KR20030048716A - Composition of Polyurethane Polymer Containing Hydrophilic Polymer Having Active Compounds for Adhesion and Preparation Method Thereof - Google Patents

Abstract

PURPOSE: A polyurethane-based adhesive composition containing a pharmacologically active hydrophobic material encapsulated with a hydrophilic polymer, an antimicrobial agent and a deodorant is provided. Therefore, the composition maintains pharmacological activity for a long period of time and also has removal and reduction effects on a smell, moisture and bacteria when applied to the skin or a wound site. CONSTITUTION: A polyurethane-based adhesive composition contains 35 to 60% by weight of a polyurethane, 0 to 0.2% by weight of imidazolidinyl urea, 20 to 40% by weight of an encapsulated pharmacologically active material and additionally 6 to 21% by weight of a spherical porous material and/or 1.3 to 2.6% by weight of an antimicrobial agent and/or 4.2 to 7.9% by weight of a deodorant.

Description

Composition of Polyurethane Polymer Containing Hydrophilic Polymer Having Active Compounds for Adhesion and Preparation Method Thereof}

The present invention relates to an adhesive polyurethane polymer adhesive comprising a thermoplastic polyurethane and an adhesive resin, and more particularly, contains a pharmacologically active substance, an antimicrobial substance and a deodorizing substance and can perform a high adhesive function on an adherend. It relates to an adhesive polyurethane polymer composition.

In general, medical supplies, cosmetics, environmental pollution prevention facilities, and electrical and electronic industries, surface protection, effective material transfer, contamination prevention, shock absorption, deodorization of contaminated gas, and certain liquids while maintaining adhesion to the adherend for a certain period of time. There is a need for an adhesive having functions such as adsorption and blocking bacterial propagation.

In particular, adhesives used as medical supplies protect the affected areas from external irritation and pollutants and require effective properties for bacterial propagation and prevention of secondary contamination. Therefore, adhesive products have been used in patients who need regular dressing after surgery to attach or fix an adhesive made by applying an acrylic synthetic adhesive material and / or a natural rubber adhesive material on natural fibers to the affected part. However, these products are applied to the natural fibrous material with a material having a high adhesion for the continuous adhesion, because of the high adhesive force when removing the adhesive from the affected area, the problem of peeling the skin or hair root and hair detachment occurred .

In addition, in patients with anus obstruction due to the development of colorectal cancer or colorectal cancer (commonly referred to as "ostomy patient"), it is a common surgical procedure to make a human intestine by making an incision in the lower abdomen. A bowel bag is used to receive bowel movements, and patients should wear it permanently. In particular, the skin of the lower abdomen with protruding phosphorus is exposed to a number of strains including sweat, digestive fluid, stool, urine, and E. coli parasitic parasites. Many problems arise. In order to attach such a luteal sac to the skin, a synthetic or natural adhesive is applied to the surface of the luteal sac adhered to the skin, and the adhesive-coated luteal sac is adhered to the periphery of the lower abdominal stoma of the stoma patient for defecation. In this case, when the worn-out ruyong sac is removed, a skin peeling phenomenon occurs, a wound may occur, and a problem may occur such that an adhesive remains on the skin.

Meanwhile, in the cosmetics industry, products for applying or adhering cellulose, vinyl monomers, and polymers produced from natural or synthetic substances to parts of the face or body for skin beauty have been used, which function as cells by exfoliating epidermal cells on the skin surface. It has been used for the purpose of removing the layer existing as a tissue that stops or preventing the drying of the epidermis to increase the moisturizing effect and absorb some of the cosmetic ingredients under the epidermal layer of the skin. However, products designed to adhere to the skin has a problem that you need to wash off with water or remove from the skin. The purpose of overcoming this problem is to develop and use a low-adhesive product, but these products are easy to remove, but there is a problem that is easily detached by the user's physical activity.

Although various adhesive compositions such as single polymer and semisynthetic polymer have been developed for the purpose of solving the above problems, few of them are completely satisfactory for human skin. Accordingly, a polyurethane polymer based on polyurethane foams produced by mixing a blowing agent, a surfactant and a catalyst with a polyether polyol and a polyester polyol and reacting with an isocyanate has been developed to solve the above problems. Development of a medical pressure-sensitive adhesive with high adhesion to human skin has been made using Korean Patent Publication No. 2000-0069881.

