes having multiple SiH groups can be crosslinked by an addition reaction in the presence of a platinum catalyst.

[0218] Examples of platinum catalysts include platinum catalysts such as chloroplatinic acid, alcohol 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 siloxane, platinum-olefin complexes, platinum-vinyl group-containing siloxane complexes, platinum group metal catalysts such as rhodium complexes and ruthenium complexes, etc. Furthermore, these catalysts may be used in the form of a solution or dispersion in an alcohol-based, hydrocarbon-based, or siloxane-based solvent.

[0219] The amount of the platinum catalyst added is preferably within a range of 5 to 2,000 ppm, and particularly preferably 10 to 500 ppm, per 100 parts by mass of the resin consisting of components (A) and (B) combined.

[0220] In the bioelectrode composition of the present invention, the blending amount of the (B) component is preferably 0 to 2000 parts by mass, more preferably 10 to 1000 parts by mass, per 100 parts by mass of the ionic resin (A). Moreover, the (A) component and the (B) component may each be used alone or in combination of two or more kinds.

[0221] When an addition-curing silicone resin is used, an addition reaction inhibitor may be added as a quencher to prevent the platinum catalyst from acting in the solution and in a low-temperature environment before heat curing after coating formation. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0222] The amount of the addition reaction inhibitor added is preferably within a range of 0 to 10 parts by mass, and particularly preferably 0.05 to 3 parts by mass, per 100 parts by mass of the resin consisting of components (A) and (B) combined.

[0223] In addition, as the (B) component, R x SiO (4-x) / 2 units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.5) and SiO 2 It is preferable that the silicone resin contains a silicone resin having a unit.

[0224] When component (B) has a radically crosslinkable double bond, it is effective to add a radical generator. Radical generators include photoradical generators and thermal radical generators.

[0225] Examples of photoradical generators include acetophenone, 4,4'-dimethoxybenzyl, benzil, 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, 2-benzoylbenzoic acid methyl ester, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzoylbenzoic acid methyl ester ... Examples of suitable acetophenones include 2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthioxanthen-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-isonitrosopropiophenone, and 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone.

[0226] It can also be cured by adding a thermally decomposable 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(2-methylbutyronitrile), 2,2'-azobis(cyclohexane-1-carbonitrile), 1[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis[2-methyl-N -(2-hydroxyethyl)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, and the like.

[0227] The amount of the radical generator added is preferably within a range of 0.1 to 50 parts by mass per 100 parts by mass of the resin, which is the combined total of the components (A) and (B).

[0228] As described later, the biocontact layer is a cured product of the bioelectrode composition. By curing, the adhesion of the biocontact layer to both the skin and the conductive substrate is improved. The curing method is not particularly limited, and a general method can be used, for example, heat and / or light, or a crosslinking reaction using an acid or base catalyst. The crosslinking reaction can be carried out by appropriately selecting a method described in, for example, Crosslinking Reaction Handbook, Nakayama Hiroharu, Maruzen Publishing (2013), Chapter 2, p. 51 to p. 371.

[0229] [Ionic polymer] In addition to the component (A), an ionic polymer can be added to the bioelectrode composition of the present invention. The ionic polymers shown in JP 2018-126496 A and JP 2018-130533 A are preferably used. The amount of the ionic polymer added is preferably in the range of 0.1 to 100 parts by mass per 100 parts by mass of the resin, which is the combined resin of the components (A) and (B).

[0230] [Metal powder] In order to enhance electronic conductivity, the bioelectrode composition of the present invention may contain a metal powder selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium. The amount of metal powder or carbon added is preferably within the range of 1 to 50 parts by mass per 100 parts by mass of the resin, which is the combined total of components (A) and (B).

[0231] As the type of metal powder, gold, silver, and platinum are preferred from the viewpoint of electrical conductivity, and silver, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, and chromium are preferred from the viewpoint of cost. From the viewpoint of biocompatibility, noble metals are preferred, and from these viewpoints overall, silver is the most preferred.

[0232] The shape of the metal powder can be spherical, disk-like, flake-like, or needle-like, but the addition of flake-like powder is the most conductive and is preferred. The size of the metal powder is 100 μm or less, and the tap density is 5 g / cm. 3 Below, the specific surface area is 0.5m 2 Flakes with a relatively low density and large specific surface area of ​​100 / g or more are preferred.

[0233] [Carbon materials] A carbon material can be added as a conductivity improver. Examples of the carbon material include carbon black, graphite, carbon nanotubes, carbon fibers, graphene, etc. The carbon nanotubes may be either single-walled or multi-walled, and the surface may be modified with an organic group. The amount of the carbon material added is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the resin, which is the combined resin of components (A) and (B).

[0234] [Silicon powder] Silicon powder can be added to the bioelectrode composition of the present invention in order to increase the sensitivity of ion reception. Examples of silicon powder include powders made 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. Since finer particles have a larger surface area, they can receive more ions, 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, which is the combined resin of components (A) and (B).

[0235] [Lithium titanate powder] In order to enhance the sensitivity of ion reception, lithium titanate powder can be added to the bioelectrode composition of the present invention. The lithium titanate powder is Li 2 TiO 3 , LiTiO 2 , spinel structure Li 4 Ti 5 O 12 The molecular formula of the lithium titanate powder is as follows, and a spinel structure is preferable. Lithium titanate particles composited with carbon can also be used. The particle size of the powder is preferably smaller than 100 μm, more preferably 1 μm or less. Since finer particles have a larger surface area, they can receive more ions, resulting in a highly sensitive bioelectrode. These may 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 (A) and (B) combined.

