Electrically-conductive, pressure-sensitive adhesive and biomedical electrodes

• US 4,848,353 A
• Filed: 09/05/1986
• Issued: 07/18/1989
• Est. Priority Date: 09/05/1986
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Engel, Michael R.
• Primary Examiner(s): Cohen, Lee S.
• Application Number:
  US06/902,396
• Time in Patent Office: 1,047 Days
• Field of Search: 128/639-641, 128/798, 128/802, 128/803, 128/303.13, 427/2, 252/500
• US Class Current: 600/391
• CPC Class Codes: A61B 2562/0215 Silver or silver chloride containing
• CPC Class Codes: A61B 5/259 using conductive adhesive means, e.g. gels
• CPC Class Codes: C08F 2/10 Aqueous solvent
• CPC Class Codes: C08F 220/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 220/04 Acids; Metal salts or ammonium salts thereof
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Abstract

An electrically-conductive, pressure-sensitive adhesive composition having a polymeric matrix comprised of copolymers of hydrogen bond donating monomer (for example acrylic acid) and hydrogen bond accepting monomers (for example N-vinylpyrrolidone) is disclosed. The polymeric matrix is homogeneously mixed with a electrically-conductive plasticizing solution comprised of from 0% to 98% by weight water-soluble, polar organic compound (for example glycerol), 2% to 100% by weight water, and 0 to 12% by weight water-soluble salt. The compsition contains from about 12% to 50% by weight non-volatile copolymer matrix and the hydrogen bond donating sites on the copolymer matrix are from about 5% to about 95% neutralized. Free radical polymerization methods of making the composition and biomedical electrodes incorporating the composition are also described.

Claims

1. A composition comprising:

a conformable, cohesive, adhesive copolymer matrix formed by free radical polymerizing an adhesive precursor comprising a carboxylic acid as a water-soluble hydrogen bond donating monomer, N-vinyl pyrrolidone as a water-soluble hydrogen bond accepting monomer, and a polymerization initiator, wherein the molar ratio of hydrogen bond accepting sites to hydrogen bond donating sites available on the monomers is from about 1;

3 to about 6;

1 and wherein the weight ratio of carboxylic acid to N-vinyl pyrrolidone is from about 1;

2 to about 3;

1; and

a plasticizing, electrically-conductive solution comprised of from about 0 to 98% by weight water-soluble, polar organic compound, about 2 to 100% by weight water, and about 0 to 12% by weight water-soluble salt;

wherein the composition contains from about 12% to about 50% by weight non-volatile copolymer matrix, the hydrogen bond donating sites on the copolymer matrix are from about 5% to about 80% neutralized, and the composition is substantially homogeneous and pressure-sensitive adhesive.

2. The composition of claim 1 wherein the copolymer matrix is covalently crosslinked and the adhesive precursor further comprises a multifunctional crosslinker present up to about 2.5% by weight of the total monomers in the adhesive precursor.

3. The composition of claim 1 wherein the hydrogen bond donating monomer is selected from the group of carboxylic acids consisting of α

,β

-ethylenically unsaturated carboxylic acids having up to eight carbon atoms.

4. The composition of claim 1 wherein the hydrogen bond donating monomer is acrylic acid and the final composition comprises from about 15% to about 25% by weight copolymer matrix.

5. The composition of claim 1 wherein the water-soluble, polar organic compound is selected from a group consisting of monomeric and polymeric polyhydric alcohols.

6. The composition of claim 1 wherein the water-soluble polar organic compound is glycerol.

7. The composition of claim 1 wherein the soluble salt is a chloride, bromide, or iodide salt of sodium or potassium and comprises from 0 to 6% by weight of the plasticizing, electrically-conductive solution.

8. The composition of claim 1 wherein the soluble salt is potassium chloride and it comprises about 1.25% by weight of the plasticizing, electrically-conductive solution.

13. The composition of claim 3 wherein the adhesive precursor comprises by weight

from about 8% to 12% acrylic acid

from about 8% to 12% N-vinylpyrrolidone

from about 0.10% to 0.15% triethylene-glycol-bis-methacrylate

from about 0.05% to 0.07% benzildimethylketal

from about 23% to 27% water

from about 0.75% to 1.25% potassium chloride

from about 48% to 52% glycerol, and the acrylic acid is from about 45% to 55% neutralized with sodium hydroxide.

9. An electrically-conductive, pressure-sensitive adhesive formed by the free radical copolymerization of an adhesive precursor comprising:

a carboxylic acid as a water-soluble hydrogen bond donating monomer;

N-vinyl pyrrolidone as a water-soluble hydrogen bond accepting monomer;

a free radical initiator; and

a plasticizing, electrically-conductive solution comprised of from about 0 to 98% by weight water-soluble, polar organic compound, from about 2 to 100% by weight water, and from about 0 to 12% by weight soluble salt;

wherein the ratio of hydrogen bond accepting sites to hydrogen bond donating sites on the monomers is from about 1;

3 to about 6;

1, the weight ratio of carboxylic acid to N-vinyl pyrrolidone is from about 1;

2 to about 3;

1, the adhesive precursor contains from about 12% to about 50% by weight total monomers, the acid sites on the hydrogen bond donating monomer are from about 5% to about 80% neutralized, and the composition is substantially homogeneous and pressure-sensitive adhesive.

