Biological electrode composition, biological electrode, and method for manufacturing biological electrode

Abstract

The invention relates to a biological electrode composition, a biological electrode, and a method for manufacturing the biological electrode. The purpose of the present invention is to provide: a biological electrode composition capable of forming a biological contact layer for a biological electrode, said biological contact layer having excellent electrical conductivity and biological suitability, being lightweight, being capable of being manufactured at low cost, being soft and having excellent elasticity and adhesiveness, and being free from a significant decrease in electrical conductivity even if the biological contact layer is dried even if the biological contact layer is wetted with water; a biological electrode in which a biological contact layer is formed using the biological electrode composition; and a method for producing the biological electrode. A bioelectrode composition containing (A) an ionic resin, the bioelectrode composition being 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.

Description

Technical Field

[0001] The present invention relates to a biological electrode that contacts the skin of a living body and can detect body conditions such as heart rate by using electrical signals from the skin, a method for manufacturing the same, and a biological electrode composition suitable for the biological electrode. Background Art

[0002] In recent years, with the popularization of IoT (Internet of Things), the development of wearable devices has also progressed. Clocks and glasses that can be connected to the Internet are representative examples. In addition, in the medical field and sports field, there is also a need for wearable devices that can monitor the body's condition at any time, which is a field with future growth potential.

[0003] In the medical field, for example, some people are studying wearable devices that monitor the status of body organs by sensing weak currents, such as electrocardiogram measurement, which uses electrical signals to sense heartbeats. Electrocardiogram measurement is performed by installing electrodes coated with conductive paste on the body, but this is a short-term measurement that is only performed once. In contrast, the development of medical wearable devices such as the above is aimed at developing devices that monitor health status at any time for several weeks. Therefore, for biological electrodes used in medical wearable devices, it is required that there will be no changes in conductivity and no skin allergies even when used for a long time. In addition, it is also required to be lightweight and able to be manufactured at a low cost.

[0004] There are two types of medical wearable devices: those that are attached to the body and those that are incorporated into clothing. As for the type that is attached to the body, a biological electrode using a water-soluble gel containing water and electrolytes as the material of the above-mentioned conductive paste has been proposed (Patent Document 1). Regarding the water-soluble gel, sodium, potassium, and calcium are contained as electrolytes in a water-soluble polymer for retaining water, which 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 cloth having a conductive polymer such as PEDOT-PSS (Poly-3,4-ethylenedioxythiophene-Polystyrenesulfonate) and a silver paste incorporated into the fiber 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 will disappear when the water disappears due to drying. On the other hand, when using metals with a high tendency to dissociate such as copper, there is a risk of causing skin allergies in some people. When using conductive polymers such as PEDOT-PSS, there is also a risk of causing skin allergies due to the strong acidity of the conductive polymer, and the conductive polymer may peel off from the fiber during washing.

[0006] In addition, metal nanowires, carbon black, and carbon nanotubes have excellent electrical conductivity, so some people have explored using them as electrode materials (Patent Documents 3, 4, 5). Metal nanowires have a high probability of contact between the wires, so a small amount of addition can be energized. However, metal nanowires are fine materials with pointed front ends, so they can cause skin allergies. As mentioned above, even if the material itself does not cause an allergic reaction, it may sometimes cause biocompatibility to deteriorate due to the shape and irritation of the material, and it is difficult to have both conductivity and biocompatibility.

[0007] It is believed that the conductivity of metal films is very high, so they will function as excellent biological electrodes, but this is not necessarily the case. The current released from the skin due to the beating of the heart is not just a weak current, but also sodium ions, potassium ions, and calcium ions. Therefore, the concentration change of ions must be converted into current, but precious metals that are not easy to dissociate are not efficient in converting ions from the skin into current. Therefore, the impedance of biological electrodes using precious metals is high, and the current passing through the skin is high resistance.

[0008] On the other hand, some people have studied batteries that add ionic liquids (Patent Document 6). Ionic liquids have high thermal stability, chemical stability and excellent conductivity, and their application in battery applications is becoming more and more widespread. However, as shown in Patent Document 6, ionic liquids with small molecular weights are soluble in water. Therefore, if biological electrodes to which they are added are used, the ionic liquids will be extracted by sweat from the skin, not only reducing conductivity, but also penetrating into the skin and causing skin roughness.

[0009] In addition, some people have studied batteries using lithium salts of polymer-type sulfonyl imide (Non-Patent Document 1). However, lithium has high ion mobility and can be used in batteries, but it is not a material with biocompatibility. In addition, some people have studied lithium salts of fluorosulfonic acid suspended in polysilicone (Non-Patent Document 2).

[0010] Some people have proposed a solution of biological electrode materials mixed with ionic polymers in polysilicone adhesives (Patent Documents 7, 8). They not only have high ionic conductivity, but also have high electronic conductivity when conductive powders such as carbon and silver are added, so they act as excellent biological electrodes. By combining a polysilicone adhesive with low skin allergy, high water repellency, and the effect of suppressing itching and skin redness after peeling with an ionic polymer with high ionic conductivity and that does not pass through the skin, it is possible to obtain stable biological signals even if it is attached for a long time during daily bathing and exercise without peeling, but it is more sought to improve the comfort during long-term attachment and wearing.

[0011] Here, the health effects of perfluoroalkyl compounds (PFAS) have been criticized, and European REACH is tending to limit the manufacture and sale of PFAS compounds. Therefore, it is urgent to develop materials without PFAS structures.

[0012] Prior art literature

[0013] Patent Literature

[0014] [Patent Document 1] International Publication No. WO2013-039151 Pamphlet

[0015] [Patent Document 2] Japanese Patent Application Publication No. 2015-100673

[0016] [Patent Document 3] Japanese Patent Application Laid-Open No. 5-095924

[0017] [Patent Document 4] Japanese Patent Application Publication No. 2003-225217

[0018] [Patent Document 5] Japanese Patent Application Publication No. 2015-019806

[0019] [Patent Document 6] Japanese Patent Publication No. 2004-527902

[0020] [Patent Document 7] Japanese Patent Application Publication No. 2018-126496

[0021] [Patent Document 8] Japanese Patent Application Publication No. 2018-130533

[0022] Non-patent literature

[0023] [Non-patent document 1] J. Mater. Chem. A, 2016, 4, p10038-10069

[0024] [Non-patent document 2] J. of the Electrochemical Society, 150 (8) A1090-A1094 (2003) Summary of the invention

[0025] [Problems to be solved by the invention]

[0026] In order to solve the above-mentioned problems, the present invention aims to provide a biological electrode composition that can form a biological contact layer for a biological electrode that has excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, does not significantly reduce conductivity even when wetted or dried, is soft, has excellent stretchability and adhesion, a biological electrode with a biological contact layer formed by the biological electrode composition, and a manufacturing method thereof.

[0027] [Methods for solving problems]

[0028] In order to solve the above-mentioned problems, the present invention provides a biological electrode composition, which is a biological electrode composition containing (A) an ionic resin, wherein the aforementioned (A) component contains a resin having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0029] The biological electrode composition of the present invention can form a biological contact layer for a biological electrode that has excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, does not significantly reduce conductivity even when wetted or dried, and is soft, stretchable and has excellent adhesion.

[0030] Furthermore, 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).

[0031] [Chemistry 1]

[0032]

[0033] In the formula, R 1 is trifluoromethyl or difluoromethyl. 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 + It is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0034] In this case, the chemical structure represented by the general formula (1) is preferably bonded to a resin selected from a resin obtained by polymerizing a monomer having a double bond, a polysilicone resin, and a polyurethane resin.

[0035] In this case, the resin having the chemical structure represented by the general formula (1) is preferably a resin obtained by polymerizing a monomer having a double bond containing a repeating unit represented by the following general formula (2)-1, a polysilicone resin containing a repeating unit represented by the following general formula (2)-2-1, a polysilicone resin represented by the following general formula (2)-2-2, a polysilicone resin represented by the following general formula (2)-2-3, and a polysilicone 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.

[0036] [Chemistry 2]

[0037]

[0038] [Chemistry 3]

[0039]

[0040] [Chemistry 4]

[0041]

[0042] [Chemistry 5]

[0043]

[0044] [Chemistry 6]

[0045]

[0046] [Chemistry 7]

[0047]

[0048] [Chemistry 8]

[0049]

[0050] In the formula, R 1 , R 2 , m, n, and M + As above. 3 is a hydrogen atom or a methyl group. 4 is a single bond, or a linear, branched, or cyclic alkylene group or a divalent hydrocarbon group having 1 to 15 carbon atoms, and may also have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group, or a sulfonate group. X1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate group, and X2 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 bond thereof, and may also have an ether group, an ester group, a carbonyl group, a nitrogen atom, a thioether group, a sulfonyl group, or a sulfonate group. R 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 It 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, and the alkylene group may also have an oxygen atom, R 10 With R 12 It will not be a single bond at the same time. 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. 10 ~R 12The carbon atoms in the formula to which they are bonded may also combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may also contain an aromatic ring and / or a heteroatom. X3 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 also have an aromatic group, and may also bond with R 11 to form a ring, and the ring may also 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, 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.

[0051] In the present invention, such an ionic resin can be specifically used as the component (A).

[0052] Further, it is preferable that the component (A) contains an ammonium ion represented by the following general formula (3) as the aforementioned M + Preferably.

[0053] [Chemical formula 9]

[0054]

[0055] In the formula, R 101d , R 101e , R 101f , and R 101g are each 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 also have one or more selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. R 101d and R 101e , R 101d and R 101e and R 101f may also form a ring together with the nitrogen atom to which they are bonded. When forming a ring, R 101d and R 101e and R 101d and R 101e and R 101f are an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring in the formula. )

[0056] When the component (A) contains a resin having an ammonium salt structure, the ammonium ion may be such.

[0057] Further, it is preferable that the biological electrode composition of the present invention further contains a resin different from the ionic resin as the component (A) as the component (B).

[0058] By including such a component (B), the elution of the salt of the component (A) can be prevented and the adhesiveness can be further improved.

[0059] Furthermore, the component (B) is preferably at least one selected from silicone resins, (meth)acrylate resins, and urethane resins.

[0060] Furthermore, it is preferred that the resin as the component (B) has adhesiveness.

[0061] Furthermore, it may further contain R x SiO (4-x) / 2 The component (B) is a polysilicone resin having a unit (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 a SiO2 unit.

[0062] Specifically, the following resins can be used as the component (B).

[0063] Furthermore, the bioelectrode composition of the present invention preferably further contains carbon powder and / or metal powder as component (C).

[0064] By including such a component (C), the electrical conductivity can be further improved.

[0065] Furthermore, the carbon powder is preferably any one or both of carbon black and carbon nanotubes.

[0066] Furthermore, it is also desirable 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.

[0067] In this case, the metal powder is more preferably silver powder.

[0068] Specifically, such a conductivity enhancer can be used as the component (C).

[0069] Furthermore, the aforementioned bioelectrode composition preferably further contains an organic solvent as component (D).

[0070] By including such a component (D), coating properties can be further improved.

