JP4916200B2 - Skin adhesive material and method for producing the same - Google Patents

Description

  The present invention relates to a skin adhesive material and a method for producing the same. In particular, the present invention relates to a skin adhesive material that can exhibit sufficient antibacterial properties even after undergoing a sterilization process by electron beam irradiation, in particular, a surgical drape, a bandage, and a surgical tape used in surgery. And a manufacturing method thereof.

  In recent years, the trend toward cleanliness and safety has increased, and the number of processed products that have added antibacterial properties to textiles such as clothing, kitchen appliances, bathrooms and toilets, as well as electrical appliances, stationery, toys and automobiles has increased. . For example, there is an antibacterial pressure-sensitive adhesive tape in which an inorganic antibacterial agent is blended with a film base mainly composed of polyvinyl chloride resin (for example, Patent Document 1). The adhesive tape described in Patent Document 1 prevents the film from being contaminated with mold or bacteria by adding an antibacterial agent to the base material for the purpose of bundling indoor wiring or terminal treatment.

Commonly used antibacterial agents include inorganic, natural organic, and synthetic organic antibacterial agents. Examples of inorganic antibacterial agents include metals such as silver, copper and zinc and their compounds, and oxide photocatalytic systems. Metals and their compound antibacterial agents are generally used as carriers, have heat resistance, antibacterial effects are semi-permanent, and have a wide antibacterial spectrum, but compared to organic antibacterial agents Therefore, the antibacterial effect is weak, and it is necessary to increase the amount of addition to obtain the same effect. Silver antibacterial agents may be discolored by the action of additives in the polymer due to heat during processing. Furthermore, the antibacterial property is actually manifested only by the antibacterial agent present on the surface of the adhesive layer , and the buried antibacterial agent is not utilized. In addition, anatase-type titanium oxide is known as an oxide photocatalyst. It reacts with water vapor and oxygen in the air using charge separation by light irradiation to generate active oxygen, and it has antibacterial properties with strong oxidizing power. Is expressed. Therefore, there is a disadvantage in that there is no effect without light irradiation.

  Natural organic antibacterial agents include hinokitiol, chitosan, and chili extracts, and are used as food additives and food packaging materials. The advantages of natural organic systems are the highest safety and mild antibacterial properties to prevent the growth of microorganisms, but the effective period is extremely short and there is no heat resistance, so they are mixed with resin to form a film (molding) However, there is a disadvantage that it cannot be used because it requires heat treatment.

  Next, synthetic organic antibacterial agents include nitrogen-containing heterocyclics, phenols, biguanides, nitriles, halogens, anilides, organosilicon quaternary ammonium salts, quaternary ammonium salts, amino acids, There are organic metal type and ester type. These have been used for many years, accounting for 80% of antibacterial agents, and many types. Synthetic organic antibacterial agents have the advantages that they are effective when added in small amounts, have immediate effects, and are relatively inexpensive. However, sufficient safety is not ensured, and there are those that are highly toxic, drugs that are soluble in water, and those that are volatile, and few are particularly suitable for medical use. In addition, synthetic organic antibacterial agents have the disadvantages that they are easily decomposed into water and have a short lifetime and a short effective period.

  On the other hand, iodine exhibits excellent broad spectrum antibacterial properties, is relatively safe for the human body, and has been widely used as a disinfectant. However, iodine has a peculiar odor and color and sublimates, which causes a problem in handling. Therefore, for easy handling, povidone iodine in which iodine is complexed with polyvinylpyrrolidone is used. However, since iodine itself is volatile, there is a problem in storage stability, and there is a problem that the effect is lost in a relatively short time and antibacterial properties are not sustained.

  In addition to the above-mentioned processed products, conventionally, in surgical operations such as laparotomy, thoracotomy, appendicitis, etc., the patient's body is covered with a surgical covering cloth that covers the patient's body and is provided with a fenestration for exposing the surgical field. Covering is done. Surgery requires that the organ be exposed to a very high degree of sterilization, and in recent years, nosocomial infections have been seen as a problem. In addition, a particularly high antibacterial property is required for the fixing portion of the fenestration portion located near the incised portion to the human body surface. For this reason, an antibacterial agent is often contained in the fixed (adhesive) portion. Similarly, antibacterial agents are also applied to adhesive layers of medical tapes such as emergency bandages, surgical bands, dressing tapes, etc., in order to prevent the healing of wounds or worsening of wounds due to the growth of various bacteria. Often included.

Needless to say, such a medical tape and an adhesive used for the tape are life-threatening in some cases. For this reason, sterilization management is stricter than the above general processed products. Considering such points, several medical tapes and adhesives used for the tapes have been reported. For example, in Patent Document 2, metal silver is supported on titanium oxide, this is mixed with an acrylic adhesive substance to prepare an adhesive, and this is coated on a release paper and dried. It describes that a medical tape is produced by transferring it to a substrate. Furthermore, what uses iodine as an antibacterial agent has also been reported (for example, Patent Documents 3 and 4). In Patent Documents 3 to 6, iodine (or iodine / sodium iodide) -polyvinylpyrrolidone composite is used as an adhesive. (PVP-I) as an antibacterial agent is blended with 2-ethylhexyl acrylate / N-vinylpyrrolidone adhesive, and this is applied to a free liner, dried to produce a dry film, and this dry film can be laminated to a polyethylene film. Are listed.

  However, since the medical tape described in Patent Document 2 uses metallic silver, as the concentration of the antibacterial agent increases, the compatibility with the pressure-sensitive adhesive decreases, and the physical properties of the adhesive also decrease. There is a problem that it is difficult to achieve a good balance with physical properties. Moreover, although the adhesive tape described in patent documents 3-6 exhibits the antibacterial property which was excellent as mentioned above, since it volatilizes itself, there is an odor peculiar to iodine during storage. In addition to the problem of coloring, there is a problem in storage stability, and the effect is lost in a relatively short time, and the antibacterial property is not maintained. In addition, the surgical covering as described above is generally sterilized by electron beam irradiation. However, when the sterilization process by electron beam irradiation is performed, iodine is decomposed and its antibacterial properties are greatly reduced.

  Therefore, the present invention has been made in view of conventional circumstances, and provides a skin adhesive that can exhibit excellent antibacterial properties even after electron beam irradiation, which is generally used in the sterilization process in the medical field. The purpose is to do.

  Another object of the present invention is that it is safe for organisms, is durable, has excellent deodorizing properties, has a broad antibacterial spectrum against microorganisms, can be sterilized in a few seconds to a few minutes, and can be resistant. It is to provide a difficult skin patch.

  Another object of the present invention is to provide a method by which such a skin adhesive can be easily produced without reducing antibacterial properties.

The inventors of the present invention have made extensive studies to achieve the above-mentioned objects. As a result, cyclodextrin iodine inclusion bodies have stronger antibacterial activity than chlorine and bromine (three times as much as chlorine), and have an oxidizing action and corrosion. since less sex, safe is point to the organism; because it has a sustained release of iodine, a point is sustained; no iodine peculiar odor, oxidation-iodination of inclusion reaction of iodine cyclodextrin Excellent deodorant by action; cyclodextrin iodine inclusion body as an antibacterial agent, taking into account that it has a broad antibacterial spectrum against microorganisms, sterilizes in a few seconds to a few minutes and is difficult to resist Focused on using. First, since the inventors can easily adjust the amount of iodine included in the inclusion product of iodine-cyclodextrin, the most commonly used β-cyclodextrin iodine inclusion product has been used as an antibacterial agent. When dissolved in ethanol or acetone, which is generally used for the adhesive layer, iodine is scattered from the inclusion, and β-cyclodextrin is precipitated in the solution and cannot be used for the adhesive layer. It has been found. For this reason, as a result of further intensive studies on various cyclodextrin iodine clathrate, methylcyclodextrin iodine clathrate which clathrates iodine with a methylated cyclodextrin, while maintaining the clathrate of iodine, It discovered that it could melt | dissolve in solutions, such as methanol, ethanol, propylene glycol. Moreover, when an adhesive tape was prepared using this methylcyclodextrin iodine clathrate, and this was irradiated with an electron beam, most of the electron beam was irradiated to the cyclodextrin serving as a shell, Since it did not reach the iodine, it was found that iodine did not decompose and its antibacterial properties hardly decreased. Based on the above findings, the present invention has been completed.

  That is, the object is achieved by a skin adhesive material in which an adhesive layer containing methylcyclodextrin iodine inclusion complex as an antibacterial agent is provided on a base material.

  Another object of the present invention is to produce the skin adhesive material of the present invention having a step of dissolving in at least one solvent selected from the group consisting of methanol, ethanol and propylene glycol, and applying this solution to a substrate. Achieved by the method.

  The skin adhesive material of the present invention is characterized by having an adhesive layer containing a methylcyclodextrin iodine inclusion body as an antibacterial agent. For this reason, the skin adhesive material of the present invention can exhibit excellent antibacterial properties for a long period of time, such as a broad antibacterial spectrum, high bactericidal ability, and resistance to resistant bacteria, by inclusion of iodine. In the present invention, since iodine is included in cyclodextrin, there is no iodine-specific odor, and since iodine can be gradually released over time, it exhibits excellent antibacterial properties over a long period of time. Can do. For this reason, the skin adhesive material of the present invention is not limited to surgical coverings (draps), bandages and surgical tapes that are used temporarily such as surgical operations, but also long-term indwelling catheters that require longer antibacterial properties. The fixing tape can be suitably used without causing discomfort to the patient.

