JPH0698184B2 - Resin used for medical adhesive and medical adhesive sheet or tape using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an acrylic resin used for an antibacterial medical pressure-sensitive adhesive, and a medical pressure-sensitive adhesive sheet or tape using the pressure-sensitive adhesive containing the resin.

(Prior art) As a pressure-sensitive adhesive for medical adhesive sheets or tapes such as patches and adhesive plasters containing a drug in an adhesive, a drug that has relatively good adhesiveness to the skin and excellent aging resistance Conventionally, acrylic adhesives have been most frequently used because they have excellent properties such as not separating or deteriorating and not irritating the skin. For example, Japanese Patent Publication No. 52-31
Japanese Patent No. 405 discloses a patch in which a layer of a pressure-sensitive adhesive containing a steroid hormone drug is provided on a water vapor impermeable film, and the pressure-sensitive adhesive is composed of an acrylic acid alkyl ester and acrylic acid. It is a copolymer. JP 57-
Japanese Patent No. 77617 discloses a patch containing nitroglycerin as a drug for treating angina, and the adhesive is a copolymer of methacrylic acid dodecyl ester, (meth) acrylic acid and vinyl acetate. In addition,
Japanese Patent Laid-Open No. 56-45412 discloses a drug-containing patch using an adhesive having high drug solubility. The pressure-sensitive adhesive is a copolymer of (meth) acrylic acid ester having an ether bond in the molecule, acrylic acid and (meth) acrylic acid alkyl ester.

As described above, the medical sheet or tape using the acrylic pressure-sensitive adhesive is suitably used for various purposes. However, the above-mentioned conventional acrylic adhesives are inherently poor in hydrophilicity. In other words, since the adhesive has poor water absorption capacity and poor air permeability, sticking a sheet or tape using such an adhesive to the skin for a long time causes stuffiness. As a result, the skin is easily sensitized to slight irritation caused by a drug and causes a rash. Bacteria, fungi and other miscellaneous bacteria abnormally propagate on the part where the stuffiness has occurred, and rashes due to secondary sensitization are also likely to occur. To suppress the rash caused by stuffiness, for example, Japanese Patent Publication No. 39-4728.
The publication discloses a medical pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive having an acrylic acid alkyl ester, acrylic acid or the like as a copolymerization component is provided on a porous fibrous substrate in a layered form having open cells. Since such an adhesive sheet is highly breathable, it does not stuff. However, the base material and adhesive layer are water,
Since liquids such as blood also pass through, the affected area such as a wound cannot be sufficiently protected. Japanese Examined Patent Publication No. 55-14108 discloses that on a film having high water vapor permeability (for example, a polyurethane film), polyvinyl ethyl ether having a hydrophilic group in the molecule or an acrylate copolymer having a hydrophilic group in the molecule is used. There is disclosed a medical pressure-sensitive adhesive sheet provided with the pressure-sensitive adhesive layer. Such a pressure-sensitive adhesive sheet has relatively good air permeability, and since the base material does not easily permeate a liquid such as water, it has a relatively good wound protection state. However, since the adhesive itself does not have bactericidal properties, it is not possible to prevent infection of wounds and secondary rash caused by microorganisms propagated in the adhesive layer.

Sheets or tapes using such adhesives,
There are also the following drawbacks due to the inherently poor hydrophilicity or insolubility of water of acrylic adhesives: Wet (or wet) sheet or tape
It is difficult to attach to the surface to be attached. For example, it has poor adhesion to the sweating skin surface. If the amount of sweat is high even after application, remove it.

It is not possible to wash off the adhesive that has extruded from the periphery of the applied sheet or tape to the outside, or the adhesive that remains on the skin surface after peeling the sheet or tape with water.

For example, water-soluble drugs in the form of sodium salts, potassium salts, ammonium salts, hydrochlorides, etc. are usually soluble only in water or alcohol. Therefore, it is difficult to dissolve such a drug in an adhesive, and thus it is difficult to prepare an adhesive sheet or tape containing the drug.

In addition to the drawbacks due to its poor hydrophilicity, acrylic adhesives have a relatively high adhesive force, which causes a large mechanical irritation to the skin when the sheet or tape attached to the skin is peeled off. There is also the drawback of causing pain.

(Problems to be Solved by the Invention) The present invention is intended to solve the above-mentioned conventional drawbacks, and an object thereof is to provide a medical adhesive having antibacterial properties (bactericidal or bacteriostatic). It is to provide an acrylic resin that can form an agent. Another object of the present invention is to provide a medical pressure-sensitive adhesive sheet or tape having a pressure-sensitive adhesive layer containing the above resin and free from secondary sensitization rash due to microbial infection or microbial propagation. Another object of the present invention is to provide an acrylic resin capable of forming a hydrophilic medical adhesive. Still another object of the present invention is to
An adhesive layer using the above hydrophilic resin is provided on a substrate to provide a medical adhesive sheet or tape having the following excellent properties: Adhesion to wet (wet) skin surface A sheet or tape that can be used and does not easily peel off even if it sweats during application.

It can be easily peeled off without causing pain by swelling or dissolving it with water, and even if the adhesive sticks out to the surrounding area during sticking or remains on the skin surface after peeling, it can be easily washed off with water. Sheet or tape.

A water-soluble drug that could not be dissolved and contained in an acrylic pressure-sensitive adhesive, for example, a drug having a salt form such as sodium salt, potassium salt, ammonium salt, or hydrochloride, can be dissolved and contained in a high concentration. Sheet or tape with adhesive.

A sheet or tape in which the pressure-sensitive adhesive has a water-absorbing ability and / or water vapor permeability, and is unlikely to cause stuffiness during application, and thus is unlikely to cause rash due to this stuffiness.

Still another object of the present invention is, in addition to the above excellent properties,
It is an object of the present invention to provide a pressure-sensitive adhesive resin having the inherent advantages of an acrylic pressure-sensitive adhesive and a medical pressure-sensitive adhesive sheet or tape provided with a pressure-sensitive adhesive layer using the resin.

(Means for Solving Problems) The resin used for the medical adhesive of the present invention is a resin containing a copolymer containing a first copolymerization component and a second copolymerization component, ) The first copolymerization component is (a) a (meth) acrylamide derivative having a chemical structure in which a group having a quaternary ammonium group is bonded to a (meth) acrylamide group by an amide bond, and / or (b) a quaternary A (meth) acrylic acid ester derivative having a chemical structure in which a group having an ammonium group is bonded to a (meth) acryloxy group by an ester bond; and (2) a second copolymerization component is a glycol mono (meth) acryl It is an acid ester, which achieves the above object. Furthermore, the medical adhesive sheet or tape of the present invention is a medical adhesive sheet or tape in which a layer of an adhesive is provided on at least one side of a substrate, the adhesive comprising a first copolymerization component and a second copolymerization component. A chemistry in which a copolymer resin containing a polymerization component is a main component, and (1) the first copolymerization component has (a) a group having a quaternary ammonium group bound to a (meth) acrylamide group through an amide bond. A (meth) acrylamide derivative having a structure and / or (b) a (meth) acrylic acid ester derivative having a chemical structure in which a group having a quaternary ammonium group is bound to a (meth) acryloxy group through an ester bond; (2) The second copolymerization component is a mono (meth) acrylic acid ester of glycols, which achieves the above object.

