KR100924273B1 - Antimicrobial Polyurethane Resin Composition and Method for Preparing It - Google Patents

Abstract

The present invention relates to a polyurethane resin composition and a method for producing the antimicrobial polyurethane resin, characterized in that it comprises a guanidine-based antimicrobial agent which is a low toxicity organic antibacterial agent covalently bonded to the polyurethane resin and excellent antimicrobial and antimicrobial persistence. The present invention can be used as an antimicrobial material such as food packaging materials, cosmetic containers, stationery and toys that require the maintenance of freshness of vegetables and meat, while retaining the basic characteristics of the conventional polyurethane resin while having excellent long-term antimicrobial and water resistance. .

Polyurethane resin, antibacterial agent, polyhexamethyleneguanidine phosphate, polyester polyol, diisocyanate, dibutyl tin dilaurate

Description

Antimicrobial Polyurethane Resin Composition and Manufacturing Method Thereof {Antimicrobial Polyurethane Resin Composition and Method for Preparing It}

The present invention relates to an antimicrobial polyurethane resin composition comprising a polyurethane resin and a guanidine-based antimicrobial agent covalently bonded to the polyurethane resin, and a method of manufacturing the same.

With the improvement of living standards, the use of thermoplastic resins is gradually expanding. However, bacteria that live on the surface of electronic products and household goods used around the living area cause deterioration of the resin, and deteriorate product performance.Bacteria that live on the surface of the resin infect the human body, air, or foods Due to this secondary infection caused a disease or have a fatal effect on health has emerged as a big problem. Recently, as interest in health and hygiene has increased, many products including antibacterial hygiene functions have emerged, not just thermoplastic resin products. In other words, the number of products that are antimicrobial treatment on the thermoplastic resin is increasing, accordingly, the development of antimicrobial agent that can be easily processed to the resin and give the desired antibacterial function is in progress.

Existing antimicrobial agents added to resins can be roughly divided into inorganic and organic antimicrobial agents. Inorganic antimicrobial agent means an antimicrobial agent containing metal such as silver or copper. It is used for the production of antimicrobial resin due to the high temperature condition of resin processing, but it has a high antibacterial activity compared to organic antimicrobial agent, and has a high amount of antibacterial activity against mold. Relatively weak, the price is relatively expensive and difficult to disperse the processing conditions, there is a disadvantage such as discoloration due to metal ions during or after processing is not widely used. On the other hand, organic antimicrobial agents have the advantage of being relatively inexpensive and having a good antimicrobial effect even in small amounts, but they are sometimes toxic and effective only against specific bacteria. Is mostly lost, discolored after processing, and can be easily eluted compared to inorganic antimicrobial agents, and thus has a disadvantage in that the antimicrobial performance is shortened. Therefore, the range of organic antimicrobial agents that can be used for antimicrobial resins is extremely limited.

For example, benzimidazole-based antimicrobial agent is used in the processing of thermoplastic resins, while the processability is also good, but the antibacterial activity against bacteria is weak and may cause problems of discoloration after processing. In addition, 10,10'-oxybisphenoxyalgin (10,10'-oxybisphenoxyarsine) has excellent antibacterial properties and good processability, but has the disadvantage of being easily decomposed by ultraviolet rays, and has a problem in stability due to the arsenic content. It is decreasing.

The required performance of the antimicrobial agent for thermoplastic resins may include product stability against heat or ultraviolet rays, antibacterial activity, human stability, and antimicrobial durability when applied to resins. As a substance for satisfying this, there is a group of antimicrobial agents including guanidine salts and are well known as low toxicity antimicrobial agents.

However, when the antimicrobial agent is applied to the field of antimicrobial thermoplastic resin, the product is leaked to the surface of the product when it is used for a long time, and as a result, the antimicrobial property is degraded. There is this. For example, in the case of polyurethane resins, which are mostly used in patents, the fluidity between molecules is quite active at room temperature due to the characteristics of polyurethane, so that the binding strength of the antimicrobial agents is weakened, and the antimicrobial substance is released to the surface of the resin. Over time, there is a problem that the antimicrobial activity is rapidly lowered.

