JPS62321A - 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 3.1] (Industrial Application Field) The present invention provides a medical adhesive having excellent conductivity and adhesiveness, and a medical adhesive electrode using the same. Regarding.

(Prior art) When using electrical medical measuring devices such as electrocardiographs, electromyographs, and electroencephalograms, and electrical treatment devices such as low-frequency therapy devices,
Electrodes are attached to the skin surface and predetermined locations on the skin surface are electrically connected to these devices. 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. An example is shown below.

(1) The method of using a water-impregnated sponge as an electrode and pressing it against a predetermined area of the skin is used in low-frequency treatment devices, etc., but it has the following drawbacks: (1)-1 Use It is a complicated operation to impregnate the sponge with water each time, and when the sponge is pressed against the skin surface, water may seep into the surrounding area.

(2) -2 If water evaporates during use, it is necessary to impregnate it with water again.

(1) Fixing means for fixing the -3 electrode to the skin surface is required.

(2) Conductive liquid or paste containing electrolyte.

The method of attaching a metal electrode plate to the skin surface via a conductive medium such as jelly or aqueous gel allows the skin surface and the electrode to be in close contact with this conductive medium.

Suitable for use in electrocardiographs that measure weak currents, etc. However, this method has the following drawbacks: (2)-1 Skill is required to uniformly apply the conductive medium to the skin surface or electrode plate surface, and the application process is complicated. It is necessary to wipe the skin surface after use: +2) -2 The electrode plate is fixed by pressing it against the skin surface using a suction tool, but if the measurement is for a long time or if the person being measured is exercising, If measurements are taken while the skin is on the ground, the electrodes tend to lift off the skin, resulting in incomplete signal transmission between the skin surface and the measuring device.

(3) Japanese Patent Application Laid-Open No. 54-21080 discloses a medical electrode having an electrical terminal for extracting electrical signals from a living body to the outside through a sponge containing a conductive liquid or gel-like substance. Disclosed. In this electrode, a sponge is pressed against the skin surface using a porous adhesive sheet.

Such medical electrodes.

It can be easily fixed to the skin surface using an adhesive sheet, and the electrodes will not be lifted off the skin surface due to body movements of the subject. However, this medical electrode also has the following drawbacks; Therefore, the electrical contact may be incomplete or may become incomplete over time, resulting in variations in measured values.

(31-2 The moisture in the conductive liquid contained in the sponge evaporates and changes the conductivity, which tends to cause variations in measured values. The product (electrode) must be sealed and packaged to prevent moisture evaporation. The cost will be high.

(3) When the −3 electrode is peeled off from the skin, some of the conductive liquid or gel adheres to and remains on the skin surface, so it is necessary to wipe it off.

(3) -4 If the area of the sponge portion is set to a size sufficient for measurement, the area of the entire electrode including the adhesive sheet becomes large, which limits the range of use of the electrode. It also increases costs.

(4) JP-A-51-124082 discloses that inorganic conductive particles such as metals are blended into adhesives (rubber-based adhesives and resin-based adhesives such as near-acrylate adhesives) commonly used in patches. A medical electrode is disclosed in which a layer of conductive adhesive is provided on the surface of a metal electrode. Such an electrode can be easily fixed to the skin surface, similar to the method (3) in which a sponge containing a conductive liquid is pressed into contact with an adhesive sheet.

Since the adhesive itself has conductivity, the entire electrode can be made smaller. Since the adhesive does not contain water, there is no change in conductivity due to evaporation of water.

Moreover, no special packaging is required to prevent moisture evaporation.

However, such adhesives and electrodes using them have the following drawbacks: (The conductivity of the 41-1 adhesive depends on the amount of conductive particles blended, the particle size, the dispersion state, etc.) influenced.

It is difficult to obtain adhesives with stable conductivity necessary for measurement. Further, unless a large amount of conductive particles are incorporated into the adhesive, a desired conductivity cannot be obtained. For this reason, when a large amount of conductive particles are incorporated into an adhesive, the adhesive strength is significantly reduced.

(4) -2 When this electrode is used, electrical noise due to the gap between the conductive particles in the adhesive and the adhesive is likely to mix in.

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

The purpose is to provide a medical electrode that can be used in various medical measuring instruments and can be attached to a predetermined location on the skin with N simple operations.

Another object of the present invention is to provide a medical adhesive electrode in which an adhesive layer having excellent conductivity and adhesiveness is provided on the surface of an electrode plate. Yet another object of the present invention is that it can be used in the above electrode. The object of the present invention is to provide an adhesive having excellent conductivity and adhesiveness, and having the following characteristics.

