Compound and molded body containing same

Abstract

The present specification relates to a compound represented by Chemical Formula 1, which is soluble in at least two of ether, toluene, and ethyl acetate at room temperature, and a molded article containing the compound.

Description

[Technical Field]

[0001] The present specification relates to a compound and a molded article comprising the same.

[0002] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0131730 filed with the Korean Intellectual Property Office on October 13, 2022, and Korean Patent Application No. 10-2023-0136265 filed with the Korean Intellectual Property Office on October 12, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] In recent years, there has been a demand for high antibacterial properties in a variety of products, including household goods and hygiene products.

[0004] The required level of antibacterial properties and the requirements for materials that provide antibacterial properties vary depending on the material of the product that requires antibacterial properties and the final state of use. For example, the properties of the material that provides antibacterial properties and the level of antibacterial properties vary depending on the amount of antibacterial material used in the product and the materials used together.

[0005] However, when introducing antibacterial agents that inhibit bacterial growth into resins, it is not easy to select and introduce antibacterial components that exhibit excellent bacterial growth inhibition properties, are harmless to the human body, are economical, and do not deteriorate the basic physical properties of the polymer resin.

[0006] For example, most widely used quaternary ammonium antibacterial agents are substituted with halogen anions. However, this has the problem of being only soluble in certain solvents, reducing their practicality, and consumers have a negative view of antibacterial agents containing halogens.

[0007] Therefore, there is a need to develop a material that can be dissolved in various solvents, exhibits high antibacterial properties, does not release antibacterial substances, and is harmless to the human body. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent Publication No. 10-2009-0131847 Summary of the Invention [Problem to be solved by the invention]

[0009] The present specification provides a compound and a molded article containing the same. [Means for solving the problem]

[0010] One embodiment of the present specification is represented by the following chemical formula 1: Provided is a compound that is soluble in at least two of ether, toluene, and ethyl acetate at room temperature.

[0011] [ka]

[0012] In the above Chemical Formula 1, L1 is an alkylene group, R1 to R3 are the same or different and each independently represent an alkyl group, and at least one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms; R4 is hydrogen or an alkyl group; R - is a salicylate-based anion, a sulfate-based anion, a bisulfate-based anion, a benzoate-based anion, a sorbate-based anion, or a lactate-based anion.

[0013] Another embodiment herein provides an antibacterial composition comprising the aforementioned compound.

[0014] Another embodiment herein provides a molded body comprising or made from the aforementioned compound. [Effects of the Invention]

[0015] The compounds according to some embodiments herein are soluble in a variety of solvents.

[0016] The compounds according to some embodiments of the present invention have both hydrophilic and hydrophobic properties and have excellent antibacterial properties.

[0017] Compounds according to some embodiments herein can address safety concerns due to antimicrobial spillage.

[0018] Compounds according to some embodiments herein can exert antibacterial properties within a short period of time.

[0019] The compounds according to some embodiments of the present specification have little change in antibacterial activity depending on the amount of antibacterial material used, so that even if unintentional variations in concentration occur when applied to a product, the antibacterial activity can be maintained within a predicted range. Therefore, the antibacterial activity can be controlled within a specific range, and antibacterial activity with excellent safety can be imparted.

[0020] The compounds according to some embodiments herein have low toxicity, which can solve safety issues. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 shows the results of NMR measurement of Compound 12 in which R- is Br-. [Figure 2] FIG. 1 shows the results of NMR measurement of Compound 13 in which R- is Br-. [Figure 3] The NMR measurement results of compound 13, in which R- is salicylate, are shown below. [Figure 4] FIG. 1 shows the results of NMR measurement of Compound 13 in which R- is citrate. [Figure 5] FIG. 1 shows the results of NMR measurement of Compound 13 in which R- is sorbate. [Figure 6]FIG. 1 shows the NMR measurement results of compound 13 in which R- is benzoate. [Figure 7] FIG. 1 shows the results of NMR measurement of compound 12 in which R- is sulfate. [Figure 8] FIG. 1 shows the results of NMR measurement of Compound 12 in which R- is bisulfate. [Figure 9] FIG. 1 shows the results of TGA measurements. DETAILED DESCRIPTION OF THE INVENTION

[0022] This specification will be explained in detail below.

