Antibacterial composition

Abstract

The present specification relates to an antibacterial composition comprising at least one compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group, and having an antibacterial intensity A of 90% or more and an acute oral toxicity dose LD50 of 300 mg / Kg or more, the antibacterial intensity A being measured by the following Method 1 on at least one strain of Gram-positive bacteria and Gram-negative bacteria.

Description

TECHNICAL FIELD

[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0093569, filed on July 16, 2021, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

[0002] The present application relates to an antibacterial composition. BACKGROUND

[0003] Recently, various products such as daily necessities or sanitary products need to have antibacterial properties.

[0004] The degree of antibacterial properties required and the material required for imparting antibacterial properties differ depending on the material of the product requiring antibacterial properties and the end use state. For example, the properties of the material for imparting antibacterial properties and the degree of antibacterial properties differ depending on the amount of antibacterial material applied to the product and the material used together.

[0005] Therefore, there is a need to develop antibacterial materials suitable for application to various different products. SUMMARY

[0006] TECHNICAL PROBLEM

[0007] The present application is directed to providing an antibacterial composition comprising an antibacterial material having hydrophilicity and hydrophobicity, and thus is advantageous for imparting antibacterial properties, and by forming a copolymer with an acryl-based resin or the like, not only can antibacterial properties be imparted, but also safety problems due to leakage of the antibacterial material can be solved.

[0008] TECHNICAL SOLUTION

[0009] One exemplary embodiment of the present application provides an antibacterial composition comprising at least one compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group, and having an antibacterial strength A of 90% or more and an acute oral toxicity dose LD50 of 300 mg / Kg or more, the antibacterial strength A being measured by the following Method 1 on at least one strain of gram-positive bacteria and gram-negative bacteria:

[0010] [Method 1]

[0011] After putting 25 ml of a broth type medium (nutrient broth, BD DIFCO., 8 g / L) inoculated with 3,000 CFU / ml of bacteria into a 50 mL conical tube, 0.015 g of an antibacterial composition was added thereto and suspended (vortexed), and the well-mixed solution was cultured in a shaking water bath maintained at 35°C for 16 hours,

[0012] After diluting the cultured solution to 1 / 5 using a 1X PBS buffer solution, the absorbance (λ = 600 nm) is measured using a UV / Vis spectrophotometer, and the antibacterial strength as the antibacterial reduction rate is calculated from the following equation by comparing the measured absorbance with that of a solution cultured without the addition of the antibacterial composition,

[0013] Antibacterial strength (%) = (1 - A 样品 / A 参照 ) x 100

[0014] A 样品 = absorbance of the medium solution cultured by the addition of the antibacterial composition

[0015] A 参照 = absorbance of the medium solution cultured without the addition of the antibacterial composition.

[0016] According to another exemplary embodiment of the present application, the Method 1 is measured for at least one strain of Proteus mirabilis, E. coli, S. aureus, E. Cloaceae, and E. faecalis.

[0017] According to still another exemplary embodiment of the present application, the Method 1 is measured for each strain of Proteus mirabilis, E. coli, S. aureus, E. Cloaceae, and E. faecalis.

[0018] According to still another exemplary embodiment of the present application, the antibacterial strength A of the antibacterial composition is expressed within 1 hour.

[0019] According to still another exemplary embodiment of the present application, the ratio (C / B) of the antibacterial strength C of the antibacterial composition measured by the following Method 3 to the antibacterial strength B measured by the following Method 2 is 1 or more and less than 2:

[0020] [Method 2]

[0021] This method is the same as Method 1, except that 0.005 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition,

[0022] [Method 3]

[0023] This method is the same as Method 1, except that 0.02 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

[0024] According to still another exemplary embodiment of the present application, there is provided a product comprising or prepared from the antibacterial composition.

[0025] According to still another exemplary embodiment of the present application, there is provided a compound selected from the group consisting of monomers 1 to 10 below.

[0026]

[0027]

[0028] Advantages

[0029] The antibacterial composition according to some exemplary embodiments of the present application is an antibacterial composition including an antibacterial material having hydrophilicity and hydrophobicity, and thus is advantageous for imparting antibacterial properties, and by forming a copolymer with an acryl-based resin, not only can the antibacterial properties be imparted, but also the safety problem due to leakage of the antibacterial material can be solved, has antibacterial properties controlled within a characteristic range and an acute oral toxicity dose, and can be used as a material capable of safely imparting excellent antibacterial properties.

[0030] The antibacterial composition according to some exemplary embodiments of the present application can exhibit antibacterial properties within a short period of time.

