KR100748041B1 - Antibacterial imidazolium salt derivatives and antibacterial polymers prepared therefrom - Google Patents

Abstract

Antibacterial imidazolium salt derivatives and antibacterial polymers prepared therefrom are provided to be easily applied to life products such as detergent, antiseptic, wall paper, floor paper and electric products, and maintain antibacterial effects for a long period of time. The antibacterial imidazolium salt derivatives represented by the formula(1) are provided, wherein X^- is an anion selected from chlorine ion, bromine ion, BF4^-, PF6^-, SbF6^-, NO3^-, CF3SO3^-, (CF3SO3)2N^-, ArSO3^-, CF3CO2^- and CH3CO2^-; m is an integer from 1 to 12; R^1 and R^2 are each independently alkyl group represented by -(CH2)xY in which x is an integer from 0 to 20; R^3, R^4, R^5 and R^6 are each independently H or CH=CH2; and Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH2, OH or CO2H. The antibacterial polymers containing styrene-based imidazolium salt represented by the formula(4) which are prepared by polymerization of the antibacterial imidazolium salt derivatives represented by the formula(1) are provided, wherein M is a repeated unit derived from a vinyl comonomer selected from (meta)acrylic acid, (meta)acrylic acid ester, vinylacetate, acrylonitrile, (meta)acrylamide, styrene and butadiene monomers; and a is 3-100%, b is 0-97% and a+b = 100.

Description

Antimicrobial imidazolium salt derivatives and antimicrobial polymer materials using the same {ANTIBACTERIAL IMIDAZOLIUM SALT DERIVATIVES AND ANTIBACTERIAL POLYMERS PREPARED THEREFROM}

The present invention relates to an antimicrobial imidazolium salt derivative and an antimicrobial polymer material using the same.

Recently, as hygienic life is actively demanded in daily life, antibacterial agents are used in various fields. Many products with antimicrobial properties have been developed, and it is necessary to prevent bacterial contamination in various industries such as food, beverages, cosmetics, storage containers, toothbrushes, stationery, home appliances, bedding, etc. It is applied in various fields. If the interior materials such as public telephones, public toilets, subways, buses, etc., which are used by multiple people from all daily household items related to human consciousness, are made of polymer antimicrobial materials that are easy to process, the living environment may be more hygienic and safe. There is a need for an antimicrobial polymer material with good processability.

Although many antimicrobial materials have been commercialized, most of them are mixed with an antimicrobial agent in a liquid or polymer material, and thus have low processability. In addition, conventional antimicrobial agents are generally used in the form of additives, which is convenient, but is mainly used in excess, and only a part of the added antimicrobial substance exhibits limited antimicrobial activity on the surface of the substrate. Due to the lapse of time, and after a certain period of time, the antimicrobial activity rapidly decreases.

Therefore, there is a demand for the development of a polymer type antibacterial material in which antibacterial activity is maintained semi-permanently, so that the applicability to a substrate is large and the antimicrobial property is added to the organic polymer chain itself so as to be convenient for use.

In general, quaternary ammonium salts, phosphonium salts, pyridine compounds, organic halogen compounds, thiazolin compounds, phenols and the like are known as organic antimicrobial agents exhibiting antimicrobial properties. Compounds which combine these functional groups to show cationicity are effective. Currently, thiazole-imidazolium salts, chlorophenol compounds, pyridinethiol oxide salts, nitro group-containing morpholine compounds, triazine chloride compounds and the like have been put to practical use as antibacterial agents.

Polymers having an antimicrobial function exhibit antimicrobial properties by causing damage to cell membranes and cell walls of microorganisms, degeneration of enzyme proteins or inhibition of respiration. The action of an antimicrobial agent on bacteria is greatly affected by the physical and chemical properties of the antimicrobial agent and the diversity of bacteria and cell structures.

By introducing such an antimicrobial agent into the polymer chain, research into an antimicrobial polymer material in which antimicrobial activity is maintained even after long-term use has been made.