Korean Patent Application No. 2001-0029524 describes a method for preparing a polyurethane containing a pharmacologically active substance, and a method for preparing an adhesive for use in the form of a solvent using polyether, polyester polyol and isocyanate is disclosed in Korea Patent Application. No. 1996-0016329. Meanwhile, Korean Patent Application No. 2000-706437 describes a method of preparing a polymer including a polydimethylsiloxane structure by reacting an -OH group and an isocyanate of a polylactone block. However, the above known inventions have a hydrophobic group in themselves, so that the organic substances discharged from the adherend, in particular in the human body, can effectively absorb and / or absorb sweat, fatty acids and salts from the skin glands or pores. The problem is inadequate to eliminate.

In addition, in the case of an adhesive made of a polymer containing a pharmacologically active substance, when the active substance is delivered to the adherend, it is not easy to control the rate of delivery and the pharmacological activity rapidly decreases after a predetermined time. There is this.

The present invention was derived to solve the above problems, using a pharmacologically active material encapsulated with a hydrophilic polymer containing -OH group, a spherical porous material and / or an antimicrobial agent, adhesive polyurethane polymer containing a deodorant as an adhesive As a result, the hydrophilic polymer is modified while the polymer performs the adhesive function, and the pharmacologically active substance is eluted from the blood adhesive and transferred, and the sweat and secretions generated from the skin and organic substances generating specific odors are absorbed and removed. It provides a polyurethane polymer composition comprising.

The present invention also provides a polyurethane polymer composition that maintains pharmacological activity for a long time by encapsulating the pharmacologically active substance.

In addition, the present invention provides a method for preparing a polyurethane polymer composition for adhesion.

The adhesive polyurethane polymer composition of the present invention is characterized in that it comprises 35 to 60% by weight of polyurethane polymer, 0 to 0.2% by weight of imidazolidinylurea and 20 to 40% by weight of encapsulated pharmacologically active substance. do.

The adhesive polyurethane polymer composition of the present invention comprises 35 to 60% by weight of polyurethane polymer, 0 to 0.2% by weight of imidazolidinylurea and 20 to 40% by weight of encapsulated pharmacologically active substance and 6 to 9% by weight. Spherical porous material of, optionally 1.3 to 2.6% by weight of the antimicrobial agent and / or 4.2 to 7.9% by weight of the deodorant.

In the preparation of the polyurethane polymer composition according to the present invention, (1) the pharmacologically active substance is encapsulated with a hydrophilic polymer, (2) a polyol, isocyanate and other additives are mixed and stirred in a separate reactor, and (3) the A method for producing an adhesive polyurethane polymer composition is prepared by mixing and stirring the mixture prepared in (1) in the step (2).

In the preparation of the polyurethane polymer composition according to the present invention, (1) the pharmacologically active substance is encapsulated with a hydrophilic polymer, (2) the prepared capsule and the antimicrobial agent and deodorant, and (3) a polyol in a separate reactor, Isocyanate and other additives are mixed and stirred, and (4) a method for producing an adhesive polyurethane polymer by mixing and stirring the mixture prepared in the above (2) in the step (3).

In general, polyisocyanates having urethane groups formed of polyalcohols and diisocyanates have been known for a long time. When a polymer is prepared by reacting polyalcohol and diisocyanate, an excess of diisocyanate may be used to produce a polyisocyanate polymer having an isocyanate free group. The use of excess polyalcohols produces polyurethanes having —OH groups, which are important materials for the manufacture of lacquers and adhesives.

As described above, in preparing a polyurethane polymer composition by reacting a polyol such as polyalcohol and an isocyanate with each other, an additive such as an encapsulated pharmacologically active substance, an antimicrobial agent, a deodorant, etc. may be added to exhibit pharmacological activity. Polyurethane polymer composition to which the twill and the deodorizing function are added can be prepared.

The polyol is an all-hydrogen compound having an active hydrogen component capable of participating in a reaction and including a material having an average of one or more hydroxyl groups per molecule, the molecular weight of preferably 500 to 5,000, most preferably 600 to 2,000 It has an average molecular weight. Such polyol materials are polyester-, polyether- or polycarbonate diols, hydroxyl-terminated polybutadiene, hydroxyl-terminated polysiloxanes, more specifically polymerizable such as mixtures of polyester polyols and polyether polyols Polyols such as these large polyols and polyester polyols, polyhydroxy polyester amides, hydroxyl group-containing polycaprolactones, hydroxyl group-containing acrylic polymers, hydroxyl group-containing epoxy and hydrophobic polyalkylene ether polyols can be used. .

However, it should not be overlooked that the polyols may be used alone or in combination of two or more.