[0236] [Crosslinking agent] An epoxy-based crosslinking agent can 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 one molecule. The amount of the crosslinking agent to be added is 1 to 30 parts by mass per 100 parts by mass of the resin, which is the combined resin of components (A) and (B).

[0237] [Crosslinking catalyst] A catalyst for crosslinking epoxy groups or oxetane groups can also be added to the bioelectrode composition of the present invention. In this case, the catalysts described in paragraphs 0027 to 0029 of JP2019-503406 can be used. The amount of the catalyst added is 0.01 to 10 parts by mass per 100 parts by mass of the resin (A) and (B) combined.

[0238] [Ionic additives] The bioelectrode composition of the present invention can be added with an ionic additive to increase ionic conductivity. In consideration of biocompatibility, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, saccharin sodium 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 disclosed in JP-A-2018-44147, JP-A-2018-59050, JP-A-2018-59052, and JP-A-2018-130534 can be mentioned.

[0239] [Organic solvents] In addition, the bioelectrode composition of the present invention may contain (D) an organic solvent. Specific examples of the organic solvent 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 tetrahydrofuran. naphthalene, 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-diisopropylbenzene, Aromatic hydrocarbon solvents such as isopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, and 1,3,5-triethylbenzene, n-heptane, isoheptane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexyne, norbornane, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, 1-heptyne, 2-heptyne, cycloheptane, and cyclohexene. 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-octyne, 2-octyne, 3-octyne, 4-octyne, n-nonane, 2,3-dimethylheptane, 2,4-dimethylheptane, 2,5-dimethylheptane, 3,3-dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4-ethylhexene, ethylheptane, 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, hydrindane, 1,8-nonadiene, 1-nonyne, 2-nonyne, 3-nonyne, 4-nonyne, 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-Decadiene, Decahydronaphthalene, 1-Decyne, 2-Decyne, 3-Decyne, 4-Decyne, 5-Decyne, 1,5,9-Decyne katriene, 2,6-dimethyl-2,4,6-octatriene, limonene, myrcene, 1,2,3,4,5-pentamethylcyclopentadiene, α-phellandrene, pinene, terpinene, tetrahydrodicyclopentadiene, 5,6-dihydrodicyclopentadiene, dicyclopentadiene, 1,4-decadiyne, 1,5-decadiyne, 1,9-decadiyne, 2,8-decadiyne, 4,6-decadiyne, n-undecane, amylcyclohexane, 1-undecene, 1,10-undecadiene, 1-undecyne, 3-undecyne, 5-undecyne, tricyclo[6.2.1.0, 2,7]Undec-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 isoparaffin; 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 monoheptyl ether. Examples of the solvent include ether solvents such as ethyl 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, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether, di-n-hexyl ether, and anisole; ester 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, and propylene glycol mono-tert-butyl ether acetate; lactone solvents such as γ-butyrolactone; and water.

[0240] The amount of the (D) organic solvent added is preferably within a range of 10 to 50,000 parts by mass per 100 parts by mass of the resin, which is the combined total of the (A) and (B) components.

[0241] In the case where the resin of the component (B) is a silicone adhesive that undergoes crosslinking by hydrosilylation reaction, if the content of water in the solvent is 0.2 mass% or less, the risk of the progress of the hydrosilylation reaction being hindered is further reduced. It is preferable that the crosslinking reaction proceeds sufficiently in order to exert sufficient adhesiveness and not leave a residue of the bioelectrode composition on the skin after the bioelectrode is peeled off from the skin. Therefore, it is particularly preferable to remove water from the solution in which the ionic polymer of the present invention is dissolved. For the removal of water, methods such as azeotropic dehydration, centrifugation, adsorption by molecular sieves, and filtration by a water removal filter can be applied.

[0242] [Other additives] The bioelectrode composition of the present invention can also be mixed with silica particles, polyether silicone, and polyglycerin silicone. The silica particles have a hydrophilic surface, and are compatible with hydrophilic ionic polymers, polyether silicone, and polyglycerin silicone, and can improve the dispersibility of ionic polymers, polyether silicone, and polyglycerin silicone in hydrophobic silicone adhesives. Silica particles can be used preferably in either dry or wet methods.

[0243] [Silicone compounds having polyglycerin structure] In the bioelectrode composition of the present invention, a silicone compound having a polyglycerin structure can be added in order to improve the moisture retention of the membrane and improve the sensitivity and ion 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, more preferably 0.5 to 60 parts by mass, per 100 parts by mass of the total of the (A) component and the (B) component. The silicone compound having a polyglycerin structure may be used alone or in a mixture of two or more types.

[0244] The silicone compound having a polyglycerin structure is preferably one represented by the following general formulas (4)' and (5)'.