[0031] Since the antibacterial strength of the antibacterial composition according to some exemplary embodiments of the present application is hardly changed according to the amount of the antibacterial material used, even when unevenness in concentration occurs accidentally during application to a product, the antibacterial properties within an intended range can be exhibited. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a graph showing the synthesis of monomer 1 as one exemplary embodiment of the present application. 1 a graph of H-NMR spectrum ((CD3)2SO).

[0033] Figure 2 is a graph showing the synthesis of monomer 2 as one exemplary embodiment of the present application. 1 a graph of H-NMR spectrum ((CD3)2SO).

[0034] Figure 3 is a graph showing the synthesis of monomer 3 as one exemplary embodiment of the present application. 1 a graph of H-NMR spectrum ((CD3)2SO). DETAILED DESCRIPTION

[0035] One exemplary embodiment of the present invention provides an antibacterial composition including at least one compound having a quaternary ammonium structure with an acrylate group or a methacrylate group, and having an antibacterial intensity A of 90% or more and an acute oral toxicity dose LD50 of 300 mg / Kg or more, the antibacterial intensity A being measured by the following Method 1 on at least one strain of gram-positive bacteria and gram-negative bacteria:

[0036] [Method 1]

[0037] After putting 25 ml of a broth type medium (nutrient broth, BD DIFCO., 8 g / L) inoculated with 3,000 CFU / ml of bacteria into a 50 mL conical tube, 0.015 g of an antibacterial composition was added thereto and suspended (vortexed), and the well-mixed solution was cultured in a shaking water bath maintained at 35°C for 16 hours,

[0038] After diluting the cultured solution to 1 / 5 using a 1X PBS buffer solution, the absorbance (λ = 600 nm) was measured using a UV / Vis spectrophotometer, and the antibacterial intensity as the bacteriostatic reduction rate was calculated from the measured absorbance by comparison with a solution cultured without the addition of an antibacterial composition, by the following formula,

[0039] Antibacterial intensity (%) = (1 - A 样品 / A 参照 ) x 100

[0040] A 样品 = absorbance of the medium solution cultured by the addition of an antibacterial composition

[0041] A 参照 = absorbance of the medium solution cultured without the addition of an antibacterial composition.

[0042] When the cation of the ammonium molecule of the quaternary ammonium-based compound is electrostatically adsorbed on the anionic site on the cell surface of bacteria or microorganisms, and the substituent bound to the quaternary ammonium structure is hydrophobic, the compound including a quaternary ammonium structure with an acrylate group or a methacrylate group included in the antibacterial composition can physically and chemically destroy and kill the cell surface layer structure through hydrophobic interaction. In addition, the antibacterial function can be introduced via copolymerization of the acrylate group or the methacrylate group with an acryl-based resin or the like, in which case safety can be improved by preventing leakage of the antibacterial material. According to the exemplary embodiment of the present invention, a high antibacterial property can be safely imparted by including a compound having a quaternary ammonium structure as described above while limiting the antibacterial intensity and the acute oral toxicity dose of the antibacterial composition to a certain range.

[0043] The antibacterial strength referred to in the present specification can be measured against at least one strain of Proteus mirabilis, Escherichia coli, Staphylococcus aureus, Enterobacter cloacae, and Enterococcus faecalis. Preferably, the antibacterial strength referred to in the present specification can be measured against each of Proteus mirabilis, Escherichia coli, Staphylococcus aureus, Enterobacter cloacae, and Enterococcus faecalis. The antibacterial composition according to the exemplary embodiment of the present application can have a certain level or higher antibacterial strength against Gram-positive bacteria and Gram-negative bacteria. ATCC 29906 and CCUG 4637 can be used as Proteus mirabilis, ATCC 13047, ATCC 13048, and CCUG 71839 can be used as Enterobacter cloacae, and ATCC 29212 and CCUG 9997 can be used as Enterococcus faecalis.

[0044] According to another exemplary embodiment of the present application, the antibacterial strength A of the antibacterial composition is expressed within 1 hour. This enables the desired antibacterial strength to be exhibited immediately after the antibacterial composition is applied to a predetermined use or product.

[0045] According to still another exemplary embodiment of the present application, the ratio (C / B) of the antibacterial strength C of the antibacterial composition measured by the following Method 3 to the antibacterial strength B measured by the following Method 2 is 1 or more and less than 2:

[0046] [Method 2]

[0047] This method is the same as Method 1, except that 0.005 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition,

[0048] [Method 3]

[0049] This method is the same as Method 1, except that 0.02 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

[0050] When the antibacterial composition is applied to a predetermined use or product, there can be regions of accidental high and low concentrations of the antibacterial material, and the regions of low concentration can not exhibit the desired antibacterial properties. However, according to the exemplary embodiments, since the antibacterial strength hardly changes depending on the amount of the antibacterial material used, even when inhomogeneity of the concentration accidentally occurs during application to the predetermined use or product, the antibacterial properties within the expected range can be exhibited.