Suitable polyether diols, on the other hand, can be prepared by reacting at least one alkylene oxide containing 2 to 4 carbon atoms in a alkylene radical with a starting material containing hydrogen atoms bonded to two active groups. Suitable alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide, preferably ethylene oxide, propylene oxide and 1,2 A mixture of propylene oxide and ethylene oxide is preferred. Examples of suitable starting materials are water, amino alcohols such as N-alkyl-diethanolamine (eg N-methyl-diethanolamine) and diols (eg ethylene glycol, 1,3-propylene glycol, 1 , 4-butanediol and 1,6-hexanediol). Other suitable polyether diols are the polymerization products of tetrahydrofuran containing hydroxyl groups. Trifunctional polyethers in a ratio of 0 to 30 weight relative to the difunctional polyether may be used, but the maximum amount should be such that a thermoplastically processable product is obtained. Such linear polyether diols may be used alone or in the form of a mixture of two or more.

For example, suitable polyester diols, dicarboxylic acids containing from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms, can be prepared from polyhydric alcohols. Suitable dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. These dicarboxylic acids may be used alone or in the form of mixtures, for example mixtures of succinic acid, glutaric acid and adipic acid. For the preparation of polyester diols instead of dicarboxylic acids the corresponding dicarboxylic acid derivatives, for example carboxylic acid diesters, carboxylic anhydrides or carboxylic acids containing 1 to 4 carbon atoms in the alcohol radical It may be advantageous to use chlorides. Examples of polyhydric alcohols are glycols containing 2 to 10, preferably 2 to 6 carbon atoms, for example ethylene glycol, diethylene glycol, 1,4-butadiol, 1,5-pentanediol, 1, 6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1, 3-propanediol and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or in a mixture of two or more. Furthermore, esters of carbonic acid and the diols, in particular of 1,4-butanediol or 1,6-hexanediol, containing 4 to 6 carbon atoms, of hydroxycarboxylic acids, for example of hydroxycaproic acid Materials that include condensation products and polymerization products of lactones such as optionally substituted caprolactone are suitable. Polyester diols which are preferably used are ethanediol polyadipate, 1,4-butanediol polyadipate, 4-butanediol polyadipate, 1,6-hexanediol-neopentyl glycol polyadipate and polycaprolactone. Polyester diols may be used alone or in the form of a mixture of two or more.

In the present invention, since the hydrophilic component is extremely limited, it is added to the polyol of the constituent components having a preservative ability to impart antiseptic power, the component that can impart such preservatives, benzoic acid and its salts, paraoxybenzoic acid ester, It can be added to chemical products such as salicylic acid and salts thereof, but can be used only for raw materials that are less harmful to human body. In particular, the imidazolidinyl urea is recommended.

The imidazolidinyl urea is also referred to as "Germall 115" and is usually used at a concentration of 0.1 to 0.5%, the solubility of water 200%, glycerin 100%, IPA 0.05%, ethyl alcohol 0.05%, ethylene glycol 150% and propylene glycol About 120%. On the other hand, imidazolidinyl urea having the aforementioned properties is a preservative used stably in a wide range of pH, and is mainly used for the sterilization of Gram-positive bacteria and Gram-negative bacteria in chemical products.

Isocyanates of the present invention refer to isocyanates for use in polyurethane foaming mechanisms, and are known to those skilled in the art as di- and polyisocyanates having excess isocyanates available for reaction with addition polyols and prepolymers of polyols and isocyanates. Contains "prepolymers" that are known. The above-mentioned isocyanate is a component which improves the reactivity in the preparation of the adhesive polyurethane polymer according to the present invention, and the polymer suitable for use is particularly easy from the basic polymer containing two or more isocyanate-reactive functional groups, preferably -OH groups in the polymer molecule. Can be manufactured. The required functional groups can be attached particularly easily to the basic polymers by reaction with polyisocyanates or suitable functionalized monoisocyanates. Substances having such an effect include monomer isocyanates and / or polyisocyanates including 1 to 4 -NCO groups, and preferably, toluene diisocynte (TDI) and diphenylmethane 4,4 'diisocyanate (MDI) alone or two. The above can be mixed and used. Here, MDI may be pure MDI, natural MDI, synthetic MDI, and the like, and these may be used alone or in combination of two or more thereof.

The encapsulated pharmacologically active substance of the present invention is mixed with the polyurethane polymer to slowly elute the pharmacologically active substance to the adherend. These encapsulated pharmacologically actives comprise 2 to 6% by weight of pharmacologically active substance per weight of total encapsulated pharmacologically active substance, 4.1 to 11.5% by weight of chain extender and chains used in the chain stretching reaction to modify the hydrophilic polymer. 51 to 66% by weight hydrophilic polymer with a hydrophilic group modified by a chain extension reaction.

