CA1332010C - Electrically conductive adhesive materials - Google Patents
Electrically conductive adhesive materialsInfo
- Publication number
- CA1332010C CA1332010C CA000602036A CA602036A CA1332010C CA 1332010 C CA1332010 C CA 1332010C CA 000602036 A CA000602036 A CA 000602036A CA 602036 A CA602036 A CA 602036A CA 1332010 C CA1332010 C CA 1332010C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- percent
- molecular weight
- present
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/251—Means for maintaining electrode contact with the body
- A61B5/257—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes
- A61B5/259—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes using conductive adhesive means, e.g. gels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Abstract
ABSTRACT ELECTRICALLY CONDUCTIVE ADHESIVE MATERIALS Electrically conductive adhesive material possessing good adhesive, cohesive, elastomeric and conductive properties is disclosed. The present adhesive material also has improved electrical stability since it is less susceptible to drying out in most ambients. The material comprises a plasticizer, a high molecular weight water-soluble polymer, uncrosslinked polyvinylpyrrolidone as the tackifier, and an electrolyte dopant.
Description
1 3320 t 0 ELECTRICALLY CONDUCTIVE ADHESIVE MATERIALS
The present invention relates to electrically conductive adhesive materials and more particularly concerns such materials suitable for use with biomedical electrodes.
In accordance with the present invention an improved electrically conductive adhesive material is disclosed. The conductive adhesive suitable for use with, for example, biomedical electrodes comprises a low molecular weight plasticizer selected from alcohols and polyhydric alcohols; a high molecular weight water soluble, cxoss-linkable polymer, which is also soluble in said plasticizer;
uncrosslinked polyvinylpyrrolidone in an amount sufficient to tackify the plasticizer and polymeri and, an electrolyte dopant in an amount sufficient to render the adhesive material electrically conductive.
'~
~ 33201 0 The electrically conductive adhesive material of the present invention is suitable for use in any of the biomedical electrodes known in the art. Referring to the FIGURE, a typical biomedical electrode 10 comprises an electrode plate 12 (which may be a plate probe or element) integral with a backing layer 14 of a web-like or foam-like material as known in the art.
The backing layer 14 is typically larger in diameter than the electrode plate 12 so as to provide a relatively broad area of contact with the skin for electrical and adhesive purposes. As shown in the FIGURE, the electrode plate 12 may -actually extend through the backing layer 14. The electrically conductive adhesive material 16 is contacted to that side of the backing layer 14 which is to be directed to the skin. The electrode 10 may optionally include a conductive film (not shown) interposed the backing layer 14 and the conductive adhesive 16 as known in the art.
Alternatively, the backing layer 14 may be a conductive film. While the FIGURE illustrates one ~ type of biomedical electrode, it should be apparent `~ that other electrode designs and any application ~` 25 requiring electrically conductive adhesive materials would be benefited by the present invention.
The electrically conductive adhesive material of the present invention is advantageous ~,~
-` 1 3320 1 0 in that it functions as a highly flexible, elastomeric gel-like substance with excellent electrical, cohesive and adhesive properties while having a water content of about 10 to 20 percent by weight or less in a preferred embodiment. In general, the conductivity, and often the elastomeric properties, of these types of material are highly dependent on the amount of water formulated into the material. Prior art materials which rely upon a high water content (e.g. 50 weight percent and above) are typically susceptible to drying out in most ambients. To prevent possible loss of conductivity and/or elastomeric properties, stringent packaging and storing are ; 15 necessary when using these prior art materials.
Since materials containing about 20 percent by weight of water are less subject to drying out, more stable, electrically conductive adhesive materials are provided by the present invention.
Polyvinylpyrrolidone is an ingredient found in prior art conductive adhesives as a basic polymer around which the composition is built, or as a thickening agent. Such compositions in which polyvinylpyrrolidone is the basic polymer typically include a tackifier, such as abietic acid and the like, to impart adhesive qualities to the material.
Unexpectedly, polyvinylpyrrolidone in combination with polymer/plasticizer blends otherwise known to require a tackifying agent produces a gel-like polymeric substance with excellent adhesive and cohesive properties. These prior art uses of ~ 3320 1 0 polyvinylpyrrolidone utilize the cross-linked form of the polymer which gives it the desired properties.
Unexpectedly, it has been found that uncrosslinked polyvinylpyrrolidone functions as well as a tackifying agent in the compositions of the present invention.