[0023] One embodiment of the present specification is represented by the following chemical formula 1: The compound is soluble in at least two of ether, toluene, and ethyl acetate at room temperature.

[0024] [ka]

[0025] In the above Chemical Formula 1, L1 is an alkylene group, R1 to R3 are the same or different and each independently represent an alkyl group, and at least one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms; R4 is hydrogen or an alkyl group; R - is a salicylate-based anion, a sulfate-based anion, a bisulfate-based anion, a benzoate-based anion, a sorbate-based anion, or a lactate-based anion.

[0026] Conventionally, quaternary ammonium antibacterial agents have been used in the form of substituted halogen anions. However, in this case, there is a problem that they are dissolved only in specific solvents, which reduces their practicality. Specifically, the halogen anions (F - , Cl - , Br- or I - ) substituted quaternary ammonium compounds, particularly those represented by the above formula 1, - Compounds in which the halogen anion is present only dissolve in specific solvents such as ethanol, methylene chloride, and acetone, but not in ether, toluene, and ethyl acetate, which limits their application and makes them unable to be used in lacquer-based paints, synthetic resin paints, acrylic paints, etc. Furthermore, there is a trend toward stricter government regulations on halogen-containing antibacterial agents due to their toxicity, the possibility of environmental pollution, and handling issues due to their high reactivity, and there is also the problem of negative consumer perception.

[0027] Meanwhile, the compounds according to the present invention do not contain halogen groups but contain other specific anions, which allows them to dissolve in various solvents, thereby improving their practicality. Specifically, the compounds according to the present invention, which are represented by Chemical Formula 1, exhibit the effect of dissolving in various solvents that would not dissolve in halogen anions by changing the anion to a type other than halogen anions. Therefore, by selectively using solvents as needed, the application fields of the compounds can be diversified.

[0028] In this specification, when a part is said to "comprise" a certain component, this means that it may further include other components, rather than excluding other components, unless specifically stated to the contrary.

[0029] In this specification, physical properties that are affected by temperature are measured at room temperature unless otherwise specified.

[0030] In this specification, "room temperature" refers to a natural temperature that is neither heated nor cooled, and means, for example, any temperature within a range of about 10°C to 30°C, such as a temperature of about 15°C, about 18°C, about 20°C, about 23°C, or about 25°C. Unless otherwise specified in this specification, the unit of temperature is °C.

[0031] In this specification, when pressure affects the results of physical properties, the physical properties are measured at normal pressure unless otherwise specified.

[0032] In this specification, "normal pressure" refers to the natural pressure that is neither increased nor decreased, and generally refers to approximately 1 atmosphere (approximately 700 to 800 mmHg).

[0033] In this specification, when humidity affects the results of physical properties, the physical properties are measured at room temperature and pressure at unadjusted humidity, unless otherwise specified.

[0034] In this specification, the "alkyl group" may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably is 1 to 60. In one embodiment of the specification, the number of carbon atoms in the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group.

[0035] In this specification, the term "alkylene group" refers to an alkyl group having two bonding positions, i.e., a divalent group. The above description of the alkyl group can be applied to these groups, except that they are both divalent groups.

[0036] In this specification, the "aryl group" may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but preferably is 6 to 30. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a triphenyl group.

[0037] In this specification, "dissolved" means that the solubility measured by the following method 2 is 3 g / L or more.

[0038] [Method 2] 0.2 g of the sample to be measured is taken and a solvent is added to bring the total weight to 6.6 g. After stirring at 25°C for 30 minutes, the remaining insoluble solutes are removed. The amount of the removed remaining solutes is measured, and the amount of solute dissolved in the solvent is then calculated. The measured amount is converted to a value per 1 L of solvent to evaluate the solubility. The remaining solutes are removed by filtering the solution with a pore size of 0.45 μm.

