JP5020141B2 - Adhesive hydrogel, composition for production thereof and use thereof - Google Patents

Description

  The present invention relates to an adhesive hydrogel, a composition for its production, and its use. More specifically, the present invention relates to an adhesive hydrogel having improved repeated adhesiveness to the skin, a composition for production thereof, and an application thereof.

  The adhesive hydrogel of the present invention is a surgical tape to be applied to a living body, a catheter or drip tube / electrocardiogram electrode / other sensor fixing tape, a poultice, a wound dressing, an anus fixing tape, electrotherapy, etc. As an adhesive for use on a living body, such as a device guide / adhesive for fixing a magnetic treatment device / carrier / adhesive for a transdermal absorbent, and as a coupling material for hydrogel dressing and ultrasonic measurement, Can also be suitably used as an industrial adhesive such as building materials / electronic materials.

  Hydrogel is a material that is gentle to human skin because it is hypoallergenic to the skin and can reduce stuffiness. Furthermore, since adhesiveness and conductivity can be imparted, it is used in a wide range of fields such as a bioelectrode pad, an electrocardiogram electrode, and a wound dressing to be applied to a living body.

  In the medical field in recent years, actions such as flowing electricity into the body and taking out electrical signals in the body and copying them to a monitor are frequently performed. Even at home, there are treatment methods that use muscles to relax muscles and stimulate nerves. This generally requires a conductor for conducting electricity from the outside and some conductive medium on the skin surface. Hydrogel is used for this conductive medium. This is because the hydrogel has adhesiveness, so that it is less likely to peel from the skin during use, and stable electricity can be flowed by being in close contact with the skin. In addition, since hydrogel contains water, electrolyte, and the like, even weak electricity can flow stably, and it can be said that the material is very suitable for the field of bioelectrodes and the like.

  It is considered that the adhesive strength of such an adhesive hydrogel is mainly caused by the surface tension and viscoelasticity of the hydrogel. That is, by controlling the surface tension of the hydrogel and increasing the wettability with the adherend, it is considered that the effective contact area for adhesion increases and as a result, the adhesive strength increases. Moreover, it is thought that by controlling viscoelasticity, the deformation behavior at the time of contact or peeling changes, which affects the adhesive force. These are also described in JP-T-2002-521140 (Patent Document 1).

  According to Patent Document 1, the diagnostic electrode is not required to have a long-term adhesion, but must adhere to dry and moist skin covered with hair over 5 to 10 minutes of use. Also, the monitoring electrode must adhere for a longer time, and the halter electrode is subject to physical strength, sweating, water, etc., and its adhesive strength is easily destroyed, so it needs the best adhesion and comfort It is described.

  This adhesive gel controls the above-mentioned factors to control the adhesive force, and it is highly adhesive and at the same time reduces the pain felt at the time of peeling, but it is only intended for single use. is there. That is, since these biomedical electrodes are mainly used in medical sites where insurance points are applied, they also have a meaning of preventing infection and are disposable in principle. Therefore, it has not been necessary to consider repeated use, and has been developed for the purpose of increasing the initial adhesive strength.

  Japanese Patent Application Laid-Open No. 2007-112972 (Patent Document 2) also describes improvement of the adhesive strength of the adhesive hydrogel. According to this publication, a polymer matrix composed of a copolymer of a nonionic polymerizable monomer and a crosslinkable monomer is a non-crosslinked acrylic acid / methacrylic acid copolymer, The hydrogel containing 0.15-15 weight part with respect to 100 weight part of polymerizable monomers to form is disclosed. This hydrogel has an adhesive force improved by 1.5 times or more as compared with a conventional hydrogel to which a water-soluble polymer such as polyvinylpyrrolidone is added, and is suitably used for a single use. However, this gazette also aims to increase the initial adhesive strength and does not describe repeated use.

  JP-A-6-319793 (Patent Document 3) discloses an adhesive containing an acrylic polymer and a liquid or paste-like component that is compatible with the acrylic polymer at room temperature. According to this, an adhesive composition comprising 100 parts by weight of an acrylic polymer and 30 to 100 parts by weight of a liquid or paste component at room temperature compatible with the polymer, the liquid or paste component Is an ester of a monobasic acid or polybasic acid having 8 to 18 carbon atoms and a branched alcohol having 14 to 18 carbon atoms and / or an unsaturated fatty acid having 14 to 18 carbon atoms or a branched acid and an alcohol having 4 or less valences. A medical pressure-sensitive adhesive comprising an ester and 40-80% by weight of the acrylic polymer is insolubilized by crosslinking so that the skin adhesion is good, there is almost no skin irritation, and the keratinous damage is extremely slight and safe. Is obtained. In addition, for example, when used for medical devices and medical devices, liquid or paste-like components contained in the adhesive do not migrate to the medical devices and medical devices, so there is no risk of damaging the devices and further support. Since there is no transfer to the body, a medical pressure-sensitive adhesive capable of expanding the selection range of the support is obtained.

  Further, Patent No. 3014188 (Patent Document 4) and Patent No. 2,800,845 (Patent Document 5) copolymerize a copolymerizable monomer with an alkyl alkyl ester having an alkyl group of 4 or more as a main component. A crosslinked gel layer containing a liquid component compatible with the copolymer is disclosed. According to this, the alkyl acrylate ester obtained by copolymerizing a monomer capable of copolymerization with a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group as a main component on at least one side of the support. By containing a copolymer and a (organic) liquid component that is compatible with the copolymer, it has good adhesion and adhesion to the skin surface, and is physically stimulated when it is peeled off from the skin surface. A pressure-sensitive adhesive which does not damage the skin surface as much as possible is disclosed.

