# US 11,998,339 B2 · Bio-electrode composition, bio-electrode, and method for manufacturing bio-electrode

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,998,339 B2
- Document ID: US11998339B2
- Status: Granted
- Kind: B2
- Application number: 17/155,845
- Filed: 2021-01-22
- Published: 2022-04-14
- Granted: 2024-06-04
- Earliest claimed: 2020-01-22
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama; Motoaki Iwabuchi; Joe Ikeda; Koji Hasegawa; Yasuyoshi Kuroda
- Web page: https://patentgrep.com/patent/US11998339B2

## CPC

- A61B 5/268: containing conductive polymers, e.g. PEDOT:PSS polymers
- C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- A61B 5/26: maintaining contact between the body and the electrodes by the action of the subjects, e.g. by placing the body on the electrodes or by grasping the electrodes
- A61B 5/265: containing silver or silver chloride
- A61B 5/28: for electrocardiography [ECG]
- C08G 18/673: {containing two or more acrylate or alkylacrylate ester groups}
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- C08L 51/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L 51/085: {on to polysiloxanes}
- C08L 83/12: containing polyether sequences
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- C09D 151/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D 151/085: {on to polysiloxanes}
- A61B 2562/0215: Silver or silver chloride containing
- A61B 2562/125: characterised by the manufacture of electrodes
- C08F 212/30: {Sulfur}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- C08F 220/387: {and containing nitrogen and oxygen}
- C08F 220/585: {and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]}
- C08G 77/46: containing polyether sequences
- Y02E 60/50: Fuel cells
- A61B: DIAGNOSIS; SURGERY; IDENTIFICATION (usefulness limited to only animals A61D)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A bio-electrode composition contains: (A) a polymer compound containing a repeating unit-a having a structure selected from the group consisting of salts of ammonium, sodium, potassium, and silver formed with any of fluorosulfonic acid, fluorosulfonimide, and N-carbonyl-fluorosulfonamide; and (B) a silicone compound having a polyglycerin structure. This bio-electrode composition is able to form a living body contact layer for a bio-electrode which enable quick signal collection after attachment to skin.

## Claims

### Claim 1

A bio-electrode composition comprising:
(A) a polymer compound comprising a repeating unit-a having a structure selected from the group consisting of salts of ammonium, sodium, potassium, and silver formed with any of fluorosulfonic acid, fluorosulfonimide, and N-carbonyl-fluorosulfonamide; and
(B) a silicone compound having a polyglycerin structure.

### Claim 2 (depends on 1)

The bio-electrode composition according to claim 1, wherein the repeating unit-a is shown by any of the following general formulae (1)-1 to (1)-4,
wherein Rf1 and Rf2 each represent a hydrogen atom, a fluorine atom, an oxygen atom, a methyl group, or a trifluoromethyl group, provided that when Rf1 and Rf2 represent an oxygen atom, the single oxygen atom represented by Rf1 and Rf2 bonds to a single carbon atom to form a carbonyl group; and Rf3 and Rf4 each represent a hydrogen atom, a fluorine atom, or a trifluoromethyl group, provided that at least one of Rf1 to Rf4 is a fluorine atom or a trifluoromethyl group;
Rf5, Rf6, and Rf7 each represent a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms and at least one or more fluorine atoms;
M+ represents an ion selected from the group consisting of an ammonium ion, a sodium ion, a potassium ion, and a silver ion; and
“m” represents an integer of 1 to 4.