[0039] In one embodiment herein, the compound is dissolved in two of ether, toluene, and ethyl acetate at room temperature.

[0040] In one embodiment herein, the compound is dissolved in all three of ether, toluene, and ethyl acetate at room temperature.

[0041] In one embodiment of the present specification, the compound has a solubility in ether at room temperature of 3 g / L or more. Specifically, it is 5 g / L or more, or 10 g / L or more. The upper limit of the solubility is not particularly limited, and for example, the solubility is 100 g / L or less, 90 g / L or less, or 80 g / L or less.

[0042] In one embodiment of the present specification, the compound has a solubility in toluene at room temperature of 3 g / L or more. Specifically, it is 5 g / L or more, or 10 g / L or more. The upper limit of the solubility is not particularly limited, and for example, the solubility is 100 g / L or less, 90 g / L or less, or 80 g / L or less.

[0043] In one embodiment of the present specification, the compound has a solubility in ethyl acetate at room temperature of 3 g / L or more. Specifically, it is 5 g / L or more, or 10 g / L or more. The upper limit of the solubility is not particularly limited, and for example, the solubility is 100 g / L or less, 90 g / L or less, or 80 g / L or less.

[0044] In this specification, the solubility being 3 g / L or more means that 3 g or more of the compound is dissolved in 1 L of the solvent.

[0045] In one embodiment herein, the compound is also soluble in ethanol, methylene chloride and acetone (ACT) at room temperature.

[0046] In one embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0047] In one embodiment of the present specification, L1 is an alkylene group having 1 to 5 carbon atoms.

[0048] In one embodiment of the present specification, L1 is a methylene group; an ethylene group; a propylene group; or a butylene group.

[0049] In one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0050] In one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms.

[0051] In one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.

[0052] In one embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest of R1 to R3 are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0053] In one embodiment of the present specification, L1 is an alkylene group having 1 to 5 carbon atoms, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest of R1 to R3 are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0054] In one embodiment of the present specification, L1 is a methylene group, an ethylene group, or a butylene group, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest of R1 to R3 are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0055] In one embodiment of the present specification, two or more of R1 to R3 are alkyl groups having 6 to 30 carbon atoms, or the difference in carbon number between the alkyl group with the largest carbon atom number and the alkyl group with the smallest carbon atom number among R1 to R3 is 4 or more.

[0056] Specifically, three of R1 to R3 are alkyl groups having 6 to 30 carbon atoms; two of R1 to R3 are alkyl groups having 6 to 30 carbon atoms and the remaining one is an alkyl group having 1 to 30 carbon atoms; or the difference in carbon number between the alkyl group with the largest carbon atom and the alkyl group with the smallest carbon atom among R1 to R3 is 4 or more. In this case, excellent antibacterial effect is exhibited.

[0057] In one embodiment of the present specification, the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number being 4 or more means that asymmetry is high, and the difference in carbon number may be 4 to 30, 5 to 30, or 5 to 10.

[0058] In one embodiment of the present specification, the compound has any one of the following structures:

[0059] [ka]

[0060] In the above structure, R - is as mentioned above.

[0061] In one embodiment of the present specification, the salicylate-based anion is

[0062] [ka]

[0063] wherein R10 is a hydrogen atom, an alkyl group, or an aryl group, and r10 is an integer of 1 to 4.

[0064] In one embodiment of the present specification, R - When is a salicylate anion, the compound exhibits solid properties.

[0065] In one embodiment of the present specification, R10 is hydrogen.

[0066] In one embodiment of the present specification, the benzoate-based anion is

[0067] [ka]

[0068] wherein R11 is a hydrogen atom, an alkyl group, or an aryl group, and r11 is an integer of 1 to 5.

[0069] In one embodiment of the present specification, R - When is a benzoate-based anion, the compound exhibits liquid properties.

[0070] In one embodiment of the present specification, R11 is hydrogen.

[0071] In one embodiment of the present specification, the sorbate-based anion is

[0072] [ka]

[0073] It is expressed as:

[0074] In one embodiment of the present specification, R - When is a sorbate-type anion, the compound exhibits solid properties.

