Antibacterial resin and molded article comprising same

Abstract

The present specification relates to an antibacterial resin and a molded article comprising the same, the antibacterial resin comprising a copolymer comprising: a first unit derived from a monomer represented by chemical formula 1; and a second unit derived from an alkyl acrylate or an alkyl methacrylate.

Description

Technical Field

[0001] This application claims the priority and benefit of Korean Patent Application Nos. 10-2023-0082165 and 10-2024-0072520, filed with the Korean Intellectual Property Office on June 26, 2023 and June 3, 2024, respectively, the entire contents of which are incorporated herein by reference.

[0002] This specification relates to an antibacterial resin and a molded article containing the same. Background Art

[0003] Recently, with the diversification of lifestyles, the improvement of living standards, and the change and enhancement of awareness, the interest in improving hygiene and comfort in the personal living environment has been increasing. Therefore, research has been conducted on the microorganisms that threaten them, but many types of microorganisms exist in the daily living environment and are widely distributed in nature, causing serious problems.

[0004] In particular, microorganisms such as bacteria and molds can inhabit various environments such as diet, living environment, clothing, and industrial products. In such cases, microorganisms are problematic because bacteria can cause various inflammations or food poisoning, and molds can not only produce odors but also cause various skin diseases, respiratory diseases, allergies, etc. In addition, microorganisms living on the surfaces of electronic products and household items may cause deterioration of product performance.

[0005] Therefore, in order to prevent human damage caused by these microorganisms, various antibacterial substances have been developed to inhibit the growth of microorganisms or kill microorganisms.

[0006] In this case, the degree of antibacterial properties required and the materials used to impart antibacterial properties vary depending on the materials of the products that require antibacterial properties and the final use state.

[0007] Previously developed antibacterial substances can be roughly classified into inorganic antibacterial agents and organic antibacterial agents. Inorganic antibacterial agents are antibacterial agents containing metals such as silver or copper, and have the advantage of maintaining antibacterial properties even under high-temperature conditions due to excellent thermal stability. However, there are problems that inorganic antibacterial agents are expensive and there is a possibility of discoloration due to the inclusion of metal ions after processing. Organic antibacterial agents have the advantages that they are cheaper than inorganic antibacterial agents and exhibit excellent antibacterial effects even in small amounts, but organic antibacterial agents have the problem that their antibacterial durability is poor because there is a possibility of elution after being applied to products.

[0008] As described above, when introducing an antibacterial agent or the like that inhibits bacterial growth into a resin, it is not easy to select and introduce such an antibacterial component that is harmless to the human body, satisfies economic feasibility, does not deteriorate the basic physical properties of the polymer resin, and at the same time exhibits excellent bacterial growth inhibition properties.

[0009] As an example, general purpose polystyrene (GPPS) is widely used because it is transparent and has good strength. To impart antibacterial activity to GPPS, an inorganic antibacterial agent (such as Cu, Ag, etc.) is added, but depending on the addition method, the sustainability deteriorates, and problems arise due to the toxicity of the materials used.

[0010] Therefore, there is a need to develop highly antibacterial materials that are suitable for each of various products applied and do not release antibacterial materials and are thus harmless to the human body. Summary of the Invention

[0011] Technical Problem

[0012] This specification provides an antibacterial resin and a molded article containing the same.

[0013] Technical Solution

[0014] An exemplary embodiment of this specification provides an antibacterial resin containing a copolymer, the copolymer comprising: a first unit derived from a monomer represented by the following Chemical Formula 1; and a second unit derived from an alkyl acrylate or an alkyl methacrylate.

[0015] [Chemical Formula 1]

[0016]

[0017] In Chemical Formula 1,

[0018] L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0019] Two of R1 to R3 are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms,

[0020] R4 to R6 are the same as or different from each other, and each independently is hydrogen or methyl, and

[0021] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0022] Another exemplary embodiment of the present specification provides a molded article comprising the above antibacterial resin or prepared therefrom.

[0023] Advantageous Effects

[0024] The antibacterial resin according to some exemplary embodiments of the present specification has excellent antibacterial properties.

[0025] The antibacterial resin according to some exemplary embodiments of the present specification can exhibit antibacterial properties within a short period of time.

[0026] Since the antibacterial activity of the antibacterial resin according to some exemplary embodiments of the present specification hardly varies depending on the amount of the antibacterial material used, even when concentration non-uniformity inadvertently occurs during application to a product, antibacterial properties within the expected range can be exhibited. Therefore, the antibacterial properties are controlled within a specific range, enabling excellent antibacterial properties to be safely imparted.

[0027] The antibacterial resin according to some exemplary embodiments of the present specification has low toxicity and can thus solve safety problems.

[0028] The antibacterial resin according to some exemplary embodiments of the present specification can solve safety problems caused by the release of antibacterial materials.

[0029] The antibacterial resin according to some exemplary embodiments of the present specification is characterized in that, due to its excellent heat resistance, it can maintain antibacterial activity even after high-temperature processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 A graph showing the NMR measurement results of monomer 1-1' prepared in Preparation Example 1.

[0031] Figure 2 A graph showing the TGA measurement results of antibacterial resin 1, antibacterial resin 2, and antibacterial resin A prepared in Preparation Example 1, Preparation Example 2, and Comparative Preparation Example 1, respectively.

[0032] Figure 3 (a) is a graph showing the appearance of antibacterial resin 1 and antibacterial resin A prepared in Preparation Example 1 and Comparative Preparation Example 1, respectively, after heat treatment at 180°C.

[0033] Figure 3 (b) is a graph showing the appearance of antibacterial resin 1 and antibacterial resin A prepared in Preparation Example 1 and Comparative Preparation Example 1, respectively, after heat treatment at 220°C. DETAILED DESCRIPTION

[0034] Hereinafter, the present specification will be described in detail.

[0035] One exemplary embodiment of the present specification provides an antibacterial resin containing a copolymer, the copolymer including: a first unit derived from a monomer represented by the following Chemical Formula 1; and a second unit derived from an alkyl acrylate or an alkyl methacrylate.

[0036] [Chemical Formula 1]

[0037]

[0038] In Chemical Formula 1,

[0039] L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0040] Two of R1 to R3 are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms,

[0041] R4 to R6 are the same as or different from each other, and each independently is hydrogen or methyl, and

[0042] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0043] There are many different types of bacteria, and more than 5,000 species have been identified. Specifically, according to the degree of oxygen required by bacteria, bacteria can be classified into aerobic bacteria, facultative bacteria, and anaerobic bacteria, and their shapes can also be classified into spherical shapes, rod-shaped shapes, spiral-shaped shapes, etc. Therefore, it is not easy for a single type of antibacterial agent to have a physical and / or chemical mechanism capable of destroying or altering the cell membranes and / or cell walls of various bacteria.