Related prior art documents include Korean Unexamined Patent Publication No. 1999-0078100 (Daniichi Saki Seika High School Kabuki Kaisha), US Patent No. 6,492,445 (Stepan Company, Northfield, IL), Korean Unexamined Patent Publication No. 2000-0031489 There is [Esuke Co., Ltd.].

As such, polycation polymers such as ammonium salts or phosphonium salts appear to have excellent antimicrobial activity. This antimicrobial action is an anionic phospholipid bilayer membrane, which is similar to other organisms. It is known to be caused by the breakdown of cell membranes and the death of bacteria. It has been reported that m-cresol-containing acrylate polymers and polystyrenes combined with m-dimethylaminophenol diammonium salts are polymers exhibiting antimicrobial activity.

It has also been reported to exhibit excellent antimicrobial properties when the bicyclic amine 1,4-diazabicyclo [2,2,2] octane [DABCO] is bound to the sugar chain units of cellulose in the form of ammonium salts. At this time, the long-term alkyl group of 16 carbon atoms was substituted for the antimicrobial activity. It has been reported that the antimicrobial activity of polyoxyzolines having an ammonium base group having at least 12 carbon atoms of alkyl chains is very good.

Since the antimicrobial polymer material bound to the surface can be maintained antimicrobial even after washing, the application potential for handles, clothing, and medical products used by multiple people is very high. In particular, there is a demand for the development of antimicrobial polymers that can exhibit high antimicrobial activity even when the antimicrobial functional group is directly bonded to the polymer chain and fixed.

An object of the present invention is a new type of antibacterial and odor-free antimicrobial agent containing an antimicrobial imidazolium salt which is water soluble, organic solvent soluble, and has excellent environmental stability and is well mixed with a general solvent. As an organic material to be used, it is providing an antimicrobial polymer material which maintains antimicrobial activity for a long time.

An object of the present invention as described above to produce an antimicrobial imidazolium salt-containing derivatives by maximizing the antimicrobial activity by replacing various functional groups by varying the number of carbon of the alkyl group chain in the imidazole which is a component of histidine amino acid of the human body, By using an antimicrobial polymer material. Accordingly, the present invention relates to an antimicrobial imidazolium salt derivative which is nonvolatile and odorless and has excellent environmental stability, its use as an antimicrobial agent and a bactericide, and an antimicrobial polymer material having excellent physical properties using the same.

The antimicrobial imidazolium salt derivative according to the present invention is represented by the following formula (1).

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion, such as, ^- CO ₂ ^-, or CH ₃ CO ₂

m is an integer from 1 to 12,

R ¹ and R ² is an alkyl group represented by-(CH ₂ ) _x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH or CO ₂ H and the like. Represents a functional group of

R ³ , R ⁴ , R ⁵ and R ⁶ are each represented by H, CH = CH ₂ or -A- (CH ₂ ) nY, where A is CH ₂ , O, NH or S,

n is an integer of 0-12, Y is the same as what was demonstrated above.

The compound of Formula 1 may be obtained by reacting a compound represented by the following Formula 2 with an imidazole derivative represented by the following Formula 3.

In the formula 2 and 3, R ¹ to R ⁶ and m are as as the same and, Z is bromine or chlorine atom as defined in formula (1), by then reacting _{^{BF 4 -, PF 6 -,}} SbF 6 -, NO 3 - ^{_{, CF 3 SO 3 -, (}} CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 CO 2 - , or CH ₃ CO ₂ ^- it may be converted to an anion, such as.

In addition, the present invention is a styrene-based imidazolium salt-containing antimicrobial compound represented by the following formula (4) obtained by the polymerization of a styrene-based antimicrobial imidazolium salt monomer wherein R ³ and / or R ⁴ is CH = CH ₂ in the formula (1) A polymer and an antimicrobial polymeric material comprising the same.