[0075] In one embodiment of the present specification, the lactate-based anion is

[0076] [ka]

[0077] It is expressed as:

[0078] In one embodiment of the present specification, R - When is a lactate-based anion, the compound exhibits solid properties.

[0079] In one embodiment of the present specification, the sulfate-based anion is

[0080] [ka]

[0081] and R12 is an alkyl group.

[0082] In one embodiment of the present specification, R - When is a sulfate-based anion, the compound exhibits solid properties.

[0083] In one embodiment of the present specification, the bisulfate-based anion is

[0084] [ka]

[0085] and R12 is hydrogen.

[0086] In one embodiment of the present specification, R - When is a bisulfate anion, the compound exhibits solid properties.

[0087] In the present specification, unless otherwise specified, the number of carbon atoms in the alkyl group refers to an alkyl group having 1 to 30 carbon atoms, and the number of carbon atoms in the aryl group refers to an aryl group having 6 to 30 carbon atoms, and the substituents thereof are well known in the art and are not particularly limited as long as they do not deviate from the intent of the present invention.

[0088] As described above, the properties of a compound vary depending on the type of anion group. That is, in one embodiment of the present specification, the properties of the compound can be adjusted through anion substitution. Therefore, the compound according to one embodiment of the present specification exhibits the effect of diversifying the application fields of the compound by selectively substituting the anion as needed.

[0089] In one embodiment of the present specification, the R - is one of the following structures:

[0090] [ka]

[0091] In the above configuration, R10 to R12 are the same or different and each independently represent a hydrogen atom, an alkyl group, or an aryl group; r10 is an integer of 1 to 4, and when r10 is 2 or more, the two or more R10's may be the same or different from each other; r11 is an integer of 1 to 5, and when r11 is 2 or more, the two or more R11's are the same or different.

[0092] In one embodiment of the present specification, the compound does not precipitate after a certain period of time and remains dissolved in the solvent, i.e., the compound exhibits solubility stability.

[0093] In one embodiment herein, the compound has antibacterial properties.

[0094] In this specification, having antibacterial properties means that the antibacterial activity measured according to the following method 1, that is, the bacteriostatic reduction rate, is 90% or more.

[0095] In one embodiment of the present specification, the compound has a bacteriostatic reduction rate of 90% or more against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by Method 1 below.

[0096] [Method 1] 20 mL of broth-type medium (Nutrient broth, BD DIFCO, 8 g / L) inoculated with 3000 CFU / mL of bacteria was transferred to a 50 mL conical tube, and 0.005 g, 0.01 g, 0.015 g, or 0.020 g of compound was added and vortexed. The thoroughly mixed solution was incubated for 16 hours in a shaking water bath maintained at 35°C. After incubation, the solution was diluted 1 / 5 with 1x PBS buffer solution and the absorbance at 600 nm was measured using a UV / Vis spectrophotometer. The measured absorbance was compared to a solution incubated without the bacteriostatic agent, and the bacteriostatic reduction rate was calculated using the following formula.

[0097]

number

[0098] In the present specification, the bacteriostatic substance of Formula 1 is a compound of Chemical Formula 1.

[0099] As used herein, CFU (Colony Forming Unit) means colony forming unit, and CFU / mL means the number of CFU per mL.

[0100] When the bacteriostatic reduction rate of the compounds of the present invention was evaluated by the above-mentioned method 1, only cases where the bacteriostatic reduction rate (antibacterial activity) was 92% or more were observed. As a result, it was confirmed that the compounds of the present invention have excellent antibacterial activity.

[0101] In this specification, Gram-positive bacteria is a general term for bacteria that stain purple when stained by the Gram staining method. The cell walls of Gram-positive bacteria are composed of multiple layers of peptidoglycan, and after staining with a basic dye such as crystal violet, the color does not fade and remains purple even when treated with ethanol.

[0102] In one embodiment of the present specification, the Gram-positive bacterium is selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, it is any one selected from the aforementioned examples, but is not limited thereto.