[0044] In the related art, in order to impart antibacterial activity to a material, an antibacterial agent is simply mixed with a polymer, and in this case, an inorganic antibacterial agent or an organic antibacterial agent is used. Inorganic antibacterial agents are expensive, easily cause discoloration of the material, and may deteriorate the physical properties of the polymer during processing such as extrusion or injection. In addition, inorganic antibacterial agents also have the disadvantage of low immediate antibacterial effect.

[0045] Organic antibacterial agents themselves have the disadvantage of deteriorated antibacterial persistence due to poor stability to the human body, poor thermal stability, etc. In addition, when a polymerizable organic antibacterial agent is applied to the polymerization of a polymer, there are problems such as reduced polymerization efficiency or conversion rate, or the inherent advantages of the polymer are often impaired.

[0046] In contrast, since the antibacterial resin according to the present invention does not contain an inorganic antibacterial agent, it is possible to overcome drawbacks such as discoloration and reduced transparency. In addition, the antibacterial resin of the present invention has the advantages of being highly stable in the human body and maintaining antibacterial persistence, because the antibacterial substance is not included as a separate substance in the antibacterial resin itself, but is polymerized as a monomer and included as a repeating unit forming the main chain in the polymer, and thus there is no risk of elution of the antibacterial substance. That is, the antibacterial resin of the present invention exhibits the effects of having excellent antibacterial properties and persistent antibacterial properties.

[0047] Meanwhile, during the application process, typical polymers often undergo a molding process at high temperatures, such as injection or extrusion, and most known antibacterial polymers have the problem that their antibacterial properties are reduced or lost during the process. In contrast, the antibacterial resin of the present invention can maintain its antibacterial properties even after undergoing the aforementioned high-temperature molding process by applying a specific anion.

[0048] In this specification, when a part "comprises" a constituent element, unless otherwise specifically described, this does not mean excluding other constituent elements, but means that other constituent elements can also be included.

[0049] In this specification, a "monomer" means a unit compound that can be converted into a polymer compound through a polymerization reaction, and the structure derived therefrom can become a repeating unit in a polymer or copolymer. Specifically, this means that in the state where the corresponding compound is polymerized and bonded in the polymer, in the structure of the compound, all or a part of two or more substituents are omitted, and the radical for bonding to other units of the polymer is located at this position. In this case, the corresponding compound can be included in the state of being polymerized and bonded in the polymer in any order.

[0050] In this specification, the term "derived" means generating a new bond while breaking the bond between at least two adjacent elements in a compound or detaching hydrogen or a substituent, and the unit derived from the compound can mean a unit forming one or more of the main chain and side chains in a polymer. The unit can be included in the main chain of the polymer to constitute the polymer.

[0051] In this specification, the "weight-average molecular weight" is one of the average molecular weights where the molecular weights are non-uniform and the molecular weight of any polymer material is used as a reference, and is a value obtained by averaging the molecular weights of the component molecular species of a polymer compound having a molecular weight distribution according to the weight fraction.

[0052] In this specification, the terms "first" and "second" are used to describe a plurality of components, and the above terms are only for the purpose of distinguishing one component from other components.

[0053] In this specification, unless the phrase clearly indicates the contrary, the singular form also includes the plural form.

[0054] In this specification, among physical properties, unless otherwise specified, the physical properties affected by temperature are the physical properties measured at room temperature.

[0055] In this specification, "room temperature" means the natural temperature at which the system is not heated or cooled, for example, any temperature within the 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. In addition, in this specification, unless otherwise specified, the unit of temperature is °C.

[0056] In this specification, unless otherwise specified, when the pressure in the physical properties affects the result, the corresponding physical property is the physical property measured under normal pressure.

[0057] In this specification, "normal pressure" is the natural pressure when the system is not pressurized or depressurized, and refers to a pressure that is usually about 1 atmosphere (about 700 mmHg to 800 mmHg).

[0058] In this specification, unless otherwise specified, when the humidity in the physical properties affects the result, the corresponding physical property is the physical property measured under the humidity that is not particularly controlled at room temperature and normal pressure.

[0059] In this specification, "alkyl" can be linear or branched, and there is no particular limitation on the number of its carbon atoms, but it is preferably 1 to 60. In one exemplary embodiment of this specification, the number of carbon atoms in the alkyl is 1 to 30. Specific examples of the alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, etc., but are not limited thereto.

[0060] In this specification, "alkylene" means a group having two bonding positions in the alkyl, that is, a divalent group. The above description of the alkyl can be applied to the alkylene, with the difference that the alkylene is divalent.

[0061] In this specification, "*" means the attachment point in the copolymer. In this case, the attachment point can be the point where the same units are attached to each other, and can also be the point where one unit is attached to another unit. As an example, in the following Chemical Formula 1-A, * means both the part where the first unit is attached and the part where the first unit and the second unit are attached.

[0062] In one exemplary embodiment of this specification, the first unit is represented by the following Chemical Formula 1-A.

[0063] [Chemical Formula 1-A]

[0064]

[0065] In Chemical Formula 1-A,

[0066] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0067] Two of R1 to R3 are the same as or different from each other and are each independently a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms,

[0068] R4 to R6 are the same as or different from each other and are each independently hydrogen or methyl, and

[0069] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0070] n1 is an integer from 1 to 10,000, and

[0071] * is the attachment point in the copolymer.

[0072] In an exemplary embodiment of the present specification, the quaternary ammonium cation contained in the first unit has a linking group (L1) connected to the main chain and three end groups (R1 to R3).

[0073] In an exemplary embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0074] In an exemplary embodiment of the present specification, L1 is a straight-chain alkylene group having 1 to 10 carbon atoms.

[0075] In an exemplary embodiment of the present specification, L1 is an alkylene group having 1 to 4 carbon atoms.

[0076] In an exemplary embodiment of the present specification, L1 is methylene, ethylene, or propylene.

[0077] In an exemplary embodiment of the present specification, L1 is ethylene.

[0078] In an exemplary embodiment of the present specification, two of R1 to R3 are the same as or different from each other and are each independently an alkyl group having 1 to 4 carbon atoms, and the other is an alkyl group having 5 to 20 carbon atoms.