The conductive adhesive of the present invention includes a low molecular weight plasticizer selected from alcohols and polyhydric alcohols. The alcohols suitable for use as the plasticizer should be re-latively non-volatile at room temperature, i.e. they should have a vapor pressure higher than that of water. Typical alcohols include isooctylalcohol, decanol and the like. Polyhydric alcohols suitable for use as the plasticizer include polyethylene glycol, methoxy polyethylene glycols, propylene glycol, higher alkyl glycols and glycerin, with the latter being preferred. The plasticizer preferably has a ~
molecular weight of less than about 4000. The low `
molecular weight plasticizer is typically present in an amount of from about 40 to 92 percent by weight, and preferably from about 50 to 70 percent by weight of the total adhesive material.
The high molecular weight water soluble polymer must be susceptible to chemical and/or ionic cross-linking and must also be soluble in said plasticizer. The cross-linking (of one type , ~ or the other) gives the desired viscosity to the adhesive. Polymers suitable typically have a molecular weight above 4000 and include gelatin, ;~ polyethylene oxides, and polyvinylalcohols. Poly-vinylalcohols having a molecular weight of between ~ 1332010 about 20,000 and 108,000 are preferred and polyvinylalcohol which is about 88% hydrolyzed having a molecular weight of about 78,000 is most preferred because of the excellent flexibility it imparts to the conductive adhesive. The high molecular weight polymer is typically present in an amount of from about 2 to 54 percent by weight, and preferably from about 2 to 10 percent by weight of the total adhesive material.
The uncrosslinked-polyvinylpyrrolidones suitable for use in the present invention have a molecular weight between about 10,000 and 360,000 with 10,000 being preferred. The uncrosslinked polyvinylpyrrolidone should be present in an amount of from about 1 to about 53 percent by weight, and preferably from about 5 to 30 percent by weight of the total adhesive material.
The electrolyte dopant of the present invention may be any organic or inorganic ionizable salt whlch will provide the desired conductivity and does not interfere with the physical properties of the adhesive. For use on electrocardiograph electrodes, the salt must also be capable of re-covering rapidly following defibrillation overload.
Inorganic ionizable salts, particularly inorganic halide salts are well~suited as electrolyte dopants for the present invention. The salts can be mono-valent such as sodium chloride, potassium chloride, or silver chloride or polyvalent such as magnesium chloride, magnesium acetate, zinc chloride, zinc acetate, calsium chloride, or ferric chloride with magnesium chloride being preferred. The polyvalent salts such as magnesium chloride are ~- 1 3320 1 0 preferred as the electrolyte dopant because they can ionically cross-link numerous of the high molecular weight, water-soluble polymers, such as the polyvinylalcohols, described above. When the polyvalent salts, such as magnesium chloride serve the dual function of electrolyte and cross-linking agent, the further addition of a cross-linking - agent is optional. The electrolyte dopant is typically present in an amount of from about 5 to about 57 percent by weight, and preferably from about 10 to 35 percent by weight of the total adhesive.
The electrolyte dopant may also contain water. For example, the preferred dopant is typically in hydrated form, i.e. magnesium chloride hexahydrate (MgCl2 6H2O) which is approximately 50 percent by weight of water. Additionally the hydrated or nonhydrated salts used as the electrolyte may be in an aqueous solution. For those dopants containing water (i.e. salts which are hydrated and/or in aqueous solution), the salt to water weight ratio should be from about 1:1 to about 1:40. For example, in one embodiment the dopant is an aqueous solution comprising 20 weight percent of magnesium chloride hexahydrate (consisting of 10 weight percent MgCl2 and 10 weight percent water) in 10 weight percent of water. Such a dopant composition is illustrative of the preferred 1:2 salt to water ratio for the electrolyte of the present invention.
1332~1~
Alternatively, water can be added, as necessary for conductivity, viscosity, etc., independent of the dopant. In any case, the total water in the conductive adhesives of the present invention is typically up to about 40 percent by weight and preferably from about 10 to about 20 percent by weight of the total adhesive.
In accordance with the present invention, when the electrolyte dopant comprises a monovalent salt, i.e. a salt which does not ionically cross-link the high molecular weight polymer, a cross-linking agent should be added to enhance the viscosity of the material. Typical chemical cross-linking agents include boric acid, sodium borate, and the like which may be present in an amount of from about 0.1 to about 5 percent by weight of the total adhesive. The cross-linking agent may be in hydrated form or may be included by way of solution. The cross-linking agents employed will not cross-link the polyvinylpyrrolidone and irradiative methods of cross-linking are not employed.
To prepare the electrically conductive adhesives of the present invention, conventional mixing machines can be used to combine the ingredients, for example, those manufactured by Brabender, Charles Ross & Son, and the like. In some cases it may be desirable to use a mixer capable of operating under vacuum to eliminate voids in the resultant material. In a typical preparation, the plasticizer such as glycerin is -~` 1 3320 1 0 put into the mixer and while mixing, the polyvinylpyrrolidone and the high molecular weight polymer, such as polyvinylalcohol, are added.