Throughout this specification, many papers and patent documents are referenced and their citations are indicated. The disclosures of cited papers and patent documents are incorporated herein by reference in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly explained.

The present inventors conducted extensive research to solve the above-mentioned problems of the prior art, as a result of the antimicrobial agent seeping out of the existing antimicrobial polyurethane resin product and / or the dissolution of the antimicrobial agent by contact with moisture, etc. The antimicrobial agent shows excellent antimicrobial and long-lasting antimicrobial activity, and selects a low-toxic organic antimicrobial guanidine-based antimicrobial agent and adds it in the manufacture of polyurethane resin and covalently binds it to prevent the antimicrobial agent from leaking out even after prolonged use. The present antimicrobial polyurethane resin was maintained.

An object of the present invention is to provide an antimicrobial polyurethane resin composition comprising a polyurethane resin and a guanidine-based antimicrobial agent covalently bonded to the polyurethane resin.

Another object of the present invention to provide a method for producing the antimicrobial polyurethane resin composition.

Other objects and advantages of the present invention will become apparent from the following examples and claims.

According to an aspect of the present invention, the present invention provides an antimicrobial polyurethane resin composition comprising (a) a polyurethane resin, and (b) a guanidine-based antimicrobial agent covalently bonded to the polyurethane resin.

The present inventors conducted extensive research in order to solve the problems of the prior art, and as a result, antimicrobial agent leaks out of the existing antimicrobial polyurethane resin product and / or the dissolution of the antimicrobial agent due to contact with moisture. As an antimicrobial agent, it shows excellent antimicrobial and long-lasting antimicrobial properties, and selects a guanidine-based antimicrobial agent that is a low-toxic organic antimicrobial agent. This antibacterial polyurethane resin was completed.

In the antimicrobial polyurethane resin composition of the present invention, a polyurethane resin and a guanidine-based antimicrobial agent added are covalently bonded.

According to a preferred embodiment of the present invention, the guanidine-based antimicrobial agent of the present invention is represented by the following general formula (1) or (2):

Formula 1

In Formula 1, R ₁ is independently of each other hydrogen, a straight or crushed alkyl group having 1 to 20 carbon atoms, or an aryl group; X is independently of each other an inorganic acid salt or an organic acid salt; And n is an integer from 1-1,000;

 Formula 2

In Formula 2, X is independently an inorganic acid salt or an organic acid salt and n is an integer of 1-1,000.

In Formula 1 or Formula 2, X is independently of each other an inorganic acid salt or an organic acid salt. Preferably X is HCl, HBr, HI, HNO _{3 ,} carbonic acid, sulfonic acid, phosphoric acid, acetic acid, benzoic acid, dihydroacetic acid, propionic acid, gluconic acid, sobic acid, fumaric acid, malic acid or epichloro Hydrin, more preferably HCl, HBr, HI, HNO _{3 ,} carbonic acid, sulfonic acid or phosphoric acid, most preferably phosphoric acid.

In formula (1), R 1 is independently of each other hydrogen, a straight or crushed alkyl group having 1 to 20 carbon atoms, or an aryl group. The alkyl group or aryl group located at R 1 may be substituted. The term “alkyl” refers to a straight or pulverized saturated hydrocarbon group of 1-20 carbon atoms and includes, for example, methyl, ethyl, n -propyl, isopropyl, isobutyl, n -butyl, t -butyl, octyl, decyl and steryl do. The term "aryl" refers to a substituted or unsubstituted monocyclic or polycyclic carbon ring which is wholly or partially unsaturated, preferably monoaryl or biaryl. For example, aryl includes phenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, benzyl group, chlorobenzyl group, bromobenzyl group, iodobenzyl group, phenethyl group or naphthyl group.

According to a preferred embodiment of the present invention, in formula (1) R1 is hydrogen or a linear or pulverized alkyl group having 1-20 carbon atoms, more preferably R1 is hydrogen.

In formula (1) or (2), n is an integer of 1-1,000, preferably an integer of 1-50, more preferably 1-14, most preferably an integer of 4-7.

According to a preferred embodiment of the present invention, the guanidine-based antimicrobial agent of the present invention is represented by the following general formula (3):

Formula 3

In the above formula, m is an integer of 1-1,000, n is an integer of 1-50.

