KR20070046261A - Anti-bacterial polyurethane resin composition and anti-bacterial products treated thereof - Google Patents

Abstract

The present invention relates to an antimicrobial polyurethane resin composition and an antimicrobial processed product thereof, wherein the antimicrobial polyurethane resin composition of the present invention comprises an aminoglycoside-based antimicrobial agent which forms a covalent bond with the polyurethane resin.

The antimicrobial polyurethane resin composition of the present invention exhibits excellent antimicrobial properties continuously because the polyurethane resin and the aminoglycoside-based antimicrobial agent form a covalent bond, and a phenomenon in which the antimicrobial agent is buried due to a decrease in the binding force between the polyurethane resin and the antimicrobial agent (Bleeding) Phenomenon) can be effectively prevented, and the use of a small amount of the antimicrobial agent has an excellent antimicrobial effect.

Antibacterial, polyurethane, resin compositions, aminoglycosides, coatings, covalent bonds.

Description

Antibacterial polyurethane resin composition and anti-bacterial products treated thereof

The present invention relates to a polyurethane resin composition comprising an aminoglycoside-based antimicrobial agent which forms a covalent bond with a polyurethane resin, and an antibacterial processed product thereof.

In general, most synthetic resins, except for some synthetic resins such as polyvinyl chloride, have been known to be safe for bacteria because they are difficult to inhabit microorganisms, but recently, it has been found that bacteria can be grown in most synthetic resins under suitable conditions. .

As the use of synthetic resins is gradually expanded to increase the number of synthetic resins used around human life, the primary infection of the human body by bacteria inhabiting the surface of synthetic resins and the secondary infection through infections in the atmosphere or foodstuffs, etc. It has become a big problem to cause disease or have a fatal effect on health.

The resin developed to solve this problem is usually called antibacterial resin and used differently from disinfectant resin in that it shows antimicrobial effect only on the product itself and on the product surface without affecting the whole or the inside of the product. do.

In general, a method for producing an antimicrobial resin is a method of mixing an antimicrobial organic compound during resin processing as in Korean Patent Publication No. 94-31 and an inorganic antimicrobial agent containing a metal component having antimicrobial properties as in Korean Patent Publication No. 91-7590. The method of mixing at the time of resin processing, etc. are known. However, the method of mixing the antimicrobial organic compounds in the processing of the resin may be toxic or effective only against certain bacteria. In order to solve the above problems, there are cases in which resins are prepared using antibacterial agents that are not harmful to the human body. U.S. Patent No. 4,581,028, U.S. Patent No. 4,563,485, U.S. Patent No. 5,093,165, U.S. Patent No. 5,165,952, etc., coated antimicrobial materials used for injection or oral administration on the synthetic resin surface. It may also be incorporated into compound chips to impart antimicrobial properties. However, the resins used in the above patents are mostly polyurethane resins, and due to the characteristics of polyurethanes, fluidity between molecules is considerably active at room temperature, so that the binding strength of the antimicrobial agents is weakened, and the antimicrobial substance is released to the resin surface. Therefore, after a certain time after the production of the antimicrobial resin there is a problem that the antimicrobial activity is rapidly lowered.

In addition, U.S. Patent No. 6,228,393 shows a hydrogel containing an antimicrobial agent on the resin surface to slowly release the antimicrobial agent after application of the resin to maintain antimicrobial activity even for long time use. However, in this case, the manufacturing method of the resin is complicated, and when all of the antimicrobial agent is released from the hydrogel (Hydrogel) containing the drug has a disadvantage that the antimicrobial power is reduced. In addition, US Patent No. 2001/0049422 uses an organic antimicrobial agent capable of ion bonding with a polyurethane resin in order to overcome the above problems. In this case, it shows excellent antimicrobial activity at the beginning of use, but after 10 days all the antimicrobial agents disappeared. In addition, since it takes more than 24 hours to manufacture the resin, there is a disadvantage in that the productivity is greatly reduced.

In order to solve this problem, in general, in the production of antibacterial resins, an inorganic antimicrobial agent containing a metal component exhibiting antimicrobial properties is often mixed and used during resin processing.

