KR100405030B1 - New UV-curing antibacterial agents - Google Patents

Abstract

The present invention relates to a UV curable antimicrobial agent, and more particularly, the antimicrobial activity, as well as UV curing properties of the antimicrobial compound is coated with a solvent-free form on the surface of the substrate that requires antimicrobial treatment when the antimicrobial compound is polymerized ( The present invention relates to a UV curable antimicrobial agent represented by the following Chemical Formula 1, which is polymerized) and adheres to a substrate surface so that the substrate surface exhibits antibacterial activity semi-permanently.

Formula 1

In Chemical Formula 1, R represents a hydrogen atom or a methyl group; X represents a halogen atom.

Description

New UV-curing antibacterial agents

The present invention relates to a UV curable antimicrobial agent, and more particularly, the antimicrobial activity, as well as UV curing properties of the antimicrobial compound is coated with a solvent-free form on the surface of the substrate that requires antimicrobial treatment when the antimicrobial compound is polymerized ( The present invention relates to a UV curable antimicrobial agent represented by the following Chemical Formula 1, which is polymerized) and adheres to a substrate surface so that the substrate surface exhibits antibacterial activity semi-permanently.

Formula 1

In Chemical Formula 1, R represents a hydrogen atom or a methyl group; X represents a halogen atom.

Fungi can be divided into two types, bacteria and fungi. Existing antimicrobial agents that act on these two classes of bacteria are widely known as phenolic, benzoic acid, quaternary ammonium salts, imidazoles, β-lactams, and naturally occurring extracts. These antimicrobials have been used mainly as coatings and other additives where germs can grow, including clothing, home flooring, bath tubs, washbasins, telephones and public areas.

In other words, conventional antimicrobial agents have been generally used in the form of additives, but it is convenient to use them as additives, but mainly in excess, and only a part of the added antimicrobial substances exhibits antimicrobial activity on the substrate surface. It is observed that the antimicrobial activity is drastically reduced by continuous washing of the action site. Therefore, after the coating treatment on the surface of the substrate that requires antimicrobial activity, rather than using the antimicrobial agent in the form of additives, it will be possible to obtain a semi-permanent antimicrobial effect by converting and attaching the polymer structure. However, in the field of antimicrobial agents, additives are still mainly used. The reason is that when antimicrobial agents are used as additives, the antimicrobial effect is maintained for a certain period of time, but UV-curable antimicrobial is coated in monomer form and converted into polymer through UV irradiation. This is because the chemical structure of the antimicrobial substance itself is modified, which is why most cases do not exhibit an antimicrobial effect.

Therefore, the present invention has been studied for a long time to introduce a coating method by UV curing, which is widely used in other polymer industries in addition to the antibacterial field, and as a result, the present invention was completed by developing a new antibacterial agent having UV curing properties.

That is, in the present invention, rather than using an antimicrobial agent in the form of additives, the antimicrobial coating is applied to the surface of the substrate in the form of a solvent-free, and then polymerized in a short time by one UV irradiation, since the polymerized antimicrobial is evenly attached to the substrate surface. Uniform antimicrobial effect can be obtained on the entire surface of the applied substrate. In addition, since the antimicrobial coating solution of the present invention is used in the form of a solvent-free, since the evaporation phenomenon of a solvent harmful to the human body does not appear after UV curing, this may also be an advantage. In addition, even a small amount of antimicrobial coating has the advantage of sustaining antimicrobial power semi-permanently, and it is expected to minimize other side effects such as damage to the human body and environmental pollution due to evaporation of harmful solvent and loss of antimicrobial agent appearing in the existing additive method do.

Accordingly, an object of the present invention is to provide a novel UV curable antimicrobial agent comprising an imidazole quaternary ammonium salt with an acrylic or methacryl functional group which can easily cause a polymerization reaction even with low energy.

In addition, the present invention is another object to provide an antimicrobial treatment method for fixing a novel antimicrobial agent to the surface of the substrate by UV irradiation after the coating treatment on the surface of the substrate that requires antimicrobial activity.

1A and 1B are IR spectra and ¹ H NMR spectra for 1,3-bis (11-hydroxyundecyl) imidazolinium bromide synthesized in Example 1, respectively.