After mixing these components (typically at room temperature) for 5-15 minutes, heat is applied so that further mixing takes place at between about 90 and 120C. Once these components have been stirred for about 15 minutes at temperature, the electrolyte dopant and cross-linking agent (if used) are added slowly. These two ingredients can be added in crystal form or in solution. Following the dopant and cross-linking agent additions, the total formulation is mixed under somewhat reduced heat (70-90C) for another 5-10 minutes, then dumped and allowed to cool.
By adjusting the proportions of the components, numerous adhesive materials of varying conductivity and flexibility can be obtained within the scope of the present invention. The adhesive materials of this invention are not only readily adapted for the less demanding high impedance ground plate and TENS electrode area, but are also well within the stringent, industry-accepted AAMI
(Association for the Advancement of Medical Instrumentation) standards for electrocardiograph electrodes. Additionally, the electrocardiograph electrodes have extremely low noise values.
The present invention will now be described by referring to the following examples, however, the invention is not meant to be limited by the details described therein.
Example 1 An electrically conductive adhesive material in accordance with the present invention was prepared using the following ingredients by the procedure described below.
Ingredient Weight Percent GlYcerin 55.5 ~y~y~cohol (Vinol S-523;
88% hydrolyzed; M.W. 78,000;
avail. from Air Products) 4.5 Polvvinylpyrrolidone (PVP K-15;
~ ~r~7r~Dr~ ~from GAF) 9.O
Ma~nesium chloride hexahYdrate ~;
(MgCl2 6H2O) 20.0 Water 10.0 Sodium borate decahYdrate (Na2B4O7 10H20) 1.0 The glycerin (222 g) was poured at room temperature into a mixing apparatus and mixed at about 190 RPM while the pol winylpyrrolidone ~36 g) and then the polyvinylalcohol~(18 g) were added. ~;
These three components were mixed for about 5 minutes. While the mixing continued the so-formed ~
mixture was heated to between about 100 and 120C. ;
* Trade-mark ~; 1 3320 1 0 After about 15 minutes of mixing at this tempexature, 44 g of a 1:10 solution of the sodium borate decahydrate in water was slowly added followed by the addition of magnesium chloride hexahydrate crystals (80 g). These two additions were spread out over about 10 minutes of mixing during which time the temperature was allowed to drop to about 90C. The mixing was then continued for another 5 minutes, then dumped. When allowed to cool, the mixture took on a flexible, elastomeric gel-like consistency which had good adhesive and cohesive properties.
When the so-formed adhesive was later tested on an AAMI (Association for the Advancement of Medical Instrumentation) electrocardiograph electrode test apparatus, it was found to have an initial 305 ohm impedance at a frequency of 10 Hz, and a more than satisfactory 210 ohm impedance after defibrillation recovery. The complete AAMI
test data for this adhesive is listed below.
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O O Ul z; h ,1 ~1 U V ~
.
8 ~ u~
o o U~ ~. o o o o ~
~ H ~ ~
V~ V
U U
~ a~ ~n ~
~0 ~ ~ ~ ~
'~ O V~
U
V
~ O
S~ ~ ~
,4 0 ~q .~ , O
O O
rl t~
O ~ V ~I
: :
:~ ~ U~
O
. ~_1 O
;~ O O U~
~ O O
I¢ ~V
~ U~
' ~ ~ ~ P
O ~1 O
~1~1 C) ~1 V O
~,,, '' ~-~ i ~ .:
~1 , ~ U
:::
~ a~
: ~ ~1 ' ~ ~
t 3320 1 0 Example 2 Using the procedure of Example 1, an electrically conductive adhesive material suitable for ground plate electrodes for electrosurgery or for TENS electrodes, were prepared. This material contained the ingredients listed below.
Ingredlent Welght Percent Glycerin 50 Gelatin 15 Polyvinyl~yrrolidone (PVP K-90;
M.W. 360,000; avall. from GAF) 15 Magnesium chloride hexahydrate (MgCl2 6H20) 10 Water 10 As opposed to the 10 Hz frequency range for Example 1, this material was tested in the 500 KHz to 2 MHz frequency range and found to have a volume resistivity of 103 ohm-cm.
Example 3 Using the procedure of Example 1, a conductive adhesive suitable for an electrocardiograph electrode was prepared using a pre-gelled (i.e. pre-borated by the manufacturer) polyvinylalcohol.
~ 3320 ~ 0 .. . . __ Ingredient Weight Percent . . _ . . . . _ ~: GlYcerin 50 Pol w inylalcohol (Vinol MM-S1;
M.W. 78,000; pre-gelled;
avail. from Air Products) 3 :
PolyvinylPYrrolidone (PVP K-15;
M.W. 10,000; avall. from GAF) 7 : : Magnesium chloride hexahydrate (MgC12 6H2O) 2Q :~
Water 20 , ~:
At a frequency of 10 Hz, the so-formed material had an impedance value of 250 ohms as per the AAMI test apparatus.