Metals exhibiting antimicrobial properties include silver, copper and zinc, and the inorganic materials supporting them include zeolites as in Korean Patent Publication No. 91-7590, phosphate as in Japanese Patent Laid-Open No. 4-275370, Japanese Laid-Open Patent No. 5 Talc as in -112415, hydroxyapatite as in JP-A 3-21875, silica gel and activated carbon as in JP-A 5-201817, and the like are contained in the carrier. Depending on the state or the binding strength of the metal and the support or the content of the supported antimicrobial metal, there is a significant difference in the antimicrobial performance, the persistence of the antimicrobial performance and the effect on the resin.

In terms of antimicrobial performance, silver (Ag) or silver and other antimicrobial metals are best used together among antimicrobial metals, but they are disadvantageous in terms of discoloration and processing stability of the resin. In addition, some of the carriers are limited in the amount of antimicrobial metals that can be contained in the antimicrobial agent, so the antimicrobial activity may be weak. The discoloration stability and antimicrobial activity of the resin processing resulted in mutually opposite results. Antimicrobial agents with poor antimicrobial activity hardly discolor the resin, whereas antimicrobial agents having excellent antimicrobial power seriously discolor the resin and thus may not be applicable. In addition, some antimicrobial agents are not applicable because the color of the resin is black or brown because the color of the resin is severely discolored when acting on the resin. The resin containing the antimicrobial agent with weak antimicrobial power is difficult to express the antimicrobial performance sufficiently, so it is difficult to supplement the antimicrobial power in actual application, and to overcome this, when the antimicrobial agent is used excessively, the properties of the resin are weak and the price rises, which is undesirable. I can't.

In order to solve this problem, Korean Patent Publication 91-7590 attempts to solve some of the antimicrobial agents by replacing ammonium ions with a discoloration inhibitor, but it is insufficient to prevent discoloration completely. There is a problem that the resin is foamed, and some of the suggested discoloration inhibitors may rather promote discoloration. In addition, Korean Patent Publication 95-2855 proposes a method of coating liquid paraffin on the surface of an inorganic antimicrobial agent to solve this problem, but an additional process for coating is required to increase the cost and to uniformly control the thickness of the coating layer and the degree of coating. It is not easy to do. In addition, it is difficult to prevent discoloration occurring at the exposed part of the antimicrobial agent, and the proposed method has no effect on the antimicrobial activity, but there is a problem in that the antimicrobial activity is substantially reduced due to the significant effect on the ionization or activation of the metal that exhibits antimicrobial activity. In addition, Japanese Patent Laid-Open No. 4-275370 has a problem in that the antimicrobial activity is reduced due to a significant effect on ionization or activation of metals exhibiting antimicrobial activity.

The present invention has been proposed to solve the problems of the conventional antimicrobial resin, the present invention includes an aminoglycoside-based antimicrobial agent which forms a covalent bond with the polyurethane resin, excellent antimicrobial properties and at the same time the antibacterial agent (Bleeding) It is intended to provide an antimicrobial polyurethane resin composition and its antimicrobial processed product having no antimicrobial activity for a long time.

In addition, the present invention is an antimicrobial processed product having a permanent antimicrobial by coating the surface of the antimicrobial polyurethane resin composition comprising an aminoglycoside-based antimicrobial agent which forms a covalent bond with the polyurethane resin as described above by a known method To provide.

In addition, the present invention is a problem in that the antimicrobial persists rapidly due to the phenomenon that the antimicrobial is buried after a certain time (Bleeding phenomenon) due to a decrease in the binding force between the polyurethane resin and the antimicrobial agent when simply mixing the antimicrobial agent and the polyurethane resin, Due to the coating of the antimicrobial agent by the polyurethane resin, the contact with the bacteria is blocked and the antimicrobial power of the antimicrobial agent is lost, and to solve the problems such as using an excessive amount of antimicrobial agent to maintain high antimicrobial power.

The antimicrobial polyurethane resin composition of the present invention for achieving the above object is characterized by comprising an aminoglycoside-based antimicrobial agent which forms a covalent bond with the polyurethane resin.

Hereinafter, the configuration of the present invention will be described in more detail.

The antimicrobial polyurethane resin composition of the present invention can be prepared by a method of covalently bonding a polyurethane resin and an aminoglycoside-based antimicrobial agent by adding an aminoglycoside-based antimicrobial agent during a polymerization reaction of the polyurethane resin.