In Chemical Formula 3, m is an integer of 1-1,000, preferably an integer of 1-50, more preferably an integer of 1-20, most preferably an integer of 4-7. In general formula (3), n is an integer of 1-50, More preferably, it is an integer of 1-20, Most preferably, it is an integer of 1-14.

According to a preferred embodiment of the invention, the polyurethane resin of the invention is the reaction product of aliphatic diols, dipolyols and polyvalent isocyanates.

According to a preferred embodiment of the present invention, the aliphatic diol used in the present invention is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propylene glycol or 1,3-propylene glycol, 2-methyl-1 , 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7 -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol. More preferably, the aliphatic diol of the present invention is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol and 1,6-hexanediol, even more preferably ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and most preferably ethylene glycol.

According to a preferred embodiment of the invention, the dipolyols used in the invention are polyester diols or polyether diols, most preferably polyester diols.

Polyester diols can be obtained through direct esterification or transesterification of the polycarboxylic acid component and the polyol component. Polycarboxylic acid components may include, for example, polycarboxylic acids, esters and anhydrides thereof, and the like. Examples of polycarboxylic acid components include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, dodecane-diacid, 2-methylsuccinic acid, 2-methyl Adipic acid, 3-methyladiric acid, 3-methylpentane-diacid, 2-methyloctane-diacid, 3,8-dimethyldecane-diacid and 3,7-dimethyldecane-diacid and the like); Aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid and naphthalene-dicarboxylic acid, etc .; Alicyclic dicarboxylic acids (eg, 1,4-cyclohexane-dicarboxylic acid, etc.); Tricarboxylic acids (such as trimellitic acid and trimesic acid, etc.) and ester-forming derivatives thereof (such as esters, anhydrides thereof, etc.), preferably aliphatic carboxylic acids and ester-forming derivatives thereof, most preferably adipic acid to be. Polyol components include, for example, aliphatic diols such as ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl -1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol Etc); Alicyclic diols such as cyclohexane-dimethanol and cyclohexane-diol; Triols such as glycerin, trimethylolpropane, butanetriol, hexanetriol, trimethylolbutane and trimethylolpentane and the like and tetraols such as pentaerythritol. Of these, aliphatic polyols are preferred, and 1,4-butanediol is most preferred.

The polyvalent isocyanates of the present invention can be any and all organic diisocyanates that can be used in the manufacture of conventional polyurethane resins. Preferred are alicyclic diisocyanates, aliphatic diisocyanates and aromatic diisocyanates having a molecular weight of 500 or less.

 According to a more preferred embodiment of the present invention, the polyvalent isocyanate of the present invention is an aliphatic diisocyanate. The aliphatic diisocyanate is preferably 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane isocyanate, tetraalkali diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, tolidine diisocyanate, Cyclohexane-1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4,4'- diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane or methylcyclohexanediisocyanate . More preferably, the polyvalent isocyanate used in the present invention is butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, tolidine diisocyanate, cyclohexane-1,4-di Isocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4,4'- diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane or methylcyclohexanediisocyanate, still more preferably isophorone Diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane or methylcyclohexanediisocyanate, preferably dicyclohexylmethane-4,4'-di Isocyanate.

In the antimicrobial polyurethane resin composition of the present invention, the polyhexamethyleneguanidine salt of formula (1) or polyhexamethylenebaiguanidine salt of formula (2) is convenient when used as an antibacterial agent for resin processing and exhibits excellent processability to various kinds of resins, thereby In addition to urethane or polypropylene, it is also possible to mix and use 5-20% by weight of polyethylene, polystyrene, polyvinyl chloride, acrylonitrile butadiene styrene and polyester to make a masterbatch, preferably 10-15% is suitable. . The masterbatch can be used to process and produce antimicrobial plastic products. For thermoplastic antimicrobial resins, the antimicrobial agent is preferably 0.1-40% by weight, more preferably 0.1-15% by weight, and even more preferably, in the final product. 0.1-7% by weight, most preferably 0.1-2%. If the final content is less than 0.1%, the antimicrobial activity may not be properly expressed, and if it exceeds 40% by weight, it may affect the physical properties of the thermoplastic resin.