Wherein R ¹ to R ⁶ and m are the same as defined in the formula (1), M is a repeating unit derived from a radical polymerizable comonomer, examples of the comonomer include (meth) acrylic acid and (meth) acrylic acid ester Commercially available vinyl monomers such as vinyl acetate, acrylonitrile, (meth) acrylamide, butadiene, styrene, etc.

The fraction a of the antimicrobial imidazolium monomer of the formula (1) is 3 to 100%, the fraction b of the comonomer is 0 to 97% and a + b = 100.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the examples are only illustrative of the present invention, and the scope of the present invention is not limited to the examples.

Example 1 Synthesis of 1-butyl-3- (4-vinylbenzyl) imidazolium Salt

12.20 g (0.098 mol) of 1-butylimidazole is dissolved in 30 ml of dimethyl sulfoxide, 10.00 g (0.066 mol) of vinylbenzyl chloride is added thereto, and the reaction is stirred at a temperature of 50 ° C. for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a slightly yellowish viscous liquid product.

Yield 15.73 g (66%)

¹ H NMR (CDCl ₃ , 200 MHz) 10.2 (s, 1H), 7.3 to 7.7 (m, 6H), 6.6 (m, 1H), 5.6 (d, 1H), 5.5 (s, 2H), 5.2 (d, 1H), 4.3 (t, 2H), 1.8 (m, 2H), 1.2 (m, 2H), 0.9 (t, 3H).

Example 2: Synthesis of 1-hexyl-3- (4-vinylbenzyl) imidazolium salt

Dissolve 15.00 g (0.099 mol) of 1-hexylimidazole in 30 ml of dimethyl sulfoxide, add 10.00 g (0.066 mol) of vinylbenzyl chloride, and react with stirring at a temperature of 50 ° C. for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a slightly yellowish viscous liquid product.

Yield 13.80 g (69%)

¹ H NMR (CDCl ₃ , 200 MHz) 10.8 (s, 1H), 7.3 to 7.7 (m, 4H), 6.6 (m, 1H), 5.6 (d, 1H), 5.5 (s, 2H), 5.2 (d, 1H), 4.3 (t, 2H), 1.8 (m, 2H), 1.2 (m, 6H), 0.9 (t, 3H).

Example 3: Synthesis of 1-dodecyl-3- (4-vinylbenzyl) imidazolium salt (1)

15.00 g (0.099 mol) of 1-dodecylimidazole is dissolved in 30 ml of dimethyl sulfoxide (DMSO), 10.00 g (0.066 mol) of vinylbenzyl chloride is added thereto, and the reaction is stirred at a temperature of 50 ° C. for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a slightly yellowish viscous solid product.

Yield 14.00 g (55%)

¹ H NMR (CDCl ₃ , 200 MHz) 10.8 (s, 1H), 7.3 to 7.7 (m, 4H), 6.6 (m, 1H), 5.6 (d, 1H), 5.5 (s, 2H), 5.2 (d, 1H), 4.3 (t, 2H), 1.8 (m, 2H), 1.2 (m, 18H), 0.9 (t, 3H).

Example 4: Vinyl Benzylimidazole Synthesis

Dissolve 16.70 g (0.246 mol) of imidazole in 30 ml of dimethyl sulfoxide (DMSO), add 5.00 g of caustic soda, and stir to dissolve. 10.00 g (0.065 mol) of vinylbenzyl chloride was added thereto, followed by reaction at room temperature for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was extracted with ethyl acetate and water. The solvent was distilled off under reduced pressure, and the residue was purified by chromatography using a ratio of ethyl acetate and hexane (1: 8). The solvent is removed and then dried to yield a white platy solid product.

Yield 12.50 g (67%)

¹ H NMR (CDCl ₃ , 200 MHz) 8.3 (s, 1H), 8.0 (d, 2H), 7.4-7.8 (m, 4H), 7.3 (q, 1H), 6.4 (d, 1H), 5.8 (d, 1H), 4.8 (s, 2H).