[0051] According to still another exemplary embodiment of the present application, the antibacterial strength A is 99% or more, preferably 99.3% or more, more preferably 99.5% or more, even more preferably 99.7% or more, still even more preferably 99.9% or more.

[0052] According to still another exemplary embodiment of the present application, the antibacterial intensity D measured by the following Method 4 is 65% or more:

[0053] [Method 4]

[0054] This method is the same as Method 1, except that 0.01 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

[0055] According to the exemplary embodiments, excellent antibacterial properties can be provided even when the antibacterial composition is added in an amount of 0.01 g.

[0056] According to another exemplary embodiment of the present application, the antibacterial intensity D can be 65% or more, 68% or more, 68.2% or more, 70% or more. Further, the antibacterial intensity D can be 99% or more, preferably 99.3% or more, more preferably 99.5% or more, even more preferably 99.7% or more, still even more preferably 99.9% or more.

[0057] According to still another exemplary embodiment of the present application, the antibacterial intensity B measured by the following Method 2 is 55% or more:

[0058] [Method 2]

[0059] This method is the same as Method 1, except that 0.005 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

[0060] According to the exemplary embodiments, excellent antibacterial properties can be provided even when the antibacterial composition is added in an amount of 0.005 g.

[0061] According to another exemplary embodiment of the present application, the antibacterial intensity B can be 55% or more, 59% or more, 59.3% or more, 60% or more, 61.2% or more. Further, the antibacterial intensity B can be 99% or more, preferably 99.3% or more, more preferably 99.5% or more, even more preferably 99.7% or more, still even more preferably 99.9% or more.

[0062] According to still another exemplary embodiment of the present application, the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment is 300 mg / Kg or more, more than 300 mg / Kg, 500 mg / Kg or more, preferably 800 mg / Kg or more, more preferably 1000 mg / Kg or more. According to a specific example, the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment can be 800 mg / Kg or more, 843 mg / Kg or more, 869 mg / Kg or more, 900 mg / Kg or more, or 998 mg / Kg or more. The acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment can be 1,000 mg / Kg or more, 1,050 mg / Kg or more, 1,078 mg / Kg or more, 1,100 mg / Kg or more, 1,111 mg / Kg or more, 1,200 mg / Kg or more, 1,242 mg / Kg or more, 1,300 mg / Kg or more, 1,369 mg / Kg or more, 1,400 mg / Kg or more, 1,442 mg / Kg or more, 1,498 mg / Kg or more, 1,500 mg / Kg or more, 1,600 mg / Kg or more, 1,700 mg / Kg or more, 1,708 mg / Kg or more. According to a specific example, the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment can be 843 mg / Kg, 869 mg / Kg, 998 mg / Kg, 1078 mg / Kg, 1111 mg / Kg, 1242 mg / Kg, 1369 mg / Kg, 1442 mg / Kg, 1498 mg / Kg, or 1708 mg / Kg.

[0063] The greater the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment, the lower the toxicity, making the acute oral toxicity dose advantageous. However, the value of LD50 can be determined from the viewpoint that the above antibacterial strength also needs to be satisfied. For example, the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment can be 50,000 mg / Kg or less, for example, 10,000 mg / Kg or less, 5,000 mg / Kg or less, or 2,000 mg / Kg or less. According to one example, the acute oral toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment can be 1,708 mg / Kg or less.

[0064] According to another exemplary embodiment of the present application, the acute percutaneous toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment is 1,000 mg / Kg or more, greater than 1,000 mg / Kg, preferably 1,500 mg / Kg or more, more preferably 2,000 mg / Kg or more. The greater the acute percutaneous toxicity dose LD50 of the antibacterial composition according to the above exemplary embodiment, the lower the toxicity, making the acute percutaneous toxicity dose advantageous.

[0065] According to one exemplary embodiment of the present application, the compound having a quaternary ammonium structure with an acrylate group or a methacrylate group can be selected from those capable of exhibiting the above antibacterial intensity and acute oral toxicity dose LD50 among the compounds represented by the following Chemical Formula 1:

[0066] [Chemical Formula 1]

[0067]

[0068] In Chemical Formula 1,

[0069] L1 is an alkylene group having 2 to 4 carbon atoms,

[0070] R1, R2, and R3 are the same as or different from each other, and each is an alkyl group having 1 to 20 carbon atoms, and

[0071] R4 is hydrogen or a methyl group.