[0245] [ka] (In formulas (4)' and (5)', R 1 are each independent and may be the same or different, each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms, or a phenyl group, each independently represent a silicone chain represented by the general formula (6)' ... 2 R′ is a group having a polyglycerin group structure represented by formula (4)′-1 or formula (4)′-2, 3 ' are each independent and may be the same or different, 1 ' group or the R 2 ' group, R 4 ' are each independent and may be the same or different, 1 ' group, the R 2 R is a ' group or an oxygen atom. 4 If ' is an oxygen atom, then two R 4 The a' groups may be bonded to form a single ether group to form a ring together with the silicon atom. a' may be the same or different and is 0 to 100, b' is 0 to 100, and a'+b' is 0 to 200. However, when b' is 0, R 3 At least one of the R 2 In formulae (4)'-1, (4)'-2, (5)', and (6)', R 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 ' is an alkylene group having 2 to 6 carbon atoms, and R 7 ' may be an ether bond, c' is 0 to 20, and d' is 1 to 20.

[0246] Examples of such silicone compounds having a polyglycerin structure include the following.

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] [ka]

[0253] [ka]

[0254] [ka]

[0255] [ka]

[0256] [ka] (wherein a', b', c' and d' are as defined above).

[0257] A bioelectrode composition containing a silicone compound having such a polyglycerin structure can exhibit better moisturizing properties, and as a result, can form a biocontact layer that can exhibit better sensitivity to ions released from the skin.

[0258] As described above, the bioelectrode composition of the present invention is a bioelectrode composition that can form a biocontact layer for a bioelectrode that has high adhesion, has sufficient adhesion even when peeled off from the skin and reattached, can efficiently transmit electrical signals from the skin to the device (i.e., has excellent conductivity), is not likely to 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 does not significantly decrease in conductivity even when wet or dried. In addition, the conductivity can be further improved by adding a carbon material, and a bioelectrode with particularly high adhesion and high elasticity can be manufactured by combining it with a resin having adhesiveness and elasticity. Furthermore, the elasticity and adhesiveness to the skin can be improved by additives, and the elasticity and adhesiveness can be adjusted by appropriately adjusting the composition of the resin and the thickness of the biocontact layer.

[0259] <Bioelectrode> The present invention also 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.

[0260] The bioelectrode of the present invention will be described in detail below with reference to the drawings, but the present invention is not limited thereto.

[0261] FIG. 1 is a schematic cross-sectional view showing an example of the bioelectrode of the present invention. The bioelectrode 1 in FIG. 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 contains an ionic resin (A) 5. The biocontact layer 3 may further contain a resin (B) 6 other than the ionic resin (A) 5, and a conductive powder 4. Hereinafter, with reference to FIGS. 1 and 2, a case will be described in which the biocontact layer 3 is a layer in which the ionic resin (A) 5 and the conductive powder 4 are dispersed in the resin (B) 6, but the bioelectrode of the present invention is not limited to this embodiment.

[0262] When using such a bioelectrode 1 of Fig. 1, as shown in Fig. 2, the biocontact layer 3 (i.e., a layer in which ionic resin (A) 5 and conductive powder 4 are dispersed in resin (B) 6) is brought into contact with a living body 7, and an electrical signal is extracted from the living body 7 by the ionic resin (A) 5 and the conductive powder 4, and this is conducted to a sensor device or the like (not shown) via the conductive substrate 2. In this way, with the bioelectrode of the present invention, the aforementioned ionic resin (A) 5 can achieve both electrical conductivity and biocompatibility, and since it also has adhesiveness, the contact area with the skin is constant, and electrical signals from the skin can be obtained stably and with high sensitivity.

[0263] Each of the constituent materials of the bioelectrode of the present invention will be described in more detail below.

[0264] [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 an electrical signal extracted from a living body via a living body contact layer to the sensor device or the like.

[0265] The conductive substrate is not particularly limited as long as it has conductivity, but it is preferable that the conductive substrate contains at least one material selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0266] The conductive substrate is not particularly limited and may be a hard conductive substrate, a flexible conductive film, a fabric coated with a conductive paste, or a fabric with a conductive polymer kneaded in. The conductive substrate may be flat or uneven, or may be a mesh of woven metal wires, and may be appropriately selected depending on the application of the bioelectrode.

[0267] [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 has electrical conductivity and adhesiveness. The biocontact layer is a cured product of the bioelectrode composition of the present invention described above, that is, an adhesive resin layer made of a cured product of a composition containing the above-mentioned component (A) and, if necessary, components (B), (C), (D), and other components.

[0268] The adhesive strength of the living body contact layer is preferably in the range of 0.01 N / 25 mm to 20 N / 25 mm. The adhesive strength is generally measured by the method shown in JIS Z 0237. A metal substrate such as SUS (stainless steel) or a PET (polyethylene terephthalate) substrate can be used as the substrate, but human skin can also be used for measurement. 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 to the skin.

[0269] For applications where application and peeling are repeated many times, peelability is more important than adhesion, so adhesion is not necessarily required.

[0270] The thickness of the biocontact layer of the bioelectrode is preferably 1 μm to 5 mm, more preferably 2 μm to 3 mm. The thinner the biocontact layer, the weaker the adhesive strength, but the more flexible it is, the lighter it is, and the better it fits to the skin. The thickness of the biocontact layer can be selected based on the balance between adhesiveness and texture on the skin.