According to a preferred embodiment of the present invention, the content of the polyurethane resin of the present invention is 60-99.9% by weight, and the antimicrobial agent is 0.1-40% by weight.

The content of the polyurethane resin in the composition of the present invention is preferably 60-99.9% by weight, more preferably 85-99.9% by weight, even more preferably 93-99.9% by weight, most preferably 98- 99.9% by weight.

According to another aspect of the present invention, the present invention provides a method for preparing an antimicrobial polyurethane resin composition covalently bonded to a guanidine-based antimicrobial agent comprising the following steps:

(a) mixing aliphatic diols with guanidine-based antimicrobials; And

(b) mixing the resultant of (a) with a dipolyol and a polyvalent isocyanate and carrying out a polymerization reaction.

Since the method of the present invention is a process for preparing the antimicrobial polyurethane resin composition to which the guanidine-based antimicrobial agent of the present invention is covalently bonded, the common content between the two is to avoid excessive complexity of the specification according to the repetitive description. Omit the description.

The antimicrobial polyurethane resin of the present invention can be produced by a one shot method in which a chain extender or a polymerization terminator is reacted once in a suitable solvent to a polyol and a diisocyanate compound of a polymer as necessary. In addition, the antimicrobial polyurethane resin of the present invention reacts the polymer polyol with the diisocyanate under excessive conditions, prepares a prepolymer having isocyanate groups at both ends of the polymer polyester polyol, and then terminates the chain extender or polymerization in a suitable solvent. It can be manufactured by a two-stage method to react with an agent. The two-step method can obtain a more uniform polyurethane resin solution.

In order to manufacture a polyurethane resin, a well-known method can be used. In this case, the reaction temperature is preferably in the range of 30 to 150 ° C., and the reaction can be carried out in the presence or absence of an organic solvent. Organic solvents include, for example, ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran and dioxane, etc .; Esters such as ethyl acetate and butyl acetate; Amides such as dimethylformamide and N-methylpyrrolidone and the like and aromatic hydrocarbons such as toluene and xylene and the like.

In the production of the antimicrobial polyurethane resin of the present invention, when using the master batch or the final product made of the additive thermoplastic antimicrobial resin described above, the antimicrobial agent may be exposed to a phenomenon such as blooming or bleeding to the surface. When exposed, the antimicrobial agent is easily eluted, resulting in a sharp drop in antimicrobial activity. The reason is that the compatibility of the known polymer with the antimicrobial agent is low. In the preparation of the matrix polymer, the antimicrobial agent was mixed with the monomer to react with each other to form a covalent bond with the matrix polymer so that 0.1-40% by weight of the antimicrobial agent was finally included in the polymer.

In preparing the polyurethane resin, a reaction catalyst may optionally be added to the reaction system. According to a preferred embodiment of the present invention, the catalyst used is preferably triethylenediamine, morpholine, N-ethylmorpholine, pyrazine, triethanolamine, triethylamine, dibutyltindilaurate, steniusoctano Ate, dioctyl tin diacetate, red octanoate, phenius oleate and dibutyl tin oxide, preferably dibutyl tin dilaurate, stenius octanoate, dioctyl tin diacetate and red octanoate, Most preferably dibutyltindilaurate.

In preparing the polyurethane resin of the present invention, a chain extender may be used. Chain extenders include compounds such as 1-mercapto-3-aminopropane; Optionally substituted amino acids such as clycine, alanine, valine, serine and lysine; And optionally substituted dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, 4-hydrociphthalic acid and 4-aminophthalic acid, and the like.

The antimicrobial polyurethane resin composition of the present invention may optionally include various conventional additives. Such materials may include, but are not limited to, fillers such as silicates, TiO ₂ , glass fibers, carbon black, graphite, calcium carbonate, talc and mica, additives such as reinforcing agents, light stabilizers, UV absorbers, and dyes.

The features and advantages of the present invention are summarized as follows:

(a) The antimicrobial polyurethane resin composition of the present invention can overcome the disadvantage that the antimicrobial agent is susceptible to blooming or moisture by covalently bonding with the polyurethane.