[0072] According to one exemplary embodiment, at least one of R1, R2, and R3 of Chemical Formula 1 is an alkyl group having 8 or more carbon atoms, preferably an alkyl group having 8 to 14 carbon atoms, more preferably an alkyl group having 8 to 12 carbon atoms.

[0073] According to one exemplary embodiment, the sum of the number of carbon atoms of the alkyl groups included in R1, R2, and R3 of Chemical Formula 1 is 12 to 24.

[0074] According to one exemplary embodiment, the sum of the number of carbon atoms of two of R1, R2, and R3 of Chemical Formula 1 having a greater number of carbon atoms is 2 to 24, preferably 8 to 20, more preferably 8 to 16. According to one example, the sum of the number of carbon atoms of two of R1, R2, and R3 of Chemical Formula 1 having a greater number of carbon atoms can be 9 to 15.

[0075] According to one exemplary embodiment, the number of carbon atoms of the one of R1, R2, and R3 of Chemical Formula 1 having the greatest number of carbon atoms is 12 or less, preferably 11 or less.

[0076] According to one exemplary embodiment, when either of the two having the largest number of carbon atoms among R1, R2, and R3 of Chemical Formula 1 has 10 or more carbon atoms, the other has less than 8 carbon atoms.

[0077] Here, when selecting a group having the largest number of carbon atoms, in the case where groups having the same number of carbon atoms are present, either is selected.

[0078] When having the number of carbon atoms according to the aforementioned exemplary embodiment, acute oral toxicity and acute dermal toxicity can be controlled. When the acute oral toxicity and / or the acute dermal toxicity is too great, there is a limitation on the intended use, particularly, use in infant products such as diapers.

[0079] According to one exemplary embodiment, L1 in Chemical Formula 1 is ethylene or butylene.

[0080] According to one exemplary embodiment, R4 in Chemical Formula 1 is hydrogen.

[0081] According to one exemplary embodiment, R4 in Chemical Formula 1 is methyl.

[0082] The antibacterial composition can be composed of only a compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group, and if necessary, an additive or a solvent can be additionally added.

[0083] According to another exemplary embodiment of the present application, the water solubility of the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group is 50% or more, preferably 60% or more. The solubility can be measured at room temperature.

[0084] According to yet another exemplary embodiment of the present application, the ethanol solubility of the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group is 50% or more, preferably 60% or more. The solubility can be measured at room temperature.

[0085] According to still another exemplary embodiment of the present application, the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group can be dissolved in at least one of methanol, acetone, dichloromethane, DMSO, THF, and chloroform, preferably in all of them.

[0086] According to still another exemplary embodiment of the present application, the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group can be selected from the following monomers 1 to 10:

[0087]

[0088]

[0089]

[0090] The antibacterial composition according to the above exemplary embodiment or the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group contained therein can exist in the form of a powder or an oil.

[0091] Since the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group exhibits cationic characteristics, the compound can exist in the form in which a salt is formed together with a group exhibiting anionic characteristics. In this case, the group exhibiting anionic characteristics is not particularly limited, and a material known in the art can be used as long as the material does not impair the purpose of the antibacterial composition. For example, the group exhibiting anionic characteristics can be a halide anion, specifically, Br - .

[0092] According to still another exemplary embodiment of the present application, there is provided a product containing the antibacterial composition according to the above exemplary embodiment or prepared therefrom. The product is not particularly limited as long as an antibacterial property is required. According to an example, the product can be used in the state of a copolymer, for example, a copolymer with a (meth)acrylate-based resin, a copolymer with polyvinyl chloride, a copolymer with polylactic acid (PLA), and a copolymer with urethane, or can be a product containing at least one of the copolymers, for example, a sanitary product, an antibacterial film, a diaper, etc. The copolymer is preferably a copolymer with a compound based on an acrylate or a methacrylate. As a copolymerization method, a known copolymerization method can be applied.

[0093] According to still another exemplary embodiment of the present application, there is provided a compound selected from the following monomers 1 to 10. The same description for the above compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group can be applied to the following monomers 1 to 10.

[0094]

[0095]

[0096]

[0097] The compound selected from the monomers 1 to 10 can be applied as a constituent component of the antibacterial composition. Further, since the compound selected from the monomers 1 to 10 exhibits cationic characteristics, the compound can exist in the form in which a salt is formed together with a group exhibiting anionic characteristics. In this case, the group exhibiting anionic characteristics is not particularly limited, and a material known in the art can be used as long as the material does not impair the purpose of the antibacterial composition. For example, the group exhibiting anionic characteristics can be a halide anion, specifically, Br- .

[0098] Inventive embodiments

[0099] Hereinafter, the present application will be described in more detail by examples. However, the following examples are provided to illustrate the present application, and the scope of the present application is not limited thereto.