  In addition, methylcyclodextrin iodine inclusions can be dissolved in solvents such as methanol, ethanol, propylene glycol and the like that have been used for forming conventional adhesive layers without detaching the inclusion of iodine. The same method as the formation of can be applied as it is, and the formation of the adhesive layer on the substrate can be performed very simply.

  The first of the present invention relates to a skin adhesive material comprising an adhesive layer containing a methylcyclodextrin iodine inclusion complex as an antibacterial agent on a base material. Even if the methylcyclodextrin iodine inclusion body used as an antibacterial agent for the skin adhesive material of this invention irradiates an electron beam at the time of a sterilization process, antibacterial property is hardly impaired. The reason why the antibacterial property is hardly impaired even when the electron beam is irradiated to the methylcyclodextrin iodine clathrate is not clear, but the methylcyclodextrin iodine clathrate completely surrounds iodine in the cyclodextrin. This is thought to be because the cyclodextrin that is clad in iodine plays a role of a defensive wall and prevents the electron beam from hitting. In addition, the methylcyclodextrin iodine inclusion body can exhibit excellent antibacterial properties such as a broad antibacterial spectrum, high bactericidal ability and resistance to resistant bacteria due to the included iodine. In addition to the above-mentioned advantages, methyl cyclodextrin iodine inclusion body in which iodine is included in cyclodextrin is used for the adhesive layer, so there is no iodine-specific odor, and iodine is gradually released over time. Therefore, excellent antibacterial properties can be exhibited for a long time. The skin adhesive material of the present invention is used for fixing not only a surgical wrap (drape), a bandage, a surgical tape, and a long-term indwelling catheter that require a longer period of antibacterial properties. This tape can be preferably used without causing discomfort to the patient.

  The methylcyclodextrin iodine inclusion body according to the present invention can be produced by a known method such as JP-A Nos. 51-88625 and 2002-193719. Preferably, the method described in JP-A-2002-193719 is used. That is, iodine is dissolved in a solution containing iodine at a ratio of 1 mol: 1.5 to 5 mol of iodine-containing auxiliary, and 0.67 to 100 mol of methylcyclodextrin is added to 1 mol of iodine. Then, the iodine-dextrin inclusion compound can be precipitated.

The methylcyclodextrin used in the present invention may be in the form of methyl-α-cyclodextrin, methyl-β-cyclodextrin or methyl-γ-cyclodextrin, or in the form of a mixture of these two or three types. There may be. If you considering the ease of formulation of the material for forming the adhesive layer, excellent methyl -β- cyclodextrin solvent solubility is preferably used.

  Alternatively, a commercially available product may be used as the methylcyclodextrin iodine clathrate according to the present invention. Specific examples include MCDI (manufactured by Nihon Ho Chemical Co., Ltd.).

  In this invention, the addition amount of the methylcyclodextrin iodine inclusion body as an antibacterial agent will not be restrict | limited especially if the desired antibacterial property can be provided to a skin sticking material. Specifically, the addition amount of the methylcyclodextrin iodine inclusion body as an antibacterial agent is 0.01 to 20% by mass, more preferably 1 to 18% by mass with respect to the nonvolatile content of the adhesive constituting the adhesive layer. %, Most preferably 5 to 15% by mass. At this time, if the addition amount of the methyl cyclodextrin iodine inclusion body is below the lower limit of the above range, the amount of the methyl cyclodextrin iodine inclusion body is too small, and the desired antibacterial property may not be achieved. Even if the upper limit of the above range is exceeded, antibacterial properties commensurate with the addition cannot be obtained and it is not economical, and the amount of methylcyclodextrin iodine inclusions is excessively contained relative to the pressure-sensitive adhesive. May be reduced.

According to the present invention, even when sterilization treatment with an electron beam is performed, it is possible to effectively prevent the cyclodextrin portion from serving as a shell and the electron beam from reaching iodine in the cyclodextrin. For this reason, even if the addition amount of methylcyclodextrin iodine inclusion bodies is small, antibacterial properties against various microorganisms such as Escherichia coli and Staphylococcus aureus can be sufficiently exhibited. For this reason, under general usage conditions (for example, in the case of normal electron beam irradiation sterilization used in a general period after production), the amount of methylcyclodextrin iodine inclusion complex added as an antibacterial agent is: It is 0.01-5 mass% with respect to the non volatile matter of the adhesive which comprises an adhesion layer, More preferably, it is 0.5-5 mass%, Most preferably, it is about 1-3 mass%. In addition, the said addition amount changes with how to arrange | position in the adhesion layer of a methylcyclodextrin iodine inclusion body. For example, to deposit a methyl cyclodextrin iodine Mototsutsumi Settai the surface tacky adhesion layer or the adhesive layer a two-layer structure, it was added methyl cyclodextrin iodine Mototsutsumi Settai only the layer side in contact with the skin, and methylcyclohexane When the ratio of the non-volatile content of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the layer containing dextrin iodine inclusion body and the layer not containing it is 1: 9, the non-volatile content of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is 0. It is preferable that it is 01-0.5 mass%, More preferably, it is 0.05-0.5 mass%, Most preferably, it is 0.1-0.3 mass% . The methylation cyclodextrin iodine Mototsutsumi Settai when used mixed in the adhesive, the amount of methyl cyclodextrin iodine Mototsutsumi contact body as an antibacterial agent to be non-volatile component of the pressure-sensitive adhesive constituting the adhesive layer, It is preferable that it is 0.3-5 mass%, More preferably, it is 0.5-5 mass%, Most preferably, it is 1-3 mass%.

In addition, when the skin adhesive is sterilized by electron beam irradiation at a relatively high irradiation intensity, there is a possibility that a part of iodine in the methylcyclodextrin iodine inclusion body is deactivated. In the field of skin adhesives, the quality assurance period is generally about 5 years at room temperature. Therefore, when the skin adhesive is used after it has been stored for a long time to near the quality assurance period, methylcyclodextrin iodine There is a possibility that some iodine in the clathrate is deactivated. Furthermore, the skin adhesive material of the present invention is coated and dried during the production process as described in detail below. In general, iodine is more difficult to disperse even under heating conditions due to the presence of methylcyclodextrin as a shell compared to the case of a simple substance. Part of the iodine may volatilize due to coating drying. Furthermore, the skin adhesive is usually applied to areas that have been disinfected with isodine etc. and then decolorized with hypoalcohol, such as those that have been disinfected for surgery. It is described to put a dressing. However, in actual sites, there are many situations in which body fluids such as blood and lymph fluid come into contact with the adhesive surface during surgery, and in such a case, iodine is deactivated. For this reason, when such a point is considered, it may be preferable that the addition amount is larger than the above amount. Specifically, for example, addition of methyl cyclodextrin iodine Mototsutsumi Settai only in the layer side to adhere the methyl cyclodextrin iodine Mototsutsumi Settai the surface tacky adhesive layer or the adhesive layer a two-layer structure, in contact with skin And when the ratio of the non-volatile content of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the layer including and not including the methylcyclodextrin iodine inclusion body is 1: 9, On the other hand, it is preferable that it is 1-20 mass%, More preferably, it is 2-15 mass%, Most preferably, it is 5-10 mass%. Or, when methylcyclodextrin iodine clathrate is mixed with an adhesive and used, the amount of methylcyclodextrin iodine clathrate added as an antibacterial agent is less than the non-volatile content of the adhesive constituting the adhesive layer. 2 to 20% by mass, more preferably 5 to 20% by mass, and most preferably 10 to 20% by mass. Within such a range, sufficient antibacterial activity can be exhibited even under the severe conditions described above. In addition, the addition amount of the above-mentioned methylcyclodextrin iodine clathrate is just after the pressure-sensitive adhesive product is produced (including the step of coating the pressure-sensitive adhesive composition on the release paper to a certain thickness and drying it in a hot air dryer). The amount of

Moreover, the adhesion layer which concerns on this invention contains the adhesive substance for providing adhesiveness in addition to the said methylcyclodextrin iodine inclusion body. The adhesive substance that can be used at this time is not particularly limited, and a known adhesive substance can be used. For example, polymers such as acrylic polymers, silicone polymers, polyurethane polymers, polyvinyl polymers, polyester polymers, natural rubber, synthetic rubber, vinyl ether polymers, and the like can be preferably used. At this time, as the rubber-based adhesive substance, for example, neoprene rubber, polyisoprene, styrene-butadiene rubber, chloroprene rubber, butadiene-acrylonitrile rubber can be used. The acrylic adhesive substance is usually composed of a base polymer, a comonomer, a functional group-containing monomer, etc., and a silicone-based, polyvinyl-based, polyester-based, or polyurethane-based adhesive substance is usually a base polymer, Consists of softeners and the like.

  These adhesive substances can be used in various usage states such as a water or solvent type solution type or suspension type, a hot melt type, a solid paste type, and a reaction type.

  Alternatively, as the adhesive substance, a plurality of star-shaped structures in which at least three chain polymer portions extend radially around a mercapto group are connected to each other by a chain polymer portion, and the entire structure of the polymer portion A star-type acrylic block polymer (hereinafter also simply referred to as “star-type acrylic block polymer”) in which 50 to 100% by mass of the unit is a (meth) acrylic acid alkyl ester structural unit having 7 to 17 carbon atoms is preferably used. The As for the said polymer, it is especially preferable that the residual amount of a C7-C17 (meth) acrylic-acid alkylester is 900 ppm or less with respect to the total non volatile matter. Thus, by reducing the residual amount of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms, the polymer can exhibit an excellent balance between adhesive force and cohesive force even without the presence of a crosslinking agent. For this reason, by using such a polymer for the adhesive layer of the skin adhesive material of the present invention, the obtained skin adhesive material is particularly excellent in terms of safety and performance as skin adhesive.

