JPS62159639A - Medical conductive adhesive and medical adhesive electrode using the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed description of the invention 3. Narrow mouth of -H (industrial application field) The present invention provides a medical conductive adhesive having excellent conductivity and adhesiveness, and a method for using the adhesive. The present invention relates to a medical adhesive electrode in which a layer is provided on the surface of an electrode plate.

(Conventional technology) When using medical electrical equipment such as electrocardiographs, electromyographs, electroencephalograms, and surgical electric scalpels, signal electrodes and grounding electrodes should be attached to the skin surface. However, electrical connections are made between predetermined locations on the skin surface and these devices, and the skin surface is grounded. Various improvements have been made to the materials and shapes of medical electrodes, as well as the means for fixing the electrodes to the skin surface. For example:

(1) Conductive paste cream containing electrolytes,
A method in which metal electrode plates are attached to the skin surface using a conductive medium such as a water-based gel.

(2) The sponge surface of a medical electrode, which integrates a sponge containing a conductive liquid or gel-like substance, an electrode plate, and an adhesive sheet for application, is pressed against the skin surface.

How to fix with the sheet. and.

(3) A method using an adhesive electrode in which a conductive adhesive layer is provided on the surface of an electrode plate.

Among these methods, method (3) using an adhesive electrode is preferred because it is simple, there is little change in conductivity even if the electrode is attached to the skin surface for a long time, and the electrode is manufactured at a relatively low cost. be. As adhesives that can be used in such adhesive electrodes, conductive adhesives such as 1st order, for example, have been proposed.

■ The electrode adhesive disclosed in JP-A No. 52-95895 is a polymer containing an ester of an α,β-olefinically unsaturated carboxylic acid and a monohydric or polyhydric alcohol whose terminal end is a quaternary ammonium group. and polyhydric alcohol.

■ The electrode adhesive disclosed in JP-A-56-36939 contains salts of organic carboxylic acids (alkali metal salts, amine salts, etc.) such as (meth)acrylic acid and maleic acid in a proportion of 5 mol% or more. It contains a polymer containing 10% and a polyhydric alcohol such as glycerin.

(2) The electrode adhesive disclosed in JP-A-56-36940 contains a nonionic hydrophilic polymer such as polyacrylic acid and polyvinyl alcohol, and a water-soluble plasticizer such as glycerin.

However, the electrical conductivity of the three adhesives described above cannot be said to be sufficient. In particular, the adhesive (3) itself has extremely low conductivity and requires the addition of an electrolyte such as sodium chloride. All of them are insufficient in terms of adhesion and cannot keep the electrodes attached to the skin surface for a long period of time.

Generally, when the tackiness of an adhesive is set high, the conductivity tends to decrease, and when the conductivity is set high, the tackiness tends to decrease.

(Problem that the invention attempts to solve) The present invention solves the above-mentioned conventional drawbacks.

The purpose is to provide a conductive adhesive that can be used in various medical measuring instruments and has excellent conductivity and adhesiveness. Another object of the present invention is to provide a medical adhesive electrode in which a layer of adhesive having the above-mentioned excellent properties is provided on the surface of the electrode plate.

(Means for Solving the Problems) The conductive adhesive of the present invention contains polymer 9 water having a substituted ammonio group and magnesium chloride, thereby achieving the above object.

The conductive adhesive of the present invention contains a polymer having a substituted ammonio group; water; magnesium chloride; and a corrosion inhibitor consisting of hydroquinone and/or a hydroquinone derivative; thereby achieving the above object.

In the medical adhesive electrode of the present invention, a conductive adhesive layer is provided on at least a portion of an electrode plate, and the adhesive is.

It contains a polymer with substituted ammonio groups, water and magnesium chloride, thereby achieving the above object.

In the medical adhesive electrode of the present invention, a conductive adhesive layer is provided on at least a portion of an electrode plate, and the adhesive is.

The above object is achieved by containing a polymer having substituted ammonio groups; water; magnesium chloride; and a corrosion inhibitor consisting of hydroquinone and/or hydroquinone derivatives.

The polymer that is the main component of the medical conductive adhesive of the present invention is a (meth)acrylamide derivative (
1) and/or a (meth)acrylic acid ester derivative (ff) as a copolymerization component (first copolymerization component).

P.

(Here, R7 is H or C1h; R2 has 1 carbon number
~6 saturated hydrocarbon groups; R3, Ra and R5 are alkyl groups having 1 to 4 carbon atoms; and X is a halogen atom such as CI, Br) - (where + R6 is H or CH3; Rt is carbon Number 1
-6 saturated hydrocarbon group or a saturated hydrocarbon group having 1 to 6 carbon atoms having a hydroxyl group; R1, R9 and R1° are alkyl groups having 1 to 4 carbon atoms; and X is a halogen atom such as CLBr. ).

