Antibacterial resin and molded body comprising same

Abstract

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

Description

Antibacterial resin and molded article containing the same

[0001] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2023-0082165, filed with the Korean Intellectual Property Office on June 26, 2023, and Korean Patent Application No. 10-2024-0072520, filed with the Korean Intellectual Property Office on June 3, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present specification relates to an antibacterial resin and a molded article comprising the same.

[0003] Recently, with the diversification of lifestyles, improvements in living standards, and changes and improvements in awareness, interest in improving hygiene and comfort in one's living environment has grown. Consequently, research is being conducted on the microorganisms that threaten this environment. The diversity of microorganisms present in our daily lives and their widespread distribution throughout nature have led to significant damage.

[0004] In particular, microorganisms such as bacteria and mold can inhabit various environments, including eating habits, living environments, clothing, and industrial products. Bacteria can cause various inflammations and food poisoning, while mold can cause problems not only by producing unpleasant odors but also by triggering various skin diseases, respiratory diseases, and allergies. Furthermore, microorganisms that inhabit the surfaces of electronic products and household goods can also deteriorate their performance.

[0005] Accordingly, various antibacterial substances are being developed to prevent damage to humans caused by these microorganisms by inhibiting their growth or killing them.

[0006] At this time, depending on the material of the product requiring antibacterial properties or the final use condition, the required degree of antibacterial properties and the requirements for materials to provide antibacterial properties are different.

[0007] Existing antibacterial agents can be broadly divided into inorganic and organic antibacterial agents. Inorganic antibacterial agents, which contain metals such as silver or copper, offer excellent thermal stability, allowing them to maintain antibacterial properties even at high temperatures. However, they are expensive and prone to discoloration due to metal ions contained after processing. Organic antibacterial agents, however, offer the advantages of being cheaper and exhibiting excellent antibacterial effects even in small quantities, but they also suffer from poor antibacterial durability due to the potential for dissolution after application to the product.

[0008] In introducing antibacterial agents that inhibit bacterial growth into the resin, it was not easy to select and introduce an antibacterial agent component that exhibits excellent bacterial growth inhibition properties, is harmless to the human body, satisfies economic feasibility, and does not deteriorate the basic physical properties of the polymer resin.

[0009] For example, GPPS (general-purpose polystyrene) is widely used due to its transparency and high strength. To enhance antibacterial properties, inorganic antibacterial agents (e.g., copper, silver) are added to GPPS. However, depending on the method of addition, durability may be reduced, and problems arise due to toxicity depending on the substance used.

[0010] Accordingly, there is a need to develop a highly antibacterial material suitable for application to each of various products, while also being harmless to the human body because the antibacterial substance does not leak out.

[0011] The present specification provides an antibacterial resin and a molded article comprising the same.

[0012] One embodiment of the present specification provides an antibacterial resin comprising a 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.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0017] Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms,

[0018] R4 to R6 are the same or different and are each independently hydrogen or a methyl group,

[0019] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0020] Another embodiment of the present disclosure provides a molded article comprising the antibacterial resin described above or manufactured therefrom.

[0021] Antibacterial resins according to some embodiments of the present specification have excellent antibacterial properties.

[0022] Antibacterial resins according to some embodiments of the present specification can exhibit antibacterial properties within a short period of time.

[0023] The antibacterial resins according to some embodiments of this specification exhibit minimal variation in antibacterial activity depending on the amount of antibacterial material used. Therefore, even when unintentional concentration variations occur during product application, they can exhibit antibacterial activity within the expected range. Therefore, the antibacterial activity can be controlled within a specific range, safely providing superior antibacterial activity.

[0024] The antibacterial resin according to some embodiments of this specification has low toxicity, which can solve safety issues.

[0025] Antibacterial resins according to some embodiments of the present specification can solve safety problems caused by leakage of antibacterial substances.

[0026] The antibacterial resin according to some embodiments of the present specification has excellent heat resistance and thus has the characteristic of maintaining antibacterial activity even after a high-temperature process.

[0027] Figure 1 is a diagram showing the NMR measurement results of monomer 1-1' manufactured in Manufacturing Example 1.

[0028] Figure 2 is a diagram showing the TGA measurement results for each of antibacterial resins 1, 2, and A manufactured in Manufacturing Examples 1 and 2 and Comparative Manufacturing Example 1.

[0029] Figure 3 (a) is a diagram showing the appearance of antibacterial resins 1 and A manufactured in Manufacturing Example 1 and Comparative Manufacturing Example 1, respectively, after heat treatment at 180°C.

[0030] Figure 3 (b) is a diagram showing the appearance of antibacterial resins 1 and A manufactured in Manufacturing Example 1 and Comparative Manufacturing Example 1, respectively, after heat treatment at 220°C.

[0031] Hereinafter, the present specification is described in detail.

[0032] One embodiment of the present specification provides an antibacterial resin comprising a 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.

[0033] [Chemical Formula 1]

[0034]

[0035] In the above chemical formula 1,

[0036] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0037] Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms,

[0038] R4 to R6 are the same or different and are each independently hydrogen or a methyl group,

[0039] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0040] There are over 5,000 identified species of bacteria, representing a vast array of species. Specifically, they can be categorized as aerobic, facultative, and anaerobic based on their oxygen requirements, and their shapes vary widely, including spherical, rod-shaped, and spiral-shaped. Therefore, it is difficult for a single antimicrobial agent to possess the physical and / or chemical mechanisms to damage or denature the cell membrane and / or cell wall of various bacteria.

