KR101112050B1 - composition of polyurethane hydrogel for medical use - Google Patents

Abstract

The present invention provides a polyurethane hydrogel composition comprising a polyurethane prepolymer, a polyol, and a crosslinking agent, wherein the polyurethane prepolymer is 3-15 wt%, the polyol 10-50 wt%, and the acrylic acid starch copolymer is 0.5-10 wt%. It relates to a composition for preparing a medical polyurethane hydrogel, which is composed of water.

Polyurethane hydrogel prepared from the composition of the present invention is colorless, odorless, transparent, no toxic to the human body, and has a gelling property that can be post-processed in the form of a film, the polyurethane hydrogel can be continuously produced in a film form. .

By providing a polyurethane hydrogel film in the form of a roll (roll) there is an advantage that can be used as a material of automated production.

Polyurethane prepolymer, crosslinking agent, acrylic acid starch copolymer, medical polyurethane hydrogel

Description

Composition of Polyurethane Hydrogel for Medical Use

The present invention relates to a composition for producing a hydrogel (polyurethane hydrogel) of medical polyurethane that can be used to treat wounds by attaching to human skin. The composition of the present invention has the property of continuously molding a polyurethane hydrogel into a film. The composition of the present invention has an advantageous gelling time for producing a film, and the polyurethane hydrogels prepared with this composition exhibit a characteristic of having a water absorption rate suitable for wound healing. Polyurethane hydrogel prepared by the composition of the present invention is applied to the care of skin, protection of damaged skin, as a carrier of the active ingredient as a material for the production of plaster, cataplasma, patch Can be used.

The colloidal solution is called sol, the solidification of the sol into the jelly phase is called gel, and the phenomenon that the sol is converted into gel is called gelation. The time required for conversion to this gel is called gelation time, and it can be subdivided into gel start point and gel completion point according to the gelation process. The gel start point is the point where the sol fluidity is significantly reduced, and the gel completion point is solidified, It is time to complete.

The dispersion medium of the gel is to be contained in the solid bone irradiated, water is contained between the skeleton is called a hydrogel, that is, hydrogel (hydrogel).

Hydrogels made of high molecular materials have recently been spotlighted as a replacement for biological gels. Research into bioreplacement materials such as soft contact lances, artificial grass itself, and artificial joints has been actively conducted.

Hydrogel is a swelling gel that sucks water, and is a two-component aggregate in which a polymer, which is a three-dimensional network structure as a gel-forming material, absorbs a medium (water). Therefore, in the open system, the solvent may migrate and transpire, so that the initial physicochemical properties cannot be maintained due to changes over time.

Polyurethane hydrogel has the advantage of maintaining the properties of the gel for a long period of time in the open system by maintaining the polymer (mesh) and some chemical bonding state of the network structure.

Many methods have already been proposed for the preparation of medical polyurethane hydrogels.

U.S. Patent No. 5,106,629 discloses a polymer for wound treatment by uniformly mixing 12 wt% of isophorone diisocianate terminated prepolymer, 17 wt% of propylene glycol, 9 wt% of polyethylene oxide diamine, 1 wt% of salt, and 61 wt% of water. A method for preparing a urethane hydrogel is described. In addition, U.S. Patent No. 6,861,067 discloses a mixture of 10 g of prepolymer composed of isophorone diisocyanate and 10 g of polyethylene glycol, and a mixture of 10 g of furopropylene glycol, 0.5 g of polyethylenediamine and 30 g of water, and then poured into a mold. A method of producing a polyurethane hydrogel by standing for 90 minutes and gelling is described.

When the composition is to produce a polyurethane hydrogel in the form of a film, it is possible to obtain a thin plate by pouring thinly in the mold and left for a certain time to gelate, and because it contains excess moisture in the composition, there is a limit to additional moisture absorption There is.

US Patent No. 6,960,625 discloses a polyol having three hydroxyl groups, a copolymer of ethylene oxide / propylene oxide having 75% ethylene oxide and 25% propylene oxide, and adding 20 ppm of phosphoric acid to a polyol having a molecular weight of 7000. The polyol 1687.47 g and isophorone di 165.0 g of isocyanate was heated at 70 ° C. for 14 days to prepare a prepolymer, and the gelation time was 55 sec to 120 sec by uniformly mixing 5 wt% of the prepolymer, 94.8 to 94.96 wt% of water, and 0.2 to 0.04 wt% of polyethyleneimine or ethylenediamine. A method for producing a phosphorus polyurethane hydrogel is described.