Examples 4-8 ; The following additional adhesive materials : within the scope of the present invention were prepared using the procedure of Example 1.
:, ~, .~ ` ~` .
o o o o o ~` ~ . . .
X d~ o o ~1 ,~
N--~ , ~C N d~OD N rl ~1 Il) g a~ o o o o o 1~ ~ . . .
X d~d~ao o o ~1 Ul ~ r) o o o o X 0 ~ r~ o o ~1 I L1 d1 ~ N
O O O O O
I~
d''P ~D O O ~1 t~ ~
~1 .
_ ~ O
.
X rl :~ aJ
.~ ~ X
O O ~ ~ O
O L~ ~:: O ~ ~
.a~ .~ ~ P ~ wC~I ~ O
~ S~ ~1 ~ tR c~
~ ~ ~ ~ ~ ~ ~
h o ~ ~ 1: o o ,1 , ,1 o o ~ ~ ~ o ~
1~ ~ _ 3 u~ _ Upon testing these materials at 10 Hz, as in Example 1, the following impedance values were obtained.
Impedance Ex. No. Initial After Defib. Recovery . . . ~ . _ . . _ .
4 215 ohms 175 ohms 265 ohms 200 ohms 6 170 ohms 120 ohms : 7 245 ohms 205 ohms 8 270 ohms 200 ohms ~::
: ::
:::
~, ~
The present invention relates to electrically conductive adhesive materials and more particularly concerns such materials suitable for use with biomedical electrodes.
In accordance with the present invention an improved electrically conductive adhesive material is disclosed. The conductive adhesive suitable for use with, for example, biomedical electrodes comprises a low molecular weight plasticizer selected from alcohols and polyhydric alcohols; a high molecular weight water soluble, cxoss-linkable polymer, which is also soluble in said plasticizer;
uncrosslinked polyvinylpyrrolidone in an amount sufficient to tackify the plasticizer and polymeri and, an electrolyte dopant in an amount sufficient to render the adhesive material electrically conductive.
'~
~ 33201 0 The electrically conductive adhesive material of the present invention is suitable for use in any of the biomedical electrodes known in the art. Referring to the FIGURE, a typical biomedical electrode 10 comprises an electrode plate 12 (which may be a plate probe or element) integral with a backing layer 14 of a web-like or foam-like material as known in the art.
The backing layer 14 is typically larger in diameter than the electrode plate 12 so as to provide a relatively broad area of contact with the skin for electrical and adhesive purposes. As shown in the FIGURE, the electrode plate 12 may -actually extend through the backing layer 14. The electrically conductive adhesive material 16 is contacted to that side of the backing layer 14 which is to be directed to the skin. The electrode 10 may optionally include a conductive film (not shown) interposed the backing layer 14 and the conductive adhesive 16 as known in the art.
Alternatively, the backing layer 14 may be a conductive film. While the FIGURE illustrates one ~ type of biomedical electrode, it should be apparent `~ that other electrode designs and any application ~` 25 requiring electrically conductive adhesive materials would be benefited by the present invention.
The electrically conductive adhesive material of the present invention is advantageous ~,~
-` 1 3320 1 0 in that it functions as a highly flexible, elastomeric gel-like substance with excellent electrical, cohesive and adhesive properties while having a water content of about 10 to 20 percent by weight or less in a preferred embodiment. In general, the conductivity, and often the elastomeric properties, of these types of material are highly dependent on the amount of water formulated into the material. Prior art materials which rely upon a high water content (e.g. 50 weight percent and above) are typically susceptible to drying out in most ambients. To prevent possible loss of conductivity and/or elastomeric properties, stringent packaging and storing are ; 15 necessary when using these prior art materials.
Since materials containing about 20 percent by weight of water are less subject to drying out, more stable, electrically conductive adhesive materials are provided by the present invention.
Polyvinylpyrrolidone is an ingredient found in prior art conductive adhesives as a basic polymer around which the composition is built, or as a thickening agent. Such compositions in which polyvinylpyrrolidone is the basic polymer typically include a tackifier, such as abietic acid and the like, to impart adhesive qualities to the material.
Unexpectedly, polyvinylpyrrolidone in combination with polymer/plasticizer blends otherwise known to require a tackifying agent produces a gel-like polymeric substance with excellent adhesive and cohesive properties. These prior art uses of ~ 3320 1 0 polyvinylpyrrolidone utilize the cross-linked form of the polymer which gives it the desired properties.