[0041] Traditionally, antimicrobial agents were simply mixed with polymers to impart antibacterial properties to materials. Inorganic or organic antimicrobial agents were used. These inorganic antimicrobial agents are expensive, easily cause discoloration, and can degrade the physical properties of polymers during processing such as extrusion or injection molding. Furthermore, inorganic antimicrobial agents have the disadvantage of low immediate antibacterial efficacy.

[0042] The above organic antibacterial agents themselves have poor stability in the human body and poor thermal stability, resulting in poor antibacterial durability. Furthermore, when polymerizable organic antibacterial agents are applied to polymerization, polymerization efficiency or conversion rates often decline, or the inherent advantages of the polymer are compromised.

[0043] On the other hand, the antibacterial resin according to the present invention does not contain an inorganic antibacterial agent, thereby overcoming disadvantages such as discoloration and reduced transparency. Furthermore, the antibacterial agent is not incorporated as a separate substance within the antibacterial resin itself, but is polymerized as a monomer and incorporated as a repeating unit forming the main chain within the polymer. This eliminates concerns about leaching, resulting in excellent human safety and the ability to maintain antibacterial persistence. In other words, the antibacterial resin of the present invention exhibits excellent antibacterial properties and antibacterial persistence.

[0044] Meanwhile, conventional polymers often undergo high-temperature molding processes, such as injection or extrusion, during their application. Most known antibacterial polymers suffer from a reduction or loss of antibacterial properties during these processes. In contrast, the antibacterial resin of the present invention maintains its antibacterial properties even after undergoing such high-temperature molding processes by applying specific anions.

[0045] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0046] In this specification, "monomer" means a unit compound that can be converted into a polymer compound by a polymerization reaction, and structures derived therefrom can become repeating units in a polymer or copolymer. Specifically, this means that the compound is polymerized and bound to a polymer, with all or part of two or more substituents in the structure of the compound being removed, and a radical for bonding to another unit of the polymer being positioned at that position. At this time, the compound can be polymerized in any order and included in a bound state in the polymer.

[0047] In this specification, the term "derived" means that a bond between at least two adjacent elements in a compound is broken, or a new bond is formed as a hydrogen or substituent is removed, and a unit derived from the compound may mean a unit forming one or more of the main chain and side chain of a polymer. The unit may be included in the main chain of the polymer to form the polymer.

[0048] In this specification, the term "weight average molecular weight" refers to one of the average molecular weights in which the molecular weight of a polymer substance is not uniform and is used as a standard, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

[0049] In this specification, the terms “first,” “second,” etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0050] In this specification, singular forms also include plural forms unless the phrases clearly indicate the opposite.

[0051] In this specification, properties whose properties are affected by temperature are properties measured at room temperature, unless otherwise specified.

[0052] In this specification, "room temperature" means a natural temperature that is neither heated nor cooled, for example, any temperature within the range of about 10°C to 30°C, for example, a temperature of about 15°C, about 18°C, about 20°C, about 23°C, or about 25°C. In addition, unless specifically specified otherwise in this specification, the unit of temperature is ℃.

[0053] In this specification, if pressure affects the results among the properties, the properties are properties measured at atmospheric pressure, unless otherwise specified.

[0054] In this specification, “normal pressure” refers to the natural pressure that is neither pressurized nor depressurized, and is usually about 1 atmosphere (about 700 to 800 mmHg).

[0055] In this specification, when humidity affects the results among the physical properties, unless otherwise specified, the physical properties are those measured at room temperature and pressure and at a humidity that is not specifically controlled.

[0056] In the present specification, the "alkyl group" may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. In one embodiment of the present specification, the number of carbon atoms of 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, a tridecyl group, and the like.

[0057] In this specification, "alkylene group" means a divalent group, i.e., an alkyl group having two bonding positions. The description of the alkyl group described above may be applied to each of these groups, except that they are each divalent.

[0058] In this specification, "*" denotes an attachment point within the copolymer. The attachment point may be a point where identical units are attached to each other, or a point where different units are attached. For example, in the following chemical formula 1-A, * denotes both a portion where the first units are attached to each other, and a portion where the first unit and the second unit are attached.

[0059] In one embodiment of the present specification, the first unit is represented by the following chemical formula 1-A.

[0060] [Chemical Formula 1-A]

[0061]

[0062] In the above chemical formula 1-A,

[0063] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0064] Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms,

[0065] R4 to R6 are the same or different and are each independently hydrogen or a methyl group,

[0066] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tetratrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0067] n1 is an integer from 1 to 10,000,

[0068] * is the attachment point within the copolymer.

[0069] In one embodiment of the present specification, the quaternary ammonium cation included in the first unit has a linker (L1) connected to the main chain and three terminal groups (R1 to R3).

[0070] In one embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0071] In one embodiment of the present specification, L1 is a straight-chain alkylene group having 1 to 10 carbon atoms.

[0072] In one embodiment of the present specification, L1 is an alkylene group having 1 to 4 carbon atoms.

[0073] In one embodiment of the present specification, L1 is a methylene group; an ethylene group; or a propylene group.

[0074] In one embodiment of the present specification, L1 is an ethylene group.