However, the polyurethane hydrogel prepared by the above method is characterized in that the gelation occurs even though a large amount of water is contained, and thus is suitable for the production of fragrances because it has the ability to gradually evaporate moisture contained in the open system.

In the conventional polyurethane hydrogel, in terms of water absorption rate and absorption rate, when used for medical purposes, when a large amount of skin exudate is generated, it may be difficult to handle this. Therefore, in this field, it was necessary to develop a polyurethane hydrogel that can further increase the water absorption rate and absorption rate.

Korean Patent No. 10-0846141 discloses a medical polyurethane hydrogel having 3-15 wt% of polyurethane prepolymer, 10-50 wt% of polyol, 0.5-15 wt% of polymethoxyethylene maleic acid, 0.5-10 wt% of organic amine, and the remainder being composed of water. A composition for preparation and a method for continuously producing a polyurethane hydrogel film are described. The polyurethane hydrogel film produced by this method has superior properties in terms of absorption rate and absorption rate.

)을 갖는 고분자 물질로서 반응을 원활히 진행시키기 위하여 아민계 화합물을 촉매로 사용하는 것이 일반적이다.Polyurethane is a urethane bond obtained by reacting a polyol and an isocyanate compound (

It is common to use an amine compound as a catalyst in order to smoothly proceed the reaction as a polymer material having a).

In order to facilitate the polyurethaneization reaction, first, a polyol is reacted with a diisocyanate compound to prepare an oligomer in which a part of the functional group of the diisocyanate is a urethane bond with the polyol, and the oligomer is a polyurethane prepolymer. It is called.

In order to prepare a polyurethane hydrogel, a gel is formed by reacting the polyurethane prepolymer with another polyol, which is a chain extender, and water and an organic amine, if necessary.

That is, organic amines are commonly used to promote the urethane reaction in the process of preparing a polyurethane hydrogel. Organic amines used herein are called reaction catalysts or crosslinkers.

The organic amine compounded in the above-mentioned invention is mix | blended for the purpose of promoting the gelation reaction as a crosslinking agent. As a theory well known in the art for the use of a crosslinking agent, it has a reactive functional group and can increase the reaction rate of several tens to tens of thousands depending on the type and quantity thereof. Reactive functional group means active hydrogen in the molecule of the crosslinking agent that can react with the unreacted isocyanate group of the prepolymer, and the active hydrogen group includes hydroxyl group (-OH), mercaptyl group (-SH), amino group (-NH2), etc. May be included.

Organic amine is an irritating substance that emits ammonia odor and is highly corrosive to metals and easily absorbed by the human body through skin.

Therefore, the polyurethane hydrogel containing the organic amine has a problem that not only has a bad effect on the human body when used for medical use, but also has a large corrosiveness to a manufacturing facility.

 In preparing the polyurethane hydrogel of the present invention, in view of safety, the organic amine used in the conventional polyurethane hydrogel is an irritant substance having basic irritation and absorbing properties through the skin, Since it is classified as a dangerous substance according to the Health Law, it is difficult to handle it with strict standards.

In this field, it is necessary to find a crosslinking agent that can maintain the required gelation reaction rate without being irritating like organic amines.

In addition, aromatic diisocyanates such as toluene diisocyanate, metaphenylene diisocyanate, etc. may be classified by the International Cancer Research Organization (IARC) as a group 3 carcinogen (unclassifiable substance for human carcinogenicity). Medical polyurethane prepolymers are not preferred and it is suitable to use polyurethane prepolymers using isophorone diisosinate which is an alicyclic compound.

SUMMARY OF THE INVENTION An object of the present invention is to provide a medical polyurethane hydrogel that is capable of rapidly absorbing body fluids such as wound exudates when applied to human skin, thereby preventing local invasion caused by excessive presence of exudates, while not irritating the human body.

In preparing a medical polyurethane hydrogel, it is important to explore a crosslinking agent that promotes an equivalent gelation reaction without using an organic amine.