[0100] [Synthesis of compound containing quaternary ammonium structure]

[0101] Synthesis of monomer 1, monomer 2 and monomer 3

[0102]

[0103] Step 1

[0104] 1. To 100 mL of THF (solvent), 0.1 mol of 2-(dibutylamino)ethanol (DBAE), 0.1 mol of trimethylamine and 0.001 mol of hydroquinone were added.

[0105] 2. While stirring the materials (room temperature), 0.1 mol of acryloyl chloride was added dropwise to the reaction solution.

[0106] 3. The resulting mixture was stirred for 2 hours.

[0107] 4. After removing the triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0108] 5. The residue was dried under vacuum at 83 to 87°C.

[0109] Step 2

[0110] 1. The product of Step 1 and 1-bromooctane (preparation of monomer 1), 1-bromodecane (preparation of monomer 2) or 1-bromododecane (preparation of monomer 3) were dissolved in acrylonitrile (solvent) at a ratio of 1:1 at 50 wt%.

[0111] 2. Subsequently, p-methoxyphenol (ratio 1:0.001 equivalent to the reactant) was added as a polymerization inhibitor.

[0112] 3. The resulting mixture was reacted at 50°C for 20 hours.

[0113] 4. After static precipitation in methyl tert-butyl ether (MTBE) (MTBE: reaction solution = 15:1), the mixture was filtered. Here, while a static precipitation method in which a reactant is added to a non-solvent is used, a reverse precipitation method in which a non-solvent is added to a reactant can also be used. In addition, in addition to 15:1, other ratios of MTBE to reaction solution can also be used, for example, 12:1 and 26:1 can be used.

[0114] 5. The resulting product was dried under vacuum at 45°C.

[0115] The following Figure 1 The synthesis of monomer 1 is shown in 1 H-NMR spectrum ((CD3)2SO), the following Figure 2 The synthesis of monomer 2 is shown in 1 H-NMR spectrum ((CD3)2SO), the following Figure 3 The synthesis of monomer 3 is shown in 1 H-NMR spectrum ((CD3)2SO).

[0116] Synthesis of monomer 4

[0117]

[0118] Step 1

[0119] 1. To 100 mL THF (solvent) was added 0.1 mol 2-(dioctylamino)ethanol (DOAE), 0.1 mol trimethylamine and 0.001 mol hydroquinone.

[0120] 2. While stirring the material (room temperature), 0.1 mol acryloyl chloride was added dropwise to the reaction solution.

[0121] 3. The resulting mixture was stirred for 2 hours.

[0122] 4. After removal of the triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0123] 5. The residue was dried under vacuum at 83°C to 87°C.

[0124] Step 2

[0125] 1. The product of step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) in a ratio of 1 : 1 at 50 wt.-%.

[0126] 2. Subsequently, p-methoxyphenol was added as polymerization inhibitor (ratio 1 : 0.001 equivalent to the reaction).

[0127] 3. The resulting mixture was reacted at 50°C for 20 hours.

[0128] 4. After static precipitation in methyl-tert-butyl ether (MTBE) (MTBE: reaction solution = 15: 1), the mixture was filtered.

[0129] 5. The resulting product was dried under vacuum at 45°C.

[0130] In a similar manner to monomers 1 to 3 described above, monomers 4 to 6 were synthesized by 1The synthesis of monomer 4 was confirmed by H-NMR spectroscopy ((CD3)2SO).

[0131] Synthesis of Monomer 5

[0132]

[0133] Step 1

[0134] 1. Add 0.1 mol of 2-(dihexylamino)ethanol (DHAE), 0.1 mol of trimethylamine and 0.001 mol of hydroquinone to 100 mL of THF (solvent).

[0135] 2. While stirring the materials (at room temperature), add 0.1 mol of methacryloyl chloride dropwise to the reaction solution.

[0136] 3. Stir the resulting mixture for 2 hours.

[0137] 4. After removing the triethylamine salt by filtering the mixture, the solvent is removed by a rotary evaporator.

[0138] 5. Dry the residue under vacuum at 83°C to 87°C.

[0139] Step 2

[0140] 1. Dissolve the product of step 1 and 1-bromodecane in a 1:1 ratio at 50% by weight in acrylonitrile (solvent).

[0141] 2. Subsequently, p-methoxyphenol (at a ratio of 1:0.001 equivalents to the reactants) was added as a polymerization inhibitor.

[0142] 3. React the resulting mixture at 50°C for 20 hours.

[0143] 4. After static precipitation in methyl tert-butyl ether (MTBE) (MTBE:reaction solution = 15:1), the mixture is filtered.