Unexpectedly, it has been found that uncrosslinked polyvinylpyrrolidone functions as well as a tackifying agent in the compositions of the present invention.
The conductive adhesive of the present invention includes a low molecular weight plasticizer selected from alcohols and polyhydric alcohols. The alcohols suitable for use as the plasticizer should be re-latively non-volatile at room temperature, i.e. they should have a vapor pressure higher than that of water. Typical alcohols include isooctylalcohol, decanol and the like. Polyhydric alcohols suitable for use as the plasticizer include polyethylene glycol, methoxy polyethylene glycols, propylene glycol, higher alkyl glycols and glycerin, with the latter being preferred. The plasticizer preferably has a ~
molecular weight of less than about 4000. The low `
molecular weight plasticizer is typically present in an amount of from about 40 to 92 percent by weight, and preferably from about 50 to 70 percent by weight of the total adhesive material.
The high molecular weight water soluble polymer must be susceptible to chemical and/or ionic cross-linking and must also be soluble in said plasticizer. The cross-linking (of one type , ~ or the other) gives the desired viscosity to the adhesive. Polymers suitable typically have a molecular weight above 4000 and include gelatin, ;~ polyethylene oxides, and polyvinylalcohols. Poly-vinylalcohols having a molecular weight of between ~ 1332010 about 20,000 and 108,000 are preferred and polyvinylalcohol which is about 88% hydrolyzed having a molecular weight of about 78,000 is most preferred because of the excellent flexibility it imparts to the conductive adhesive. The high molecular weight polymer is typically present in an amount of from about 2 to 54 percent by weight, and preferably from about 2 to 10 percent by weight of the total adhesive material.
The uncrosslinked-polyvinylpyrrolidones suitable for use in the present invention have a molecular weight between about 10,000 and 360,000 with 10,000 being preferred. The uncrosslinked polyvinylpyrrolidone should be present in an amount of from about 1 to about 53 percent by weight, and preferably from about 5 to 30 percent by weight of the total adhesive material.
The electrolyte dopant of the present invention may be any organic or inorganic ionizable salt whlch will provide the desired conductivity and does not interfere with the physical properties of the adhesive. For use on electrocardiograph electrodes, the salt must also be capable of re-covering rapidly following defibrillation overload.
Inorganic ionizable salts, particularly inorganic halide salts are well~suited as electrolyte dopants for the present invention. The salts can be mono-valent such as sodium chloride, potassium chloride, or silver chloride or polyvalent such as magnesium chloride, magnesium acetate, zinc chloride, zinc acetate, calsium chloride, or ferric chloride with magnesium chloride being preferred. The polyvalent salts such as magnesium chloride are ~- 1 3320 1 0 preferred as the electrolyte dopant because they can ionically cross-link numerous of the high molecular weight, water-soluble polymers, such as the polyvinylalcohols, described above. When the polyvalent salts, such as magnesium chloride serve the dual function of electrolyte and cross-linking agent, the further addition of a cross-linking - agent is optional. The electrolyte dopant is typically present in an amount of from about 5 to about 57 percent by weight, and preferably from about 10 to 35 percent by weight of the total adhesive.
The electrolyte dopant may also contain water. For example, the preferred dopant is typically in hydrated form, i.e. magnesium chloride hexahydrate (MgCl2 6H2O) which is approximately 50 percent by weight of water. Additionally the hydrated or nonhydrated salts used as the electrolyte may be in an aqueous solution. For those dopants containing water (i.e. salts which are hydrated and/or in aqueous solution), the salt to water weight ratio should be from about 1:1 to about 1:40. For example, in one embodiment the dopant is an aqueous solution comprising 20 weight percent of magnesium chloride hexahydrate (consisting of 10 weight percent MgCl2 and 10 weight percent water) in 10 weight percent of water. Such a dopant composition is illustrative of the preferred 1:2 salt to water ratio for the electrolyte of the present invention.
1332~1~
Alternatively, water can be added, as necessary for conductivity, viscosity, etc., independent of the dopant. In any case, the total water in the conductive adhesives of the present invention is typically up to about 40 percent by weight and preferably from about 10 to about 20 percent by weight of the total adhesive.
In accordance with the present invention, when the electrolyte dopant comprises a monovalent salt, i.e. a salt which does not ionically cross-link the high molecular weight polymer, a cross-linking agent should be added to enhance the viscosity of the material. Typical chemical cross-linking agents include boric acid, sodium borate, and the like which may be present in an amount of from about 0.1 to about 5 percent by weight of the total adhesive. The cross-linking agent may be in hydrated form or may be included by way of solution. The cross-linking agents employed will not cross-link the polyvinylpyrrolidone and irradiative methods of cross-linking are not employed.