The material encapsulated by the stretching reaction is called a sustained release formulation, which is uniformly dispersed in the polyurethane polymer composition to deliver the pharmacologically active substance to the adhesive. Most of these sustained-release preparations contain inorganic substances, which are generally hydrophobic. Therefore, when the hydrophobic inorganic pharmacologically active substance is coated with a hydrophilic polymer, the hydrophobic pharmacologically active substance that is poorly absorbed due to poor water solubility is gradually eluted to the skin when the adhesive is adhered to the skin, especially sweat, moisture, and the like. To be able to exercise.

On the other hand, the materials used in the chain stretching reaction to modify the hydrophilic polymer (hereinafter referred to as "chain extender") are polyhydric alcohols, diols, amines, diamines, amino alcohols having a molecular weight of 50 to 500, preferably 2 to 14 Diols containing 2 carbon atoms, for example ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and 1,4-butadiol. In particular, preferably diols such as glycerin, polyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, 1,3-butylene glycol, 1,4-butanediol or Amines such as polyhydric alcohols, triethanolamine, 1,5-naphthalenediamine, 4,4'-methylene-bis (2-chloroaniline) may be used, and may be used alone or in combination of two or more compounds.

As the hydrophilic polymer modified by the chain stretching reaction, any of polymers originating in natural polymers, polymers originating in semi-synthetic polymers and those originating in synthetic polymers may be used. Herein, polymers derived from natural polymers, for example, guar gum, locust bean gum, queen's seed, carrageenan, galactan, arabic gum, tragiant gum, pectin, mannan, starch xanthan gum, dextrin, succinoglucan, caffeine, Hyaluronic acid, gelatin, casein, albumin and collagen and semisynthetic polymers such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methylhydroxypropyl cellulose, soluble Starch, carboxymethyl starch, methyl starch, argin propylene glycol ester, argin and synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene oxide, Ethylene oxide, propylene oxide block may be used alone or in combination of two or more.

Other additives other than the above polyols, isocyanates, imidazolidinylureas and encapsulated pharmacologically active substances, ie spherical porous materials, antimicrobials and deodorants, are added to the adhesive polyurethane polymer composition to perform certain functions.

The spherical porous material is a powder having adsorption capacity, the size of which is generally spherical or plate-shaped having a diameter of 1 to 100㎛. These spherical porous materials are uniformly distributed in the polyurethane polymer together with the encapsulated sustained-release preparation to adsorb foreign substances having the size of odor, salt, moisture and / or molecular units generated from the adhesive. It is preferred to add 6 to 9% by weight of.

The spherical porous materials used for the above-mentioned uses include activated carbon, kaolin, calcium carbonate, magnesium carbonate, silica, powder, porous silica beads, porous cellulose powder, porous talc, porous nylon powder, titanium dioxide, and mica alone or two or more. Can be used in combination.

The pharmacologically active substance may be used by encapsulation, but may be dispersed and used in a polyurethane polymer together with the spherical porous substance without encapsulation. Such pharmacologically active materials may be incorporated into the pores of the spherical porous material and dispersed in the adhesive polyurethane polymer composition of the present invention.

The above-mentioned pharmacologically active substance is absorbed by the human body, shows activity as a therapeutic agent, and can be carried out as a preventive measure against invading pathogens, and has anti-thrombotic or antibacterial effects, anti-inflammatory and analgesic substances, and aromatherapy. Natural flavors and the like can be used. However, the present invention is not particularly limited. In particular, the natural fragrance, which is a temperature-sensitive active ingredient, generally exhibits an unstable property at a temperature of 80 to 150 ° C. generated during the formation of a polymer, which is encapsulated by a stretching reaction and mixed with a spherical porous material. When accompanied by improved thermal stability it is possible to maintain a sustained sustained release.

In addition to the pharmacologically active substance encapsulated, as an organic / inorganic antimicrobial substance that can be used evenly distributed in the polyurethane polymer together with the pharmacologically active substance encapsulated by the chain stretching reaction according to the present invention, ciprofloxacin and phosphomycin And 0.5 to 5% by weight, preferably 1.3 to 2.5% by weight, based on the total amount of the total composition.