  However, even the above-mentioned adhesive is intended to reduce the damage to the skin during transfer of the adhesive component during application or peeling and removal. There is almost no description about processability. Furthermore, in Patent Documents 4 and 5, there is a description in the specification that an N-alkylsulfonic acid acrylamide monomer can be used for the polymer or copolymer forming the pressure-sensitive adhesive, but this forms a gel. The above monomer is used as a main skeleton, and the present invention is characterized by containing an N-alkyl sulfonic acid acrylamide polymer separately from the polymer or copolymer forming the main skeleton of the gel. Therefore, it is very different from the above patent document.

  However, in recent years, EMS for the purpose of slimming and strength training has become widespread beyond the medical field, and the opportunity to be used in ordinary households has increased. When used in general households, durability of electrode pads is required. That is, in the adhesive gel, it is necessary that the adhesive strength does not decrease even if it is repeatedly applied.

  Further, when the repeated adhesiveness of the adhesive gel is improved, there is a merit in use at a medical site that is originally disposable. For example, when the pasting position is not accurate, it can be said that it is advantageous to have excellent repeated adhesiveness when performing the pasting for correcting the pasting position.

  The main cause of the repeated decrease in adhesive strength is that when the gel is peeled from the skin, keratin that has fallen from the skin surface adheres to the surface of the gel, and the effective adhesive area decreases.

  As a method for solving the above problem, it is conceivable to reduce the initial adhesive strength to suppress the amount of keratin adhering at the time of peeling, but reducing the initial adhesive strength impairs the adhesion to the skin. Therefore, it is difficult to say that it is the best means for solving the above-mentioned problem. Further, even if the adhesive force is reduced, the adherence of keratin does not disappear, and thus the weak adhesive force is originally lowered further.

  On the other hand, it is conceivable that by imparting flexibility to the gel, it becomes easy to follow uneven skin, and the initial adhesive force can be easily developed even if the affinity with the skin is low. Since the affinity with the skin is low, the amount of keratin adhering at the time of peeling is reduced, and a relatively large number of places where adhesion occurs when it is applied next time, so that adhesive strength can be obtained even during repeated use.

  However, such flexible gels are difficult to cut at the time of processing, and the cut surface is not neatly arranged, dust adheres to the periphery of the gel during application to the skin, and the gel adheres to clothes. Problems are likely to occur.

  As another method for improving the adhesive strength repeatedly, it relates to a hydrogel which can be reused by recovering the adhesive strength by washing the adhesive surface soiled by applying the skin several times to Patent No. 3437124 (Patent Document 6). There is a patent.

  According to this, as described above, when the adhesive surface is markedly deteriorated due to the keratin that has fallen off the skin when the gel is peeled from the skin, the gel surface is washed with a fingertip when the adhesive surface is drastically reduced. The adhesive strength can be restored to the initial value by lightly wiping with a cloth soaked in the cloth. Thereby, it can be repeatedly used many times at the time of use for home use, etc., and it is extremely economical and resource-saving, and can be suitably used for repeated use.

  However, since the hydrogel described above needs to be washed with water in order to recover the adhesive strength after repeated use, care must be taken in handling the recovery method, particularly when used at home. In other words, in order to reliably recover the adhesive strength, the conditions specified in the instruction manual, such as a cleaning method and a drying method, must be observed. That is, since it is a hydrogel, it has the property of absorbing water when it comes into contact with water, and does not exhibit adhesive strength when absorbed. Therefore, in order to reuse, it is necessary to evaporate excess water under specified conditions and restore it to its original state. Moreover, when it is made to contact with water for a long time more than necessary, it may absorb water excessively and it will become difficult to restore | restore a composition.

Special table 2002-521140 gazette JP 2007-112972 A JP-A-6-319793 Patent No. 3014188 Japanese Patent No. 2700835 Japanese Patent No. 3437124

  Therefore, if it can be used repeatedly without being washed with water, the labor of washing with water can be saved, and it can be reused without waiting for the gel to dry, so that a beneficial effect for the user can be expected.

  Moreover, repeated washing with water does not mean that the function of the gel gradually deteriorates, so that it cannot be used repeatedly indefinitely. Therefore, in order to extend the service life, instead of washing with each use, it can be used repeatedly without water washing for a certain number of times. Life expectancy can be expected.

  Therefore, there is a need to provide an adhesive hydrogel with improved repeated adhesiveness to the skin, that is, a reduction in adhesive strength even when repeatedly applied to the skin.

  As a result of intensive studies, the inventors of the present invention, as a result of including a polymer containing N-alkylsulfonic acid acrylamide as a structural unit in a crosslinked polymer gel matrix, can be repeatedly applied to the skin. The present invention unexpectedly found a tacky hydrogel having no workability and no gel adhesion to the clothes being applied.

Thus, according to the present invention, a polymer containing water, a polyhydric alcohol, and N-alkylsulfonic acid acrylamide as a structural unit in a polymer matrix comprising a copolymer of a polymerizable monomer and a crosslinkable monomer. The polymer containing N-alkylsulfonic acid acrylamide in the structural unit is 0.1 to 45 parts by weight when the components other than water in the hydrogel are 100 parts by weight. And
The polymerizable monomer is (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N. -Diethyl (meth) acrylamide, acryloylmorpholine, tertiary butylacrylamide sulfonic acid and / or its salt, N, N-dimethylaminoethylacrylamide hydrochloride, N, N-dimethylaminopropylacrylamide hydrochloride, (meth) acrylic acid , Maleic acid, itaconic acid, sulfopropyl methacrylate and / or its salt, methacryloyloxyethyltrimethylammonium chloride, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, vinyl pyrrolidone, Sulfonyl acetamide, vinyl formamide is selected from allyl alcohol,
The crosslinkable monomer is N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate , poly Selected from ripropylene glycol di (meth) acrylate, polyglycerin di (meth) acrylate, trimethylol propane triacrylate, pentaerythritol triacrylate,
The polyhydric alcohol is ethylene glycol, propylene glycol, butanediol, glycerol, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, Po Li glycerin, adhesive hydrogel is selected from polyoxyethylene glycerol is provided.