Among the compounds represented by the above structural formula, the 2 (meth)acrylamide 8ffi j triplet (1) includes 2 (acrylamido)ethyltrimethylammonium chloride, 2 (methacrylamido)ethyltrimethylammonium chloride, and 3 (acrylamido)propyltrimethylammonium chloride. , 3(methacrylamido)propyltrimethylammonium chloride, 3 (
Methacrylamide) propyldiethylmethylammonium chloride, 3 (methacrylamide) propyltrimethylammonium bromide, 3 (acrylamide)
Examples include isopentyltrimethylammonium chloride. Examples of the (meth)acrylic acid ester derivative (II) include 2 (acryloxy)ethyltrimethylammonium chloride and 2 (methacryloxy)ethyltrimethylammonium chloride.

Examples include 3 (acryloxy)propyltrimethylammonium chloride, 3 (methacryloxy)propyltrimethylammonium chloride, and 3 (methacryloxy)2-hydroxypropyltrimethylammonium chloride.

Copolymerization components (second copolymerization components) that form a copolymer together with the first copolymerization component include butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate, butylene glycol monoacrylate, butylene glycol monomethacrylate, ethyl acrylate butoxyethyl acrylate, butoxyethyl methacrylate.

Ethoxybutyl acrylate, tetrahydrofurfuryl acrylate, glycerin monoacrylate, glycerin monomethacrylate polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, acrylamide, methacrylamide, N-dimethylacrylamide.

N-diethylacrylamide, N-butoxymethylacrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethyl aminoethyl methacrylate vinyl acetate.

Examples include vinyl propionate, vinyl pyrrolidone, and diacetone acrylamide. Two or more types of the first and second copolymer components may be mixed.

Monomers with relatively low copolymerizability among the second copolymerization components include monomers 9 with high copolymerizability, such as butyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate.

It is recommended to mix it with vinylpyrrolidone and vinyl acetate and subject it to the copolymerization reaction described below.

The copolymer contains the first copolymer component in a proportion of 20 to 80% by weight, and the second copolymer component in a proportion of 80 to 20% by weight. If the first copolymer component is too small, conductivity will not be obtained substantially, and if it is too large, the a-gathering force of the resulting pressure-sensitive adhesive will be reduced.

What is the electrical conductivity of adhesives prepared using copolymers?

This is mainly due to the first copolymer component in the copolymer. Therefore, the degree of conductivity of the adhesive is determined by both the proportion of the first copolymer component in the copolymer and the proportion of the copolymer in the adhesive.

For example, a relatively small amount of the copolymer as the first copolymer component needs to be contained in a relatively large amount in the adhesive in order to ensure conductivity. The conductivity is further related to ammonium nitrogen in the first copolymer component.

If the molecular weight of the first copolymer component is large, the proportion of ammonium nitrogen in the molecule becomes relatively small, so in order to obtain the necessary conductivity, it is necessary to increase the content of the first copolymer component. The degree of conductivity also varies depending on the chemical structure of the first copolymer component.

When the first copolymerization component is a (meth)acrylamide derivative, the resulting adhesive has higher conductivity than when it is a (meth)acrylic acid ester derivative. Therefore, when a (meth)acrylic acid ester derivative is used, it is necessary to increase the amount of the first copolymerization component slightly. Two or more types of the first and second copolymer components may be mixed.

A copolymer is obtained by subjecting the first copolymerization component and the second copolymerization component (both monomers) to a polymerization reaction by a conventional radical polymerization method 1, for example, a solution polymerization method. In the case of the solution polymerization method, a solvent capable of dissolving each monomer used and the copolymer to be produced is used as the solvent. Such solvents vary depending on the composition of the monomers used.

For example, alcohol, water-alcohol mixture (alcohol includes methanol, ethanol, isopropanol, etc.)
is used.

To Obtain a Copolymer 2 For example, first, each of the above monomers and a solvent are charged into a reactor equipped with a reflux condenser.

The monomer concentration is preferably 30 to 80%. next.

The inside of the reactor is replaced with an inert gas such as nitrogen.

Start adding the catalyst while heating and stirring. As the catalyst, an azobis-based catalyst, a peroxide-based catalyst, etc., which are commonly used in pentapolymerization reactions, are preferably used. The amount of catalyst is usually 9.

A range of 0.1 to 1.0 mol % of the total number of monomer moles is adopted. The catalyst is suitably divided into 1,720 to 115 parts of the total amount and added to the reaction solution. What is the catalyst injection interval?

It is preferably 0.2 to 1.5 times the half-life of the catalyst used. The reaction temperature is usually 50 to 80°C. In particular, when the monomer concentration is 50% or more, prevent runaway reactions and gelation by adding a solvent to the reaction system several times to more than ten times to reduce the viscosity. is preferred. The reaction time varies depending on the monomer composition, the type and amount of catalyst, the reaction conditions, etc., but is usually about 20 to 50 hours. In this way, a viscous solution containing the copolymer is obtained.

The copolymer thus obtained becomes the main component of the adhesive. Depending on the type and amount of the copolymerized components, this copolymer may itself have tackiness; however, it is usually non-adhesive and in a dry state is relatively brittle and hard in the form of a resin. In a dry state, conductivity is not developed. However, when water is added to it, the copolymer softens and becomes sticky, allowing it to function as an adhesive. The internal force concentration is also moderate, and it has viscoelastic properties and exhibits electrical conductivity.