(11 Water is not an essential component of the adhesive,
Therefore, an adhesive that does not cause a change in conductivity due to moisture evaporation; (2) an adhesive that has excellent internal cohesive force and leaves no adhesive residue after the electrode is peeled off; (3) an adhesive that does not cause skin irritation; and (4) ) Adhesive whose adhesiveness and conductivity can be adjusted depending on the intended use of the electrode.

Still another object of the present invention is to provide a medical adhesive electrode in which the conductive adhesive described above is provided on the surface of an electrode plate and has the following characteristics.

(1) An electrode that does not peel off from the skin surface even when used for a long time and maintains a certain level of conductivity; (2) An electrode that does not easily allow electrical noise to enter; and (3) A simple structure and sufficient electrode. Electrodes that have high performance and can be manufactured at low cost.

(Means for Solving the Problems) The medical conductive adhesive of the present invention is made by uniformly mixing an ammonium compound into an adhesive base mainly composed of a polymer soluble in water and/or alcohol. This achieves the above objective.

The medical adhesive electrode of the present invention is a medical adhesive electrode in which a conductive adhesive layer is provided on one side of an electrode plate.

The adhesive is made by uniformly mixing an ammonium compound into an adhesive base whose main component is a polymer soluble in water and/or alcohol, thereby achieving the above object.

The adhesive base contained in the medical conductive adhesive of the present invention is mainly composed of a polymer soluble in water and/or alcohol. For such polymers.

For example, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, acrylic acid alkyl ester-vinylpyrrolidone copolymer, acrylic acid alkyl ester-
Diacetone acrylamide copolymer, acrylic acid alkyl ester-acrylic acid hydroxide? Alkyl ester copolymer, polyvinyl methyl ether, vinyl methyl ether-maleic anhydride copolymer, polyacrylic acid, acrylic acid-acrylic acid alkyl ester copolymer, Borihini) Ltflucol, partially saponified polyvinyl alcohol,
Examples include polyethyleneimine and hydroxyethyl cellulose.

The adhesive base contains a plasticizer in addition to the above polymer.

The plasticizer is a liquid or solid that is soluble in water and/or alcohol and compatible with the above polymer.

The film obtained by applying the above polymer is hard and its surface is non-adhesive.

Addition of the plasticizer imparts adhesive and viscoelastic properties to the polymer. Such plasticizers include glycerin; diglycerin; propylene glycol; α-butylene glycol, 2,3-butylene glycol, β-
Butylene glycols such as butylene glycol; amylene gelicols; 1,5-bentanediol; trimethylolethane; dipropylene glycol; polypropylene glycol; polyethylene glycol; polyoxyethylene/polyoxypropylene glycol; polyoxyethylene/polyoxypropylene Butyl ether; polyoxypropylene butyl ether; alkyl sulfate triethanolamine; jetanolamine; triethanolamine; aminoalkyl propatool; alkyl trimethyl ammonium chloride; fatty acid jetanolamide; and so on. In particular, diglycerin, glycerin and polypropylene glycol are preferably used. Two or more kinds of plasticizers may be mixed. What is the mixing ratio of the above polymer and plasticizer?

The amount of plasticizer is usually 10 to 100 parts by weight, preferably 30 to 70 parts by weight, per 100 parts by weight of the polymer, although it varies depending on the chemical structure of each, the degree of tackiness of the adhesive to be prepared, the thickness of the adhesive layer, etc. be. If the amount of plasticizer is too small, the resulting adhesive will have low tackiness.

If it is in excess, the fluidity of the adhesive will be too high.

The adhesive base obtained in this way has sufficient adhesiveness as an adhesive but does not have electrical conductivity.The medical conductive adhesive of the present invention contains an ammonium compound in addition to the above adhesive base Contains. Therefore, good conductivity is imparted. As such an ammonium compound, a quaternary ammonium salt and/or an ammonium salt is used. Examples of quaternary ammonium salts include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut trimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, and dimethylalkyl betaine. Ammonium salts include, for example, ammonium sulfamate.

Ammonium salicylate, ammonium benzoate.

Ammonium citrate, amber M ammonium, ammonium valerate, coconut alkylamine hydrochloride.