In addition, in addition to the pharmacologically active substance encapsulated by the stretching reaction according to the present invention and the spherical porous material having excellent adsorption capacity, the organic and inorganic deodorant may be dispersed in the polyurethane polymer to improve the deodorizing power. Any organic or inorganic deodorant can be used as long as it has a deodorizing power. Specifically, inorganic materials such as silicon, aluminum, magnesium, zinc-based composite oxides, zinc, and copper are supported on titanium oxide. It is good to use after making.

The chain extender and the isocyanate which are used in the preparation of the adhesive polyurethane polymer for bonding according to the present invention and the hydrophilic polymer and the chain extender reaction can control the properties of the polyurethane polymer prepared according to the mixing ratio. Therefore, a molar ratio of polyol and chain extender is suitable for a molar ratio of 1: 1 to 1:12, and a molar ratio of isocyanate to polyol is preferably 1: 1 to 30: 1. In particular, molar ratios of preferably 2: 1 to 12: 1 ratio of polyol and isocyanate are preferred.

The adhesive polyurethane polymer according to the present invention can be prepared without a catalyst. However, in some cases it may be possible to use catalysts. The catalyst is generally used in amounts of up to 100 ppm relative to the total amount of starting material. Suitable catalysts according to the invention are conventional tertiary amines known in the art, for example triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpyrazine, 2- (dimethylamino Organometallic compounds, especially esters of titanic acid, iron compounds, tin compounds, for example tin diacetate, tin dioctaate, as well as -ethoxy) -ethanol, diazabicyclo- (2,2,2) -octane, etc. , Tin dilaurate, or dialkyl tin salt of aliphatic carboxylic acid. Particularly preferably, dibutyltin diacetate and dibutyltin dilaurate are good, and the amount thereof may be sufficient catalyst amount if it is about 1 to 10 ppm.

Other additives and auxiliaries may be added together with the aforementioned polymers and catalysts, as suitable examples include internal lubricants such as fatty acid esters, metal soaps, fatty acid amides, silicon compounds, fusion inhibitors, inhibitors, hydrolysis, light, heat and taracks. Stabilizers, flame retardants, colorants, pigments and inorganic or organic fillers and reinforcing agents. Here, the internal lubricant functions as a solvent for controlling the adhesion of the final product and has the property of leaving no residue after removing the adhesive from the object, and the usable material is not limited to the fatty acid ester. As the ester compound of fatty acid and glycerin, any of oils, liquid hydrocarbons, higher fatty acids, higher alcohols and esters existing in liquid phase at room temperature can be added as liquids. Usable reinforcing agents also include fibrous reinforcing agents such as inorganic fibers prepared according to the prior art. More detailed information on these additives and auxiliary substances is described in the expert literature [J.H. Saunders, K. C. Frisch: "High Polymers", Volume XVI, Polyurethane Parts 1 and 2, Interscience Publishers 1962 and 1964; R. Gachter, H. Muller (Eds.): Taschenbuch der Kunststoff-Additive, 3rd Edition, Hanser Verlag, Munich 1989 or DE-A 29 01 77].

Hereinafter, the manufacturing method of the adhesive polyurethane polymer composition according to the present invention will largely include the following steps.

Iii) encapsulating the hydrophobic inorganic powder (pharmacologically active substance) with a hydrophilic polymer;

Ii) mixing the antimicrobial and deodorant into the capsule prepared in step iii);

Iii) mixing and stirring the polyol, isocyanate and other additives; And

Iii) adding and stirring the mixture of step ii) during the process of step iii) or adding and stirring the mixture of step iii) during the process of step ii).

Here, the antimicrobial agent, deodorant, and other additives may be added or omitted depending on the required function. In addition, a catalyst may be added to facilitate the reaction in step iii), and if the deodorizing function is not required, the reaction may be performed without the deodorant.

Hereinafter, the method for preparing the polyurethane polymer composition will be described in more detail.

Step iii) can be divided into the process of supporting the active material and the modification process of the hydrophilic polymer, the active material supporting step encapsulates the pharmacologically active material in the hydrophilic polymer to be effective for inorganic powders having a porous structure or a large specific surface area. It is to adsorb a substance containing a factor. On the other hand, the modification process of the hydrophilic polymer is to modify the hydrophilic polymer into polyhydric alcohols separately from the process of supporting the active substance, which encapsulates the surface of the hydrophobic inorganic powder in which the modified hydrophilic polymer carries the active substance and performs a polyurethane polymerization reaction. It prevents the loss of the active material in and serves to add adhesion to the completed composition. In the process of reforming the hydrophilic polymer can be used as a catalyst of the reforming reaction using deionized purified water.