[0271] In addition, in the bioelectrode of the present invention, similar to conventional bioelectrodes (for example, the bioelectrode described in JP 2004-033468 A), a separate adhesive film may be provided on the biocontact layer to prevent the bioelectrode from peeling off from the living body during use. When providing a separate adhesive film, it is sufficient to form the adhesive film using an adhesive film material such as an acrylic type, a urethane type, or a silicone type. In particular, the silicone type has high oxygen permeability, so that the skin can breathe while it is attached, and has high water repellency, so that the adhesiveness is less likely to decrease due to sweat, and further, is less irritating to the skin, so it is preferable. In addition, in the bioelectrode of the present invention, as described above, peeling off from the living body can be prevented by adding an adhesive imparting agent to the bioelectrode composition or using a resin that has good adhesiveness to the living body, so that the above-mentioned separate adhesive film is not necessarily required.

[0272] When the bioelectrode of the present invention is used as a wearable device, the wiring between the bioelectrode and the sensor device and other components are not particularly limited, and for example, those described in JP 2004-033468 A can be applied.

[0273] As described above, the bioelectrode of the present invention has a biocontact layer formed of the cured product of the bioelectrode composition of the present invention, so that the bioelectrode can efficiently transmit electrical signals from the skin to the device (i.e., has excellent electrical conductivity), is not likely to 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 does not significantly decrease in electrical conductivity even when wet or dried. In addition, the electrical conductivity can be further improved by adding conductive powder, and a bioelectrode with particularly high adhesive strength and high elasticity can be manufactured by combining it with a resin having adhesiveness and elasticity. Furthermore, the elasticity and adhesiveness to the skin can be improved by additives, and the 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 a medical wearable device.

[0274] <Manufacturing method of bioelectrodes> The present invention also provides a method for manufacturing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, in which the bioelectrode composition of the present invention described above is applied to the conductive substrate and cured to form the biocontact layer.

[0275] The conductive substrate and the like used in the method for producing a bioelectrode of the present invention may be the same as those described above.

[0276] The method for applying the bioelectrode composition onto the conductive substrate is not particularly limited, but suitable methods include, for example, dip coating, spray coating, spin coating, bar coating, comma coating, die coating, roll coating, flow coating, doctor coating, calendar coating, screen printing, flexographic printing, gravure printing, and inkjet printing.

[0277] The resin curing method is not particularly limited and may be appropriately selected depending on the components (A) and (B) used in the bioelectrode composition, but it is preferable to cure the resin by, for example, heat or light, or both. In addition, a catalyst that generates an acid or base may be added to the bioelectrode composition to cause a crosslinking reaction and cure the resin.

[0278] The temperature for heating is not particularly limited and may be appropriately selected depending on the components (A) and (B) used in the bioelectrode composition, but is preferably about 50 to 250°C, for example.

[0279] In addition, when heating and light irradiation are combined, heating and light irradiation may be performed simultaneously, or 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.

[0280] After the film has hardened, applying water droplets or spraying water vapor or mist on the surface improves its compatibility with the skin, allowing for quick biosignals to be obtained. Water mixed with alcohol can also be used to reduce the size of the vapor or mist droplets. The film surface can also be wetted by contacting it with absorbent cotton or cloth soaked in water.

[0281] The water that wets the surface of the cured film may contain a salt, and the water-soluble salt that is mixed with the water is selected from sodium salts, potassium salts, calcium salts, magnesium salts, and betaines.

[0282] Specifically, the water-soluble salt may be a salt selected from sodium chloride, potassium chloride, calcium chloride, magnesium chloride, saccharin sodium 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. The above-mentioned ionic resin (A) is not included in the water-soluble salt.

[0283] 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 butyrate, sodium 2-hydroxybutyrate, sodium 3-hydroxybutyrate, sodium 2-oxobutyrate, sodium stearate, sodium glutamate ... Examples of betaines include sodium conate, sodium methanesulfonate, sodium 1-nonanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-undecanesulfonate, sodium cocoyl ethionate, sodium lauroyl methyl alanine, sodium cocoyl methyl taurate, sodium cocoyl glutamate, sodium cocoyl sarcosine, sodium lauroyl methyl taurate, laumidopropyl, 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 a compound in which three methyl groups are added to the amino group of an amino acid, and more specifically, trimethylglycine, carnitine, trimethylglycine, and proline betaine can be mentioned.

[0284] The water that wets the surface of the cured film may further contain a monohydric alcohol or polyhydric alcohol having 1 to 4 carbon atoms. The alcohol is preferably selected from ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, polyethylene glycol, polypropylene glycol, polyglycerin, diglycerin, or a silicone compound having a polyglycerin structure, and it is more preferable that the silicone compound having a polyglycerin structure is one represented by the above general formula (4)' or (5)'.

[0285] The pretreatment method using a water-soluble salt-containing aqueous solution can be applied to the bioelectrode membrane after hardening by spraying, dispensing water droplets, etc. It can also be applied in a high temperature and high humidity state such as a sauna. After application, in order to prevent drying, a protective film can be further laminated on the permeation layer to cover it. Since the protective film needs to be peeled off just before applying it to the skin, it can be coated with a release agent or a peelable Teflon (registered trademark) film can be used. For long-term storage, the dry electrode covered with the release film is preferably sealed in a bag covered with aluminum or the like. In order to prevent drying in the aluminum-covered bag, it is preferable to seal moisture in it.

[0286] Before attaching the bioelectrode of the present invention to the skin, the skin side can be moistened with water, alcohol, etc., or the skin can be wiped with a cloth or absorbent cotton containing water, alcohol, etc. The above-mentioned salt can also be contained in the water or alcohol.