[0103] As used herein, Gram-negative bacteria are a collective term for bacteria that stain red when stained with the Gram staining method, and instead of having a cell wall with a relatively small amount of peptidoglycan compared to Gram-positive bacteria, have an outer membrane composed of lipopolysaccharides, lipid proteins, and / or other complex polymeric substances.

[0104] In one embodiment of the present specification, the Gram-negative bacterium is selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, it is any one selected from the aforementioned examples, but is not limited thereto.

[0105] In one embodiment of the present specification, the fungus may be, but is not limited to, Candida albicans.

[0106] In one embodiment of the present specification, the compound has an antibacterial activity of 90% or more against Gram-positive bacteria as measured by the above method 1.

[0107] In one embodiment of the present specification, the compound has an antibacterial activity of 90% or more against Gram-negative bacteria as measured by the above method 1.

[0108] Since the above Gram-positive, Gram-negative and fungal strains can cause various diseases when contacted, as well as secondary infections, it is preferable to use a single compound that exhibits antibacterial properties against all of the above Gram-positive, Gram-negative and fungal strains.

[0109] In one embodiment of the present specification, the compound has an acute oral toxicity concentration LD50 of more than 300 mg / kg, preferably 320 mg / kg or more. The higher the acute oral toxicity concentration LD50 of the compound according to the above embodiment, the lower the toxicity, which is advantageous. However, the LD50 value can be determined from the viewpoint that the aforementioned antibacterial activity must also be satisfied. For example, the acute oral toxicity concentration LD50 of the compound may be 50,000 mg / kg or less, e.g., 10,000 mg / kg or less, 5,000 mg / kg or less, or 2,000 mg / kg or less. In one example, the acute oral toxicity concentration LD50 of the compound according to the above embodiment may be 1,000 mg / kg or less.

[0110] One embodiment herein provides an antibacterial composition comprising the aforementioned compound.

[0111] In one embodiment herein, the aforementioned antimicrobial composition further comprises a solvent, wherein the solvent is at least one of ether, toluene, ethyl acetate, acetone, water, acetonitrile, ethanol, dichloromethane, chloroform, and hexane.

[0112] In one embodiment of the present specification, the solvent contained in the antibacterial composition is 1 to 10, 1 to 7, 1 to 5, 1 to 3, or 1 type of the above-mentioned solvents.

[0113] In one embodiment of the present specification, the solvent contained in the antibacterial composition is one to three of ether, toluene, and ethyl acetate.

[0114] In one embodiment herein, the solvent contained in the antimicrobial composition is one of ether, toluene, and ethyl acetate.

[0115] One embodiment of the present specification provides a molded article containing or produced from the antibacterial resin. The molded article may be, but is not limited to, an automobile part, a blow-molded article, an inflation-molded article, a cast-molded article, an extrusion-laminated article, an extrusion-molded article, a foam-molded article, an injection-molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric. The automobile part may be an interior or exterior material for an automobile. [Example]

[0116] Hereinafter, the present specification will be described in detail with reference to examples. However, the examples of the present invention can be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to those skilled in the art.

[0117] <Production Example 1> Preparation Example 1-1. Synthesis of Compound 1 Step 1. (1) 0.1 mol of 2-(dibutylamino)ethanol (DBAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove triethylamine salts, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0118] Step 2. (1) The product of Step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 to form a 50 wt % solution. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (ratio to reactants: 1:0.001 (eq)). (3) The reaction was carried out at 50°C for 20 hours. (4) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (5) Vacuum dried at 45°C.

[0119] Step 3. (1) The product of step 2 was dissolved in water. (2) Salt was dissolved in water. (3) The two solutions prepared in (1) and (2) above were mixed and stirred overnight. (4) After the reaction was completed, the organic layer was extracted with ethyl acetate to produce Compound 1.

[0120] The salt used in step 3 was sodium salicylate, sodium citrate, or sodium benzoate depending on the type of compound to be prepared.