  The star-shaped acrylic block polymer has a structure in which a plurality of star-shaped structures in which at least three chain polymer portions extend radially around a mercapto group are connected to each other by the chain polymer portions. The star acrylic block polymer is a (meth) acrylic acid alkyl ester structural unit in which 50 to 100% by mass of all structural units of the chain polymer portion of the block polymer has 7 to 17 carbon atoms. The content ratio of the (meth) acrylic acid alkyl ester structural unit having 7 to 17 carbon atoms is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably, in all the structural units of the chain polymer portion. Is 80 to 100% by mass, particularly preferably 90 to 100% by mass. When the content ratio of the (meth) acrylic acid alkyl ester structural unit having 7 to 17 carbon atoms is less than 50% by mass in all the structural units of the chain polymer portion, the tackiness cannot be sufficiently imparted. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “structural unit” of the polymer portion means a unit consisting of a structure derived from a polymerizable monomer constituting the polymer. .

  As the polymerizable monomer corresponding to the (meth) acrylic acid alkyl ester structural unit having 7 to 17 carbon atoms, that is, the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms, for example, (meth) acrylic acid butyl ester, (Meth) acrylic acid t-butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid isooctyl ester , (Meth) acrylic acid nonyl ester, (meth) acrylic acid isononyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid 2- Examples include ethyl hexyl ester. In order to fully exhibit the effects of the present invention, (meth) acrylic acid octyl ester, (meth) acrylic acid isooctyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) Acrylic acid 2-ethylhexyl ester is more preferable, acrylic acid octyl ester, acrylic acid isooctyl ester, acrylic acid nonyl ester, acrylic acid decyl ester, acrylic acid 2-ethylhexyl ester is more preferable, and acrylic acid 2-ethylhexyl ester is particularly preferable. . These may be used alone or in combination of two or more.

  The chain polymer portion of the star-shaped acrylic block polymer is composed of a structural unit derived from a polymerizable monomer other than the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms (other polymerizable monomers) in a total mass of 50 mass. It may be contained at a content ratio of less than%.

  Examples of other polymerizable monomers include polymerizable monomers that can be homopolymerized or copolymerized by radical polymerization. For example, (meth) methyl (meth) acrylate, ethyl (meth) acrylate and the like having 6 or less carbon atoms (meth ) Acrylic acid alkyl esters; (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide; (meth) acrylic acid; α-methylstyrene, vinyltoluene, styrene, etc. Styrene monomers such as phenylmaleimide, cyclohexylmaleimide, and other maleimide monomers; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether; fumaric acid and fumaric acid mono Diesters of alkyl esters and fumaric acid Maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid; itaconic acid, monoalkyl esters of itaconic acid, dialkyl esters of itaconic acid; vinyl pyrrolidones such as N-vinyl-2-pyrrolidone; methoxytriethylene glycol acrylate (Meth) acrylic acid alkoxypolyalkylene glycol ester represented by the following formula (1) such as methoxypolyethylene glycol methacrylate, ethoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, etc .; (meth) acrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride And other vinyl compounds such as vinyl acetate, vinyl ketone, vinyl pyridine and vinyl carbazole.

In the above formula (1), X and Y each independently represent a hydrogen atom (H) or a methyl group (—CH ₃ ); Z represents an alkyl group having 1 to 18 carbon atoms; and n Is an integer from 2 to 12.

  In order to achieve a sufficient balance between adhesiveness, cohesiveness, and adhesive strength and cohesive strength, methyl methacrylate (meth) acrylate, (meth) acrylic acid, and vinyl acetate should be used in combination as other polymerizable monomers. Is preferred.

  Further, when vinylpyrrolidone such as N-vinyl-2-pyrrolidone (NVP) is used as the other polymerizable monomer, the skin irritation of the resulting star-shaped acrylic block polymer is reduced. (Meth) acrylic acid as another polymerizable monomer can impart cohesion to the resulting star-shaped acrylic block polymer, but has strong skin irritation and is suitable for the final product (for example, skin adhesive). Remaining trace amounts can cause irritation to people with sensitive skin. Vinylpyrrolidone such as N-vinyl-2-pyrrolidone has the advantage that it can impart cohesion to the resulting star acrylic block polymer and has lower skin irritation than (meth) acrylic acid.

  Moreover, when the (meth) acrylic acid alkoxy polyalkylene glycol ester represented by the above formula (1) is used as the other polymerizable monomer, the moisture permeability of the obtained star-shaped acrylic block polymer can be improved. In general, as one of the causes of skin itching and rash caused by the skin adhesive material, moisture (water vapor) evaporated from the skin is blocked by the adhesive layer in the skin adhesive material and is steamed inside. The (meth) acrylic acid alkoxy polyalkylene glycol ester represented by the above formula (1) can improve the moisture permeability of the resulting star-shaped acrylic block polymer, and the skin when adhered to the skin as an adhesive. It has the advantage that itching and rash can be reduced. In order to express this advantage, when the (meth) acrylic acid alkoxy polyalkylene glycol ester represented by the above formula (1) is included as another polymerizable monomer, the structural unit derived from the monomer is changed to a star-shaped acrylic block. The content is preferably 1 to 45% by mass and more preferably 10 to 40% by mass based on the total polymer structural unit. When the content of the (meth) acrylic acid alkoxy polyalkylene glycol ester represented by the above formula (1) is less than 1% by mass, there is no effect of improving moisture permeability. The physical property balance will be lost.

  One of the other polymerizable monomers may be used, or two or more may be used in combination.

  In the star-type acrylic block polymer, the remaining amount of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms is 900 ppm or less, preferably 700 ppm or less, more preferably 500 ppm or less, and still more preferably. 400 ppm or less, particularly preferably 300 ppm or less, and most preferably 200 ppm or less. When the residual amount of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms is 900 ppm or less with respect to the total nonvolatile content, a skin adhesive having an excellent balance between adhesive force and cohesive force can be formed. In addition, since the skin irritation is extremely small, it can be applied to the skin adhesive material very preferably.

  The star acrylic block polymer has a characteristic star-shaped block polymer structure that allows physical cross-linking due to the micro-layer separation structure, and achieves a balance between adhesion and cohesion without using a cross-linking agent. it can.

  The method for producing a star-shaped acrylic block polymer is a conventional method for producing a star-shaped acrylic block polymer in which multi-stage radical polymerization of a polymerizable monomer is performed in the presence of a polyvalent mercaptan. The carbon number after polymerization by using 50 to 100% by mass of (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms and using a polyfunctional monomer described later in at least one elementary stage among the multiple stages. What is necessary is just to set polymerization conditions suitably so that the residual amount of 7-17 (meth) acrylic-acid alkylester may be 900 ppm or less with respect to the total non volatile matter. Hereinafter, a production method particularly suitable for obtaining a star-shaped acrylic block polymer will be described.

  As a production method particularly suitable for obtaining a star-shaped acrylic block polymer, in a multi-stage radical polymerization method using a polyvalent mercaptan, a polyfunctional monomer described later is used in at least one of the multi-stages. Examples thereof include a method in which a polymerization initiator is further added after the completion of the supply of all the polymerizable monomers to the reaction system, in combination with the polymerizable monomer. The polymerization initiator added later is referred to as “booster” in the present invention.

  When radical polymerization of the first polymerizable monomer is performed in the presence of the polyvalent mercaptan, the first polymerizable monomer is radically polymerized starting from the mercapto group of the polyvalent mercaptan, and at least three chain polymer portions have mercapto groups. A first star structure is formed extending radially from the center. At that time, some mercapto groups of the polyvalent mercaptan remain without being the starting point of this radical polymerization. Therefore, when radical polymerization is carried out by adding a second polymerizable monomer, the second polymerizable monomer radically polymerizes starting from the remaining mercapto group of the polyvalent mercaptan, and the second star shape is different from the first star structure. Configure the structure. In the case of radical polymerization carried out in such a multistage (two stages in this example), when the polyfunctional monomer is used in combination in at least one polymerization stage, the star-shaped structures obtained as described above can be obtained. It is bonded via a polyfunctional monomer to form a star block polymer. At this time, the homopolymer of the polymerizable monomer that is a by-product during radical polymerization (a chain polymer that does not form a mercapto group as a starting point) is also bonded to the chain polymer portion of the star block polymer via the polyfunctional monomer. Can also be expected.

  In order to obtain a star acrylic block polymer, it is particularly preferable that the multistage radical polymerization method comprises two stages. That is, a first polymerization step for performing radical polymerization of a polymerizable monomer in the presence of a polyvalent mercaptan, and a radical polymerization of the polymerizable monomer in the presence of an intermediate polymer and a polyfunctional monomer obtained in the first polymerization step. The second polymerization step is performed, and 50 to 100% by mass of the total use amount of the polymerizable monomer is a (meth) acrylic acid alkyl ester having 7 or more carbon atoms, and the supply of the total polymerizable monomer to the reaction system is Particularly preferred is a production method in which further boosters are added after completion.

  In the second polymerization step, polymerization is carried out by mixing the polymerizable monomer and polyfunctional monomer used in the second polymerization step with the polymer solution obtained in the first polymerization step.