[0071] The present invention provides a biological electrode comprising a conductive substrate and a biological contact layer formed on the conductive substrate, wherein the biological contact layer is a hardened product of the biological electrode composition.

[0072] The biological electrode of the present invention is a biological electrode formed by a biological electrode composition that can form a biological contact layer for a biological electrode that has excellent conductivity and biocompatibility, is lightweight and can be manufactured at low cost, does not significantly reduce conductivity even when wetted or dried, and is soft, stretchable and has excellent adhesion.

[0073] In this case, the conductive substrate preferably contains one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

[0074] The biological electrode of the present invention can use such a conductive substrate.

[0075] Furthermore, the present invention provides a method for manufacturing a biological electrode, which is a method for manufacturing a biological electrode having a conductive substrate and a biological contact layer formed on the conductive substrate, by coating the above-mentioned biological electrode composition on the above-mentioned conductive substrate and curing it to form the above-mentioned biological contact layer.

[0076] The biological electrode of the present invention can be manufactured in this manner.

[0077] In this case, the conductive substrate preferably contains one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

[0078] The method for producing a biological electrode of the present invention can use such a conductive substrate.

[0079] [Effects of the Invention]

[0080] As described above, the biological electrode composition of the present invention can provide a biological electrode composition that can form a biological contact layer for a biological electrode that has excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, does not significantly reduce conductivity even when wetted or dried, is soft, and has excellent stretchability and adhesion, a biological electrode with a biological contact layer formed by the biological electrode composition, and a manufacturing method thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 This is a schematic cross-sectional view showing an example of the biological electrode of the present invention.

[0082] Figure 2 This is a schematic cross-sectional view showing an example of the biological electrode of the present invention being installed in a living body.

[0083] Figure 3 This is a schematic diagram of a bio-electro-printed body produced according to an embodiment of the present invention.

[0084] Figure 4 This is a schematic diagram showing a bioelectrode produced in an embodiment of the present invention cut out and attached with an adhesive layer and wires.

[0085] Figure 5This is a diagram showing the positions of electrodes attached to a human body and a ground when measuring a biological signal according to an embodiment of the present invention.

[0086] Figure 6 This is an electrocardiogram waveform obtained using the biological electrode of the embodiment of the present invention. DETAILED DESCRIPTION

[0087] As described above, we seek to develop a biological electrode composition that can form a biological contact layer for a biological electrode that has excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, is soft and stretchable and has strong adhesion, can be attached to the skin for a long time, can stably collect biological signals even when wetted by water or dried after taking a shower, and leaves no residue on the skin even after being peeled off from the skin; a biological electrode that forms a biological contact layer with the biological electrode composition; and a manufacturing method thereof.

[0088] Sodium, potassium, and calcium ions are released from the skin surface in conjunction with the heartbeat. The biological electrodes must convert the increase or decrease of ions released from the skin into electrical signals. Therefore, materials with excellent ion conductivity are required to transmit the increase or decrease of ions.

[0089] In order to attach to the skin and stably obtain biological signals, the biological electrode film needs to be soft, stretchable, and sticky. The epidermal keratin regenerates every day, and old keratin (scale) accumulates between the attached biological electrode film and the skin. The old keratin is easily peeled off from the epidermis, so the biological electrode will not be able to collect biological signals due to peeling. Therefore, the biological electrode must not lose its adhesion even if it is attached for a long time. On the other hand, if there is residue on the skin after peeling after long-term attachment, it is easy to cause rashes and rough skin.

[0090] If the acidity of the acid forming the neutralized salt is high, the ions will be strongly polarized and the ionic conductivity will increase. In the case of lithium-ion batteries, the lithium salts of bis(trifluoromethanesulfonyl)imidic acid and tris(trifluoromethanesulfonyl)methyl acid show high ionic conductivity for this reason. On the other hand, the state of the acid before becoming a neutralized salt has the problem that the higher the acid strength, the stronger the irritation of the salt to the organism. In other words, there is a trade-off between ionic conductivity and biological irritation. However, the salt used in biological electrodes must take into account both high ionic conductivity and low biological irritation.

[0091] The larger the molecular weight of the ionic compound, the lower the permeability to the skin and the lower the irritation to the skin. Therefore, the ionic compound is preferably a high molecular weight polymer. The inventors of the present application prepared the ionic compound into a form with a polymerizable double bond, polymerized it into a polymer, and bonded it with polysilicone, polyurethane, polyether, polyester, etc. to avoid the problem of irritation to the skin.

[0092] Furthermore, the inventors of the present application have found that by mixing the salt with a silicone-based, acrylic-based, or urethane-based adhesive (resin) and using the adhesive, the salt can adhere very closely to the skin and a stable electrical signal can be obtained for a long period of time.

[0093] That is, the present invention is a biological electrode composition, which is a biological electrode composition containing (A) an ionic resin, wherein the aforementioned (A) component contains a resin having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide.

[0094] The present invention is described in detail below, but the present invention is not limited thereto.

[0095] <Biological Electrode Composition>

[0096] The bioelectrode composition of the present invention is a bioelectrode composition containing (A) an ionic resin, wherein the component (A) contains a resin having a structure selected from ammonium salts, lithium salts, sodium salts, potassium salts, and silver salts of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide. Each component is described in more detail below.

[0097] [(A) Ionic resin]

[0098] (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.

[0099] The resin (ionic 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 (partial structure) represented by the following general formula (1).

[0100] [Chemistry 10]

[0101]

[0102] In the formula, R 1 is trifluoromethyl or difluoromethyl. 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 + It is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0103] In this case, the chemical structure represented by the general formula (1) is preferably bonded to a resin selected from a resin obtained by polymerizing a monomer having a double bond, a polysilicone resin, and a polyurethane resin.

[0104] The above-mentioned resin bonded with the chemical structure represented by the general formula (1) is preferably a resin obtained by polymerizing a monomer having a double bond containing a repeating unit represented by the following general formula (2)-1, a polysilicone resin containing a repeating unit represented by the following general formula (2)-2-1, a polysilicone resin represented by the following general formula (2)-2-2, a polysilicone resin represented by the following general formula (2)-2-3, and a polysilicone 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.

[0105] [Chemistry 11]

[0106]

[0107] [Chemistry 12]

[0108]

[0109] [Chemistry 13]

[0110]

[0111] [Chemistry 14]

[0112]

[0113] [Chemistry 15]

[0114]

[0115] [Chemistry 16]

[0116]

[0117] [Chemistry 17]

[0118]

[0119] In the formula, R 1 , R 2 , m, n, and M + As above. 3 is a hydrogen atom or a methyl group. 4 is a single bond, or a linear, branched, or cyclic alkylene group or a divalent hydrocarbon group having 1 to 15 carbon atoms, and may also have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group, or a sulfonate group. X1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate group, and X2 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 bond thereof, and may also have an ether group, an ester group, a carbonyl group, a nitrogen atom, a thioether group, a sulfonyl group, or a sulfonate group. R5 ~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 also 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 also have an oxygen atom, and R 10 and R 12 will not both be a single bond at the same time. R 11 is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms and may also have a hydroxyl group or an ether group. Or R 10 ~R 12 and the carbon atoms in the formula to which they are bonded may also combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may also contain an aromatic ring and / or a heteroatom. X3 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 also have an aromatic group, and may also bond with R 11 to form a ring, and the ring may also be an aromatic ring. a1 represents the ratio of the repeating unit, and 0 < a1 ≤ 1.0. a2-1 and a2-3 represent the ratios of the 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.

[0120] [Resin polymerized from monomers having double bonds]

[0121] In order to obtain the monomer of the repeating unit a1 represented by the above general formula (2)-1, it is represented by the following general formula (2)-1-1.

[0122] [Chemical formula 18]

[0123]

[0124] In the general formula, R 1 ~R 4 , X1, M + , m, n are as described above.

[0125] Regarding the monomer represented by the above general formula (2)-1-1, specifically, the following can be listed.

[0126] [Chemical formula 19]

[0127]

[0128] [Chemical formula 20]

[0129]

[0130] [Chemical formula 21]

[0131]

[0132] [Chemistry 22]

[0133]

[0134] [Chemistry 23]

[0135]

[0136] [Chemistry 24]

[0137]

[0138] [Chemistry 25]

[0139]

[0140] [Chemistry 26]

[0141]

[0142] [Chemistry 27]

[0143]

[0144] [Chemistry 28]

[0145]

[0146] In the formula, R 3 , M as described above.

[0147] In addition, the component (A) contains an ammonium ion (ammonium cation) represented by the following general formula (3) as M in the repeating unit a (repeating unit a1): + Better.

[0148] [Chemistry 29]

[0149]

[0150] In the formula, R 101d , R 101e , R 101f , R 101g Each 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 selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d With R 101e , R 101d With R 101e With R101f They can also form a ring with the nitrogen atom to which they are bonded. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0151] Specific examples of the ammonium ion represented by the general formula (3) include the following.

[0152] [Chemistry 30]

[0153]

[0154] [Chemistry 31]

[0155]

[0156] [Chemistry 32]

[0157]

[0158] [Chemistry 33]

[0159]

[0160] [Chemistry 34]

[0161]

[0162] [Chemistry 35]

[0163]

[0164] [Chemistry 36]

[0165]

[0166] [Chemistry 37]

[0167]

[0168] [Chemistry 38]

[0169]

[0170] [Chemistry 39]

[0171]

[0172] [Chemistry 40]

[0173]

[0174] [Chemistry 41]

[0175]

[0176] [Chemistry 42]

[0177]

[0178] [Chemistry 43]

[0179]

[0180] [Chemistry 44]

[0181]

[0182] [Chemistry 45]

[0183]

[0184] The ammonium ion represented by the general formula (3) is preferably a tertiary or quaternary ammonium ion.

[0185] (Repeating unit b1)

[0186] In the component (A) of the biological electrode composition of the present invention, in addition to the above-mentioned repeating unit a1 polymerized with a monomer having a polymerizable double bond, a repeating unit b1 having an ethylene glycol dimethyl ether chain may be copolymerized to improve conductivity. The monomers for obtaining the repeating unit b1 having an ethylene glycol dimethyl ether chain are specifically listed below. By copolymerizing the repeating unit having an ethylene glycol dimethyl ether chain, the ions released from the skin can be helped to move within the dry electrode film, thereby improving the sensitivity of the dry electrode.

[0187] [Chemistry 46]

[0188]

[0189] [Chemistry 47]

[0190]

[0191] [Chemistry 48]

[0192]

[0193] [Chemistry 49]

[0194]

[0195] R is a hydrogen atom or a methyl group.

[0196] (Repeating unit c1)

[0197] In the component (A) of the biological electrode composition of the present invention, in addition to the above-mentioned repeating units a1 and b1, in order to improve the conductivity, 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 a sulfonic acid, or a potassium salt of a sulfonic acid may be copolymerized. The monomers for obtaining the hydrophilic repeating unit c1 are specifically listed below. By adding these repeating units containing hydrophilic groups, the sensitivity of the ions released from the skin can be improved, and the sensitivity of the dry electrode can be improved.