(b) The antimicrobial polyurethane resin composition of the present invention can maintain and express antimicrobial activity for a long time by overcoming the problems of the prior art, as well as its application to products in contact with water.

(c) In addition, the antimicrobial polyurethane resin composition of the present invention can be used as a conventional polyurethane resin processing and molding method as it is, long-term antibacterial effect and water resistance and low toxicity through injection, compression, extrusion, hollow, film, inflation molding, etc. It can be widely applied to manufacture high quality antibacterial products and antimicrobial containers having the same.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example

Example  Ⅰ: Preparation of Antimicrobial Powder

Polyhexamethylene guanidine phosphate (SKYBIO 1100, SK Chemicals), polyhexamethylene guanidine hydrochloride (SKYBIO, SK Chemicals) and polyhexamethylene viguanidine hydrochloride (Arch Chemicals) in the form of an aqueous solution were prepared in powder form.

Example  II: Preparation of Antibacterial Polyurethane Resin

After dissolving 2.9 g of the polyhexamethylene guanidine phosphate powder prepared above in 12.4 g of ethylene glycol, it was preheated to 100 ° C. and 200 g of polyester polyol having a molecular weight of 2,000 consisting of molten adipic acid and 1,4-butanediol and dicyclohexyl 78.7 g of methane diisocyanate (dicyclohexylmethane-4,4 diisocyanate) were put together in a 500 ml barrel and 1,000 ppm of dibutyltin dilaurate was added as a catalyst. This was poured into a high speed stirring and release paper for about 20 seconds with a mechanical stirrer (RW20DZM, IKA), and then placed in a forced circulation oven (NDO-700, Eyela) set at 100 ° C for about 24 hours to prepare a plate-like test piece. For comparison, a polyurethane resin test piece containing no antimicrobial agent was prepared in the same manner.

Example  III: Preparation of Antimicrobial Polyurethane Resin Test Specimens Removed Unreacted Antimicrobial Agent

In order to remove the unreacted antimicrobial agent, 5 g of the antimicrobial polyurethane resin prepared in Example II was dissolved in dimethylformamide to prepare a 100 ml solution, and the excess distilled water and a mechanical stirrer (RW20DZM , IKA). At this time, since the antimicrobial agent is easily dissolved in water, the unreacted antimicrobial agent is completely removed. While filtering the precipitate and the solution under reduced pressure, the antimicrobial polyurethane resin on the filter paper was washed several times with distilled water to dissolve and remove the antimicrobial agent that may remain on the surface, and then dried in an oven (NDO-700, Eyela) to prepare an antimicrobial polyurethane resin test piece. It was. For comparison, a polyurethane resin test piece containing no antimicrobial agent was prepared in the same manner.

Example  Ⅳ: Antimicrobial Evaluation of Antimicrobial Polyurethane Resin without Unreacted Antibiotic

The antimicrobial activity of the polyurethane resin prepared in Example III was confirmed. The evaluation method was measured by the shaking flask method of the Japan Textile Hygiene Association (SEK), and included the polyurethane resin test piece containing no antimicrobial agent and the antimicrobial polyurethane resin test piece from which unreacted antimicrobial agent was removed. First, the phosphate buffer solution was UV sterilization processing the specimen (phosphate buffer solution) into a 250 ml flask containing 70 ml pre-culture of E. coli (Escherichia coli ) was inoculated with 5 ml with a population of about 1.3 × 10 5 cfu / ml. After 1 hour shaking culture at 150 rpm, the culture medium was plated according to the serial dilution method and cultured at 37 ° C. for 24 hours to count the number of grown bacteria. The number of bacteria obtained in the polyurethane resin test piece and the number of bacteria obtained in the antimicrobial polyurethane resin test piece were compared to calculate a reduction ratio. The results are shown in Table 4 below. The percent reduction was calculated as follows: percent reduction (%) = [(AB) / A] x 100, A: Number of bacteria after incubation of the polyurethane resin test piece, B: Number of bacteria after incubation of the antimicrobial polyurethane resin test piece.