The amount of water depends on the composition of the copolymer components and the thickness of the adhesive layer.

It varies depending on the desired degree of tackiness, etc., but is usually 1.

The amount is in the range of 5 to 50 parts by weight based on 100 parts by weight of the copolymer. The larger the proportion of the first copolymer component in the copolymer is, the more water and magnesium chloride described below are required to soften the copolymer.

If the amount of water is too small, not only tackiness will not be developed but also conductivity will not be obtained. The copolymer contains water and becomes soft,
As long as it functions as an adhesive, it has sufficient conductivity. If the amount of water is excessive, the adhesive properties of the resulting adhesive will increase, but it will become soft and fluid.

The adhesive contains magnesium chloride in addition to the above copolymer and water. Magnesium chloride has the function of retaining water in the adhesive at a predetermined ratio. For example, the presence of magnesium chloride prevents water in the adhesive from disappearing by evaporation.

Even if the copolymer does not contain any water in a dry state, if it contains magnesium chloride, it will absorb water from the air, and as a result, the adhesive will contain a certain percentage of water. The amount of magnesium chloride varies depending on the composition of the copolymer component, the thickness of the adhesive layer, the desired degree of tackiness, etc.2, but is usually in the range of 6 to 50 parts by weight per 100 parts by weight of the copolymer.

If the amount is too small, not only adhesiveness will not be developed but also conductivity will not be obtained. Conductivity may become unstable because water cannot be retained at a constant rate.

If it is excessive, the amount of water contained will be excessive.

It becomes soft and fluid.

The adhesive further contains a metal corrosion inhibitor, if necessary. As corrosion inhibitors, hydroquinone and/or
Alternatively, hydroquinone derivatives are used. Examples of hydroquinone derivatives include hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, and hydroquinone monobutyl ether. Two or more of these may be used in combination.

Such corrosion inhibitors are usually blended into the adhesive in an amount of 15 parts by weight or less per 100 parts of copolymer.

If it is in excess, the tackiness of the adhesive will decrease. Furthermore, the adhesive may be a skin irritant due to the corrosion inhibitor. Generally, 0.5 parts by weight or more of a corrosion inhibitor is required to obtain a corrosion inhibiting effect. Adhesives to which a corrosion inhibitor is added in the range of 0.5 to 15 parts by weight do not corrode metals such as aluminum or tin at all, or the corrosion rate is slow enough to cause no practical problems when commercialized. . Moreover.

Although the details of the mechanism of action of corrosion inhibitors are not known, they do not affect the conductivity and adhesion of adhesives and are not irritating to the skin.

It is thought to trap oxygen radicals thought to cause corrosion reactions and other radicals involved in corrosion reactions, thereby preventing or delaying corrosion reactions.

For example, when a corrosion inhibitor is contained in the adhesive of the present invention, the copolymer is usually present in an amount of 60 to 90% by weight in the total amount of copolymer, water, magnesium chloride, and corrosion inhibitor. , water in a proportion of 3 to 30% by weight and magnesium chloride in a proportion of 4 to 40% by weight.

A corrosion inhibitor is contained in a proportion of 0.3 to 12% by weight.

In addition to the above-mentioned corrosion inhibitors, the adhesive may also contain fillers (fillers), strength modifiers (cohesive force modifiers) when the adhesive is used as a film, tack modifiers, and conductivity modifiers. Additives such as regulators are included.

Among these, fillers include inorganic fillers such as calcium carbonate, magnesium carbonate, zinc white, calcium chloride, talc, and silicic anhydride; and polystyrene.

There are organic fillers made of water-insoluble resins such as polymethyl methacrylate, polyamide, polyester, and polyurethane. All fillers are used in fine powder form. Film strength modifiers include polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, vinyl methyl ether-maleic anhydride copolymer, and hydroxyethyl cellulose.

Examples include sodium carboxymethylcellulose, gum arabic, glue, gum tragacanth, and gum karaya. Adhesive modifiers include glycerin, diglycerin, polyethylene glycol, polypropylene glycol, butylene glycol, amylene gelicol, trimethylolethane, and sorbitol.

Examples include jetanolamine, triethanolamine alkyl sulfate, fatty acid jetanolamide, and aminoalkylpropertools. Behenyltrimethylammonium chloride is used as a conductivity modifier.

Lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride.

Examples include dimethyldodecyl ammonium acetate.

The amount of the additives mentioned above varies depending on the individual, but is usually 9.

Approximately 4% of the total weight of copolymer, water and magnesium chloride
It is less than 0% by weight, preferably less than about 30% by weight. If it is in excess, for example, the tackiness and conductivity of the adhesive will decrease.

To prepare the adhesive of the present invention, for example, first.