  Further, according to the present invention, there is provided a composition used for producing the above-mentioned adhesive hydrogel, comprising a polymerizable monomer, a crosslinkable monomer, water, a polyhydric alcohol, and a constituent unit. A composition for producing a tacky hydrogel comprising a polymer comprising N-alkyl sulfonic acid acrylamide is provided.

Furthermore, according to this invention, the gel sheet containing the said adhesive hydrogel is provided.
Furthermore, an electrode having a gel layer made of the adhesive hydrogel and a conductive layer is provided.

  The pressure-sensitive adhesive hydrogel of the present invention adds a polymer containing N-alkylsulfonic acid acrylamide to the structural unit, and keeps the adhesive force following the unevenness on the skin as compared with the conventional pressure-sensitive adhesive hydrogel. Since the cohesiveness is maintained, the processability is excellent, and the gel does not adhere to the clothes during the pasting. In addition, an adhesive hydrogel can be obtained that does not require troublesome work such as washing after repeated use, and maintains 80% or more of the initial skin adhesive strength after being applied to the skin 10 times.

  Furthermore, after repeated use, there is no need for water washing or other work to restore the adhesive strength, so the gel composition does not change during the washing operation or the gel is not destroyed by the washing method. Is possible.

Hereinafter, the present invention will be described in more detail.
The adhesive hydrogel of the present invention comprises a polymer matrix comprising a copolymer of a polymerizable monomer and a crosslinkable monomer, water, a polyhydric alcohol, and a polymer containing N-alkylsulfonic acid acrylamide in the structural unit. It is characterized by including.

  Specific polymerizable monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Non-electrolyte acrylamide derivatives such as N, N-diethyl (meth) acrylamide, acryloylmorpholine, tertiary butyl acrylamide sulfonic acid (TBAS) and / or its salt, N, N-dimethylaminoethylacrylamide (DMAEAA) hydrochloride, Electrolytic acrylamide derivatives such as N, N-dimethylaminopropyl acrylamide (DMAPAA) hydrochloride, (meth) acrylic acid, maleic acid, itaconic acid, sulfopropyl methacrylate (SPM) and / or its salts, methacryloyloxyethyltri Electrolytic acrylic derivatives such as tilammonium chloride (QDM), nonelectrolytic acrylic derivatives such as hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, vinylamide derivatives such as vinylpyrrolidone, vinylacetamide, vinylformamide, allyl alcohol, etc. Is mentioned. These polymerizable monomers can be used alone or in combination.

  The crosslinkable monomer is not particularly limited as long as it has two or more carbon-carbon double bonds having polymerizability in the molecule. Specifically, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, polyethylene glycol di ( Examples include polyfunctional (meth) acrylamides and polyfunctional (meth) acrylates such as (meth) acrylate, polypropylene glycol di (meth) acrylate, polyglycerin di (meth) acrylate, trimethylol propane triacrylate, and pentaerythritol triacrylate. These crosslinkable monomers can be used alone or in combination.

  In the present specification, (meth) acrylate means acrylate or methacrylate.

  A polymer matrix is formed by polymerizing and crosslinking the polymerizable monomer and the crosslinkable monomer. The proportion of the polymer matrix contained in the adhesive hydrogel of the present invention is preferably 10 to 70 parts by weight, when the components other than water in the adhesive hydrogel are 100 parts by weight. More preferred are parts by weight.

  Furthermore, the proportion of the crosslinkable monomer in the production of the polymer matrix varies depending on the polymerizable monomer species and the crosslinkable monomer species to be used, but is generally 100 parts by weight of the polymerizable monomer. It is preferable that it is 0.01-0.5 weight part with respect to it, and it is more preferable that it is 0.05-0.25 weight part. In order to give shape stability, the crosslinkable monomer is preferably 0.01 parts by weight or more, and the one having flexibility so as not to impair the shape-retaining property is the initial stage when used as an adhesive. The amount is preferably 0.5 parts by weight or less because tackiness is easily obtained.

  Examples of the polyhydric alcohol used in the present invention include diols such as ethylene glycol, propylene glycol, and butanediol, polyhydric alcohols such as glycerin, pentaerythritol, and sorbitol, polyethylene glycol, polypropylene glycol, diglycerin, polyglycerin, and the like. Polyhydric alcohol condensates, polyhydric alcohol modified products such as polyoxyethylene glycerin and the like can be used. These polyhydric alcohols can be used alone or in combination.

  Among these polyhydric alcohols, it is preferable to use liquid polyhydric alcohols in a temperature range where hydrogel is actually used (for example, around 20 ° C. when used indoors).

  The content of the polyhydric alcohol is preferably 20 to 80 parts by weight, and more preferably 30 to 60 parts by weight when the components other than water in the adhesive hydrogel are 100 parts by weight. When the addition amount of the polyhydric alcohol is in the above-described range, it is preferable because a change in physical properties due to drying of the obtained gel body is small and high adhesive strength is obtained.

  The present invention is characterized in that it comprises the above polymer matrix and a polymer containing N-alkylsulfonic acid acrylamide as a constituent unit. The weight average molecular weight of the polymer containing N-alkyl sulfonic acid acrylamide in the structural unit is not particularly limited, but it is preferably 7 million or less because it is easy to adjust the blended liquid and the obtained gel has optimum adhesive strength. Moreover, 500,000 or more is preferable in order to obtain a coherent gel.

  When the content of the polymer containing N-alkylsulfonic acid acrylamide in the structural unit is 100 parts by weight of components other than water in the gel in order to obtain a gel having the desired adhesive properties and processing properties 0.1 to 45 parts by weight, preferably 0.5 to 40 parts by weight, 0.5 to 35 parts by weight, 0.5 to 30 parts by weight, 0.5 to 25 parts by weight, 0.5 to 20 parts by weight, 0.5 to 15 parts by weight, more specifically, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, and 15 parts by weight.