[0075] In one embodiment of the present specification, two of R1 to R3 are the same or different from each other, and each independently is an alkyl group having 1 to 4 carbon atoms, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

[0076] In one 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, if all of R1 to R3 are alkyl groups having less than 5 carbon atoms, there is a problem that antibacterial properties are not exhibited, and if even one of R1 to R3 is an alkyl group having more than 20 carbon atoms, there is a problem that the starting material for producing the copolymer does not dissolve in the solvent, making synthesis impossible.

[0077] In one embodiment of the present specification, two of R1 to R3 are the same or different from each other, and each independently represents a methyl group or an ethyl group, and the remaining one represents an alkyl group having 5 to 20 carbon atoms.

[0078] In one embodiment of the present specification, two of R1 to R3 that are not alkyl groups having 5 to 20 carbon atoms are the same.

[0079] In one embodiment of the present specification, two of R1 to R3 are each a methyl group, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

[0080] In one 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.

[0081] In one 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.

[0082] In one embodiment of the present specification, R4 to R6 are the same as or different from each other, and are each independently hydrogen or a methyl group.

[0083] In one embodiment of the present specification, R5 and R6 are each hydrogen.

[0084] In one embodiment of the present specification, R4 is hydrogen or a methyl group.

[0085] In one embodiment of the present specification, the chemical formula 1 is the following chemical formula 1-1 or 1-2.

[0086] [Chemical Formula 1-1]

[0087]

[0088] [Chemical Formula 1-2]

[0089]

[0090] In the above chemical formulas 1-1 and 1-2,

[0091] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0092] R4 is hydrogen or a methyl group,

[0093] b1 is an integer from 2 to 9,

[0094] b2 is an integer from 1 to 8,

[0095] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0096] In one embodiment of the present specification, the first unit is the following chemical formula 1-A-1 or 1-A-2.

[0097] [Chemical Formula 1-A-1]

[0098]

[0099] [Chemical Formula 1-A-2]

[0100]

[0101] In the above chemical formulas 1-A-1 and 1-A-2,

[0102] R4 is hydrogen or a methyl group,

[0103] b1 is an integer from 2 to 9,

[0104] b2 is an integer from 1 to 8,

[0105] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tetratrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0106] n1 is an integer from 1 to 10,000,

[0107] * is the attachment point within the copolymer.

[0108] In one embodiment of the present specification, the trifluoromethanesulfonate is CF3SO3 - or is displayed as .

[0109] In one embodiment of the present specification, the methanesulfonate is CH3SO3 - or is displayed as .

[0110] In one embodiment of the present specification, the tetrafluoroborate is BF4 - or is displayed as .

[0111] In one embodiment of the present specification, the methylsulfate is CH3OSO3 - or is displayed as .

[0112] In one embodiment of the present specification, the maleate is It is displayed as .

[0113] In one embodiment of the present specification, the tartrate is It is displayed as .

[0114] In one embodiment of the present specification, the vanillate is It is displayed as .

[0115] In one embodiment of the present specification, the syringeate is It is displayed as .

[0116] In one embodiment of the present specification, the hexafluorophosphate is PF6 - or It is displayed as .

[0117] In one embodiment of the present specification, the thiocyanate is SCN - or It is displayed as .

[0118] In one embodiment of the present specification, the trifluoroacetate is CF3COO - or It is displayed as .

[0119] In one embodiment of the present specification, the chemical formula 1 has one of the following structures.

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] In one embodiment of the present specification, n1 is an integer from 3 to 10,000. Specifically, it 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.

[0127] In one embodiment of the present specification, the first unit is an antibacterial material. That is, the copolymer exhibits antibacterial properties by including the first unit. Specifically, the copolymer exhibits antibacterial properties against bacteria (at least one of gram-positive bacteria, gram-negative bacteria, and Escherichia coli) by including the first unit. More specifically, in general, the cell walls of bacteria and the like are often negatively charged. In the first unit, a cation of a quaternary ammonium having an alkyl group of a specific carbon number is electrostatically adsorbed to the cell wall of the bacteria, and thereafter, by interaction with the alkyl group (R1 to R3) of the quaternary ammonium salt exhibiting hydrophobicity, the cell surface structure of the bacteria is coated and / or destroyed, thereby exhibiting antibacterial properties.

[0128] In one embodiment of the present specification, the second unit derived from the alkyl acrylate or alkyl methacrylate may have a structure in which a double bond of an acrylate group is broken to form a repeating unit.

[0129] In one embodiment of the present specification, the alkyl acrylate or alkyl methacrylate is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-ethylhexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, n-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, lauryl acrylate, ceryl acrylate, stearyl acrylate, It may be lauryl methacrylate, cetyl methacrylate, or stearyl methacrylate. Preferably, it may be methyl methacrylate.

[0130] In one embodiment of the present specification, the second unit is represented by the following chemical formula 2.

[0131] [Chemical Formula 2]

[0132]

[0133] In the above chemical formula 2,

[0134] R11 is an alkyl group,

[0135] R12 is hydrogen or methyl group,

[0136] n2 is an integer from 1 to 10,000,

[0137] * is the attachment point within the copolymer.

[0138] In one embodiment of the present specification, n2 is an integer from 3 to 10,000. Specifically, it 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.

[0139] In one embodiment of the present disclosure, the copolymer exhibits a glass transition temperature (Tg) by including the second unit. This enhances processability in processing processes such as extrusion and injection molding. Furthermore, compatibility with other polymers, such as polyethylene and polypropylene, is improved.