Example 5: Synthesis of 1-dodecyl-3- (4-vinylbenzyl) imidazolium salt (2)

10.00 g (0.055 mol) of vinylbenzylimidazole synthesized in Example 4 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 13.53 g (0.055 mol) of bromododecane was added thereto, followed by reaction at 50 ° C. for 12 hours. . After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a slightly yellowish viscous solid product.

Yield 14.58 g (61%)

¹ H NMR (CDCl ₃ , 200 MHz) 10.8 (s, 1H), 7.3 to 7.7 (m, 4H), 6.6 (m, 1H), 5.6 (d, 1H), 5.5 (s, 2H), 5.2 (d, 1H), 4.3 (t, 2H), 1.8 (m, 2H), 1.2 (m, 18H), 0.9 (t, 3H).

Example 6 Synthesis of 1-butyl-3-benzylimidazolium Salt

Dissolve 15.00 g (0.12 mol) of 1-butylimidazole in 50 ml of dimethyl sulfoxide (DMSO), add 10.00 g (0.079 mol) of benzyl chloride, and react with stirring at a temperature of 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a white solid product.

Yield 12.05 g (61%), mp 30-37 ° C.

¹ H NMR (CDCl ₃ , 200 MHz) 10.6 (s, 1H), 7.2-7.8 (m, 7H), 5.6 (d, 2H), 4.3 (t, 2H), 1.8 (m, 2H), 1.3 (m, 2H), 0.9 (t, 3H).

Example 7: 1-dodecyl-3-benzylimidazolium salt synthesis

20.00 g (0.085 mol) of 1-dodecylimidazole is dissolved in 50 ml of dimethyl sulfoxide (DMSO), and 10.00 g (0.079 mol) of benzyl chloride are added and reacted with stirring at a temperature of 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a white solid product.

Yield 13.12 g (51%), mp 50-57 ° C.

¹ H NMR (CDCl ₃ , 200 MHz) 10.6 (s, 1H), 7.2-7.8 (m, 7H), 5.6 (d, 2H), 4.3 (t, 2H), 1.8 (m, 2H), 1.2 (m, 18H), 0.9 (t, 3H).

Example 8: Copolymerization of 1-butyl-3- (4-vinylbenzyl) imidazolium salt with methylmethacrylate

3.00 g (0.011 mol) of 1-butyl-3- (4-vinylbenzyl) imidazolium salt synthesized in Example 1 was placed in a 20 ml Pyrex glass polymerization tube and 1.08 g (0.011 mol) of methyl methacrylate and initiator AIBN. (0.036 g, 1 mol% based on the monomer) was added thereto, dissolved in 4.0 ml of chloroform, and then sealed in three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 3.12 g (76%)

Example 9: Copolymerization of 1-hexyl-3- (4-vinylbenzyl) imidazolium salt with methylmethacrylate

3.00 g (0.0098 mol) of 1-hexyl-3- (4-vinylbenzyl) imidazolium salt synthesized in Example 2 was placed in a 20 ml Pyrex glass polymerization tube, 0.98 g (0.0098 mol) of methyl methacrylate and an initiator. AIBN (0.026 g, 1 mol% based on the monomer) was added thereto, dissolved in 4.0 ml of chloroform, and sealed after 3 cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 3.05 g (77%)

Example 10 Copolymerization of 1-dodecyl-3- (4-vinylbenzyl) imidazolium salt with methylmethacrylate

3.00 g (0.008 mol) of 1-dodecyl-3- (4-vinylbenzyl) imidazolium salt synthesized in Example 3 was placed in a 20 ml Pyrex glass polymerization tube and 0.77 g (0.008 mol) of methyl methacrylate and initiator AIBN (0.026 g, 1 mol% based on the monomer) was added thereto, dissolved in 4.0 ml of chloroform, and sealed after 3 cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.