2A and 2B are IR spectra and ¹ H NMR spectra for 1,3-bis (11-hydroxyundecyl) imidazolinium chloride synthesized in Example 2, respectively.

Figure 3a, a 1,3-bis prepared in Example 3 3b and 3c are each IR spectrum for the [11 - [(1-oxo-2-propenyl) oxy] undecyl] imidazolidine bromide, ¹ H NMR spectrum and ¹³ C NMR spectrum.

4A and 4B show IR spectra and ¹ H NMR for 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium chloride synthesized in Example 4, respectively. Spectrum.

5A, 5B and 5C show the 1,3-bis [11-[(1-oxo-2-methyl-2-propenyl) -oxy] undecyl] imidazolinium bromide synthesized in Example 5, respectively. IR spectrum, ¹ H NMR spectrum and ¹³ C NMR spectrum.

The present invention is characterized by a UV curable antimicrobial agent represented by the following formula (1).

Formula 1

In Chemical Formula 1, R represents a hydrogen atom or a methyl group; X represents a halogen atom.

The present invention will be described in more detail as follows.

The imidazolinium compound represented by Chemical Formula 1 according to the present invention is a novel compound, and has antibacterial activity as well as UV curing properties. The imidazolinium compound is polymerized to form a polymer film on the surface of the substrate. In addition, the formed polymer membrane is uniformly coated on the surface of the substrate, and thus exhibits uniform antimicrobial activity on the entire surface of the applied substrate. Also, since the antimicrobial substance and the coating liquid composition are chemically bonded to each other, the excellent antimicrobial activity is maintained even if it takes a long time. You can.

Specific examples of the imidazolinium compound represented by Chemical Formula 1 according to the present invention are as follows:

1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium halide,

1,3-bis [11-[(1-oxo-2-methyl-2-propenyl) -oxy] undecyl] imidazolinium halide.

In addition, the method for preparing the imidazolinium compound represented by Chemical Formula 1 may be easily prepared by a two-step reaction as described below: First, a general organic solvent containing no halogen Quaternary ammonium salt intermediates are synthesized by the reaction of imidazole with 11-haloundecan-1-ol. An excess of acryloyl chloride or methacryloyl chloride is reacted to synthesize a compound represented by Chemical Formula 1 as desired.

In addition, the novel antimicrobial agent represented by the formula (1) as described above is treated with antimicrobial treatment by UV irradiation after coating the surface of the substrate requiring antimicrobial activity. For example, 1 to 10% by weight of the antimicrobial agent represented by Formula 1, 30 to 80% by weight of aliphatic urethane triacrylate oligomer, 1 to 10% by weight of hydroxypropyl acrylate (HPA), 1 to 3% of trimethylpropane triacrylate (TMPTA) 10% by weight, 5 to 20% by weight 1,6-hexanedioldiacrylate (HDDA), 5 to 20% by weight tripropylneoglycoldiacrylate (TPGDA) and 1 to 5% by weight photoinitiator (e.g. Irgacure 184) The antimicrobial coating solution is prepared by mixing% and the like in an appropriate ratio. If the content of the antimicrobial agent contained in the antimicrobial coating solution is less than 1% by weight, the antimicrobial effect desired by the present invention cannot be obtained, and the content of the antimicrobial agent is greater than 10% by weight. Even if it does not get a significant antimicrobial effect can be said to be uneconomical and other properties such as yellowing may appear. In addition, in order to form the antimicrobial polymer film of the antimicrobial agent represented by Chemical Formula 1 by UV curing, in the present invention, an aliphatic urethane triacrylate oligomer, hydroxypropyl acrylate (HPA), trimethyl propane triacryl based on the total coating solution Latex (TMPTA), 1,6-hexanedioldiacrylate (HDDA), tripropylneoglycoldiacrylate (TPGDA). When the content of each component used to form the antimicrobial polymer film is used below the above range, the crosslink density of the cured coating film is low, resulting in a problem of low hardness and weather resistance, and exceeds the content range of each component When used, there is a problem in that the crosslink density of the cured coating film becomes high, thereby decreasing the flexibility of the coating film. If the content of the photoinitiator is less than 1% by weight, the coating is not cured. If the content of the photoinitiator is greater than 5% by weight, unreacted species that do not participate in curing remain, causing odors, and deteriorating coating properties such as hardness and weather resistance. In addition, the antimicrobial coating liquid may contain a solvent, but is preferably used in a solvent-free state. Coating the antimicrobial coating solution on the surface of the substrate that requires antimicrobial activity is a coating method according to a known method, when the UV irradiation after coating is converted to the polymer imidazolinium compound represented by the formula (1) and the coating It forms a chemical bond with the compositions and adheres firmly to the substrate surface.

