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

Patent metadata

Field	Value
Publication number	US-10759938-B2
Application number	US-201816130184-A
Country	US
Kind code	B2
Filing date	Sep 13, 2018
Priority date	Oct 26, 2017
Publication date	Sep 1, 2020
Grant date	Sep 1, 2020

Abstract

The present invention provides a bio-electrode composition including: a resin containing a main chain having a urethane bond and two side chains each having a silicon-containing group; 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

The invention claimed is:

1. A bio-electrode composition comprising:
a resin containing a main chain having a urethane moiety and two side chains each having a silicon-containing group; and
an electro-conductive material,
wherein the electro-conductive material is a polymer compound having one or more fragments 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 alkenyl group having 2 to 14 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, optionally having an ether group, an ester group, a carbonyl group, a sulfonyl group, a cyano group, an amino group, a nitro group, hydroxy group, a sulfur atom except in the sulfonyl group, or 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 fragments are present in 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 13 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 containing a sulfonamide salt shown by the formula (1)-4.

4. The bio-electrode composition according to claim 1 , wherein the resin containing a main chain having a urethane moiety and two side chains each having a silicon-containing group has a structure shown by the following formula (3),

wherein R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each represent a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a group shown by —(OSiR 25 R 26 ) n —OSiR 27 R 28 R 29 ; R 25 , R 26 , R 27 , R 28 , and R 29 have the same meanings as R 19 to R 24 ; “n” is a number in a range of 0 to 100; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and X represents a methylene group or an ether group.

5. The bio-electrode composition according to claim 2 , wherein the resin containing a main chain having a urethane moiety and two side chains each having a silicon-containing group has a structure shown by the following formula (3),

wherein R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each represent a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a group shown by —(OSiR 25 R 26 ) n —OSiR 27 R 28 R 29 ; R 25 , R 26 , R 27 , R 28 , and R 29 have the same meanings as R 19 to R 24 ; “n” is a number in a range of 0 to 100; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and X represents a methylene group or an ether group.

6. The bio-electrode composition according to claim 3 , wherein the resin containing a main chain having a urethane moiety and two side chains each having a silicon-containing group has a structure shown by the following formula (3),

wherein R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each represent a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a group shown by —(OSiR 25 R 26 ) n —OSiR 27 R 28 R 29 ; R 25 , R 26 , R 27 , R 28 , and R 29 have the same meanings as R 19 to R 24 ; “n” is a number in a range of 0 to 100; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; and X represents a methylene group or an ether group.

7. The bio-electrode composition according to claim 1 , wherein the resin containing a main chain having a urethane moiety and two side chains each having a silicon-containing group has a structure containing a polyether main chain shown by the following formula (4),

wherein R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each represent a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3,3,3-trifluoropropyl group, or a group shown by —(OSiR 25 R 26 ) n —OSiR 27 R 28 R 29 ; R 25 , R 26 , R 27 , R 28 , and R 29 have the same meanings as R 19 to R 24 ; “n” is a number in a range of 0 to 100; “A” represents a linear or branched alkylene group having 1 to 4 carbon atoms; X represents a methylene group or an ether group; R 30 represent a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms; and “v” and “w” satisfy 0<v<1.0, 0<w<1.0, and 0<v+w≤1.0.

8. The bio-electrode composition according to claim 2 , wherein the resin containing a main chain having a urethane moiety and two side chains each having a s

Assignees

• Shinetsu Chemical Co

Inventors

• Hatakeyama Jun
• Watanabe Osamu
• Iwabuchi Motoaki
• Nonaka Shiori

Classifications

• A61B5/24 Primary

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

• A61B2562/125

  characterised by the manufacture of electrodes · CPC title

• A61B5/024 Primary

  Measuring pulse rate or heart rate · CPC title

• C08G18/4854

  Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group · CPC title

• C08K2201/00

  Specific properties of additives · CPC title