To prepare the electrically conductive adhesives of the present invention, conventional mixing machines can be used to combine the ingredients, for example, those manufactured by Brabender, Charles Ross & Son, and the like. In some cases it may be desirable to use a mixer capable of operating under vacuum to eliminate voids in the resultant material. In a typical preparation, the plasticizer such as glycerin is -~` 1 3320 1 0 put into the mixer and while mixing, the polyvinylpyrrolidone and the high molecular weight polymer, such as polyvinylalcohol, are added.
After mixing these components (typically at room temperature) for 5-15 minutes, heat is applied so that further mixing takes place at between about 90 and 120C. Once these components have been stirred for about 15 minutes at temperature, the electrolyte dopant and cross-linking agent (if used) are added slowly. These two ingredients can be added in crystal form or in solution. Following the dopant and cross-linking agent additions, the total formulation is mixed under somewhat reduced heat (70-90C) for another 5-10 minutes, then dumped and allowed to cool.
By adjusting the proportions of the components, numerous adhesive materials of varying conductivity and flexibility can be obtained within the scope of the present invention. The adhesive materials of this invention are not only readily adapted for the less demanding high impedance ground plate and TENS electrode area, but are also well within the stringent, industry-accepted AAMI
(Association for the Advancement of Medical Instrumentation) standards for electrocardiograph electrodes. Additionally, the electrocardiograph electrodes have extremely low noise values.
The present invention will now be described by referring to the following examples, however, the invention is not meant to be limited by the details described therein.
Example 1 An electrically conductive adhesive material in accordance with the present invention was prepared using the following ingredients by the procedure described below.
Ingredient Weight Percent GlYcerin 55.5 ~y~y~cohol (Vinol S-523;
88% hydrolyzed; M.W. 78,000;
avail. from Air Products) 4.5 Polvvinylpyrrolidone (PVP K-15;
~ ~r~7r~Dr~ ~from GAF) 9.O
Ma~nesium chloride hexahYdrate ~;
(MgCl2 6H2O) 20.0 Water 10.0 Sodium borate decahYdrate (Na2B4O7 10H20) 1.0 The glycerin (222 g) was poured at room temperature into a mixing apparatus and mixed at about 190 RPM while the pol winylpyrrolidone ~36 g) and then the polyvinylalcohol~(18 g) were added. ~;
These three components were mixed for about 5 minutes. While the mixing continued the so-formed ~
mixture was heated to between about 100 and 120C. ;
* Trade-mark ~; 1 3320 1 0 After about 15 minutes of mixing at this tempexature, 44 g of a 1:10 solution of the sodium borate decahydrate in water was slowly added followed by the addition of magnesium chloride hexahydrate crystals (80 g). These two additions were spread out over about 10 minutes of mixing during which time the temperature was allowed to drop to about 90C. The mixing was then continued for another 5 minutes, then dumped. When allowed to cool, the mixture took on a flexible, elastomeric gel-like consistency which had good adhesive and cohesive properties.
When the so-formed adhesive was later tested on an AAMI (Association for the Advancement of Medical Instrumentation) electrocardiograph electrode test apparatus, it was found to have an initial 305 ohm impedance at a frequency of 10 Hz, and a more than satisfactory 210 ohm impedance after defibrillation recovery. The complete AAMI
test data for this adhesive is listed below.
~a ~1 o h rl p O O
O O Ul z; h ,1 ~1 U V ~
.
8 ~ u~
o o U~ ~. o o o o ~
~ H ~ ~
V~ V
U U
~ a~ ~n ~
~0 ~ ~ ~ ~
'~ O V~
U
V
~ O
S~ ~ ~
,4 0 ~q .~ , O
O O
rl t~
O ~ V ~I
: :
:~ ~ U~
O
. ~_1 O
;~ O O U~
~ O O
I¢ ~V
~ U~
' ~ ~ ~ P
O ~1 O
~1~1 C) ~1 V O
~,,, '' ~-~ i ~ .:
~1 , ~ U
:::
~ a~
: ~ ~1 ' ~ ~
t 3320 1 0 Example 2 Using the procedure of Example 1, an electrically conductive adhesive material suitable for ground plate electrodes for electrosurgery or for TENS electrodes, were prepared. This material contained the ingredients listed below.
Ingredlent Welght Percent Glycerin 50 Gelatin 15 Polyvinyl~yrrolidone (PVP K-90;
M.W. 360,000; avall. from GAF) 15 Magnesium chloride hexahydrate (MgCl2 6H20) 10 Water 10 As opposed to the 10 Hz frequency range for Example 1, this material was tested in the 500 KHz to 2 MHz frequency range and found to have a volume resistivity of 103 ohm-cm.
