# US 10,864,366 B2 · Bio-electrode composition, bio-electrode, and method for manufacturing bio-electrode

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- Number: US 10,864,366 B2
- Document ID: US10864366B2
- Status: Granted
- Kind: B2
- Application number: 16/169,321
- Filed: 2018-10-24
- Published: 2019-05-23
- Granted: 2020-12-15
- Earliest claimed: 2017-11-21
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama; Motoaki Iwabuchi; Osamu Watanabe; Keisuke Niida
- Web page: https://patentgrep.com/patent/US10864366B2

## CPC

- A61N 1/0472: {Structure-related aspects}
- A61B 5/268: containing conductive polymers, e.g. PEDOT:PSS polymers
- A61L 27/50: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials}
- A61L 31/126: {containing carbon fillers}
- A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials}
- A61N 1/0496: {characterised by using specific chemical compositions, e.g. hydrogel compositions, adhesives}
- C07C 381/12: Sulfonium compounds
- C08G 18/3206: {aliphatic}
- C08G 18/3212: {containing cycloaliphatic groups}
- C08G 18/3893: {containing silicon}
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4833: {Polyethers containing oxyethylene units}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/61: Polysiloxanes
- C08G 18/6666: {Compounds of group C08G18/48 or C08G18/52}
- C08G 18/718: {containing silicon}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates}
- C08L 43/04: Homopolymers or copolymers of monomers containing silicon
- C08L 71/02: Polyalkylene oxides
- H01B 1/12: organic substances {(organic macromolecular compounds or compositions C08)}
- H01B 1/24: the conductive material comprising carbon-silicon compounds, carbon or silicon
- H05K 1/09: Use of materials for the {conductive, e.g. } metallic pattern
- H05K 1/095: {for polymer thick films, i.e. having a permanent organic polymeric binder}
- A61B 2562/0209: Special features of electrodes classified in A61B5/24, A61B5/25, A61B5/283, A61B5/291, A61B5/296, A61B5/053
- A61B 2562/125: characterised by the manufacture of electrodes
- A61N 1/0408: {Use-related aspects}
- H05K 2201/0209: Inorganic, non-metallic particles
- H05K 2201/0221: Insulating particles having an electrically conductive coating
- H05K 2201/0257: Nanoparticles
- H05K 2201/026: Nanotubes or nanowires
- H05K 2201/0323: Carbon
- A61N: ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY (measurement of bioelectric currents A61B; surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body A61B18/00; anaesthetic apparatus in general A61M; incandescent lamps H01K; infrared radiators for heating H05B)
- A61B: DIAGNOSIS; SURGERY; IDENTIFICATION (usefulness limited to only animals A61D)
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS

## Abstract

The present invention provides a bio-electrode composition including: a resin containing a urethane bond in a main chain and a silsesquioxane in a side chain; and an electro-conductive material, wherein the electro-conductive material is a polymer compound having one or more repeating units selected from fluorosulfonic acid salts shown by the following general formulae (1)-1 and (1)-2, sulfonimide salts shown by the following general formula (1)-3, and sulfonamide salts shown by the following general formula (1)-4. This can form a living body contact layer for a bio-electrode that is excellent in electric conductivity and biocompatibility, light in weight, manufacturable at low cost, and free from large lowering of the electric conductivity even when it is wetted with water or dried. The present invention also provides a bio-electrode in which the living body contact layer is formed from the bio-electrode composition, and a method for manufacturing the bio-electrode.

## Claims

### Claim 1

A bio-electrode composition comprising:
a resin containing a urethane bond in a main chain and a silsesquioxane in a side chain; and
an electro-conductive material,
wherein the electro-conductive material is a polymer compound having one or more repeating units selected from the group consisting of fluorosulfonic acid salts shown by the following general formulae (1)-1 and (1)-2, sulfonimide salts shown by the following general formula (1)-3, and sulfonamide salts shown by the following general formula (1)-4,
wherein Rf1 and Rf2 each represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, or an oxygen atom, provided that when Rf1 represents an oxygen atom, Rf2 also represents an oxygen atom to form a carbonyl group together with a carbon atom bonded therewith; Rf3 and Rf4 each represent a hydrogen atom, a fluorine atom, or a trifluoromethyl group, provided that one or more fluorine atoms are contained in Rf1 to Rf4; Rf5, Rf6, and Rf7 each represent a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, provided that one or more fluorine atoms are contained; X+ represents a sodium ion, a potassium ion, or a cation having an ammonium ion structure shown by the following formula (1)-5; and “m” is an integer of 1 to 4,
wherein Rl to R4 each represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an ether group, a thiol group, an ester group, a carbonyl group, a sulfonyl group, a cyano group, an amino group, a nitro group, or an alkenyl group having 6 to 10 carbon atoms, optionally having a halogen atom, and optionally bonded to each other to form a ring.