The resin used in the medical adhesive of the present invention is a (meth) acrylamide derivative (I) having the following structural formula and /
Or a copolymer containing the (meth) acrylic acid ester derivative (II) as the first copolymerization component: (Wherein R ₁ is H or CH ₃ ; R ₂ is a saturated hydrocarbon group having 1 to 6 carbon atoms; R ₃ , R ₄ and R ₅ are alkyl groups having 1 to 4 carbon atoms; and X is Cl, Br. Is a halogen atom such as) (Here, R ₆ is H or CH ₃ ; R ₇ is a saturated hydrocarbon group having 1 to 6 carbon atoms or 1 to 6 carbon atoms having a hydroxyl group.
Saturated hydrocarbon group; R ₈ , R ₉ and R ₁₀ are alkyl groups having 1 to 4 carbon atoms; and X is a halogen atom such as Cl and Br).

Among the compounds represented by the above structural formulas, the (meth) acrylamide derivative (I) includes 3 (acrylamido) propyltrimethylammonium chloride, 3 (methacrylamido) propyltrimethylammonium chloride,
(Acrylamido) isopentyl trimethyl ammonium chloride. As the (meth) acrylic acid ester derivative (II), 2 (methacryloxy) ethyltrimethylammonium chloride, 3 (methacryloxy) 2-hydroxypropyltrimethylammonium chloride, 2 (acryloxy) ethyldiethylmethylammonium chloride, 3 (acryloxy) ) Propyl trimethyl ammonium chloride and the like.

Mono (meth) acrylic acid esters of glycols as the second copolymerization component include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, There are 2 hydroxybutyl methacrylate, 3 hydroxybutyl acrylate, and 3 hydroxybutyl methacrylate. Furthermore, in addition to the above first and second copolymerization components, a third copolymerization component is contained if necessary. At least one of (meth) acrylic acid alkyl ester, (meth) alkyl acid alkoxy ester, and fatty acid vinyl ester is used as the third copolymerization component. Of these (meta)
Examples of alkyl acrylates include ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauroyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, methacrylic acid. 2-ethylhexyl, octyl methacrylate, lauroyl methacrylate and the like. Examples of the (meth) acrylic acid alkoxy ester include butoxyethyl acrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate and the like. Examples of the aliphatic vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl octanate.

The first copolymerization component is contained in the copolymer in an amount of 5 to 70% by weight, and the second copolymerization component is contained in an amount of 20% by weight or more of the remaining components of the first copolymerization component. When the third copolymerization component is contained, the third copolymerization component is contained in a proportion of 50% by weight or more of the remaining components of the first and second copolymerization components. Two or more kinds of each of the first, second and third copolymerization components may be mixed.

The degree of antibacterial property (bactericidal property or bacteriostatic property) of the pressure-sensitive adhesive prepared using the copolymer resin mainly increases in proportion to the proportion of the first copolymerization component in the copolymer. Therefore, if the first copolymerization component is too small, the antibacterial property cannot be substantially obtained. The first copolymerization component is preferably contained in a proportion of 30% by weight or more. The degree of antibacterial property also depends on the chemical structure of the first copolymerization component. Also with respect to the second copolymer component, the antibacterial property increases as the content rate increases. First
If the content of the copolymerization component is the same, the antibacterial activity of the copolymer having a higher content of the second copolymerization component is higher. Thus, the antibacterial property of the pressure-sensitive adhesive is also influenced by the amount of the second copolymerization component and the influence of the other copolymerization components on the first copolymerization component, the amount of the softening agent described later, and the like.

The degree of water solubility or hydrophilicity of the copolymer resin depends on the content ratio of the first copolymerization component and / or the second copolymerization component, and the larger the ratio of these components in the copolymer, the higher the water solubility. Increase. Although it depends on the chemical structures of the first and second copolymerization components, the first copolymerization component usually has 2-3 times as much hydrophilizing effect as the second copolymerization component. For example, when the content of the first copolymerization component increases by 10% by weight, the content of the second copolymerization component is 20% in terms of hydrophilicity.
It shows the same effect as the increase of ~ 30% by weight. When the copolymer resin does not require such strong antibacterial properties and requires strong water solubility or hydrophilicity, the content of the first copolymerization component is reduced and the content of the second copolymerization component is increased. It is also possible. For example, if the first copolymerization component is 10
When the amount of the second copolymerization component is 1% by weight, the property of the copolymer changes from hydrophilic (water swelling or water absorbing) to water-soluble when the amount of the second copolymerization component is About 50% by weight of the components other than the copolymerization component.

When the water solubility of the copolymer resin composed of only the first and second copolymer components is too large, it is possible to add the third copolymer component to reduce the degree of water solubility of the copolymer. When the amount of the first and second copolymerization components is decreased and the amount of the third copolymerization component is increased, the water solubility of the copolymer decreases and the copolymer becomes hydrophilic. The third copolymerization component can thus be added for the purpose of relaxing the properties of the copolymer consisting only of the first and second copolymerization components such as water solubility and antibacterial properties.

The degree of water solubility or hydrophilicity of the copolymer depends on the content ratio of the above-mentioned first, second and third copolymerization components, the type of each component and the micro-crosslinking agent (polyfunctional monomer) described below. It also depends on the amount used.

If the resulting copolymer is highly hydrophilic, it will dissolve in water. When the degree of hydrophilicity becomes low, it becomes insoluble in water but soluble in alcohols. Among the alcohols, as the hydrophilicity of the copolymer decreases, the type of solvent that can dissolve methyl alcohol, ethyl alcohol, and isopropyl alcohol changes in that order. Further, when the degree of hydrophilicity becomes lower, it becomes soluble in a mixed solvent of alcohols and ethyl acetate. The degree of hydrophilicity (water solubility) of a copolymer is determined by the ease with which water droplets spread on the surface of the copolymer, the water absorption capacity, the amount of water dissolved, and the turbidity when dissolved in water (the higher the transparency, the higher the transparency. It has a high hydrophilicity). On the contrary, the degree of hydrophilicity (water solubility) can be known from the solubility in a water-insoluble solvent such as ethyl acetate.

When a small amount of a polyfunctional monomer (micro-crosslinking agent) is added to the above-mentioned copolymerization components to carry out the copolymerization, the internal cohesive force of the resulting copolymer can be improved. As the polyfunctional monomer, a monomer having two or more (meth) acryloxy groups in the molecule is preferably used. Examples of such compounds include 1,4-butylene glycol di (meth) acrylic acid ester and 1,6-hexane glycol di (meth) acrylate.
Alkylene glycol di (meth) acrylates such as acrylic acid esters; polyethylene glycol di (meth)
Polyalkylene glycol di (meth) acrylates such as acrylic acid esters and polypropylene glycol di (meth) acrylic acid esters; polyhydric alcohol poly (s such as trimethylolpropane tri (meth) acrylic acid ester and tetramethylolmethane triacrylic acid ester) There is (meth) acrylate. When a polyfunctional monomer is contained, it is slightly crosslinked during copolymerization (fine crosslinking).
As a result, the internal cohesive force of the copolymer increases. Therefore, when a sheet or tape using the obtained resin-containing adhesive is applied, the adhesive may stick out to the surrounding area, or when the sheet or tape is peeled off, part of the adhesive may remain on the skin surface. Absent. When the amount of the polyfunctional monomer added during the polymerization is large, the degree of fine crosslinking of the copolymer also increases. The fine crosslinks give rise to a network structure, which reduces the water solubility of the copolymer. Therefore, it is possible to reduce the water solubility of the pressure-sensitive adhesive to an appropriate level by adjusting the degree of slight crosslinking. Even if the resin is slightly crosslinked, the copolymer resin does not precipitate from the solution and is stably maintained at a normal coating concentration (about 20% or more) for a long period of time.