- If necessary, a solvent is added to the copolymer solution prepared by the above copolymerization reaction to adjust the viscosity. Water, magnesium chloride, and, if necessary, the above-mentioned corrosion inhibitor, filler, film strength adjuster, etc. are added to this to obtain an adhesive solution. Magnesium chloride is commercially available6
It is convenient to use hydrate (MgCh.611□0). Typically, magnesium chloride is added as a concentrated aqueous solution and corrosion inhibitors are added as concentrated solutions in water or alcohol. The amount of water may be too much or too little, and by drying or controlling the humidity after preparing the pressure-sensitive adhesive, a pressure-sensitive adhesive having desired tackiness can be obtained.

The materials of the electrode plate used in the medical adhesive electrode of the present invention include tin, aluminum, nickel, and lead.

Chromium, silver, gold, platinum, iron, copper, and alloys thereof are used. In particular, tin, aluminum, and tin-aluminum alloys, which have excellent conductivity and are relatively inexpensive, are preferably used. An electrode plate is formed from these metals as a metal foil having a thickness of 20 to 200 μm or as a laminate with a reinforcing backing member.

The size of the electrode plate varies depending on its use; for example, in the case of an electrode for an electrocardiograph, the diameter is 20 to 50 cm. Examples of reinforcing backing members include polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, nylon, polyurethane, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer,
There are films or sheets made of resins such as cellulose derivatives; paper, wa cloth, and nonwoven fabrics made of natural fibers, synthetic fibers, etc. The reinforcing backing member itself may be a laminate.

To prepare an adhesive electrode, for example, the above-mentioned adhesive solution to which water, magnesium chloride, etc. are added is cast onto such a conductive substrate either continuously or in spots according to the size of the desired electrode. After drying it to the extent that it has an appropriate level of tackiness or completely drying it to remove moisture and alcohol, it is left in an atmosphere of appropriate humidity to absorb moisture and develop tackiness. A release paper is usually attached to the surface of the adhesive layer thus formed to protect the adhesive layer. In order to form the adhesive layer, the adhesive solution may be cast onto a release paper, dried, and then transferred onto the surface of the conductive substrate. The thickness of the adhesive layer is 100 to 1000
μm, preferably 100 to 600 μm. Sufficient adhesion can be obtained even with such a relatively thin layer. The conductive base material on which the adhesive layer is formed in this manner is subjected to punching, for example, with a release paper applied thereto, to obtain an adhesive electrode of a desired shape. The adhesive layer may be formed on the conductive substrate after it is prepared into a desired shape.

As shown in FIGS. 1 and 2, the adhesive electrode 1 of the present invention
2 has, for example, a disc-shaped metal foil electrode plate 11 and a conductive adhesive layer 12 provided on one side of the electrode plate 11.

A release paper 13 coated with a thin layer of silicone or the like and cured is pasted on the surface of the conductive adhesive layer 12 (the side that contacts the skin surface of the subject). This peeling M113 protects the conductive adhesive layer 12, and is peeled off when the electrode is attached to the skin. A portion of the electrode plate 11 is provided with a protrusion 110 that protrudes outward. The protrusion 110 is not provided with an adhesive layer, and as shown in FIG. 3, the protrusion 110 is electrically connected to a medical electrical device 3 such as an electrocardiograph via a conductive wire 31. . Protrusion 1
Connection of the conducting wire to 10 is made via a clip or the like.

As the electrode plate, a laminate of metal foil and a backing member can also be used. When using a laminate, the appropriate thickness of the metal foil is 10 to 508 m. As such an electrode, an electrode having a structure similar to that shown in FIGS. 1 and 2 may be used, except that a laminate body is used instead of the metal foil electrode plate 11. Furthermore, as shown in FIGS. 4 and 5, a reinforcing backing member 211 and a metal foil 21
An electrode in which a metal terminal 213 is passed through a part of the projection 210 of the electrode plate 21 made of a laminate with the electrode plate 21 is also suitably used. This metal terminal 213 is made of iron, nickel, or the like, which has excellent conductivity. The metal terminal 213 is located at the portion where the metal terminal 213 protrudes from the metal foil surface of the electrode plate 21.
to avoid contact with skin.

An insulating sheet 214 is adhered. A conductive wire is connected with a clip or the like to the tip of a metal terminal 213 protruding from the surface of the lining member of the protrusion 210, and the electrode 2 and medical electrical equipment are connected via the conductive wire. In FIG. 5, 22 and 23 indicate an adhesive layer and a release paper, respectively, similar to 12 and 13 in FIG. 2.

(Hereinafter, blank spaces) (Function) According to the present invention, an adhesive having excellent conductivity and adhesiveness can be obtained. The degree of conductivity and tackiness of the adhesive can be adjusted by the composition of the copolymer used and the amount of magnesium chloride, so that a desired adhesive can be easily obtained. The copolymer is easy to prepare, and the adhesive can be obtained at low cost.

Since the adhesive electrode provided with the adhesive layer of the present invention on the surface of the electrode plate has excellent conductivity, good measurement sensitivity can be obtained when it is used in a measuring instrument such as an electrocardiograph. The method of using such an electrode is extremely simple compared to the conventional method of attaching an electrode using conductive gel. Adhesive electrodes are also easy to prepare.