[0144] 5. Dry the obtained product under vacuum at 45°C.

[0145] In a manner similar to that of monomers 1 to 3 mentioned above, through 1 The synthesis of monomer 5 was confirmed by H-NMR spectroscopy ((CD3)2SO).

[0146] Synthesis of Monomer 6

[0147]

[0148] Step 1

[0149] 1. To 100 mL THF (solvent) was added 0.1 mol (butylhexylamino)ethanol (BHAE), 0.1 mol trimethylamine and 0.001 mol hydroquinone.

[0150] 2. While stirring the material (room temperature), 0.1 mol methacryloyl chloride was added dropwise to the reaction solution.

[0151] 3. The resulting mixture was stirred for 2 hours.

[0152] 4. After removing the triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0153] 5. The residue was dried under vacuum at 83°C to 87°C.

[0154] Step 2

[0155] 1. The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a ratio of 1 : 1 at 50 wt%.

[0156] 2. Subsequently, p-methoxyphenol was added as a polymerization inhibitor (ratio 1 : 0.001 equivalent to the reactants).

[0157] 3. The resulting mixture was reacted at 50°C for 20 hours.

[0158] 4. After static precipitation in methyl tert-butyl ether (MTBE) (MTBE: reaction solution = 15: 1), the mixture was filtered.

[0159] 5. The resulting product was dried under vacuum at 45°C.

[0160] Monomer 6 was synthesized in a similar manner to monomers 1 to 3 described above by 1 The synthesis of monomer 6 was confirmed by H-NMR spectrum ((CD3)2SO).

[0161] Synthesis of monomer 7

[0162]

[0163] Step 1

[0164] 1. To 100 mL THF (solvent) was added 0.1 mol 2-(butyloctylamino)ethanol (BOAE), 0.1 mol trimethylamine and 0.001 mol hydroquinone.

[0165] 2. While stirring the material (room temperature), 0.1 mol methacryloyl chloride was added dropwise to the reaction solution.

[0166] 3. The resulting mixture was stirred for 2 hours.

[0167] 4. After removing triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0168] 5. The residue was dried under vacuum at 83-87 °C.

[0169] Step 2

[0170] 1. The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at 50 wt% in a ratio of 1:1.

[0171] 2. Subsequently, p-methoxyphenol was added as a polymerization inhibitor (ratio 1:0.001 equivalent to the reactants).

[0172] 3. The resulting mixture was reacted at 50 °C for 20 hours.

[0173] 4. After static precipitation in methyl tert-butyl ether (MTBE) (MTBE: reaction solution = 15:1), the mixture was filtered.

[0174] 5. The resulting product was dried under vacuum at 45 °C.

[0175] Synthesis of monomer 7 was carried out in a similar manner to monomers 1-3 described above by 1 The synthesis of monomer 7 was confirmed by H-NMR spectrum ((CD3)2SO).

[0176] Synthesis of monomer 8

[0177]

[0178] Step 1

[0179] 1. To 100 mL THF (solvent) was added 0.1 mol 2-(butyldecylamino)ethanol (BOAE), 0.1 mol trimethylamine, and 0.001 mol hydroquinone.

[0180] 2. While stirring the material (room temperature), 0.1 mol methacryloyl chloride was added dropwise to the reaction solution.

[0181] 3. The resulting mixture was stirred for 2 hours.

[0182] 4. After removing triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0183] 5. The residue was dried under vacuum at 83-87 °C.

[0184] Step 2

[0185] 1. The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at 50 wt% in a ratio of 1:1.

[0186] 2. Subsequently, p-methoxyphenol was added as a polymerization inhibitor (ratio 1:0.001 equivalent to the reactants).

[0187] 3. The resulting mixture was reacted at 50°C for 20 hours.

[0188] 4. After static precipitation in methyl-tert-butyl ether (MTBE) (MTBE: reaction solution = 15:1), the mixture was filtered.

[0189] 5. The resulting product was dried under vacuum at 45°C.

[0190] The synthesis of monomer 8 was determined by H-NMR spectrum ((CD3)2SO) in a similar manner to monomers 1 to 3 described above. 1 The synthesis of monomer 8 was determined by H-NMR spectrum ((CD3)2SO) in a similar manner to monomers 1 to 3 described above.

[0191] Synthesis of monomer 9

[0192]

[0193] Step 1

[0194] 1. To 100 mL of THF (solvent), 0.1 mol of 2-(dibutylamino)butanol (DBAB), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added.

[0195] 2. While stirring the material (room temperature), 0.1 mol of acryloyl chloride was added dropwise to the reaction solution.

[0196] 3. The resulting mixture was stirred for 2 hours.