The present inventors used starch grafted acrylate copolymer instead of organic amine which is generally used as a gelling reaction accelerator in urethane reaction of diisocyanate pure polymer and polyol which is a chain extender in water. When the polyurethane hydrogel was prepared by addition, it was confirmed that there is an action to promote the gelation reaction with organic amines, thereby completing the present invention.

Starch Grafted Acrylate Copolymer is a mild substance with no irritation, and the present invention using the same has also confirmed that a polyurethane hydrogel having an absorption rate and an absorption rate capable of absorbing moisture exuded from a skin wound to an appropriate level is formed. .

Polyurethane hydrogel prepared by the polyurethane hydrogel composition of the present invention has a feature that can quickly absorb body fluids, such as wound exudate to prevent a local infiltration phenomenon due to the excessive presence of the exudate, while maintaining a suitable wet atmosphere.

Polyurethane hydrogel prepared from the composition of the present invention is colorless, odorless, transparent, no toxic to the human body, and has a gelling property that can be post-processed in the form of a film, the polyurethane hydrogel can be continuously produced in a film form. .

By providing a polyurethane hydrogel film in the form of a roll (roll) there is an advantage that can be used as a material of automated production.

The polyurethane hydrogel composition of the present invention is a composition for producing a medical polyurethane hydrogel which exhibits a gelation reaction rate equivalent to that of an organic amine without using an organic amine as a urethane reaction accelerator.

The polyurethane hydrogel composition of the present invention has an appropriate water absorption and absorption rate, and is particularly advantageous for continuously preparing a polyurethane hydrogel in a film form with a gel starting point of 60 seconds or less.

In order to continuously manufacture a polyurethane hydrogel in a film form, the gelation rate is a very important factor. The gelation rate can be expressed as the gel starting point and the gel completion point. The gel initiation point is the point at which the sol fluidity is remarkably reduced, and the gel completion point is the point at which the gel is solidified. . When the polyurethane hydrogel is continuously produced in the form of a film, if the gel start point is too fast, there is a difficulty in uniformly mixing the components, and if the gel start point is too late, the polyurethane hydrogel is continuously formed on a substrate that proceeds continuously in the coating machine for film production. Even after coating the gel composition with uniform thickness, it is difficult to maintain its shape as it is sol state until it reaches the gel starting point, and it may be out of the base, requiring sophisticated mechanism to solve this problem. There is discomfort. When the polyurethane hydrogel is continuously produced in the form of a film, if the gel completion point is too fast, there is an obstacle in forming the film, and the coated polyurethane hydrogel causes stress such as shrinkage, swelling, and collapse, resulting in a uniform film shape. If it is difficult to achieve and the gel completion point is too late, the gel is deformed due to external pressure, so that it cannot be wound onto a roll until the gel completion point is reached. It is necessary to adjust the coating speed so that the winding process proceeds, but if the coating speed is too slow, continuous work is impossible. The gelation reaction rate for continuously preparing the polyurethane hydrogel in the form of a film is preferably 30 seconds to 1 minute at the gel start point and 1 to 10 minutes at the gel completion point. More preferably, the gel completion point is suitable for 2 to 5 minutes.

When explaining the present invention in more detail 3-15 parts polyurethane polyurethane, 10-50 parts polyol. 0.5 to 10 parts of acrylic acid starch copolymer was added to make 100 parts.

Polyurethane pure polymer As used herein, a hydrophobic segment is isophorone diisocyanate, and the hydrophilic part is an oxyethylene (-CH ₂ CH ₂ -O-) and oxy-furo propylene _{(-CH 2 CH 2 CH 2 -O-} ) a copolymer Polyoxyalkylpolyols having a hydroxyl group of 2 to 3 and having a molecular weight of 2000 to 7000 were reacted with a ratio of about 3: 7, and one isocyanate group was modified with a urethane bond and 0.3 to 0.9 m eq / g. Polyols are chain expending agents that bind to the -NCO moiety of a polyurethane prepolymer to form a net skeleton. As the water-soluble polyhydric alcohol serving as), any one capable of achieving this purpose can be used. In more detail, for example, propylene glycol, butylene glycol, glycerol, polyethylene glycol, and the like or sugar alcohols such as sorbitol, chisiritol, mannitol, or the like can be used alone or in combination, but is not limited to those listed above. Starch grafted acryrate copolymer is produced by graft polymerization of acrylic acid on starch. It is a super absorbent material and used as a water absorbent, a viscosity enhancing agent, or a swelling agent. It is a well known non-toxic substance.