[0287] As described above, the manufacturing method of the bioelectrode of the present invention makes it possible to easily manufacture, at low cost, the bioelectrode of the present invention which has excellent conductivity and biocompatibility, is lightweight, and whose conductivity does not decrease significantly whether it is wetted with water or dried. EXAMPLES

[0288] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these.

[0289] Synthesis example of (2)-1 monomer with double bond [ka]

[0290] A mixed solution of 22 g of 4-trifluoromethoxybenzenesulfonamide, 14 g of potassium carbonate, and 60 g of acetonitrile was cooled on ice, and then a mixed solution of 10 g of acrylic acid chloride and 30 g of acetonitrile was added dropwise under ice cooling. After warming to room temperature, the mixture was stirred for 22 hours and dried under reduced pressure to obtain the target (2)-1 monomer 1. (2)-1 monomers 2 to 7, 9, and 10 were synthesized in the same manner.

[0291] (2)-1 Monomer 8 was synthesized by the reaction of 4-trifluoromethoxybenzenesulfonic acid chloride with ethanolamine, followed by the reaction of methacrylic acid chloride.

[0292] (2)-1 Monomers 1 to 10 are shown below. [ka]

[0293] Ionic resins 1-1 to 1-11, which were blended as ionic materials (conductive materials) in the bioelectrode composition solution, were synthesized as follows. A 30% by mass solution of each monomer in cyclopentanone was mixed in a reaction vessel, 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 heating to room temperature, 0.02 mol of azobisisobutyronitrile (AIBN) was added as a polymerization initiator per mol of the total monomers, and the mixture was heated to 60°C and reacted for 15 hours. The composition of the obtained polymer was as follows, after drying the solvent: 1The molecular weight (Mw) and dispersity (Mw / Mn) of the obtained polymer were confirmed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The ionic resins 1-1 to 1-11 thus synthesized are shown below.

[0294] Ionic Resin 1-1 Mw=66,800 Mw / Mn=2.62 [ka]

[0295] Ionic Resin 1-2 Mw=43,100 Mw / Mn=2.46 [ka]

[0296] Ionic Resin 1-3 Mw=55,600 Mw / Mn=2.34 [ka]

[0297] Ionic Resin 1-4 Mw=48,100 Mw / Mn=2.67 [ka]

[0298] Ionic Resin 1-5 Mw=56,900 Mw / Mn=2.61 [ka]

[0299] Ionic Resin 1-6 Mw=71,300 Mw / Mn=2.67 [ka]

[0300] Ionic Resin 1-7 Mw=39,400 Mw / Mn=2.26 [ka] (The number of repetitions in the formula indicates the average value.)

[0301] Ionic Resin 1-8 Mw=26,700 Mw / Mn=1.91 [ka] (The number of repetitions in the formula indicates the average value.)

[0302] Ionic Resin 1-9 Mw=34,400 Mw / Mn=2.22 [ka] (The number of repetitions in the formula indicates the average value.)

[0303] Ionic Resin 1-10 Mw=28,500 Mw / Mn=1.98 [ka]

[0304] Ionic Resin 1-11 Mw=24,700 Mw / Mn=1.98 [ka]

[0305] The ionic resins 2-1 to 2-6, which were blended as ionic materials (conductive materials) in the bioelectrode composition solution, were synthesized by subjecting a silicone compound having a SiH group and a sulfonamide salt compound having an alkenyl group (monomers 1 to 3 in (2)-2 below) to a hydrosilylation reaction in the presence of a platinum catalyst.

[0306] [ka]

[0307] Ionic Resin 2-1 Mw=661 Mw / Mn=1.0 [ka]

[0308] Ionic Resin 2-2 Mw=7100 Mw / Mn=1.60 [ka]

[0309] Ionic Resin 2-3 Mw=4,400 Mw / Mn=1.46 [ka]

[0310] Ionic Resin 2-4 Mw=5,600 Mw / Mn=1.63 [ka]

[0311] Ionic Resin 2-5 Mw=1,690 Mw / Mn=1.10 [ka]

[0312] Ionic Resin 2-6 Mw=5,600 Mw / Mn=1.63 [ka]

[0313] Using the following (2)-3 monomers 1 to 11, an isocyanate compound, optionally a dihydroxy compound for chain extension, a monohydroxy compound or a monoisocyanate compound for terminal blocking, a solvent propylene glycol monomethyl ether acetate in an amount twice the mass of the raw material compound, and 0.02 mass% of catalyst XK-640 (manufactured by KING INDUSTRIES) per 100 mass parts of the raw material compound were mixed and reacted at 90°C for 9 hours to synthesize ionic resins 3-1 to 3-14.

[0314] [ka]

[0315] [ka]

[0316] [ka]

[0317] [ka]

[0318] [ka]

[0319] [ka]

[0320] [ka]

[0321] [ka]

[0322] [ka]

[0323] [ka] In the figure, * represents a bond.

[0324] [ka]

[0325] Ionic Resin 3-14 Mw=1,580 Mw / Mn=1.09 [ka]

[0326] Comparative ionic resin 1 Mw=26,500 Mw / Mn=1.85 [ka]

[0327] Siloxane compounds 1 to 4 that were blended as silicone resins in the bioelectrode composition solution are shown below.