[0198] [Chemistry 50]

[0199]

[0200] [Chemistry 51]

[0201]

[0202] [Chemistry 52]

[0203]

[0204] R is a hydrogen atom or a methyl group.

[0205] The component (A) of the bioelectrode composition of the present invention may contain a repeating unit d1 that imparts adhesion.

[0206] To obtain the monomer of the repeating unit d1, specifically, the following can be mentioned.

[0207] [Chemistry 53]

[0208]

[0209] [Chemistry 54]

[0210]

[0211] [Chemistry 55]

[0212]

[0213] [Chemistry 56]

[0214]

[0215] [Chemistry 57]

[0216]

[0217] A crosslinkable repeating unit e1 may be further copolymerized. The crosslinkable repeating unit is, for example, a repeating unit having an oxirane ring or an oxetane ring.

[0218] Specific examples of monomers for obtaining the repeating unit e1 having an oxirane ring or an oxetane ring include the following.

[0219] [Chemistry 58]

[0220]

[0221] [Chemistry 59]

[0222]

[0223] Here, R is a methyl group or a hydrogen atom.

[0224] The component (A) of the bioelectrode composition of the present invention may have a repeating unit f1 containing silicon in addition to the repeating units selected from the above a1, b1, c1, d1, and e1. Specifically, the following are exemplified.

[0225] [Chemistry 60]

[0226]

[0227] [Chemistry 61]

[0228]

[0229] The repeating unit having an alkoxysilyl group may be copolymerized and the alkoxysilyl group may be hydrolyzed to form a silsesquioxane structure as disclosed in Japanese Unexamined Patent Application Publication No. 2022-164579, or may be reacted with silanol on the surface of silica to form silica as disclosed in Japanese Unexamined Patent Application Publication No. 2022-64291.

[0230] The component (A) of the bioelectrode composition of the present invention may have a repeating unit g1 containing fluorine in addition to the repeating unit selected from the above a1 and b1 to f1.

[0231] Specific examples of monomers for obtaining the repeating unit g1 having fluorine include the following.

[0232] [Chemistry 62]

[0233]

[0234] [Chemistry 63]

[0235]

[0236] [Chemistry 64]

[0237]

[0238] [Chemistry 65]

[0239]

[0240] [Chemistry 66]

[0241]

[0242] [Chemistry 67]

[0243]

[0244] [Chemistry 68]

[0245]

[0246] Here, R is a hydrogen atom or a methyl group.

[0247] The component (A) of the bioelectrode composition of the present invention may have a repeating unit h1 having a cyano group in addition to the repeating unit selected from the above a1 and b1 to g1.

[0248] Specific examples of monomers for obtaining the repeating unit h1 having a cyano group include the following.

[0249] [Chemistry 69]

[0250]

[0251] [Chemistry 70]

[0252]

[0253] [Chemistry 71]

[0254]

[0255] [Chemistry 72]

[0256]

[0257] Here, R is a hydrogen atom or a methyl group.

[0258] The component (A) of the bioelectrode composition of the present invention may have a repeating unit i1 having a nitro group in addition to the repeating units selected from a1 and b1 to h1.

[0259] Specific examples of monomers for obtaining the repeating unit i1 having a nitro group include the following.

[0260] [Chemistry 73]

[0261]

[0262] [Chemistry 74]

[0263]

[0264] [Chemical Formula 75]

[0265]

[0266] [Chemical Formula 76]

[0267]

[0268] [Chemical Formula 77]

[0269]

[0270] [Chemical Formula 78]

[0271]

[0272] Here, R is a hydrogen atom or a methyl group.

[0273] As one method of the ionic resin (polymer compound) containing a1 having a polymerizable double bond as the component (A), for example, a method of obtaining a copolymer polymer compound by heating and polymerizing the desired monomers among the monomers giving the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 in an organic solvent with a radical polymerization initiator added.

[0274] The organic solvents used in the polymerization include, for example, toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, etc. The polymerization initiators include, for example, 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.

[0275] Here, the ratios of the repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 in the ionic resin of the 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.

[0276] Furthermore, for example: a1+b1+c1+d1+e1+f1+g1+h1+i1=1, means that in the polymer compound containing repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1, the total amount of repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 is 100 mol% relative to the total amount of all repeating units; a1+b1+c1+d1+e1+f1+g1+h1+i1<1, means that the total amount of repeating units a1, b1, c1, d1, e1, f1, g1, h1, i1 is less than 100 mol% relative to the total amount of all repeating units and the polymer compound contains other repeating units in addition to a1, b1, c1, d1, e1, f1, g1, h1, i1.

[0277] The molecular weight of the ionic resin containing a1 having a polymerizable double bond in the component (A) is preferably 500 or more in terms of 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 ionic monomer (residual monomer) of the ionic resin that is not incorporated into the component (A) after polymerization is small, there is no risk of it penetrating into the skin and causing allergies in the biological suitability test, so it is better to reduce the amount of residual monomer. The amount of residual monomer is preferably 10 parts by mass or less relative to 100 parts by mass of the ionic resin before the condensation reaction of the component (A). In addition, the component (A) can be used alone or as a mixture of two or more types having different molecular weights, dispersities, and polymerizable monomers.

[0278] [Silicone resin]

[0279] Specific examples of the repeating unit a2-1 represented by the general formula (2)-2-1 include the following.

[0280] [Chemistry 79]

[0281]

[0282] [Chemistry 80]

[0283]

[0284] [Chemistry 81]

[0285]

[0286] [Chemistry 82]

[0287]

[0288] [Chemistry 83]

[0289]

[0290] Here, M + As mentioned above.

[0291] (Repeating unit b2)

[0292] The component (A) of the bioelectrode composition of the present invention may have, in addition to the repeating unit a2-1, a repeating unit b2 having an ethylene glycol dimethyl ether chain in order to improve conductivity. The repeating unit b2 is specifically described in paragraphs 0068 and 0069 of Japanese Patent Application Laid-Open No. 2020-851.

[0293] (Repeating unit c2)

[0294] The component (A) of the biological electrode composition of the present invention may have repeating units a2-1 and b2 as described above, and may further have repeating units c2 having hydrogen atoms, alkyl groups, or aryl groups in order to improve the miscibility with the resin of the component (B). The alkyl group and the aryl group may also have hydroxyl groups, halogen atoms, ester groups, ether groups, carboxyl groups, thiol groups, (meth) acrylic acid groups, cyano groups, and nitro groups. The repeating unit c2 may specifically be those described in paragraph 0071 of Japanese Patent Application Laid-Open No. 2020-851.

[0295] One of the methods for synthesizing the polysilicone compound of the a2-1 unit of component (A) is to obtain the polysilicone compound by hydrosilylation of a sulfonamide salt having a double bond and a polysilicone compound having a Si-H group in the presence of a platinum catalyst. In order to obtain the repeating unit b2, the polysilicone compound having a double bond and an ether group and a polysilicone compound having a Si-H group can be hydrosilylated in the presence of a platinum catalyst. The a2-1 unit and the b2 and c2 units can be present simultaneously in the polysilicone 1 molecule, or polysilicone compounds having the a2-1 unit and the b2 and c2 units can be mixed. 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。

[0296] The polysiloxane compound before hydrosilylation may be in a chain, branched or cyclic shape, but is preferably a high molecular weight compound with a molecular weight of 300 to 1,000,000. Sulfonamide salts can be suspended in high molecular weight polysiloxane to prevent them from passing through the skin and causing allergies.

[0297] In addition, regarding the component (A), a sulfonamide salt having a double bond and a polysiloxane compound having a Si—H group at the terminal can be subjected to a hydrosilylation reaction in the presence of a platinum catalyst to obtain a polysiloxane compound represented by the general formula (2)-2-2 or (2)-2-3 having a sulfonamide salt at the terminal. The reaction conditions are as described above.

[0298] The terminal part of the polysiloxane compound represented by the above general formula (2)-2-2 and (2)-2-3 is specifically as follows.

[0299] [Chemistry 84]

[0300]

[0301] [Chemistry 85]

[0302]

[0303] [Chemistry 86]

[0304]

[0305] [Chemistry 87]

[0306]

[0307] [Chemistry 88]

[0308]

[0309] Here, * is the bonding position with the polysilicone polymer, M + As mentioned above.

[0310] The component (A) may be a silsesquioxane having a three-dimensional ladder structure containing a repeating unit a2-3 represented by the general formula (2)-2-4. Specific examples of the structure of the repeating unit a2-3 are as follows.

[0311] [Chemistry 89]

[0312]

[0313] [Chemistry 90]

[0314]

[0315] [Chemistry 91]

[0316]

[0317] [Chemistry 92]

[0318]

[0319] [Chemistry 93]

[0320]

[0321] Here, M + As mentioned above.

[0322] (Repeating unit b3)

[0323] The component (A) of the bioelectrode composition of the present invention may have, in addition to the above-mentioned repeating units a2-3, a repeating unit b3 having an ethylene glycol dimethyl ether chain in order to improve conductivity. The repeating unit b3 may specifically be those described in paragraphs 0069 and 0070 of Japanese Patent Application Laid-Open No. 2020-6069.

[0324] (Repeating unit c3)

[0325] The component (A) of the biological electrode composition of the present invention may have repeating units a2-3 and b3 as described above, and may further have repeating units c3 having hydrogen atoms, alkyl groups, or aryl groups in order to improve the miscibility with the resin of the component (B). The alkyl group and the aryl group may also have hydroxyl groups, halogen atoms, ester groups, ether groups, carboxyl groups, thiol groups, (meth) acrylic acid groups, cyano groups, and nitro groups. The repeating unit c3 is specifically described in paragraphs 0072 and 0073 of Japanese Patent Application Laid-Open No. 2020-6069.

[0326] [Urethane resin]

[0327] The polyurethane 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 the following general formula (2)-3-1-1 with a compound having an isocyanate group.

[0328] [Chemistry 94]

[0329]

[0330] In the formula, R 1 , R 2 , R 4 , R 10 ~R 12 , X3, M + , m, n are as described above.

[0331] Specific examples of the monomer having a dihydroxy group of the general formula (2)-3-1-1 include the following.

[0332] [Chemistry 95]

[0333]

[0334] [Chemistry 96]

[0335]

[0336] [Chemistry 97]

[0337]

[0338] [Chemistry 98]

[0339]

[0340] [Chemistry 99]

[0341]

[0342] [Chemical 100]

[0343]

[0344] [Chemistry 101]

[0345]

[0346] [Chemistry 102]

[0347]

[0348] [Chemistry 103]

[0349]

[0350] [Chemistry 104]

[0351]

[0352] As for the synthesis method of the above-mentioned dihydroxy-containing sulfonamide salt, sulfonamide can be synthesized by the method described in paragraph 177 of Japanese Patent Application Laid-Open No. 2022-078861, and then neutralized and ion-exchanged with ammonium hydroxide, ammonium chloride, sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride, silver hydroxide, silver chloride, silver nitrate, etc.

[0353] 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. The compound having an isocyanate group is exemplified in paragraphs 0067 and 0068 of Japanese Patent Application Laid-Open No. 2020-55300.