The adhesive containing a corrosion inhibitor does not corrode metal, so even if the electrode is stored for a long time, the electrode plate will not be corroded and its conductivity will not change, and the conductivity of the adhesive itself will not change. There's nothing to do. Since it has become possible to use tin and aluminum, which have excellent conductivity but are relatively susceptible to corrosion, as electrode plates, adhesive electrodes with good sensitivity can be prepared at low cost. The adhesive does not irritate the skin, so it is unlikely to cause a rash even if the electrode is attached to the skin surface for a long time.

(Example) The invention will now be explained with reference to examples.

Preparation of Adhesive (A) by Daitanemasu: 42 parts by weight of 3(methacrylamide)propyltrimethylammonium chloride as the (meth)acrylamide derivative (first copolymerization component), 58 parts by weight of butyl acrylate as the second copolymerization component parts by weight, and ethyl alcohol-water mixture (90:10
) into a reaction vessel equipped with a reflux condenser, and
% solution. 12 at 50°C under a stream of N, with R stirring.
12 hours at 60°C.

The reaction was further carried out at 70°C for 24 hours. As a polymerization catalyst, azobisisobutyronitrile was used by dissolving 0.4% by weight of the total amount of the above monomers in a mixed solution of ethyl alcohol and ethyl acetate (90:10) to give a total concentration of 0.4% by weight. The catalyst was applied twice every 6 hours at 50°C, three times every 4 hours at 60°C, and 7 times every 3 hours at 70°C.
The mixture was divided into portions and added to the reaction system.

If the viscosity of the reaction solution increases significantly during the polymerization reaction,
The reaction solution was diluted with a solvent because stirring would be difficult and there was a risk of gelation or runaway reactions.

The resulting reaction solution was a viscous transparent solution. This reaction solution (copolymer solution) is diluted with a solvent and has a viscosity suitable for blending magnesium chloride etc. (polymer component 28 to
32%). Magnesium chloride hexahydrate (MgC1,.6
11□0) 30 parts by weight (MgC1, 14 parts by weight)
was added as a 60% aqueous solution to obtain an adhesive solution.

(B) Adhesive evaluation of adhesive; 60% lead and 40% tin
The conductive base material was a laminate of a 43 μm thick sheet of a polyethylene terephthalate (PET) alloy and a 50 μm thick sheet of polyethylene terephthalate (PET). The adhesive solution obtained in section (A) was cast onto the metal surface of this conductive base material so that the thickness after drying was 180 to 200 μm. After drying this, it is again placed at room temperature in a high humidity atmosphere (70 to 75% RH).
), and the humidity was adjusted. When the adhesive layer has an appropriate adhesiveness (when it has the best adhesiveness), stop controlling the humidity and cover the adhesive layer surface with a protective PET sheet to allow moisture to evaporate or absorb moisture. I tried to prevent this from happening. The protective sheet is a PET sheet whose surface is coated with a silicone release agent and cured.

When the formed adhesive layer was touched with a finger, it was found that it had excellent adhesiveness. The adhesive force value of the adhesive layer was measured by the probe tack method (ASTM D 2979). Separately, the moisture contained in the adhesive layer was measured by a heating loss method. The results are shown in Table 1. Example 1-
The results of sections 2 to 1-5 (B) are also shown in Table 1. Table 1
In the tackiness section, the O symbol indicates excellent tackiness when touched with a finger.

(C) Conductivity evaluation of adhesive: A small adhesive layer (2 cIII The width of the part where the adhesive layer is not provided is 1 c
m or more, and this was used as the lower electrode.

Separately, a homogeneous conductive base material (2CIIX3(
J) was prepared and brought into close contact with the adhesive layer of the lower electrode so that the 2C11X2C11 area on the base metal surface was in contact with the adhesive layer to prepare a test piece. The remaining l cm portion of the upper electrode not in contact with the lower electrode adhesive layer was folded back at 90° to serve as an upper electrode terminal, and the portion of the lower electrode on which the adhesive layer was not formed was used as a lower electrode terminal. Connect conductor wires to the upper electrode terminal and lower electrode terminal, respectively, and connect tott through the adhesive layer.
, , t.

A sinusoidal voltage of mV was applied. The current value (■) flowing at that time was measured. The electrical resistance value R (impedance) of the test piece was calculated from this current value.

The above measurements were performed at 23° C. and 63% RH. The results are shown in Table 1. The results of Examples 1-2 to 1-5 (C) and Comparative Examples 1-1 to 1-2 (B) are also shown in Table 1.

Step 1 (A) Preparation of adhesive: Prepare a copolymer by using 38 parts by weight of the first copolymer component and 62 parts by weight of 2-hydroxypropyl acrylate as the second copolymer component. The amount of MgC1z・611.0 added was 28 parts by weight (
The procedure was the same as in Example 1-1(A) except that the amount of MgC was 13 parts by weight (based on 1 g of MgC).

(B) Adhesive evaluation of adhesive 2 Using the adhesive obtained in Example (A), the adhesive was evaluated according to Example 1-1 (B).

(C) Evaluation of conductivity of adhesive 2 Using the adhesive obtained in Example (A), conductivity was evaluated according to Example 1-1 (C).