Polyurethane hydrogel of the present invention has an active free energy because it is composed of a large molecular structure of a network containing water, and when used as a carrier of the active ingredient capable of transdermal absorption, it is possible to control the dissolution rate by the designed time dependence. There is this. According to the purpose of use in the polyurethane hydrogel of the present invention, in order to prevent the disinfection and further infection of the wound, a bactericidal component, local anesthetic component, analgesic anti-inflammatory component, irritant component for local action, and also percutaneous absorption theory of the drug. It is possible to formulate a pharmacological ingredient capable of systemic action based on, and the formulation of such a medicinal ingredient does not limit the scope of the present invention.

In preparing the polyurethane hydrogel of the present invention, additives such as dyes, flavoring surfactants, dissolving aids, thickeners, defoamers, PH adjusting agents, tonicity preservatives, and antioxidants can be added as necessary. It is not limiting.

The present invention will be described in detail with reference to the following Examples.

Example 1

Prepolymer having -NCO content of 0.4 m eq / g made of isophorone diisocyanate and three hydroxyl groups in the molecule and copolymerization of 75:25 of oxyethylene and oxyfuropropylene and molecular weight of 7000 (Polymer Hypo G50 of Dow Chemical, USA) 5g, 20g of propylene glycol, 5g of acrylic acid starch copolymer (trade name SANWET IM 300 of Sanyokasei Co., Ltd.) and 70g of water were stirred and mixed for 20 seconds at 40 ° C at 3000rpm. The gel start point and gel completion point were measured immediately after obtaining the gel composition, and the values thereof were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below. The acrylic acid starch copolymer has a molar ratio of starch and acrylic acid of 1: 4. In this embodiment, the polyoxyalkylpolyol is suitably selected and used in the range of molecular weight 2000 ~ 7000.

Example 2

A mixture of 5 g of the prepolymer of Example 1, 20 g of polyethylene glycol having a molecular weight of 400, 5 g of acrylic acid starch copolymer (trade name SANWET IM 300 of Sanyo Kasei Co., Ltd.) and 70 g of water was operated in the same manner as in Example 1 to prepare a polyurethane hydrogel composition. Immediately after the gel start and gel completion point was measured and the values were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Example 3

A mixture of 5 g of the prepolymer of Example 1, 10 g of propylene glycol, 10 g of polyethylene glycol having a molecular weight of 400, 5 g of acrylic acid starch copolymer (trade name SANWET IM 300, manufactured by Sanyokasei Co., Ltd.) and 70 g of water was operated in the same manner as in Example 1. The gel initiation point and gel completion point were measured immediately after obtaining the urethane hydrogel composition, and the values thereof were as shown in Table 1 below. In addition, it was placed in a container so that the thickness is 2.0 mm and left for 1 day to measure the absorption rate, the values were as shown in Table 2 below.

The acrylic acid starch copolymer (SANWET IM 300) used in Examples 1 to 3 is a sodium salt whose molar ratio of starch and acrylic acid is 1: 4. The acrylic acid starch copolymer used in the present invention may be selected from a molar ratio of starch and acrylic acid of 1: 4 to 5 and an alkali metal salt thereof.

In order to compare the effect of the acrylic acid starch copolymer provided in the present invention, the same Comparative Examples 1) to 3) were performed except that the acrylic acid starch copolymer was not used. In addition, Comparative Examples 4) to 6) using an organic amine (trade name Voranol RA 640 of Dow Chemical Co., Ltd.) were used instead of the acrylic acid starch copolymer.