[0354] Isocyanate compounds and hydroxyl-containing compounds have high reactivity, so it is sometimes difficult to control. In addition, isocyanate compounds may react with moisture in the atmosphere during storage to deactivate the isocyanate group, so sufficient care must be taken to prevent humidity during storage. Therefore, in order to prevent these situations, a compound having a blocked isocyanate group in which the isocyanate group is protected by a substituent is sometimes used.

[0355] The blocked isocyanate group is one that is deprotected to an isocyanate group by heating, and specifically includes an isocyanate group substituted with alcohol, phenol, thiol, imine, ketimine, amine, lactam, pyrazole, oxime, β-diketone, or the like.

[0356] In order to lower the deprotection temperature of the blocked isocyanate group, a catalyst may be added. As such a catalyst, organic tin such as dibutyltin dilaurate, bismuth salts, zinc carboxylates such as zinc 2-ethylhexanoate and zinc acetate are known.

[0357] In particular, Japanese Patent Application Laid-Open No. 2012-152725 discloses that the deprotection reaction can be lowered in temperature by containing an α,β-unsaturated carboxylic acid zinc as a blocked isocyanate dissociation catalyst in the carboxylic acid.

[0358] A compound having a hydroxyl group other than the monomer of the general formula (2)-3-1-1 may be copolymerized. Compounds having a hydroxyl group other than the monomer of the general formula (2)-3-1-1 are disclosed, for example, in paragraphs 0054 to 0064 and 0077 to 0082 of Japanese Patent Application Laid-Open No. 2020-55300.

[0359] In order to promote the urethane bond formation reaction during the polymerization of polyurethane, it is preferred to add a catalyst as needed.

[0360] The urethanization catalyst can be appropriately selected from known catalysts, for example, amine catalysts, ammonium salt catalysts, potassium salt catalysts, organic metal catalysts and the like.

[0361] Amine catalysts, for example: 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-hydroxy 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, 1-(2-hydroxyethyl ...

[0362] Ammonium salt catalysts, for example, quaternary ammonium salts such as tetraethylhydroxyl ammonium, ammonium salts composed of 1,8-diazabicyclo(5,4,0)-undec-7-ene or 1,5-diazabicyclo(4,3,0)-non-5-ene and octanoic acid, oleic acid, p-toluenesulfonic acid, formic acid, phenolic acid, phthalic acid, acetic acid, maleic acid or boric acid, etc.

[0363] Potassium salt catalysts, such as potassium carbonate, potassium acetate, potassium octoate, etc.

[0364] Organic metal catalysts, for example: organic tin compounds such as tin acetate, tin octanoate (2-ethylhexanoate tin), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dithiol, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiol, dioctyltin dilaurate, dibutyltin dichloride, etc., organic lead compounds such as lead octanoate and lead naphthenate, organic nickel compounds such as nickel naphthenate, for example: organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenate, organic bismuth compounds such as bismuth octanoate and bismuth neodecanoate, etc.

[0365] 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 in the range of 0.1 to 2 parts by mass, relative to 100 parts by mass of the total amount of the polyurethane constituent components.

[0366] In addition, the component (A) may be a resin having a sulfonamide salt bonded to a carbamate group and having a terminal, 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.

[0367] [Chemistry 105]

[0368]

[0369] R 1 , R 2 , R 4 , X3, M + , m, n are as described above.

[0370] The compound having an isocyanate group is, for example, a polyurethane compound obtained by reacting the aforementioned compound or a compound having an isocyanate group with a compound having a dihydroxy group to form an isocyanate group at the end. The reaction conditions are as described above.

[0371] In the bioelectrode composition of the present invention, the amount of component (A) is not particularly limited. For example, the amount of component (A) is preferably 1 to 95 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the total amount of the composition. In the bioelectrode composition of the present invention, the amount of component (A) is preferably 0.1 to 300 parts by mass, more preferably 1 to 200 parts by mass, relative to 100 parts by mass of component (B) described later. Component (A) may be used alone or in combination of two or more.

[0372] [(B) Resin]

[0373] The (B) resin blended into the biological electrode composition of the present invention is a component that is compatible with the ionic resin of the above-mentioned (A) component to prevent the dissolution of salts, and retains the conductivity enhancers such as metal powder, carbon powder, silicon powder, lithium titanate powder, etc., to further improve the adhesion. When the ionic resin of the (A) component has already imparted sufficient adhesion, the (B) resin is not necessary. In addition, the resin can be any resin other than the above-mentioned (A) component, and is preferably any one of a thermosetting resin and a photocuring resin, or both of them, and is particularly preferably selected from one or more of the resins of the silicone series, acrylic series, and urethane series.

[0374] As the adhesive silicone resin, for example, an addition reaction curing type or a free radical crosslinking reaction curing type can be used. For the addition reaction curing type, for example, a diorganosiloxane containing an alkenyl group, a R3SiO 0.5 and SiO2 units, an organohydrogen polysiloxane having multiple SiH groups, a platinum catalyst, an addition reaction control agent, and an organic solvent. In addition, the free radical crosslinking reaction curing type, for example, can use a diorganopolysiloxane containing an optionally alkenyl group, a R3SiO 0.5 and MQ resins containing SiO2 units, organic peroxides, and organic solvents. Here, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0375] Alternatively, a polysiloxane / resin integrated compound formed by condensing a polysiloxane having silanols at the polymer end or side chain with an MQ resin may be used. MQ resin contains many silanols, so by adding the MQ resin, the adhesion is improved, but since it is not cross-linked, it does not form a molecular bond with the polysiloxane. By integrating the polysiloxane and the resin as described above, the adhesion can be increased.

[0376] Furthermore, the polysilicone resin may be added with a modified siloxane having a group selected from an amino group, an oxirane group, an oxetane group, a polyether group, a hydroxyl group, a carboxyl group, a mercapto group, a methacrylic group, an acrylic group, a phenol group, a silanol group, a carboxylic anhydride group, an aryl group, an aralkyl group, an amide group, an ester group, and a lactone ring. By adding the modified siloxane, the dispersibility of the component (A) in the polysilicone resin is improved. The modified siloxane may be a siloxane having one end, both ends, or a side chain modified.

[0377] The adhesive acrylic resin may be, for example, one having a hydrophilic (meth)acrylate or a long-chain hydrophobic (meth)acrylate as a repeating unit as described in Japanese Patent Application Laid-Open No. 2016-011338. Depending on the situation, a (meth)acrylate having a functional group or a (meth)acrylate having a siloxane bond may be copolymerized.

[0378] As the adhesive urethane-based resin, for example, those having a urethane bond, a polyether bond, a polyester bond, a polycarbonate bond, or a siloxane bond as described in Japanese Patent Application Laid-Open No. 2016-065238 can be used.

[0379] Furthermore, in order to prevent the (A) component from falling off from the biological contact layer and causing a decrease in conductivity, in the biological electrode composition of the present invention, it is preferred that the (B) resin has high compatibility with the above-mentioned (A) component. Furthermore, in order to prevent the biological contact layer from peeling off from the conductive substrate, in the biological electrode composition of the present invention, it is preferred that the (B) resin has high adhesion to the conductive substrate. In order to make the compatibility of the resin with the conductive substrate and the salt high, it is effective to use a resin with high polarity. Such a resin, for example, has one or more selected from ether bonds, ester bonds, amide bonds, imide bonds, carbamate bonds, thiol bonds, and thiol groups, or polyacrylic resins, polyamide resins, polyimide resins, polyurethane resins, and polythiocarbamate resins. Furthermore, on the other hand, the biological contact layer will contact the biological body, so it is easily affected by the sweat from the biological body. Therefore, in the biological electrode composition of the present invention, it is preferred that the (B) resin has high water repellency and is not easily hydrolyzed. In order to make the resin highly water-repellent and less susceptible to hydrolysis, it is effective to use a resin containing silicon.

[0380] Polyacrylic resins containing silicon atoms include polymers with polysiloxane in the main chain and polymers with silicon atoms in the side chain, and both can be used ideally. For polymers with polysiloxane in the main chain, siloxane or silsesquioxane with (meth)acrylic propyl groups can be used. At this time, by adding a photo-radical generator, the (meth)acrylic acid can be partially polymerized and hardened.

[0381] The polyamide resin containing silicon atoms may be preferably polyamide polysilicone resins described in Japanese Patent Application Publication No. 2011-079946 and U.S. Patent No. 5981680. Such polyamide polysilicone resins may be synthesized by combining polysilicone having amino groups at both ends or non-polysilicone compounds having amino groups at both ends with non-polysilicone having carboxyl groups at both ends or polysilicone having carboxyl groups at both ends.

[0382] Alternatively, polyamic acid obtained by reacting carboxylic anhydride with amine before cyclization may be used. The carboxyl groups of polyamic acid may be crosslinked using epoxy or oxetane crosslinking agents, or the (meth)acrylate moiety may be crosslinked by photoradical reaction of the carboxyl groups with hydroxyethyl (meth)acrylate.

[0383] As the polyimide resin containing silicon atoms, for example, the polyimide polysilicone resin described in Japanese Patent Application Laid-Open No. 2002-332305 can be preferably used. The viscosity of the polyimide resin is very high, but the viscosity can be reduced by blending a (meth)acrylic monomer as a solvent and a crosslinking agent.

[0384] Polyurethane resins containing silicon atoms include polyurethane polysiloxane resins. Such polyurethane polysiloxane resins can be cross-linked by a carbamate bond by mixing and heating a compound having an isocyanate group at both ends and a compound having a hydroxyl group at the end. Again, in this case, it is necessary to make the compound having an isocyanate group at both ends or the compound having a hydroxyl group at the end contain a silicon atom (siloxane bond). Or as described in Japanese Patent Publication No. 2005-320418, polysiloxane can be mixed with a carbamate (meth) acrylate monomer and photo-crosslinked. Again, a polymer having both a siloxane bond and a carbamate bond and having a (meth) acrylate group at the end can also be photo-crosslinked. In particular, the side chain attached siloxane chain and the main chain of the material of polyurethane recorded in Japanese Patent Publication No. 2018-123304 and the same 2019-70109 Publication have high strength and high elasticity, so it is ideal.

[0385] The polythiourethane resin containing silicon atoms can be obtained by the reaction of a compound containing a thiol group and a compound containing an isocyanate group, and any of them may contain silicon atoms. In addition, if a (meth)acrylate group is present at the terminal, it can also be photocured.

[0386] In the polysiloxane resin, in addition to adding the above-mentioned diorganosiloxane having alkenyl groups, R3SiO 0.5The MQ resin having SiO2 units and the organohydrogenpolysiloxane having multiple SiH groups can improve the compatibility with the above-mentioned salts by further adding a modified siloxane having a group selected from amino, oxirane, oxetane, polyether, hydroxyl, carboxyl, mercapto, methacrylate, acrylic, phenol, silanol, carboxylic anhydride, aryl, arylalkyl, amide, ester and lactone ring.

[0387] Diorganosiloxanes having alkenyl groups and organohydrogenpolysiloxanes having multiple SiH groups can be cross-linked by an addition reaction using a platinum catalyst.