Examples include sodium ammonium phosphate and ammonium sulfate. The mixing ratio of the ammonium compound to the adhesive base varies depending on the respective chemical structure (particularly the chemical structure of the ammonium compound) and the degree of conductivity and adhesiveness of the adhesive to be prepared. 10 to 100 parts by weight per part, preferably 25 to 55 parts by weight
Parts by weight. If it is too small, sufficient conductivity cannot be obtained,
If it is in excess, the tackiness will decrease. In addition to the above-mentioned adhesive base and ammonium compound, the adhesive of the present invention may contain fillers and the like within a range that does not affect the characteristics of these components. For example, if it is preferable to include water in the adhesive, magnesium chloride, sorbitol, sand W,! Powder or the like can be added as a water retention agent, and this water retention agent has the effect of keeping the water content constant without decreasing due to evaporation.

To obtain the medical conductive adhesive of the present invention, the ammonium compound is mixed with the adhesive base containing the polymer and plasticizer. Typically, a solution containing the polymer is first prepared. If the polymer is commercially available, it can be obtained by dissolving the polymer in a suitable solvent. When newly preparing a polymer, a desired polymer solution can be obtained by a conventional method such as solution polymerization. A plasticizer is added to this polymer solution to obtain an adhesive base solution. Next, an ammonium compound is added to this adhesive base solution to obtain an adhesive solution. The ammonium compound is added to the adhesive base solution as it is or dissolved in a small amount of a solvent such as water or alcohol. The adhesive solution is appropriately diluted by adding a solvent such as methyl alcohol to a viscosity suitable for coating or casting.

The content ratios of the polymer, plasticizer, and ammonium compound in the adhesive solution are appropriately determined in consideration of the adhesiveness and conductivity of the adhesive to be prepared. For example, first, the mixing ratio of polymer and plasticizer is set to provide the best adhesive properties. next.

The amount of ammonium compound added is determined so as to obtain optimal conductivity, taking into consideration the area of the electrode formed using the adhesive and the material of the substrate. moreover.

It is preferable to experimentally confirm how the adhesive properties change by adding the ammonium compound, and then finally determine the content ratios of the polymer, plasticizer, and ammonium compound.

It is also possible to add a crosslinking agent such as dibutyltin dilaurate when preparing the adhesive base solution or when adding the ammonium compound. When a crosslinking agent is added, the polymer is crosslinked, and the resulting adhesive becomes poorly soluble or insoluble in water or alcoholic solvents. When using an electrode with such an adhesive layer, the fluidity of the adhesive is extremely suppressed, so it is less likely that the electrode will shift during use or that the adhesive will protrude around the area and contaminate the surrounding area. Become. It also becomes possible to use it many times.

The adhesive of the present invention obtained by removing the solvent from the adhesive solution has excellent adhesiveness and conductivity.

A medical adhesive electrode is prepared by providing a layer of such a conductive adhesive on one side of a conductive base material (electrode plate). The material of the electrode plate is tin or aluminum.

Nickel, silver, and alloys thereof are used.

These metals are made into metal foil with a thickness of 30 to 500 μm.

Alternatively, the electrode plate is formed as a laminate with a reinforcing backing member. Examples of reinforcing backing members include polyethylene terephthalate and polyethylene.

There are films made of resins such as polypropylene, semi-rigid polyvinyl chloride, nylon, and plasticized cellulose acetate; recycled cellulose films; and papers, woven fabrics, and nonwoven fabrics using natural fibers, synthetic fibers, and the like.

The reinforcing backing member itself may be a laminate.2 For example, a conductive woven fabric with metal vapor-deposited on its surface or a conductive woven fabric with &I weaving of threads with metal vapor-deposited on its surface can also be used to prevent bending and stretching of the skin. It is suitable for use because it can be deformed according to the following.

To apply the adhesive to the surface of the electrode plate, for example, the obtained adhesive solution is cast onto the conductive substrate and dried. The adhesive solution may be cast onto release paper and dried, and then transferred onto the surface of the conductive substrate. The conductive base material on which the adhesive layer is formed in this manner is subjected to, for example, punching, 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.

An example of the adhesive electrode of the present invention is shown in FIGS. 1 to 3.

The adhesive electrode 1 shown in FIGS. 1 to 3 includes a metal foil electrode plate 11 and a conductive adhesive layer 13 provided on one side of the electrode plate 11. A projection 110 is provided at one end of the electrode plate 11, and is electrically connected to a medical measuring device such as an electrocardiograph (not shown) via a conductive wire. The conductive wires of the protrusion 110 are connected via clips or the like. A shallow cut groove 113 is provided in a part of the protrusion 110.