(A) Preparation of adhesive: 25 parts by weight of 2(methacryloxy)ethyltrimethylammonium chloride and 25 parts by weight of 3(acrylamide)propyltrimethylammonium chloride as first copolymerization components, and second copolymerization. 2-hydroxyethyl acrylate as a component
0 parts by weight and 30 parts by weight of 2-hydroxypropyl acrylate
Prepare a copolymer using parts by weight, MgCIg・6
The procedure was the same as in Example 1-1(A) except that the amount of H20 added was 35 parts by weight (16 parts by weight as MgC1z).

(B) Evaluation of adhesiveness of adhesive: Using the adhesive obtained in Section (A) of this Example, the adhesiveness was evaluated according to Section (B) of Example 1-1.

(C) Conductivity evaluation of adhesive Using the adhesive obtained in Example (A), conductivity was evaluated according to Example 1-1 (C).

↓ (A) Preparation of adhesive: 55 parts by weight of 3(acrylamido)isopentyltrimethylammonium chloride as the first copolymerization component, and 25 parts by weight of butyl acrylate and 2 parts by weight of acrylic acid as the second copolymerization component. - A copolymer was prepared using 20 parts by weight of hydroxyethyl, and Mg
The same as in Example 1-1(A) except that the amount of Cl2.6H20 added was 43 parts by weight (20 parts by weight as MgCb).

(B) Adhesive evaluation of adhesive 2 Using the adhesive obtained in Example (A), the adhesive was evaluated according to Example 1-1 (B).

(C) Evaluation of electrical conductivity of adhesive 9. Using the adhesive obtained in Example 2 (A). Conductivity was evaluated according to Example 1-1 (C).

Preparation of adhesive (A): 65 parts by weight of 3(acryloxy)propyltrimethylammonium chloride as the first copolymerization component, and 20 parts by weight of vinylpyrrolidone and 15 parts by weight of vinyl acetate as the second copolymerization component. The procedure was the same as in Example 1-1(A) except that the copolymer was prepared using parts by weight and the amount of MgC1,.61hO added was 50 parts by weight (23 parts by weight as MgCh).

(B) Evaluation of adhesiveness of adhesive: Using the adhesive obtained in Section (A) of this Example, the adhesiveness was evaluated according to Section (B) of Example 1-1.

(C) Evaluation of conductivity of adhesive 2 Using the adhesive obtained in Example (A), conductivity was evaluated according to Example 1-1 (C).

Preparation of adhesive (A): Polyvinylpyrrolidone (Koll
A concentrated alcohol solution containing 100 parts by weight of idon K-90 (trade name) and 55 parts by weight of glycerin was prepared and used as an adhesive solution.

(B) Evaluation of conductivity of adhesive: Using the adhesive obtained in section (A) of this comparative example, conductivity was evaluated according to section (C) of Example 1-1.

(A) Preparation of adhesive: A concentrated alcohol solution containing 100 parts by weight of polyvinyl pyro 91 and 55 parts by weight of glycerin was prepared. A concentrated aqueous solution containing 20 parts by weight of sodium chloride was added to this to prepare an adhesive solution.

(B) R Conductivity Evaluation Two Comparative Examples Using the adhesive obtained in section (A), conductivity was evaluated according to section (C) of Example 1-1.

(The following is a blank space) Table 1 shows that the conductive adhesive of the present invention has excellent adhesiveness and conductivity. When adhesive electrodes for electrocardiographs having a diameter of 3 cm are prepared using the adhesives of Examples 1-1 to 1-5, the resistance value of the obtained electrodes is calculated to be about 760 to 1160 Ω. Normally, there is no problem in practical use with adhesive electrodes for electrocardiographs if the resistance value is 4Ω or less, and it can be seen that the adhesive of the present invention has excellent conductivity even when compared with this value.

Example (A) Preparation of adhesive: Same as Example 1-1(A) except that 2 parts by weight of hydroquinone as a corrosion inhibitor was further added to the polymer solution as a concentrated aqueous solution.

(B) Evaluation of corrosivity of adhesive: The adhesive solution obtained in section (A) was applied and dried on a tin substrate and an aluminum substrate, respectively, to form an adhesive layer with a thickness of about 180 to 200 μm. Example 1 Humidity was controlled in the same manner as in section (B), and the adhesive layer was covered with a protective sheet.

The tin base material used here is a 15 μm thick tin foil and a 50 μm thick tin foil.
It is a laminate of μm PET film. Cut lines were previously formed on the surface of the i-foil at three-way intervals only in areas where the adhesive layer was to be provided, and the adhesive layer was formed on this surface. The thickness of the aluminum base material is 30 μm.
using soft aluminum foil. Each base material on which the adhesive layer was formed was left under conditions of 60°C and 175% RH, and the time required for the base material to corrode to a predetermined degree was measured. here.

Corroded to a predetermined degree means that when a tin base material is used, the tin foil surface is corroded at a rate of 25%. When an aluminum base material is used, a state in which one hole is formed per base material IQcJ is shown. In this example, although it was left for 240 hours, neither the tin base material nor the aluminum base material was corroded to the above extent. The results of Examples 2-2 to 2-5 (B) are also shown in Table 2.