[0388] Platinum catalysts include, for example, platinum-based catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohols, reaction products of chloroplatinic acid and olefin compounds, reaction products of chloroplatinic acid and vinyl-containing siloxanes, platinum-olefin complexes, platinum-vinyl-containing siloxane complexes, and platinum-based metal catalysts such as rhodium complexes and ruthenium complexes. In addition, those in which these catalysts are dissolved / dispersed in alcohol-based, hydrocarbon-based, and siloxane-based solvents may be used.

[0389] The amount of the platinum catalyst added is preferably in the range of 5 to 2,000 ppm, particularly preferably 10 to 500 ppm, based on 100 parts by mass of the total resin of the components (A) and (B).

[0390] In the bioelectrode composition of the present invention, the amount of component (B) is preferably 0 to 2000 parts by mass, more preferably 10 to 1000 parts by mass, relative to 100 parts by mass of the ionic resin (A). Components (A) and (B) may be used alone or in combination of two or more.

[0391] When an addition-curing silicone resin is used, an addition reaction control agent may be added. This addition reaction control agent is added as a quencher to prevent the platinum catalyst from acting in the solution and in a low temperature environment before heat curing after the coating is formed. 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-trimethylsilyloxy-1-butyne, 3-methyl-3-trimethylsilyloxy-1-pentyne, 3,5-dimethyl-3-trimethylsilyloxy-1-hexyne, 1-ethynyl-1-trimethylsilyloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0392] The amount of the addition reaction control agent added is preferably in the range of 0 to 10 parts by mass, and particularly preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total resin of the components (A) and (B).

[0393] In addition, the component (B) contains 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 polysilicone resins containing SiO2 units are preferred.

[0394] When the component (B) has a double bond that can be cross-linked by radicals, it is effective to add a radical generator. Examples of radical generators include photoradical generators and thermalradical generators.

[0395] Photo radical generators, for example: acetophenone, 4,4'-dimethoxybenzyl, benzyl, benzoin, diphenyl ketone, 2-benzoylbenzoic acid, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether, 4-benzoylbenzoic acid, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3 ,5-triazine, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-dichlorodiphenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthiothioxanthen-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, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone.

[0396] It can also be cured by adding a thermally decomposable free radical generator. Thermal free 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-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, di-n-butyl peroxide, diisopropylphenyl peroxide, etc.

[0397] The amount of the radical generator added is preferably in the range of 0.1 to 50 parts by mass based on 100 parts by mass of the total resin of the components (A) and (B).

[0398] Furthermore, as described later, the biological contact layer is a hardened material of the biological electrode composition. By hardening it, the adhesion of the biological contact layer to both the skin and the conductive substrate becomes good. Furthermore, the hardening means is not particularly limited, and general means can be used, such as heat and light, or both, or a cross-linking reaction using an acid or base catalyst. For the cross-linking reaction, for example, the method described in Chapter 2, p51 to p371, of the Handbook of Cross-linking Reaction, Nakayama Yoshiharu, Maruzen Publishing (2013) can be appropriately selected.

[0399] [Ionic polymer]

[0400] In the biological electrode composition of the present invention, an ionic polymer may be added in addition to component (A). The ionic polymer is preferably one shown in Japanese Patent Publication No. 2018-126496 and Japanese Patent Publication No. 2018-130533. The amount of the ionic polymer added is preferably in the range of 0.1 to 100 parts by mass relative to 100 parts by mass of the total resin of components (A) and (B).

[0401] [Metal powder]

[0402] In order to improve the electronic conductivity, metal powder selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium and indium may be added to the biological electrode composition of the present invention. The amount of metal powder and carbon component added is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the total resin of the components (A) and (B).

[0403] Regarding the types of metal powder, gold, silver, and platinum are more ideal from the perspective of conductivity, and silver, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, and chromium are more preferred from the perspective of price. From the perspective of biocompatibility, precious metals are more ideal, and considering all these factors, silver is the most ideal.

[0404] The metal powder can be shaped like a ball, disc, flake, or needle, but flake-shaped powder is the most ideal because it has the highest conductivity. The size of the metal powder is less than 100 μm and the tap density is 5 g / cm 3 Below, specific surface area is 0.5m 2 Chips with a density of / g or more and a low specific surface area are preferred.

[0405] [Carbon material]

[0406] A carbon material may be added as a conductivity enhancer. Examples of carbon materials include carbon black, graphite, carbon nanotubes, carbon fibers, and graphene. The carbon nanotubes may be single-layer or multi-layer, and may be surface-modified with organic groups. The amount of carbon material added is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the total resin of component (A) and component (B).

[0407] [Silica powder]

[0408] In order to improve the sensitivity of ion reception, silicon powder can be added to the biological electrode composition of the present invention. Silicon powder is, for example, a powder composed of silicon, silicon monoxide, and silicon carbide. The particle size of the powder is preferably smaller than 100 μm, and more preferably less than 1 μm. Smaller particles have a larger surface area and can receive many ions, thus becoming a highly sensitive biological electrode. The amount of silicon powder added is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the resin of component (A) and component (B) combined.

[0409] [Lithium titanate powder]

[0410] In order to improve the sensitivity of ion reception, lithium titanate powder can be added to the biological electrode composition of the present invention. Examples of lithium titanate powder include Li2TiO3, LiTiO2, and spinel-structured Li4Ti5O 12The molecular formula of the present invention is spinel structure, and the spinel structure is preferred. In addition, lithium titanate particles composited with carbon can also be used. The particle size of the powder is preferably smaller than 100μm, and more preferably less than 1μm. The surface area of ​​finer particles is larger, and they can accept many ions to become highly sensitive biological electrodes. It can also be a composite powder of them and carbon. The amount of lithium titanate powder added is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the resin of the (A) component and the (B) component combined.

[0411] [Crosslinking agent]

[0412] An epoxy-based crosslinking agent may also be added to the bioelectrode composition of the present invention. The crosslinking agent in this case is a compound having a plurality of epoxy groups or oxetane groups in one molecule. The amount added is 1 to 30 parts by mass relative to 100 parts by mass of the total resin of the components (A) and (B).

[0413] [Cross-linking catalyst]

[0414] The biological electrode composition of the present invention may also contain a catalyst for crosslinking epoxy groups and oxetane groups. In this case, the catalyst described in paragraphs 0027 to 0029 of Japanese Patent Application No. 2019-503406 may be used. The amount added is 0.01 to 10 parts by mass relative to 100 parts by mass of the total resin of component (A) and component (B).

[0415] [Ionic additives]

[0416] The biological electrode composition of the present invention may be added with an ionic additive for improving ionic conductivity. If biological compatibility is considered, 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 Japanese Patent Application Laid-Open No. 2018-44147, Japanese Patent Application Laid-Open No. 2018-59050, Japanese Patent Application Laid-Open No. 2018-59052, and Japanese Patent Application Laid-Open No. 2018-130534 may be cited.

[0417] [Organic solvents]

[0418] In addition, (D) an organic solvent may be added to the biological electrode composition of the present invention. Specifically, the organic solvent includes 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, tetralin, 4-phenyl-1-butene, tert-pentylbenzene, pentylbenzene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, Aromatic hydrocarbon solvents such as 5-tert-butyl-m-xylene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, 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, cycloheptene, 1,3-dimethylcyclopentane, ethylcyclopentane, methylcyclohexane, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, methylenecyclohexane, 4-methyl-1-cyclohexene Hexene, 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-hexane olefins, 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-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, propyl Cyclohexane, 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-decatriene, 2,6-dimethyl-2,4,6-octatriene, lemon ene, 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, pentylcyclohexane, 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, 1,2,4-trivinylcyclohexane, aliphatic hydrocarbon solvents such as isoalkanes, cyclohexanone, cyclopentanone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, methyl-n-amyl ketone and other ketone solvents, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and other alcohol solvents, 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, diethylene glycol monoheptyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methyl cyclopentyl ether, methyl cyclohexyl ether, di-n-butyl ether, di Ether solvents such as sec-butyl ether, diisoamyl ether, di-sec-amyl 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 monotert-butyl ether acetate; lactone solvents such as γ-butyrolactone; water, and the like.

[0419] The amount of the organic solvent (D) added is preferably in the range of 10 to 50,000 parts by mass based on 100 parts by mass of the total resin of the components (A) and (B).

[0420] When the resin of component (B) is a silicone adhesive cross-linked by hydrosilylation, if the water content in the solvent is less than 0.2% by mass, the risk of hindering the hydrosilylation reaction will be smaller. If the cross-linking reaction is fully carried out, sufficient adhesion will be exerted, and no residue of the biological electrode composition will be generated on the skin after the biological electrode is peeled off from the skin, which is ideal from this point of view. Therefore, it is particularly preferred to remove water from the solution in which the ionic polymer of the present invention is dissolved. For water removal, methods such as azeotropic dehydration, centrifugal separation, adsorption using molecular sieves, and filtration using a water removal filter can be used.

[0421] [Other additives]

[0422] In the biological electrode composition of the present invention, silicon dioxide particles, polyether polysilicone, and polyglycerol polysilicone can also be mixed. The surface of the silicon dioxide particles is hydrophilic, and has good compatibility with the hydrophilic ionic polymer, polyether polysilicone, and polyglycerol polysilicone, and can improve the dispersibility of the ionic polymer, polyether polysilicone, and polyglycerol polysilicone in the hydrophobic polysilicone adhesive in the polysilicone adhesive. The silicon dioxide particles can be used ideally in both dry and wet forms.

[0423] [Polysilicone compound having a polyglycerol structure]

[0424] In the biological electrode composition of the present invention, a polysilicone compound having a polyglycerol structure may be added to improve the moisture retention of the membrane and the sensitivity and ion conductivity of ions released from the skin. The amount of the polysilicone compound having a polyglycerol structure is preferably 0.01 to 100 parts by mass, and more preferably 0.5 to 60 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B). The polysilicone compound having a polyglycerol structure may be used alone or in combination of two or more.

[0425] The polysilicone compound having a polyglycerol structure is preferably represented by the following general formula (4)' and (5)'.

[0426] [Chemistry 106]

[0427]

[0428] In formula (4)' and (5)', R 1 ' may be the same or different, and are independently a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, or a phenyl group, and may contain an ether group, or may be a polysiloxane chain represented by the general formula (6)', R 2 ' is a group having a polyglyceryl structure represented by formula (4)'-1 or formula (4)'-2, R 3 ' are independent of each other, may be the same or different, and are the aforementioned R 1 ' or the aforementioned R 2 'Ki, R 4 ' are independent of each other, may be the same or different, and are the aforementioned R 1 'base, the aforementioned R 2 ' group or oxygen atom. 4 When ' is an oxygen atom, two R 4 The ' group can also be bonded to form an ether group and form a ring with the silicon atom. a' can 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 ' is the aforementioned R 2 In formula (4)'-1, (4)'-2, (5)', (6)', R5 ' 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 with 2 to 6 carbon atoms, R 7 ' may also be an ether bond, c' is 0-20, and d' is 1-20.

[0429] Examples of such polysilicone compounds having a polyglycerol structure are shown below.