[0197] 4. After removing the triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0198] 5. The residue was dried under vacuum at 83°C to 87°C.

[0199] Step 2

[0200] 1. The product of Step 1 and 1-bromo octane were dissolved in acrylonitrile (solvent) at a ratio of 1:1 at 50 wt%.

[0201] 2. Subsequently, p-methoxyphenol was added as a polymerization inhibitor (ratio 1:0.001 equivalent to the reactants).

[0202] 3. The resulting mixture was reacted at 50°C for 20 hours.

[0203] 4. After static precipitation in methyl-tert-butyl ether (MTBE) (MTBE: reaction solution = 15:1), the mixture was filtered.

[0204] 5. The resulting product was dried under vacuum at 45 °C.

[0205] The synthesis of monomer 9 was determined by H-NMR spectroscopy ((CD3)2SO) in a similar manner to monomers 1 to 3 described above. 1 The synthesis of monomer 9 was determined by H-NMR spectroscopy ((CD3)2SO) in a similar manner to monomers 1 to 3 described above.

[0206] Synthesis of monomer 10

[0207]

[0208] Step 1

[0209] 1. To 100 mL THF (solvent) was added 0.1 mol 2-(dioctylamino)butanol (DOAB), 0.1 mol trimethylamine and 0.001 mol hydroquinone.

[0210] 2. While stirring the material (room temperature), 0.1 mol acryloyl chloride was added dropwise to the reaction solution.

[0211] 3. The resulting mixture was stirred for 2 hours.

[0212] 4. After removal of the triethylamine salt by filtering the mixture, the solvent was removed by a rotary evaporator.

[0213] 5. The residue was dried under vacuum at 83 °C to 87 °C.

[0214] Step 2

[0215] 1. The product of step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) in a ratio of 1 : 1 at 50 wt.-%.

[0216] 2. Subsequently, p-methoxyphenol was added as polymerization inhibitor (ratio 1 :0.001 equivalent to the reactants).

[0217] 3. The resulting mixture was reacted for 20 hours at 50 °C.

[0218] 4. After static precipitation in methyl-tert-butyl ether (MTBE) (MTBE: reaction solution = 15: 1), the mixture was filtered.

[0219] 5. The resulting product was dried under vacuum at 45 °C.

[0220] The synthesis of monomer 9 was determined by H-NMR spectroscopy ((CD3)2SO) in a similar manner to monomers 1 to 3 described above. 1 The synthesis of monomer 9 was determined by H-NMR spectroscopy ((CD3)2SO) in a similar manner to monomers 1 to 3 described above.

[0221] Synthesis of comparative monomer 1

[0222] The synthesis was performed in the same manner as in the synthesis of monomer 1, except that 1-bromohexane was used instead of 1-bromooctane in step 2 of the synthesis of monomer 1.

[0223] The synthesis was performed in the same manner as in the synthesis of monomer 1, except that 1-bromohexane was used instead of 1-bromooctane in step 2 of the synthesis of monomer 1. 1 The synthesis of comparative monomer 1 was confirmed by H-NMR spectrum ((CD3)2SO).

[0224]

[0225] The synthesis of comparative monomer 2

[0226] The synthesis was performed in the same manner as in the synthesis of monomer 10, except that 2-(dimyristylamino)ethanol was used instead of 2-(dioctylamino)butanol in step 1 of the synthesis of monomer 10, and bromotetradecane was used instead of 1-bromooctane in step 2.

[0227] The synthesis was performed in the same manner as in the synthesis of monomer 1, except that 1-bromohexane was used instead of 1-bromooctane in step 2 of the synthesis of monomer 1. 1 The synthesis of comparative monomer 2 was confirmed by H-NMR spectrum ((CD3)2SO).

[0228]

[0229] The antibacterial strength of monomers 1 to 10 and comparative monomers 1 and 2 by methods 1 to 4 was measured and shown in Table 1 below. In this case, Proteus mirabilis (ATCC 29906) bacteria were used.

[0230] [Table 1]

[0231]

[0232] According to Table 1, all monomers 1 to 10 had an antibacterial strength A of 99.9% measured by method 1.

[0233] The time at which the antibacterial strength of monomers 1 to 10 and comparative monomers 1 and 2 was determined to be 99.9% was determined and shown in Table 2 below.

[0234] [Table 2]

[0235]

[0236] According to Table 2, all monomers 1 to 10 were determined to have an antibacterial strength A of 99.9% measured by method 1 within 1 hour.

[0237] The acute oral toxicity dose LD50 of monomers 1 to 10 and comparative monomers 1 and 2 is shown in Table 3 below.