The polyfunctional monomer is a component of all copolymerization components (all monomers) during polymerization.
It is added in a proportion of 0.001 to 0.1% by weight. The amount is determined in consideration of the desired degree of internal cohesive force, the type and amount of each copolymerization component, and the like. When the amount of the polyfunctional monomer is excessive, the solubility of the resulting copolymer in a solvent such as alcohol or water becomes poor. It is preferable to add the polyfunctional monomer at the initial stage of polymerization in order to effectively form fine crosslinks.

Other polymerizable monomers may be copolymerized within a range that does not impair the properties such as bactericidal property, which is a characteristic of the copolymer resin of the present invention. Such polymerizable monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylamide, dimethylaminopropylmethacrylamide, dimethylaminoethylacrylic acid ester, tetrahydrofurfurylacrylic acid ester, grinsidylmethacrylic acid ester, acrylamide, Methacrylamide, diethylaminoethylmethacrylamide, butoxymethylacrylamide, phenoxyethyl acrylate, 2-
Acrylamide 2-methyl propane sulfonic acid, methacryl sulfonic acid, phosphoric acid oxyethyl methacrylic acid ester, N-vinyl dipyrrolidone, diacetone acrylamide.

These other polymerizable monomers are copolymerized so that the content thereof is less than 50% by weight of the remaining components of the first copolymerization component and the second copolymerization component.

The above first copolymerization component and second copolymerization component, and optionally a third copolymerization component (both are monomers), a polyfunctional monomer and another polymerizable monomer are subjected to ordinary radical polymerization. A copolymer is obtained by subjecting to a polymerization reaction by a method, for example, a solution polymerization method. In the case of the solution polymerization method, water or an organic solvent is used as the solvent, and an alcohol solvent (methanol, ethanol, isopropanol, etc.) is preferably used as the organic solvent. As the solvent, a solvent capable of dissolving each of the used monomers and the resulting copolymer is used. When the obtained copolymer is soluble in an organic solvent, it is preferable to use an organic solvent.

To obtain the copolymer, for example, each of the above monomers and the solvent are charged into a reactor equipped with a reflux condenser to obtain a 50 to 90% by weight solution. The inside of this reactor is replaced with an inert gas such as nitrogen, and the catalyst is started while heating (60 ° C or less) and stirring. The catalyst needs to be soluble in the solvent system during polymerization. Therefore, when the solvent of the reaction system is an organic solvent, an azobis type catalyst is preferably used. The azobis catalyst is usually used by dissolving it in ethyl acetate, alcohol or a mixed solvent of ethyl acetate and alcohol. When the solvent of the reaction system is an aqueous solvent, a catalyst such as potassium persulfate is preferably used. Potassium persulfate is used as an aqueous solution. The amount of catalyst is usually in the range of 0.1 to 0.5 mol% based on the total number of monomers. The catalyst is usually dissolved in a solvent of about 1/5 or less of the volume of the reaction solution, and the catalyst is added to the reaction solution in 10 to 15 times within a time period shorter than the total reaction time by at least about 5 hours. The interval at which the catalyst is charged is determined by the half-life of the catalyst at the reaction temperature (eg 60 ° C). For example, in the first half of the polymerization reaction, it is preferable to add the catalyst at intervals of 1/3 to 1 times its half-life. The reaction temperature is usually 50-80 ° C. Preferably, for example, about 20 to 25 hours in the first half of the polymerization reaction are under relatively mild conditions of about 60 ° C, and about 70 ° C for the latter half of about 20 hours.
It is under temperature conditions around.

When the polymerization reaction starts, the viscosity of the reaction solution increases and the reaction temperature also increases. Since the polymerization rate is high for several hours after the initiation of polymerization, a runaway reaction or gelation occurs if left unattended. for that reason,
It is necessary to add a solvent to the reaction system to reduce the viscosity and control the reaction temperature. Especially, it is important to control the reaction by diluting the solvent. It is preferable that the viscosity of the solution is high in the range where gelation does not occur. Its apparent viscosity is
It is usually 10,000 to 20,000 cps. When the polymerization reaction is carried out in a reaction system in which a third copolymerization component is appropriately contained as a copolymerization component, the reactivity is higher than in a reaction system containing only the first and second copolymerization components, and Even when the viscosity rises, it can be easily lowered to smoothly advance the copolymerization component. The reaction time is set so that the polymerization rate of the obtained polymer is 97% or more, and is usually 40 hours or more.

The copolymer obtained in this manner is non-adhesive and is transparent to milky white in the dry state and is relatively fragile and hard, although it varies depending on the type and amount of the copolymerization component. No antibacterial property is exhibited in the dry state. However, when a suitable softening agent is added thereto, the copolymer softens and becomes tacky. The internal cohesive force also becomes appropriate and it has viscoelastic properties and exhibits antibacterial properties. Water can also be used as a softening agent. However, since a constant stickiness cannot be obtained due to evaporation of water, a water-soluble or hydrophilic liquid or solid having a high boiling point is usually used. Examples of the softening agent include glycerin, diglycerin, propylene glycol, trimethylene glycol, α-butylene glycol, 2.3-butylene glycol, β-butylene glycol, α-amylene glycol, 2.3-amylene glycol, 2,4-Amylene glycol, 1,4-Amylene glycol, 1,5-pentanediol, trimethylolethane, polyethylene glycol, polypropylene glycol, diethanolamine, triethanolamine, diisopropanolamine, polyoxyethylene / polyoxypropylene Glycols, polyoxyethylene / polyoxypropylene butyl ethers, polyoxypropylene butyl ethers, starch sugar, sucrose, sorbitol, urea, alkyl or allylalkyl trialkylammonium Cationic surfactants such as chlorides, polyoxyethylene alkyl ethers, fatty acid diethanolamides, nonionic surfactants such as sorbitan alkyl ethers or esters, amphoteric surfactants such as dimethylalkyl betaines, and liquid amino acids. Two or more kinds of softening agents may be mixed and used. Among the above, particularly diglycerin and glycerin are effective as a softening agent for the copolymer of any composition of the present invention. If the copolymer cannot be sufficiently plasticized by using a softening agent other than diglycerin and glycerin alone, it is recommended to use it in combination with another softening agent, particularly diglycerin and / or glycerin.

When the above softening agent is added to the copolymer resin of the present invention, the molecular motion of the copolymer molecules is activated and softened. In particular, it is considered that this softening agent specifically collects around the first and second copolymerization components and dissolves (plasticizes) this portion. The plasticized first and second copolymerization components exhibit high polarity and exhibit high affinity for the adhesive surface. In other words, high tackiness can be obtained by adding the softening agent. Since the softening agent exists around the first and second copolymerization components, the "blooming phenomenon" in which the softening agent separates and precipitates over time does not occur.