When using this adhesive electrode 1, the protrusion 110 is folded back at the cut groove 113 and a clip for connecting the conductor is sandwiched between the protrusions 110 and the adhesive on the electrode plate 11 is removed without the clip or the like coming into contact with the skin. The agent layer 13 can be brought into close contact with the skin. For example, as shown in FIGS. 4 and 5, a laminate of a metal foil 212 and a backing member 211 may be used as the electrode plate.

When the electrode is an electrode for an electrocardiograph, the diameter of the electrode plate is preferably 20 to 40 mm. The thickness of the adhesive 7113 or 23 is 200 to 1. It is OOOμm. If the thickness is relatively thick, a reinforcing material 230 may be used, as shown in FIG. 5, to keep the entire electrode in a predetermined shape. 1 is normal as a reinforcement material.

Rough mesh fabrics such as gauze are used.

For example, there are two adhesive electrodes 3 using this reinforcing material 230.

After the reinforcing material 230 is impregnated with an adhesive solution and dried.

This can be obtained by adhering this to the surface of the electrode plate 21.

(effect) The medical adhesive of the present invention has excellent electrical conductivity.

When a 10 Hz sinusoidal alternating current is applied to the adhesive electrode obtained by applying this adhesive layer to the surface of the electrode plate, the impedance of the electrode is less than 100Ω per l ctA. One such adhesive electrode with excellent conductivity
For example, good measurement sensitivity can be obtained when used in measurement equipment such as electrocardiograms. The adhesive has excellent adhesiveness and is
o” Folded hocho adhesion strength (JIS-Z-1522) is 40
0g/15+nm, and the ball tack value (Pharmaceutical Manufacturing Guidelines (1984) p. 51) is 14 or more. In this way, the adhesive electrode of the present invention using an adhesive with excellent adhesive strength can be easily adhered and fixed to a predetermined skin surface, and can be kept in close contact with the skin surface for a long time without using reinforcing means for fixation. is possible. Unlike conventional electrodes using water-based gel, they do not lift off the skin surface during use and cause variations in measured values. Because the adhesive itself is conductive.

Unlike conventional electrodes in which a conductive gel is fixed with an adhesive sheet, the electrodes do not become large, and an electrode with performance can be formed even if it is small and has a simple shape. Therefore,
Electrodes can be provided at low cost.

Since the adhesive does not need to contain water as a plasticizer or electrolyte solvent, the conductivity does not change due to evaporation of water during use or storage of the electrode, which does not affect the measured values. Furthermore, since it does not contain metal powder, almost no electrical noise is detected. Since the internal cohesive force of the adhesive is also large, so-called adhesive residue phenomenon does not occur. It does not cause skin irritation, so even if the electrode is attached to the skin for a long time, it is unlikely to cause a rash due to the adhesive. By adjusting the composition of the polymer, plasticizer, ammonium compound, etc. contained in the adhesive, an adhesive having a desired degree of conductivity and adhesiveness can be obtained. Therefore, electrodes having adhesiveness and conductivity depending on the purpose of use can be prepared. Such electrodes are widely used in various medical measuring instruments, therapeutic devices, and the like.

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

(A) Preparation of adhesive solution: A methyl alcohol solution containing 20% polyvinylpyrrolidone (Kollidon K-90; trade name) was prepared. To this, 60 parts by weight of Jigukuse 9F as a plasticizer was added to 100 parts by weight of the polyvinylpyrrolidone to obtain an adhesive base solution. Furthermore, 40 parts by weight of dodecyltrimethylammonium chloride was added as an ammonium compound to obtain an adhesive solution. The total solute content of the adhesive solution is 28%.

(B) Formation of adhesive layer and performance evaluation of adhesive strength: (A)
The pressure-sensitive adhesive solution obtained in Section 3 was applied onto a 50 μm thick insolubilized polyvinyl alcohol film substrate, and the thickness after drying was 40 μm.
- It was cast and dried so that it became -.

The adhesive properties of the adhesive sheet thus obtained were tested using the following methods for (1) 180'' folded square paper adhesion, (2) pole tack value, and (3) cohesive failure property.180' folded square paper adhesive strength was 500 g. /15m+i
width.

The pole tack value was 21, and no cohesive failure was observed.

(11180° Folding Method Adhesive Crab The adhesive sheet obtained in section (B) was cut into pieces with a width of 15 tm and a length of about 180 m5 to obtain an adhesive tape. This adhesive tape was polished with sandpaper (JIS 11280) and made of stainless steel. It was pasted over the length of about 80 fins on a steel plate (5CIIXIQcm) and crimped by making one reciprocation using a 2 kg rubber-covered roller.After crimping, it was left at 21°C for 30 minutes, and one end was folded back 180 degrees. Forced peeling was performed at a constant speed of 300 mm/min, and the adhesive force at this time was measured using the Tensilon peel force test (JIS-Z-1522).