[0079] In an exemplary embodiment of the present specification, any one of R1 to R3 is a straight-chain alkyl group having 5 to 20 carbon atoms. In this case, when all of R1 to R3 are alkyl groups having less than 5 carbon atoms, there is a problem that the antibacterial properties cannot be exhibited, and when any one of R1 to R3 is an alkyl group having more than 20 carbon atoms, there is a problem that the starting material for preparing the copolymer is insoluble in the solvent, making synthesis impossible.

[0080] In an exemplary embodiment of the present specification, two of R1 to R3 are the same as or different from each other, and each independently is a methyl group or an ethyl group, and the other is an alkyl group having 5 to 20 carbon atoms.

[0081] In an exemplary embodiment of the present specification, among R1 to R3, the other two that are not alkyl groups having 5 to 20 carbon atoms are the same as each other.

[0082] In an exemplary embodiment of the present specification, two of R1 to R3 are each a methyl group, and the other is an alkyl group having 5 to 20 carbon atoms.

[0083] In an exemplary embodiment of the present specification, R2 and R3 are the same as or different from each other, and each independently is an alkyl group having 1 to 4 carbon atoms, and R1 is an alkyl group having 5 to 20 carbon atoms.

[0084] In an exemplary embodiment of the present specification, R2 and R3 are each a methyl group, and R1 is an alkyl group having 5 to 20 carbon atoms.

[0085] In an exemplary embodiment of the present specification, R4 to R6 are the same as or different from each other, and each independently is hydrogen or a methyl group.

[0086] In an exemplary embodiment of the present specification, R5 and R6 are each hydrogen.

[0087] In an exemplary embodiment of the present specification, R4 is hydrogen or a methyl group.

[0088] In an exemplary embodiment of the present specification, Chemical Formula 1 is the following Chemical Formula 1-1 or Chemical Formula 1-2.

[0089] [Chemical Formula 1-1]

[0090]

[0091] [Chemical Formula 1-2]

[0092]

[0093] In Chemical Formula 1-1 and Chemical Formula 1-2,

[0094] L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0095] R4 is hydrogen or methyl,

[0096] b1 is an integer from 2 to 9,

[0097] b2 is an integer from 1 to 8, and

[0098] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0099] In an exemplary embodiment of the present specification, the first unit is represented by the following Chemical Formula 1-A-1 or Chemical Formula 1-A-2.

[0100] [Chemical Formula 1-A-1]

[0101]

[0102] [Chemical Formula 1-A-2]

[0103]

[0104] In Chemical Formula 1-A-1 and Chemical Formula 1-A-2,

[0105] R4 is hydrogen or methyl,

[0106] b1 is an integer from 2 to 9,

[0107] b2 is an integer from 1 to 8,

[0108] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0109] n1 is an integer from 1 to 10,000, and

[0110] * is the attachment point in the copolymer.

[0111] In an exemplary embodiment of the present specification, trifluoromethanesulfonate is represented by CF3SO3 - or represented by.

[0112] In an exemplary embodiment of the present specification, methanesulfonate is represented by CH3SO3 - or represented by.

[0113] In one exemplary embodiment of the present specification, the tetrafluoroborate is represented by BF4 - or represented.

[0114] In one exemplary embodiment of the present specification, the methyl sulfate is represented by CH3OSO3 - or represented.

[0115] In one exemplary embodiment of the present specification, the maleate is represented by represented.

[0116] In one exemplary embodiment of the present specification, the tartrate is represented by represented.

[0117] In one exemplary embodiment of the present specification, the vanillate is represented by represented.

[0118] In one exemplary embodiment of the present specification, the syringate is represented by represented.

[0119] In one exemplary embodiment of the present specification, the hexafluorophosphate is represented by PF6 - or represented.

[0120] In one exemplary embodiment of the present specification, the thiocyanate is represented by SCN - or represented.

[0121] In one exemplary embodiment of the present specification, the trifluoroacetate is represented by CF3COO - or represented.

[0122] In one exemplary embodiment of the present specification, Chemical Formula 1 is any one of the following structures.

[0123]

[0124]

[0125]

[0126]

[0127] In one exemplary embodiment of the present specification, n1 is an integer from 3 to 10,000. Specifically, n is an integer from 10 to 8,000, an integer from 20 to 5,000, an integer from 20 to 1,000, or an integer from 20 to 500.

[0128] In one exemplary embodiment of the present specification, the first unit is an antibacterial substance. That is, the copolymer exhibits antibacterial properties by including the first unit. Specifically, the copolymer exhibits antibacterial properties against at least one of bacteria (Gram-positive bacteria, Gram-negative bacteria, and Escherichia coli). More specifically, in many cases, the cell walls of bacteria and the like are usually negatively charged. The quaternary ammonium cation having an alkyl group with a specific number of carbon atoms in the first unit is electrostatically adsorbed to the cell wall of the bacteria, and then the cell surface structure of the bacteria can be coated and / or destroyed by interacting with the alkyl groups (R1 to R3) of the quaternary ammonium salt exhibiting hydrophobicity, so as to exhibit antibacterial properties.

[0129] In one exemplary embodiment of the present specification, the second unit derived from an alkyl acrylate or an alkyl methacrylate may have a structure in which the double bond of the acrylate group forms a repeating unit while being broken.

[0130] In one exemplary embodiment of the present specification, the alkyl acrylate or the alkyl methacrylate may be methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-ethylhexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, lauryl acrylate, hexacosyl acrylate, stearyl acrylate, lauryl methacrylate, cetyl methacrylate, or stearyl methacrylate. Preferably, the alkyl acrylate or the alkyl methacrylate may be methyl methacrylate.

[0131] In one exemplary embodiment of the present specification, the second unit is represented by the following Chemical Formula 2.

[0132] [Chemical Formula 2]

[0133]

[0134] In Chemical Formula 2,

[0135] R11 is an alkyl group,

[0136] R12 is hydrogen or methyl,

[0137] n2 is an integer from 1 to 10,000, and

[0138] * is an attachment point in the copolymer.

[0139] In an exemplary embodiment of the present specification, n2 is an integer from 3 to 10,000. Specifically, n2 is an integer from 10 to 8,000, an integer from 20 to 5,000, an integer from 20 to 1,000, or an integer from 20 to 500.

[0140] In an exemplary embodiment of the present specification, the copolymer exhibits a glass transition temperature (Tg) by including a second unit. Therefore, the processability during processing such as extrusion and injection is improved. In addition, the miscibility with other polymers such as polyethylene and polypropylene is improved.

[0141] In an exemplary embodiment of the present specification, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer. Specifically, the copolymer is a random copolymer.

[0142] In an exemplary embodiment of the present specification, the first unit and the second unit are included in the main chain of the copolymer.