The amount of the softening agent depends on the composition of the copolymerization component, the type of the softening agent, the thickness of the adhesive layer, the desired degree of adhesiveness, etc.
Usually, 10 to 100 parts by weight (10 to 100 parts by weight per 100 parts by weight of the copolymer)
The range is 100 phr). If the amount is too small, not only does the tackiness not be exhibited, but also antibacterial properties cannot be obtained. Antibacterial properties are sufficient if a softening agent is added to the copolymer to soften it and function as an adhesive. When the amount of the softening agent is excessive, the adhesiveness of the obtained pressure-sensitive adhesive increases, but it becomes soft and fluid.

A larger amount of the softening agent is required as the content ratio of the first and second copolymerization components, especially the larger the content ratio of the first copolymerization component. This is because as the proportion of the first and second copolymerization components in the copolymer resin increases, the tackiness becomes poorer and the resin becomes more resin-like, and the proportion of the first and second copolymerization components decreases and the third copolymerization component decreases. This is because the higher the content ratio of the polymerization component, the more viscoelastic the property. When the amount of the first copolymerization component in the copolymer is increased by 10% by weight, the amount of the softening agent is increased at a rate of about 10 parts by weight per 100 parts by weight of the copolymer in order to achieve the same adhesiveness. is necessary.
When the amount of the second copolymerization component increases by 10 parts by weight, the same tackiness can be exhibited by increasing the amount of the softening agent at a rate of 2 to 5 parts by weight. When the content of the first copolymerization component and / or the second copolymerization component in the copolymer is high, the adhesive having low tackiness can be obtained by reducing the amount of the softening agent.
By increasing the amount of the softening agent, a pressure-sensitive adhesive having high tackiness can be obtained. On the other hand, when the content of the first copolymerization component and / or the second copolymerization component is low and the content of the third copolymerization component is high, the softening required for obtaining sufficient tackiness The amount of agent is small and the degree of stickiness is almost constant. Therefore, the softening agent cannot significantly change the degree of tackiness.

Since the above-mentioned softening agent itself has high water absorption and hygroscopicity, care must be taken so that the adhesive obtained by blending the softening agent does not absorb moisture during storage and its properties do not change.

The pressure-sensitive adhesive prepared using the copolymer resin thus obtained and the softening agent has antibacterial properties, and also has hydrophilicity (water solubility), water absorption, moisture permeability and conductivity. .
Regarding antibacterial properties, it has been known that low-molecular compounds having a quaternary ammonium salt have antibacterial properties.
Also in the copolymer resin of the present invention, the quaternary ammonium salt portion of the first copolymerization component is considered to have antibacterial properties. In the pressure-sensitive adhesive, the second copolymerization component of the copolymer, other copolymerization components, the added softening agent, etc. may be the above-mentioned 4
It is presumed that it acts to activate molecular chain movements such as bending, vibration, and rotation of the quaternary ammonium salt portion, and enhances the antibacterial action. It is considered that the second copolymerization component also has an ability to adsorb and immobilize bacteria and therefore effectively exhibits an antibacterial action. In addition, a polymer containing only the first copolymerization component lacks viscoelastic properties and cannot serve as an adhesive. The same applies to the polymer containing only the second component.
The above-mentioned copolymer resin has an arrangement in which the first and second copolymerization components, and optionally the third copolymerization component, etc., are arranged so as to make the best use of their respective properties, and have a molecular chain length capable of expressing appropriate viscoelasticity. It is considered that they are copolymerized so that It is considered that the addition of a softening agent softens the entire resin as described above and further enhances such properties.

The adhesive layer is formed on at least one side of the substrate to obtain a desired medical adhesive sheet or tape. Examples of the base material include polyurethane, polyurethane-polyamino acid cocondensate, polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, polyvinyl chloride, non-soft plastic polyvinyl chloride (internal copolymer Combined or blended), polypropylene, nylon, polyester, soluble polyvinyl alcohol, insolubilized polyvinyl alcohol, insolubilized polyvinyl acetal, regenerated cellulose, cellulose esters, cellulose ethers, silicone rubber. Foamed polyethylene, foamed polyurethane, foamed ethylene-vinyl acetate copolymer and the like are used after being formed into a film or sheet. In addition, papers, non-woven fabrics, woven fabrics, knitted fabrics and the like made of natural fibers or synthetic fibers can also be used, and a breathable substrate or a non-breathable substrate is appropriately selected according to the purpose. .
Further, it is possible to combine the above films, woven fabrics, etc. appropriately and perform heavy bonding (laminating) to use as a laminate.

When a sheet or tape intended for treatment with a drug is obtained, the drug is mixed in the adhesive. Drugs include anti-inflammatory agents, antiphlogistic analgesics, antihistamines, antiallergic agents, bactericidal / antibacterial agents, antifungal agents, antihypertensive agents, coronary vasodilators, sedatives, stimulants, anti-vehicle sickness agents, anesthetics, etc. There is. When the drug is in the form of a salt such as an alkali metal salt or a hydrochloride, the drug is softened in the state where it is adsorbed to the portion corresponding to the first and second copolymerization components of the molecular chain or in the vicinity thereof. It is considered to exist stably in a state of being partially dissolved in the agent. When the drug is insoluble or lipophilic in water, a copolymer resin containing a third copolymer component is preferably used. It is considered that such a drug is adsorbed or dissolved in the portion corresponding to the third copolymer component.

The method for forming the pressure-sensitive adhesive or the pressure-sensitive adhesive layer containing a drug on the substrate can be performed by a known method. For example, a direct coating method in which a solution containing an adhesive (copolymer resin and softening agent) is directly applied to the surface of a substrate and dried;
A direct transfer method or the like is used in which a flat endless belt having a peelable surface is coated and dried, and then a base material is pressure-bonded to this surface and peeled off to transfer an adhesive to the surface of the base material. In addition, an indirect transfer method in which a pressure-sensitive adhesive solution is once coated on release paper, dried, and then a substrate is pressure-bonded to the coated surface is also suitably used.

(Function) The pressure-sensitive adhesive obtained by using the copolymer resin of the present invention has excellent adhesiveness, does not cause skin irritation, and does not deteriorate the drug.
It has the characteristics of conventional acrylic adhesives, such as, and has excellent antibacterial properties. The medical sheet or tape provided with such an adhesive layer can be used in a wide range of applications. For example, it is applied directly or indirectly through gauze or the like to protect the wound. Due to the antibacterial action of the adhesive, infection due to bacterial invasion is prevented, and thus healing of wounds can be accelerated. Even if stuffiness occurs during application of the sheet or tape, microorganisms do not propagate in the area and rash due to secondary sensitization does not occur. It is also possible to attach such a sheet to the surgical site in advance and perform surgery from there. In this way, when used as a drape, it is possible to eliminate excessive pre-operative disinfection and prevent infection due to infiltration of various bacteria into the incision site during surgery.