  By including N-alkylsulfonic acid acrylamide in the structural unit, electrostatic repulsion in the polymer chain is increased due to dissociation, and the polymer unit tends to expand. Since the cohesiveness due to the entanglement of the molecular weight polymer becomes high, it is considered that the obtained gel becomes an adhesive substance having a high cohesive force.

  There is no problem even if the polymer containing N-alkylsulfonic acid acrylamide in the structural unit is copolymerized with other monomers. Commercially available products include, for example, a copolymer of acrylic acid and N-alkyl sulfonic acid acrylamide, which is preferably used (for example, a copolymer of acrylic acid and acrylamidomethylpropane sulfonic acid (Nippon Junyaku Co., Ltd.). Product name Aronbis AH-305)).

  When the polymer containing N-alkylsulfonic acid acrylamide in the structural unit is a copolymer with another monomer, the copolymerization ratio is preferably 2: 8 to 8: 2, more preferably 2: 8 to 5: 5. preferable.

  Furthermore, a conductive gel can be obtained by adding an electrolyte to the adhesive hydrogel. For example, when the use of the conductive gel is a bioelectrode such as an electrocardiogram measurement electrode, a low-frequency treatment device electrode, and various ground electrodes, the specific resistance is preferably 0.1 to 10 kΩ · cm.

  As the electrolyte, alkali metals such as lithium, sodium and potassium, halides of alkaline earth metals such as magnesium and calcium, mineral salts such as carbonic acid, sulfuric acid and phosphoric acid, organic salts and ammonium salts can be used. . Among these, in the case of a bioelectrode, those that are neutral to weakly acidic are preferred.

  When the electrolyte content is used as an electrode, it is necessary to reduce the impedance. As a preferable addition amount, 0.1 wt% of components other than water in the adhesive hydrogel is used. -10 parts by weight is good. Moreover, it is preferable that it is 10 weight part or less in order to dissolve the electrolyte to add in a compounding liquid uniformly. A more preferable content is 2 to 8 parts by weight.

  The content of water contained in the adhesive hydrogel is not particularly limited, but in order to optimize the adhesive properties and electrical properties of the finally obtained gel, it is 10 to 40 weights with respect to the entire adhesive hydrogel. % Is considered preferable. It is necessary to maintain a moisture content that does not greatly change the physical properties of the gel depending on the surrounding environment. If the amount of water in the matrix is extremely low, water absorption is expected to occur over time depending on the environment in which it is left. On the other hand, if the amount of water in the matrix is extremely large, it is expected that moisture will evaporate over time. In this way, it is necessary to determine the moisture content in consideration of the physical properties of the selected polymerizable monomer and polyhydric alcohol so that the adhesive strength and electrical performance do not change significantly due to the extreme change in moisture content in the gel. There is.

  The adhesive hydrogel may contain other additives as required. Other additives include antiseptics, bactericides, antifungal agents, rust inhibitors, antioxidants, antifoaming agents, stabilizers, fragrances, surfactants, colorants, medicinal ingredients (for example, anti-inflammatory agents, Vitamins, whitening agents, etc.).

  Among the above-mentioned other additives, examples of the method of adding a medicinal component include a method of dissolving or dispersing in a composition in advance and polymerizing / crosslinking, and a method of adding to a once produced adhesive hydrogel later. Among these methods, the former method is more preferably added by the latter method because the medicinal component may be attacked by radicals and lose its medicinal effect during gel formation accompanied by radical polymerization reaction.

Since the adhesive hydrogel of the present invention is gelled by polymerizing and crosslinking a liquid monomer compounded solution, it can be appropriately molded according to the intended use.
For example, when used as an adhesive, it may be molded into a gel sheet having a thickness of 0.01 mm to 2.0 mm. In that case, it is preferable to provide a protective film on at least one side of the adhesive hydrogel.

  In the case where a protective film provided on one side of the adhesive hydrogel is used as a separator, it is preferable that a release treatment is performed on both sides. In this case, it is preferable to adjust to different peel strengths. Moreover, when using the said protective film as a support body, the function as a separator can be provided to the opposite surface (back surface) with which adhesive hydrogel is adhere | attached by performing a mold release process to one side. Is possible.

  Moreover, the gel sheet of this invention may provide a protective film on both surfaces. The protective film may be peeled off in the middle of the process as a separator and attached to another film or the like, or may be attached to a final product as a support or a mount and used as it is for the final user.

  Usually, the pressure-sensitive adhesive is coated on a support and used as a so-called pressure-sensitive adhesive tape. Moreover, in the case of the gel sheet which has electroconductivity (ionic conductivity), it can be used as a bioelectrode by combining the support body which has a conductive layer instead of a support body.

  When using a protective film as a separator, there is no particular limitation as long as it is a resin or paper that can be molded into a film. Among them, polyester, polyolefin, polystyrene, paper or paper laminated with a resin film is preferably used. The surface of the separator that contacts the gel is preferably subjected to a mold release treatment. Moreover, it does not interfere even if the mold release process is carried out on both surfaces as needed. When releasing treatment on both sides, there may be a difference in peel strength between the front and back sides. Examples of the mold release treatment method include a silicone coating, and in particular, a baking type silicone coating which is crosslinked or cured by heat or ultraviolet rays is preferable.

  On the other hand, when used as a support, it is preferable to use a resin film such as polyester, polyolefin, polystyrene, polyurethane, etc. without performing a release treatment. In particular, polyurethane is particularly preferred because it is flexible and some have water vapor permeability. At the same time, some polyol-modified polyesters have flexibility and water vapor permeability. Some of the polyol-modified polyesters have water vapor permeability better than that of polyurethane, and are most preferable supports when the adhesive hydrogel of the present invention is used as a bioadhesive. Since these flexible films are usually too soft and difficult to handle in the production process, polyolefin, polyester, paper or the like is laminated as a carrier.