[0430] [Chemistry 107]

[0431]

[0432] [Chemistry 108]

[0433]

[0434] [Chemistry 109]

[0435]

[0436] [Chemistry 110]

[0437]

[0438] [Chemistry 111]

[0439]

[0440] [Chemistry 112]

[0441]

[0442] [Chemistry 113]

[0443]

[0444] [Chemistry 114]

[0445]

[0446] [Chemistry 115]

[0447]

[0448] [Chemistry 116]

[0449]

[0450] In the formula, a', b', c' and d' are as described above.

[0451] If a polysilicone compound having such a polyglycerol structure is contained, it can exhibit better moisturizing properties, and as a result, it can become a bioelectrode composition capable of forming a biocontact layer that exhibits better sensitivity to ions released from the skin.

[0452] As described above, if it is a biological electrode composition of the present invention, it can form a biological electrode composition that has high adhesion, has sufficient adhesion even when peeled off from the skin and re-attached, can transmit electrical signals from the skin to the device with good efficiency (that is, excellent conductivity), does not cause allergies even if installed on the skin for a long time (that is, excellent biocompatibility), is lightweight, can be manufactured at low cost, and has a biological contact layer for biological electrodes that does not significantly decrease in conductivity even when wetted or dried. In addition, by adding carbon materials, the conductivity can be further improved, and by combining with a resin having adhesion and elasticity, a biological electrode with particularly high adhesion and high elasticity can be manufactured. Moreover, the elasticity and adhesion to the skin can be improved by additives, and the elasticity and adhesion can be adjusted by appropriately adjusting the composition of the resin and the thickness of the biological contact layer.

[0453] <Biological Electrode>

[0454] Furthermore, the present invention provides a bioelectrode comprising 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.

[0455] The biological electrode of the present invention will be described in detail below with reference to the drawings, but the present invention is not limited to these drawings.

[0456] Figure 1 This is a schematic cross-sectional view showing an example of the biological electrode of the present invention. Figure 1 The bioelectrode 1 has a conductive substrate 2 and a biocontact layer 3 formed on the conductive substrate 2. The biocontact layer 3 is composed 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. Figure 1 , 2 Although the description is made with respect to a case where the biological contact layer 3 is a layer in which the ionic resin (A) 5 and the conductive powder 4 are dispersed in the resin (B) 6 , the biological electrode of the present invention is not limited to this aspect.

[0457] When using such Figure 1When the biological electrode 1 is used, as shown in the figure, the biological contact layer 3 (that is, the layer obtained by dispersing the ion resin (A) 5 and the conductive powder 4 in the resin (B) 6) is brought into contact with the biological body 7, and the electric signal is taken out from the biological body 7 by using the ion resin (A) 5 and the conductive powder 4, and is conducted to the sensor device or the like (not shown) through the conductive substrate 2. In this way, if it is the biological electrode of the present invention, it is possible to take into account both conductivity and biocompatibility by using the above-mentioned ion resin (A) 5, and it also has adhesiveness, so that the contact area with the skin is constant and the electric signal from the skin can be stably obtained with high sensitivity.

[0458] The constituent materials of the biological electrode of the present invention are described in more detail below.

[0459] [Conductive substrate]

[0460] The biological electrode of the present invention has a conductive substrate, which is usually electrically connected to a sensor device or the like, and transmits an electrical signal extracted from the biological body through the biological contact layer to the sensor device or the like.

[0461] The conductive substrate is not particularly limited as long as it has conductivity, and preferably contains at least one selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon and a conductive polymer.

[0462] Furthermore, the conductive substrate is not particularly limited, and may be a hard conductive substrate, a flexible conductive film, a cloth coated with a conductive paste, or a cloth mixed with a conductive polymer. The conductive substrate may be flat, uneven, or meshed with metal wires, and may be appropriately selected according to the purpose of the biological electrode.

[0463] [Biological contact layer]

[0464] The bioelectrode of the present invention has a biocontact layer formed on a conductive substrate. The biocontact layer is the portion that actually contacts the bioelectrode when the bioelectrode is used, and has conductivity and adhesiveness. The biocontact layer is a cured product of the bioelectrode composition of the present invention, that is, an adhesive resin layer composed of a cured product of a composition containing the above-mentioned component (A), optionally the component (B), the component (C), the component (D), and other components.

[0465] Furthermore, the adhesion of the biological contact layer is preferably in the range of 0.01 N / 25 mm or more and 20 N / 25 mm or less. The method for measuring the adhesion is generally the method shown in JIS Z 0237. The substrate can be a metal substrate such as SUS (stainless steel) or a PET (polyethylene terephthalate) substrate, or human skin can be used for measurement. The surface energy of human skin is lower than that of metal and various plastics, and is close to the low energy of Teflon (registered trademark), which is not easy to adhere.

[0466] When used in applications where the adhesive is to be repeatedly pasted and peeled off, the peeling property is more important than the adhesion property, so the adhesion property is not necessary.

[0467] The thickness of the biocontact layer of the bioelectrode is preferably 1 μm to 5 mm, and more preferably 2 μm to 3 mm. The thinner the biocontact layer, the lower the adhesion, but the flexibility is improved, the lighter the layer is, and the compatibility with the skin becomes better. The thickness of the biocontact layer can be selected by considering both the adhesion and the texture with the skin.

[0468] Furthermore, the biological electrode of the present invention, like the known biological electrode (for example, the biological electrode described in Japanese Patent Gazette No. 2004-033468), can also be provided with an additional adhesive film on the biological contact layer in order to prevent the biological electrode from peeling off from the biological body during use. When the additional adhesive film is provided, the adhesive film can be formed using an adhesive film material such as an acrylic type, a urethane type, or a polysilicone type. In particular, the polysilicone type has high oxygen permeability, so the skin can breathe while maintaining the attached state, and has high water repellency, so the decrease in adhesion due to sweat is small, and the irritation to the skin is low, so it is ideal. Furthermore, the biological electrode of the present invention, as described above, can be prevented from peeling off from the biological body by adding an adhesiveness imparting agent to the biological electrode composition, or by using a resin with good adhesion to the biological body, so the additional adhesive film described above is not necessarily provided.

[0469] When the bioelectrode of the present invention is used as a wearable device, wiring and other components of the bioelectrode and sensor device are not particularly limited, and for example, those described in Japanese Patent Application Laid-Open No. 2004-033468 may be used.

[0470] As described above, if it is a biological electrode of the present invention, the biological contact layer can be formed by the hardened material of the biological electrode composition of the present invention, so it can transmit the electrical signal from the skin to the device with good efficiency (that is, excellent conductivity), even if it is installed on the skin for a long time, there is no risk of allergies (that is, excellent biological compatibility), it is lightweight, can be manufactured at low cost, and the conductivity will not drop significantly even if it is wetted or dried. In addition, by adding conductive powder, the conductivity can be further improved, and by combining with a resin having adhesion and elasticity, a biological electrode with high adhesion and high elasticity can be manufactured. In addition, the elasticity and adhesion to the skin can be improved by additives, and the elasticity and adhesion can be adjusted by appropriately adjusting the composition of the resin and the thickness of the biological contact layer. Therefore, if it is such a biological electrode of the present invention, it is particularly suitable as a biological electrode used in a medical wearable device.

[0471] <Method for producing biological electrode>

[0472] Furthermore, the present invention provides a method for manufacturing a biological electrode, which is a method for manufacturing a biological electrode having a conductive substrate and a biological contact layer formed on the conductive substrate, by coating the above-mentioned biological electrode composition of the present invention on the aforementioned conductive substrate and hardening it to form the aforementioned biological contact layer.

[0473] Furthermore, the conductive substrate and the like used in the method for producing the biological electrode of the present invention may be the same as described above.

[0474] The method for coating the biological electrode composition on the conductive substrate is not particularly limited, and methods such as dip coating, spray coating, spin coating, rod coating, notch wheel coating, die coating, roller coating, flow coating, blade coating, calender coating, screen printing, flexographic printing, gravure printing, and inkjet printing are ideal.

[0475] The curing method of the resin is not particularly limited and can be appropriately selected depending on the components (A) and (B) of the bioelectrode composition. For example, curing by heat or light, or both of them, is preferred. Alternatively, a catalyst that generates an acid or a base may be added to the bioelectrode composition to generate a crosslinking reaction and cure the composition.

[0476] The temperature during heating is not particularly limited and can be appropriately selected depending on the components (A) and (B) used in the bioelectrode composition, and is preferably about 50 to 250°C, for example.

[0477] When heating and light irradiation are combined, heating and light irradiation may be performed simultaneously, heating may be performed after light irradiation, or light irradiation may be performed after heating. In addition, air drying may be performed before heating after coating in order to evaporate the solvent.

[0478] If water drops are dripped onto the surface of the hardened film, or water vapor or water mist is blown, the compatibility with the skin is improved, and biological signals can be quickly obtained. In order to make the droplet size of water vapor or water mist small, water mixed with alcohol can also be used. The surface of the film can also be wetted by contacting with water-containing absorbent cotton or cloth.

[0479] The water that wets the surface of the hardened film may also contain salt. The water-soluble salt mixed with water is selected from sodium salt, potassium salt, calcium salt, magnesium salt, and betaine.

[0480] The water-soluble salt may be specifically 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 water-soluble salt does not include the ionic resin (A).

[0481] More specifically, in addition to the above, sodium acetate, sodium propionate, sodium trimethylacetate, sodium glycolate, sodium butyrate, sodium valerate, sodium caproate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium undecylate, sodium laurate, sodium tridecylate, sodium myristate, sodium pentadecylate, sodium palmitate, sodium heptadecanoate, sodium stearate, sodium benzoate, disodium adipate, disodium maleate, disodium phthalate, sodium butyrate, sodium 2-hydroxybutyrate, sodium 3-hydroxybutyrate, sodium 2-oxobutyrate, sodium stearate, sodium gluconate, sodium methanesulfonate, 1-nonanoic acid, sodium benzoate, sodium adipate, sodium maleate, sodium ... benzoate, sodium benzoate, sodium Sodium alkanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-undecanesulfonate, sodium coconut fat acetoethanesulfonate, sodium lauroyl methylalanine, sodium coconut fat methyl taurate, sodium coconut fat glutamate, sodium coconut fat (sarcosine), sodium lauroyl methyl taurate, lauramide propyl, potassium isobutyrate, potassium propionate, potassium trimethylacetate, potassium glycolate, potassium gluconate, potassium methanesulfonate, calcium stearate, calcium glycolate, calcium gluconate, calcium 3-methyl-2-oxobutyrate, 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 cited.

[0482] The water used to wet the surface of the hardened film may further contain a monohydric alcohol or a polyhydric alcohol having 1 to 4 carbon atoms. The alcohol is preferably selected from ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, polyethylene glycol, polypropylene glycol, polyglycerol, diglycerol, or a polysilicone compound having a polyglycerol structure. The polysilicone compound having a polyglycerol structure is preferably represented by the general formula (4)' or (5)'.