10. The composition of claim 9 wherein the adhesive precursor further comprises a multifunctional crosslinker present up to about 2.5% by weight of the total monomers in the adhesive precursor.

11. The composition of claim 9 wherein the hydrogen bond donating monomer is selected from the group of carboxylic acids consisting of α

,β

-ethylenically unsaturated carboxylic acids having up to eight carbon atoms.

12. The composition of claim 9 wherein the adhesive precursor comprises by weight:

from about 5% to 43.5% acrylic acid,

from about 7% to 45% N-vinylpyrrolidone,

from about 0.05% to 0.3% triethylene-glycol-bis-methacrylate,

from about 0.02% to 0.1% benzildimethylketal,

from about 5% to 60% water,

from about 0.5% to 12% potassium chloride, and

from about 30% to 70% glycerol; and

wherein the acrylic acid is from about 5% to about 80% neutralized with sodium hydroxide.

14. A process for making an electrically-conductive, pressure-sensitive adhesive comprising:

(a) providing an adhesive precursor comprising a carboxylic acid as a hydrogen bond donating monomer, N-vinyl pyrrolidone as a hydrogen bond accepting monomer, a free radical initiator, and a plasticizing, electrically-conductive solution comprised of from about 0 to 98% by weight water-soluble organic compound, from about 2 to 100% by weight water, and from about 0 to 12% by weight soluble salt;

wherein the ratio of hydrogen bond accepting sites to hydrogen bond donating sites on the monomers is from about 1;

3 to about 6;

1, the weight ratio of carboxylic acid to N-vinyl pyrrolidone is from about 1;

2 to about 3;

1, the adhesive precursor contains from about 12% to about 50% by weight of total monomers, the hydrogen bond donating sites on the hydrogen bond donating monomer are from about 5% to about 80% neutralized, and the composition is substantially homogeneous and pressure-sensitive adhesive;

(b) coating the adhesive precursor on a substrate; and

(c) initiating copolymerization of the monomers in the adhesive precursor.

15. A biomedical electrode comprising:

an electrical conductor, means integrally associated with the conductor for connecting the electrode to an electromedical instrument, an electrically-conductive, pressure-sensitive adhesive in electrical contact with the conductor comprising a conformable, cohesive, adhesive copolymer matrix formed by free radical polymerizing an adhesive precursor comprising a carboxylic acid as a water-soluble hydrogen bond donating monomer, N-vinyl pyrrolidone as a water-soluble hydrogen bond accepting monomer, and a polymerization initiator, wherein the molar ratio of hydrogen bond accepting sites to hydrogen bond donating sites available on the monomers is from about 1;

3 to about 6;

1 and wherein the weight ratio of carboxylic acid to N-vinyl pyrrolidone is from about 1;

2 to about 3;

1, and a plasticizing, electrically-conductive solution comprised of from about 0 to 98% by weight water-soluble, polar organic compound, about 2 to 100% by weight water, and about 0 to 12% by weight water-soluble salt;

wherein the electrically-conductive, pressure-sensitive adhesive contains from about 12% to about 50% by weight non-volatile copolymer matrix, the hydrogen bond donating sites on the copolymer are from about 5% to about 80% neutralized, and the composition is substantially homogeneous and pressure-sensitive adhesive.

16. The biomedical electrode of claim 15 further comprising a medical tape comprised of a backing and a biocompatible pressure-sensitive adhesive coated on one surface of the backing wherein the conductor adheres to a portion of the medical tape and the remainder of the medical tape extends beyond the perimeter of the conductor.

17. A method of making a biomedical electrode comprising:

(a) providing a web of conductor;

(b) covering the conductor with an electrically-conductive, pressure-sensitive adhesive comprised of a conformable, cohesive, adhesive copolymer formed by free radical polymerizing an adhesive precursor comprising a carboxylic acid as a water-soluble hydrogen bond donating monomer, N-vinyl pyrrolidone as a water-soluble hydrogen bond accepting monomer, and a polymerization initiator, wherein the molar ratio of hydrogen bond accepting sites to hydrogen bond donating sites available on the monomers is from about 1;

3 to about 6;

1 and wherein the weight ratio of carboxylic acid to N-vinyl pyrrolidone is from about 1;

2 to about 3;

1, and a plasticizing, electrically-conductive solution comprised of from about 0 to 98% by weight water-soluble, polar organic compound, about 2 to 100% by weight water, and about 0 to 12% by weight water-soluble salt;

wherein the electrically-conductive, pressure-sensitive adhesive contains from about 12% to about 50% by weight non-volatile copolymer matrix, the hydrogen bond donating sites on the copolymer matrix are from about 5% to about 80% neutralized, and the composition is substantially homogeneous and pressure-sensitive adhesive; and

(c) cutting the laminate of steps a and b to form electrodes.

18. The method of claim 17 further comprising laminating onto the surface of the conductor opposing the electrically-conductive, pressure-sensitive adhesive a medical tape comprised of a backing and a biocompatible pressure-sensitive adhesive coated on one surface of the backing and cutting the medical tape to a shape and size that provides an apron of medical tape extending beyond the perimeter of the conductor.