Commonly used antimicrobial agents include penicillin, cephalosporins, sulfonamides, fluoroquinolones, tetracyclines, aminoglucosides, macrolides, and the like. Among them, they are widely used and can form bonds with resins such as penicillin, cephalosporin, tetracycline, sulfonamide, quinolone and aminoglucoside. In the present invention, an aminoglycoside-based antimicrobial agent which provides antimicrobial activity by inhibiting cell wall destruction and protein synthesis of microorganisms is used.

Aminoglycoside is an antimicrobial agent that plays an important role in the treatment of Gram-negative bacterial infections, and 15 species have been developed to date, starting with Streptomycin extracted from Streptomyces griseus in 1944. Aminoglycosides have a strong bactericidal action for two reasons, but it is not clear which one is more important.

The first is the action of breaking down the cell membrane and causing intracellular substances to flow out of the cell. The second is the action of acting on the ribosomes to irreversibly inhibit the synthesis of proteins. The aminoglycosides once pass through the protein pathway of the extracellular membrane and then actively enter the cytoplasm by an oxygen dependent pump. The aminoglycosides transported into the cytoplasm bind to bacterial 30S ribosomes, leading to misreading of mRNA nucleotide sequences, which results in the synthesis of unnecessary proteins that have nothing to do with bacteria.

There are various types of aminoglycoside-based antimicrobial agents used in the present invention, but there are various types of streptomycin, stranatomycin, kanamycin, gentamicin, tonicamycin, tobramycin, amikacin, and somimycin. Sisomicin, Dibekacin, Netilmicin, Micronomicin, Astromicin, Isepamicin, Spectinomicin, Ribostamycin It may be selected from the group consisting of, among these, it is most preferable to use a micromycin (Micronomicin) excellent in antibacterial action.

The aminoglycoside-based antimicrobial agents having strong antimicrobial properties used in the present invention include the following types.

Streptomycin

Kanamycin

Gentamicin

(Wherein R ₁ And R ₂ Is H or CH ₃ )

Tobramycin

Amikacin

Sisomycin

Dibekacin

Netylmicin

Micronomicin

Astromicin

Isepamicin

Spectinomicin

Ribostamycin

In addition, the polyurethane resin used by this invention can also be manufactured by the one-step method which makes the polymer polyol, the diisocyanate compound, the chain extender or the polymerization terminator used as needed once in a suitable solvent.

In addition, the isocyanate reacts the polymer polyester polyol and the diisocyanate compound in an excess condition, to prepare a prepolymer having isocyanate groups at both ends of the polymer polyester polyol, and this is a chain extender or a polymerization terminator in a suitable solvent. It can be prepared by a two-stage method to react with. If it is a two-stage method, a more uniform polyurethane resin solution can be obtained.

As the polymer polyol, (i) polyether polyols composed of a polymer or copolymer such as ethylene oxide, propylene oxide, tetrahydrofuran, etc. may be used, and (ii) 3,3,5-trimethyl-1,6hexane Diol, 2,2,4-trimethyl-1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol, Sorbitol, ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, pentanediol, hexanediol, octanediol, 1,4-butanediol, diethylene glycol, triethylene Saturated and unsaturated low molecular glycols such as glycol and dipropylene glycol, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pielic acid, azeraic acid, seba To poly which is obtained by dehydrating and condensing dibasic acids such as succinic acid or acid anhydrides corresponding thereto The polyester polyols containing polyether glycol can be used.

Diisocyanate compounds used in the present invention include aromatic, aliphatic and alicyclic diisocyanates.

Specifically, 1,5-naphthalene diisocyanate, 4,4'- diphenylmethane diisocyanate, 4,4'- dibenzyl isocyanate, dialkyl diphenylmethane isocyanate, tetraalkali diphenylmethane diisocyanate, 1,3 -Phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 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, methylcyclohexane diisocyanate etc. are illustrated. Can be.

As a solvent used in the synthesis | combination of a polyurethane resin, Usually, aromatic solvents, such as benzene, toluene, and xylene, which are well-known as a solvent for printing ink, ester solvents, such as ethyl acetate and butyl acetate, methanol, ethanol, and iso Alcohol solvents, such as propyl alcohol and n-butanol, ketone solvents, such as methyl ethyl ketone and a methyl isobutyl ketone, can be used individually or in mixture.