(2) Pole tack value: The adhesive sheet obtained in section (B) was cut into pieces of about 30 m in width and about 120 m in length to obtain adhesive tapes. This adhesive tape was fixed at room temperature with the adhesive side facing outward on a sloped surface with a slope of 30" and a slope of 30 cm or more. A tape with a thickness of 20 μm was applied approximately halfway down from the top of the slope of the adhesive surface. covered with cellophane film.

A clean ball bearing ball was allowed to roll naturally from a point 100 fins up the slope from the boundary line. The maximum diameter of a ball that stops naturally within 100 mm from the boundary line between the adhesive and non-adhesive surfaces (in units of 1/32 inch, expressed by the number of its molecules; for example, 15 for 15/32 inch). Paul tank value (Pharmaceutical Manufacturing Guidelines (1)
984) p. 51).

(3) Cohesive failure property: It was investigated whether a portion of the adhesive remained on the surface of the stainless steel plate when measuring the adhesive strength of the 180° folded paper. If adhesive remains, it is determined that cohesive failure has occurred.

(C) Conductivity evaluation of adhesive layer: thickness 5 as conductive base material
A laminate plate made by dry bonding of a 0 μm polyethylene terephthalate stretched film and a 20 μm thick tin foil was used. The adhesive solution obtained in section (A) was applied onto a release paper so that the thickness after drying was 400 μm, and dried to form an adhesive layer of about 4 cm x 4 cm. This adhesive layer was transferred to the tin surface of a laminate board. Separately, a homogeneous laminate plate was cut into a size of 2 ctm x 3 cm, and one end in the longitudinal direction was folded back at 90° toward the polyethylene terephthalate side at a position 1 cm from the end. This was used as an upper electrode, and the silver surface portion of a square measuring 2C111X2C11 was brought into close contact with the adhesive layer. First, the laminate plate on which the adhesive layer was formed was used as the lower electrode, and a sinusoidal voltage of 10 o + V was applied at 10 Hz between the tin foils of the upper and lower electrodes. The current value (μA) when voltage was applied was measured, and the electrical resistance (impedance; R) per LED was calculated from the following formula using the value (1): R = −(
KΩ)×4 ■ The impedance was 41.9Ω.

Preparation of adhesive solution (A): Example 1 The adhesive base solution in section (A) was used as an adhesive solution.

(B) Performance evaluation of adhesive layer formation and adhesive strength: Using the adhesive solution obtained in section (A) of this comparative example, Example 1 (
It was carried out according to section B). The 180' folded binding force was 530g/15II1m, the pole tack value was 23, and no cohesive failure was observed.

(C) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (A) of this comparative example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. The impedance is 1.
It was 0OOKΩ or more.

Example 1 and Comparative Examples 1 to 1 The adhesive of the present invention (Example 1) is almost the same as the conventional adhesive (Comparative Example 1) in terms of adhesive physical properties, and has high adhesive properties that are not found in conventional adhesives. It is clear that it exhibits electrical conductivity.

(A) Preparation of adhesive solution: Polyvinylpyrrolidone (Ko
A methyl alcohol solution containing 20% of llidon K-90) was prepared. To this, the above vinylpyrrolidone 1
An adhesive base solution was obtained by adding 70 parts by weight of diglycerin as a plasticizer to 00 parts by weight. 50 parts by weight of ammonium citrate was dissolved in 180 parts by weight of water.

This was added to the above adhesive base solution to obtain an adhesive solution. The total solute content of the adhesive solution is 28% by weight.

(B) Formation of adhesive layer and performance evaluation of adhesive strength: Using the adhesive solution obtained in section (A) of this example, Example 1 (B)
). 180' folding hocho force is 5
The weight was 60 g/15 mm, the pole tack value was 24, and no cohesive failure was observed.

(C) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (A) of this example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. Impedance is 39
．． It was 6Ω.

Calibration Charcoal I (A) Preparation of Adhesive Solution: Example 2 The adhesive base solution in section (A) was used as an adhesive solution.

(B) Performance evaluation of adhesive layer formation and adhesive strength Two comparative examples Example 1 (B) using the adhesive solution obtained in section (A)
). 180 ”Folding hocho force is 5
The weight was 50 g/15 mm, the pole tack value was 24, and no cohesive failure was observed.