The adhesive has even more excellent hydrophilicity. Since it can absorb water, it is possible to adhere the sheet or tape obtained using this adhesive to the wet (wet) skin surface. Even when sweating during application, the adhesive has a large water absorption capacity, so it is less likely that the sheet or tape will peel off due to absorption of water and the adhesive will fluidize, causing a so-called adhesive residue phenomenon. It is less likely that the adhesive will be softened or hardened due to the influence of humidity during storage. Due to its excellent water vapor permeability, even if a sheet or tape is attached to the skin for a long time, rash due to stuffiness is hardly observed. If the substrate itself is permeable to water vapor, no stuffiness will occur. When water is used to peel off the attached sheet or tape, the adhesive dissolves in the water or swells with water, so that the sheet or tape can be easily peeled off. Therefore, even if it is applied to a weak skin surface such as an infant, it does not cause pain or damage the skin surface when peeling. Also, when the sheet or tape is attached, for example, if the adhesive squeezes out due to the movement of the body or the adhesive remains on the skin after peeling, it can be easily removed by washing it with water. it can. Furthermore, not only the drugs conventionally used in adhesives, but also water-soluble drugs (for example, alkali metal salts, ammonium salts,
Drugs in the form of salts such as the hydrochloride) can also be dissolved in high concentrations. Therefore, a medical adhesive sheet or tape containing a water-soluble drug, which has been difficult to prepare conventionally, can be easily obtained.

Furthermore, since the adhesive has conductivity, it has a large antistatic effect. For example, when a conventional roll-shaped adhesive tape using a highly electrically insulating base material such as polyethylene or polypropylene is unwound, the tape may be charged with static electricity of several thousand to tens of thousands of volts. Therefore, it may adhere to another object or cause a spark discharge before being attached to the object. Sparking also creates a risk of ignition, for example in operating rooms using anesthetic ethers. On the other hand, when the sheet or tape of the present invention is used, the adhesive used there has no electrostatic property, so that there is no such danger.

Since the adhesiveness of the adhesive is higher than that of conventional acrylic adhesives, a sheet or tape having excellent adhesive strength can be obtained with a small amount. The degree of antibacterial property, hydrophilicity, conductivity, etc., including the tackiness of the pressure-sensitive adhesive, can be arbitrarily adjusted by setting the copolymer composition and adjusting the amount of the softening agent.

If a polyfunctional monomer is added during the preparation of the copolymer, a pressure-sensitive adhesive having a further excellent internal cohesive force can be obtained due to slight crosslinking. A sheet or tape using such an adhesive does not cause a so-called adhesive cracking phenomenon or adhesive residue phenomenon regardless of the film thickness of the adhesive.

(Examples) The present invention will be described with reference to Examples.

Example 1 Preparation of (A) Copolymer: 60 g of 3 (methacrylamido) propyltrimethylammonium chloride as (meth) acrylamide derivative (first copolymerization component), 50 g of 2-hydroxyethyl acrylate as second copolymerization component, Butyl acrylate 70 g as the third copolymer component, 1,6-hexane glycol dimethacrylate 0.01 as the polyfunctional monomer
8 g, and 80 g of methyl alcohol as a solvent were charged into a reaction vessel (1) equipped with a reflux cooling device, and heated to 60 ° C. with stirring under a N ₂ stream. As the polymerization catalyst, 0.5 g of azobisisobutyronitrile was used. The catalyst was dissolved in 100 ml of ethyl acetate, and 5 ml was added to the reaction system every 3 hours. After adding 4 times (12 hours passed), 10 ml each is added 4
Added every hour. 28 hours after the start of the reaction, the reaction temperature was 70 ° C.
Then, 10 ml of the catalyst solution was added every 3 hours. During the polymerization reaction, especially at the beginning of the polymerization (2 to 10 hours after the catalyst solution is charged),
If the viscosity of the reaction solution increases significantly, stirring may become difficult and gelation or runaway reaction may occur. Therefore, 20 to 30 ml of ethyl alcohol was added 11 times. After no increase in viscosity was observed, only heating and stirring were continued. In this way, the reaction solution has an apparent viscosity.
It was kept below 10,000-20,000 cps (Senachi Poise).
After the addition of the catalyst solution was completed, the reaction was terminated by continuing stirring at the same temperature (70 ° C.) for 8 hours. The obtained reaction liquid was a viscous transparent solution, and the concentration of the copolymer contained was 31.8% and the viscosity was
It was 28,000 cps at 21 ° C. When the polymerization rate was calculated from the residual monomer rate, it was 97.8% for the copolymer as a whole.
The copolymerization component was 97.7%, the second copolymerization component was 99.1%, and the third copolymerization component was 97.0%.

(B) Preparation of adhesive sheet: When the copolymer solution obtained in (A) was cast and dried, a hard coating having no tackiness was obtained. Thus, the resinous polymer obtained from the copolymer solution prepared in (A) is toluene, ethyl acetate,
It is not a solvent for non-aqueous solvents such as methyl ethyl ketone. On the other hand, it can be dissolved in water such as water, methyl alcohol, ethyl alcohol, and isopropyl alcohol, and alcohol solvents. A small amount of the above-mentioned copolymer solvent was sampled, and a small amount of water was added to it to dry it, whereby it was plasticized to obtain an adhesive having viscoelastic properties. Similar results were obtained when glycerin or diglycerin was used instead of water. Moderate tackiness was obtained when 40 to 90 parts by weight of glycerin or diglycerin was added to 100 g of the polymer component. Diglycerin was added to 100 g of the polymer component of the copolymer solution obtained in the item (A).
55 parts by weight was added to obtain an adhesive solution. This was applied and dried on the surface of the substrate by a transfer coating method so that the thickness after drying was 50 μm. As the substrate, a stretched crosslinked polyvinyl alcohol film having a thickness of 50 μm was used.

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in (B). The following methods were used to measure (1) 180 ° folding back adhesion and (2) ball tack value. (3) Tests were also conducted for cohesive failure and wet surface adhesion. The 180 ° fold-back adhesive strength was 720 g / 15 mm width, ball tack value was 28, cohesive failure was not observed, and adhesion to wet surface was 300 seconds or more.

(1) 180 ° folding back adhesive force: The adhesive sheet obtained in the item (B) was cut into a width of 15 mm to obtain an adhesive tape. Affix this adhesive tape to a stainless steel plate surface sanded with sandpaper (# 280), and use a 2 kg rubber roller to 300 mm /
It crimped back and forth once at a speed of a minute. After crimping, room temperature (20-22
After leaving it for 30 minutes or longer at 180 ° C., one end was folded back 180 ° to perform constant speed forced peeling at 300 mm / min, and the adhesive strength at this time was measured (JIS-Z-1522).

(2) Ball tack value: The adhesive sheet obtained in the item (B) was cut into a width of 30 mm or more to obtain an adhesive tape. At room temperature, the adhesive surface of this adhesive tape was fixed to a 30 ° inclined surface with the adhesive surface facing outward. The non-adhesive thin film covered the middle part of the adhesive surface from the top to the bottom. A ball bearing ball that had been wiped cleanly was allowed to roll naturally from a point 100 mm above the boundary line to the slope. From the boundary line between adhesive and non-adhesive surfaces
The diameter of the largest sphere that stops naturally within 100 mm (1/3
Indicated by the number of the molecule in units of 2 inches; for example, 1
If it is 7/32 inch, 17) was used as the ball tack value (Pharmaceutical Manufacturing Guidelines (1984), page 51).