Mixing methods commonly used in the active material supporting step of the above-mentioned step iii) and the modification process of the hydrophilic polymer use a shaker or homogenizer, and in the case of a shaker, the stirring speed is 300 to 3000 rpm, preferably 600 to 1500 rpm. Stir for 20 minutes and stir for 1 to 10 minutes at 500 to 2000 rpm, preferably 800 to 1300 rpm for homogenizer. At this time, the reaction temperature is room temperature, the relative humidity is not more than 80% in consideration of the nature of the hydrophilic polymer to absorb the moisture in the air.

The encapsulated product of step ii) may be added with antimicrobial agents, deodorants and necessary ingredients in the range usefully used in the present invention, and the addition method is the same as the mixing method using the shaker or homogenizer described in step iii). .

The step of mixing and stirring the polyol, isocyanate and other additives of the step iii) is carried out in the same manner as the step iii), in the case of a shaker 2 to 20 at a stirring speed of 1000 to 3000rpm, preferably 1200 to 1500rpm Stirring for minutes, preferably for 1000 to 2500 rpm, preferably 1200 to 2000 rpm for 1 to 10 minutes for homogenizers.

In the above-described method for preparing the adhesive polyurethane polymer composition, each manufacturing step is independent, so that the final product may be obtained by adding a mixture produced from another manufacturing step to each independent manufacturing step.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

<Example 1>

0.11 g of fragrance was added to the reactor, and talc and mica 9 g in a 1: 1 ratio were added to the reactor and stirred at 500 rpm at room temperature. Then, 28.8 g of carboxyl vinyl polymer (Carbopol, BF Goodrich, USA), a hydrophilic polymer modified with polyhydric alcohol, was added to the mixture, followed by stirring at 1000 rpm for about 20 minutes. Material) 0.22g and 4.95g of inorganic deodorant (mixture of anico m601 and m602, Korea Aiko Industry) were added dropwise to the reactor and stirred for 5 minutes to encapsulate the hydrophobic inorganic powder containing the active material with a hydrophilic polymer.

45 g of polyol containing 0.1 to 0.5 wt% of the total amount of stabilizer, extender, pigment and blowing agent was added to a separate reactor and stirred at 100 rpm for 2.25 g of fatty acid ester and 9 g of isocyanate and stirred at 500 rpm for about 5 minutes. . A mixture of the hydrophobic inorganic powder encapsulated with a hydrophilic polymer was added to the stirred mixture, followed by solidification by stirring at 700 rpm for 5 minutes to obtain a self-adhesive polyurethane polymer composition containing the active material according to the present invention. As used herein, the term "self-adhesiveness" refers to a property of having a lower adhesive strength than normal adhesion but adheres easily to the surface of the skin or the object to be adhered, and leaves no residue when the adhesive is removed.

In addition, the said composition is shown in Table 1.

<Example 2>

The same procedure as in Example 1 was carried out, except that the composition was carried out according to the composition of Example 2 described in Table 1.

Polyurethane Polymer Composition Ratio Composition Example 1 (% by weight) Example 2 (% by weight) Comparative Example 1 (% by weight) Comparative Example 2 (% by weight) Polyol 45.0 30 83.2 66.6 Imidazolidinyl urea 0.2 0.2 0.2 0.2 Spices 0.1 0.1 - - Allantoin 0.2 0.2 - - Talc 4.5 3 - - Mica 4.5 3 - - Polyhydric alcohol 1.8 6 - - Hydrophilic polymer 22 34 - - Antimicrobial 2.6 1.3 - - deodorant 7.9 4.2 - - Fatty acid ester 2.2 3..0 - - Isocyanate 9 15 16.6 33.2

A comparative example for comparing the adhesive polyurethane polymer composition according to the present invention with the adhesive polyurethane polymer composition not including the pharmacologically active substance and other additives is as follows.

Comparative Example 1

The procedure was carried out in the same manner as in Example 1, but the composition was carried out according to the composition of Comparative Example 1 described in Table 1.

Comparative Example 2

The procedure was carried out in the same manner as in Example 1, but the composition was carried out according to the composition of Comparative Example 1 described in Table 1.

In order to effectively exhibit the properties of the polyurethane composition according to the present invention, the following experiment was conducted with respect to Examples 1, 2, Comparative Example 1 and Comparative Example 2.

Experimental Example 1

Hygroscopic experiment.

