ELECTRICALLY CONDUCTIVE COMPOSITIONS AND ELECTRODES UTILIZING SAME

Abstract: Electrically conductive compositions particularly useful for biomedical electrodes wherein the conductive composi­ tion comprises the physical and electrical interface between the electrode and the skin of a subject. The conductive composition is conformable, flexible, adhesive and forms a cohesive body (12) readily adaptable to use at the interface area of the electrode (10). The compositions comprise in interpenetrating polymer network consisting essentially of a hydrophyllic crosslinked polymer formed from a water soluble monomer and a hydrophyllic, polymer which is not crosslinked, a humectant, and water.

Description: ELECTRICALLY CONDUCTIVE COMPOSITIONS AND ELECTRODES UTILIZING SAME I. DESCRIPTION Background of Prior Art This invention relates to electrically conductive compositions per se and electrodes utilizing the compositions as a conductive interface. More particularly, the invention relates to biomedical electrodes utilizing the conductive compositions described herein for establishing electrical contact with the skin of a subject. Consequently, in its preferred embodiments, this invention is directed to medical electrodes for application to the skin. Skin electrodes are of varying types and may be used either as transmission electrodes or as sensing or monitoring electrodes. A wide variety of design configurations have been provided in the past for these kinds of electrodes, all of which are applicable to this invention. A variety ot electrically conductive compositions for biomedical electrodes is known in the art. Generally, they comprise pastes, creams or gels which are relied upon to conduct electric current and improve or establish the electrical connection between the skin of a subject and the electrode per se. Hydrogels have been particularly popular for the conductive composition. Some hydrogels are even self-adhesive in that they are inherently tacky. None of the known compositions is completely satisfactory from all standpoints i.e., as to electrical conductivity, adhesiveness, cohesiveness, flexibility, etc. The electrically conductive compositions of this invention are more satisfactory overall than the prior art compositions. Additionally, they do not tend to dry out as readily. They are based on a unique polymer configuration known as an interpenetrating polymer network. Such networks have not been considered heretofore for use in forming conductive compositions, particularly in the preferred use herein i.e., biomedical electrodes. For purposes herein, an interpenetrating polymer network is a combination of two polymers in network form, which occupy a specific volume and provide a single phase but are essentially not connected by primary chemical bonds. The networks referred to herein are prepared by synthesizing a crosslinked polymer from a water soluble monomer in the presence of an aqueous solution of a water soluble polymer, the first polymer being present in a predominant amount in the resultant interpenetrating polymer network relative to the amount of the second polymer. Additional information concerning interpenetrating networks may be found in the article "Interpenetrating Polymer Networks: Now Thermoplastic" by L.H. Sperling, published in Modern Plastics, October, 1981, the content of which is hereby incorporated by reference. The term "conformable" as used herein refers generally to the flexibility of the bulk conductive compositions or materials of the invention. The materials must be sufficiently flexible to conform to the surface of the skin or the like to which they or the electrode is attached and to provide a high surface area of contact to the skin or the like. The term "cohesive" refers to the internal integrity of the conductive compositions or materials. Generally, the conductive material is self-supporting and must have more cohesive strength than adhesion to the skin or the like so that, when the electrode is removed from the skin or the like, the conductive material remains intact and does not leave an objectionable residue on the skin. Summary of the Invention The conductive compositions of the invention essentially comprise an interpenetrating polymer network including a hydrophyllic, crosslinked polymer, preferably of an N-sulfohydrocarbon-substituted acrylamide, and an organic, hydrophillic, non-crosslinked polymer blended with a humectant and water. Preferably, the molecular weight of this polymer will be about at least 1800, about 5000 or 5100 being especially convenient, but molecular weight is not critical and may vary over a wide range. Two of the essential components of the compositions