(C) Conductivity evaluation of adhesive: The adhesive solution obtained in section (A) of this example and the same tin base material as that used in section (B) of this example (however, there is a cut in the upper electrode) A test piece was prepared according to Section (C) of Example 1 using a test piece (no wire was formed), and its electrical resistance value was measured. Next, take this test piece (B)
After storage under the same conditions as described above (60° C., 75% R1+), measurements were taken again 240 hours later and the impedance was calculated. The results of Examples 2-2 to 2-5 (C) are also shown in Table 2.

(D) Evaluation of Adhesive Adhesiveness Second Example In section (C), the adhesiveness of the adhesive after being stored under high temperature and high humidity was evaluated. The results are shown in Table 2. In Table 2, the ○ mark indicates that the adhesiveness is almost the same as before the experiment.

The mark △ indicates that although there is tackiness, the degree of tackiness is considerably reduced. The results of Examples 2-2 to 2-5 (D) are also shown in Table 2.

For dog care 1 (A) Preparation of adhesive: Example 1-2 (A) except that 5 parts by weight of hydroquinone 7-methyl ether as a corrosion inhibitor was further added to the polymer solution as a concentrated aqueous solution.
Same as section.

(B) Corrosivity evaluation of adhesive: Corrosivity was evaluated according to Example 2-1 (B) using the adhesive obtained in Section (A) of this Example.

(C) Conductivity evaluation of adhesive 2 Using the adhesive obtained in Example (A), conductivity was evaluated according to Example 2-1 (C).

(D) Evaluation of Adhesive Adhesiveness Second Example In section (C), the adhesiveness of the adhesive after being stored under high temperature and high humidity was evaluated.

Preparation of adhesive (A): Example 1-3 (A) except that 8 parts by weight of hydroquinone monoethyl ether as a corrosion inhibitor was further added to the polymer solution as a concentrated aqueous solution.
Same as section.

(B) Corrosivity evaluation of adhesive: Corrosivity was evaluated according to Example 2-1 (B) using the adhesive obtained in Section (A) of this Example.

(C) Evaluation of conductivity of adhesive: Using the adhesive obtained in section (A) of this example, conductivity was evaluated according to section (C) of Example 2-1.

(D) Evaluation of adhesiveness of adhesive: In section (C) of this example, the adhesiveness of the adhesive after being stored under high temperature and high humidity was evaluated.

Next 110-1 Preparation of adhesive (A): Same as Example 1-4 (A) except that 8 parts by weight of hydroquinone as a corrosion inhibitor was further added to the polymer solution as a concentrated aqueous solution.

(B) Evaluation of Corrosivity of Adhesive 2 Using the adhesive obtained in Example (A), the corrosivity was evaluated according to Example 2-1 (B).

(C) Evaluation of conductivity of adhesive: Using the adhesive obtained in section (A) of this example, conductivity was evaluated according to section (C) of Example 2-1.

(D) Evaluation of Adhesive Adhesiveness Second Example In section (C), the adhesiveness of the adhesive after being stored under high temperature and high humidity was evaluated.

- (A) Preparation of adhesive: Same as Example 1-5 (A) except that 11 parts by weight of hydroquinone as a corrosion inhibitor was further added to the polymer solution as a concentrated aqueous solution. .

(B) Evaluation of Corrosivity of Adhesive 2 Using the adhesive obtained in Example (A), the corrosivity was evaluated according to Example 2-1 (B).

(C) Conductivity evaluation of adhesive: The conductivity was evaluated according to Example 2-1 (C) using the adhesive obtained in this example (A> section).

(D) Evaluation of Adhesive Adhesiveness Second Example In section (C), the adhesiveness of the adhesive after being stored under high temperature and high humidity was evaluated.

Using the adhesive obtained in Example 1-1, the corrosivity, conductivity, and adhesiveness of the adhesive were evaluated in accordance with Example 2-1. The results are shown in Table 2.

Using the adhesive obtained in Example 1-2, the corrosivity, conductivity, and tackiness of the adhesive were evaluated in accordance with Example 2-1.The results are shown below. Shown in 2.

Using the adhesives obtained in Examples 1 to 3, the corrosivity, conductivity, and tackiness of the adhesives were evaluated according to Example 2-1. It is shown in Table 2.

Using the adhesive obtained in Example 1-4, the corrosivity, conductivity, and adhesiveness of the adhesive were evaluated in accordance with Example 2-1. The results are shown in Table 2.

Using the adhesive obtained in Example 1-5, the corrosivity, conductivity, and adhesiveness of the adhesive were evaluated in the same manner as in Example 2-1. The results are shown in Table 2.

(The following is a blank space) From Table 2, it can be seen that the conductive Ti adhesive of the present invention to which a corrosion inhibitor is added does not corrode metals such as tin or aluminum, and does not change the conductivity or adhesiveness.

Adhesive electrodes prepared using such adhesives can be stored for long periods of time.