As the protective film, an optimum material is selected according to the product form of the gel sheet. For example, when handling a gel sheet as a strip, it is preferable to provide protective films on both sides. The material of these protective films is not particularly limited as long as it is a resin or paper that can be formed into a film as described above. Moreover, even when winding up in roll shape, a protective film may be provided on both surfaces. In this case, the protective film (in many cases a separator) provided on one side has an elongation of 5.0% or more when a load of 300 g per 1 mm ² cross-sectional area is applied, and is provided on the other side. The protective film (separator or support) is preferably 1.0% or less in elongation when a load of 300 g per 1 mm ² is applied.

  In the case of a thin gel sheet with a thickness of 0.1 mm or less, it is not necessary to consider the characteristics of the film etc. provided on the front and back, but if the thickness is 0.5 mm or more, the inner circumference when wound into a roll shape・ The difference in the outer circumference becomes remarkable, and if the balance of the stretch ratio of the front and back films etc. is not taken into account, phenomena such as roll collapse, step shift, tunneling, etc. occur, the roll appearance deteriorates and the sheet gets wrinkled It causes many problems such as deformation.

  When the adhesive hydrogel of the present invention is formed into a sheet, it is possible to embed a non-woven fabric or a woven fabric as an intermediate substrate as necessary. These intermediate base materials are used to improve gel retention and shape retention during cutting. For example, when an adhesive hydrogel is distributed as an intermediate material for processing, it may be necessary to facilitate handling by a terminal processor. Nonwoven fabrics and woven fabrics can be made of natural fibers such as cellulose, silk and hemp, synthetic fibers such as polyester, nylon, rayon, polyethylene, polypropylene and polyurethane, or blends thereof. A binder is used and may be further colored.

  The manufacturing method of the adhesive hydrogel of this invention is demonstrated. The adhesive hydrogel of the present invention comprises: 1. Create a compounded solution; It can be obtained by molding into an arbitrary shape simultaneously with the polymerization crosslinking reaction.

  1. Preparation of compounded solution: A polymerizable monomer, a crosslinkable monomer, a polymerization initiator, and ion-exchanged water are mixed and stirred to dissolve. If necessary, an electrolyte and additives are added. Next, the polymer containing N-alkyl sulfonic acid acrylamide is added little by little with stirring, and stirred until a colorless transparent uniform solution is obtained.

  In addition, when adding the polymer containing N-alkylsulfonic acid acrylamide, it is preferable to add little by little. Alternatively, a solution dispersed in a polyhydric alcohol or the like is preferably added little by little. Since the polymer has a very high water absorption property, it can easily cause lumps when mixed with water instantaneously, and it takes a very long time to completely dissolve the polymer. This is because the handling becomes difficult.

  2. Polymerization cross-linking reaction and molding: The obtained monomer compounded solution is poured into a mold and subjected to a polymerization cross-linking reaction, whereby an adhesive hydrogel can be obtained in an arbitrary shape. A monomer-containing liquid is poured between the base film and the protective film, and a polymerization cross-linking reaction is performed in a state where the liquid is maintained at a constant thickness, whereby a sheet-like adhesive hydrogel can be obtained. Furthermore, a thin film-like adhesive hydrogel can be obtained by coating a thin layer of the monomer compound solution on the protective film (support) and carrying out a polymerization crosslinking reaction.

  As a method for polymerization crosslinking, redox polymerization, photopolymerization, radiation polymerization, and the like are possible in addition to general radical polymerization. For example, redox polymerization or general radical polymerization is suitable for injecting into a mold having a thickness or depth of 10 mm or more for polymerization crosslinking. On the other hand, photopolymerization is suitable for forming into a sheet or film having a thickness of several millimeters to several micrometers. Polymerization by light irradiation has a high reaction rate, but in the case of a thick material, it attenuates when light is transmitted, and there is a possibility that variation in the thickness direction occurs. Polymerization by radiation is more transparent than light, but is suitable for large production scales because of the large equipment.

When polymerization / crosslinking is performed by irradiating with ultraviolet rays, the cumulative irradiation amount irradiated to the adhesive hydrogel composition is preferably 1000 mJ / cm ² or more. In order to sufficiently accelerate the polymerization reaction, the integrated irradiation amount may be 1000 mJ / cm ² or more, and if the integrated irradiation amount is 2000 mJ / cm ² or more, the residual monomer amount in the gel can be reduced to 100 ppm or less. More preferable. Further, the upper limit of the integrated irradiation amount is not necessarily limited, and it is sufficient that the irradiation amount is sufficient for the polymerization reaction to proceed sufficiently as described above. However, excessive irradiation may cause problems such as an increase in equipment size, use of extra energy, and the need to remove generated heat. Is desirable.

  In addition, when two resin films are arrange | positioned on both surfaces of a gel and a gel is produced | generated by light irradiation, it is necessary to select the material which does not shield light for the top film arrange | positioned at the light irradiation side.

  The photopolymerization initiator is not particularly limited as long as it can be cleaved by ultraviolet rays or visible rays to generate radicals, among which α-hydroxyketone, α-aminoketone, benzylmethyl ketal, bisacylphosphine oxide, metallocene and the like. preferable.

  Specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl. -Ketone (product name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (product name: Irgacure 2959, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropan-1-one (product name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-Benzyl-2-dimethylamino-1- (4-morpholinov Enyl) -butan-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.). These can be used alone or in combination.

  The concentration of the photopolymerization initiator is preferably 0.01% by weight or more based on the monomer compounding solution in order to sufficiently perform the polymerization reaction and reduce the residual monomer, and discoloration due to the residual initiator after the reaction. In order to prevent (yellowing) and odor, the content is preferably 1.0% by weight or less.

