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

Patent metadata

Field	Value
Publication number	US-10743788-B2
Application number	US-201816137885-A
Country	US
Kind code	B2
Filing date	Sep 21, 2018
Priority date	Oct 19, 2017
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

The present invention provides a bio-electrode composition including: a resin containing a urethane bond in a main chain and a siloxane bond 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 formulae (1)-1 and (1)-2, sulfonimide salts shown by the following formula (1)-3, and sulfonamide salts shown by the following 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.

First claim

What is claimed is:

1. A bio-electrode composition comprising:
a resin containing a urethane bond in a main chain and a siloxane bond in a side chain; and
an electro-conductive material,
wherein the electro-conductive material is a polymer compound having one or more repeating units comprising a structure selected from the group consisting of fluorosulfonic acid salts shown by the following formulae (1)-1 and (1)-2, sulfonimide salts shown by the following formula (1)-3, and sulfonamide salts shown by the following formula (1)-4,

wherein Rf 1 and Rf 2 each represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, or an oxygen atom, provided that when Rf 1 represents an oxygen atom, Rf 2 also represents an oxygen atom to form a carbonyl group together with a carbon atom bonded therewith; Rf 3 and Rf 4 each represent a hydrogen atom, a fluorine atom, or a trifluoromethyl group, provided that one or more fluorine atoms are contained in Rf 1 to Rf 4 ; Rf 5 , Rf 6 , and Rf 7 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 R 1 to R 4 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.

2. The bio-electrode composition according to claim 1 , wherein the one or more repeating units comprising a structure selected from the group consisting of fluorosulfonic acid salts shown by the formulae (1)-1 and (1)-2, sulfonimide salts shown by the formula (1)-3, and sulfonamide salts shown by the formula (1)-4 is one or more repeating units selected from repeating units a1 to a7 shown by the following formulae (2),

wherein R 5 , R 7 , R 9 , R 12 , R 14 , R 15 , and R 17 each independently represent a hydrogen atom or a methyl group; R 6 , R 8 , R 10 , R 13 and R 16 each independently represent any of a single bond, an ester group, or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms optionally having either or both of an ether group and an ester group; R 11 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R 11 are optionally substituted with a fluorine atom; Z 1 , Z 2 , Z 3 , Z 4 , and Z 6 each independently represent any of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, or an amide group; Z 5 represents any of a single bond, an ether group, or an ester group; Z 7 represents a single bond, an arylene group having 6 to 12 carbon atoms, or —C(═O)—O—Z 8 —; and Z 8 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 Z 8 ; Y represents an oxygen atom or an —NR 18 — group; R 18 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, optionally bonded to R 8 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 Rf 5 , Rf 6 , Rf 7 , and X + have the same meanings as defined above.

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

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

5. The bio-electrode composition according to claim 1 , wherein the resin containing a urethane bond in a main chain and a siloxane bond in a side chain has a structure shown by the following formula (3),

wherein R 20 , R 21 , R 22 , R 24 , R 25 , and R 26 each represent a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 3,3,3-trifluoropropyl group; R 23 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a trialkylsiloxy group; R 27 and R 29 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 27 and R 29 is 1 or 2; R 28 represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; R 30 represents a hydrogen atom or a methyl group; “A” represents a linear or branched alkylene group having 3 to 7 carbon atoms; “s” and “t” are integers of 0 to 10 in the range of 1≤s+t≤10.

6. The bio-electrode composition according to claim 2 , wherein the resin containing a urethane bond in a main chain and a siloxane bond in a side chain has a structure shown by the following formula (3),

wherein R 20 , R 21 , R 22 , R 24 , R 25 , and R 26 each represent a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 3,3,3-trifluoropropyl group; R 23 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a trialkylsiloxy group; R 27 and R 29 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 27 and R 29 is 1 or 2; R 28 represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; R 30 represents a hydrogen atom or a methyl group; “A” represents a linear or branched alkylene group having 3 to 7 carbon atoms; “s” and “t” are integers of 0 to 10 in the range of 1≤s+t≤10.

7. The bio-electrode composition according to claim 3 , wherein the resin containing a urethane bond in a main chain and a siloxane bond in a side chain has a structure shown by the following formula (3),

wherein R 20 , R 21 , R 22 , R 24 , R 25 , and R 26 each represent a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 3,3,3-trifluoropropyl group; R 23 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a trialkylsiloxy group; R 27 and R 29 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 27 and R 29 is 1 or 2; R 28 represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; R 30 represents a hydrogen atom or a methyl group; “A” represents a linear or branched alkylene group having 3 to 7 carbon atoms; “s” and “t” are integers of 0 to 10 in the range of 1≤s+t≤10.

8. The bio-electrode composition according to claim 4 , wherein the resin containing a urethane bond in a main chain

Assignees

• Shinetsu Chemical Co

Inventors

• Hatakeyama Jun
• Watanabe Osamu
• Iwabuchi Motoaki

Classifications

• A61B2562/125

  characterised by the manufacture of electrodes · CPC title

• A61B5/24 Primary

  Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof · CPC title

• C08G18/4825 Primary

  Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title

• A61B5/25

  Bioelectric electrodes therefor · CPC title

• C08G18/8025

  Masked aliphatic or cycloaliphatic polyisocyanates · CPC title