### Claim 2 (depends on 1)

The bio-electrode composition according to claim 1, wherein the one or more repeating units selected from the group consisting of fluorosulfonic acid salts shown by the general formulae (1)-1 and (1)-2, sulfonimide salts shown by the general formula (1)-3, and sulfonamide salts shown by the general formula (1)-4 are one or more repeating units selected from repeating units a1 to a7 shown by the following general formulae (2),
wherein R5, R7, R9, R12, R14, R15, and R17 each independently represent a hydrogen atom or a methyl group; R6, R8, R10, R13, and R16 each independently represent any of a single bond, an ester group, and a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms and optionally having either or both of an ether group and an ester group; R11 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R11 are each optionally substituted with a fluorine atom; Z1, Z2, Z3f Z4, and Z6 each independently represent any of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group; Z5 represents any of a single bond, an ether group, and an ester group; Z7 represents a single bond, an arylene group having 6 to 12 carbon atoms, or —C(═O)—O—Z8—; Z8 represents a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, optionally having an ether group, a carbonyl group, or an ester group in Z8; Y represents an oxygen atom or an —NR18—group; R18 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, optionally bonded to R8 to form a ring; “m” is an integer of 1 to 4; a1, a2, a3, a4, a5, a6, and a7 satisfy 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, 0≤a7≤1.0, and 0<a1+a2+a3+a4+a5+a6+a7 1.0; and Rf5, Rf6, Rf7, and X+ have the same meanings as defined above.

### Claim 3 (depends on 1)

The bio-electrode composition according to claim 1, wherein the electro-conductive material is a polymer compound having a repeating unit of a sulfonamide salt shown by the general formula (1)-4.

### Claim 4 (depends on 2)

The bio-electrode composition according to claim 2, wherein the electro-conductive material is a polymer compound having a repeating unit of a sulfonamide salt shown by the general formula (1)-4.

### Claim 5 (depends on 1)

The bio-electrode composition according to claim 1, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain has a structure shown by the following general formula (3),
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms;
“A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 6 (depends on 2)

The bio-electrode composition according to claim 2, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain has a structure shown by the following general formula (3),
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 7 (depends on 1)

The bio-electrode composition according to claim 1, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain has a structure containing a polyether main chain shown by the following general formula (4),
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0; R25 represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms; and “v” and “w” satisfy 0<v<1.0 and 0<w<1.0.

### Claim 8 (depends on 2)

The bio-electrode composition according to claim 2, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain has a structure containing a polyether main chain shown by the following general formula (4),
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0; R25 represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms;
and “v” and “w” satisfy 0<v<1.0 and 0<w<1.0.

### Claim 9 (depends on 1)

The bio-electrode composition according to claim 1, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain is a reaction product of a diol compound shown by the following general formula (5), a polyether compound having a hydroxy group at a terminal, and a compound having an isocyanate group,
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 10 (depends on 2)

The bio-electrode composition according to claim 2, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain is a reaction product of a diol compound shown by the following general formula (5), a polyether compound having a hydroxy group at a terminal, and a compound having an isocyanate group,
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R21 and R23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R21 and R23 is 1 or 2; R22 and R24 each represent a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 11 (depends on 1)

The bio-electrode composition according to claim 1, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain is a reaction product of a diol compound shown by the following general formula (6) and a compound having an isocyanate group,
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R22 represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 12 (depends on 2)

The bio-electrode composition according to claim 2, wherein the resin containing a urethane bond in a main chain and a silsesquioxane in a side chain is a reaction product of a diol compound shown by the following general formula (6) and a compound having an isocyanate group,
wherein R20 represents a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, optionally substituted with a halogen atom, an amino group, a cyano group, or a mercapto group, and optionally having an ether group, a carbonyl group, an acid anhydride group, an amide group, a nitrogen atom, or a sulfur atom, provided that the aryl group is optionally substituted with a halogen atom, a nitro group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; R22 represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; and “s” and “t” satisfy 0<s≤0.2 and 0.8≤t<1.0.

### Claim 13 (depends on 11)

The bio-electrode composition according to claim 11, wherein the diol compound shown by the general formula (6) is a reaction product of substances shown by the following general formulae (7)-1 and (7)-2,
wherein R20 and R22 have the same meanings as defined above; R26 to R28 each represent an alkyl group having 1 to 6 carbon atoms; and R29 and R30 each represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms and optionally bonded to the other to form a ring, or an aryl group having 6 to 10 carbon atoms.

### Claim 14 (depends on 1)

The bio-electrode composition according to claim 1, further comprising an organic solvent.

### Claim 15 (depends on 1)

The bio-electrode composition according to claim 1, further comprising a carbon material.

### Claim 16 (depends on 15)

The bio-electrode composition according to claim 15, wherein the carbon material is either or both of carbon black and carbon nanotube.

### Claim 17 (depends on 1)

A bio-electrode comprising an electro-conductive base material and a living body contact layer formed on the electro-conductive base material,
wherein the living body contact layer is a cured material of the bio-electrode composition according to claim 1.

### Claim 18 (depends on 17)

The bio-electrode according to claim 17, wherein the electro-conductive base material comprises one or more species selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

### Claim 19 (depends on 1)

A method for manufacturing a bio-electrode having an electro-conductive base material and a living body contact layer formed on the electro-conductive base material, comprising:
applying the bio-electrode composition according to claim 1 onto the electro-conductive base material; and
curing the bio-electrode composition; thereby forming the living body contact layer.

### Claim 20 (depends on 19)

The method for manufacturing a bio-electrode according to claim 19, wherein the electro-conductive base material comprises one or more species selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.