Furthermore, in the present invention, a composition for producing an adhesive hydrogel is provided.
The composition includes a polymerizable monomer, a crosslinkable monomer, water, a polyhydric alcohol, and a polymer containing N-alkylsulfonic acid acrylamide as a structural unit.

  In the above composition, the proportion of the polymerizable monomer and the crosslinkable monomer combined is preferably 10 to 70 parts by weight, more preferably 100 parts by weight when the entire composition excluding water is 100 parts by weight. Is 10 to 50 parts by weight.

  The ratio of the polyhydric alcohol in the composition is preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight when the entire composition excluding water is 100 parts by weight.

  The proportion of the polymer containing N-alkylsulfonic acid acrylamide in the structural unit in the composition is 0.1 to 45 parts by weight, preferably 0.1. 5 to 40 parts by weight, 0.5 to 35 parts by weight, 0.5 to 30 parts by weight, 0.5 to 25 parts by weight, 0.5 to 20 parts by weight, and 0.5 to 15 parts by weight.

The ratio of the polymerizable monomer and the crosslinkable monomer is preferably 0.01 to 0.5 parts by weight of the crosslinkable monomer with respect to 100 parts by weight of the polymerizable monomer. More preferably, it is 0.05-0.25 weight part.
The composition for producing the adhesive hydrogel may have one component or two components as its constituent components.

The composition for producing the adhesive hydrogel may contain a polymerization initiator as necessary.
Although the kind of polymerization initiator is not specifically limited, A photoinitiator is preferable. The above description is referred to for examples and amounts of the photopolymerization initiator.

  The adhesive hydrogel of the present invention maintains safety and adhesiveness to the skin, and can be easily used as an adhesive conductive part such as an electrode pad because it can easily impart conductivity by the addition of an electrolyte. Such a use example will be described. An adhesive hydrogel is laminated on one side of a conductive layer in which a conductive substance such as carbon is kneaded, and a non-conductive support is laminated on the opposite side of the layer. Adhesiveness that a conductive substance such as copper wire is attached to this laminate in contact with the conductive layer, and that serves as a terminal, allowing electricity to flow from the outside or to an external monitor through the conductive layer and hydrogel It becomes an electrode containing hydrogel.

  The electrode containing the above-mentioned adhesive hydrogel is an example, and any structure that allows electricity to flow to the outside or from the outside by a method other than the described method can be suitably used as the electrode.

  The conductive layer includes a carbon coat layer formed of a carbon paste using a polyester-based or polyurethane-based resin as a binder, a layer coated with a conductive ink containing a metal such as Ag / AgCl, carbon, etc., a metal foil on the resin film (Aluminum, stainless steel, Ag, etc.) or a layer laminated with a conductive film kneaded with carbon or the like is used. It is desirable for the conductive layer to have a strength that does not easily break when a force is applied from the outside, such as a tensile force. When the electrode is easily broken, the conductive layer may be cut off during the production of the electrode, the electrode of the final product may be deformed due to stretching, and the conductive layer in the electrode may be broken depending on how the user handles it. There is a possibility of causing burns and the like by cutting. On the other hand, since it sticks to an uneven skin surface, flexibility is also required. It is necessary to select a conductive layer having physical properties that do not cause problems during use.

  The material of the non-conductive support is not particularly limited, but a synthetic paper suitable for printing (in which an inorganic filler is added to polypropylene), PET, an OPP film, and the like are preferable. In addition, in order to improve the appearance, cosmetic printing is applied to the surface of the support opposite to the surface in contact with the conductive layer, or paper, nonwoven fabric, foam (soft foam sheet such as polyethylene, polyethylene vinyl acetate, polyurethane) ), A film or sheet of polyurethane or the like may be laminated. When the non-conductive support and the conductive layer are bonded together, it is preferable that the surface of the support to be bonded to the conductive layer is subjected to an adhesive treatment, and a laminate obtained by combining a plurality of conductive layers and supports is used. There is no problem. The non-conductive layer needs to be prevented from being easily peeled off from the conductive layer during use or torn off. Moreover, in order to follow the uneven | corrugated skin surface, the direction with a softness | flexibility is preferable.

  In the case of a film in which the support and the conductive layer are laminated on the terminal, when laminating the above-mentioned adhesive hydrogel, a part where the hydrogel is not laminated is formed on a part of the film, and the part is It becomes a terminal and is sandwiched between clips and connected to the lead wire. In the case of an electrode having a caulking structure, there is no particular limitation as long as it has electrical conductivity. However, Ag / AgCl or the like is used for a snap terminal and a resin molded product in which a metal such as stainless steel or carbon is kneaded and a resin molded product. The part of the structure in which the element coated with metal is crimped becomes a terminal and is connected to the outside.

  When using a metal wire, etc., the metal wire is partly sandwiched between the conductive layer and the support, and the portion that protrudes from the laminated portion of the conductive layer and the support is covered with a non-conductive resin or the like. The tip of the metal wire is connected to the outside by being connected to the lead wire.

  Therefore, the adhesive hydrogel of the present invention comprises a surgical tape to be applied to a living body, a catheter or drip tube / electrocardiogram electrode / other sensor fixing tape, a poultice, a wound dressing, a fixing tape for an artificial anus, As an adhesive for use on living bodies, such as electrotherapy devices, adhesives for fixing magnetic treatment devices, and carriers and adhesives for transdermal absorbents, and as a coupling agent for hydrogel dressing and ultrasonic measurement Furthermore, it can be suitably used as an industrial adhesive such as a building material / electronic material.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. In addition, the evaluation method of each property in an Example and a comparative example is described below.