of the invention form the required interpenetrating polymer network (IPN). These constituents are the aforementioned polymers. The first polymer or polymeric constituent is at least one (usually only one) hydrophyllic, crosslinked polymer, preferably of an N-sulfohydrocarbonsubstituted acrylamide of the type described in U.S. Patent 4,136,078, which is incorporated herein by reference. These polymers contain at least one polymer unit represented by the formula: EMI3.1 in which R1 is hydrogen or a lower (as defined hereinafter) alkyl group and R2 is a divalent or trivalent hydrocarbon group. As used herein, the term "hydrocarbon group" includes aliphatic, cycloaliphatic and aromatic (including aliphatic and cycloaliphatic substituted aromatic and aromatic-substituted aliphatic and cycloaliphatic) groups. It also includes cyclic groups wherein the ring is completed through another portion of the molecule; that is, any two indicated substituents may together form a cyclic hydrocarbon group. Substituted hydrocarbon, alkylaryl, alkylene, arylene, etc., groups are considered fully equivalent to the hydrocarbon, alkyl, aryl, alkylene, arylene, etc., groups and to be part of this invention. By "substituted" is meant groups containing substituents which do not alter significantly the character of reactivity of the group. Preferably, the hydrocarbon or substituted hydrocarbon groups in the N-sulfohydrocarbon-substituted acrylamides are free from ethylenic and acetylenic unsaturation and have no more than about 30 carbon atoms, desirably no more than about 12 carbon atoms. Lower hydrocarbon groups are particularly preferred, the word "lower" denoting groups containing up to seven carbon atoms. Still more preferably, they are lower alkylene or arylene groups, most often alkylene. In the formula, M is hydrogen or one equivalent of a cation and is usually hydrogen or an alkali metal. R1 is hydrogen or lower alkyl as already defined, but is preferably hydrogen or methyl, usually hydrogen. R2 may be any diva lent or trivalent hydrocarbon group, preferably lower alkylene or arylene and usually lower alkylene. In a preferred embodiment of this invention, R2 is EMI4.1 wherein R3 is hydrogen or a lower alkyl group, R4 is a lower alkyl group and the sulfonic acid group is attached to the unsubstituted methylene carbon. These polymers may be obtained by the polymerization, either alone or in combination with other polymerizable vinyl monomers, of the corresponding monomeric N-sulfohydrocarbon-substituted acylamides of which the following acids, and their salts, are examples. EMI5.1 EMI6.1 From the standpoint of economy, ease of preparation and polymerization, and effectiveness, the most desirable polymers are those of 2-acrylamido-2-methylpropanesulfonic acid or its salts. The term "N-sulfohydrocarbon-substituted acrylamide" when used hereinafter will refer to this class of compounds generally, with the understanding that the above named acid and its salts, particularly the sodium and potassium salts are especially preferred. The N-sulfohydrocarbon-substituted acrylamide polymers used in the compositions of this invention may be homopolymers or copolymers, the latter containing at least about 5% by weight, and preferably at least about 50%, of N-sulfohydrocarbon-substituted acrylamide units. The identity of the other monomer or monomers is not critical except that the polymer must be watersoluble or capable of forming a stable aqueous suspension. The most useful polymers are homopolymers (which are preferred) and copolymers with about 5-95%, preferably about 5-50% and most desirably about 5-30%, of an unsaturated acid (e.g., maleic acid) or a derivative thereof, especially an acrylic monomer such as acrylic or methacrylic acid or a salt or amide thereof, notably acrylamide, methacrylamide, N-methylacrylamide, diacetone acrylamide and the like. The N-sulfohydrocarbon-substituted acrylamide polymer is prepared in aqueous solution. The polymerization may be promoted by typical initiators used in aqueous systems, especially peroxides, persulfates, persulfate-bisulfite and the like. The alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid may be polymerized in the absence of polymerization initiator. It is sometimes advantageous to carry out the polymerization in the presence of a small amount of chain transfer agent, which tends to cause formation of a polymer with more uniformity in molecular weight than is otherwise produced. Suitable chain transfer agents are known to those skilled in the art. Preferably, the first polymeric constituent will possess inherent tackiness, as do the N-sulfohydrocarbon-substituted acrylamides, but this is