Yield 2.95 g (78%)

Example 11: Antimicrobial Activity Test of Imidazolium Salt Monomer

In Example 11, benzalkonium chloride [BKC: alkylbenzyldimethylammonium chloride, C ₁₂ H ₂₅ N (CH ₃ ) ₂ C ₇ is generally used as an antimicrobial or preservative in the preparation of disinfectants, household detergents and cosmetics used in hospitals. H ₇ Cl] and a water-soluble chitosan (Mwt. 20,000, Co., Ltd.), an antimicrobial polymer processed with natural chitin, were used as a control for antimicrobial activity test.

(1) Preparation of Test Microorganisms

Gram-positive bacteria Staphylococcus aureus (ATCC 25923) and Gram-negative bacteria Escherichia coli (ATCC 25922) were used for the antimicrobial activity test. In order to obtain a Staphylococcus aureus culture, a small amount of colonies formed on nutrient agar plates were inoculated into brain heart infusion broth (BHIB) and inoculated in brain heart infusion broth (BHIB). The aerobic shake (120 rpm) was incubated for hours. In addition, a small amount of colonies formed on trypticase soy agar plate medium were obtained from platinum to inoculate in tryticase soy broth (TSB) in order to obtain an E. coli exponent culture. Shaking culture was aerobic at 37 ℃ in the same manner. The exponential cultures of each bacteria were collected, diluted in Mueller-hinton broth (MHB), and the final concentration of the bacteria was 1x10 ⁶ ~. Adjust to 1 × ^{10 8} CFU / ml.

(2) Test contents and method

A) antimicrobial activity test by disk diffusion method

In order to test the antimicrobial activity of the imidazolium salt monomer samples synthesized in the present invention against non-suspendable bacteria, Kirby-Bauer modification was performed. In order to produce an antimicrobial test disc, the monomers synthesized in the present invention were dissolved in a solvent of water or methanol, respectively, to make a final concentration of 100 mg / ml. 20 μl of each of these solutions was taken and dropped in the center of a sterile filter paper (6 mm in diameter) containing no antimicrobial agent, and dried at room temperature for at least 6 hours. In addition, in order to confirm whether the solvent itself affects the antimicrobial test, the disc was manufactured by the same method as above using only the solvent containing no monomer at all. Ultraviolet rays were irradiated at room temperature for 1 hour to sterilize a disk containing a solvent or 2 mg of antimicrobial test substance. Staphylococcus or E. coli An exponential culture (1 × ^{10 8} CFU / ml) was evenly coated on a MHA plate medium using a sterile swab, and then different types of antimicrobial test sample discs were placed thereon at regular intervals. After incubation of MHA plate medium at 35-37 ° C. for 24 hours, the growth inhibition zone formed around the disc was measured and recorded in mm to evaluate the antimicrobial activity.

B) determination of the sensitivity of the microorganisms to the sample;

In order to test the susceptibility of the bacteria to the sample synthesized in the present invention, the minimum inhibitory concentration (MIC) was measured according to the broth dilution method. Sterile distilled water was used to make sample dilutions in the range of 0-1600 μg / ml with a 2-fold concentration gradient, and then each sample dilution was dispensed into the test tube by 3 ml. Here, 3 ml of each of the exponential cultures of each bacterium previously adjusted to 1 × 10 ⁶ CFU / ml was added thereto, and then incubated at 35-37 ° C. for 18 to 20 hours. The final concentration of the antimicrobial agent in vitro, in which no growth of bacteria was observed visually after incubation, was determined by the MIC value.

(3) Evaluation result of microorganism's antimicrobial activity on sample

As a result of the antimicrobial activity test of the imidazolium salt monomer synthesized in the present invention by the disk diffusion method for two bacteria, it showed antimicrobial activity similar to the water-soluble chitosan (WSC) used as a general antimicrobial agent. Since the disk diffusion method is an antimicrobial evaluation against non-suspendable bacteria, MIC measurement was performed to evaluate the antimicrobial activity against suspended bacteria. Table 1 shows the bacterial susceptibility in MIC comparing four imidazolium salt monomers and BKC and WSC used as antimicrobial agents as controls. As a result of testing the susceptibility to the two bacteria, the MIC of BKC was much better than the water-soluble polymer chitosan. In the imidazolium salt antimicrobial sample, the long alkyl group substituted imidazolium salt of dodecyl (Examples 3 and 7) showed better antimicrobial activity than BKC. Also in the synthetic polymer sample containing an imidazolium salt monomer substituted with a long alkyl group of dodecyl (Example 10), antibacterial activity was superior to that of water-soluble chitosan.