Example 3 Using the procedure of Example 1, a conductive adhesive suitable for an electrocardiograph electrode was prepared using a pre-gelled (i.e. pre-borated by the manufacturer) polyvinylalcohol.
~ 3320 ~ 0 .. . . __ Ingredient Weight Percent . . _ . . . . _ ~: GlYcerin 50 Pol w inylalcohol (Vinol MM-S1;
M.W. 78,000; pre-gelled;
avail. from Air Products) 3 :
PolyvinylPYrrolidone (PVP K-15;
M.W. 10,000; avall. from GAF) 7 : : Magnesium chloride hexahydrate (MgC12 6H2O) 2Q :~
Water 20 , ~:
At a frequency of 10 Hz, the so-formed material had an impedance value of 250 ohms as per the AAMI test apparatus.
Examples 4-8 ; The following additional adhesive materials : within the scope of the present invention were prepared using the procedure of Example 1.
:, ~, .~ ` ~` .
o o o o o ~` ~ . . .
X d~ o o ~1 ,~
N--~ , ~C N d~OD N rl ~1 Il) g a~ o o o o o 1~ ~ . . .
X d~d~ao o o ~1 Ul ~ r) o o o o X 0 ~ r~ o o ~1 I L1 d1 ~ N
O O O O O
I~
d''P ~D O O ~1 t~ ~
~1 .
_ ~ O
.
X rl :~ aJ
.~ ~ X
O O ~ ~ O
O L~ ~:: O ~ ~
.a~ .~ ~ P ~ wC~I ~ O
~ S~ ~1 ~ tR c~
~ ~ ~ ~ ~ ~ ~
h o ~ ~ 1: o o ,1 , ,1 o o ~ ~ ~ o ~
1~ ~ _ 3 u~ _ Upon testing these materials at 10 Hz, as in Example 1, the following impedance values were obtained.
Impedance Ex. No. Initial After Defib. Recovery . . . ~ . _ . . _ .
4 215 ohms 175 ohms 265 ohms 200 ohms 6 170 ohms 120 ohms : 7 245 ohms 205 ohms 8 270 ohms 200 ohms ~::
: ::
:::
~, ~
Claims (14)
1. An electrically conductive adhesive mat-erial comprising:
a low molecular weight plasticizer selected from non-volatile alcohols and polyhydric alcohols;
a high molecular weight, water soluble, cross-linkable polymer which is also soluble in said plas-ticizer;
a tackifier comprising uncross-linked polyvi-nylpyrrolidone; and an electrolyte dopant in an amount sufficient to render said adhesive material electrically conduc-tive.
a low molecular weight plasticizer selected from non-volatile alcohols and polyhydric alcohols;
a high molecular weight, water soluble, cross-linkable polymer which is also soluble in said plas-ticizer;
a tackifier comprising uncross-linked polyvi-nylpyrrolidone; and an electrolyte dopant in an amount sufficient to render said adhesive material electrically conduc-tive.
2. The material of claim 1 wherein said plasticizer is present in an amount of from about 50 to about 70 percent by weight of the total adhesive material and comprises a polyhydric alcohol having a molecular weight of about 4000 or less selected from polyethylene glycols, methoxy polyethylene glycols, propylene glycol, higher alkyl glycols and glycerin.
3. The material of claim 1 wherein said high molecular weight polymer is present in an amount of from about 2 to about 10 percent by weight of the to-tal adhesive material, has a molecular weight in ex-cess of about 4000, and is selected from gelatin, poly-vinylalcohols, and polyethylene oxides.
4. The material of claim 3 wherein said high molecular weight polymer comprises a polyvinylalcohol having a molecular weight of between about 20,000 and about 108,000.
5. The material of claim 1 wherein said un-cross-linked polyvinylpyrrolidone is present in an amount of from about 5 to about 30 percent by weight of the total adhesive material, and has a molecular weight of from about 10,000 to about 360,000.
6. The material of claim 1 wherein said elec-trolyte dopant comprises an ionizable monovalent salt selected from sodium chloride, potassium chloride, and silver chloride or a polyvalent salt which may be hyd-rated selected from magnesium chloride, magnesium ace-tate, zinc chloride, zinc acetate, calcium chloride and ferric chloride, and said electrolyte dopant is present in an amount of from about 10 to about 35 per-cent by weight of the total adhesive material.
7. The material of claim 1 further including water present at up to about 40 percent by weight of the total adhesive material.
8. The material of claim 1 further including water present at from about 10 percent to about 20 percent by weight of the total adhesive material.
9. The material of claim 6 further including water present at up to about 40 percent by weight of the total adhesive material.
10. The material of claim 6 further including water present at from about 10 percent to about 20 percent by weight of the total adhesive material.
11. The material of claim 9 or 10 wherein said salt and water are present within the electrolyte dopant in a salt-to-water weight ratio of between ab-out 1:1 and about 1:40.