not necessary. Examples of other polymers which may be used as the first polymeric constituent are: hydroxymethylmethacrylate and potassium acrylate polymers. The second polymeric constituent of the compositions and of the interpenetrating polymer network of this invention comprises an organic, non-crosslinked, hydrophillic polymer which possesses inherent tackiness. The most preferred non-crosslinked polymer of this type is polyacrylic acid, available commerically as an aqueous 50% solution GOODRITE# K-732. Other exampls of polymers useful as the second polymeric constituent are: polyvinylpyrollidone, and the various N-sulfohydrocarbon-substituted acrylamide polymers referred to above in non-crosslinked form. The inclusion of the tacky non-crosslinked, hydrophillic second polymer constituent in the interpenetrating polymer network provides the tacky quality of the compositions of the invention along with any tackiness which may be provided by the first polymeric constituent. Preferably, however, the first polymeric constituent is also tacky as already pointed out. As already indicated, the interpenetrating polymer network is formed by polymerizing and crosslinking the first polymeric constituent in the presence of the second polymeric constituent, as is described in detail hereinbelow. In addition to the interpenetrating polymer network formed by the first and second polymeric constituents as described above, the compositions of the invention also essentially include a humectant. Applicable and preferred humectants include glycerol, propylene glycol, sorbitol, polyethylene glycol. Other non-volatile alcohols may be used as the humectant. The only requirement of the humectant is that it be compatible with the material and that it maintain a range of moisture content such that the stated properties of adhesiveness, conformability and conductivity be maintained. The balance of the compositions of the invention essentially comprise water which need not be distilled or deionized or the like although that is preferred. Any water is acceptable although it should at least be potable for medical uses. Ordinarily, the water content of a composition according to the invention will be on the order of about 12 to 45% by weight after the composition has been prepared and dried. During preparation in a preferred way, the water content is deliberately arranged to be higher for ease of preparation and is brought down to the desired range by drying, preferably oven drying. Also, when exposed to high humidity conditions, the compositions will absorb water and may increase the content thereof to as high as 508. Consequently, when water content is referred to herein, unless otherwise specified, the water content being referred to is that of the composition as initially prepared and dried. Generally, in preparing the compositions of the invention, the humectant and water may be included so as to be present during the formation of the interpenetrating polymer network. The compositions of the invention will include the essential constituents in the following ranges (% by weight used throughout) Interpenetrating polymer network (IPN) about 25-75%, about 55% preferred. Humectant ---about 5-50%, about 30% preferred. Water ----the balance. As to the relative amounts of the two polymer constituents in the IPN, the first constituent is most preferably present from about 80% to about 90% and the second constituent is most preferably present from about 10% to about 20%. However, generally speaking, the first constituent must be present in an amount of at least about 35% in the IPN, amounts greater than about 50% being more preferred. As to the relative amounts of the two polymeric constituents in terms of the overall composition, it is preferred that the first polymeric constituent be present within the range of about 24% to 74%, about 45% preferred, the second being present within the range of about 1% to 40%, about 10% preferred. The compositions also include minor amounts of catalytic initiators which are insignificant as to the final properties of these compositions. As is apparent to those skilled in the art, specific minimum amounts and specific relative amounts of the constituents of the compositions of the invention will vary considerably depending on the specific constituents combined and the purpose for which the composition is to be used. In general, it is necessary to select those amounts which will provide a cohesive, flexible, conductive, self-supporting, conformable body of material suitable to a particular intended purpose. In addition to the interpenetrating polymer network, humectant, water i.e., the essential constituents, and the