[0328] (Siloxane Compound 1) The viscosity of a 30% toluene solution is 27,000 mPa s, the alkenyl group content is 0.007 mol / 100 g, and the molecular chain terminal is SiMe 2 The vinyl group-containing polydimethylsiloxane blocked with Vi groups was designated as siloxane compound 1.

[0329] (Siloxane Compound 2) Me 3 SiO 0.5 Units and SiO 2 Polysiloxane of MQ resin consisting of units (Me 3 SiO 0.5 Unit / SiO 2 A 60% toluene solution of siloxane compound 2 (unit = 0.8) was used as the siloxane compound 2.

[0330] (Siloxane Compound 3) 40 parts by mass of vinyl-containing polydimethylsiloxane whose molecular chain ends are capped with OH and whose viscosity in a 30% toluene solution is 42,000 mPa s and whose alkenyl group content is 0.007 mol / 100 g, Me 3 SiO 0.5 Units and SiO 2 Polysiloxane of MQ resin consisting of units (Me 3 SiO 0.5 Unit / SiO 2 A solution consisting of 100 parts by mass of a 60% toluene solution of 1,2-dichlorophenyl ether (unit = 0.8) and 26.7 parts by mass of toluene was heated for 4 hours while being dry distilled, and then cooled to obtain the compound in which polydimethylsiloxane was bonded to the MQ resin, which was named Siloxane Compound 3.

[0331] (Siloxane Compound 4) As the methyl hydrogen silicone oil, KF-99 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

[0332] The acrylic resins blended in the bioelectrode composition solution as the acrylic resins are shown below. Acrylic Resin 1 Mw=129,000 Mw / Mn=2.45 [ka]

[0333] The urethane resins blended in the bioelectrode composition solution as urethane-based resins are shown below. Urethane resin 1 Mw=83,000 Mw / Mn=4.02 [ka]

[0334] Urethane Resin 2 Mw=84,000 Mw / Mn=4.22 [ka]

[0335] The polyglycerin silicone compound blended in the bioelectrode composition solution is shown below. [ka]

[0336] The crosslinking agents contained in the bioelectrode composition solution are shown below. Epoxy Crosslinker 1 [ka]

[0337] The organic solvents contained in the bioelectrode composition solution are shown below. EDE: Diethylene glycol diethyl ether Isopar G TM : Isoparaffin solvent made by Standard Oil Isopar M TM : Isoparaffin solvent made by Standard Oil

[0338] The lithium titanate powder, radical generator, platinum catalyst, and conductivity enhancer (carbon black, carbon nanotubes) blended as additives in the bioelectrode composition solution are shown below. Lithium titanate powder, spinel: Sigma-Aldrich, size 200nm or less 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 Multi-walled carbon nanotubes: Sigma-Aldrich, diameter 110-170 nm, length 5-9 μm

[0339] [Examples 1 to 31, Comparative Example 1] Ionic resin, resin, organic solvent, and additives (radical generator, platinum catalyst, conductivity enhancer) were blended in the compositions shown in Tables 1 to 3 to prepare bioelectrode compositions (bioelectrode solutions 1 to 31, comparative bioelectrode solution 1).

[0340] [Table 1]

[0341] [Table 2]

[0342] [Table 3]

[0343] (Biological signal evaluation) As shown in FIG. 3, a conductive paste manufactured by Fujikura Kasei, Dotite FA-333, was coated on ST-604 of a thermoplastic urethane (TPU) film 20 manufactured by Bemis by screen printing, and baked in an oven at 120°C for 10 minutes to print a keyhole-shaped conductive pattern 2 with a circular diameter of 2 cm. The bioelectrode solution shown in Tables 1 to 3 was applied by screen printing on the circular part on top of the conductive pattern, 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 harden the pattern, forming a biocontact layer 3 and a bioelectrode 1. In the case of the bioelectrode solution 30, 500 mJ / cm was applied using a 1,000 W xenon lamp under a nitrogen atmosphere. 2 The composition coating film was cured by irradiating light of 1000 nm. Next, as shown in FIG. 4, the urethane film on which the bioelectrode 1 was printed was cut out, and a double-sided tape 21 was attached to the cut piece, to prepare three bioelectrode samples 10 for each bioelectrode solution.

[0344] (Measurement of the thickness of the biological contact layer) The thickness of the biocontact layer of the bioelectrode prepared above was measured using a micrometer. The results are shown in Table 4.

[0345] (Measurement of biological signals) The conductive wiring pattern made of conductive paste of the bioelectrode was connected with a portable electrocardiograph HCG-901 manufactured by Omron Healthcare Co., Ltd. with a conductive wire, and the positive electrode of the electrocardiograph was attached to the LA position of the human body in Figure 5, the negative electrode to the LL position, and the earth to the RA position. Immediately after attachment, the 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.

[0346] [Table 4]

[0347] As shown in Table 4, in Examples 1 to 31 in which a biocontact layer was formed using a bioelectrode composition of the present invention containing a resin having a structure selected from the group consisting of ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide, a biosignal could be obtained in a short time after application to the body. On the other hand, when the ion component of the specific structure was not contained, a biosignal could not be obtained.

[0348] This specification includes the following inventions.