12. The material of claim 9 or 10 wherein said salt and water are present within the electrolyte dopant in a salt-to-water ratio of about 1:2.
13. An electrically conductive adhesive mat-erial comprising in a homogeneous combination:
about 55 percent by weight if glycerin;
about 5 percent by weight of an 88% hydro-lyzed, cross-linked polyvinylalcohol having a mol-ecular weight of about 78,000;
about 9 percent by weight of an uncrosslinked polyvinylpyrrolidone having a molecular weight of about 10,000;
about 1 percent by weight of sodium borate de-cahydrate;
about 20 percent by weight of magnesium chlor-ide hexahydrate; and about 10 percent by weight of water exclusive of the water contained in said magnesium chloride hexa-hydrate.
about 55 percent by weight if glycerin;
about 5 percent by weight of an 88% hydro-lyzed, cross-linked polyvinylalcohol having a mol-ecular weight of about 78,000;
about 9 percent by weight of an uncrosslinked polyvinylpyrrolidone having a molecular weight of about 10,000;
about 1 percent by weight of sodium borate de-cahydrate;
about 20 percent by weight of magnesium chlor-ide hexahydrate; and about 10 percent by weight of water exclusive of the water contained in said magnesium chloride hexa-hydrate.
14. In a biomedical electrode suitable for establishing an electrical connection between the skin of the human anatomy and an electromedical apparatus;
said biomedical electrode comprising:
an electrode plate, probe or element electri-cally connected to said electromedical apparatus;
a backing layer integral with, and having a larger diameter than, said electrode plate; and an electrically conductive adhesive means con-tacted to a major surface of said backing layer which is to contact said skin, which adhesive means main-tains physical and electrical contact between said electrode plate, probe or element and said skin;
the improvement wherein said electrically conductive adhesive means comprises a low molecular weight plasticizer selected from non-volatile alcohols and polyhydric alcohols;
a high molecular weight, water soluble, cross-linkable polymer which is also soluble in said plasti-cizer;
a tackifier comprising uncross-linked polyvi-nylpyrrolidone; and an electrolyte dopant in an amount sufficient to render said adhesive means electrically conductive.
said biomedical electrode comprising:
an electrode plate, probe or element electri-cally connected to said electromedical apparatus;
a backing layer integral with, and having a larger diameter than, said electrode plate; and an electrically conductive adhesive means con-tacted to a major surface of said backing layer which is to contact said skin, which adhesive means main-tains physical and electrical contact between said electrode plate, probe or element and said skin;
the improvement wherein said electrically conductive adhesive means comprises a low molecular weight plasticizer selected from non-volatile alcohols and polyhydric alcohols;
a high molecular weight, water soluble, cross-linkable polymer which is also soluble in said plasti-cizer;
a tackifier comprising uncross-linked polyvi-nylpyrrolidone; and an electrolyte dopant in an amount sufficient to render said adhesive means electrically conductive.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/294,970 US4860754A (en) | 1987-04-01 | 1989-01-03 | Electrically conductive adhesive materials |
| CA000602036A CA1332010C (en) | 1987-04-01 | 1989-06-07 | Electrically conductive adhesive materials |
| EP89110465A EP0401416A1 (en) | 1987-04-01 | 1989-06-09 | Electrically conductive adhesive materials |
| JP1149288A JPH0326777A (en) | 1987-04-01 | 1989-06-12 | Electroconductive adhesive material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3331387A | 1987-04-01 | 1987-04-01 | |
| US07/294,970 US4860754A (en) | 1987-04-01 | 1989-01-03 | Electrically conductive adhesive materials |
| CA000602036A CA1332010C (en) | 1987-04-01 | 1989-06-07 | Electrically conductive adhesive materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1332010C true CA1332010C (en) | 1994-09-13 |
Family
ID=27168342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000602036A Expired - Fee Related CA1332010C (en) | 1987-04-01 | 1989-06-07 | Electrically conductive adhesive materials |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4860754A (en) |
| EP (1) | EP0401416A1 (en) |
| JP (1) | JPH0326777A (en) |
| CA (1) | CA1332010C (en) |
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-
1989
- 1989-01-03 US US07/294,970 patent/US4860754A/en not_active Expired - Lifetime
- 1989-06-07 CA CA000602036A patent/CA1332010C/en not_active Expired - Fee Related
- 1989-06-09 EP EP89110465A patent/EP0401416A1/en not_active Withdrawn
- 1989-06-12 JP JP1149288A patent/JPH0326777A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4860754A (en) | 1989-08-29 |
| EP0401416A1 (en) | 1990-12-12 |
| JPH0326777A (en) | 1991-02-05 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20080915 |