[0140] In one 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.

[0141] In one embodiment of the present specification, the first unit and the second unit are included in the main chain of the copolymer.

[0142] In one 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.

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

[0144] In one embodiment of the present specification, the copolymer includes a third unit represented by the following chemical formula 3.

[0145] [Chemical Formula 3]

[0146]

[0147] In the above chemical formula 3,

[0148] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

[0149] Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms,

[0150] R11 is an alkyl group,

[0151] R4 and R12 are the same or different and are each independently hydrogen or methyl group,

[0152] X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tetratrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate,

[0153] n1 and n2 are integers from 1 to 10,000, respectively,

[0154] * is the attachment point within the copolymer.

[0155] In one embodiment of the present specification, a copolymer including a first unit derived from a monomer represented by the chemical formula 1; and a second unit derived from an alkyl acrylate or an alkyl methacrylate is represented by the chemical formula 3.

[0156] In one embodiment of the present specification, R11 is an alkyl group having 1 to 10 carbon atoms.

[0157] In one embodiment of the present specification, R11 is a straight-chain alkyl group having 1 to 10 carbon atoms.

[0158] In one embodiment of the present specification, R11 is a methyl group; an ethyl group; or a propyl group.

[0159] In one embodiment of the present specification, the copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000 g / mol. If 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, which may easily be eluted, and furthermore, the low molecular weight may cause problems with absorption into the human body. In addition, if the weight average molecular weight of the copolymer exceeds 1,000,000 g / mol, there may be problems with processability.

[0160] More specifically, the copolymer may have a weight average molecular weight (Mw; g / mol) of 10,000 or more, 15,000 or more, 20,000 or more, 23,000 or more, or 25,000 or more, 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.

[0161] According to one embodiment of the present specification, the number average molecular weight (Mn) of the antibacterial resin is 10,000 g / mol to 800,000 g / mol. More preferably, the number average molecular weight (Mn; g / mol) of the antibacterial resin may be 15,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, or 40,000 or more, and 150,000 or less, 100,000 or less, 90,000 or less, or 80,000 or less.

[0162] In one embodiment of the present specification, the weight average molecular weight (Mw) of the copolymer can be measured using gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample for calibration. 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 measured using an RI detector at a flow rate of 1 mL / min using an Agilent 1200 series GPC instrument. At this time, the molecular weight of the sample can be calculated based on a calibration curve prepared using 8 types of standard PMMA standards.

[0163] According to one embodiment of the present specification, the molecular weight distribution (Mw / Mn) of the copolymer may be within a range of 1 to 3. In other examples, the molecular weight distribution may be 1.1 or more, 1.2 or more, 1.3 or more, or 1.4 or more, 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.

[0164] In one embodiment of the present specification, the copolymer is an antibacterial copolymer exhibiting antibacterial activity.

[0165] In one embodiment of the present specification, the weight average molecular weight, number average molecular weight, and molecular weight distribution of the antibacterial resin may be the same as those of the copolymer.

[0166] In one embodiment of the present specification, the molar ratio of the first unit and the second unit in the copolymer is 10:90 to 80:20.

[0167] In one embodiment of the present specification, the first unit is included in an amount of 10 to 80 mol% based on the total number of moles of the first and second units in the copolymer. If the content of the first unit is less than 10 mol%, it is difficult to exhibit a sufficient antibacterial effect, and if the content of the first unit exceeds 80 mol%, there is a problem that processability is reduced, making it difficult to apply in real life.

[0168] More specifically, the first unit is included in an amount of 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, or 30 mass% or more, and 75 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less, based on the total mass of the first unit and the second unit in the copolymer.

[0169] In one embodiment of the present specification, the antibacterial resin exhibits antibacterial properties against at least one of gram-positive bacteria, gram-negative bacteria, and fungi.

[0170] In this specification, Gram-positive bacteria are a general term for bacteria that are stained purple when stained with the Gram staining method. The cell wall of Gram-positive bacteria is composed of multiple layers of peptidoglycan, so that even when stained with a basic dye such as crystal violet and then treated with ethanol, the bacteria do not decolorize and show a purple color.

[0171] In one embodiment of the present specification, the Gram-positive bacteria is selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, any one selected from the examples described above is not limited thereto.

[0172] In this specification, Gram-negative bacteria are a general term for bacteria that are stained 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, they have an outer membrane composed of lipopolysaccharides, lipoproteins, and / or other complex polymeric substances.

[0173] In one embodiment of the present specification, the Gram-negative bacteria are selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, any one selected from the examples described above is not limited thereto.

[0174] In one embodiment of the present specification, the fungus may be, but is not limited to, Candida albicans.

[0175] The antimicrobial activity of the above copolymer against bacteria can be measured according to JIS Z 2801 (Measurement of antimicrobial activity on plastic and non-porous surfaces) or ASTM E2149 (Determining the Antimicrobial Activity of Immobilized Antimicrobial Agents Under Dynamic Contact Conditions).

[0176] Specifically, the antibacterial property can be measured by ASTM E2149 as follows.