(Effects of the Invention) According to the present invention, an adhesive having excellent conductivity and adhesiveness can be obtained. The adhesive electrode of the present invention has such an adhesive layer provided on the surface of the electrode plate.

Since it has excellent adhesion to the skin and excellent conductivity, it can provide good measurement sensitivity when used in medical measuring instruments such as electrocardiographs. Adhesives containing corrosion inhibitors do not corrode metals.

It is possible to retain the adhesive electrode for a long period of time. As the electrode plate can be selected from metals such as tin and aluminum that have excellent conductivity and are relatively inexpensive, highly accurate electrodes can be manufactured at low cost. Even if the electrode is stored for a long time, the electrode plate will not be corroded and its conductivity will not change, and the conductivity of the adhesive itself will not change. Because the adhesive does not irritate the skin.

Even if the electrode is attached to the skin surface for a long time, rash is unlikely to occur. Such adhesive electrodes are used in electrocardiographs and electromyography.

It can be widely used in medical electrical equipment such as electroencephalographs and low-frequency therapy devices.

4. Figures 1 and 2 are a plan view and a side view, respectively, showing an example of the medical adhesive electrode of the present invention, and Figure 3 is an explanatory view showing how the adhesive electrode is used. 4 and 5 are a plan view and a side view, respectively, showing other examples of the medical adhesive electrode of the present invention.

1.2... Adhesive electrode, 11.21... Electrode plate,
12.22... Adhesive layer, 110.210...
protrusion.

that's all

Claims (1)

[Claims] 1. A medical conductive adhesive containing a polymer having a substituted ammonio group, water and magnesium chloride. 2. The polymer is a (meth)acrylamide derivative having a chemical structure in which a group having a substituted ammonio group is bonded to a (meth)acrylamide group through an amide bond, and/or a group having a substituted ammonio group is an ester with a (meth)acryloxy group. Claim 1, which is a copolymer having as a copolymerization component a (meth)acrylic acid ester derivative having a chemical structure bonded by a bond.
Adhesives listed in section. 3. The amount of water is 5 to 5 parts by weight based on 100 parts by weight of the polymer.
0 parts by weight, and said magnesium chloride is 6 to 6 parts by weight.
The adhesive according to claim 1, which is contained in an amount of 50 parts by weight. 4. A medical conductive adhesive containing a polymer having a substituted ammonio group; water; magnesium chloride; and a corrosion inhibitor consisting of hydroquinone and/or a hydroquinone derivative. 5. The polymer is a (meth)acrylamide derivative having a chemical structure in which a group having a substituted ammonio group is bonded to a (meth)acrylamide group through an amide bond, and/or a group having a substituted ammonio group is an ester with a (meth)acryloxy group. Claim 4, which is a copolymer having as a copolymer component a (meth)acrylic acid ester derivative having a chemical structure bonded by a bond.
Adhesives listed in section. 6. The water content is 5 to 5 parts by weight based on 100 parts by weight of the polymer.
Adhesive according to claim 4, wherein the magnesium chloride is contained in a proportion of 0 parts by weight, the magnesium chloride is contained in a proportion of 6 to 50 parts by weight, and the corrosion inhibitor is contained in a proportion of 0.5 to 15 parts by weight. agent. 7. A medical adhesive electrode in which a conductive adhesive layer is provided on at least a portion of an electrode plate, the adhesive containing a polymer having a substituted ammonio group, water, and magnesium chloride. . 8. The polymer is a (meth)acrylamide derivative having a chemical structure in which a group having a substituted ammonio group is bonded to a (meth)acrylamide group through an amide bond, and/or a group having a substituted ammonio group is an ester with a (meth)acryloxy group. Claim 7 which is a copolymer having as a copolymerization component a (meth)acrylic acid ester derivative having a chemical structure bonded by a bond.
Medical adhesive electrodes described in section. 9. According to claim 7, the adhesive contains the water in a proportion of 5 to 50 parts by weight and the magnesium chloride in a proportion of 6 to 50 parts by weight, based on 100 parts by weight of the polymer. Medical adhesive electrode described. 10. A medical adhesive electrode in which a conductive adhesive layer is provided on at least a portion of an electrode plate, the adhesive being a polymer having a substituted ammonio group; water;
A medical adhesive electrode containing magnesium chloride; and a corrosion inhibitor consisting of hydroquinone and/or a hydroquinone derivative. 11. The polymer is a (meth)acrylamide derivative having a chemical structure in which a group having a substituted ammonio group is bonded to a (meth)acrylamide group through an amide bond, and/or a group having a substituted ammonio group is an ester with a (meth)acryloxy group. Claim 1, which is a copolymer having as a copolymerization component a (meth)acrylic acid ester derivative having a chemical structure bonded by a bond.
The medical adhesive electrode according to item 0. 12. The water content is 5 to 5 parts by weight based on 100 parts by weight of the polymer.
In a proportion of 50 parts by weight, the magnesium chloride is 6 to 50 parts by weight.
in proportions by weight, and the corrosion inhibitor is 0.5 to 15 parts by weight.
The medical adhesive electrode according to claim 10, which is contained in the proportion of parts by weight.