[0483] The pretreatment method using an aqueous solution containing a water-soluble salt can be used to coat the biological electrode membrane on the hardened biological electrode membrane by spraying, water drop dispensing, etc. It can also be coated in a high temperature and high humidity state like a sauna. In order to prevent drying after coating, a protective film can be further laminated on the permeable layer for covering. The protective film needs to be peeled off just before being attached to the skin, so a Teflon (registered trademark) film coated with a peeling agent or peelable can be used. For long-term storage, the dry electrode covered with a peeling 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 better to seal water in it in advance.

[0484] Before attaching the biological electrode of the present invention to the skin, the skin side may be wetted with water, alcohol, etc., or the skin may be wiped with a cloth or absorbent cotton containing water, alcohol, etc. The water or alcohol may also contain the aforementioned salt.

[0485] As described above, the method for manufacturing the biological electrode of the present invention can easily manufacture the biological electrode of the present invention at low cost, which has excellent conductivity and biocompatibility, is lightweight, and does not significantly reduce conductivity even when wetted by water or dried.

[0486] [Example]

[0487] The present invention will be specifically described below using Examples and Comparative Examples, but the present invention is not limited thereto.

[0488] (2)-1 Monomer Synthesis Example with Double Bond

[0489] [Chemistry 117]

[0490]

[0491] After cooling a mixed solution of 22 g of 4-trifluoromethoxybenzenesulfonamide, 14 g of potassium carbonate and 60 g of acetonitrile with ice, a mixed solution of 10 g of acryloyl chloride and 30 g of acetonitrile was added dropwise under ice cooling. After heating 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.

[0492] (2)-1 Monomer 8 was synthesized by reacting 4-trifluoromethoxybenzenesulfonyl chloride with ethanolamine and then reacting with methacryloyl chloride.

[0493] (2)-1 Monomers 1 to 10 are shown below.

[0494] [Chemistry 118]

[0495]

[0496] Ionic resins 1-1 to 1-11 as ionic materials (conductive materials) mixed in a biological electrode composition solution were synthesized as follows. A 30% by weight cyclopentanone solution of each monomer was placed in a reaction vessel and mixed. The reaction vessel was cooled to -70°C in a nitrogen environment, and degassing under reduced pressure and nitrogen blowing were repeated three times. After the temperature was raised to room temperature, 0.02 mol of azobisisobutyronitrile (AIBN) as a polymerization initiator was added to 1 mol of the total monomers. After the temperature was raised to 60°C, the reaction was carried out for 15 hours. The composition of the obtained polymer was determined by using 1 The molecular weight (Mw) and the degree of dispersion (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 synthesized in this manner are shown below.

[0497] Ionic resin 1-1

[0498] Mw=66,800

[0499] Mw / Mn=2.62

[0500] [Chemistry 119]

[0501]

[0502] Ionic resin 1-2

[0503] Mw=43,100

[0504] Mw / Mn=2.46

[0505] [Chemistry 120]

[0506]

[0507] Ionic resin 1-3

[0508] Mw=55,600

[0509] Mw / Mn=2.34

[0510] [Chemistry 121]

[0511]

[0512] Ionic resin 1-4

[0513] Mw=48,100

[0514] Mw / Mn=2.67

[0515] [Chemistry 122]

[0516]

[0517] Ionic resin 1-5

[0518] Mw=56,900

[0519] Mw / Mn=2.61

[0520] [Chemistry 123]

[0521]

[0522] Ionic resin 1-6

[0523] Mw=71,300

[0524] Mw / Mn=2.67

[0525] [Chemistry 124]

[0526]

[0527] Ionic resin 1-7

[0528] Mw=39,400

[0529] Mw / Mn=2.26

[0530] [Chemistry 125]

[0531]

[0532] The number of replicates in the formula represents the average value.

[0533] Ionic resin 1-8

[0534] Mw=26,700

[0535] Mw / Mn=1.91

[0536] [Chemistry 126]

[0537]

[0538] The number of replicates in the formula represents the average value.

[0539] Ionic resin 1-9

[0540] Mw=34,400

[0541] Mw / Mn=2.22

[0542] [Chemistry 127]

[0543]

[0544] The number of replicates in the formula represents the average value.

[0545] Ionic resin 1-10

[0546] Mw=28,500

[0547] Mw / Mn=1.98

[0548] [Chemistry 128]

[0549]

[0550] Ionic resin 1-11

[0551] Mw=24,700

[0552] Mw / Mn=1.98

[0553] [Chemistry 129]

[0554]

[0555] Ionic resins 2-1 to 2-6 as ionic materials (conductive materials) added to the biological electrode composition solution are synthesized by hydrosilylation reaction of a polysiloxane compound having a SiH group and a sulfonamide salt compound having an olefin group (the following (2)-2 monomers 1 to 3) in the presence of a platinum catalyst.

[0556] [Chemistry 130]

[0557]

[0558] Ionic resin 2-1

[0559] Mw=661

[0560] Mw / Mn=1.0

[0561] [Chemistry 131]

[0562]

[0563] Ionic resin 2-2

[0564] Mw=7100

[0565] Mw / Mn=1.60

[0566] [Chemistry 132]

[0567]

[0568] Ionic resin 2-3

[0569] Mw=4,400

[0570] Mw / Mn=1.46

[0571] [Chemistry 133]

[0572]

[0573] Ionic resin 2-4

[0574] Mw=5,600

[0575] Mw / Mn=1.63

[0576] [Chemistry 134]

[0577]

[0578] Ionic resin 2-5

[0579] Mw=1,690

[0580] Mw / Mn=1.10

[0581] [Chemistry 135]

[0582]

[0583] Ionic resin 2-6

[0584] Mw=5,600

[0585] Mw / Mn=1.63

[0586] [Chemistry 136]

[0587]

[0588] The following (2)-3 monomers 1 to 11 were used, mixed with an isocyanate compound, a dihydroxy compound for extending the chain length as appropriate, a monohydroxy compound for end-capping, a monoisocyanate compound, a solvent propylene glycol monomethyl ether acetate in an amount twice the mass of the raw material compound, and a catalyst XK-640 (manufactured by KING INDUSTRIES) in an amount of 0.02 mass % relative to 100 mass parts of the raw material compound, and reacted at 90°C for 9 hours to synthesize ionic resins 3-1 to 3-14.

[0589] [Chemistry 137]

[0590]

[0591] [Chemistry 138]

[0592]

[0593] [Chemistry 139]

[0594]

[0595] [Chemistry 140]

[0596]

[0597] [Chemistry 141]

[0598]

[0599] [Chemistry 142]

[0600]

[0601] [Chemistry 143]

[0602]

[0603] [Chemistry 144]

[0604]

[0605] [Chemistry 145]

[0606]

[0607] [Chemistry 146]

[0608]

[0609] In the figure, * represents an atomic bond.

[0610] [Chemistry 147]

[0611]

[0612] Ionic resin 3-14

[0613] Mw=1,580

[0614] Mw / Mn=1.09

[0615] [Chemistry 148]

[0616]

[0617] Comparative ionic resin 1Mw = 26,500

[0618] Mw / Mn=1.85

[0619] [Chemistry 149]

[0620]

[0621] Siloxane compounds 1 to 4 as polysilicone-based resins blended in the bioelectrode composition solution are shown below.

[0622] (Siloxane compound 1)

[0623] The viscosity of a 30% toluene solution is 27,000 mPa·s, the alkenyl content is 0.007 mol / 100 g, and the vinyl-containing polydimethylsiloxane whose molecular chain ends are capped with SiMe2Vi groups is named as Siloxane Compound 1.

[0624] (Siloxane compound 2)

[0625] Me3SiO 0.5 Polysiloxane (Me3SiO 0.5 Unit / SiO2 unit = 0.8) was prepared as a 60% toluene solution and named as Siloxane Compound 2.

[0626] (Siloxane compound 3)

[0627] 40 parts by weight of vinyl-containing polydimethylsiloxane with OH-terminated molecular chain ends and Me3SiO 0.5 Polysiloxane (Me3SiO 0.5 A solution consisting of 100 parts by mass of a 60% toluene solution of 1,4-dimethylsiloxane (1,4-dimethylsiloxane unit / SiO2 unit = 0.8) and 26.7 parts by mass of toluene was heated for 4 hours while undergoing dry distillation, and then cooled to bond the MQ resin to the polydimethylsiloxane, which was named Siloxane Compound 3.

[0628] (Siloxane compound 4)

[0629] As the methyl hydrogen polysilicone oil, KF-99 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

[0630] The acrylic resin as the acrylic resin blended in the bioelectrode composition solution is as follows.

[0631] Acrylic resin 1

[0632] Mw=129,000

[0633] Mw / Mn=2.45

[0634] [Chemistry 150]

[0635]

[0636] The urethane resin as the urethane resin blended in the bioelectrode composition solution is as follows.

[0637] Urethane resin 1

[0638] Mw=83,000

[0639] Mw / Mn=4.02

[0640] [Chemistry 151]

[0641]

[0642] Urethane resin 2Mw = 84,000

[0643] Mw / Mn=4.22

[0644] [Chemistry 152]

[0645]

[0646] The polyglycerol-polysilicon compound blended in the bioelectrode composition solution is shown below.

[0647] [Chemistry 153]

[0648]

[0649] The cross-linking agent blended into the bioelectrode composition solution is shown below.

[0650] Epoxy crosslinker 1

[0651] [Chemistry 154]

[0652]

[0653] The organic solvents blended into the bioelectrode composition solution are as follows.

[0654] EDE: Diethylene glycol diethyl ether

[0655] ISOPARG TM :Isoparaffin solvent standard petroleum

[0656] ISOPARM TM :Isoparaffin solvent standard petroleum

[0657] The following are the additives of lithium titanate powder, free radical generator, platinum catalyst, and conductivity enhancer (carbon black, carbon nanotube) mixed into the bioelectrode composition solution.

[0658] Lithium titanate powder, spinel: Made by Sigma-Aldrich, size less than 200nm

[0659] Free radical generator: Irgacure TPO manufactured by BASF

[0660] Platinum catalyst: CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.

[0661] Carbon black: Denka Black Li-400 manufactured by Denka Corporation

[0662] Multilayered carbon nanotubes: Sigma-Aldrich, diameter 110-170 nm, length 5-9 μm

[0663] [Examples 1 to 31, Comparative Example 1]

[0664] Ionic resins, resins, organic solvents, and additives (free radical generators, platinum catalysts, conductivity enhancers) were mixed according to the compositions listed in Tables 1 to 3 to prepare bioelectrode compositions (bioelectrode solutions 1 to 31, comparative bioelectrode solution 1).

[0665] [Table 1]

[0666]

[0667]

[0668] [Table 2]

[0669]

[0670] [Table 3]

[0671]

[0672] (Biological signal evaluation)

[0673] like Figure 3 As shown, on the ST-604 thermoplastic urethane (TPU) film 20 of Bemis, the conductive paste DOTITE FA-333 manufactured by Fujikura Chemical was applied by screen printing, and then 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 circular portion overlapped thereon was coated with the bioelectrode solution described in Tables 1 to 3 by screen printing, and after air-drying at room temperature for 10 minutes, it was baked in an oven at 125°C for 10 minutes to evaporate the solvent and harden it to form a biocontact layer 3, thereby manufacturing a bioelectrode 1. In the case of the bioelectrode solution 30, 500 mJ / cm was irradiated with a 1,000 W xenon lamp in a nitrogen environment. 2 The composition coating film is hardened by light. Figure 4As shown, the urethane film on which the bioelectrode 1 is printed is cut, and a double-sided tape 21 is pasted thereon, so that three bioelectrode samples 10 are prepared for one portion of the bioelectrode solution.