[0177] Put 1g of antibacterial resin into a 250mL Erlenmeyer flask and add 2x10 5Inject 50 mL of phosphate-buffered saline (PBS) inoculated with E. coli ATCC 25922 strain (CFU / mL) and cultured in a shaking incubator maintained at 35°C for 1 hour. The culture solution is diluted 10-fold and 100-fold and spread on agar plates. The spread agar plates are then cultured in a static manner at 37°C for 24 to 48 hours. Based on the CFU count of the diluted sample, the antibacterial activity is derived by calculating the following mathematical formula 1.

[0178] [Mathematical Formula 1]

[0179]

[0180] In this specification, exhibiting antibacterial properties means an antibacterial power measured according to the above method, in other words, a case where the bacteriostatic reduction rate is 99% or higher.

[0181] Specifically, the bacteriostatic reduction rate of the antibacterial resin measured according to ASTM E2149 may be 99.1% or more, 99.5% or more, or 99.9% or more but 100% or less.

[0182] In one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 99% or more against Gram-positive bacteria as measured by ASTM E2149.

[0183] In one embodiment of the present specification, the compound has an antibacterial activity of 99% or more against Gram-negative bacteria as measured by ASTM E2149.

[0184] In one embodiment of the present specification, the compound has an antibacterial activity of 99% or more against fungi as measured by ASTM E2149.

[0185] In this specification, “CFU (Colony Forming Unit)” means colony forming unit, and CFU / mL means the number of CFU per 1 mL.

[0186] In one embodiment of the present specification, the CFU value measured in the above method 1 is introduced as the A value (microbial concentration) of mathematical formula 1.

[0187] Since the above-mentioned Gram-positive bacteria, Gram-negative bacteria and fungal strains can cause various diseases upon contact as well as secondary infections, it is desirable to use a single compound to exhibit antibacterial properties against all of the above-mentioned Gram-positive bacteria, Gram-negative bacteria and fungi.

[0188] In one embodiment of the present specification, the antibacterial resin has a primary thermal decomposition temperature of 200°C or higher.

[0189] In one 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.

[0190] In this specification, the thermal decomposition temperature can be measured using a TGA (Thermogravimetric Analyzer).

[0191] Specifically, the thermal decomposition temperature can be determined by measuring TGA in a nitrogen atmosphere with the following section-by-section temperature conditions set.

[0192] Step 1) Increase temperature from 30℃ to 110℃ at a rate of 10℃ / min.

[0193] Step 2) Keep at 110℃ for 10 minutes

[0194] Step 3) Cooling from 110℃ to 50℃ at a rate of 10℃ / min

[0195] Step 4) Increase temperature from 50℃ to 600℃ at a rate of 10℃ / min.

[0196] In the above sections, the first temperature reduction section among the four stages of the mass reduction curve was determined as the first thermal decomposition temperature. Specifically, the thermal decomposition temperature was defined as the extrapolated intersection point between the initial mass baseline measured by TGA and the tangent line of the maximum slope point in the first mass reduction section of the mass reduction curve.

[0197] In one embodiment of the present specification, the upper limit of the primary thermal decomposition temperature is not particularly limited, and may be, for example, 500°C or less, 480°C or less, or 450°C or less.

[0198] According to one embodiment of the present specification, the glass transition temperature (Tg) of the antibacterial resin is 80°C or higher.

[0199] In this specification, the glass transition temperature can be measured using DSC (Differential Scanning Calorimetry).

[0200] Specifically, the glass transition temperature can be determined by measuring DSC with the following section-by-section temperature conditions set.

[0201] Step 1) Increase temperature from 30℃ to 200℃ at a rate of 10℃ / min.

[0202] Step 2) Maintain at 200℃ for 5 minutes

[0203] Step 3) Cooling from 200℃ to -50℃ at a rate of -10℃ / min.

[0204] Step 4) Keep at -50℃ for 5 minutes

[0205] Step 5) Temperature increase from -50℃ to 200℃ at a rate of 10℃ / min

[0206] In one embodiment of the present specification, the upper limit of the glass transition temperature is not limited and may be, for example, 150°C or less, 140°C or less, or 130°C or less.

[0207] The above antibacterial resin has the thermal decomposition temperature and glass transition temperature described above, thereby exhibiting an effect of improving processability in processes such as extrusion and injection.

[0208] In one embodiment of the present specification, the antibacterial resin can be manufactured by copolymerizing a monomer represented by the chemical formula 1 (hereinafter, the first monomer); and an alkyl acrylate or alkyl methacrylate (hereinafter, the second monomer).

[0209] In one embodiment of the present specification, the antibacterial resin can be polymerized in the presence of a polymerization initiator. This polymerization initiator can be appropriately selected depending on the polymerization method. When using a thermal polymerization method, a thermal polymerization initiator is used. When using a photopolymerization method, a photopolymerization initiator is used. When using a hybrid polymerization method (a method using both heat and light), both a thermal polymerization initiator and a photopolymerization initiator can be used. However, even when using a photopolymerization method, a certain amount of heat is generated by light irradiation such as ultraviolet irradiation, and a certain amount of heat is generated as the polymerization reaction, which is an exothermic reaction, progresses, so a thermal polymerization initiator can be additionally used.

[0210] In one embodiment of the present specification, the photopolymerization initiator may be used without limitation in its composition as long as it is a compound that can form radicals by light such as ultraviolet rays. For example, the photopolymerization initiator may be at least one selected from the group consisting of benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal, acyl phosphine, and α-aminoketone. Meanwhile, specific examples of the acylphosphine include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate. A more detailed description of various photoinitiators is given in Reinhold Schwalm's book "UV Coatings: Basics, Recent Developments and New Applications (Elsevier 2007)" p115, and is not limited to the examples described above.