### Claim 3 (depends on 1)

The bio-electrode composition according to claim 1, wherein the repeating unit-a comprises at least one repeating unit selected from the group consisting of repeating units-a1 to -a7 shown by the following general formula (2),
wherein R1, R3, R5, R8, R10, R11, and R13 each independently represent a hydrogen atom or a methyl group; R2, R9, R4, R6, and R12 each independently represent a single bond, or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group optionally having either or both of an ester group and an ether group; R7 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two hydrogen atoms in R7 are optionally substituted with a fluorine atom; X1, X2, X3, X4, X6, and X7 each independently represent any of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group; X5 represents any of a single bond, an ether group, and an ester group; Y represents an oxygen atom or a —NR19— group; R19 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms; Rf1′ represents a fluorine atom or a trifluoromethyl group; Rf5′ represents a fluorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms and at least one or more fluorine atoms; “m” represents 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 M+ represents an ion selected from the group consisting of an ammonium ion, a sodium ion, a potassium ion, and a silver ion.

### Claim 4 (depends on 2)

The bio-electrode composition according to claim 2, wherein the polymer compound (A) comprises an ammonium ion shown by the following general formula (3) as the M+,
wherein R101d, R101e, R101f, and R101g each represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and optionally have one or more selected from the group consisting of an ether group, a carbonyl group, an ester group, a hydroxy group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom; and R101d and R101e, or R101d, R101e, and R101f are optionally bonded to each other together with a nitrogen atom bonded therewith to form a ring in which R101d and R101e, or R101d, R101e, and R101f, represent an alkylene group having 3 to 10 carbon atoms, or to form a heteroaromatic ring having the nitrogen atom in the formula (3) within the ring.

### Claim 5 (depends on 1)

The bio-electrode composition according to claim 1, wherein the silicone compound (B) having the polyglycerin structure is shown by the following general formula (4) or (5),
wherein each R1′ is identical to or different from each other and independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, a phenyl group, or a silicone chain shown by a general formula (6); R2′ represents a group having a polyglycerin group structure shown by a formula (4)-1 or (4)-2; each R3′ is identical to or different from each other and independently represents the R1′ group or the R2′ group; and each R4′ identical to or different from each other and independently represents the R1′ group, the R2′ group, or an oxygen atom, provided that when R4′ represents an oxygen atom, the R4′ moieties bond to each other and optionally constitute an ether group to form a ring together with silicon atoms;
each a′ is identical to or different from each other and represents 0 to 100, b′ represents 0 to 100, and a′+b′ is 0 to 200, provided that when b′ is 0, at least one R3′ is the R2′ group;
R5′ represents an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms; c′ represents 0 to 20; and d′ represents 1 to 20; and
R6′ and R7′ each represent an alkylene group having 2 to 6 carbon atoms; R8′ represents an alkylene group having 2 to 6 carbon atoms, or an ether group; and R9′ represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, or a phenyl group.

### Claim 6 (depends on 2)

The bio-electrode composition according to claim 2, wherein the silicone compound (B) having the polyglycerin structure is shown by the following general formula (4) or (5),
wherein each R1′ is identical to or different from each other and independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, a phenyl group, or a silicone chain shown by a general formula (6); R2′ represents a group having a polyglycerin group structure shown by a formula (4)-1 or (4)-2; each R3′ is identical to or different from each other and independently represents the R1′ group or the R2′ group; and each R4′ identical to or different from each other and independently represents the R1′ group, the R2′ group, or an oxygen atom, provided that when R4′ represents an oxygen atom, the R4′ moieties bond to each other and optionally constitute an ether group to form a ring together with silicon atoms;
each a′ is identical to or different from each other and represents 0 to 100, b′ represents 0 to 100, and a′+b′ is 0 to 200, provided that when b′ is 0, at least one R3′ is the R2′ group;
R5′ represents an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms; c′ represents 0 to 20; and d′ represents 1 to 20; and
R6′ and R7′ each represent an alkylene group having 2 to 6 carbon atoms; R8′ represents an alkylene group having 2 to 6 carbon atoms, or an ether group; and R9′ represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, or a phenyl group.