Antimicrobial Evaluation Results for Antimicrobial Polyurethane Resins  sample  Polyurethane Resin Test Piece  Antibacterial Polyurethane Resin Test Piece  Number of bacteria after culture (cfu / ml) 2.7 x 10 ⁶  <10  Reduction rate (%) -  > 99.9%

As shown in Table 1, these results indicate that the antimicrobial polyurethane resin of the present invention has excellent efficacy in antimicrobial effect compared to the polyurethane resin containing no antimicrobial agent. It overcomes the weakness of blooming or moisture by forming a covalent bond between polyurethane resin and antibacterial agent. It can not only maintain and express excellent antibacterial power for a long time but also can be applied to products in contact with water. In addition, it is possible to use processing and molding methods with existing polyurethane resins as it is, so that high quality antibacterial products and antimicrobial containers having long-term antibacterial effect, water resistance and low toxicity through injection, compression, extrusion, hollow, film and inflation molding, etc. It can be widely applied to manufacturing.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (13)

An antimicrobial polyurethane resin composition comprising (a) a polyurethane resin that is a reaction product of an aliphatic diol, dipolyol, and polyvalent isocyanate, and (b) a guanidine-based antimicrobial agent covalently bonded to the polyurethane resin. The antimicrobial polyurethane resin composition according to claim 1, wherein the guanidine-based antimicrobial agent is represented by the following Chemical Formula 1 or Chemical Formula 2: Formula 1

In the above formula, R ₁ is independently of each other hydrogen, a straight-chain or crushed alkyl group having 1-20 carbon atoms, or an aryl group; X is independently of each other an inorganic acid salt or an organic acid salt; And n is an integer from 1-1,000;  Formula 2

In the above formula, X is independently from each other an inorganic acid salt or an organic acid salt and n is an integer of 1-1,000. delete The method of claim 1, wherein the aliphatic diol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propylene glycol or 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol antimicrobial polyurethane resin composition, characterized in that selected from the group consisting of. The antimicrobial polyurethane resin composition according to claim 2, wherein the guanidine-based antimicrobial agent of Chemical Formula 1 is represented by the following Chemical Formula 3: Formula 3

In the above formula, m is an integer of 1-1,000, n is an integer of 1-50. The antimicrobial polyurethane resin composition according to claim 1, wherein the content of the polyurethane resin is 60-99.9% by weight and the antimicrobial agent is 0.1-40% by weight. Guanidine-based antimicrobial agent is covalently bonded to the antimicrobial polyurethane resin composition comprising the following steps: (a) mixing aliphatic diols with guanidine-based antimicrobials; And (b) mixing the resultant of (a) with dipolyol and polyvalent isocyanate and carrying out a polymerization reaction. The method of claim 7, wherein the guanidine-based antimicrobial agent is represented by the following formula (1) or (2): Formula 1

In the above formula, R ₁ is independently of each other hydrogen, a straight-chain or crushed alkyl group having 1-20 carbon atoms, or an aryl group; X is independently of each other an inorganic acid salt or an organic acid salt; And n is an integer from 1-1,000; Formula 2

In the above formula, X is independently of each other an inorganic acid salt or an organic acid salt and n is an integer of 1-1,000. The method of claim 7, wherein the aliphatic diol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propylene glycol or 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol. The method of claim 8, wherein the guanidine-based antimicrobial agent of Chemical Formula 1 is represented by the following Chemical Formula 3: Formula 3

In the above formula, m is an integer of 1-1,000, n is an integer of 1-50. 8. The method of claim 7, wherein the dipolyol is a polyester diol or a polyether diol. The method of claim 7, wherein the polyvalent isocyanate is 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane isocyanate, tetraalkali diphenylmethane Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Tolidine diisocyanate, cyclohexane-1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4,4'- diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane or methylcyclo Hexane diisocyanate. 8. The method of claim 7, wherein step (b) comprises: triethylenediamine, morpholine, N-ethylmorpholine, pyreazine, triethanolamine, triethylamine, dibutyltindilaurate, steniusoctanoate, dioctyl A process characterized in that it is carried out in the presence of a catalyst selected from the group consisting of tindiacetate, red octanoate, phenius oleate and dibutyl tin oxide.