[0211] In one embodiment of the present specification, the photopolymerization initiator may be included in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the first monomer and the second monomer. If the content of the photopolymerization initiator is less than 0.001 part by weight, the polymerization speed may be slowed down, and if the content of the photopolymerization initiator exceeds 1 part by weight, the molecular weight of the polymer may be low and the physical properties may become uneven. More specifically, the photopolymerization initiator may be included in an amount of 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 based on 100 parts by weight of the monomers.

[0212] In one embodiment of the present specification, the thermal polymerization initiator may be at least one selected from the group of initiators consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid. Specifically, examples of persulfate-based initiators include sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), and ammonium persulfate ((NH4)2S2O8), and examples of azo-based initiators include azobisisobutyronitrile, 2-azobis-(2-amidinopropane) dihydrochloride, 2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride, Examples include 2-(carbamoylazo)isobutylonitril, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, and 4,4-azobis-(4-cyanovaleric acid). A more diverse range of thermal polymerization initiators is well described in Odian's book, 'Principle of Polymerization (Wiley, 1981),' p. 203, and is not limited to the examples described above.

[0213] In one embodiment of the present specification, the thermal polymerization initiator may be included in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the first monomer and the second monomer. If the content of the thermal polymerization initiator is less than 0.001 parts by weight, additional thermal polymerization hardly occurs, so that the effect of adding the thermal polymerization initiator may be minimal, and if the content of the thermal polymerization initiator exceeds 3 parts by weight, the molecular weight of the polymer may become small and the physical properties may become uneven. More specifically, the thermal polymerization initiator may be included in an amount of 0.005 parts by weight or more, or 0.01 parts by weight or more, or 0.1 parts 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, based on 100 parts by weight of the total of the monomers.

[0214] According to one embodiment of the present specification, the terminal group of the copolymer may have a structure derived from the first unit, the second unit, and the initiator used in the preparation of the copolymer. Specifically, the first unit and the second unit may have a single bonding position, or a structure corresponding to half of the initiator used.

[0215] For example, the terminal group of the copolymer has one of the following structures.

[0216]

[0217] In the above structure, L1, R1 to R6, R11, R12 and X - is consistent with that defined in Chemical Formulas 1 and 2, and * is a moiety attached to the copolymer.

[0218] The first monomer, the second monomer, and the polymerization initiator can be prepared in the form of a solution dissolved in a solvent.

[0219] In one embodiment of the present specification, the solvent may be used without limitation in its composition as long as it can dissolve the above-described components, and for example, one or more selected from 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, and N,N-dimethylacetamide may be used in combination.

[0220] In one embodiment of the present specification, the copolymerization of the first monomer and the second monomer can be performed without any special configuration limitations as long as it is a commonly known method. For example, the copolymerization can be performed at a temperature of 60°C to 100°C, or 60°C to 90°C, for 1 hour to 24 hours, and upon completion of the reaction, the produced polymer can be extracted and dried to finally obtain the desired copolymer.

[0221] One embodiment of the present specification provides a molded article comprising the above-described antibacterial resin or manufactured therefrom.

[0222] In this specification, a molded body means a material including the antibacterial resin, a material manufactured from the antibacterial resin, or a product including the antibacterial resin.

[0223] Specifically, the molded body is at least one selected from among materials for maintaining leading edge, fabric products, agricultural films, automobile parts, various office supplies, various packaging materials, and medical supplies.

[0224] More specifically, the molded body may be packaging materials such as food packaging materials, vegetable packaging materials, grain packaging materials, fruit packaging materials, meat packaging materials, aquatic product packaging materials, processed food packaging materials, and freshness-maintaining materials such as containers for vegetables, grains, fruits, meat, aquatic products, and processed foods; fabric products such as food tray mats, table mats, tablecloths, carpets, and seat covers; agricultural films; automotive parts such as automotive 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, standing bags, transparent packaging boxes, automatic packaging films, electronic component packaging materials, and mechanical component packaging materials; and medical supplies such as medical films, medical tapes, and cell culture packs.

[0225] In addition, the molded body may be a blow molded body, an inflation molded body, a cast molded body, an extrusion laminate molded body, an extrusion molded body, a foam molded body, an injection molded body, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric, but is not limited to the above examples.

[0226] Hereinafter, experimental examples will be used to specifically explain this specification. However, the experimental examples described herein may be modified in various ways, and the scope of this specification is not limited to the experimental examples described below. The experimental examples described herein are provided to more fully explain this specification to those of average skill in the art.

[0227] Manufacturing Example 1. Manufacturing of antibacterial resin 1

[0228] (1) Preparation of monomer 1

[0229]

[0230] A 2 L round-bottomed flask was charged with 70 mL of acetonitrile, 2 mol of 2-(dimethylamino)ethyl methacrylate, 2 mol of 1-bromododecane, and 0.32 g of p-methoxyphenol. The mixture was stirred at 45°C using a magnetic bar for 16 hours to produce a quaternary ammonium salt by substituting an alkyl group on the amino group. Afterwards, the solution in which the reaction was completed was added to 10 L of methyl tert-butyl ether (MTBE) to perform extraction. Afterwards, the reactant was filtered using a vacuum filter, and the remaining MTBE was completely removed to produce an antibacterial monomer 1-1'.