[0121] Preparation Example 1-2. Synthesis of Compounds 2 and 3 Compounds 2 and 3 were prepared in the same manner as in Preparation Example 1-1, except that 1-bromodecane (1-boromodecane, preparation of compound 2) or 1-bromododecane (1-boromododecane, preparation of compound 3) was used instead of 1-bromooctane in step 2(1) of Preparation Example 1-1.

[0122] Preparation Example 1-3. Synthesis of Compound 4 Compound 4 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dioctylamino)ethanol (DOAE) was used instead of 2-(dibutylamino)ethanol in step 1(1) of Preparation Example 1-1.

[0123] Preparation Example 1-4. Synthesis of Compound 5 Step 1. (1) 0.1 mol of 2-(dihexylamino)ethanol (DHAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After filtering to remove triethylamine salts, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0124] Step 2. (1) The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (ratio to reactants: 1:0.001 (eq)). (3) The reaction was carried out at 50°C for 20 hours. (4) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (5) Vacuum dried at 45°C.

[0125] Step 3. (1) The product of step 2 was dissolved in water. (2) Salt was dissolved in water. (3) The two solutions prepared in (1) and (2) above were mixed and stirred overnight. (4) After the reaction was completed, the organic layer was extracted with ethyl acetate to produce Compound 1.

[0126] The salt used in step 3 was sodium salicylate, sodium citrate, or sodium benzoate depending on the type of compound to be prepared.

[0127] Preparation Example 1-5. Synthesis of Compound 6 Compound 6 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butylhexylamino)ethanol (BHAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0128] Preparation Example 1-6. Synthesis of Compound 7 Compound 7 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyloctylamino)ethanol (BOAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0129] Preparation Example 1-7. Synthesis of Compound 8 Compound 8 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyldecylamino)ethanol (BOAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0130] Preparation Example 1-8. Synthesis of Compound 9 Compound 9 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dibutylamino)butanol (DBAB) was used instead of 2-(dibutylamino)ethanol in step 1 (1) of Preparation Example 1-1.

[0131] Preparation Example 1-9. Synthesis of Compound 10 Compound 10 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dioctylamino)butanol (DOAB) was used instead of 2-(dibutylamino)ethanol in step 1(1) of Preparation Example 1-1.

[0132] Preparation Example 1-10. Synthesis of Compound 11 Step 1. (1) 5.3 g of 1-bromooctane, 3.7 g of 2-(dimethylamino)ethyl methacrylate, 89.4 mg of 4-methoxyphenol, and 12 mL of acetonitrile were placed in a two-neck round bottom flask (RBF). (2) The reaction was carried out at 60°C for 6 hours. (3) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (4) Vacuum dried at 45°C.

[0133] Step 2. (1) The product of step 1 was dissolved in water. (2) The salt to be replaced was dissolved in water. (3) The two solutions prepared in (1) and (2) above were mixed and stirred overnight. (4) After the reaction was completed, the organic layer was extracted with ethyl acetate to produce Compound 1.

[0134] The salt used was sodium salicylate, sodium citrate, sodium benzoate, sodium sorbate, or sodium bisulfate depending on the type of compound to be prepared. However, when sodium dodecyl sulfate was used as the salt to be substituted, after the reaction in step 3(4) was completed, an excess amount of sodium chloride was added to extract the compound (salting out).

[0135] Preparation Example 1-11. Synthesis of Compounds 12 and 13 Compounds 12 and 13 were prepared in the same manner as in Preparation Examples 1-10, except that 1-bromodecane (1-boromodecane, preparation of compound 12) or 1-bromododecane (1-boromododecane, preparation of compound 13) was used instead of 1-bromooctane in Preparation Examples 1-10.

[0136] R - Br - Compounds 12 and 13 were obtained by terminating the reaction in step 1 of the above Preparation Examples 1-10 and 1-11.

[0137] In the above Preparation Examples 1-1 to 1-11, a static precipitation method was used in which the reactants were added to a nonsolvent, but a reverse precipitation method in which the nonsolvent is added to the reactants may also be used. Furthermore, the ratio of MTBE to the reaction solution may be other than 15:1, such as 12:1 or 26:1.