As described above, as a result of searching for the antimicrobial activity and the antimicrobial retention ability of the substrate treated with the antimicrobial coating of the imidazolinium compound represented by the formula (1) according to the present invention, the activity on the surface of the substrate evenly search for It was possible to search for a good antibacterial activity even if left in water for 24 hours.

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Synthesis of 1,3-bis (11-hydroxyundecyl) imidazolinium bromide

A mixed solution of 3.41 g (50 mmol) of imidazole, 25 g (100 mmol) of 11-bromo-1-undecanol and 50 mL of ethanol was stirred at 100 ° C. for 48 hours. The ethanol was distilled off under reduced pressure, and the reaction mixture was washed successively with 30 mL of ethyl acetate, 30 mL of 2M hydrogen bromide, and 30 mL of water, and dried under reduced pressure to obtain 14.8 g of a white solid product.

Yield 60%; mp 112-115 ° C .; IR (KBr) ν _max 3386 (OH), 3103 (Aromatic CH), 2928, 2850 (CH) cm ⁻¹ ; ¹ H NMR (CD ₃ OD, 500 MHz) δ 8.97 (s, 1H, H -2), 7.57 (s, 2H, H -4,5), 4.13 (t, 4H, 2N ⁺ C H ₂ , J = 7.2 Hz), 3.43 (t, 4H, 2C H ₂ OH, J = 6.6 Hz), 1.81 (m, 4H), 1.42 (m, 4H), 1.23 (m, 28H).

Example 2 Synthesis of 1,3-bis (11-hydroxyundecyl) imidazolinium chloride

A mixed solution of 3.41 g (50 mmol) of imidazole, 25 g (100 mmol) of 11-bromo-1-undecanol, and 50 mL of ethanol was stirred at 100 ° C. for 48 hours. Ethanol was distilled under reduced pressure, and 30 mL of 2M hydrogen chloride was added to the reaction mixture, followed by stirring for 30 minutes. The solid product was filtered from the reaction solution, washed with 40 mL of ethyl acetate and 20 mL of water, and dried under reduced pressure to obtain 13.5 g of a white solid product.

Yield 61%; mp 115 ° C; IR (KBr) ν _max 3376 (OH), 3156 (Aromatic CH), 2920, 2851 (CH) cm ⁻¹ ; ¹ H NMR (CD ₃ OD, 300 MHz) δ7.90 (s, 1H, H -2), 7.66 (s, 2H, H -4,5), 4.22 (t, 4H, 2N ⁺ C H ₂ , J = 7.2 Hz), 3.53 (t, 4H, 2C H ₂ OH, J = 6.6 Hz), 1.89 (m, 4H), 1.51 (m, 4H), 1.31 (m, 28H).

Example 3 Synthesis of 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium bromide

8.5 g (17 mmol) of 1,3-bis (11-hydroxyundecyl) imidazolinium bromide and 0.22 g of hydroquinone were dissolved in 90 mL of acryloyl chloride, followed by addition of 1 mL of anhydrous sulfuric acid. The reaction solution was stirred at 50 ° C. for 6 hours and then excess acryloyl chloride was distilled off under reduced pressure. The reaction mixture was dissolved in 40 mL of ethyl acetate, washed with 20 mL of water, and dried under reduced pressure to obtain 5.8 g of a white solid product.