(C) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (A) of this comparative example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. The impedance is 1.
It was 0OOKΩ or more.

Sff1 (A) Preparation of adhesive solution: Polyvinylpyrrolidone (Ko
A methyl alcohol solution containing 20% of llidon K-90) was prepared. Separately, an aqueous solution containing 20% polyacrylic acid was prepared, and this was added to the above methyl alcohol solution so that the amount of polyacrylic acid was 5 parts by weight per 100 parts by weight of polyvinylpyrrolidone. Furthermore, 120 parts by weight of polypropylene glycol (UNIOL P-400; trade name) was added to obtain an adhesive base solution. To this, 5 parts by weight of dibutyltin dilaurate as an ionic crosslinking agent,
Then, 60 parts by weight of dimethylalkyl betaine (Anon BF, trade name) was added as an ammonium compound. It was further diluted with methyl alcohol to obtain an adhesive solution with a total solute content of 38%.

(B) Performance evaluation of adhesive layer formation and adhesive strength (2) Example 1 (B) using the adhesive solution obtained in Example (A)
). 18o0 folded hocho landing strength is 61
0 g/15 mm, pole tack value was 25, and no cohesive failure was observed.

(C) Conductivity evaluation of adhesive layer 2 Using the adhesive solution obtained in Example 1 (A), an adhesive layer was formed according to Example 1 (C), and measurements were performed. Impedance is 37
．． It was 2Ω.

Preparation of lu-Kyusho (A) adhesive solution: The adhesive base solution of Example 3 (A) was used as an adhesive solution.

(B) Performance evaluation of adhesive layer formation and adhesive strength: Using the adhesive solution obtained in section (A) of this comparative example, Example 1 (B)
). 180° folded hocho adhesion strength is 64
0g/15mm, ball tack value was 26, and no cohesive failure was observed.

(C) Conductivity Evaluation of Adhesive Layer Two Comparative Examples Using the adhesive solution obtained in Section (A), an adhesive layer was formed according to Section (C) of Example 1, and measurements were performed. The impedance is 1.
It was 00OKΩ or more.

Preparation of adhesive solution (A): An aqueous solution containing 50% polyethyleneimine with an average degree of polymerization of 500 was prepared. Separately, polyvinyl alcohol (PVC) with an average degree of polymerization of 400 2
An aqueous solution containing 0% was prepared and added to the polyethyleneimine aqueous solution so that PvC was 30 parts by weight based on 70 parts by weight of polyethyleneimine. Furthermore, 20 parts by weight of polyethylene glycol having an average degree of polymerization of 20 was added to obtain an adhesive base solution.

To this was added 30 parts by weight of hexadecyltrimethylammonium chloride as an ammonium compound.

Furthermore, an aqueous solution of 30 parts by weight of ammonium sulfate dissolved in 80 parts by weight of water was added. This was diluted with methyl alcohol to obtain an adhesive solution containing 38% by weight of all solute components.

(B) Formation of adhesive layer and performance evaluation of adhesive strength Example 1 (2) Using the adhesive solution obtained in Example (A)
It was carried out according to section B). 180° folded hocho adhesion strength is 4
60g/15mm, pole tack value is 15 and 1wi
No collection or destruction was observed.

(C) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (A) of this example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. Impedance is 4
It was 4.2Ω.

(A) Preparation of adhesive solution: The adhesive base solution of Example 4 (A) was used as an adhesive solution.

(B) Performance evaluation of adhesive layer formation and adhesive strength: Using the adhesive solution obtained in section (A) of this comparative example, Example 1 (B)
). 180° folded hocho adhesion strength is 45
0g/15mm, ball tack value was 18, and no cohesive failure was observed.

(C) Conductivity Evaluation of Adhesive Layer Two Comparative Examples Using the adhesive solution obtained in Section (A), an adhesive layer was formed according to Section (C) of Example 1, and measurements were performed. Impedance is 1
, 000Ω or more.

Five big ships] (A) Synthesis of polymer 50 g of butyl diacrylate.

130 g of N-vinyl 2-pyrrolidone and 0.1 g of polyethylene glycol dimethacrylate (NK Ester 4G; trade name) were placed in a reaction vessel, and ethyl alcohol was added to make a 70% solution. A catalyst solution was prepared by adding 100 nl of ethyl acetate to 0.4 g of azobisisobutyronitrile, and this was used to initiate a polymerization reaction by heating and stirring according to a normal solution polymerization method. After starting the polymerization reaction, the temperature was adjusted to 60°C while controlling the viscosity by diluting with ethyl alcohol as appropriate.
Stirring of the reaction solution was continued for 30 hours at 70° C. and for further 8 hours at 70°C. the result.