[0349] [1]: A bioelectrode composition containing an ionic resin (A), characterized in that the component (A) contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0350] [2]: The resin having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide has a chemical structure represented by the following general formula (1). The bioelectrode composition according to [1] above. [ka] (In the formula, R 1 R is a trifluoromethyl group or a difluoromethyl group. 2 is a hydrogen atom, a linear, branched or cyclic alkyl or alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, or a halogen atom. m is an integer of 1 to 5, and n is an integer of 0 to 4. M + is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0351] [3]: The bioelectrode composition according to [2] above, characterized in that the chemical structure represented by the general formula (1) is bonded to a resin selected from a resin polymerized from a monomer having a double bond, a silicone resin, and a polyurethane resin.

[0352] [4]: The resin having the chemical structure represented by the general formula (1) bonded thereto is any one of a resin obtained by polymerizing a monomer having a double bond containing a repeating unit represented by the following general formula (2)-1, a silicone resin containing a repeating unit represented by the following general formula (2)-2-1, a silicone resin containing a repeating unit represented by the following general formula (2)-2-2, a silicone resin containing a repeating unit represented by the following general formula (2)-2-3, and a silicone resin containing a repeating unit represented by the following general formula (2)-2-4, a polyurethane resin having a repeating unit represented by the following general formula (2)-3-1, and a urethane resin having a terminal structure represented by the following general formula (2)-3-2. The bioelectrode composition according to the above [2] or [3]. [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, R 1 , R 2 , m, n, and M + As mentioned above. R 3 is a hydrogen atom or a methyl group. 4is a single bond, or a linear, branched, or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms, which may have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group, or a sulfonic acid ester group. X 1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonic acid ester group, X 2 is a linear, branched, or cyclic alkylene group having 1 to 14 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a combination thereof, which may have an ether group, an ester group, a carbonyl group, a nitrogen atom, a sulfide group, a sulfonyl group, or a sulfonic acid ester group. R 5 ~R 8 is a linear, branched, or cyclic alkyl group having 1 to 66 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 9 is a linear or branched alkyl group having 1 to 20 carbon atoms, which may have an ether group or an ester group. R 10 and R 12 is a single bond, or a linear or branched alkylene group having 1 to 4 carbon atoms, and the alkylene group may have an oxygen atom, R 10 and R 12 will not both be single bonds. R 11 is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a hydroxyl group or an ether group. Or, R 10 ~R 12 and the carbon atom in the formula to which these are attached may combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may contain an aromatic ring and / or a heteroatom. X 3 is a single bond, a carbonyl group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, which may have an aromatic group, R 11 and may combine with R to form a ring, and the ring may be an aromatic ring. a1 represents the ratio of the repeating unit, and 0 < a1 ≤ 1.0. a2-1 and a2-3 represent the ratio of the repeating unit, and 0 < a2-1 ≤ 1.0 and 0 < a2-3 ≤ 1.0. a2-2 represents the number of repetitions, and it is a number of 0 or more. a3 represents the number of repetitions, and it is a number greater than 0.)

[0353] [5]: The component (A) is + The bioelectrode composition according to any one of the above [2] to [4], which contains an ammonium ion represented by the following general formula (3) as the cation: [ka] (In the formula, R 101d , R 101e , R 101f , and R 101g R is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 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 groups selected from an ether group, a carbonyl group, an ester group, a hydroxy group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d and R 101e , R 101d and R 101e and R 101f may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R 101d and R 101e and R 101d and R 101e and R 101f is an alkylene group having 3 to 10 carbon atoms, or forms a heteroaromatic ring having the nitrogen atom in the ring.

[0354] [6]: The bioelectrode composition according to any one of the above [1] to [5], further comprising a resin as a component (B) different from the ionic resin as the component (A).

[0355] [7]: The bioelectrode composition according to the above [6], wherein the component (B) is at least one selected from the group consisting of silicone resins, (meth)acrylate resins, and urethane resins.

[0356] [8]: The bioelectrode composition according to the above [6] or [7], wherein the resin as the component (B) has adhesive properties.

[0357] [9]: The component (B) further includes R x SiO (4-x) / 2 units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.5) and SiO 2 The bioelectrode composition according to any one of the above [6] to [8], which contains a silicone resin having a unit.

[0358]

[10] : The bioelectrode composition according to any one of the above [1] to [9], further comprising carbon powder and / or metal powder as component (C).

[0359]

[11] : The bioelectrode composition according to the above

[10] , characterized in that the carbon powder is either or both of carbon black and carbon nanotubes.

[0360]

[12] : The bioelectrode composition according to

[10] or

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

[0361]

[13] : The bioelectrode composition according to any one of the above

[10] to

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

[0362]

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

[13] , further comprising an organic solvent as component (D).

[0363]

[15] : A bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, characterized in that the biocontact layer is a cured product of the bioelectrode composition according to any one of [1] to

[14] above.

[0364]

[16] : The bioelectrode according to

[15] above, characterized in that the conductive base material 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.

[0365]

[17] : A method for producing a bioelectrode having a conductive substrate and a biocontact layer formed on the conductive substrate, comprising applying a bioelectrode composition according to any one of [1] to

[14] above onto the conductive substrate and curing the composition to form the biocontact layer.