various initiators, the compositions of this invention may contain other compatible ingredients which modify the characteristics thereof, e.g., by improving their remoistening ability, modifying their setting speed, and increasing their thermal stability. These additives may include fillers such as clay, chalk, fiberglass and carbon and antioxidants such as butylated hydroxyanisole, butylated hydroxytoluene and sodium benzoate, as well as others. As already stated, for interface use with biomedical electrodes, the most preferred embodiment of the invention uses, as the crosslinked polymer of the interpenetrating polymer network, a salt of 2-acrylamido-2-methylpropanesulfonic acid, sodium, potassium and lithium salts being typical, the sodium salt being most readily available commercially at the present time. The preferred organic, non-crosslinked hydrophillic polymer is polyacrylic acid. The preferred humectant is glycerol. Compositions including these constituents within the following ranges are preferred for biomedical electrode use (% expressed in terms of overall composition): polymerized 2-acrylamido-2-methyl propanesulfonic acid or one of its sodium salt most preferred about 2 about 45% preferred polyacrylic acid about 1-40%, about 10% preferred EMI10.1 IPN% overall about 25%-75t glycerol about 5-50%, about 308 preferred methylene bis-acrylamide cross-linking agent and initiators . . . up to about 5%, about 0.1% preferred water . . . the balance Brief Description of the Drawings Fig. 1 is a schematic perspective view of an electrode according to the invention. Fig. 2 is a plan view of the electrode of Fig. 1. Fig. 3 is a cross-sectional view taken along line 3-3 of Fig. 2. Fig. 4 is an elevational view of a preferred electrode. Fig. 5 is a plan view of the electrode shown in Fig. 4. Description of Specific Preferred Embodiments The preferred usage of the compositions of the invention lies in their use as the interfacing material for biomedical electrodes. In this usage the compositions provide efficient and effective signal transmission media between a subject's skin and various kinds of electro-medical apparatus. The compositions of the invention and electrodes utilizing same are intended to possess inherent adhesive properties for maintaining contact with the skin as well as possessing a certain amount of flexibility and conformability for movement with the skin in addition to a uniform configuration and homogeneity of composition for contact with the skin and the passage of uniform current densities to or from the skin. The electrodes utilizing the compositions of the invention are easily handled, have an effective operating life without substantial drying out and are non-irritating to the subject. As previously pointed out, this invention particularly lends itself to medical electrodes of varying types, shapes and configurations. For exemplary purposes herein, a skin electrode 10 is shown in one of the common rectangular configurations. Electrode 10 includes flexible, adhesive and conductive member 12 for contacting the skin. The composition of member 12 is in accordance with this invention. An electrical lead means 14, including a conductive member 14a and an insulating sheath or covering 14b, electrically contacts member 12. The embodiment of the electrode as shown in the Figures 1-3 also includes a support or backing 18, the chief purpose of which is to provide a protective and supportive member for the substrate. A preferred backing material is polyethylene foam. One such material is commercially available from Fasson, Inc., a division of Avery International of Paynesville, Ohio, under the trade designation MED 416. The material is a four pound density cross-linked polyethylene foam coated with a tacky adhesive material of an acrylic type. The foam is 1/16th of an inch thick. However, various thicknesses may be used. The foam need not be coated with the adhesive since it will in most instances, readily adhere to substrate 12 which, as previously pointed out, is inherently adhesive. The preferred embodiment makes use of the adhesive coated foam as backing 18, the stainless steel foil current distribution member 16 and substrate member 12. The substrate member may be of various thicknesses, about .05 to .250 inches being preferred. Greater thicknesses may be used as dimension is not critical so long as the electrical resistance is not excessive for the particular use involved. In operation and use, electrode 10 is applied with conductive substrate 12 in direct contact with the skin. The adhesive properties of substrate 12 eliminate the need for separate adhesive tape or any other separate securing measures to