  In the second polymerization step, the polymer solution obtained in the first polymerization step, the polymerizable monomer used in the second polymerization step, and the polyfunctional monomer may be mixed and polymerized, or in the first polymerization step. The polymerizable monomer and polyfunctional monomer used in the second polymerization step may be added and mixed little by little to the obtained polymer solution.

  Particularly preferred forms of the second polymerization step include (1a) the polymer solution obtained in the first polymerization step, (1b) a part of the polymerizable monomer used in the second polymerization step, and (1c) in the second polymerization step. (2a) a polymer solution obtained in the first polymerization step, and (2b) after adding a polymerization initiator to the initial charge mixture (1) essentially containing a part of the polyfunctional monomer to be used and starting polymerization. A monomer mixture (2) essentially containing the remainder of the polymerizable monomer used in the second polymerization step and (2c) the remainder of the polyfunctional monomer used in the second polymerization step and a polymerization initiator are added and mixed little by little (preferably Are added dropwise), and after the addition and mixing are completed (that is, after the supply of all polymerizable monomers to the reaction system is completed), the booster is further post-added. With this method, the polymer solution obtained in the first polymerization step and the polymerizable monomer used in the second polymerization step can be sufficiently uniformly mixed.

  When a polymerization initiator is added to the initial charge mixture (1) to start polymerization, and then the monomer mixture (2) and the polymerization initiator are added and mixed little by little, the addition and mixing is preferably dropwise. The time is preferably 20 to 300 minutes, more preferably 40 to 200 minutes, still more preferably 60 to 120 minutes. 30-200 degreeC is preferable and, as for the temperature of the reaction system at the time of performing addition mixing, 50-150 degreeC is more preferable.

  The polymer solution obtained in the first polymerization step (above (1a) and (2a)) is preferably stopped when used in the second polymerization step, and the polymerization rate at that time is preferably 50. -90%, More preferably, it is 55-85%, More preferably, it is 60-80%. Examples of the method for stopping the polymerization include a method of adding a polymerization inhibitor to the polymer solution obtained in the first polymerization step and a method of lowering the temperature of the polymer solution.

  Examples of the polymerization inhibitor that can be used to stop the polymerization include hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, and 2,5-bis (1,1- (Dimethylbutyl) phenols such as hydroquinone, methoxyphenol, 6-tertiarybutyl-2,4-xylenol, 3,5-ditertiarybutylcatechol; N-nitrosophenylhydroxylamine aluminum salt; phenothiazine; Only one of these may be used, or two or more may be used in combination. The amount used is preferably 1 to 10000 ppm, more preferably 10 to 1000 ppm, and still more preferably 20 to 200 ppm with respect to the polymerizable monomer used in the first polymerization step. When the amount of the polymerization inhibitor used is less than 1 ppm, the polymerization may not be stopped efficiently. On the other hand, if it is more than 10,000 ppm, the polymerization in the second polymerization step may not start.

  The polymerization in the first polymerization step can be substantially stopped if the temperature of the polymer solution is lowered to 40 ° C. or lower. This is because since the decomposition rate of the polymerization initiator depends on the temperature, radicals are hardly generated when the temperature of the polymer solution is 40 ° C. or lower. In order to more reliably stop the polymerization, the temperature of the polymer solution may be lowered to 20 ° C. or lower.

  In the following, raw materials used in a suitable method for producing a star-shaped acrylic block polymer will be described in detail.

  The polymerizable monomer that can be used in the present invention is a (meth) acrylic acid alkyl ester having 50 to 100% by mass in the total amount of use and having 7 to 17 carbon atoms. The content of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms in the total polymerizable monomer is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass. Especially preferably, it is 90-100 mass%. When the content ratio of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms in the total polymerizable monomer is less than 50% by mass, sufficient tackiness cannot be imparted.

  Preferred specific examples of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms are as described above, and these may be used alone or in combination of two or more.

  The polymerizable monomer that can be used in the present invention is a content of less than 50% by mass of the polymerizable monomer (other polymerizable monomer) other than the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms in the total amount used. May be included.

  Other polymerizable monomers include polymerizable monomers that can be homopolymerized or copolymerized by radical polymerization, and preferred specific examples are as described above. These may be used alone or in combination of two or more. May be used in combination.

  In a suitable method for producing a star-shaped acrylic block polymer, radical polymerization in the presence of a polyvalent mercaptan is carried out in multiple stages, but it is preferable to use different types of polymerizable monomers in each elementary stage. Here, different types of polymerizable monomers mean not only polymerizable monomers having different chemical structures, but also cases where the blending ratios differ in combinations of polymerizable monomers having the same chemical structure. As an example of using different types of polymerizable monomers at each elementary stage, for example, for the combination of polymerizable monomers used in the first polymerization step consisting of 90 parts by weight of methyl methacrylate and 10 parts by weight of butyl acrylate, A combination of polymerizable monomers used in the second polymerization step consisting of 10 parts by weight of methyl methacrylate and 90 parts by weight of butyl acrylate can be mentioned. In this case, the resulting star-shaped acrylic block polymer is greatly different in Tg. Since it has a chain polymer portion, the effects of the present invention can be fully exerted, and practical performance is enhanced.

  Examples of the polyvalent mercaptan that can be used in the above method include ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, 1,4-butanediol dithioglycolate, 1,4-butanediol dithiopropionate, and the like. Diesters of diols and carboxyl group-containing mercaptans such as glycol and 1,4-butanediol; Triols and carboxyl group-containing mercaptans such as trimethylolpropane, such as trimethylolpropane trithioglycolate and trimethylolpropane trithiopropionate Triesters: Compounds having four hydroxyl groups such as pentaerythritol, such as pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate And a carboxyl group-containing mercaptan polyester; a compound having six hydroxyl groups such as dipentaerythritol hexakisthioglycolate and dipentaerythritol hexakisthiopropionate, and a carboxyl group-containing mercaptan polyester compound; Other compounds having 3 or more hydroxyl groups and polyester compounds of carboxyl group-containing mercaptans; compounds having 3 or more mercapto groups such as trithioglycerin; 2-di-n-butylamino-4,6-dimercapto-S-triazine Triazine polyvalent thiols such as 2,4,6-trimercapto-S-triazine; compounds obtained by introducing a plurality of mercapto groups by adding hydrogen sulfide to a plurality of epoxy groups of a polyvalent epoxy compound; carboxylic acid Ester compounds obtained by esterification of a plurality of carboxyl groups and mercaptoethanol; and the like can be illustrated, it may be used only one kind of them may be used in combination of two or more thereof. Here, the carboxyl group-containing mercaptans refer to compounds having one mercapto group and one carboxyl group, such as thioglycolic acid, mercaptopropionic acid, and thiosalicylic acid.

  The polyfunctional monomer that can be used in the above method is a compound having two or more polymerizable unsaturated groups per molecule. A monomer having 2 polymerizable unsaturated groups per molecule is called a bifunctional monomer, and a monomer having 3 is called a trifunctional monomer. The polyfunctional monomer that can be used in the above method is a compound having two or more polymerizable unsaturated groups (that is, a monomer having two or more functionalities) from the viewpoint of bonding the polymers having a star structure. In general, the number of polymerizable unsaturated groups should not be too large, and it is preferable to use a bifunctional monomer or a trifunctional monomer. A compound having 4 or more polymerizable unsaturated groups is considered to be more preferable from the viewpoint of increasing the number of bond structures that bind the star-shaped polymers to each other, but the number of polymerizable unsaturated groups is 4 or more. In some cases, the polymer forms a network structure and gelation easily occurs during the polymerization.

  Examples of polyfunctional monomers that can be used in the above method include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, 2,2 -Bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2, 2-bis [4- (methacryloxy Polyethoxy) phenyl] propane, diols such as 2-hydroxy-1-acryloxy-3-methacryloxypropane, and diester compounds of (meth) acrylic acid; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, A compound having three or more hydroxyl groups per molecule such as tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetrakis (meth) acrylate, dipentaerythritol hexakis (meth) acrylate, and a polyester compound of (meth) acrylic acid; allyl (Meth) acrylate; divinylbenzene; and the like can be used, and only one of these may be used, or two or more may be used in combination.

  In the present invention, the mass ratio of the polyfunctional monomer and the polyvalent mercaptan (polyfunctional monomer mass / polyvalent mercaptan mass) is preferably less than 2, more preferably 0.05 to 1.5, and more preferably 0.05 to 1. Is more preferable. If this mass ratio is 2 or more, the number of polyfunctional monomers contained in one molecule of the star-shaped block polymer may be too large, and the polymer may form a network structure and cause gelation during the polymerization. Because there is.

  In the present invention, the mass ratio of the polyfunctional monomer to the polymerizable monomer (polyfunctional monomer mass / total polymerizable monomer mass) is preferably less than 0.05, more preferably 0.001 to 0.03, More preferably, 001 to 0.01. This is because when the mass ratio is 0.05 or more, the viscosity during production increases, which is not preferable in terms of productivity. When the mass ratio is further increased, the polymer forms a network structure and is polymerized. This is because gelation may occur inside. Here, the total amount of polymerizable monomers used is the total mass of polymerizable monomers used in radical polymerization at each stage.

  In the present invention, radical polymerization can be carried out by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., which are ordinary radical polymerization.

  The temperature at which radical polymerization is performed is preferably 30 to 200 ° C., more preferably 50 to 150 ° C., in any polymerization process.