(3) Cohesive failure: 15% of the pressure-sensitive adhesive sheet obtained in (B)
The adhesive tape was obtained by cutting into a width of mm. Stick this adhesive tape on the steel plate surface sanded with sandpaper (# 280),
Using a 2 kg rubber-covered roller, one round trip was performed at a speed of 300 mm / min to perform pressure bonding. After crimping, leave at 40 ℃ for 30 minutes or more,
Immediately, one end thereof was folded back by 180 ° and 100 mm / min constant speed forced peeling was performed. At this time, it was investigated whether part of the adhesive remained on the surface of the steel plate. If the adhesive remains, it is judged that cohesive failure has occurred.

(4) Adhesion to wet surface: 50 μm thick cellophane and 50 thickness
A laminate film of polyethylene having a thickness of μm was used as an adherend. The cellophane surface side of this laminate film was used as the adhered surface, and the adhered surface was lightly rubbed several times with gauze containing water. The adhesive tape (adhesive sheet cut into a width of 15 mm) obtained in the item (B) was attached to the wet surface, and a 2 kg rubber-covered roller was reciprocated once to perform pressure bonding. However, one end of the tape is open without being bonded. The adherend was hung vertically with the adhesive end down and the open end up. Then, the open end of the adhesive tape was folded back 180 ° and a load of 100 g was applied. With this load, the time (second) required for 100 mm of the tape adhered to the adherend surface to peel was measured.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: The pressure-sensitive adhesive sheet obtained in the item (B) was cut into 5 cm square pieces to obtain 10 test pieces. Approximately 1.0 × 1 of E. coli was applied to the surface of the adhesive on each of the two test pieces.
1 ml of the bacterial cell liquid containing 0 ⁶ cells / ml was sprayed almost uniformly. This is left at 35 ° C, and one hour later, one test piece is collected.
Wash out in 100 ml of SCDLP broth, and count the number of viable bacteria in it by SC
The reduction rate (bacterial killing rate) of the bacterial cells was calculated from the difference between the number of bacterial cells before the standing and the measurement by the pour plate culture method using DLP agar medium. After 2 hours, another test piece was collected, and the cell reduction rate was measured by the same method. The respective values are shown in Table 1. Pseudomonas aeruginosa, Staphylococcus aureus, Trichophyton, and Aspergillus niger were tested in the same manner instead of E. coli. For fungi (Trichophyton and Aspergillus niger), the test pieces were left at 25 ° C and GPLP was used instead of SCDLP agar.
Agar medium was used. The bacterial cells used are as follows.

Escherichia coli: Escherichia coli IID 0-55 Pseudomonas aeruginosa IID p-1 Staphylococcus aureus FDA 209P Trichophyton mentagrophytes IFO 6202 Aspergillus niger IFO 4414 Each result is shown in Table 1. Show.

Comparative Example 1 An adhesive having the following composition having water-soluble properties was prepared, and the same test as in Example 1 was conducted.

Polyvinylpyrrolidone (kollidon-K-90; trade name) 1
00 parts by weight Diglycerin 60 parts by weight 180 ° folding method Adhesive force 390 g / 15 mm, ball tack value 1
4 and cohesive failure was observed. Adhesion to wet surface is 300
A value of more than a second was obtained. The results of the antibacterial test are shown in Table 1.

(E) Structure of various pressure-sensitive adhesive sheets or tapes: The pressure-sensitive adhesive obtained using the copolymer obtained in this example has excellent bactericidal properties as shown in the item (D). In addition to pressure-sensitive adhesive sheets or tapes whose main purpose is sterilization, pressure-sensitive adhesive sheets or tapes for various purposes can be prepared by taking advantage of their excellent adhesiveness and hydrophilicity. This Example and Examples 2 to be described later
Table 7 (pages 61 to 63) shows various constitutions of the sheet or tape using the pressure-sensitive adhesive obtained in 6 and its preferable use.
A sheet or tape for administering the drug by transdermal (transmucosal) absorption after containing and dissolving various drugs in the adhesive can also be prepared. The constitution and indications of such a sheet or tape are shown in Table 8 (page 64) together with the examples using the adhesives of Examples 2 to 6 described later.

Example 2 (A) Preparation of Copolymer: 40 g of 3 (methacrylamido) propyltrimethylammonium chloride as (meth) acrylamide derivative (first copolymerization component), 80 g of 2-hydroxypropyl acrylate as second copolymerization component, 3 Copolymer in the same manner as in Example 1 (A), using 60 g of ethylhexyl acrylate as a copolymerization component, 0.015 g of 1.6-hexane glycol dimethacrylate as a polyfunctional monomer, and 80 g of methyl alcohol as a solvent. Was prepared. However, the amount of catalyst used was 0.46 g. The obtained reaction liquid was a transparent viscous liquid, and the concentration of the copolymer contained was 29.2.
%, The viscosity at 21 ° C was about 26,000 cps. When the polymerization rate was calculated from the residual monomer rate, it was 98.6% for the entire copolymer, 98.0% for the first copolymerization component, 99.0% for the second copolymerization component, and 98.6% for the third copolymerization component. there were.

(B) Preparation of pressure-sensitive adhesive sheet: The polymer obtained from the copolymer solution obtained in the section (A) of the present Example is a hard and non-tacky resinous substance, and the solubility in a solvent was obtained in Example 1. Similar to the polymer obtained. Moderate tackiness was obtained when 35 to 75 parts by weight of diglycerin was added to 100 g of the polymer component. An adhesive solution was obtained by adding 55 parts by weight of diglycerin to 100 g of the polymer component of the copolymer solution obtained in the section of this Example (A). Using this pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet was prepared according to the method of Example I (B).

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive strength by the folding method was 670 g / 15 mm, and the ball tack value was 24, and no cohesive failure was observed. Adhesion to wet surface
It was over 300 seconds.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: Performed according to the item (D) of Example 1. Separately, an adhesive was prepared under the same conditions as in Comparative Example 1, and antibacterial properties were evaluated by the same method (Comparative Example 1-
). The respective results are shown in Table 2.

(E) Structure of various adhesive sheets or tapes: Tables 7 and 8 show examples.

Example 3 Preparation of (A) Copolymer: 110 g of 3 (acrylamide) isopentyltrimethylammonium chloride as the (meth) acrylamide derivative (first copolymerization component), 25 g of 2-hydroxyethyl methacrylate as the second copolymerization component, 45g vinyl acetate as a copolymerization component, polyethylene glycol dimethacrylate as a polyfunctional monomer (molecular weight approx.
338) A copolymer was prepared according to the procedure of Example 1 (A) using 0.03 g and 80 g of methyl alcohol as a solvent. However, the amount of catalyst used was 0.55 g. The obtained reaction liquid was a nearly transparent viscous liquid. The copolymer concentration was 33.3%, and the viscosity of the contained copolymer at 21 ° C was about 31,000 cps.
Met. The polymerization rate is 97.8% for the whole copolymer,
The copolymerization component was 96.7%, the second copolymerization component was 100%, and the third copolymerization component was 99.3%.