[0143] In an exemplary embodiment of the present specification, the first unit is included in the main chain of the copolymer, and the second unit is included in the side chain of the copolymer.

[0144] In an exemplary embodiment of the present specification, the first unit is included in the side chain of the copolymer, and the second unit is included in the main chain of the copolymer.

[0145] In an exemplary embodiment of the present specification, the copolymer includes a third unit represented by Chemical Formula 3 below.

[0146] [Chemical Formula 3]

[0147]

[0148] In Chemical Formula 3,

[0149] L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

[0150] Two of R1 to R3 are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms,

[0151] R11 is an alkyl group,

[0152] R4 and R12 are the same as or different from each other, and each independently is hydrogen or methyl,

[0153] X -is a trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0154] n1 and n2 are each an integer from 1 to 10,000, and

[0155] * is an attachment point in the copolymer.

[0156] In one exemplary embodiment of the present specification, a copolymer comprising a first unit derived from a monomer represented by Chemical Formula 1 and a second unit derived from an alkyl acrylate or an alkyl methacrylate is represented by Chemical Formula 3.

[0157] In one exemplary embodiment of the present specification, R11 is an alkyl group having 1 to 10 carbon atoms.

[0158] In one exemplary embodiment of the present specification, R11 is a straight-chain alkyl group having 1 to 10 carbon atoms.

[0159] In one exemplary embodiment of the present specification, R11 is methyl, ethyl, or propyl.

[0160] In one exemplary embodiment of the present specification, the weight-average molecular weight (Mw) of the copolymer is from 10,000 g / mol to 1,000,000 g / mol. When the weight-average molecular weight of the copolymer is less than 10,000 g / mol, some molecules may exist in the form of monomers or oligomers rather than polymers and may therefore be easily eluted. In addition, there may be a problem that the copolymer is absorbed into the human body due to its low molecular weight. Further, when the weight-average molecular weight of the copolymer is greater than 1,000,000 g / mol, there may be problems in terms of processability.

[0161] More specifically, the weight-average molecular weight (Mw; g / mol) of the copolymer may be 10,000 or greater, 15,000 or greater, 20,000 or greater, 23,000 or greater, or 25,000 or greater and 1,000,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less.

[0162] According to an exemplary embodiment of the present specification, the number average molecular weight (Mn) of the antibacterial resin is from 10,000 g / mol to 800,000 g / mol. More preferably, the number average molecular weight (Mn; g / mol) of the antibacterial resin can be 15,000 or greater, 20,000 or greater, 25,000 or greater, 30,000 or greater, 35,000 or greater, or 40,000 or greater and 150,000 or less, 100,000 or less, 90,000 or less, or 80,000 or less.

[0163] In an exemplary embodiment of the present specification, the weight average molecular weight (Mw) of the copolymer can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a calibration standard sample. More specifically, 200 mg of the copolymer is diluted in 200 mL of N,N-dimethylformamide (DMF) solvent to prepare a sample of about 1000 ppm, and then the weight average molecular weight can be determined by an Agilent 1200 series GPC instrument with a flow rate of 1 mL / minute through an RI detector. In this case, after preparing a calibration curve using eight PMMA standards, the molecular weight of the sample can be calculated based on the calibration curve.

[0164] According to an exemplary embodiment of the present specification, the molecular weight distribution (Mw / Mn) of the copolymer can be in the range of 1 to 3. In other examples, the molecular weight distribution can be 1.1 or greater, 1.2 or greater, 1.3 or greater, or 1.4 or greater, or 2.8 or less, 2.6 or less, 2.4 or less, 2.2 or less, 2.0 or less, 1.8 or less, or 1.6 or less.

[0165] In an exemplary embodiment of the present specification, the copolymer is an antibacterial copolymer that exhibits antibacterial activity.

[0166] In an exemplary embodiment of the present specification, the weight average molecular weight, number average molecular weight, and molecular weight distribution of the antibacterial resin can be the same as those of the copolymer.

[0167] In an exemplary embodiment of the present specification, the molar ratio of the first unit to the second unit in the copolymer is from 10:90 to 80:20.

[0168] In an exemplary embodiment of the present specification, relative to the total molar amount of the first unit and the second unit in the copolymer, the first unit is present in an amount of 10 mol% to 80 mol%. When the content of the first unit is less than 10 mol%, it is difficult to exhibit a sufficient antibacterial effect, while when the content of the first unit is greater than 80 mol%, there is a problem that it is difficult to apply the copolymer to real life because the processability deteriorates.

[0169] More specifically, relative to the total mass of the first unit and the second unit in the copolymer, the first unit is included in the following amounts: 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and 75% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0170] In an exemplary embodiment of the present specification, the antibacterial resin exhibits antibacterial properties against at least one of Gram-positive bacteria, Gram-negative bacteria, and molds.

[0171] As used herein, the term Gram-positive bacteria is a general term for bacteria that are stained purple when stained using the Gram staining method, and even when Gram-positive bacteria are stained with a basic dye such as crystal violet and then treated with ethanol, the Gram-positive bacteria exhibit purple and do not change color because the cell wall of Gram-positive bacteria is composed of several layers of peptidoglycan.

[0172] In an exemplary embodiment of the present specification, the Gram-positive bacteria are selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, the Gram-positive bacteria are any one selected from the above examples, but are not limited thereto.

[0173] As used herein, the term Gram-negative bacteria is a general term for bacteria that are stained red when stained using the Gram staining method, and Gram-negative bacteria have an outer membrane composed of lipopolysaccharide, lipoprotein, and / or other complex polymer substances, rather than having a cell wall with a relatively small amount of peptidoglycan compared to Gram-positive bacteria.

[0174] In an exemplary embodiment of the present specification, the Gram-negative bacteria are selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, the Gram-negative bacteria are any one selected from the above examples, but are not limited thereto.

[0175] In an exemplary embodiment of the present specification, the mold can be Candida albicans, but is not limited thereto.

[0176] The antibacterial properties of the copolymer against bacteria can be evaluated according to JIS Z 2801 (Measurement of antibacterial activity on plastics and non-porous surfaces) or ASTM E2149 (Determination of antibacterial activity of immobilized antibacterial agents under dynamic contact conditions).

[0177] Specifically, the antibacterial properties can be measured by ASTM E2149 as follows.