  A normal polymerization initiator can be used for radical polymerization. Examples of the polymerization initiator include dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2-methylbutyronitrile). ), 2,2′-azobis (2,4-dimethylvaleronitrile), azo-based initiators such as dimethyl 2,2′-azobisisobutyrate; peroxide-based polymerization initiators such as benzoyl peroxide; . The amount of the polymerization initiator used in radical polymerization is, by mass ratio, preferably 1/3 or less, more preferably 1/5 or less of polyvalent mercaptan. If the polymerization initiator is used in a larger amount than the above ratio, in addition to the chain polymer portion extending from the mercapto group, a polymer extending from the polymerization initiator is also generated in a large amount, and the production efficiency of the star block polymer is lowered. This is because the physical properties of the obtained star-shaped block polymer are likely to deteriorate. When adding the polymerization initiator to the reaction system, it may be added at once or dividedly. In the case of divided input, each of them may be input all at once or sequentially.

  A normal solvent can be used for radical polymerization. Examples of the solvent include ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as methyl ethyl ketone and cyclohexanone; aromatic solvents such as benzene and toluene; cellosolv solvents such as methyl cellosolve and ethyl cellosolve; Etc., and only one of these may be used, or two or more may be used in combination.

  In a particularly preferred method for producing a star-shaped acrylic block polymer, all reaction systems of polymerizable monomers used in the second polymerization step (the last polymerization step when three or more polymerization steps are included) are used. It is preferred to add further boosters after the feed to is completed. Examples of the booster include the aforementioned polymerization initiators, and only one of these may be used, or two or more may be used in combination. Although the usage-amount of a booster is not specifically limited, Preferably it is 0.1-5 mass% with respect to the usage-amount of all the polymerizable monomers, More preferably, it is 0.2-2 mass%, More preferably, it is 0.3- 1% by mass. When the amount of the booster used is less than 0.1% by mass, the effect of the booster cannot be exhibited. When the amount used exceeds 5% by mass, a low molecular weight product is remarkably generated and the physical properties are lowered, which is uneconomical. Although it does not specifically limit as an addition method of a booster, For example, the continuous dripping method dripped continuously and the division | segmentation dripping method added every fixed time are mentioned. Although it does not specifically limit as temperature at the time of adding a booster, 30-200 degreeC is preferable and 50-150 degreeC is more preferable. Although it does not specifically limit as addition time of a booster, 1 to 10 hours are preferable and 2 to 8 hours are more preferable.

  After the addition of the booster is completed, the reaction system may be further aged at 30 to 200 ° C., more preferably 50 to 150 ° C. Specifically, it is preferably carried out under reflux conditions of the solvent to be used (within the above temperature range). The aging time is not particularly limited, but is preferably 1 hour or longer, more preferably 2 hours or longer, and further preferably 3 hours or longer. The upper limit of the aging time is not particularly limited, but usually it is preferably within 10 hours.

  In a particularly suitable method for producing a star-shaped acrylic block polymer, the total time from the start of polymerization to the end of aging in the second polymerization step is preferably 8 to 20 hours, more preferably 9 to 15 hours. More preferably, it is 10 to 12 hours. If the total time from the start of polymerization to the end of aging in the second polymerization step is shorter than 8 hours, the effect of the present invention cannot be sufficiently exerted in the resulting star-shaped acrylic block polymer, Since the residual amount of 17 (meth) acrylic acid alkyl ester increases, it is not preferable. When the total time from the start of polymerization in the second polymerization step to the end of the ripening is longer than 20 hours, the productivity decreases significantly and the energy cost increases, and the resulting star acrylic block polymer This is not preferable because there is a possibility that the performance of the resin may deteriorate.

  As a suitable method for producing the star-shaped acrylic block polymer, a general method used in a conventional production method of a star-shaped block polymer may be appropriately used in addition to the above-described method.

  The star-shaped acrylic block polymer is generally obtained in a polymer solution state. When the star-shaped acrylic block polymer is obtained in the state of a solution, the content of nonvolatile components in the solution is preferably 40 to 70% by mass, more preferably 45 to 65% by mass, and still more preferably 50 to 60% by mass. It is. If the content of the non-volatile content in the solution is less than 40% by mass, the solution viscosity becomes low and coating becomes difficult, and the amount of the solvent to be volatilized increases. It is. When it exceeds 70% by mass, the viscosity of the solution is remarkably increased, resulting in poor handling. Moreover, the viscosity of a solution becomes like this. Preferably it is 1000-30000 mPa * s, More preferably, it is 2000-20000 mPa * s, More preferably, it is 3000-10000 mPa * s.

  In the present invention, the adhesive substance may be used alone or in the form of a mixture of two or more. Of these, acrylic polymers and star acrylic block polymers are preferred, and star acrylic block polymers are particularly preferred due to an excellent balance between adhesive strength and cohesive strength. In addition, the pressure-sensitive adhesive layer according to the present invention may be blended with a crosslinking agent, a tackifier, a softener, a plasticizer, an antioxidant, and the like as necessary. The crosslinking agent, tackifier, softener, plasticizer, and antioxidant that can be used as needed are not particularly limited, and known ones can be used in the same manner.

  Moreover, the adhesive substance may contain the conventionally well-known additive used for the adhesive agent for skin sticking as another additive. The adhesive substance is, for example, a plasticizer typified by a polyhydric alcohol such as glycerin, polyethylene glycol, or polypropylene glycol; a water-soluble or water-absorbing resin typified by polyacrylic acid, a cross-linked polyacrylic acid, or polyvinylpyrrolidone; It may contain a tackifier resin represented by rosin resin, terpene resin, petroleum resin; softener; filler; pigment and the like.

  When the adhesive for skin application according to the present invention is a polymer solution containing a solvent, the content of the nonvolatile content in the solution is preferably 40 to 70% by mass, more preferably 45 to 65% by mass, and still more preferably 50 to 50%. 60% by mass. If the content of the non-volatile content in the solution is less than 40% by mass, the solution viscosity becomes low and coating becomes difficult, and the amount of the solvent to be volatilized increases. It is. When it exceeds 70% by mass, the viscosity of the solution is remarkably increased, so that handling during coating is deteriorated. Moreover, the viscosity of a solution becomes like this. Preferably it is 1000-30000 mPa * s, More preferably, it is 2000-20000 mPa * s, More preferably, it is 3000-10000 mPa * s.

  In the present invention, the methylcyclodextrin iodine inclusion body used as an antibacterial agent dissolves in the same solvent used for forming an adhesive layer in conventional medical tapes such as methanol, ethanol, propylene glycol and the like. be able to. For this reason, the formation method in particular of the adhesion layer on a base material is not restrict | limited, A conventionally well-known method is applicable. Accordingly, the second aspect of the present invention includes the step of dissolving the methylcyclodextrin iodine clathrate in at least one solvent selected from the group consisting of methanol, ethanol and propylene glycol, and applying this solution to the substrate. The present invention relates to a method for producing the skin adhesive material of the present invention.

  In this invention, an adhesive layer is formed on a base material and a skin sticking material is manufactured. Here, the skin adhesive can be used in various applications where antibacterial properties are required. For example, a surgical drape, a bandage, a surgical tape, a dressing tape, a tape for fixing a long-term indwelling catheter, First-aid unit bandage, wound closure tape (Wound Closure Strip), and the like.

  In the present invention, the substrate may be in any form, but when used for medical applications such as a surgical covering (drape), bandage, surgical tape, etc., it is in the form of a tape or a sheet. Is preferred. The substrate is not particularly limited as long as the adhesive layer can be provided thereon, but preferably has moisture permeability for the purpose of skin adhesion.

  The material of the base material used in the present invention in the form of a tape or sheet is not particularly limited, and materials similar to those used in medical applications such as a conventional surgical covering (drape), adhesive bandage, and surgical tape are available. Can be used. Specifically, for example, urethane polymers such as polyurethane, polyether urethane, and polyester urethane; amide polymers such as polyamide and polyether polyamide block polymer; poly (meth) acrylic acid, poly (meth) acrylic acid ester, etc. (Meth) acrylic polymer; polyolefin polymer such as polyethylene, polypropylene, ethylene / vinyl acetate copolymer; polyester polymer such as polyester, polyether polyester, polyethylene terephthalate; polyvinyl chloride, polystyrene, polyacrylonitrile, polyacrylamide, Polyvinyl alcohol, polymaleic anhydride, polyethyleneimine, polyvinyl acetate, silicone resin, various latexes, copolymers and blends of these It is below. Among these, urethane-based polymers and amide-based polymers are preferable in that they have water vapor permeability.

  Or in this invention, you may use the conventionally well-known porous film which is water-vapor-permeable and water-impermeable as a base material. Specific examples of the substrate suitable for the porous film include porous plastic films made of polyolefin polymers such as polyethylene, polypropylene, and ethylene / vinyl acetate copolymers; papers, nonwoven fabrics, and the like.

  The base material may be composed of only one kind, or may be a laminate in which two or more kinds of base materials are laminated. The substrate can be selected in consideration of safety, ease of forming an adhesive layer, required mechanical properties (for example, rigidity and flexibility), moldability, laminating properties, sealing properties, and the like. .

  The thickness of the substrate is not particularly limited, and can be appropriately selected depending on the shape of the substrate and a desired application. For example, when the substrate is in the form of a tape or a sheet, the thickness of the substrate may be appropriately selected depending on the application, but is preferably 5 to 100 μm, more preferably 10 to 100 μm, and still more preferably 10 to 80 μm. Especially preferably, it is 20-60 micrometers.