(B) Preparation of pressure-sensitive adhesive sheet: The polymer obtained from the copolymer solution obtained in the item (A) of this example was a hard resinous material. This resin-like polymer dissolves in water and alcoholic solvents, but does not dissolve in methyl ethyl ketone and ethyl acetate. Diglycerin based on 100 g of polymer component
Moderate tackiness was obtained when 50-100 parts by weight was added. An adhesive solution was obtained by adding 70 parts by weight of diglycerin to 100 g of the polymer component of the copolymer solution obtained in the section of this Example (A). Example 1 (B) using this adhesive solution
The pressure-sensitive adhesive sheet was prepared according to the method described in the item 1.

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive force by folding method was 800 g / 15 mm and the ball tack value was 31, and no cohesive failure was observed. Adhesion to wet surface is 300
It was more than a second.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: Performed according to the item (D) of Example 1. Separately, an adhesive was prepared under the same conditions as in Comparative Example 1, and antibacterial properties were evaluated by the same method (Comparative Example 1-
). The respective results are shown in Table 3.

(E) Structure of various adhesive sheets or tapes: Tables 7 and 8 show examples.

Example 4 Preparation of (A) Copolymer: 50 g of 2 (methacryloxy) ethyltrimethylammonium chloride as a (meth) acrylic acid derivative (first copolymerization component) and 40 g of 2-hydroxypropyl acrylate as a second copolymerization component. Example 1 (A) using 30 g of 2-hydroxypropyl methacrylate, 60 g of butyl acrylate as the third copolymerization component, 0.01 g of trimethylolpropane trimethacrylate as the polyfunctional monomer, and 80 g of methyl alcohol as the solvent. A copolymer was prepared according to. The obtained reaction liquid was a slightly milky viscous solution, and the concentration of the contained copolymer was 30.4.
%, The viscosity at 21 ° C was 30,000 cps. The polymerization rate is 98.4% for the entire copolymer, 97.6% for the first copolymerization component, and 2nd for the second copolymerization component.
99.2% of the total amount of copolymerization components, 98.1% of the third copolymerization component
Met.

(B) Preparation of adhesive sheet: The polymer obtained from the copolymer solution obtained in the item (A) of this example was a non-adhesive resinous material. This resin-like polymer dissolves in water and alcoholic solvents, but does not dissolve in methyl ethyl ketone and ethyl acetate. Moderate tackiness was obtained when 35-80 parts by weight of diglycerin was added to 100 g of the polymer component. 50 parts by weight of diglycerin was added to 100 g of the polymer component of the copolymer solution obtained in the Example (A) to obtain an adhesive solution. Example 1 using this adhesive solution
An adhesive sheet was prepared according to the method described in (B).

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive force by folding method was 690 g / 15 mm and the ball tack value was 25, and no cohesive failure was observed. The wet adhesion was 300 seconds or more.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: Performed according to the item (D) of Example 1. Separately, a pressure-sensitive adhesive was prepared under the same conditions as in Comparative Example 1, and antibacterial properties were evaluated by the same method (Comparative Example 1-
). The respective results are shown in Table 4.

(E) Structure of various adhesive sheets or tapes: Tables 7 and 8 show examples.

Example 5 (A) Preparation of Copolymer: 18 g of 3 (acrylamido) propyltrimethylammonium chloride as (meth) acrylamide derivative (first copolymerization component), 42 g of 2 hydroxypropyl acrylate as second copolymerization component, 3rd Butyl acrylate 80g and vinyl acetate 40 as copolymerization components
A copolymer was prepared in the same manner as in Example 1 (A) using g, 0.06 g of 1.6-hexane glycol dimethacrylate as a polyfunctional monomer, and 80 g of ethyl alcohol as a solvent. However, the amount of the catalyst used was 0.6 g. The reaction solution obtained was transparent, and the concentration of the copolymer contained was 27.7.
%, The viscosity at 21 ° C was about 27,000 cps. The polymerization rate was 98.4% for the entire copolymer, 99.4% for the first copolymerization component, 99.6% for the second copolymerization component, 97.5% for butyl acrylate and 98.5% for vinyl acetate among the third copolymerization components. there were.

(B) Preparation of adhesive sheet: The copolymer obtained in the item (A) of this Example was a relatively tough resinous material having a slight adhesive property. This resin-like polymer is soluble in water, alcohols, acetone, etc., but not in toluene, acetates, etc. Moderate tackiness was obtained when 20-60 parts by weight of diglycerin was added to 100 g of the polymer component. An adhesive solution was obtained by adding 35 parts by weight of diglycerin to 100 g of the polymer component of the copolymer solution obtained in the section of this Example (A). Using this pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet was prepared according to the method of Example 1 (B).

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive strength by the folding method was 590 g / 15 mm, and the ball tack value was 18, and no cohesive failure was observed. Adhesion to wet surface is 300
It was more than a second.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: Performed according to the item (D) of Example 1. Separately, an adhesive was prepared under the same conditions as in Comparative Example 1, and antibacterial properties were evaluated by the same method (Comparative Example 1-
). The respective results are shown in Table 5.

(E) Structure of various adhesive sheets or tapes: Tables 7 and 8 show examples.

Example 6 Preparation of (A) Copolymer: 45 g and 2 of 3 (acrylamide) isopentyltrimethylammonium chloride as a (meth) acrylamide derivative (first copolymerization component)
Example 1 (A) using (methacryloxy) ethyltrimethylammonium chloride 45 g, 2-hydroxyethyl acrylate 40 g as the second copolymerization component, butoxyethyl acrylic acid 50 g as the third copolymerization component, and methyl alcohol 80 g as the solvent. A copolymer was prepared according to the section.
The obtained reaction liquid was a slightly milky viscous solution, and the concentration of the copolymer contained was 33.0% and the viscosity at 21 ° C was 32,000c.
It was ps. The polymerization rate was 98.5% for the entire copolymer, 37.3 (acrylamide) isopentyltrimethylammonium chloride for the first copolymerization component was 97.3%, 2 (methacryloxy) ethyltrimethylammonium chloride was 98.5%, and the second copolymerization component was Is 99.7%, the third copolymerization component is
It was 98.7%.

(B) Preparation of pressure-sensitive adhesive sheet: The polymer obtained from the copolymer solution obtained in the item (A) of this Example was a slightly hard non-tacky resinous material. This resin-like polymer dissolves in water and alcoholic solvents, but does not dissolve in methyl ethyl ketone and ethyl acetate. Moderate tackiness was obtained when 40 to 95 parts by weight of diglycerin was added to 100 g of the polymer component. An adhesive solution was obtained by adding 65 parts by weight of diglycerin to 100 g of the polymer component of the copolymer solution obtained in the item (A) of this example. Using this pressure-sensitive adhesive solution, a pressure-sensitive adhesive sheet was prepared according to the method of Example 1 (B).

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive strength by the folding method was 660 g / 15 mm and the ball tack value was 29, and no cohesive failure was observed. Adhesion to wet surface is 300
It was more than a second.

(D) Evaluation of bactericidal property of the pressure-sensitive adhesive: Performed according to the item (D) of Example 1. Separately, an adhesive was prepared under the same conditions as in Comparative Example 1, and antibacterial properties were evaluated by the same method (Comparative Example 1-
). The respective results are shown in Table 6.