[0178] After placing 1 g of the antibacterial resin into a 250 mL conical flask, 50 mL of phosphate buffered saline (PBS) inoculated with 2×10 5 CFU / mL of Escherichia coli ATCC 25922 strain is injected into the conical flask, and the strain is cultured in an oscillating incubator maintained at 35 °C for 1 hour. The culture solution is diluted 10-fold and 100-fold and spread on an agar medium plate. The spread agar medium plate is allowed to stand and incubated at 37 °C for 24 to 48 hours. Based on the CFU count of the diluted sample, the antibacterial activity is obtained by calculation using Mathematical Formula 1.

[0179] [Mathematical Formula 1]

[0180] Antibacterial activity (%) = (1 - A 样品 / A 参照 ) × 100

[0181] A 样品 = Concentration of microorganisms in the culture medium cultured by adding the antibacterial resin

[0182] A 参照 = Concentration of microorganisms in the culture medium cultured without adding the antibacterial resin

[0183] In the present specification, exhibiting antibacterial properties means the antibacterial activity measured based on the method. In other words, the antibacterial reduction rate is 99% or greater.

[0184] Specifically, the antibacterial reduction rate of bacteria of the antibacterial resin measured by ASTM E2149 can be 99.1% or greater, 99.5% or greater, or 99.9% or greater and 100% or less.

[0185] In one exemplary embodiment of the present specification, the antibacterial activity of the antibacterial resin against Gram-positive bacteria measured by ASTM E2149 is 99% or greater.

[0186] In one exemplary embodiment of the present specification, the antibacterial activity of the compound against Gram-negative bacteria measured by ASTM E2149 is 99% or greater.

[0187] In one exemplary embodiment of the present specification, the antibacterial activity of the compound against mold measured by ASTM E2149 is 99% or greater.

[0188] In the present specification, "colony forming unit (CFU)" means colony forming unit, and CFU / mL means the CFU count per 1 mL.

[0189] In one exemplary embodiment of the present specification, the CFU value measured by Method 1 is introduced as the A value (microbial concentration) in Mathematical Formula 1.

[0190] Since bacterial strains of Gram-positive bacteria, Gram-negative bacteria, and mold can not only induce various diseases upon contact but also cause secondary infections, it is preferable to use a compound that exhibits antibacterial properties against all of Gram-positive bacteria, Gram-negative bacteria, and mold.

[0191] In one exemplary embodiment of the present specification, the primary thermal decomposition temperature of the antibacterial resin is 200 °C or higher.

[0192] In one exemplary embodiment of the present specification, the antibacterial resin exhibits heat resistance. In the present specification, exhibiting heat resistance means that the primary thermal decomposition temperature is 200 °C or higher.

[0193] In the present specification, the thermal decomposition temperature can be measured using a thermogravimetric analyzer (TGA).

[0194] Specifically, the thermal decomposition temperature can be determined by measuring the TGA under the temperature conditions set for each section in a nitrogen atmosphere environment.

[0195] Step 1) Raise the temperature from 30 °C to 110 °C at a rate of 10 °C / minute;

[0196] Step 2) Maintain at 110 °C for 10 minutes;

[0197] Step 3) Cool from 110 °C to 50 °C at a rate of 10 °C / minute;

[0198] Step 4) Increase the temperature from 50 °C to 600 °C at a rate of 10 °C / minute.

[0199] In the said section, the first temperature drop section of the four-stage mass reduction curve is determined as the primary thermal decomposition temperature. Specifically, the thermal decomposition temperature is defined as the extrapolated intersection point between the initial mass reference line and the tangent line at the maximum slope point in the first mass loss section of the mass loss curve measured by TGA.

[0200] In an exemplary embodiment of the present specification, the upper limit of the primary thermal decomposition temperature is not particularly limited and can be, for example, 500 °C or lower, 480 °C or lower, or 450 °C or lower.

[0201] According to an exemplary embodiment of the present specification, the glass transition temperature of the antibacterial resin is 80 °C or higher.

[0202] In the present specification, differential scanning calorimetry (DSC) can be used to measure the glass transition temperature.

[0203] Specifically, the glass transition temperature can be determined by measuring DSC under the temperature conditions set for each section as follows.

[0204] Step 1) Increase the temperature from 30 °C to 200 °C at a rate of 10 °C / minute;

[0205] Step 2) Maintain at 200 °C for 5 minutes;

[0206] Step 3) Cool from 200 °C to -50 °C at a rate of -10 °C / minute;

[0207] Step 4) Maintain at -50 °C for 5 minutes;

[0208] Step 5) Increase the temperature from -50 °C to 200 °C at a rate of 10 °C / minute.

[0209] In an exemplary embodiment of the present specification, the upper limit of the glass transition temperature is not particularly limited and can be, for example, 150 °C or lower, 140 °C or lower, or 130 °C or lower.

[0210] The antibacterial resin has the above-mentioned thermal decomposition temperature and glass transition temperature, and thus exhibits the effect of improving processability during processes such as extrusion and injection.

[0211] In an exemplary embodiment of the present specification, the antibacterial resin can be prepared by copolymerizing a monomer represented by Chemical Formula 1 (hereinafter, the first monomer) with an alkyl acrylate or an alkyl methacrylate (hereinafter, the second monomer).

[0212] In an exemplary embodiment of the present specification, the antibacterial resin can be polymerized in the presence of a polymerization initiator. Such a polymerization initiator can be appropriately selected according to the polymerization method. When a thermal polymerization method is used, a thermal polymerization initiator can be used. When a photopolymerization method is used, a photopolymerization initiator can be used. And when a mixed polymerization method (a method using both heat and light) is used, both a thermal polymerization initiator and a photopolymerization initiator can be used. However, even by the photopolymerization method, a certain amount of heat is generated due to light irradiation such as ultraviolet irradiation, and in addition, a certain amount of heat is generated due to the progress of the polymerization reaction (which is an exothermic reaction). Therefore, a thermal polymerization initiator can be additionally used.

[0213] In an exemplary embodiment of the present specification, the photopolymerization initiator can be used without limitation in terms of its structure as long as it is a compound capable of forming free radicals by light such as ultraviolet light. For example, as the photopolymerization initiator, one or more selected from the following can be used: benzoin ethers, dialkylbenzophenones, hydroxyalkyl ketones, phenyl glyoxylates, benzyl dimethyl ketals, acylphosphines, and α - aminoketones. Meanwhile, specific examples of the acylphosphine include diphenyl(2,4,6 - trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide, ethyl (2,4,6 - trimethylbenzoyl)phenylphosphinate, etc. More different photoinitiators are fully described on page 115 of "UV Coatings: Basics, Recent Developments and New Application (Elsevier, 2007)" written by Reinhold Schwalm, and the photoinitiator is not limited to the above examples.