An adhesive layer is formed on the substrate. At this time, the adhesive layer is formed as described above because the methylcyclodextrin iodine clathrate is dissolved in the same solvent (for example, methanol, ethanol, propylene glycol) as in the conventional case. . For example, (1) A method of preparing a pressure-sensitive adhesive solution by dissolving methylcyclodextrin iodine clathrate in a solvent, and applying this pressure-sensitive adhesive solution directly on a substrate and then drying; (2) in a solid state A method of blending raw materials and then applying to a substrate by a method such as calender coating; (3) A pressure-sensitive adhesive solution is prepared by dissolving methylcyclodextrin iodine inclusion body in a solvent, and this pressure-sensitive adhesive solution is used as a comma coater, etc. (4) A method in which a primer is first applied on a substrate to form an undercoat layer, and then an adhesive layer is indirectly formed thereon; (5) publicly known An adhesive layer is formed in the same manner as described above, and an appropriate amount of methylcyclodextrin iodine clathrate powder is added on the layer (preferably 0.01% relative to the nonvolatile content of the adhesive constituting the adhesive layer). ~ 5% by mass) Method of attaching (6) A method in which a pressure-sensitive adhesive layer is formed in the form of a two-layer laminate in the same manner as a known method, and a methylcyclodextrin iodine inclusion body is attached to the layer side in contact with the skin; and (7) Separately prepared adhesive solution after dissolving dextrin iodine inclusion body in the above solvent (preferably the solvent for dissolving methylcyclodextrin iodine inclusion body is compatible with the solvent for dissolving the adhesive) A pressure-sensitive adhesive mixture can be prepared by mixing with, and the pressure-sensitive adhesive mixture can be applied onto a release liner such as a release paper, dried, and then transferred to a substrate. Among the above methods, the above (5) and (6) can suppress the addition amount of the methylcyclodextrin iodine clathrate. The method of the above (7), since the viscosity sealable layer can be formed by one step, are preferably used.

In the above coating step, the solvent for dissolving the methylcyclodextrin iodine clathrate is required to be able to dissolve the methylcyclodextrin iodine clathrate and to have safety. For this reason, methanol, ethanol, Propylene glycol. Of these, methanol and propylene glycol are preferable, and methanol is most preferable. Further, the amount of the methylcyclodextrin iodine clathrate added to the solution is not particularly limited as long as it is an amount that can be dissolved in the solvent, and is adjusted to be within the range of the amount introduced into the adhesive layer as described above. It is preferable. For this reason, it is preferable that a methylcyclodextrin iodine inclusion body is melt | dissolved in the said solvent so that it may become a density | concentration of 1-50 mass%, More preferably, 10-40 mass%. Moreover, the coating method on the base material of the adhesive solution is not particularly limited, and a known coating method can be used. Specific examples include brush coating, dipping treatment, spin coating, bar coating, gravure coating, reverse loose coating, knife over roll coating, and a coating method using a comma coater or a lip coater. The application amount of the pressure-sensitive adhesive solution formed on the substrate is not particularly limited, and is appropriately selected so as to be in the range of introduction amount to the pressure-sensitive adhesive layer as described above, and considering the use and adhesion / tackiness. The Specifically, the amount is such that the thickness of the pressure-sensitive adhesive layer is preferably 5 to 100 μm, more preferably 10 to 100 μm, still more preferably 10 to 80 μm, and particularly preferably 20 to 60 μm. Under the present circumstances, when the thickness of the adhesion layer is less than 5 micrometers, there exists a possibility that sufficient skin sticking property cannot be exhibited. When the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, it becomes difficult for the entire skin adhesive material to exhibit sufficient water vapor permeability, and the problem of stuffiness and the problem of reduced skin adhesiveness during sweating tend to occur. In addition, after applying the adhesive solution on the substrate, a drying process is performed to evaporate the solvent. The drying conditions at this time are not particularly limited as long as the solvent is sufficiently evaporated and an adhesive layer can be formed. Although it can select suitably according to the kind and quantity of the solvent to be used, Preferably it is 50-150 degreeC, More preferably, it should just dry at 60-120 degreeC. The drying time varies depending on the length and equipment of the drying furnace, and is not particularly limited as long as the solvent is sufficiently evaporated to form a good adhesive layer.

  In the skin adhesive material according to the present invention, when the adhesive layer has the above star-shaped acrylic block polymer as an adhesive substance, the remaining amount of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms in the adhesive layer However, it is preferably 500 ppm or less, more preferably 400 ppm or less, still more preferably 300 ppm or less, particularly preferably 200 ppm or less, and most preferably 100 ppm or less, based on the total nonvolatile content. The skin adhesive material according to the present invention has a skin irritation property even when used for a long period of time because the residual amount of the (meth) acrylic acid alkyl ester having 7 to 17 carbon atoms in the adhesive layer is extremely small. This is because there is almost no balance between the adhesive force and the cohesive force.

  The adhesive layer thus formed on the substrate is wound around a core in the case of a long film with release paper attached to the adhesive layer side. Such a skin adhesive is generally sterilized with ethylene oxide or an electron beam (for example, γ-ray), particularly an electron beam. As described above, even if the skin adhesive material of the present invention is sterilized by an electron beam, cyclodextrin serves as a defense wall and prevents the electron beam from being hit. The iodine to be used can exhibit antibacterial properties over a long period of time without scattering.

  Hereinafter, the present invention will be described in more detail. In the following examples and comparative examples, unless otherwise specified, “parts” and “%” represent “parts by mass” and “mass%”, respectively.

  The characteristics used in the examples and comparative examples are measured and evaluated by the following methods.

[1] Specification measurement of pressure-sensitive adhesive composition (1) Viscosity The viscosity was measured at 25 ° C. using a B-type viscometer. The number of rotations was 12 rotations per minute.

(2) Nonvolatile content It was dried at 200 ° C. for 15 minutes in a hot air circulating dryer and calculated from the change in mass.

[2] Preparation method of test piece (1) For antibacterial test After coating the pressure-sensitive adhesive composition on one side so that the thickness after drying is 40 μm on a release paper (trade name SL70S, manufactured by Kite Chemical Industry Co., Ltd.) , Dried at 75 ° C. for 30 seconds in a hot air circulating dryer, further dried at 100 ° C. for 30 seconds in another adjacent hot air circulating dryer, and then 55 μm thick polyolefin film (MEDIFOL elastic plus 44538/99, manufactured by RKWAG) ) Was transferred to one side and left for a day and night to make an adhesive tape for antibacterial test.

(2) For test panel adhesion test On the other hand, a 55 μm-thick polyolefin film (MEDIFOL elastic plus 44538/99, manufactured by RKWAG) cannot be measured accurately because the substrate is too stretched. The material was changed to polyethylene terephthalate (hereinafter abbreviated as PET) having a thickness of 25 μm to produce an adhesive tape.

[3] Adhesive property test An evaluation test on the adhesive property of the skin adhesive was performed according to JIS Z 0237 according to the following method.

(1) Adhesive strength (180 degree peeling)
It was carried out in an atmosphere at a temperature of 23 ° C. and a relative humidity of 65%. A tape-shaped test piece having a width of 25 mm was placed on a bakelite plate as an adherend, and the test piece was attached by reciprocating once with a rubber roller having a weight of 2 kg. Twenty-five minutes after sticking, the strength was measured when one end of the test piece was peeled off in the 180 ° direction at a speed of 300 mm / min, and this was taken as the adhesive strength (N / cm). The adhesive strength is normal (indicated by “adhesive strength (N / cm) (180 degree peeling: initial)” in Table 1) and after 1 month storage at 50 ° C. (in Table 1, “adhesive strength (N / cm) ( 180 degrees peeling: 50 ° C. × 1 month) ”) was measured.

(2) Adhesive strength (90 degree peeling)
It was carried out in an atmosphere at a temperature of 23 ° C. and a relative humidity of 65%. Sandpaper (Nippon Kenshi Co., Ltd., WTCC-SP1000), which is an adherend, is fixed to a stainless steel plate with a double-sided tape, and a tape-shaped test piece with a width of 25 mm is placed on the test piece. Adhering was performed by reciprocating once with a rubber roller. Twenty-five minutes after sticking, the strength when one end of the test piece was peeled off at a speed of 200 mm / min in the 90-degree direction was measured, and this was defined as adhesive strength (N / cm).

  Adhesive strength is measured before electron beam irradiation (indicated by “adhesive strength (N / cm) (90 degree peeling: initial)” in Table 1) and after electron beam irradiation (in Table 1, “adhesive strength (N / cm) ( Two cases of “90 ° peeling: after sterilization”) were measured.

(3) Holding power It measured according to the following method about the PET film test piece produced by said [2] (2). A PET film test piece was attached to an SUS plate as an adherend in an atmosphere of a temperature of 23 ° C. and a relative humidity of 65% so that the area to be attached was 25 mm × 25 mm, and then the temperature was raised to 50 ° C. after 25 minutes. I left it. The time (hour) until the pressure-sensitive adhesive film dropped after applying a load of 1 kg after standing for 20 minutes, or the displacement (mm) of the pressure-sensitive adhesive film after 24 hours was measured. At this time, the smaller the measured value (the smaller the deviation width) is, the better the holding force is, the smaller the measured value (time) is.