TABLE 1

Antimicrobial Activity Test Results: Minimum Inhibitory Concentration (MIC, μg / ml)

Sample (solvent) Staphylococcus (ATCC 25923) Escherichia coli (ATCC 25922) Example 1 (methanol) 100 100 Example 3 (methanol) 0.195 or less 0.781 Example 6 (Methanol) 800 200 Example 7 (Methanol) 0.39 0.781 Example 8 (Methanol) 25 25 Example 10 (Methanol) 3.125 25 BKC (distilled water) 1.563 3.125 WSC (distilled water) 25 25

According to the present invention, a water-soluble antimicrobial imidazolium salt derivative having excellent antimicrobial activity, a preparation method thereof, and an antimicrobial polymer material using the same are provided. The polymer produced by radical polymerization of the imidazolium salt derivative according to the present invention is an antimicrobial polymer material which can be variously applied.

The antimicrobial imidazolium salt according to the present invention can be used as an aqueous solution of household detergents, disinfectants, preservatives, etc., and the antimicrobial imidazolium polymer material is used for building materials such as floor coverings, wallpaper, etc. It is hygienic because it can be easily used as an antimicrobial treatment material for telephones, subways, bathroom door handles, etc., and can be applied as an antimicrobial polymer material to exterior materials, coatings and packaging materials of electric and electronic products.

Claims (5)

The antimicrobial imidazolium salt derivative represented by the following formula (1): [Formula 1]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ and R ² are each an alkyl group represented by-(CH ₂ ) _x Y, wherein x is an integer of 0 to 20, R ³ , R ⁴ , R ⁵ and R ⁶ are each H or CH = CH ₂ , n is an integer from 0 to 12, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH or CO ₂ H. A method for preparing an antimicrobial imidazolium salt derivative of Formula 1, comprising reacting a compound represented by Formula 2 with a substituted imidazole represented by Formula 3: [Formula 1]

[Formula 2]

[Formula 3]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ and R ² is an alkyl group represented by-(CH ₂ ) _x Y, where x is an integer from 0 to 20, R ³ , R ⁴ , R ⁵ and R ⁶ are each H or CH = CH ₂ , n is an integer from 0 to 12, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH or CO ₂ H, Z is a bromine or chlorine atom. An antimicrobial composition comprising the antimicrobial imidazolium salt derivative according to claim 1. A styrene-based imidazolium salt-containing antimicrobial polymer represented by the following general formula (4) obtained by radical polymerization of an antimicrobial imidazolium salt monomer represented by the following general formula (1): [Formula 1]

[Formula 4]

In formula, X ^- is a chlorine ion, bromine _{^{ion, BF 4 -, PF 6 -}} , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion selected from the group consisting of, ^- CO ₂ ^- and CH ₃ CO ₂ m is an integer from 1 to 12, R ¹ and R ² are each an alkyl group represented by-(CH ₂ ) _x Y, wherein x is an integer of 0 to 20, R ³ , R ⁴ , R ⁵ and R ⁶ are each H or CH = CH ₂ , and n is an integer from 0 to 12, provided that any one or both of R ³ and R ⁴ are necessarily CH = CH ₂ , Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH ₂ , OH or CO ₂ H, M is a repeating unit derived from a vinyl comonomer selected from (meth) acrylic acid, (meth) acrylic acid ester, vinyl acetate, acrylonitrile, (meth) acrylamide, styrene and butadiene monomers, a is 3 to 100%, b is 0 to 97%, and a + b = 100. An antimicrobial polymeric material containing the imidazolium salt containing antimicrobial polymer of Claim 4.