[0366]

[18] : A method for manufacturing a bioelectrode according to the above

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

[0367] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0368] 1...bioelectrode, 2...conductive substrate (conductive pattern), 3...biocontact layer, 4...conductive powder, 5...ionic resin (A), 6...resin (B), 7...biological body, 10: bioelectrode sample; 20: thermoplastic urethane film; 21: double-sided tape.

Claims

1. (A) a bioelectrode composition containing an ionic resin, The bioelectrode composition, characterized in that the component (A) contains a resin having a structure selected from the group consisting of ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

2. The bioelectrode composition according to claim 1, characterized in that the resin having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide has a chemical structure represented by the following general formula (1): 【Chemistry 1】 (In the formula, R １ is a trifluoromethyl group or a difluoromethyl group. ２ is a hydrogen atom, a linear, branched or cyclic alkyl or alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, or a halogen atom. m is an integer of 1 to 5, and n is an integer of 0 to 4. M ＋ is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

3. The bioelectrode composition according to claim 2, characterized in that the chemical structure represented by the general formula (1) is bonded to a resin selected from a resin polymerized from a monomer having a double bond, a silicone resin, and a polyurethane resin.

4. The resin having the chemical structure represented by the general formula (1) bonded thereto is a resin obtained by polymerizing a monomer having a double bond containing a repeating unit represented by the following general formula (2)-1, a silicone resin containing a repeating unit represented by the following general formula (2)-2-1, a silicone resin represented by the following general formula (2)-2-2, a silicone resin represented by the following general formula (2)-2-3, and a silicone resin containing a repeating unit represented by the following general formula (2)-2-4. The bioelectrode composition according to claim 3, characterized in that it is any one of a polyurethane resin having a repeating unit represented by the following general formula (2)-3-1, and a urethane resin having a terminal structure represented by the following general formula (2)-3-2. 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In the formula, R １ , R ２ , m, n, and M ＋ As mentioned above. ３ is a hydrogen atom or a methyl group. ４ X is a single bond, or a linear, branched or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms, which may have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group or a sulfonate ester group. １ represents a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate ester group; X ２ R is a linear, branched or cyclic alkylene group having 1 to 14 carbon atoms, an arylene group having 6 to 12 carbon atoms or a combination thereof, which may have an ether group, an ester group, a carbonyl group, a nitrogen atom, a sulfide group, a sulfonyl group or a sulfonate ester group. ５ ~R ８ R is a linear, branched or cyclic alkyl group having 1 to 66 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ９ R is a linear or branched alkyl group having 1 to 20 carbon atoms, which may have an ether group or an ester group. １０ , and R １２ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, which may have an oxygen atom; R １０ and R １２ Both of R cannot be single bonds. １１ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a hydroxyl group or an ether group. １０ ~R １２ and the carbon atom to which they are attached may combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may contain an aromatic ring and / or a heteroatom. ３ is a single bond, a carbonyl group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, which may have an aromatic group; R １１ may be bonded to form a ring, and the ring may be an aromatic ring. a1 represents the ratio of repeating units, and is 0<a1≦1.

0. a2-1 and a2-3 represent the ratios of repeating units, and are 0<a2-1≦1.0 and 0<a2-3≦1.

0. a2-2 represents the number of repeats, and is a number of 0 or more. a3 represents the number of repetitions and is a number greater than 0.

5. The component (A) is ＋ 3. The bioelectrode composition according to claim 2, characterized in that it contains an ammonium ion represented by the following general formula (3) as the cation: 【Chemistry 9】 (In the formula, R １０１ｄ , R １０１ｅ , R １０１ｆ , and R １０１ｇ R each represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 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 groups selected from an ether group, a carbonyl group, an ester group, a hydroxy group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. １０１ｄ and R １０１ｅ , R １０１ｄ and R １０１ｅ and R １０１ｆ may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R １０１ｄ and R １０１ｅ and R １０１ｄ and R １０１ｅ and R １０１ｆ is an alkylene group having 3 to 10 carbon atoms, or forms a heteroaromatic ring having the nitrogen atom in the ring.

6. 2. The bioelectrode composition according to claim 1, further comprising a resin as component (B) which is different from the ionic resin as component (A).

7. 7. The bioelectrode composition according to claim 6, wherein the component (B) is at least one selected from the group consisting of silicone resins, (meth)acrylate resins, and urethane resins.

8. 7. The bioelectrode composition according to claim 6, wherein the resin as component (B) has adhesive properties.

9. The component (B) further includes R ｘ SiO （４－ｘ）／２ units (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.5) and SiO ２ 8. The bioelectrode composition according to claim 7, which contains a silicone resin having a unit.

10. 7. The bioelectrode composition according to claim 6, further comprising carbon powder and / or metal powder as component (C).

11. 11. The bioelectrode composition according to claim 10, wherein the carbon powder is either or both of carbon black and carbon nanotubes.

12. 11. The bioelectrode composition according to claim 10, wherein the metal powder is selected from the group consisting of gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

13. 13. The bioelectrode composition according to claim 12, wherein the metal powder is silver powder.

14. 7. The bioelectrode composition according to claim 6, further comprising an organic solvent as component (D).

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

16. The bioelectrode according to claim 15, characterized in that the conductive base material 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, comprising applying a bioelectrode composition according to any one of claims 1 to 14 onto the conductive substrate and curing the composition to form the biocontact layer.

18. The method for manufacturing a bioelectrode according to claim 17, characterized in that the conductive base material 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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