(4) Ball tack The PET film test piece prepared in the above [2] (2) was measured according to the following method. The measurement was performed using an inclined ball tack apparatus in an atmosphere having a temperature of 23 ° C. and a relative humidity of 65%. The runway and the adhesive surface measurement part were each 100 mm, and the inclination angle was 30 °. The smaller the measured value (the smaller the ball), the worse the tackiness.

[4] Antibacterial test The antibacterial property of the skin adhesive was evaluated according to JIS Z 2801: 2000 (film adhesion method).

That is, the sample was sterilized by wiping with disinfecting ethanol and cut into a square of 25 mm × 27 mm. Separately, Staphylococcus aureus IFO No. 12732 was added to an SCDLP medium (concentration of about 3 × 10 ⁵ bacteria in 0.2 ml) at a concentration of 1,700,000 cells / ml. Antibacterial agent inactivation medium: JIS L1902: 1998) was inoculated to prepare bacterial solution 1. Similarly, Escherichia coli IFO No. 3972 is adjusted to a bacterial concentration of 1,400,000 cells / ml (concentration of about 2.5 × 10 ⁵ cells in 0.2 ml). Inoculated into SCDLP medium to prepare bacterial solution 2. The SCDLP medium was prepared by using 17.0 g of casein peptone, 3.0 g of soybean peptone, 5.0 g of sodium chloride, 2.5 g of dipotassium hydrogen phosphate, and glucose 2.1000 ml of purified water or ion-exchanged water. 5 g and 1.0 g of lecithin are weighed, mixed in a flask, and after the contents are sufficiently dissolved, 7.0 g of a nonionic surfactant is added and dissolved. This solution was prepared by adjusting with a sodium hydroxide solution or a hydrochloric acid solution so as to have a pH of 6.8 to 7.2 (25 ° C.), sterilizing by autoclaving, and then cooling to room temperature.

  Next, after inoculating 0.21 ml each of the bacterial solutions 1 and 2 in the petri dish, peeling the paper piece of the test piece and covering the petri dish so that the adhesive surface is in contact with the bacterial solution as widely as possible, The petri dish was capped and cultured at 35 ° C. for 24 hours in an incubator (FI-45 type, manufactured by Toyo Seisakusho). For petri dishes after 24 hours of culture, add 10 ml of SCDLP medium (antibacterial agent inactivation medium) per dish, wash out the bacteria, and colony counter (MC-707P type, Tokyo M.I.) by agar plate culture method. The viable cell count was measured using a commercial company. At this time, a test piece containing no antibacterial agent was used as a control. Moreover, about the petri dish immediately after seed | inoculating a microbe liquid, it carried out similarly to the above, and measured the viable cell count by the agar plate culture method.

  The antibacterial activity value was calculated from the above viable count according to the following formula, and when the antibacterial activity value was 2.0 or more, it was determined that there was antibacterial activity.

  In the above formula, A is the average number (number) of viable bacteria immediately after inoculation of the test piece not containing the antibacterial agent; B is the viable cell count after 24 hours of culturing the test piece not containing the antibacterial agent C is an average value (number) of the viable cell count after 24 hours culture of the test piece of the present invention containing an antibacterial agent.

[5] Measurement of iodine concentration After coating the pressure-sensitive adhesive composition on a release paper (trade name SL70S, manufactured by Kite Chemical Industry Co., Ltd.) so that the thickness after drying is 40 μm, it is 75 ° C. in a hot air circulating dryer. For 30 seconds, and further dried at 100 ° C. for 30 seconds in another adjacent hot air circulating dryer. Thus put the same release paper and the on viscosity adhesive layer formed by, which was used as a sample.

  The sample thus prepared (size: 10 cm × 10 cm) was immersed in methanol at room temperature for 2 hours to extract iodine, titrated by titration with iodine from an aqueous thiosulfate solution, and titrated for the iodine concentration in the adhesive. did.

[6] Storage stability After coating the pressure-sensitive adhesive composition on one side of a release paper (trade name SL70S, manufactured by Kite Chemical Industry Co., Ltd.) so that the thickness after drying is 40 μm, it is 75 ° C. in a hot air circulating dryer. For 30 seconds, and further dried at 100 ° C. for 30 seconds in another adjacent hot air circulating dryer.

Peeled Thus viscous adhesive layer formed by a release paper, which was used as a sample. The obtained pressure-sensitive adhesive tape (size: 10 cm × 25 cm) was put in an aluminum laminated polyfilm, heat-sealed and sealed, and then left in a constant temperature layer at 60 ° C. for 1 month. Then, it opened at room temperature and performed the adhesive physical property and iodine concentration titration. In this evaluation, the effectiveness of iodine is evaluated on the assumption that the skin adhesive material is stored and stored for a long period of time. For this reason, this evaluation was performed in a heating acceleration test at 60 ° C.

Production Example 1
1.1 stage polymerization: synthesis of intermediate polymer solution 24 parts of methyl methacrylate, dipentaerythritol-β- in a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel Mercaptopropionate (hereinafter abbreviated as DPMP) 1.2 parts and ethyl acetate 24.82 parts as a solvent were charged. The mixture was stirred under a nitrogen stream and maintained at 83 ± 2 ° C., and dimethyl 2,2′-azobis-2-methylpropionate (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd. (Abbreviated as 601) 0.048 parts and 0.432 parts of ethyl acetate as a dissolving solvent were added to initiate polymerization. 30 minutes after the start of the reaction, 56 parts of methyl methacrylate and 15.25 parts of ethyl acetate were added over 120 minutes, and the V-601 solution (0.084 parts of V-601, 2.8 parts of DPMP and 2.8 parts of ethyl acetate) The mixture was added dropwise over 90 minutes, and the reaction was carried out while controlling the internal temperature under reflux. After completion of the dropwise addition of methyl methacrylate, 2 parts of ethyl acetate was added, and the reaction was further continued for 130 minutes. Thereafter, a polymerization inhibitor solution (a mixture of 0.04 part of hydroquinone monomethyl ether and 0.36 part of ethyl acetate) and 38.431 parts of ethyl acetate for dilution were added and cooled, and the intermediate polymer solution (A1) for pressure-sensitive adhesive was added. Obtained. The obtained intermediate polymer solution (A1) had a non-volatile content of 34.5% and a viscosity of 90 mPa · s.

2.2 Stage reaction: Synthesis of polymer for pressure-sensitive adhesive Intermediate polymer solution obtained by the above reaction in a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel (A1) 33.02 parts, butyl acrylate 82.91 parts, 2-ethylhexyl acrylate 96.74 parts, acrylic acid 9.67 parts, tetraethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-200; hereinafter abbreviated as “TEGDA”) 0.02 part, and 150 parts of ethyl acetate as a solvent were charged. The mixture was stirred under a nitrogen stream and kept at 86 ± 2 ° C. to add a V-601 solution (a mixture of 0.165 parts of V-601 and 10 parts of ethyl acetate) as a polymerization initiator to initiate polymerization. 10 minutes after the start of the reaction, 77.05 parts of the polymer intermediate solution (A1), 193.46 parts of butyl acrylate, 225.74 parts of 2-ethylhexyl acrylate, 22.57 parts of acrylic acid, 0.04 part of TEGDA, vinyl acetate A monomer mixture consisting of 13.87 parts and 156 parts of ethyl acetate and a V-601 solution (V-601: a mixture of 0.395 parts and 40 parts of ethyl acetate) are added dropwise over 80 minutes and controlled under reflux. The reaction was carried out. 10 parts of ethyl acetate was added after completion | finish of dripping, and reaction was continued for further 60 minutes. Thereafter, a V-601 solution (a mixture of V-601: 3.36 parts and 40 parts of ethyl acetate) was added dropwise every 15 minutes as a booster, and the reaction was continued for 120 minutes under reflux. Thereafter, 247.3 parts of ethyl acetate was added as a diluting solvent, and the mixture was cooled to obtain a polymer solution for pressure-sensitive adhesive (B1). The obtained polymer solution (B1) had a nonvolatile content of 52.2% and a viscosity of 18360 mPa · s. The remaining 2-ethylhexyl acrylate was 256 ppm (vs. non-volatile content).

  Next, 10 parts of terpene phenol resin (YShara Chemical Co., Ltd .: YS Polystar T100) and ethyl acetate were mixed for viscosity adjustment with respect to 100 parts of the nonvolatile content of the polymer solution (B1) to obtain an adhesive composition (C1). . The obtained pressure-sensitive adhesive solution (C1) had a nonvolatile content of 48.0% and a viscosity of 7150 mPa · s.

Example 1
An MCDI solution was prepared by dissolving 10 g of methylated-β-cyclodextrin iodine clathrate (trade name: MCDI, effective iodine concentration of about 13%, manufactured by Niho Chemical Co., Ltd.) in 20 g of methanol. Next, an MCDI solution is added to the pressure-sensitive adhesive (C1) obtained in Production Example 1 so that the MCDI is 0.25% with respect to the non-volatile content of the pressure-sensitive adhesive (C1), and the mixture is sufficiently stirred. Thus, an MCDI-containing pressure-sensitive adhesive solution (D1) was obtained.

  After coating the MCDI-containing pressure-sensitive adhesive solution (D1) on a release paper (product name SL70S, manufactured by Kite Chemical Industries Co., Ltd.) so that the thickness after drying becomes 40 μm, it is 75 ° C. in a hot air circulating dryer. It was dried for 30 seconds, further dried at 100 ° C. for 30 seconds in another adjacent hot air circulating dryer, and then the adhesive composition was applied to one side of a 55 μm thick polyolefin film (MEDIFOL elastic plus 44538/99, manufactured by RKWAG). The adhesive tape (E1) was produced by transferring and allowing it to stand overnight. The pressure-sensitive adhesive properties of the pressure-sensitive adhesive tape (E1) thus obtained were evaluated, and the results are shown in Table 1 below.