Yield 56%; mp 116.5-118.6 ° C .; IR (CHCl ₃ ) ν _max 3175 (Aromatic CH), 3026 (CH), 1742 (C = O), 1676 (C = C) cm ⁻¹ ; ¹ H NMR (DMSO- d ₆ , 300 MHz) δ 9.05 (s, 1H, H -2), 7.65 (s, 2H, H -4,5), 6.15 (dd, 2H, 2 trans -C H ₂ , J _gem = 1.8, J _trans = 17.3 Hz, 5.95 (dd, 2H, 2C H , J _cis = 10.1 Hz), 5.75 (dd, 2H, 2 cis- C H ₂ ), 4.00 (t, 4H, 2N ⁺ C H ₂ , J = 7.1 Hz), 3.87 (t, 4H, 2C H ₂ O, J = 6.6 Hz), 1.57 (m, 4H), 1.37 (m, 4H), 1.1 (m, 28H); ¹³ C NMR (DMSO- d ₆ , 300 MHz) δ 165.5, 135.9, 131.4, 128.4, 122.5, 64.1, 48.8, 40.3, 38.7, 29.2, 28.9, 28.8, 28.6, 28.3, 28.1, 25.4, 25.3

Example 4 Synthesis of 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium chloride

5 g (11 mmol) of 1,3-bis (11-hydroxyundecyl) imidazolinium chloride and 0.13 g of hydroquinone were dissolved in 50 mL of acryloyl chloride, followed by addition of 1 mL of anhydrous sulfuric acid. The reaction solution was stirred at 50 ° C. for 5 hours, and then excess acryloyl chloride was distilled off under reduced pressure. The reaction mixture was dissolved in 40 mL of ethyl acetate, washed with 10 mL of water, dried under reduced pressure, and the remaining reaction mixture was separated and purified by column chromatography (chloroform / methanol = 1/10) to obtain 3.7 g of a syrup-like product.

Yield 60%; IR (CHCl ₃ ) ν _max 3175 (Aromatic CH), 3026 (CH), 1748 (C = O), 1676 (C = C) cm ⁻¹ ; ¹ H NMR (DMSO- d ₆ , 300 MHz) δ 9.23 (s, 1H, H -2), 7.80 (s, 2H, H -4,5), 6.34 (dd, 2H, 2 trans -C H ₂ , J _gem = 1.8, J _trans = 17.3 Hz, 6.28 (dd, 2H, 2C H , J _cis = 10.1 Hz), 5.93 (dd, 2H, 2 cis- C H ₂ ), 4.16 (t, 4H, 2N ⁺ C H ₂ , J = 7.1 Hz), 4.08 (t, 4H, 2C H ₂ O, J = 6.6 Hz), 1.78 (m, 4H), 1.46 (m, 4H), 1.23 (m, 28H)

Example 5 Synthesis of 1,3-bis [11-[(1-oxo-2-methyl-2-propenyl) -oxy] undecyl] imidazolinium bromide

5 g (10 mmol) of 1,3-bis (11-hydroxyundecyl) imidazolinium bromide and 0.15 g of hydroquinone were dissolved in 60 mL of methacryloyl chloride, followed by addition of 1 mL of anhydrous sulfuric acid. The reaction solution was stirred at 50 ° C. for 5 hours, and excess methacryloyl chloride was distilled off under reduced pressure. The reaction mixture was dissolved in 40 mL of ethyl acetate, washed with 10 mL of water, dried under reduced pressure, and the remaining reaction mixture was separated and purified by column chromatography (chloroform / methanol = 1/10) to obtain 3.6 g of a syrup form product.

Yield 58%; IR (CHCl ₃ ) ν _max 3185 (Aromatic CH), 3021 (CH), 1743 (C═O), 1676 (C═C) cm ⁻¹ ; ¹ H NMR (DMSO- d ₆ , 300 MHz) δ 9.20 (s, 1H, H -2), 7.70 (s, 2H, H -4,5), 5.83 (d, 2H, 2 trans -C H ₂ , J _gem = 1.8, Hz), 5.48 (d, 2H, 2 cis- C H ₂ ), 4.97 (t, 4H, 2N ⁺ C H ₂ , J = 7.1 Hz), 4.84 (t, 4H, 2C H ₂ 0, J = 6.5 Hz), 1.67 (m, 4H, 2C H ₃ ), 1.57 (m, 4H), 1.49 (m, 4H), 1.17 (m, 4H); ¹³ C NMR (DMSO- d ₆ , 300 MHz) δ: 167..8, 137.2, 137.1, 126.7, 123.7, 65.5, 50.1, 41.6, 39.9, 30.5, 30.1, 30.0, 29.8, 29.6, 29.3, 26.7, 26.6