hold electrode 10 in continuous contact with the skin. Upon prolonged exposure or use, the substrate may be wiped with water or alcohol to increase its adhesiveness. Electrical signals either to or from the skin, depending on the type of electrode application desired, are conducted through substrate member 12, the current distribution member 16 and electrical lead means 14 including wire 14a. Preferably, wire 14a contacts distribution member 16 by being held between it and backing 18. In a transmission type of arrangement, lead 14 receives electrical signals from an external apparatus (not shown). This signals are conducted into the current distribution member 16 which in turn conducts them into the conductive substrate 12. In this manner current densities are uniformly distributed over the area of substrate 12 and in turn uniformly transmitted to the skin surface in contact with substrate 12. In a sensing or monitoring arrangement, the flow of electricity is reversed in direction, originating at the skin and being conducted through the substrate 12, distribution member 16, lead wire 14a and to a suitable electro-medical monitoring apparatus (not shown). Referring now to Figures 4 and 5, a preferred electrode configuration is shown. The electrode includes a conductive, carbon-filled silicone rubber support body 18 including a raised rib 18a contacted by an electrical lead 14. Attached to the bottom of body 18 is substrate 12 which comprises a composition of the invention. The composition is constituted so as to be adhesive, conductive, pliant, conformable and cohesive. Attachment is by the inherent adhesive quality of the composition. Typically, about 50% carbon mixed with the silicone rubber will provide a suitable support body although this amount is not critical. Any amount providing a conductive body is generally satisfactory. Other conductive fillers such as silver and the like may be used. Also, materials other than silicone rubber may be used such as any elastomer material which is either conductive inherently or which may be rendered conductive by filling. Also, the support member 18 may be a thin flexible conductive material such as an aluminum or stainless steel foil or the like to which substrate 12 is directly attached, lead 14 then being attached to the foil member. The composition of conductive substrate member 12 is unique to the invention, as already indicated. As previously stated, it includes an interpenetrating polymer network, preferably of polymerized 2-acrylamido-2-methylpropanesulfonic (AMPS) acid or one of its salts and polyacrylic acid. In addition to the interpenetrating polymer network, the composition includes a humectant, preferably glycerol, and water so as to provide in preferred form a flexible sheet-like body. Crosslinked copolymers may also be used as the first polymeric constituent to form the interpenetrating network. Copolymers may also be used as the second polymeric constituent. Additional polymeric thickeners and the like may be blended into the composition, although they are not ordinarily needed. The various constituents are provided in such relative amounts as to form a flexible, self-supporting material with substantial shape retention which has adhesive properties and which is electrically conductive. Preferably, the interpenetrating polymer network is formed by polymerizing and crosslinking 2-acrylamido-2methylpropanesulfonic acid or one of its salts, most preferably the sodium salt form, in the presence of non-cross-linked polyacrylic acid. The polymerization is carried out in aqueous solution in the presence of the humectant. In the principle preferred embodiments, substrate member 12 comprises a sheet-like body of interpenetrating polymer network material formed from the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid monomer purchased from the The Lubrizol Corporation. The monomer upon being dissolved in water is readily polymerized. The preferred non-crosslinked polymer is polyacrylic acid dissolved in water. The preferred humectant is glycerol mixed in the aqueous solution in which polymerization and crosslinking of the first polymeric constituent is carried out in the presence of the second polymeric constituent. The following Examples are provided for illustration of the invention. EXAMPLE I 140 mls of sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) solution and 18 mls of GOODRITE K-732 solution are mixed together. The Na AMPS solution comprises 35.708 Na AMPS, 21% glycerol and 0.76% methylene bis-acrylamide (MBA) (crosslinking agent), balance water. The COODRITE K-732 solution comprises 50% by weight polyacrylic acid in water. The molecular weight of the