Examples of chain extenders for polyurethane resins include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine. Diamines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylenepropylenediamine, di-2-hydroxyethylpropylenediamine, di-2-hydroxyethylpropylenediamine and 2-hydroxy Roxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. are also used similarly.

Dialkylamine, such as di-n-butylamine, is illustrated as a polymerization terminator.

The polyurethanes of the invention can be prepared by a variety of known methods. In a generally one shot method, polyester diols, polyether diols, organic diisocyanates and difunctional chain extenders, and, if necessary, other additives are simultaneously mixed and then reacted at elevated temperature. Another method is the so-called prepolymer process, in which isomers first react a mixture comprising polyester diols and polyether diols first with organic diisocyanates to form diisocyanates and terminal prepolymers, and then the prepolymers extend this functional chain. How to react with the agent. Yet another method that can be used is called a quasi-prepolymer. The above modified method is also carried out by first reacting a bifunctional chain extender with an organic diisocyanate and then reacting the reaction product with polyester diols and polyether diols.

In some cases, additives (heat stabilizer tablets, antioxidants, UV stabilizers, etc.) may be incorporated at appropriate stages in the preparation of the polyurethanes of the present invention.

On the other hand, the antimicrobial processed product of the present invention can be produced by coating the antimicrobial polyurethane resin composition of the present invention described above on a surface of a product for which antimicrobial properties are required by a known method. The antimicrobial processed product of the present invention is coated with a resin composition comprising an aminoglycoside-based antimicrobial agent which forms a covalent bond with a polyurethane resin on the surface, and thus has excellent antimicrobial properties. maintain.

The antimicrobial polyurethane composition and its antimicrobial processed product of the present invention are harmless to human body and excellent antimicrobial durability compared to existing antimicrobial resins and antimicrobial processed products, and thus may be usefully used in medical and construction fields.

Hereinafter, the present invention will be described in more detail with reference to Examples.

However, the scope of the present invention is not limited by the following examples.

Example  One

1000 ml round-necked flask equipped with thermometer, stirrer, heater and cooler, 0.1 mole of polyester polyol with molecular weight 3500 containing adipic acid, diethylene glycol, 1,4-butanediol, 0.2 mole of toluidine diisocyanate, and chain 0.05 mole of 1,4-butanediol as an extender and methyl ethyl ketone were added together with a polymerization solvent and stirred at 70 to 80 ° C. for about 1 hour to synthesize a prepolymer having end groups of isocyanates. After completion of the first synthesis, 0.0042 mole of micronomycin, an antimicrobial agent dissolved in a solvent, is slowly stirred and added for about 1 hour after the addition. In order to remove unreacted isocyanate end groups after completion of the second reaction, 0.03 mol of diethylamine was slowly added to the reactor, followed by stirring for 30 minutes to prepare an antimicrobial polyurethane resin composition.

The resin composition obtained by the above method was coated on a release paper, and dried in a vacuum oven at 80 ° C. for about 4 hours to prepare a film having a thickness of 20 μm.

The results of the antimicrobial test of the prepared film are shown in Table 1.

Example  2

A 1000 ml round-necked flask equipped with a thermometer, stirrer, heater and cooler contains 0.1 mole of polyester polyol with molecular weight 3500 containing adipic acid, diethylene glycol, 1,4-butanediol, 0.2 mole of toludine diisocyanate, and chain 0.05 mole of 1,4-butanediol as an extender and methyl ethyl ketone were added together with a polymerization solvent and stirred at 70 to 80 ° C. for about 1 hour to synthesize a prepolymer having end groups of isocyanates. After completion of the first synthesis, 0.0084 mole of micronomycin, an antimicrobial agent dissolved in a solvent, is slowly stirred and added for about 1 hour. In order to remove unreacted isocyanate end groups after completion of the second reaction, 0.03 mol of diethylamine was slowly added to the reactor, followed by stirring for 30 minutes to prepare an antimicrobial polyurethane resin composition.

The resin composition obtained by the above method was coated on a release paper, and dried in a vacuum oven at 80 ° C. for about 4 hours to prepare a film having a thickness of 20 μm.