Example 6 Antibacterial Coating on PVC Flooring

5% by weight of the antimicrobial compound of the present invention is 60% by weight of an aliphatic urethane triacrylate oligomer, 5% by weight of Irgacure 184 as a photoinitiator, 5% by weight of trimethylpropanetriacrylate (TMPTA), 1,6-hexanedioldiacrylate (HDDA) 10% by weight, 10% by weight of tripropyl neoglycol diacrylate and 5% by weight of hydroxypropyl acrylate (HPA), a diluent, are mixed without solvent and maintained at a viscosity of 700 to 800 cps at 25 ° C. The mixture was coated on a 3 mm PVC floor using a bar coater # 7 so as to have a thickness of 15 μm to 18 μm after curing. In addition, the sample prepared by the above method was cured under the same conditions at a conveyor speed of 6 m / min UV curing machine consisting of ^two 80 watt / cm ² medium pressure mercury lamp. At this time, the amount of light received by the PVC coated sample passing down about 15 cm from the lamp (IL390B Light Bug) was measured to be approximately 400 mJ / cm ² in one pass.

Experimental Example 1 Screening of Antimicrobial Activity against Microorganisms of a UV-Coated Plate Sample I

(1) target microorganism preparation

Bacillus subtilis , Proteus vulgaricus and Staphylococcus aureus were selected as the microorganisms to be tested , and each of these microorganisms was incubated in Nutrient Agar medium or TSB medium for 12 hours. Tween 80 0.1% was added in consideration of adhesion to the substrate. Inoculation density of microorganisms in each stock solution is shown in Table 1 below.

Fungal species Bacterial Density in Inoculator badge Bacillus subtilis 8 × 10 ⁷ / mL Nutrient Agar Badge 4 × 10 ⁷ / mL TSB badge Proteus vulgaricus 5 × 10 ⁷ / mL Nutrient Agar Badge Staphylococcus aureus 2 × 10 ⁷ / mL TSB badge

(2) Test contents and method

A plate sample coated with antimicrobial coating of 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium bromide by the method of Example 6 in the form of a diameter of 35 mm Ready. And another control plate sample which was not treated with antimicrobial was prepared as a control. The prepared jangpan sample was soaked in 100% ethanol for 3 minutes and sterilized sufficiently before being used for the test.

And 30 microliters of the microbial fluid prepared above to each plate sample After spraying evenly, it was left for 1 hour. The bottom surface inoculated with the microorganisms was pressed onto the surface of the TSA medium to inoculate the long microorganisms into the medium. After culturing at 30 ° C. for 2 days, the antimicrobial activity was evaluated by counting colony counts, and the results are shown in Table 2 below.

Fungal species Number of colonies (%) Control group ^a) Antimicrobial coated flooring ^b) Bacillus subtilis 100 0 Proteus vulgaricus 100 20 Staphylococcus aureus 100 30 a): Percentage (%) of colony water grown in the plate-free self-treatment group without antibacterial treatment b): 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imida Flooring Antibacterial with Zolinium Bromide

According to Table 2, the UV coating flooring material of the formulation prepared by adding 5% by weight of 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium bromide As a result, three bacteria ( Proteus, Bacillus, Staphylococcus ) were tested as samples and showed excellent antimicrobial activity against strain Bacillus subtilis , and the efficacy of the other two strains was found to be excellent.

Experimental Example 2 Screening of Antimicrobial Activity against Microorganisms of a UV-Coated Plate Sample ∏

(1) target microorganism preparation

Klepsiella pneumoniae (aka, pneumococcal pneumoniae) was cultured in the liquid phase as a test strain to prepare a 2.0 × 10 ⁶ cfu / mL bacterial solution in a state of vigorous growth.

(2) Test contents and method (contact method)

As a control, a 40% solution of 1-iodopropynylbutylcarbamate dissolved in toluene and N -methylpyrrolidinone, i.e., IP40 (trade name) in an additive manner, 1% (A1), 2% (A2), 3 % (A3) and 8% (A8) were mixed, which was coated onto a PVC flooring to prepare a sample. In addition, 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium bromide contained 5% (ID5) and 8% (ID8), respectively, as a test zone. A coating solution was prepared, and the coating solution was coated on a PVC flooring material, followed by UV irradiation to prepare a UV coating flooring material as a sample. Samples were prepared by cutting each prepared sample to 3 cm in length and width.