[0231] Figure 1 is a diagram showing the NMR measurement results of monomer 1-1'.

[0232] (2) Preparation of antibacterial resin 1

[0233] In a 500 mL round-bottomed flask, 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 charged. The polymerization reaction was carried out by stirring for 16 hours at 65°C using a stirring bar. The solution, after the reaction was completed at room temperature, was diluted by mixing 50 mL of acetonitrile, and precipitated by adding 2 L of a 50 wt% sodium tetrafluoroborate aqueous solution. Thereafter, the solid polymer was filtered using a vacuum filter, and the remaining solvent was completely removed through vacuum drying to prepare antibacterial resin 1.

[0234] Manufacturing example 2.

[0235] Antibacterial resin 2 was manufactured in the same manner as in Manufacturing Example 1, except that sodium trifluoromethanesulfonate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0236] Manufacturing example 3.

[0237] Antibacterial resin 3 was manufactured in the same manner as in Manufacturing Example 1, except that sodium methanesulfonate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0238] Manufacturing example 4.

[0239] Antibacterial resin 4 was manufactured in the same manner as in Manufacturing Example 1, except that sodium methyl sulfate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0240] Manufacturing Example 5.

[0241] Antibacterial resin 5 was manufactured in the same manner as in Manufacturing Example 1, except that sodium malate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0242] Manufacturing example 6.

[0243] Antibacterial resin 6 was manufactured using the same method as Manufacturing Example 1, except that sodium tartrate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0244] Manufacturing example 7.

[0245] Antibacterial resin 7 was manufactured using the same method as Manufacturing Example 1, except that sodium vanillate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0246] Manufacturing example 8.

[0247] Antibacterial resin 8 was manufactured using the same method as Manufacturing Example 1, except that sodium syringate solution was used instead of sodium tetrafluoroborate solution during precipitation in (2) of Manufacturing Example 1.

[0248] Manufacturing example 9.

[0249] Antibacterial resin 9 was manufactured in the same manner as in Manufacturing Example 1, except that sodium hexafluorophosphate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0250] Manufacturing example 10.

[0251] Antibacterial resin 10 was manufactured in the same manner as in Manufacturing Example 1, except that sodium thiocyanate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0252] Manufacturing example 11.

[0253] Antibacterial resin 11 was manufactured in the same manner as in Manufacturing Example 1, except that sodium trifluoroacetate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0254] Comparative manufacturing example 1.

[0255] Antibacterial resin A was manufactured using the same method as Manufacturing Example 1, except that water was used instead of the sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0256] Comparative manufacturing example 2.

[0257] A 500 mL round-bottomed flask was charged with 188 mL of ethanol, 50 g of methyl methacrylate (0.5 M), and 2 mol% of azobisisobutyronitrile. The polymerization reaction was carried out by stirring for 16 hours at 65°C using a stirring bar. The solution, which had completed the reaction at room temperature, was diluted by mixing 50 mL of acetonitrile, and precipitated in 2 L of water. Afterwards, the solid polymer was filtered using a vacuum filter, and the remaining solvent was completely removed through vacuum drying to produce a single polymer, PMMA.

[0258] Comparative manufacturing example 3.

[0259] Antibacterial resin B was manufactured using the same method as in Manufacturing Example 1, except that sodium toluenesulfonate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0260] Comparative manufacturing example 4.

[0261] Antibacterial resin C was manufactured using the same method as Manufacturing Example 1, except that sodium phosphate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0262] Comparative manufacturing example 5.

[0263] Antibacterial resin D was manufactured using the same method as Manufacturing Example 1, except that sodium acetate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0264] Comparative manufacturing example 6.

[0265] Antibacterial resin E was manufactured in the same manner as in Manufacturing Example 1, except that sodium phenyl acetate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0266] Comparative manufacturing example 7.

[0267] Antibacterial resin F was manufactured using the same method as Manufacturing Example 1, except that sodium salicylate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0268] Comparative manufacturing example 8.

[0269] Antibacterial resin G was manufactured using the same method as Manufacturing Example 1, except that sodium benzoate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0270] Comparative manufacturing example 9.

[0271] Antibacterial resin H was manufactured in the same manner as in Manufacturing Example 1, except that sodium benzyl phosphate aqueous solution was used instead of sodium tetrafluoroborate aqueous solution during precipitation in (2) of Manufacturing Example 1.

[0272] The types of anions of the antibacterial resins manufactured in Manufacturing Examples 1 to 11 and Comparative Manufacturing Examples 1 to 9 are listed in Table 1 below.

[0273] <Experimental Example 1> Measurement of antibacterial activity

[0274] The antibacterial activity of each of the antibacterial resins 1 to 11, antibacterial resins A to H, and PMMA manufactured in Manufacturing Examples 1 to 11 and Comparative Manufacturing Examples 1 to 9 was measured according to ASTM E 2179. The specific measurement method is as follows.

[0275] Put 1g of antibacterial resin into a 250mL Erlenmeyer flask and add 2x10 5 50 mL of phosphate-buffered saline (PBS) inoculated with E. coli ATCC 25922 strain (CFU / mL) was injected and cultured in a shaking incubator maintained at 35°C for 1 hour. The culture solution was diluted 10-fold and 100-fold and spread on agar plates. The spread agar plates were cultured in a static manner at 37°C for 24 to 48 hours. The antibacterial activity was derived by calculating the following mathematical formula 1 based on the CFU count of the diluted sample.