[0214] In an exemplary embodiment of the present specification, relative to 100 parts by weight of the total of the first monomer and the second monomer, the photopolymerization initiator can be included in an amount of 0.001 part by weight to 1 part by weight. When the content of the photopolymerization initiator is less than 0.001 part by weight, the polymerization rate may be slow, while when the content of the photopolymerization initiator exceeds 1 part by weight, the molecular weight of the polymer may be small, and the physical properties may become non - uniform. More specifically, relative to 100 parts by weight of the total of the monomers, the photopolymerization initiator can be included in the following amounts: 0.005 part by weight or more, or 0.01 part by weight or more, or 0.1 part by weight or more, and 0.5 part by weight or less, or 0.3 part by weight or less.

[0215] In one exemplary embodiment of the present specification, one or more selected from persulfate-based initiators, azo-based initiators, hydrogen peroxide, and ascorbic acid can be used as thermal polymerization initiators. Specifically, examples of persulfate-based initiators include sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), ammonium persulfate ((NH4)2S2O8), etc., and examples of azo-based initiators include azobisisobutyronitrile, 2,2-azobis(2-amidinopropane) dihydrochloride, 2,2-azobis-(N,N-dimethyl) isobutamidine dihydrochloride, 2-(carbamoylazo) isobutyronitrile, 2,2-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride, 4,4-azobis-(4-cyanovaleric acid), etc. More different thermal polymerization initiators are fully elucidated on page 203 of "Principle of Polymerization (Wiley, 1981)" written by Odian, and the thermal polymerization initiators are not limited to the above examples.

[0216] In one exemplary embodiment of the present specification, relative to 100 parts by weight of the total of the first monomer and the second monomer, the thermal polymerization initiator can be included in an amount of 0.001 part by weight to 3 parts by weight. When the content of the thermal polymerization initiator is less than 0.001 part by weight, almost no additional thermal polymerization occurs, so the effect of adding the thermal polymerization initiator can be negligible, while when the content of the thermal polymerization initiator exceeds 3 parts by weight, the molecular weight of the polymer may be small and the physical properties may become non-uniform. More specifically, relative to 100 parts by weight of the total of the monomers, the thermal polymerization initiator can be included in the following amounts: 0.005 part by weight or more, or 0.01 part by weight or more, or 0.1 part by weight or more, and 3 parts by weight or less, 2.5 parts by weight or less, or 2.3 parts by weight or less.

[0217] According to one exemplary embodiment of the present specification, the end groups of the copolymer can have structures derived from the first unit, the second unit, and the initiator used in the preparation of the copolymer. Specifically, the end groups can have one binding site at the first unit and the second unit, or can have a structure corresponding to half of the initiator used.

[0218] For example, the end groups of the copolymer have any one of the following structures.

[0219]

[0220] In the above structures, L1, R1 to R6, R11, R12, and X - are consistent with those defined in Chemical Formula 1 and Chemical Formula 2, and * is the part attached to the copolymer.

[0221] The first monomer, the second monomer, and the polymerization initiator can be prepared in the form of a solution dissolved in a solvent.

[0222] In an exemplary embodiment of the present specification, the solvent can be used without limitation in terms of its composition as long as it can dissolve the above components. For example, a combination of one or more selected from the following can be used: water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate, N,N-dimethylacetamide, etc.

[0223] In an exemplary embodiment of the present specification, the copolymerization of the first monomer and the second monomer can be carried out by any generally known method without any specific configuration limitation. For example, the copolymerization can be carried out at a temperature of 60°C to 100°C, or 60°C to 90°C for 1 hour to 24 hours, and when the reaction is completed, the prepared polymer can be taken out and dried to obtain the finally desired copolymer.

[0224] An exemplary embodiment of the present specification provides a molded article containing the above antibacterial resin or prepared therefrom.

[0225] In the present specification, a molded article means a product containing: a material containing an antibacterial resin, a material made of an antibacterial resin, or an antibacterial resin.

[0226] Specifically, the molded article is one or more selected from the following: a fresh-keeping material, a fabric product, an agricultural film, an automotive component, various office supplies, various packaging materials, and medical supplies.

[0227] More specifically, the molded article can be: packaging materials such as food packaging materials, vegetable packaging materials, cereal packaging materials, fruit packaging materials, meat packaging materials, aquatic product packaging materials, and processed food packaging materials; fresh-keeping materials such as containers for vegetables, cereals, fruits, meats, aquatic products, processed foods, etc.; fabric products such as food tray mats, table mats, tablecloths, carpets, and seat covers; agricultural films; automotive components such as interior and exterior materials; office supplies such as tapes, adhesive tapes, masking tapes, and masking films; various packaging materials such as flower packaging materials, plastic bags, easy-open packaging bags, shopping bags, stand-up pouches, transparent packaging boxes, automatic packaging films, electronic component packaging materials, and machine component packaging materials; and medical supplies such as medical films, medical tapes, and cell culture packages.

[0228] In addition, the molded article may be a blow molded article, a blown article, a cast molded article, an extrusion laminated article, an extruded article, a foam molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric, but is not limited to the examples described above.

[0229] Embodiments of the Invention

[0230] Hereinafter, this specification will be described in detail with reference to the experimental examples used to specifically describe this specification. However, the experimental examples of this specification can be modified in various forms, and the scope of this specification is not to be construed as limited to the experimental examples described below. The experimental examples of this specification are provided to more completely describe this specification to those of ordinary skill in the art.

[0231] Preparation Example 1. Preparation of Antibacterial Resin 1

[0232] (1) Preparation of Monomer 1

[0233]

[0234] 70 ml of acetonitrile, 2 mol of 2-(dimethylamino)ethyl methacrylate, 2 mol of 1-bromododecane, and 0.32 g of p-methoxyphenol were introduced into a 2 L round-bottom flask. The mixture was stirred at 45 °C for 16 hours using a magnetic stir bar to carry out the reaction, thereby preparing a quaternary ammonium salt by substituting the amino group with an alkyl group. Thereafter, extraction was carried out by pouring the completely reacted solution into 10 L of methyl tert-butyl ether (MTBE). Thereafter, a vacuum filter was used to filter the reaction product to completely remove the remaining MTBE, thereby preparing antibacterial monomer 1-1'.

[0235] Figure 1 FIG. shows the NMR measurement results of monomer 1-1'.