Polymer concentration: 37.0%, viscosity at 21°C: approximately 24.0
A cloudy, viscous polymer solution of OOcps was obtained.

CB) Preparation of Adhesive Solution 2 To 100 parts by weight of the polymer solution obtained in Example (A) (in terms of polymer weight), 25 parts by weight and 20 parts by weight of diglycerin and butylene glycol as plasticizers were added, respectively. A base solution was obtained. To this was added 30 parts by weight of dodecyltrimethylammonium chloride.

Furthermore, an aqueous solution of 20 parts by weight of ammonium benzoate dissolved in 80 parts by weight of water was added. This was diluted with methyl alcohol to obtain an adhesive solution having a total solute component of 40 weight.

(C) Performance evaluation of adhesive layer formation and adhesive strength; Example 1 (B) using the adhesive solution obtained in section (B) of this example.
). 180 ”Folding hocho force is 6
The weight was 20 g/15 mm, the pole tack value was 23, and no cohesive failure was observed.

(D) Evaluation of electrical conductivity of adhesive layer 2 Using the adhesive solution obtained in Example (B), an adhesive layer was formed according to Example 1 (C), and measurements were performed. Impedance is 47
．． It was 4Ω.

(A) Synthesis of polymer: Same as Example 5 (A).

(B) Preparation of adhesive solution: The adhesive base solution of Example 5 (B) was used as an adhesive solution.

(C) Performance evaluation of adhesive layer formation and adhesive strength Two comparative examples Example 1 (B) using the adhesive solution obtained in section (B)
). 180 ”Folding hocho force is 6
The weight was 30 g/15 m, the ball tack value was 24, and no cohesive failure was observed.

(D) Two Comparative Examples for Evaluation of Conductivity of Adhesive Layer Using the adhesive solution obtained in Section (A), an adhesive layer was formed according to Section (C) of Example 1, and measurements were performed. The impedance is 1.
It was 0OOKΩ or more.

Synthesis of Dao Group Wudan (A) polymer 45 parts by weight of butyl niarylate;
130 ffit parts of dihydroxypropyl acrylate and 5 parts by weight of glycidyl methacrylate were placed in a reaction vessel, and ethyl alcohol was added to make a 70% solution. Example 5 A polymerization reaction was carried out according to the method in section (A), and the polymer concentration was 38.4% and the viscosity at 21°C was about 20.0OOcp.
A clear polymer solution of s was obtained.

(B) Preparation of adhesive solution 2. Polypropylene glycol (UNIOL 5H-
500 (trade name) was added to obtain an adhesive base solution. To this was added 30 g of octadecyltrimethylammonium chloride, and further added an aqueous solution of 10 parts by weight of ammonium sulfamate dissolved in 40 parts by weight of water.

This was diluted with methyl alcohol to obtain an adhesive solution containing 40% by weight of total solute components.

(C) Formation of adhesive layer and performance evaluation of adhesive strength: Using the adhesive solution obtained in section (B) of this example, Example 1 (
It was carried out according to section B). 1800 folding hocho force is 4
The weight was 30 g/15 mm, the ball tack value was 21, and no cohesive failure was observed.

(D) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (B) of this example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. Impedance is 51
．． It was 8Ω.

, (A) Synthesis of polymer: Same as Example 6 (A).

(B) Preparation of adhesive solution: The adhesive base solution of Example 6 (B) was used as an adhesive solution.

(C) Performance evaluation of adhesive layer formation and adhesive strength Two comparative examples Example 1 (B) using the adhesive solution obtained in section (B)
). 180° folded hocho adhesion strength is 41
0g/15mm, ball tack value was 18, and no cohesive failure was observed.

(D) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (A) of this comparative example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. The impedance is 1.
It was 00OKΩ or more.

1 (A) Synthesis of polymer: Methyl vinyl ether-maleic anhydride copolymer (GANTREZ-139; trade name)
100 parts by weight and 50 parts by weight of aminomethylpropertool were reacted in methyl alcohol at 60°C for 5 hours.

The polymer concentration of the obtained polymer solution was 40%.