Nutrient agar (Difco, USA) medium was dispensed in 20 mL in a sterile culture dish (8.7 cm in diameter). Then, 0.5 mL of the bacterial solution was added to the upper lid of the Nutrient agar culture dish (inoculation density 1.0 × 10 ⁶ cfu / mL), and the sample was placed on the upper portion of the bacterial solution and adhered to the culture medium. Cover the dish upside down. Incubated for 24 hours at 28 ℃ constant temperature. After removing the coating bottom material on the lid of the culture dish and washing with 1 mL of distilled water, the number of bacteria in the lid was measured by the continuous dilution method.

The following Table 3 shows the bacterial kill rate as a result of the antimicrobial activity test on the flooring as described above.

Mycelial killing rate (cfu / mL) Test Item Comparison Test strip No treatment A1 A2 A3 A8 ID5 ID8 Viable count 9 × 10 ⁵ 7 × 10 ⁵ 7 × 10 ³ 4 × 10 ³ 1 × 10 ⁵ 2.5 × 10 ² 2 × 10 ⁶ % Mortality 10 30 99.3 99.6 80 99.98

According to Table 3, the UV plate treated test plate (ID test) with the antimicrobial agent of the present invention showed an excellent antimicrobial activity against Klepsiella pneumoniae (pneumococcal dicocci ). Particularly, in ID8 jang plate, the number of viable cells was lower than that in A8 plate of comparison group, so the mortality rate was higher.

Experimental Example 3 Test of Persistence of Antimicrobial Activity

By measuring the mortality rate for Klepsiella pneumoniae (pneumococcal pneumoniae) by drying the left wood comparison sphere (A8) and the test sphere (ID8) prepared in the same manner as in Experimental Example 2 and left in water for 24 hours at 40 ℃ Antimicrobial persistence was searched. As a result, the killing rate was 70% for A8 and 99.9% for ID8.

As a result, it can be seen that the additive-type flooring material A8 is a part of the antimicrobial material coated under the above conditions is eluted in water and the antimicrobial activity is reduced. It was found that the antimicrobial substance was not eluted through the solid polymer bond.

As described in detail above, the novel UV curable antimicrobial agent according to the present invention possesses UV curing properties at the same time as antibacterial activity. When this material is coated with a solvent-free form on the surface of the substrate requiring antimicrobial treatment and then UV treated, a strong polymer bond is formed between the compound represented by Formula 1 and the coating compositions, and is attached to the surface of the substrate. It shows activity, and by uniformly coating the antimicrobial coating solution, it shows the antimicrobial activity evenly on the entire surface of the substrate. In particular, it was found that the concentration of 1,3-bis [11-[(1-oxo-2-propenyl) -oxy] undecyl] imidazolinium bromide polymers was used to detect antibacterial activity against bacteria. Also showed excellent antibacterial activity against 4 kinds of bacteria.Klepsiella pneumoniaeAbout It showed better antimicrobial activity and antimicrobial persistence than the existing additive antimicrobial IP40.

Therefore, by using the UV-curable antimicrobial agent of the present invention in the form of a solvent-free, problems such as short antimicrobial persistence, side effects on the human body and environmental pollution of the existing additive antimicrobial agent can be solved at the same time.

Claims (3)

UV curable antimicrobial agent represented by the following formula (1). Formula 1 In Chemical Formula 1, R represents a hydrogen atom or a methyl group; X represents a halogen atom. The compound according to claim 1, wherein X is a chlorine atom, a bromine atom or an iodine atom. 1 to 10% by weight of the antimicrobial agent represented by the following formula (1), 30 to 80% by weight of aliphatic urethane triacrylate oligomer, 1 to 10% by weight of hydroxypropyl acrylate, 1 to 10% by weight of trimethylpropanetriacrylate, 1,6 5-20% by weight of hexanediol diacrylate, 5-20% by weight of tripropyl neoglycol diacrylate, and 1-5% by weight of photoinitiator are coated on the surface of the substrate, followed by UV irradiation. The antimicrobial treatment method characterized in that the polymerized and attached to the antimicrobial agent of the following formula (1). Formula 1 In Chemical Formula 1, R represents a hydrogen atom or a methyl group; X represents a halogen atom.