The results of the antimicrobial test of the prepared film are shown in Table 1.

Example  3

A 1000 ml round-necked flask equipped with a thermometer, stirrer, heater and cooler contains 0.1 mole of polyester polyol with molecular weight 3500 containing adipic acid, diethylene glycol, 1,4-butanediol, 0.2 mole of toludine diisocyanate, and chain 0.05 mole of 1,4-butanediol as an extender and methyl ethyl ketone were added together with a polymerization solvent and stirred at 70 to 80 ° C. for about 1 hour to synthesize a prepolymer having end groups of isocyanates. After completion of the first synthesis, 0.021 mole of micronomycin, an antimicrobial agent dissolved in a solvent, is slowly stirred and added and reacted for about 1 hour. In order to remove unreacted isocyanate end groups after completion of the second reaction, 0.03 mol of diethylamine was slowly added to the reactor, followed by stirring for 30 minutes to prepare an antimicrobial polyurethane resin composition.

The resin composition obtained by the above method was coated on a release paper, and dried in a vacuum oven at 80 ° C. for about 4 hours to prepare a film having a thickness of 20 μm.

The results of the antimicrobial test of the prepared film are shown in Table 1.

Example  4

A 1000 ml round-necked flask equipped with a thermometer, stirrer, heater and cooler contains 0.1 mole of polyester polyol with molecular weight 3500 containing adipic acid, diethylene glycol, 1,4-butanediol, 0.2 mole of toludine diisocyanate, and chain 0.05 mole of 1,4-butanediol as an extender and methyl ethyl ketone were added together with a polymerization solvent and stirred at 70 to 80 ° C. for about 1 hour to synthesize a prepolymer having end groups of isocyanates. After completion of the first synthesis, 0.022 mole of micronomycin, an antimicrobial agent dissolved in a solvent, is slowly stirred and added and reacted for about 1 hour. In order to remove unreacted isocyanate end groups after completion of the second reaction, 0.03 mol of diethylamine was slowly added to the reactor, followed by stirring for 30 minutes to prepare an antimicrobial polyurethane resin composition.

After coating the resin composition release paper obtained by the above method, the film was dried in a vacuum oven at 80 ° C. for about 4 hours to prepare a film having a thickness of 20 μm. After the prepared film was left for 10 days, the surface of the film was washed with a methyl ethyl ketone solution and dried in a vacuum oven at 80 ° C. for about 2 hours to prepare a final film.

The results of the antimicrobial test of the prepared film are shown in Table 1.

Antimicrobial Test Results Bacteriostatic reduction (%) Strain I Strain II  Example 1  42.5  40.3  Example 2  99.9  99.9  Example 3  99.9  99.9  Example 4  99.9  99.9

Antimicrobial Test Conditions

● Test method: JIS Z 2801 (film adhesion method)

● Test species: 1) Strain I: Staphylococcus Aureus

                2) Strain Ⅱ: Eschericia Coli

● The concentration of inoculating bacteria: 1) Strain I-1.3 × 105 pcs / ml

                     2) Strain Ⅱ-1.5 × 105 pcs / ml

According to the present invention, a covalent bond is formed between the polyurethane resin and the aminoglycoside-based antimicrobial agent, which effectively prevents the phenomenon of the antimicrobial agent coming out even when used for a long time.

In addition, the present invention includes an aminoglycoside-based antimicrobial agent having a broad antibacterial and antifungal spectrum, which is excellent in antimicrobial properties and antifungal properties.

Claims (3)

An antimicrobial polyurethane resin composition comprising an aminoglycoside-based antimicrobial agent which forms a covalent bond with a polyurethane resin. The method of claim 1, wherein the aminoglycoside-based antimicrobial agents are Streptomycin, Kanamycin, Gentamicin, Tobramycin, Amikacin, Sisomycin, Dibeca Antibacterial poly, characterized in that it is one selected from the group consisting of Sin (Dibekacin), Netilmicin (Netilmicin), Micronomicin (Micronomicin), Astromycin (Astromicin), Isepamicin (Isepamicin) and Arbekacin (Arbekacin) Urethane resin composition. An antimicrobial processed product, wherein the antimicrobial polyurethane resin composition of claim 1 is coated on its surface.