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

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 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 l 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 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 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, 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; 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 each optionally substituted with a fluorine atom; Z 1 , Z 2 , Z 3f 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, and an amide group; Z 5 represents any of a single bond, an ether group, and an ester group; Z 7 represents a single bond, an arylene group having 6 to 12 carbon atoms, or —C(═O)—O—Z 8 —; 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 of a sulfonamide salt shown by the general 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 of a sulfonamide salt shown by the general 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 silsesquioxane in a side chain has a structure shown by the following general formula (3),

wherein R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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.

6. 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 R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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.

7. 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 R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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; R 25 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.

8. 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 R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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; R 25 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.

9. 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 R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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.

10. 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 R 20 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; R 21 and R 23 each represent a single bond, a methylene group, or an ethylene group, provided that the total number of carbon atoms of R 21 and R 23 is 1 or 2; R 22 and R 24 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.

11. 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 R 20 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; R 22 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.

12. 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 R 20 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; R 22 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.

13. 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 R 20 and R 22 have the same meanings as defined above; R 26 to R 28 each represent an alkyl group having 1 to 6 carbon atoms; and R 29 and R 30 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.

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

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

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

17. 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 .

18. 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.

19. 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.

20. 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.