polyacrylic acid in GOODRITEO K-732 is 5100. The mixture is purged with nitrogen for about ten minutes following which cataylic initiators are added. Preferred catalytic initiators comprise potassium metabisulfite solution (99.62% deionized water, 0.38% potassium meta-bisulfite) potassium persulfate sqlution (99.62% deionized water, 0.38% potassium persulfate) and ferrous sulfate solution (99.76% deionized water, 0.24% ferrous sulfate). The catalytic initiators are simultaneously injected, via individual 3 cc syringes into the nitrogen purged agitated monomer solution. Upon addition of the initiators, the mixture is allowed to agitate for a short time, approximately ten seconds is satisfactory, then it is quickly poured into a tray or other suitable mold in an enclosed nitrogen atmosphere. The solution polymerizes to a solid, tacky, clear gel like material in about 5 minutes following exotherm. The exotherm time is about 90 + 15 seconds. Preferably, the tray or mold (7 3/4 X 12 e inches used in this instance) into which the solution is poured will have the bottom thereof covered with a Mylar polyester sheet. Following polymerization the polymer body may then be readily removed from the mold along with the Mylar polyester sheet as a backing thereof. The body is then dried with the Mylar in place in a forced air oven. For this particular example, drying at about 3 hours at 70 C is adequate. The preparation described provides a sheet-like body 7 3/8 X 12 inches and about .060 inches thick having a composition after drying as follows (% in terms of overall cmposition): Na AMPS 49.28 Polyacrylic acid 8.9% Glycerol 28.9% MBA (including initiators) 0.1% Water 12.9% The volume resistivity of this material and all other materials reported herein can be expected to fall below about 30,000 ohm-cm. Example I represents the most preferred composition and the most preferred mode of preparation, utilizing prepared solutions which are mixed together. This technique does not utilize heat activated catalysts, which may be used if desired. Non-heat activated cata lysts are preferred from a production standpoint. Other modes of preparation are illustrated in some of the following Examples which do use heat activated catalysts. EXAMPLE II The following constituents were mixed together under ambient conditions. The mixture was poured into a mold. The mold was placed in a vacuum oven, deaerated and heated at a temperature of 65iC for about 4 hours. It was then placed in a forced air oven and dried at about 60'C to a weight of about 60 gms. Mixture Hydroxyethylmethacrylate * (HEMA) 15 gms Polyvinylpyrollidone (PVP) 24 gms Glycerol 10 gms Water 50 gms 2,2'-AzobisE2-methylpropionitrilei (AIBN) 0.02 gms *sold with 0.5-1.5% impurity ethyleneglycoldimethacrylate, a crosslinker. The composition of the resultant product is: Final Composition HEMA 25% PVP 40% Glycerol 16.78 AIBN 0.03% Water 18.27% EXAMPLE III Same as Example II with differences noted. Mixture Potassium Acrylate 10 gms (57% solution in water) GOODRITE K-732 0.5 gms Glycerol 10 gms MBA 10 gms (1t solution in water) Ammonium persulfate (AP) 0.5 gms (2% solution in water) In preparation, this material was oven dried to a weight of 20 gms. Final Composition Potassium Acrylate 28.5% GOODRI K-732 1.2% Glycerol 50.58 MBA 0.5% AP 0.05% Water 19.75% EXAMPLE IV Same as Example III with differences noted. Mixture Na AMPS 150 gms (50% solution in water) GOODRITE K-732 9 gms (508 solution in water) (MW 1800) PAA) Glycerol 5 gms MBA 50 gms (1% solution in water) AP 4 gms (2% solution in water) Dried to 100 gms. Final Composition Na AMPS 75% GOODRITE K-732 (PAA) 4.5% Glycerol 5% MBA 0.5% AP 0.08% Water 14.92% EXAMPLE V Same as Example III with differences noted. Mixture Na AMPS solution as in Example I 50 mls Carbopol 940 (tradename of B.F. Goodrich Co.) (PAA MW 4 million) 1.5 gms AP 0.5 gms Dried to 33 gms. Final Composition Na AMPS 51.9% PAA 4.5% Glycerol 30.5% MBA 1.0% AP 0.03% Water 12. 07% EXAMPLE VI Same as Example III with differences noted. Mixture Na AMPS 84 gms (50% solution in water) Acrylamide (copolymer with Na AMPS) 40 gms PVP 6 gms Glycerol 40 gms MBA 6 gms (1% solution in water) AP 2 gms No drying - as made. Final Composition Na AMPS 30.3% Acrylamide 1.9% PVP 4.3% Glycerol 28.8% MBA 0.04% AP 0.03% Water 34.63% EXAMPLE VII Same as Example III with differences noted. Mixture Na AMPS solution as in Example I 10 gms GOODRITE# K-732 (PAA) 2 gms MBA 40 gms (1% solution in water) AP 0.5 gms Dried to 9.5 gms. Final Composition Na AMPS 37.6% PAA 10.5% Glycerol 22.1% MBA 5-0% AP 0.1% Water 24.7% EXAMPLE VIII Same as Example III with differences noted. Mixture Na M4PS 80 gms (50% solution in