### Claim 7 (depends on 3)

The bio-electrode composition according to claim 3, wherein the silicone compound (B) having the polyglycerin structure is shown by the following general formula (4) or (5),
wherein each R1′ is identical to or different from each other and independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, a phenyl group, or a silicone chain shown by a general formula (6); R2′ represents a group having a polyglycerin group structure shown by a formula (4)-1 or (4)-2; each R3′ is identical to or different from each other and independently represents the R1′ group or the R2′ group; and each R4′ identical to or different from each other and independently represents the R1′ group, the R2′ group, or an oxygen atom, provided that when R4′ represents an oxygen atom, the R4′ moieties bond to each other and optionally constitute an ether group to form a ring together with silicon atoms;
each a′ is identical to or different from each other and represents 0 to 100, b′ represents 0 to 100, and a′+b′ is 0 to 200, provided that when b′ is 0, at least one R3′ is the R2′ group;
R5′ represents an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms; c′ represents 0 to 20; and d′ represents 1 to 20; and
R6′ and R7′ each represent an alkylene group having 2 to 6 carbon atoms; R8′ represents an alkylene group having 2 to 6 carbon atoms, or an ether group; and R9′ represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, or a phenyl group.

### Claim 8 (depends on 4)

The bio-electrode composition according to claim 4, wherein the silicone compound (B) having the polyglycerin structure is shown by the following general formula (4) or (5),
wherein each R1′ is identical to or different from each other and independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, a phenyl group, or a silicone chain shown by a general formula (6); R2′ represents a group having a polyglycerin group structure shown by a formula (4)-1 or (4)-2; each R3′ is identical to or different from each other and independently represents the R1′ group or the R2′ group; and each R4′ identical to or different from each other and independently represents the R1′ group, the R2′ group, or an oxygen atom, provided that when R4′ represents an oxygen atom, the R4′ moieties bond to each other and optionally constitute an ether group to form a ring together with silicon atoms;
each a′ is identical to or different from each other and represents 0 to 100, b′ represents 0 to 100, and a′+b′ is 0 to 200, provided that when b′ is 0, at least one R3′ is the R2′ group;
R5′ represents an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms; c′ represents 0 to 20; and d′ represents 1 to 20; and
R6′ and R7′ each represent an alkylene group having 2 to 6 carbon atoms; R8′ represents an alkylene group having 2 to 6 carbon atoms, or an ether group; and R9′ represents a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms and optionally containing an ether group, or a phenyl group.

### Claim 9 (depends on 1)

The bio-electrode composition according to claim 1, further comprising (C) a resin component which is one or more selected from the group consisting of silicone base resins other than the silicone compound (B), acrylic base resins, and urethane base resins.

### Claim 10 (depends on 9)

The bio-electrode composition according to claim 9, wherein the resin component (C) comprises any of:
a silicone resin having an SiO2 unit and an RxSiO(4−x)/2 unit, wherein R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and “x” is a number in a range of 2.5 to 3.5;
diorganosiloxane having an alkenyl group; and
organohydrogenpolysiloxane having an SiH group.

### Claim 11 (depends on 1)

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

### Claim 12 (depends on 1)

The bio-electrode composition according to claim 1, further comprising a carbon powder, a silver powder, a silicon powder, and/or a lithium titanate powder.

### Claim 13 (depends on 12)

The bio-electrode composition according to claim 12, wherein the carbon powder is one or both of carbon black and carbon nanotube.

### Claim 14 (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 comprises a cured material of the bio-electrode composition according to claim 1.

### Claim 15 (depends on 14)

The bio-electrode according to claim 14, wherein the electro-conductive base material 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, and carbon.

### Claim 16 (depends on 14)

The bio-electrode according to claim 14, wherein the living body contact layer is humidified.

### Claim 17 (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 to form the living body contact layer.

### Claim 18 (depends on 17)

The method for manufacturing a bio-electrode according to claim 17, wherein the electro-conductive base material 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, and carbon.

### Claim 19 (depends on 17)

The method for manufacturing a bio-electrode according to claim 17, wherein after the living body contact layer is formed, the living body contact layer is immersed in water, or the living body contact layer is humidified.