[0138] The structures of compounds 1 to 13 produced in the above Production Examples 1-1 to 1-11 are as follows.

[0139] [ka]

[0140] [ka]

[0141] NMR measurement confirmed that the compounds 1 to 13 substituted with specific anions were synthesized.

[0142] Figure 1 shows the R - Br - The NMR measurement results of Compound 12 are shown below.

[0143] Figure 2 shows the R - Br - The NMR measurement results of compound 13 are shown below.

[0144] Figure 3 shows the R - The NMR measurement results of compound 13, in which the compound is a salicylate, are shown.

[0145] Figure 4 shows the R - The NMR measurement results of Compound 13, in which the carboxylate is citrate, are shown.

[0146] Figure 5 shows the R - The NMR measurement results of Compound 13, in which the solvate is

[0147] Figure 6 shows the R - The NMR measurement results of compound 13, in which benzoate is

[0148] Figure 7 shows the R - The NMR measurement results of compound 12, in which 1 is sulfate, are shown.

[0149] Figure 8 shows the R - The NMR measurement results of Compound 12, in which 1 is a bisulfate, are shown.

[0150] <Experimental Example 1> Solubility measurement 0.2 g of the sample to be measured was taken and the solvent was added to bring the total weight to 6.6 g. After stirring at 25°C for 30 minutes, the insoluble residual solute was removed. The amount of the removed residual solute was measured, and the amount of solute dissolved in the solvent was measured. The measured amount was converted to a value per 1 L of solvent to evaluate the solubility. The residual solute was removed by filtering the solution with a pore size of 0.45 μm.

[0151] The object of measurement is Compound 13 produced in the above Production Example 1-11, and R - The types are listed in Table 1 below.

[0152] The solubility measurement results are shown in Table 1 below.

[0153] [Table 1]

[0154] From Table 1, the compound has a halogen group (specifically, Br - It has been confirmed that the inclusion of a specific anion other than citrate or methyl citrate can improve the solubility in various solvents.

[0155] <Experimental Example 2> Antibacterial activity measurement 3000 CFU / mL E. coli cells were transferred to 20 mL of broth-type medium (Nutrient broth, BD DIFCO., 8 g / L) in a 50 mL conical tube, and 0.005 g, 0.01 g, 0.015 g, or 0.020 g of compound was added and vortexed. The thoroughly mixed solution was incubated for 16 hours in a shaking incubator maintained at 35°C. After incubation, the solution was diluted 1 / 5 with 1x PBS buffer solution and the absorbance at 600 nm was measured using a UV / Vis spectrophotometer. The measured absorbance was compared to a solution incubated without the bacteriostatic agent, and the bacteriostatic reduction rate was calculated using the following formula:

[0156] The object of measurement is Compound 13 produced in the above Production Example 1-11, and R - The types are listed in Table 2 below.

[0157]

number

[0158] The derived bacteriostatic reduction rates (antibacterial activity) are shown in Table 2 below.

[0159] [Table 2]

[0160] In Table 2 above, 0.5 phr, 1 phr, 1.5 phr and 2 phr are as follows:

[0161] -0.5phr: 0.005g of compound was added to 20mL of a 3000CFU / mL bacterial solution. -1phr: 0.01g of compound added to 20mL of 3000CFU / mL bacterial solution -1.5phr: 0.015g of compound added to 20mL of 3000CFU / mL bacterial solution -2phr: 0.02g of compound was added to 20mL of a 3000CFU / mL bacterial solution.

[0162] From Table 2 above, it can be seen that the compounds according to one embodiment of the present invention can be obtained by using specific anions, such as Br - It can be confirmed that the compound exhibits the same or greater antibacterial activity as the compound containing citrate and the compound containing hydroxybenzoates.

[0163] <Experimental Example 3> Evaluation of toxicity and stability The acute oral toxicity concentration LD50 was measured according to the 3T3 Neutral Red Uptake (NRU) assay (OECD Guidance Document NO 129). Specifically, the LD50 was calculated as follows:

[0164]

number

[0165] The calculated results are shown in Table 3 below.