water) Potassium Acrylate (copolymer with NaAMPS) 20 gms (57% solution in water) PVP 6 gms Glycerol 40 gms MBA 6 gms AIBN 0.02 gms Not dried - as made. Final Composition Na AMPS 26% Potassium Acrylate 7.5% PVP 3.9% Glycerol 26.3% MBA 0.04% AIBN 0.01% Water 36.25% EXAMPLE IX Same as Example III with differences noted. Mixture 2-acrylamido-2-methylpropane sulfonic acid (AMPS) 80 gms (50% solution in water) PVP 6 gms Glycerol 40 gms MBA 6 gms (1% solution in water) AP 0.4 gms (1% solution in water) Not dried - as made. Final Composition AMPS 30.2% PVP 4.5% Glycerol 30.2% MBA 0.045% AP 0.003% Water 35.052% EXAMPLE X Same as Example I with differences noted. Mixture Na AMPS 85 gms (50% solution in water) GOODRITE# K-732 15 gms (50% solution in water) Glycerol 25 gms MBA 9 gms (1% solution in water) Each catalyst in Example I ¯ 2 gms each NaCl 0.75 gms Dried to 138 gms. Final Composition Na AMPS 30.8% PAA 5.4% Glycerol 18.1% MBA 0.07% Catalysts 0.02% NaCl 0 54% Water 45.08% EXAMPLE XI Same as Example I with differences noted. Mixture Na AMPS 85 gms (50% solution in water) GOODRITE K-732 (PAA) 20 gms (50% solution in water) Propylene glycol 15 gms MBA 2 gms Catalysts as in Example I 6 gms total Not dried - as made. Final Composition Na AMPS 29.7% PAA 7.0% Propylene Glycol 10.5% Glycerol 10.5% MBA 0.014% Catalysts 0.014% Water 42.272% As already pointed out, various additives may be included in the compositions of the invention, it only being necessary that the compositions include, in varying amounts, the essential interpenetrating polymer network with a sufficient amount of water and humectant to provide the requisite electrically conductive, conformable and flexible, cohesive, adhesive body. Various body thicknesses of the compositions may be used as desired and any electrode configuration with or without backing support and current distribution member may be used. Release paper of the waxed, siliconetreated or plastic coated variety or Mylar polyester sheet may be included to protect the substrate material prior to use. Electrodes utilizing these compositions or any other devices utilizing same or the compositions per se should be stored in a sealed container or under controlled conditions or humidity to prevent drying out. Many changes in embodiments of the invention will become apparent to those of ordinary skill in this art without departing from the scope of the invention. The description herein is not intended to be limiting in any sense and the exclusive property rights claimed are defined hereinbelow. WHAT IS CLAIMED IS:

Claims: Claims 1. An electrically conductive, adhesive, cohesive com position characterized by: an interpenetrating polymer network essentially in cluding two components: a first polymeric constituent which is crosslinked and hydrophilic and a second po lymeric constituent which is hydrophyllic and not crosslinked, the network being comprised of at least about 35% of the first constituent. humestant, and water. 2. The composition of claim 1 wherein the interpenetra ting network is comprised of an amount of the first polymeric constituent in excess of about 50% and pre ferably between about 80% and 90%. 3. The composition of claim 1 or 2 wherein the inter penetrating polymer network comprises about 25% to 70% of the overall composition. 4. The composition of any one of the preceding claims wherein the amount of the humectant is about 5% to 50%. 5. The composition of any one of the preceding claims wherein the first polymeric constituent is a hydroxy methylmethacrylate polymer. 6. The composition of any one of claims 1 to 4 wherein the first polymeric constituent is a potassium acrylate polymer. 7. The composition of any one of claims 1 to 4 wherein the first polymeric constituent is an N-sulfohydro carbon substituted acrylamide polymer. 8. The composition of any one of claims 1 to 4 wherein the second polymeric constituent is polyacrylic acid. 9. An adhesive, electrically conductive composition, characterized by essentially including between about 25% and about 75% of an interpenetrating polymer net work formed as the result of the polymerization and cross-linking of 2-acrylamido-2-methylpropanesul foni c acid or one of its salts in the presence of a hydro phyllic polymer and including between about 5S to about 50% of a humectant, the balance being substan tially water. 10. The composition of claim 9 wherein a salt form of the 2-acrylamido-2-methylpropanesulfonic acid is poly merized. 11. The composition of claim 10 wherein the salt is a sodium salt. 12. The composition of any one of claims 9 to 11 wherein the amount of the polymer network is about 50%. 