(Measurement of repeated adhesive strength at 180 ° skin)
A sample lined with a nonwoven fabric is cut into a strip of 20 mm × 100 mm, and this test piece is affixed to the inner side of the left upper arm that has been lightly wiped with alcohol in advance for 2 minutes. It is set on Tentecron manufactured by Orientec Co., Ltd., and the force at the time of peeling in the 180 ° direction at a speed of 1000 mm / min is defined as the initial adhesive strength. After the peeled test piece was applied to the other part of the body and repeated 3 times, it was applied to the inner side of the left upper arm that had been lightly wiped with alcohol in advance for 2 minutes, and peeled in the 180 ° direction in the same manner as above. Let it be the second adhesive strength. The tenth adhesive strength was measured by the same method, and the adhesive strength retention with respect to the initial adhesive strength was calculated. The measurement was performed in an atmosphere at a temperature of 23 ° C. and a humidity of 60%.

(Specific resistance measurement)
A sample is cut into a square of 20 mm × 200 mm, a stainless steel plate is bonded to both sides of the test piece, and the impedance when a current of 1 kHz and 10 Vp-p is passed between the stainless steel plates is measured. The specific resistance was calculated from the obtained impedance (I) and the area (S) and thickness (d) of the test piece according to the following formula.
Specific resistance (Ω · cm) = I (Ω) ÷ d (cm) × S (cm ² )

(Cohesion measurement)
The top film of the gel sample cut into 20 mm square is peeled off and attached to 50 mm square synthetic paper (product name: Peach Coat, manufactured by Nisshinbo Industries, Inc.) (A surface). The protective film on the other side of the gel is not peeled off, and synthetic paper of the same size is stacked (side B) and pressed for 2.5 seconds at a pressure of 3 kg / cm ² . After pressing, the B-side synthetic paper was removed, and the maximum protrusion length of the gel that protruded around the protective film was measured.

(Molecular weight measurement)
About 20 mg of the sample was weighed into a centrifuge tube, dissolved by adding 10 mL of HPLC distilled water, and the solution was measured as it was without filtering. As a standard substance, Shodex pullulan was used.
For the measurement, HPLC LC-6A manufactured by Shimadzu Corporation was used, and OHpad SB-806M HQ × 2 was used for the column. (Column temperature: 40 ° C., solvent: 0.2 M sodium nitrate, flow rate: 0.7 mL / min)

Example 1
1) 18 g of acrylamide as a polymerizable monomer, 0.027 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 55 g of glycerin as a polyhydric alcohol, and 20.4 g of water as a solvent are mixed and dissolved. The mixture was stirred to obtain an adhesive hydrogel composition. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.

  Next, 1.0 g of a copolymer of acrylic acid and acrylamide methylpropane sulfonic acid having a copolymerization ratio of 7: 3 (trade name Aronbis AH-305, weight average molecular weight 4.5 million, manufactured by Nippon Pure Chemical Co., Ltd.) and 5 g of glycerin are stirred. And the polymer was dispersed. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.

2) Next, the composition was poured into a polycarbonate mold (130 mm × 130 mm, thickness 1.0 mm) on a 100 μm-thick biaxially stretched polyester film subjected to silicon treatment placed on glass, and further the mold A 38 μm biaxially stretched polyester film on which silicon treatment was applied was placed so as not to contain air bubbles, and quartz glass was placed thereon to control the thickness. This was taken out by irradiating with ultraviolet rays for 60 seconds with an ultraviolet lamp having a peak intensity of 50 mW / cm ² , and cut out from the mold to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Example 2
31.7 g of N, N′-dimethylacrylamide as a polymerizable monomer, 0.05 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 28.6 g of glycerol as a polyhydric alcohol, and water as a solvent. 33.7 g was mixed, dissolved and stirred to obtain an adhesive hydrogel composition. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.

  Next, 1.0 g of a copolymer of acrylic acid and acrylamidomethylpropanesulfonic acid (trade name Aronbis AH-305, manufactured by Nippon Pure Chemical Co., Ltd.) and 5 g of glycerin were stirred to disperse the polymer. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.

The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Example 3
14 g of N, N′-dimethylacrylamide as a polymerizable monomer, 0.02 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 42.7 g of glycerol as a polyhydric alcohol, and 23. water as a solvent. 3 g was mixed and dissolved and stirred to obtain an adhesive hydrogel composition. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.

Next, 10 g of a copolymer of acrylic acid and acrylamidomethylpropane sulfonic acid (trade name Aronbis AH-305, manufactured by Nippon Pure Chemical Co., Ltd.) and 10 g of glycerin were stirred to disperse the polymer. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.
The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Example 4
20 g of N, N′-dimethylacrylamide as a polymerizable monomer, 0.03 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 51 g of glycerol as a polyhydric alcohol, 2 g of sodium chloride as an electrolyte, and as a solvent 20 g of water was mixed, dissolved and stirred to obtain an adhesive hydrogel composition. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.

Next, 1.5 g of a copolymer of acrylic acid and acrylamidomethylpropane sulfonic acid (trade name Aronbis AH-305, manufactured by Nippon Pure Chemical Co., Ltd.) and 5 g of glycerin were stirred to disperse the polymer. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.
The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Example 5
23 g of acrylic acid as a polymerizable monomer, 0.03 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 51 g of glycerin as a polyhydric alcohol, and 20 g of water as a solvent are mixed, dissolved and stirred to adhere A hydrogel composition was obtained. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.

Next, 1.0 g of a copolymer of acrylic acid and acrylamidomethylpropanesulfonic acid (trade name Aronbis AH-305, manufactured by Nippon Pure Chemical Co., Ltd.) and 5 g of glycerin were stirred to disperse the polymer. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.
The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Comparative Example 1
20 g of acrylamide as a polymerizable monomer, 0.027 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 59.9 g of glycerin as a polyhydric alcohol, and 20 g of water as a solvent are mixed and dissolved and stirred. Thus, an adhesive hydrogel composition was obtained. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further stirred for 2 hours to dissolve.