[0236] (2) Preparation of Antibacterial Resin 1

[0237] 188 mL of ethanol, 50 g of methyl methacrylate (0.5 M), 60.9 g of monomer 1-1', and 2 mol% of azobisisobutyronitrile were introduced into a 500 mL round-bottom flask. The mixture was stirred at 65 °C for 16 hours using a stir bar to carry out the polymerization reaction. The completely reacted solution was mixed at room temperature and diluted with 50 mL of acetonitrile, and the resulting mixture was added to a 2 L aqueous solution of sodium tetrafluoroborate with a concentration of 50 wt% to cause precipitation. Thereafter, the solid polymer was filtered using a vacuum filter, and the remaining solvent was completely removed by vacuum drying to prepare antibacterial resin 1.

[0238] Preparation Example 2.

[0239] The antibacterial resin 2 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium trifluoromethanesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0240] Preparation Example 3.

[0241] The antibacterial resin 3 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium methanesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0242] Preparation Example 4.

[0243] The antibacterial resin 4 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of methyl sulfate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0244] Preparation Example 5.

[0245] The antibacterial resin 5 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium maleate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0246] Preparation Example 6.

[0247] The antibacterial resin 6 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium tartrate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0248] Preparation Example 7.

[0249] The antibacterial resin 7 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium vanillate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0250] Preparation Example 8.

[0251] The antibacterial resin 8 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium syringate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0252] Preparation Example 9.

[0253] The antibacterial resin 9 was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium hexafluorophosphate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0254] Preparation Example 10.

[0255] The antibacterial resin 10 was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium thiocyanate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0256] Preparation Example 11.

[0257] The antibacterial resin 11 was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium trifluoroacetate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0258] Comparative Preparation Example 1.

[0259] The antibacterial resin A was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, water was used instead of the aqueous solution of sodium tetrafluoroborate.

[0260] Comparative Preparation Example 2.

[0261] 188 mL of ethanol, 50 g of methyl methacrylate (0.5 M), and 2 mol% of azobisisobutyronitrile were introduced into a 500 mL round-bottom flask. The mixture was stirred at 65 °C for 16 hours using a stir bar to carry out the polymerization reaction. The completely reacted solution was mixed at room temperature and diluted with 50 mL of acetonitrile, and the resulting mixture was added to 2 L of water to cause precipitation. Thereafter, the solid polymer was filtered using a vacuum filter, and the remaining solvent was completely removed by vacuum drying to prepare PMMA as a homopolymer.

[0262] Comparative Preparation Example 3.

[0263] The antibacterial resin B was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium toluenesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0264] Comparative Preparation Example 4.

[0265] The antibacterial resin C was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium phosphate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0266] Comparative Preparation Example 5.

[0267] The antibacterial resin D was prepared in the same manner as in Preparation Example 1, except that: during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium acetate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0268] Comparative Preparation Example 6.

[0269] The antibacterial resin E was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium phenylacetate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0270] Comparative Preparation Example 7.

[0271] The antibacterial resin F was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium salicylate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0272] Comparative Preparation Example 8.

[0273] The antibacterial resin G was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium benzoate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0274] Comparative Preparation Example 9.

[0275] The antibacterial resin H was prepared in the same manner as in Preparation Example 1, except that during the precipitation in (2) of Preparation Example 1, an aqueous solution of sodium benzylphosphate was used instead of the aqueous solution of sodium tetrafluoroborate.

[0276] The types of anions in the antibacterial resins prepared in Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 9 are shown in Table 1 below.

[0277] <Experimental Example 1> Measurement of antibacterial activity

[0278] The antibacterial activity of each of the antibacterial resins 1 to 11, antibacterial resins A to H, and PMMA prepared in Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 9 was measured according to ASTM E2179. The specific measurement method is as follows.

[0279] After placing 1 g of the antibacterial resin in a 250 mL conical flask, 50 mL of phosphate buffered saline (PBS) inoculated with 2×10 5 CFU / mL of Escherichia coli ATCC 25922 strain was injected into the conical flask, and the strain was cultured in an orbital incubator maintained at 35 °C for 1 hour. The culture solution was diluted 10-fold and 100-fold and spread on an agar medium plate. The spread agar medium plate was allowed to stand and incubated at 37 °C for 24 to 48 hours. Based on the CFU count of the diluted sample, the antibacterial activity was obtained by calculation using Mathematical Formula 1.

[0280] [Mathematical Formula 1]

[0281] Antibacterial activity (%) = (1 - A 样品 / A 参照 ) × 100

[0282] A样品 = Concentration of microorganisms in the culture medium cultured by adding antibacterial resin

[0283] A 参照 = Concentration of microorganisms in the culture medium cultured without adding antibacterial resin

[0284] The measured antibacterial activity is shown in Table 1 below.

[0285] [Table 1]

[0286]

[0287]

[0288]

[0289] According to Table 1 above, it can be determined that in the case of Comparative Examples 1-2 (which are homopolymers of methyl methacrylate), the antibacterial activity is 0.

[0290] In contrast, it can be determined that in the case of Experimental Examples 1-1 to 1-11 (Antibacterial Resins 1 to 11), the antibacterial activity is excellent, exceeding 99.9%.

[0291] <Experimental Example 2> Measurement of Thermal Decomposition Temperature

[0292] The thermal decomposition temperatures of each of the antibacterial resins 1, 2, 3, and 9, antibacterial resins A to H, and PMMA prepared in Preparation Examples 1, 2, 3, and 9 and Comparative Preparation Examples 1 to 9 were measured using a thermogravimetric analyzer (TGA, TA Instrument, DISCOVERY TGA 550W / MFC&AUTO).

[0293] TGA was measured in a nitrogen atmosphere environment, and the temperature conditions for each section were set as follows:

[0294] Step 1) Raise the temperature from 30 °C to 110 °C at a rate of 10 °C / minute;

[0295] Step 2) Hold at 110 °C for 10 minutes;

[0296] Step 3) Cool from 110 °C to 50 °C at a rate of 10 °C / minute;

[0297] Step 4) Raise the temperature from 50 °C to 600 °C at a rate of 10 °C / minute.

[0298] In the said section, the first temperature drop section of the four-stage mass reduction curve is determined as the primary thermal decomposition temperature. Specifically, the thermal decomposition temperature is defined as the extrapolated intersection point between the initial mass reference line and the tangent line at the maximum slope point in the first mass loss section of the mass loss curve measured by TGA.

[0299] The measured primary thermal decomposition temperature is described in Table 2 below.

[0300] Figure 2 The TGA measurement results of antibacterial resin 1, antibacterial resin 2, and antibacterial resin A are shown.