Comparative Example 1

Prepolymer having -NCO content of 0.4 m eq / g made of isophorone diisocyanate and three hydroxyl groups in the molecule and copolymerization of 75:25 of oxyethylene and oxyfuropropylene and molecular weight of 7000 A mixture of 5 g, 20 g of propylene glycol, and 75 g of water was stirred and mixed at 40 ° C. at 3000 rpm for 20 seconds to obtain a polyurethane hydrogel composition. The gel initiation point and gel completion point were measured immediately. The values were as described in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Comparative Example 2

A mixture of 5 g of the prepolymer of Comparative Example 1, 20 g of polyethylene glycol having a molecular weight of 400, and 75 g of water was operated in the same manner as in Comparative Example 1. A polyurethane hydrogel composition was obtained, and the gel initiation point and gel completion point were measured immediately. It was as described in Table 1. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Comparative Example 3

A mixture of 5 g of the prepolymer of Comparative Example 1, 10 g of propylene glycol, 10 g of polyethylene glycol having a molecular weight of 400, and 75 g of water was operated in the same manner as in Comparative Example 1. The gel initiation point and gel completion point were measured immediately after obtaining the polyurethane hydrogel composition, and the values thereof were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Comparative Example 4

Pre-NCO content of 0.4 m eq / g made of isophorone diisocyanate and 3 hydroxyl groups in the molecule, copolymerization of 75:25 of oxyethylene and oxyfurophilene and made of polyoxyalkylpolyol of molecular weight of 7000 Polyurethane hydrogel by stirring and mixing a mixture of 5 g of a polymer (trade name Hypol G50 of Dow Chemical, USA), 20 g of propylene glycol, 3 g of organic amine (trade name Voranol RA 640 of Dow Chemical, USA) and 72 g of water at 40 ° C. at 3000 rpm for 20 seconds. The gel starting point and gel completion point were measured immediately after obtaining the composition, and the values thereof were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Comparative Example 5

A mixture of 5 g of the prepolymer of Comparative Example 4, 20 g of polyethylene glycol having a molecular weight of 400, 3 g of an organic amine (trade name Voranol RA 640 of Dow Chemical, USA) and 72 g of water were operated in the same manner as in Comparative Example 4. The gel initiation point and gel completion point were measured immediately after obtaining the polyurethane hydrogel composition, and the values thereof were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

Comparative Example 6

A polyurethane hydrogel composition was prepared by operating a mixture of 5 g of prepolymer of Comparative Example 4, 10 g of propylene glycol, 10 g of polyethylene glycol having a molecular weight of 400, 3 g of an organic amine (trade name Voranol RA 640 of Dow Chemical, USA), and 72 g of water as in Comparative Example 4. The gel starting point and gel completion point were measured immediately, and the values were as shown in Table 1 below. In addition, in order to measure the absorption rate it was placed in a container so that the thickness is 2.0 mm and left for 1 day. Absorption measurement values were as described in Table 2 below.

The present inventors devised a test method which is extremely simple and field compatible for measuring the gelation rate, ie the gel start point and gel completion point. If you explain this in detail

Example 1) to 3) and Comparative Examples 1) to 6) to measure the gel starting point, and the composition of each of the polyurethane hydrogel obtained here was immediately placed 1.0 g each on a glass plate, and set up at a right angle after a predetermined time. The time at which the tip of the composition does not flow down 10 mm or more is calculated from the time point of mixing the composition.

In order to measure the gel completion point, Examples 1) to 3) and Comparative Examples 1) to 6) were carried out, and the composition of each of the polyurethane hydrogels obtained here was immediately placed in a flat bottomed container so that the thickness was 5 mm and After elapse of, a steel disc of about 25 mm in diameter was placed thereon, and when 0.1 Kg / Cm 2 of a non-base was added, the time at which deformation did not occur in the pressed portion of the composition was measured based on the time of mixing the composition.

Table 1 Gelation Rate

                                               Unit: second

Gel start point Gel completion point Example 1 40 240 Example 2 45 300 Example 3 40 250 Comparative Example 1 - - Comparative Example 2 - - Comparative Example 3 - - Comparative Example 4 120 300 Comparative Example 5 120 420 Comparative Example 6 120 360

In Comparative Examples 1, 2 and 3, even after 10 minutes (600 seconds) or more, the gel initiation point and the gel completion point did not appear.