Experimental Example 1 is for the polyurethane composition prepared according to the present invention to test the absorption and adsorption of organic substances, the obtained product prepared by the above Examples and Comparative Examples were each the same weight of 12g 8cm in width It was prepared as a specimen in the form of a plate. The specimen was fixed at the same interval as the surface of the water in the constant temperature water tank inside and outside and kept at a temperature of 60 ℃. It was taken out of the constant temperature water bath every 2 hours and the amount of water absorbed per unit time was measured. At this time, the weight was measured at the same time in order to reduce the error due to the evaporation of water vapor formed on the surface of the specimen taken out of the constant temperature water tank.

The results are shown in Table 2. As can be seen from Table 2, the weight by moisture absorption in Example 1 was increased to 118.2%, 160.8% in Example 2, 25% and 15.7% in Comparative Example 1 and Comparative Example 2 compared to the initial weight . This result is considered to be the result of the absorption by the hydrophilic polymer and the adsorption power of low hydrophobic components in the porous inorganic powder.

Experimental Example 2

Deodorization experiment.

This experiment is to test the decomposition and deodorization of the organic material of the prepared polyurethane composition, the specimen prepared in the form of 3cm × 12cm size of each obtained by the same amount of 15g prepared by the above Examples and Comparative Examples A plurality of were prepared. Then, 25% pure ammonia (NH ₃ ) was diluted with distilled water to prepare a 3000 ppm standard solution. 5 g of each standard solution was injected into each prepared 2000 cc sealed glass reactor, and each prepared specimen was fixed in the reactor so as not to come into contact with the ammonia standard solution. The ammonia concentration of each reactor was measured using GV-100S of Japan Gastec, and the results are shown in Table 3.

Experimental Example 3

Adhesion test.

After the specimen was prepared in the same manner as in Experimental Example 1, the specimen was attached to the upper right side of the lower abdomen of five males aged 20 to less than 30 years. Then, the specimen was removed, and then the surface of the skin was washed with a neutral detergent and dried to remove moisture. The same experiment was conducted several times. The results are shown in Table 4.

Experimental Example 4

Skin Evaluation Experiment.

After preparing the specimen in the same manner as in Experimental Example 1, by attaching the specimen on the upper right side of the lower abdomen of five men over 20 years old and less than 30 years old, and then removing the specimen again, the skin fit, the skin pain and adhesive residue when removing the specimen Was evaluated and the results are shown in Table 5.

Here, the evaluation criteria of skin fit, skin pain upon removal and residual pressure of the adhesive is as follows.

Skin Wear

Excellent and no stimulus: 4 points

No problem other than slight irritation: 3 points

Normal: 2 points

Severe irritation: 1 point

Skin pain when removed

When pain is eliminated at all: 4 points

If there is no problem other than slight pain: 3 points

If you have moderate pain: 2 points

Very painful case: 1 point

Adhesive Residual Rate

If no residue at all: 4 points

Slightly remaining: 3 points

When residues are present within 10%: 2 points

1 point if residue is present within 30%

Hygroscopic test result time Example 1 (g) Example 2 (g) Comparative Example 1 (g) Comparative Example 2 (g) Initial weight 12.1 12.0 12.0 12.1 2 hours later 14.2 14.6 12 12 4 hours later 16.2 16.9 13 13 6 hours later 18.1 19.0 13 13 8 hours later 20.3 21.2 13 13 10 hours later 22.6 23.4 14 13 12 hours later 23.8 25.4 14 14 14 hours later 24.7 27.8 14 14 16 hours later 25.4 29.9 14 14 18 hours later 26.4 31.3 15 14

Deodorization test results Example 1 (ppm) Example 2 (ppm) Comparative Example 1 (ppm) Comparative Example 2 (ppm) Initial concentration 420 420 420 420 1 hour later 180 190 370 370 6 hours later 130 140 350 360 12 hours later 90 100 340 350 24 hours later 50 60 330 340 48 hours later 30 40 330 340

Adhesion Test Results Washings (times) Example 1 Example 2 Comparative Example 1 Comparative Example 2 One ○ ○ △ × 5 ○ ○ △ × 10 ○ ○ × × 15 ○ ○ × × 20 ○ ○ × × 25 ○ ○ × × 30 ○ △ × × 35 ○ △ × × 40 △ △ × ×

[○: Good, △: Somewhat insufficient, ×: Poor]

Skin Evaluation Experiment Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Skin fit 3.9 3.0 2.3 1.9 Skin pain when removed 4.0 4.0 3.8 3.8 Adhesive Residual Rate 3.9 4.0 4.0 4.0

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the exemplary embodiments described above are to be understood as illustrative in all respects and not as restrictive. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the appended claims and their equivalents, rather than the detailed description, are included in the scope of the present invention.