[0301] <Experimental Example 3> Measurement of Glass Transition Temperature

[0302] The glass transition temperatures of each of antibacterial resins 1, 2, 3, and 9, antibacterial resins A to H, and PMMA prepared in Preparation Examples 1, 2, 3, and 9 and Comparative Preparation Examples 1 to 9 were measured using differential scanning calorimetry (DSC, TA Instrument, DISCOVERY TGA 550W / MFC&AUTO).

[0303] During the DSC measurement, the temperature conditions were set as follows:

[0304] Step 1) The temperature was raised from 30°C to 200°C at a rate of 10°C / minute;

[0305] Step 2) Held at 200°C for 5 minutes;

[0306] Step 3) Cooled from 200°C to -50°C at a rate of -10°C / minute;

[0307] Step 4) Held at -50°C for 5 minutes;

[0308] Step 5) The temperature was raised from -50°C to 200°C at a rate of 10°C / minute.

[0309] The measured glass transition temperatures are shown in Table 2 below.

[0310] [Table 2]

[0311]

[0312]

[0313] According to Table 1 and Figure 2 , it can be determined that in the case of containing Br -In the case of Comparative Example 2-1 (antibacterial resin A) as the anion, the primary thermal decomposition temperature is low, below 200 °C, and the glass transition temperature is also below 80 °C. From these results, it can be predicted that when using a halogen group as the anion, the heat resistance may deteriorate, leading to decomposition or color change.

[0314] Furthermore, from Tables 1 and 2, it can be determined that in the case of antibacterial resins containing anions different from those of the present invention, the antibacterial activity is less than 99%, or the primary thermal decomposition temperature is low, below 200 °C, and the glass transition temperature is also below 80 °C. Specifically, it can be determined that when the anion is tosylate, phosphate, or benzyl phosphate, the antibacterial activity is less than 99% (Comparative Examples 1-3, 1-4, and 1-9), and when the anion is acetate, benzyl acetate, salicylate, or benzoate, the primary thermal decomposition temperature is low, below 200 °C, and the glass transition temperature is also below 80 °C (Comparative Examples 2-5 to 2-8). Thus, it can be determined that the type of anion affects the antibacterial activity and heat resistance.

[0315] Meanwhile, from Tables 1 and 2, it can be determined that the antibacterial resin of the present invention has an antibacterial activity greater than 99.9%, and at the same time has a primary thermal decomposition temperature of 200 °C or higher, and also exhibits a glass transition temperature of 80 °C or higher. Thus, it can be predicted that the antibacterial resin of the present invention has excellent antibacterial activity and at the same time has excellent processability and improved heat resistance.

[0316] <Experimental Example 4> Visual evaluation after heat treatment

[0317] Each of the antibacterial resin 1 and antibacterial resin A prepared in the Preparation Examples was heat-treated at 180 °C and 220 °C, and the changes were determined with the naked eye.

[0318] In Figure 3 , (a) is after heat treatment at 180 °C, (b) is after heat treatment at 220 °C, "1" means antibacterial resin 1, and "A" means antibacterial resin A.

[0319] According to Figure 3 , it can be determined that in the case of antibacterial resin A containing Br - as the anion, there is a color change after heat treatment at 220 °C. In contrast, it can be determined that in the case of antibacterial resin 1 containing BF4 - as the anion, no change occurs even when heat-treated at 220 °C. Thus, it can be determined that the antibacterial resin according to an exemplary embodiment of the present invention is more thermally stable.

[0320] In summary, through Tables 1 and 2 and Figure 2 and Figure 3It can be seen that the antibacterial resin according to the present specification exhibits heat resistance while having excellent antibacterial activity and has excellent processability.

Claims

1. An antibacterial resin comprising a copolymer, the copolymer comprising: a first unit derived from a monomer represented by the following Chemical Formula 1; and a second unit derived from an alkyl acrylate or an alkyl methacrylate: [Chemical Formula 1] Among them, In Chemical Formula 1, L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, two of R1 to R3 are the same or different from each other and are each independently a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms, R4 to R6 are the same or different from each other and are each independently hydrogen or methyl, and X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

2. The antibacterial resin according to claim 1, wherein two of R1 to R3 are the same or different from each other and are each independently methyl or ethyl, and the other is an alkyl having 5 to 20 carbon atoms.

3. The antibacterial resin according to claim 1, wherein L1 is methylene, ethylene, or propylene.

4. The antibacterial resin according to claim 1, wherein Chemical Formula 1 is the following Chemical Formula 1-1 or Chemical Formula 1-2: [Chemical Formula 1-1] [Chemical Formula 1-2] In Chemical Formula 1-1 and Chemical Formula 1-2, L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, R4 is hydrogen or methyl, b1 is an integer from 2 to 9, b2 is an integer from 1 to 8, and X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

5. The antibacterial resin according to claim 1, wherein the first unit is represented by the following Chemical Formula 1-A, [Chemical Formula 1-A] In Chemical Formula 1-A, L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, two of R1 to R3 are the same or different from each other and are each independently a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms, R4 to R6 are the same or different from each other and are each independently hydrogen or methyl, X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate, n1 is an integer from 1 to 10,000, and * is the attachment point in the copolymer.

6. The antibacterial resin according to claim 1, wherein Chemical Formula 1 is any one of the following structures:

7. The antibacterial resin according to claim 1, wherein the second unit is represented by the following Chemical Formula 2: [Chemical Formula 2] In Chemical Formula 2, R11 is an alkyl, R12 is hydrogen or methyl, n2 is an integer from 1 to 10,000, and * is the attachment point in the copolymer.

8. The antibacterial resin according to claim 1, wherein the copolymer comprises a third unit represented by the following Chemical Formula 3: [Chemical Formula 3] In Chemical Formula 3, L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, two of R1 to R3 are the same or different from each other and are each independently a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, and the other is a substituted or unsubstituted alkyl having 5 to 20 carbon atoms, R11 is an alkyl, R4 and R12 are the same or different from each other and are each independently hydrogen or methyl, X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate, n1 and n2 are each an integer from 1 to 10,000, and * is an attachment point in the copolymer.

9. The antibacterial resin according to claim 1, wherein the molar ratio of the first unit to the second unit in the copolymer is from 10:90 to 80:

20.

10. The antibacterial resin according to claim 1, wherein the primary thermal decomposition temperature of the antibacterial resin is 200 °C or higher.

11. The antibacterial resin according to claim 1, wherein the antibacterial resin exhibits antibacterial properties against at least one of Gram-positive bacteria, Gram-negative bacteria, and molds.

12. A molded article comprising the antibacterial resin according to any one of claims 1 to 11 or prepared from the antibacterial resin.

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