(B) Preparation of adhesive solution: Add 20 parts by weight of polyvinylpyrrolidone (Kol 11don ~90) to 60 parts by weight (in terms of polymer weight) of the polymer solution obtained in section (A) of this example.
% methyl alcohol solution to polyvinylpyrrolidone
Added parts by weight. Next, diglycerin and polypropylene glycol having an average molecular weight of 8,000 were added as plasticizers in 35 overlapping parts each to obtain an adhesive base solution. To this was added 30 parts by weight of coconut alkyltrimethylammonium chloride. Separately, 50% aqueous solutions of ammonium citrate and sodium ammonium phosphate were prepared.

Ammonium citrate and sodium ammonium phosphate were added to the above solution in amounts of 20 parts by weight each. This was diluted with methyl alcohol to obtain an adhesive solution containing 38% by weight of all solute components.

(C) Formation of adhesive layer and performance evaluation of adhesive strength (2) Example 1 (B) using the adhesive solution obtained in Example (B)
). 180 ”Folding hocho force is 5
70g/15+m++, ball tack value is 26,
No cohesive failure was observed.

(D) Conductivity evaluation of adhesive layer: Using the adhesive solution obtained in section (B) of this example, an adhesive layer was formed according to section (C) of Example 1, and measurements were performed. The impedance is 3
It was 6.5Ω.

start of construction (A) Polymer synthesis: Same as Example 7.

(B) Preparation of adhesive solution: Example 7 The adhesive base solution in section (B) was used as an adhesive solution.

(C) Performance evaluation of adhesive layer formation and adhesive strength: Using the adhesive solution obtained in section (B) of this comparative example, Example 1 (B)
). 180 ”Folding hocho force is 5
90g/15n+m, pole tack value was 26, and no cohesive failure was observed.

(D) Two Comparative Examples for Evaluation of Conductivity of Adhesive Layer Using the adhesive solution obtained in Section (A), an adhesive layer was formed according to Section (C) of Example 1, and measurements were performed. The impedance is 1,
It was 0OOKΩ or more.

(Effects of the Invention) According to the present invention, an adhesive having excellent conductivity and adhesiveness can be obtained. A medical electrode obtained by applying this adhesive onto an electrode plate can be easily applied to the skin surface and does not require any auxiliary fixing means. Because of its high electrical conductivity, the electrodes can provide highly accurate measurements when used in medical measurement equipment.

Since the adhesive itself has conductivity, a small electrode can be formed with a simple structure, and therefore the electrode can be supplied at low cost. Since the adhesive does not need to contain water as a plasticizer or electrolyte solvent, there is no change in conductivity due to water evaporation during use or storage of the electrode, and therefore, accurate measurement values can be obtained.

Additionally, no special packaging is required to prevent water evaporation. Almost no electrical noise is observed.

This is because the internal cohesive force of the adhesive is also large.

No adhesive cracking or adhesive residue phenomenon occurs. The adhesive does not irritate the skin, so it is unlikely to cause a rash even if the electrode is attached to the skin for a long time. Since the tackiness and conductivity of the adhesive can be adjusted to a desired degree, an electrode suitable for the purpose can be obtained. Such skin electrodes can be used in various medical measurement devices and treatment devices, and desired measurements can be made easily and accurately.

[Brief explanation of the drawing]

1 and 2 are a plan view and a bottom view showing an example of the medical adhesive electrode of the present invention, FIG. 3 is a side view thereof, and FIGS. 4 and 5 are respectively a plan view and a bottom view showing an example of the medical adhesive electrode of the present invention. FIG. 7 is a side view showing another example of the electrode. 1.2.3... Adhesive electrode, 11.21... Electrode plate, 13°23... Conductive adhesive layer, 110.210
···protrusion. that's all

Claims (1)

[Scope of Claims] 1. A medical adhesive prepared by uniformly mixing an ammonium compound into an adhesive base whose main component is a polymer soluble in water and/or alcohol. 2. The adhesive according to claim 1, wherein the adhesive base contains a plasticizer. 3. The ammonium compound is an ammonium salt and/or
or a quaternary ammonium salt, Claim 1
Adhesives listed in section. 4. A medical adhesive electrode in which a conductive adhesive layer is provided on one side of an electrode plate, wherein the adhesive is an adhesive base mainly composed of a polymer soluble in water and/or alcohol, and an ammonium compound added to the adhesive base. Medical adhesive electrode made by uniformly mixing. 5. The electrode according to claim 4, wherein the adhesive base contains a plasticizer. 6. The ammonium compound is an ammonium salt and/or
or a quaternary ammonium salt, Claim 4
Electrodes described in Section. 7. The electrode according to claim 4, wherein the adhesive of the adhesive layer is crosslinked.