(E) Structure of various adhesive sheets or tapes: Tables 7 and 8 show examples.

Comparative Example 2 A commonly used acrylic pressure-sensitive adhesive was prepared and compared with the pressure-sensitive adhesive obtained from the resin of this example.

(A) Preparation of copolymer: 2-ethylhexyl methacrylate
60 g, butyl acrylate 120 g, 1.6 hexane glycol dimethacrylate ester 0.018 g and ethyl acetate 80 g were charged into a reaction vessel, and a copolymer was prepared according to the item of Example 1 (A). However, the amount of catalyst used was 0.51 g. The concentration of the copolymer contained in the obtained reaction solution was 27.6%, and the viscosity at 21 ° C was about 25,000 cps. The overall polymerization rates were 98.4%, 2-ethylhexyl methacrylate 99.6%, and butyl acrylate 97.8%. The polymer obtained by distilling off and drying the solvent of the reaction solution has tackiness and does not require a softening agent.

(B) Preparation of adhesive sheet: PET having a thickness of 50 μm as a base material
A film was used, and one side was subjected to corona discharge treatment.
The reaction solution containing the copolymer obtained in the item (A) of the present comparative example was applied to the treated surface by a transfer coating method so that the thickness after drying was 50 μm and dried to obtain an adhesive sheet.

(C) Adhesive substitute physical properties of the adhesive: The adhesive substitute physical properties were examined using the adhesive sheet obtained in the item (B) of this Example. 180 °
The adhesive force by folding method was 520 g / 15 mm, and the ball tack value was 15, and no cohesive failure was observed. However, the adhesion to the wet surface showed a low value of 7 seconds.

(D) Evaluation of antibacterial property of pressure-sensitive adhesive: Performed according to the item (D) of Example 1. The results are shown in Table 9.

(Effects of the Invention) According to this example, the acrylic adhesive has excellent properties such as excellent adhesiveness, high internal cohesive force, and low deterioration, and also has excellent antibacterial properties. A resin capable of forming a medical adhesive is obtained. When the sheet or tape of the present invention provided with such an adhesive layer is applied to the skin, for example, wounds are not infected with microorganisms, and thus healing can be promoted. No rash due to secondary sensitization of microorganisms to the part where stuffiness occurs.

Since this pressure-sensitive adhesive is also excellent in hydrophilicity, it is possible to adhere the sheet or tape of the present invention using it to a wet (wet) skin surface. Does not easily peel off when sweating when applied. This adhesive has excellent water absorbency and water vapor permeability, so that it will not become damp even if a sheet or tape is applied to the skin for a long time. Therefore, rash due to stuffiness is unlikely to occur. When water is used to peel off the attached sheet or tape, the pressure-sensitive adhesive dissolves in the water or swells with water, so that the sheet or tape can be easily peeled off. Therefore, even if it is applied to a weak skin surface such as an infant, it does not damage the skin surface when peeled. If the adhesive sticks out to the surroundings when the sheet or tape is attached, or if the adhesive remains on the skin after peeling, it can be easily removed by washing it with water. A water-soluble drug can be dissolved in the adhesive at a high concentration. Therefore, a therapeutic adhesive sheet or tape containing a high amount of a water-soluble drug, which has been difficult to prepare conventionally, can be easily obtained.

Furthermore, since the adhesive itself has conductivity, it has a large antistatic effect. Therefore, for example, when the roll-shaped adhesive tape is rewound, it may be attached to an unintended object due to static electricity, or the risk of ignition due to spark discharge. Nor.

When the resin of the present invention is used, a pressure-sensitive adhesive having an arbitrary pressure-sensitive adhesive having a higher pressure-sensitive adhesive than conventional acrylic pressure-sensitive adhesives to a low-pressure-sensitive adhesive can be obtained. for that reason,
A sheet or tape having a tackiness according to the purpose can be prepared.

Such a medical adhesive sheet or tape is used not only as a sheet-shaped or tape-shaped adhesive plaster for protecting a wounded part or fixing a fractured part, but also for example, when an intravenous drip is performed, an intravenous injection needle is used. It is also preferably used for fixing the skin to the surface of the skin and for fixing / adhering a medical member such as an artificial anus to a predetermined place. It can also be used for drape during surgery. It can also be used as a patch containing various drugs, and a patch containing a water-soluble drug in a high content can be easily obtained. It is also used for beauty purposes such as deepening wrinkles on the face, fixing and shaping hair.

Claims (11)

[Claims] 1. A resin comprising a copolymer containing a first copolymerization component and a second copolymerization component, wherein (1) the first copolymerization component comprises (a) a quaternary ammonium group. The (meth) acrylamide derivative having a chemical structure in which the group having the same is bonded to the (meth) acrylamide group by an amide bond, and / or (b) the group having a quaternary ammonium group is bonded to the (meth) acryloxy group by an ester bond. A resin for use in medical adhesives, which is a (meth) acrylic acid ester derivative having a chemical structure; and (2) the second copolymerization component is a mono (meth) acrylic acid ester of glycols. 2. The first copolymerization component in the copolymer is 5
The resin according to claim 1, wherein the second copolymerization component is contained in a proportion of ˜70% by weight, and the second copolymerization component is contained in a proportion of 20% by weight or more of the remaining components of the first copolymerization component. 3. The copolymer according to claim 1, wherein at least one of (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxy ester and fatty acid vinyl ester is contained as a third copolymerization component. The resin according to item 1. 4. The third copolymerization component in the copolymer,
Of the residual components of the first copolymerization component and the second copolymerization component
The resin according to claim 3, which is contained in a proportion of 50% by weight or more. 5. A medical sheet or tape having a pressure-sensitive adhesive layer provided on at least one side of a base material, the main component being a copolymer resin containing the first copolymerization component and the second copolymerization component. As a component, (1) the first copolymerization component, (a) a (meth) acrylamide derivative having a chemical structure in which a group having a quaternary ammonium group is bound to a (meth) acrylamide group by an amide bond, and / or b) a (meth) acrylic acid ester derivative having a chemical structure in which a group having a quaternary ammonium group is bonded to a (meth) acryloxy group by an ester bond; and (2) the second copolymerization component is a glycol. A medical sheet or tape that is a mono (meth) acrylic acid ester. 6. The first copolymerization component in the copolymer is 5
The sheet or tape according to claim 5, wherein the second copolymerization component is contained in a proportion of ˜70% by weight, and the second copolymerization component is contained in a proportion of 20% by weight or more of the remaining components of the first copolymerization component. 7. The copolymer according to claim 1, wherein the copolymer contains at least one of a (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkoxy ester and a fatty acid vinyl ester as a third copolymerization component. The sheet or tape according to item 5. 8. The third copolymerization component in the copolymer,
Of the residual components of the first copolymerization component and the second copolymerization component
The sheet or tape according to claim 7, which is contained in a proportion of 50% by weight or more. 9. The sheet or tape according to claim 5, wherein the adhesive contains a softening agent having an affinity for water. 10. The adhesive comprises the softener and the copolymer.
The sheet or tape according to claim 9, which is contained in a ratio of 10 to 100 parts by weight per 100 parts by weight. 11. The sheet or tape according to claim 5, wherein the adhesive contains a drug.