[0166] The object of measurement is Compound 13 produced in the above Production Example 1-11, and R - The names are given according to the type of material as shown in Table 3 below.

[0167] [Table 3]

[0168] From Table 3, it can be seen that the compound according to one embodiment of the present specification has an LD50 that falls within acute toxicity category 4 (300 mg / kg to 2,000 mg / kg) similarly to the case where a halogen group is applied as an anion and the case where citrate is applied as an anion. Therefore, from Tables 1 to 3, it can be seen that the compound according to one embodiment of the present specification has an acute toxicity category of Br by using a specific anion. - and citrate, which belong to the same category 4, have improved antibacterial activity and can dissolve in a variety of solvents.

[0169] <Experimental Example 4> Heat resistance evaluation In this experiment, the heat resistance evaluation was defined as the extrapolated intersection point (primary pyrolysis temperature) between the initial mass reference line and the tangent line of the maximum gradient point in the first mass loss section of the mass loss curve measured with a thermogravimetric analyzer (TGA) in an N2 atmosphere.

[0170] In the present invention, when the first thermal decomposition temperature of the compound is higher than the first thermal decomposition temperature of the substance before anion substitution, it is determined that the heat resistance is increased. The measurement results are shown in Figure 9 below.

[0171] The object of measurement is Compound 12 produced in the above Production Example 1-11, and R -The results are shown in FIG. 9 for Comparative Example 4-1 and Example 4-1 according to the type of material.

[0172] Referring to Figure 9, the anion is Br - The Td (thermal decomposition temperature) of Comparative Example 4-1 was about 230° C., and it was confirmed that the heat resistance was improved compared to Example 4-1 in which the anion was substituted with bisulfate.

Claims

1. It is represented by the following chemical formula 1 and is a non-polymer:

1. An antimicrobial composition comprising a compound dissolved in at least two of ether, toluene, and ethyl acetate at room temperature: 【Chemistry 1】 In the above Chemical Formula 1, L1 is a methylene group; an ethylene group; a propylene group; or a butylene group; any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms; R4 is hydrogen or a methyl group; R － is one of the following structures: 【Chemistry 2】 In the above structure: R10 to R12 are the same or different and each independently represent a hydrogen atom, an alkyl group, or an aryl group; r10 is an integer of 1 to 4, and when r10 is 2 or more, the two or more R10's may be the same or different from each other; r11 is an integer of 1 to 5, and when r11 is 2 or more, the two or more R11's may be the same or different.

2. 2. The antimicrobial composition of claim 1, wherein the compound has one of the following structures: 【Transformation 3】 In the above structure, R － is as defined in claim 1.

3. The antibacterial composition according to claim 1, wherein the bacteriostatic reduction rate measured by the following method 1 against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi is 90% or more: [Method 1] 20 mL of broth-type medium (Nutrient broth, BD DIFCO., 8 g / L) inoculated with 3000 CFU / mL of bacteria was transferred to a 50 mL conical tube, and 0.005 g, 0.01 g, 0.015 g, or 0.020 g of a compound was added and vortexed. The well-mixed solution was cultured in a shaking incubator maintained at 35°C for 16 hours. After the incubation, the solution was diluted 1 / 5 with 1x PBS buffer solution, and the absorbance at 600 nm was measured using a UV / Vis spectrophotometer. The measured absorbance was compared with that of a solution incubated without a bacteriostatic substance, and the bacteriostatic reduction rate was calculated using the following formula: [Equation 1]

4. 4. The antibacterial composition of claim 3, wherein the Gram-positive bacteria are selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis.

5. 4. The antibacterial composition of claim 3, wherein the Gram-negative bacteria are selected from among Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae.

6. the antimicrobial composition further comprises a solvent; 10. The antimicrobial composition of claim 1, wherein the solvent is at least one of ether, toluene, ethyl acetate, acetone, water, acetonitrile, ethanol, dichloromethane, chloroform, and hexane.

7. A molded body comprising or made from the antimicrobial composition according to any one of claims 1 to 6.

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