[0238] [Table 3]

[0239]

[0240] According to Table 3, all monomers 1 to 10 have an acute oral toxicity dose LD50 of 300 mg / Kg or more, in particular 800 mg / Kg or more. In addition, examples 1, 2, 4, 5, 6, 9 and 10 have an acute oral toxicity dose LD50 of 1,000 mg / Kg or more.

[0241] The acute dermal toxicity dose LD50 of monomers 1 to 10 is shown in Table 4 below.

[0242] [Table 4]

[0243]

[0244] According to Table 4, all monomers 1 to 10 have an acute dermal toxicity dose LD50 of 1,000 mg / Kg or more, in particular 2,000 mg / Kg or more.

[0245] The acute oral toxicity dose LD50 and the acute dermal toxicity dose LD50 are measured by the 3T3 Neutral Red Uptake (NRU) test (OECD Guideline No. 129). In particular, the acute oral toxicity dose LD50 and the acute dermal toxicity dose LD50 can be calculated by the following method.

[0246]

Claims

1. An antibacterial composition comprising at least one compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group, and having an antibacterial intensity A of 90% or more and an acute oral toxicity dose LD50 of 800 mg / Kg or more, the antibacterial intensity A being measured by the following Method 1 on at least one strain of Gram-positive bacteria and Gram-negative bacteria, wherein the compound containing a quaternary ammonium structure having an acrylate group or a methacrylate group is selected from the following monomers 1 to 10: [Method 1] After placing 25 ml of a broth-type medium inoculated with 3,000 CFU / ml of bacteria into a 50 mL conical tube, 0.015 g of the antibacterial composition is added thereto and suspended, the well-mixed solution is incubated in a shaking water bath maintained at 35°C for 16 hours, the broth-type medium is nutrient broth, BDDIFCO., 8 g / L, the suspension is performed by vortexing, After diluting the incubated solution to 1 / 5 using a IX PBS buffer solution, the absorbance at λ = 600 nm is measured using a UV / Vis spectrophotometer, and the antibacterial intensity as the bacteriostatic reduction rate is calculated from the measured absorbance by comparison with the solution incubated without the addition of the antibacterial composition, from the following formula, Antibacterial strength (%) = (1 - A 样品 / A 参照 ) x 100 A 样品 = absorbance of the medium solution cultured by adding the antibacterial composition A 参照 = absorbance of the culture medium solution cultured without the addition of the antibacterial composition, 2. The antibacterial composition according to claim 1, wherein Method 1 is measured on at least one strain of Proteus mirabilis, Escherichia coli, Staphylococcus aureus, Enterobacter cloacae and Enterococcus faecalis.

3. The antibacterial composition according to claim 1, wherein Method 1 is measured on each of the strains of Proteus mirabilis, Escherichia coli, Staphylococcus aureus, Enterobacter cloacae and Enterococcus faecalis.

4. The antibacterial composition according to any one of claims 1 to 3, wherein the antibacterial intensity A of the antibacterial composition is expressed within 1 hour.

5. The antibacterial composition according to any one of claims 1 to 3, wherein the ratio C / B of the antibacterial intensity C measured by the following Method 3 to the antibacterial intensity B measured by the following Method 2 is 1 or more and less than 2: [Method 2] This method is the same as Method 1, except that 0.005 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition, [Method 3] This method is the same as Method 1, except that 0.02 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

6. The antibacterial composition according to any one of claims 1 to 3, wherein the antibacterial intensity A is 99% or more.

7. The antibacterial composition according to any one of claims 1 to 3, wherein the antibacterial intensity D measured by the following Method 4 is 65% or more: [Method 4] This method is the same as Method 1, except that 0.01 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

8. The antibacterial composition according to claim 7, wherein the antibacterial intensity D is 99% or more.

9. The antibacterial composition according to any one of claims 1 to 3, wherein the antibacterial intensity B measured by the following Method 2 is 55% or more: [Method 2] The method is the same as Method 1, except that 0.005 g of the antibacterial composition is added instead of 0.015 g of the antibacterial composition.

10. The antibacterial composition according to claim 9, wherein the antibacterial strength B is 99% or more.

11. The antibacterial composition according to any one of claims 1 to 3, wherein the acute oral toxicity dose LD50 is 1,000 mg / Kg or more.

12. The antibacterial composition according to any one of claims 1 to 3, wherein the acute dermal toxicity dose LD50 of the antibacterial composition is 1,000 mg / Kg or more.

13. The antibacterial composition according to any one of claims 1 to 3, wherein the acute dermal toxicity dose LD50 of the antibacterial composition is 2,000 mg / Kg or more.

14. A product comprising or prepared from the antibacterial composition according to any one of claims 1 to 3.

15. A compound selected from the following monomers 1 to 10:

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