[0674] (Measurement of the thickness of the biocontact layer)

[0675] The thickness of the bio-contact layer of the bio-electrode prepared above was measured using a micrometer. The results are shown in Table 4.

[0676] (Measurement of biological signals)

[0677] The conductive wiring pattern of the biological electrode obtained by using the conductive paste is connected to the portable electrocardiograph HCG-901 manufactured by Omron Healthcare Corporation with a conductive wire, and the positive electrode of the electrocardiograph is attached to the Figure 5 The negative electrode is attached to the LA of the human body, the negative electrode is attached to the LL, and the ground electrode is attached to the RA. Immediately after attaching, start measuring the electrocardiogram until Figure 6 The results are shown in Table 4.

[0678] [Table 4]

[0679]

[0680]

[0681] As shown in Table 4, Examples 1 to 31 in which the biocontact layer was formed using the bioelectrode composition of the present invention blended with a resin having a structure selected from ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of trifluoromethoxybenzenesulfonamide and / or difluoromethoxybenzenesulfonamide, were able to obtain a biosignal in a short time after being attached to the body. On the other hand, when no ionic component of a specific structure was present, no biosignal was obtained.

[0682] This specification includes the following inventions.

[0683] [1]: A bioelectrode composition comprising (A) an ionic resin,

[0684] Its characteristics are:

[0685] 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.

[0686] [2]: The biological electrode composition of [1], wherein the 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 has a chemical structure represented by the following general formula (1):

[0687] [Chemistry 155]

[0688]

[0689] In the formula, R 1 is trifluoromethyl or difluoromethyl, R 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, n is an integer of 0 to 4, and M + It is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

[0690] [3]: The biological electrode composition as described in [2], wherein 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 polysilicone resin, and a polyurethane resin.

[0691] [4]: The biological electrode composition of [2] or [3], wherein:

[0692] The resin having the chemical structure represented by the general formula (1) 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 polysilicone resin containing a repeating unit represented by the following general formula (2)-2-1, a polysilicone resin represented by the following general formula (2)-2-2, a polysilicone resin represented by the following general formula (2)-2-3, and a polysilicone 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.

[0693] [Chemistry 156]

[0694]

[0695] [Chemistry 157]

[0696]

[0697] [Chemistry 158]

[0698]

[0699] [Chemistry 159]

[0700]

[0701] [Chemistry 160]

[0702]

[0703] [Chemical 161]

[0704]

[0705] [Chemical 162]

[0706]

[0707] In the formula, R 1 、R 2 、m, n, and M + are as described above. R 3 is a hydrogen atom or a methyl group. R 4 is a single bond, or a linear, branched, or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms and may also have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group, or a sulfonate group. X1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate group. X2 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 bonded product thereof and may also have an ether group, an ester group, a carbonyl group, a nitrogen atom, a thioether group, a sulfonyl group, or a sulfonate group. R 5 to R 8 are linear, branched, or cyclic alkyl groups having 1 to 66 carbon atoms, or aryl groups having 6 to 10 carbon atoms. R 9 is a linear or branched alkyl group having 1 to 20 carbon atoms and may also have an ether group or an ester group. R 10 , and R 12 are a single bond, or a linear or branched alkylene group having 1 to 4 carbon atoms, and the alkylene group may also have an oxygen atom. R 10 and R 12 will not both be single bonds at the same time. R 11 is a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms and may also have a hydroxyl group or an ether group. Or R 10 to R 12 and the carbon atoms in the formula to which they are bonded may also combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may also contain an aromatic ring and / or a heteroatom. X3 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 also have an aromatic group, and may also bond with R 11 to form a ring, and the ring may also be an aromatic ring. a1 represents the ratio of the repeating unit, and 0 < a1 ≤ 1.0. a2-1 and a2-3 represent the ratios of the repeating units, 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.

[0708] [5]: The biological electrode composition according to any one of [2] to [4], wherein the component (A) contains an ammonium ion represented by the following general formula (3) as the aforementioned M+ ,

[0709] [Chemistry 163]

[0710]

[0711] In the formula, R 101d , R 101e , R 101f , and R 101g Each 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 selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. 101d With R 101e , R 101d With R 101e With R 101f They can also form a ring with the nitrogen atom to which they are bonded. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0712] [6]: The bioelectrode composition according to any one of [1] to [5], further comprising a resin as component (B) different from the ionic resin as component (A).

[0713] [7]: The biological electrode composition according to [6], wherein the component (B) is selected from one or more of silicone resins, (meth)acrylate resins, and urethane resins.

[0714] [8]: The biological electrode composition as described in [6] or [7], wherein the resin as the aforementioned component (B) has adhesive properties.

[0715] [9]: The bioelectrode composition according to any one of [6] to [8], further comprising x SiO (4-x) / 2 As the component (B), a polysilicone resin having a unit (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 a SiO2 unit.

[0716]

[10] : The biological electrode composition as described in any one of [1] to [9] further contains carbon powder and / or metal powder as component (C).

[0717]

[11] : The biological electrode composition as described in

[10] , wherein the carbon powder is any one or both of carbon black and carbon nanotubes.

[0718]

[12] : The biological electrode composition of

[10] or

[11] , 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.

[0719]

[13] : The biological electrode composition as described in any one of

[10] to

[12] , wherein the metal powder is silver powder.

[0720]

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

[13] , wherein the bioelectrode composition further comprises an organic solvent as component (D).

[0721]

[15] : A biological electrode comprising a conductive substrate and a biological contact layer formed on the conductive substrate, characterized in that the aforementioned biological contact layer is a hardened material of the biological electrode composition as described in any one of [1] to

[14] .

[0722]

[16] : A biological electrode as described in

[15] , wherein the conductive substrate contains one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

[0723]

[17] : A method for manufacturing a biological electrode, comprising a conductive substrate and a biological contact layer formed on the conductive substrate, characterized in that:

[0724] The bio-electrode composition described in any one of [1] to

[14] is applied onto the conductive substrate and cured to form the bio-contact layer.

[0725]

[18] : A method for manufacturing a biological electrode as described in

[17] , wherein the conductive substrate comprises one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

[0726] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative only, and any device having substantially the same configuration and exhibiting the same function and effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

[0727] Description of Reference Numerals

[0728] 1: Biological Electrode

[0729] 2: Conductive substrate (conductive pattern)

[0730] 3: Bio-contact layer

[0731] 4: Conductive powder

[0732] 5: Ionic resin (A)

[0733] 6: Resin (B)

[0734] 7: Organisms

[0735] 10: Biological electrode samples

[0736] 20: Thermoplastic urethane film

[0737] 21: Double-sided tape

Claims

1. A bioelectrode composition comprising (A) an ionic resin, Its characteristics are: 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 biological electrode composition according to claim 1, wherein: 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 has a chemical structure represented by the following general formula (1): In the formula, R 1 is trifluoromethyl or difluoromethyl, R 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, n is an integer of 0 to 4, and M + It is an ammonium ion, a lithium ion, a sodium ion, a potassium ion, or a silver ion.

3. The biological electrode composition according to claim 2, wherein: 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 polysilicone resin, and a polyurethane resin.

4. The biological electrode composition according to claim 3, wherein: The resin having the chemical structure represented by the general formula (1) 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 polysilicone resin containing a repeating unit represented by the following general formula (2)-2-1, a polysilicone resin represented by the following general formula (2)-2-2, a polysilicone resin represented by the following general formula (2)-2-3, and a polysilicone 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. In the formula, R 1 and R 2 , m, n, and M + As described above, R 3 is a hydrogen atom or a methyl group, R 4 is a single bond or a linear, branched, or cyclic alkylene group or divalent hydrocarbon group having 1 to 15 carbon atoms and may also have an aromatic group, an ester group, an ether group, a carbonyl group, a carbon-carbon double bond, a sulfonyl group, or a sulfonate group. X1 is a single bond, a phenylene group, an ester group, a carbonyl group, a sulfonyl group, or a sulfonate group. X2 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 bonded product thereof and may also have an ether group, an ester group, a carbonyl group, a nitrogen atom, a thioether group, a sulfonyl group, or a sulfonate group. R 5 to R 8 are linear, branched, or cyclic alkyl groups having 1 to 66 carbon atoms or aryl groups having 6 to 10 carbon atoms. R 9 is a linear or branched alkyl group having 1 to 20 carbon atoms and may also have an ether group or an ester group. R 10 and R 12 are a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and the alkylene group may also have an oxygen atom. R 10 and R 12 are not simultaneously a single bond. R 11 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms and may also have a hydroxyl group or an ether group, or R 10 to R 12 and the carbon atoms in the formula to which they are bonded may also combine to form a trivalent hydrocarbon group having 6 to 15 carbon atoms, and the trivalent hydrocarbon group may also contain an aromatic ring and / or a heteroatom. X3 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 also have an aromatic group, and may also bond with R 11 to form a ring, and the ring may also be an aromatic ring. a1 represents the ratio of the repeating unit, where 0 < a1 ≤ 1.

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

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

5. The biological electrode composition according to claim 2, wherein: The component (A) contains ammonium ions represented by the following general formula (3) as the M + , In the formula, R 101d , R 101e , R 101f , and R 101g Each of 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 selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom, 101d With R 101e , R 101d With R 101e With R 101f They can also form a ring with the nitrogen atom to which they are bonded. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

6. 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. The biological electrode composition according to claim 6, wherein: The component (B) is at least one selected from silicone resins, (meth)acrylate resins, and urethane resins.

8. The biological electrode composition according to claim 6, wherein: The resin as the component (B) has adhesiveness.

9. The biological electrode composition according to claim 7, wherein: It also contains R x SiO (4-x) / 2 The component (B) is a polysilicone resin having a unit (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 a SiO2 unit.

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

11. The biological electrode composition according to claim 10, wherein: The carbon powder is any one or both of carbon black and carbon nanotubes.

12. The biological electrode 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. The biological electrode composition according to claim 12, wherein: The metal powder is silver powder.

14. The biological electrode composition according to claim 6, wherein: The bioelectrode composition further contains an organic solvent as component (D).

15. A biological electrode comprising a conductive substrate and a biological contact layer formed on the conductive substrate, characterized in that: The living body contact layer is a hardened material of the living body electrode composition according to any one of claims 1 to 14.

16. The biological electrode according to claim 15, wherein: The conductive substrate contains one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

17. A method for manufacturing a bioelectrode, comprising: a conductive substrate and a biocontact layer formed on the conductive substrate; and exist The bio-electrode composition according to any one of claims 1 to 14 is coated on the conductive substrate and cured to form the bio-contact layer.

18. The method for producing a biological electrode according to claim 17, wherein the conductive substrate contains one or more selected from the group consisting of gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and a conductive polymer.

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