In Examples 1, 2, and 3 in the above experimental example, it can be seen that the gel start point was significantly shortened as compared with the comparative examples of Comparative Examples 4, 5 and 6. This is considered to have an effect in addition to the action to promote the urethane reaction because the viscosity increases when the acrylic acid starch copolymer is mixed with water. It is presumed that the acrylic acid starch copolymer promotes the urethanation reaction and thus acts as a crosslinking agent that activates the H atom of the -OH group present in the starch molecule among the components of the copolymer to promote the urethanation reaction.

      In order to measure the water absorption, Examples 1) to 3) and Comparative Examples 1) to 6) were carried out, and each polyurethane hydrogel film obtained here was cut into 20 mm X 25 mm, weighed precisely, and immersed in water. It is shown in Table 2 to calculate the percentage (%) of absorption / time by measuring the increase in weight over time.

[Table 2] Water content according to immersion time

                                                   unit : %

5 minutes 10 minutes 15 minutes 20 minutes 25 minutes 30 minutes Example 1 55.5 85.6 91.4 110.7 126.3 140.5 Example 2 45.5 70.4 86.1 90.8 96.1 100.7 Example 3 54.6 84.4 88.9 108.9 123.9 142.2 Comparative Example 1 - - - - - - Comparative Example 2 8.7 10.5 15.2 17.0 19.4 20.0 Comparative Example 3 - - - - - - Comparative Example 4 12.8 19.0 24.7 29.4 32.5 35.5 Comparative Example 5 8.5 12.4 16.7 18.5 21.7 22.8 Comparative Example 6 10.1 14.1 19.0 21.4 23.5 25.9

However, if it did not reach the gel completion point after 24 hours or more, it was excluded from the test.

<Production of Polyurethane Hydrogel Film>

In the method of continuously producing the polyurethane hydrogel of the present invention in a film form, a coating machine capable of producing a film can be usually used. The polyurethane hydrogel composition (e) of Example 1 was continuously fed to a compression roller (f-1, f-2) while stirring mixing at 3000 rpm for 20 seconds at 40 ° C. in the mixing head (d). At this time, one side of the compression roller (f-1) is installed a release paper (b) released with silicone, the other (f-2) is installed a waterproof woven fabric (c), and then adjusted so that the gap is 0.3mm extruded Applied. At this time, in order to prevent the composition from being insufficient or overflowing at both ends, it could be performed smoothly by adjusting the supply amount of the composition (e) or by adjusting the coating speed. At this time, the traveling speed of the coating machine was about 3m / min.

After passing about 3 minutes (gel completion point) in this state, the winding roll (g) shown in FIG. 2 was obtained by winding the roller through the delivery rollers (h-1, h-2). The polyurethane hydrogel film obtained here becomes a sheet inserted between the release paper (e) and the woven fabric (c). When the release paper (b) is separated, the polyurethane hydrogel film adhered to the woven fabric (c) ( a) can be obtained. This woven fabric may be used as it is or by separating the woven fabric therein, a polyurethane hydrogel film having a thickness of 0.3 mm can be collected.

In FIG. 1, "→" shows a moving direction of a material.

1 is a schematic view showing a process for producing the polyurethane hydrogel of the present invention in a film form.

2 is a state in which a polyurethane hydrogel film made of the composition of the present invention is wound in a roll.

Explanation of symbols on the main parts of the drawing

a: polyurethane hydrogel film

b: release paper

c: waterproof fabric

d: mixing head

e: polyurethane hydrogel composition

f-1, f-2: Compression roller

g: Roll of polyurethane hydrogel film

h-1, h-2: Transmission roller

i, j: guide roller

Claims (3)

A polyurethane hydrogel composition composed of a polyurethane prepolymer, a polyol, and a crosslinking agent, wherein the isophorone diisocyanate and three hydroxyl groups in the molecule have a copolymer of 75:25 of oxyethylene and oxyfuropropylene and have a molecular weight of 2000 to 7000. Polyurethane prepolymer made of phosphorus polyoxyalkyl polyol -NCO content 0.3 ~ 0.5 meq / g polyurethane prepolymer 3 ~ 15wt%, polyol 10 ~ 50wt%, acrylic starch copolymer 0.5 ~ 10wt%, the remainder is composed of water Gel Preparation delete The composition of claim 1, wherein the polyol is selected from propylene glycol or polyethylene glycol or mixtures thereof.

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