The polyurethane polymer according to the present invention includes a pharmacologically active substance encapsulated with a hydrophilic polymer, an antimicrobial agent and a deodorant, so that the encapsulated pharmacologically active substance having sustained release upon use of the polyurethane polymer is slowly eluted to the adherend, and thus the pharmacologically active substance. Not only can it be maintained for a long time, but it is also applied to the skin where water, salts and fatty acids are released or wounds where many bacteria grow to remove and / or reduce odors, moisture and bacteria. Can be.

In addition, by encapsulating the hydrophobic inorganic active material with a hydrophilic polymer, it is possible to more easily adhere to the hydrophilic adherend.

In addition, when the polyurethane polymer according to the present invention is removed from the adhesive, there is an effect that the adhesive does not remain on the surface of the adhesive.

Claims (13)

A polyurethane adhesive composition for adhesion comprising 35 to 60 wt% polyurethane polymer, 0 to 0.2 wt% imidazolidinylurea and 20 to 40 wt% encapsulated pharmacologically active material. The method of claim 1, The polyurethane polymer is an adhesive polyurethane polymer composition, characterized in that synthesized from 30 to 45% by weight of a polyol having a primary hydroxyl group and 9 to 15% by weight of isocyanate. The method of claim 1, 6 to 21% by weight of the spherical porous material and / or 1.3 to 2.6% by weight of the antimicrobial agent and / or 4.2 to 7.9% by weight of the deodorant adhesive polyurethane polymer composition. The method of claim 1, The encapsulated pharmacologically active substance comprises 2 to 6% by weight of pharmacologically active substance, 4.1 to 11.5% by weight of chain extender, 51 to 66% by weight of hydrophilic polymer, based on the total encapsulated pharmacologically active substance. Adhesive polyurethane polymer composition. The method according to claim 1 or 4, The encapsulated pharmacologically active material is an adhesive polyurethane polymer composition, characterized in that encapsulated by the chain stretching reaction of the chain extender and hydrophilic polymer. The method according to claim 4 or 5, The polyurethane polymer composition for adhesion, characterized in that the pharmacologically active substance is aromatherapy-based natural fragrance, ciprofloxacin and fosfomycin. The method according to claim 4 or 5, The hydrophilic polymers are guar gum, locust bean gum, queen's seed, carrageenan, galactan, gum arabic, tragiant gum, pectin, met, starch xanthan gum, textine, succinoglucan, caffeine, hyaluron, gelatin, casein, albumin , Methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methylhydroxypropyl cellulose, soluble starch, carboxymethyl starch, methyl starch, arginpropylene glycol ester, poly Adhesive polyurethane polymer composition comprising a vinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene oxide, ethylene oxide and propylene oxide block alone or a mixture of two or more. The method according to claim 4 or 5, The chain extender is a polyhydric alcohol, diol, amine, diamine, amino alcohol and / or ethanediol having a molecular weight of 50 to 500, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-butadiol, Glycerin, polyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, 1,3-butylene glycol, triethanolamine, 1,5-naphthalenediamine, 4,4 ' -Adhesive polyurethane polymer composition, characterized in that methylene-bis (2-chloroaniline) consists of a single or a mixture of two or more. The method of claim 3, wherein The spherical porous material is activated carbon, kaolin, calcium carbonate, magnesium carbonate, silica, powder, porous silica beads, porous cellulose powder, porous talc, porous nylon powder, titanium dioxide and mica-based adhesives characterized in that the mixture alone or two or more Polyurethane polymer composition for use. Iii) encapsulating the pharmacologically active substance into a hydrophilic polymer; Ii) mixing and stirring the polyol, isocyanate and other additives; And Iii) a method of preparing a polyurethane polymer composition for adhesion, comprising the step of adding and stirring the mixture of step iii) during the process of step ii). The method of claim 10, Method for producing a polyurethane adhesive composition for adhesion characterized in that it further comprises mixing the antimicrobial agent and deodorant in the capsule prepared in step iii). A polyurethane adhesive for adhesion comprising 35 to 60 weight percent polyurethane polymer, 0 to 0.2 weight percent imidazolidinylurea and 20 to 40 weight percent encapsulated pharmacologically active substance. According to claim 12, The adhesive polyurethane polymer medicament further comprising 6-21 wt% spherical porous material and / or 1.3-2.6 wt% antibacterial and / or 4.2-7.9 wt% deodorant.