The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Comparative Example 2
Mix 20g of acrylamide as a polymerizable monomer, 0.06g of N, N'-methylenebisacrylamide as a crosslinkable monomer, 59.9g of glycerin as a polyhydric alcohol, and 20g of water as a solvent, and stir. Thus, an adhesive hydrogel composition was obtained. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further stirred for 2 hours to dissolve.

The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Comparative Example 3
15 g of N, N′-dimethylacrylamide as a polymerizable monomer, 0.027 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, and 50 g of water as a solvent are mixed, dissolved and stirred to be sticky. A hydrogel composition was obtained. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) 0.13 g was added and further dissolved by stirring.
Next, 25 g of a copolymer of acrylic acid and acrylamidomethylpropanesulfonic acid (trade name Aronbis AH-305, manufactured by Nippon Pure Chemical Co., Ltd.) and 10 g of glycerin were stirred to disperse the polymer. The dispersion was added little by little to the above blended solution and further stirred for 2 hours.

The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

Comparative Example 4
20 g of acrylamide as a polymerizable monomer, 0.03 g of N, N′-methylenebisacrylamide as a crosslinkable monomer, 59 g of glycerin as a polyhydric alcohol, 2 g of sodium chloride as an electrolyte, and 18 g of water as a solvent Then, the mixture was dissolved and stirred to obtain an adhesive hydrogel composition. Next, 0.7 g of a copolymer of acrylic acid and methacrylic acid (Jurimer AC-20H manufactured by Nippon Pure Chemical Co., Ltd.) was mixed and further stirred. Next, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for the blended solution. Product name Irgacure 2959) (0.13 g) was added and further dissolved by stirring for 2 hours.

The blended solution was polymerized in the same manner as described in Example 1-2) to obtain a sample.
The resulting sample was measured for 180 ° skin repetitive adhesive strength and specific resistance, confirmed cohesiveness, and the results are shown in Table 1.

  From the above results, the adhesive hydrogels obtained in Examples 1 to 5 did not decrease in adhesive strength even after the 10th test in the 180 ° skin repeated adhesive strength test (maintenance rate of 84% or more), and further aggregated. In the property test, it had excellent cohesiveness.

  On the other hand, as in Comparative Example 1, a hydrogel containing no polymer in a polymer matrix composed of a copolymer of a polymerizable monomer and a crosslinkable monomer is However, although the adhesive strength did not decrease, the cohesiveness was inferior in the cohesiveness test.

Further, the product obtained in Comparative Example 2 is not suitable for use because of its low initial skin adhesive strength.
Furthermore, as in Comparative Example 4, a hydrogel containing a water-soluble polymer in a polymer matrix composed of a copolymer of a polymerizable monomer and a crosslinkable monomer has excellent cohesiveness in a cohesion test. However, in the 180 ° repeated skin adhesive test, the adhesive strength was remarkably reduced at the 10th time.

  From these results, the polymer matrix comprising a copolymer of a polymerizable monomer and a crosslinkable monomer contains a polymer containing N-alkyl sulfonic acid acrylamide as a structural unit, thereby allowing repeated adhesion to the skin. A tacky hydrogel that expresses strength and has no workability or gel adhesion to the clothing being applied was obtained.

Claims (7)

An adhesive hydrogel comprising a polymer matrix comprising a copolymer of a polymerizable monomer and a crosslinkable monomer, water, a polyhydric alcohol, and a polymer containing N-alkylsulfonic acid acrylamide as a structural unit When the polymer containing N-alkylsulfonic acid acrylamide in the structural unit is 100 parts by weight of components other than water in the hydrogel, 0.1 to 45 parts by weight are included,
The polymerizable monomer is (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N. -Diethyl (meth) acrylamide, acryloylmorpholine, tertiary butylacrylamide sulfonic acid and / or its salt, N, N-dimethylaminoethylacrylamide hydrochloride, N, N-dimethylaminopropylacrylamide hydrochloride, (meth) acrylic acid , Maleic acid, itaconic acid, sulfopropyl methacrylate and / or its salt, methacryloyloxyethyltrimethylammonium chloride, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, vinyl pyrrolidone, Sulfonyl acetamide, vinyl formamide is selected from allyl alcohol,
The crosslinkable monomer is N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate , poly Selected from ripropylene glycol di (meth) acrylate, polyglycerin di (meth) acrylate, trimethylol propane triacrylate, pentaerythritol triacrylate,
The polyhydric alcohol is ethylene glycol, propylene glycol, butanediol, glycerol, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, Po Li glycerin, adhesive hydrogel, characterized in that polyoxyethylene-glycerol. The adhesive hydrogel according to claim 1, wherein the polymer containing N-alkylsulfonic acid acrylamide in the structural unit is a copolymer of acrylic acid and N-alkylsulfonic acid acrylamide. The adhesive hydrogel according to claim 1 or 2, further comprising an electrolyte and 0.1 to 10 parts by weight of the electrolyte when the component other than water in the adhesive hydrogel is 100 parts by weight. It is a composition used for manufacture of the adhesive hydrogel as described in any one of Claims 1-3, Comprising: A polymerizable monomer, a crosslinkable monomer, water, a polyhydric alcohol, And a polymer containing N-alkyl sulfonic acid acrylamide in a structural unit. When the total composition excluding water is 100 parts by weight, the combined ratio of the polymerizable monomer and the crosslinkable monomer is 10 to 70 parts by weight, and the ratio of the polyhydric alcohol is 20 to 80 parts by weight. The proportion of the polymer containing N-alkylsulfonic acid acrylamide in the unit is 0.1 to 45 parts by weight, and the proportion of the crosslinkable monomer is 0.01 to 100 parts by weight of the polymerizable monomer. The composition according to claim 4, which is 0.5 parts by weight. A gel sheet comprising the adhesive hydrogel according to any one of claims 1 to 3. An electrode comprising a gel layer made of the adhesive hydrogel according to claim 1 and a conductive layer.