13. The composition of any one of claims 9 to 12 wherein the hydrophyllic polymer is polyacrylic acid. 14. The composition of claim 13 wherein the molecular weight of the polyacrylic acid is about 5,000. 15. The composition of any one of the preceding claims wherein the humectant is glycerol. 16. The composition of any one of claims 1 to 14 wherein the humectant is propylene glycol, polyethylene glycol or sorbitol. 17. The composition of any one of the preceding claims wherein the amount of the humectant is about 30%. 18. An electrically conductive, adhesive, conformable and flexible, cohesive body, characterized by: an interpenetrating polymer network essentially in cluding two components: polymerized and crosslinked 2-acrylamido-2-methylpropanesulfonic acid, its salts or copolymers of the acid or its salts as the first component and, as the second component, an organic, hydrophilic polymer, the amounts of the first com ponent and the second component in terms of overall composition ranging from about 24% to 74% and 12 to 40%, respectively; a humectant ranging in amount from about 5X to 50%, and water, substantially the balance. 19. The body of claim 18 wherein the amounts of the two polymer network components are about 45% and 10%, respectively. 20. The body of claim 18 or 19 wherein the amount of the humectant is about 30%. 21. The body of any one of claims 18 to 20 wherein the amount of the interpenetrating polymer network is about 25% to 75X and preferably about 50%. 22. The body of any one of claims 18 to 21 wherein the first component is a polymerized salt of 2-acrylamido 2-methylpropanesulfonic acid. 23. The body of claim 22 wherein the salt is a sodium salt. 24. The body of any one of claims 18 to 23 wherein the second component is polyacrylic acid. 25. The body of claim 24 wherein the molecular weight of the polyacrylic acid is about 5,000. 26. An electrically conductive, adhesive, cohesive body, characterized in that the body is comprised predomi nately of an interpenetrating polymer network essen tially including two polymer components: a cross linked, hydrophilic polymer and a non-crosslinked, linear hydrophilic polymer and including in lesser amounts a humectant and water. 27. The body of claim 26 wherein the interpenetrating po lymer network is comprised of at least about 35% and preferably at least about 50X of the crosslinked poly mer. 28. The body of claim 27 wherein the amount is about 80% to 90% and the second component comprises substan tially the balance of the network. 29. The body of claim 14 wherein the humectant is glycerol. 30. The body of claim 14 wherein the humectant is propylene glycol, sorbitol or polyethylene glycol. 31. An adhesive electrode for establishing electrical con tact with a surface, comprising: support means and terminal means for connection to external electrical circuit means, and an adhesive, conductive body for electrically inter facing with the surface to be contacted, the body being contacted by the support means and being in electrical communication with the terminal means, characterized by the adhesive, conductive body comprising a compo sition of an interpenetrating polymer network essen tially including two components: a first polymeric constituent which is crosslinked and hydrophilic and, a second polymeric constituent which is hydrophilic and not crosslinked, the network including at least about 35% of the first constituent; a humectant, and water. 32. The electrode of claim 31 wherein the composition in cludes as the two components: polymerized crosslinked 2-acrylamido-2-methylpropanesulfonic acid, its salts or copolymers of the acid or its salts as the first component and, as the second polymeric component, the overall amounts of the first and second components ranging from about 24% to 74X and 1% to 40%, respec ti vely. 33. The electrode of claim 32 wherein the first component is a polymerized salt form of the 2-acrylamido-2 methylpropanesulfonic acid. 34. The electrode of claim 33 wherein the salt is a so dium salt. 35. The electrode of any one of claims 32 to 34 wherein the hydrophilic polymer is polyacrylic acid. 36. The electrode of claim 35 wherein the molecular weight of the polyacrylic acid is about 5,000. 37. The electrode of any one of claims 31 to 36 wherein the humectant is glycerol. 38. The electrode of any one of claims 31 to 36 wherein the humectant is propylene glycol, sorbitol or poly ethylene glycol. 39. The electrode of any one of claims 31 to 38 wherein the amount of the humectant is about 30%.

Inventors: CAHALAN, PATRICK T., JEVNE, ALLAN H., PERRAULT, JAMES J.
Applicants: MEDTRONIC, INC.
Application year: 1983
Main classification: A61B5
IPC codes: C09J133, A61N1, H01B1, G01N33, B32B27, A61B5