  Moreover, the adhesive tape (E1) thus obtained was sterilized by electron beam irradiation and evaluated for antibacterial properties. The results are shown in Table 2 (antibacterial results against S. aureus) and Table 3 (antibacterial results against E. coli). In Tables 2 and 3 below, the experiment is performed in triplicate for each sample, and is described as the average number of viable bacteria. In addition, the electron beam irradiation was performed by JEOL Irradiation Service Co., Ltd. so that the irradiation intensity was 20, 40, and 60 kGy. The dose was adjusted by repeating 20 kGy / pass.

Examples 2-5
MCDI-containing pressure-sensitive adhesive solutions (D2) to (D5) were produced in the same manner as in Example 1 except that the amount of MCDI blended in Example 1 was changed as shown in Table 1. Next, adhesive tapes (E2) to (E5) were prepared using MCDI-containing adhesive solutions (D2) to (D5) in the same manner as in Example 1, and the adhesive physical properties of these adhesive tapes (E2) to (E5) were determined. evaluated. The obtained results are shown in Table 1.

  Further, in the same manner as in Example 1, the antibacterial properties of the adhesive tapes (E2) to (E5) were evaluated, and the obtained results are shown in Table 2 (antibacterial results against Staphylococcus aureus) and Table 3 (Escherichia coli). Antibacterial results).

Comparative Example 1
A comparative adhesive tape (E6) was prepared in the same manner as in Example 1 except that MCDI was not blended in Example 1, and adhesive physical properties before and after electron beam irradiation and antibacterial properties were tested in the same manner as in Example 1. went. The obtained results are shown in Table 1 (adhesive properties) and Table 2 (antibacterial results against Staphylococcus aureus) and Table 3 (antibacterial results against E. coli).

  From the results of Table 1 above, the skin adhesive materials (E1) to (E5) of the present invention exhibit the same adhesive properties as the skin adhesive material (E6) to which no methylcyclodextrin iodine inclusion body is added. From the above, the skin adhesive material of the present invention has excellent adhesive properties, particularly excellent adhesive properties, without decreasing the adhesive properties, particularly adhesive strength, even when methylcyclodextrin iodine inclusions are added as an antibacterial agent. It is shown that it can be demonstrated.

  From the results of Tables 2 and 3, antibacterial activity was not observed when the amount of MCDI added was 0.25% by mass, but at 0.5% by mass, the strength was 20 kGy, and more than 1.0% by mass was added. It can be seen that the amount shows sufficient antibacterial properties at any irradiation intensity. In addition, in medical applications such as surgical wraps (draps), bandages, and surgical tapes used in surgical operations, the strength of 20 kGy is generally used in the sterilization process. In use, it is considered that 0.5 mass% or more is sufficiently put into practical use.

Production Example 2
1.1 Stage Polymerization: Synthesis of Intermediate Polymer Solution Production Example 1 In the same manner as described above, an intermediate polymer solution (A1) was produced.

2.2 Stage reaction: Synthesis of polymer for pressure-sensitive adhesive Intermediate polymer solution obtained by the above reaction in a four-necked flask equipped with a thermometer, stirrer, inert gas introduction tube, reflux condenser and dropping funnel (A1) 60.9 parts, butyl acrylate 34.46 parts, 2-ethylhexyl acrylate 136.02 parts, acrylic acid 8.98 parts, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-200; hereinafter abbreviated as “TEGDA”) 0.09 part, and 170 parts of ethyl acetate as a solvent were charged. The mixture was stirred under a nitrogen stream and kept at 86 ± 2 ° C., and the polymerization was initiated by adding a V-601 solution (a mixture of 0.336 parts of V-601 and 10 parts of ethyl acetate) as a polymerization initiator. 10 minutes after the start of the reaction, 142.1 parts of the polymer intermediate solution (A1), 220.8 parts of butyl acrylate, 163.23 parts of 2-ethylhexyl acrylate, 20.95 parts of acrylic acid, 13.77 parts of vinyl acetate, TEGDA A monomer mixture consisting of 0.21 part and 176 parts of ethyl acetate and a V-601 solution (a mixture of 0.784 part of V-601 and 40 parts of ethyl acetate) were added dropwise over 80 minutes, while controlling under reflux Reaction was performed. 10 parts of ethyl acetate was added after completion | finish of dripping, and reaction was continued for further 60 minutes. Thereafter, a V-601 solution (a mixture of 3.36 parts of V-601 and 40 parts of ethyl acetate) was added dropwise every 30 minutes as a booster, and the reaction was continued for 120 minutes under reflux. Thereafter, 100 parts of ethyl acetate was added as a diluting solvent and cooled to obtain a polymer solution for pressure-sensitive adhesive (B2). The obtained polymer solution (B2) had a nonvolatile content of 52.8 and a viscosity of 6170 mPa · s. The remaining 2-ethylhexyl acrylate was 424 ppm (vs. non-volatile content).

  Subsequently, 10 parts of terpene phenol resin (YShara Chemical Co., Ltd .: YS Polystar T100) and ethyl acetate were mixed for viscosity adjustment with respect to 100 parts of the nonvolatile content of the polymer solution (B2) to obtain an adhesive solution (C2). The obtained pressure-sensitive adhesive solution (C2) had a nonvolatile content of 52.2% and a viscosity of 5120 mPa · s.

Example 6
An MCDI solution was prepared by dissolving 30 g of methylated-β-cyclodextrin iodine inclusion body (trade name: MCDI, effective iodine concentration of about 13%, manufactured by Niho Chemical Co., Ltd.) in 70 g of methanol. Next, the MCDI solution is added to the pressure-sensitive adhesive solution (C2) obtained in Production Example 2 so that the MCDI is 2.5% with respect to the non-volatile content of the pressure-sensitive adhesive (C2). An adhesive (isopropyl myristate) was blended so as to be 2% based on the non-volatile content of the adhesive, and was sufficiently stirred to obtain an adhesive solution (D7). Next, an adhesive tape (E7) was produced in the same manner as described in Example 1 using the adhesive solution (D7).

  In addition, the adhesive tape (E7) thus obtained was sterilized by electron beam irradiation so that the irradiation intensity was 20 and 40 kGy. Thus, the adhesive tape (E7) which sterilized by electron beam irradiation measured the adhesive physical property together with the unirradiated thing. The results are shown in Table 4. In this example, in the above [3] (2) Adhesive strength (90-degree peeling), the above [ 3] Adhesive properties were evaluated in the same manner as the test method described in (2) Adhesive strength (90-degree peeling).

Example 7
A pressure-sensitive adhesive solution (D8) was produced in the same manner as in Example 6 except that the amount of MCDI blended in Example 6 was changed to 7.5% by mass. Then, to prepare a pressure-sensitive adhesive tape (E8) using a pressure-sensitive adhesive solution (D8) in the same manner as in Example 1, this pressure-sensitive adhesive tape (E8), was measured in the same manner stickies with Example 6. Table 4 shows the obtained results.

Example 8
A pressure-sensitive adhesive solution (D9) was produced in the same manner as in Example 6 except that the amount of MCDI blended in Example 6 was changed to 15% by mass. Then, to prepare a pressure-sensitive adhesive tape (E9) By using the pressure-sensitive adhesive solution (D9) in the same manner as in Example 1, this pressure-sensitive adhesive tape (E9), were measured in the same manner stickies with Example 6. Table 4 shows the obtained results.

  From the results of Table 4 above, it is shown that the skin adhesive materials (E7) to (E9) of the present invention can exhibit sufficient adhesive properties even if the amount of iodine added is large.

  In addition, from the above results, the skin adhesive materials (E7) to (E9) of the present invention are sufficiently put to practical use for medical applications such as surgical covers (drapes), bandages and surgical tapes used in surgical operations. It is considered.

Claims (3)

A methyltransferase cyclodextrin iodine Mototsutsumi Settai and adhesive material adhesive layer containing the bonded skin becomes provided on a substrate Chakuzai as an antimicrobial agent, the adhesive substance is a chain polymer portion of at least three A plurality of star-shaped structures extending radially around a mercapto group are connected to each other by a chain polymer portion, and 50 to 100% by mass of all the structural units of the polymer portion has 7 to 17 carbon atoms ( A skin adhesive material, which is a star-shaped acrylic block polymer which is a structural unit of an alkyl ester of (meth) acrylic acid . Amount of methyl cyclodextrin iodine Mototsutsumi Settai is, with respect to the nonvolatile content of the pressure-sensitive adhesive constituting the adhesive layer 0. Skin adhesive material according to 01 to 20% by mass Ru請 Motomeko 1. Dissolved in at least one solvent selected from methyl cyclodextrin iodine Mototsutsumi Settai the group consisting of an adhesive substance methanol, ethanol and propylene glycol, have a step of applying the solution to a substrate, In the adhesive substance, a plurality of star-shaped structures in which at least three chain polymer parts extend radially around a mercapto group are connected to each other by a chain polymer part, and all the structural units of the polymer part The skin adhesive material according to claim 1 or 2, wherein 50 to 100% by mass of the polymer is a star-shaped acrylic block polymer which is a (meth) acrylic acid alkyl ester structural unit having 7 to 17 carbon atoms . Production method.