[0276] [Mathematical Formula 1]

[0277]

[0278] The measured antibacterial activity is shown in Table 1 below.

[0279] Type of anion used Antibacterial power (%) Experimental example 1-1 Antibacterial resin 1 Tetrafluoroborate (BF4 - )99.9 Exceeding Experimental Example 1-2 Antibacterial Resin 2-Trifluoromethanesulfonate (CF3SO3 - )99.9 Exceeding Experimental Example 1-3 Antibacterial Resin 3-Methanesulfonate (CH3SO3- )99.9 Exceeding Experimental Example 1-4 Antibacterial Resin 4-Methyl Sulfate (CH3OSO3 - )99.9 Exceeding Experimental Example 1-5 Antibacterial Resin 5 Malate ( )99.9 Exceeding Experimental Example 1-6 Antibacterial Resin 6 Tartrate ( )99.9 Exceeding Experimental Example 1-7 Antibacterial Resin 7 Vanillate ( )99.9 Exceeding Experimental Example 1-8 Antibacterial Resin 8 Syringe Gate ( )99.9 Exceeding Experimental Example 1-9 Antibacterial Resin 9-Hexafluorophosphate (PF6) - )99.9 Exceeding Experimental Example 1-10 Antibacterial Resin 10 Thiocyanate (SCN) - )99.9 Exceeding Experimental Example 1-11 Antibacterial Resin 11 Trifluoroacetate (CF3COO - )99.9 Exceeding Comparative Example 1-1 Antibacterial Resin ABr - 99.9 Exceeding Comparative Example 1-2 PMMA-0 Comparative Example 1-3 Antibacterial Resin B Toluenesulfonate ( )98.8 Comparative Example 1-4 Antibacterial Resin C Phosphate (Na2PO4) - )98.5 Comparative Example 1-5 Antibacterial Resin D Acetate (CH3COO - )99.9 Exceeding Comparative Example 1-6 Antibacterial Resin E-Phenyl Acetate ( )99.9 Exceeding Comparative Example 1-7 Antibacterial Resin F Salicylate ( )99.9 Exceeding Comparative Example 1-8 Antibacterial Resin G-Benzoate ( )99.9 Exceeding Comparative Example 1-9 Antibacterial Resin H-Benzyl Phosphate ( )87.3

[0280] According to Table 1 above, it can be confirmed that the antibacterial activity of Comparative Example 1-2, which is a methyl methacrylate homopolymer, is 0.

[0281] On the other hand, in the case of Experimental Examples 1-1 to 1-11 (antibacterial resins 1 to 11), it can be confirmed that the antibacterial power is excellent, exceeding 99.9%.

[0282] <Experimental Example 2> Measurement of thermal decomposition temperature

[0283] The thermal decomposition temperatures of each of antibacterial resins 1, 2, 3, and 9, antibacterial resins A to H, and PMMA manufactured in Manufacturing Examples 1, 2, 3, and 9 and Comparative Manufacturing Examples 1 to 9 were measured using TGA (Thermogravimetric Analyzer, TA Instrument, DISCOVERY TGA 550 W / MFC & AUTO).

[0284] The above TGA was measured in a nitrogen atmosphere, and the temperature conditions for each section were set as follows.

[0285] Step 1) Increase temperature from 30℃ to 110℃ at a rate of 10℃ / min.

[0286] Step 2) Keep at 110℃ for 10 minutes

[0287] Step 3) Cooling from 110℃ to 50℃ at a rate of 10℃ / min

[0288] Step 4) Increase temperature from 50℃ to 600℃ at a rate of 10℃ / min.

[0289] In the above sections, the first temperature reduction section among the four stages of the mass reduction curve was determined as the first thermal decomposition temperature. Specifically, the thermal decomposition temperature was defined as the extrapolated intersection point between the initial mass baseline measured by TGA and the tangent line of the maximum slope point in the first mass reduction section of the mass reduction curve.

[0290] The measured primary pyrolysis temperatures are listed in Table 2 below.

[0291] Figure 2 shows the TGA measurement results of antibacterial resins 1, 2, and A.

[0292] <Experimental Example 3> Measurement of glass transition temperature

[0293] The glass transition temperatures of each of antibacterial resins 1, 2, 3, and 9, antibacterial resins A to H, and PMMA manufactured in Manufacturing Examples 1, 2, 3, and 9 and Comparative Manufacturing Examples 1 to 9 were measured using DSC (Differential Scanning Calorimetry, TA Instrument, DISCOVER TGA 550W / MFC&AUTO).

[0294] When measuring DSC, the temperature conditions were set as follows.

[0295] Step 1) Increase temperature from 30℃ to 200℃ at a rate of 10℃ / min.

[0296] Step 2) Maintain at 200℃ for 5 minutes

[0297] Step 3) Cooling from 200℃ to -50℃ at a rate of -10℃ / min.

[0298] Step 4) Keep at -50℃ for 5 minutes

[0299] Step 5) Temperature increase from -50℃ to 200℃ at a rate of 10℃ / min

[0300] The measured glass transition temperatures are listed in Table 2 below.

[0301] Materials used Anion type 1st thermal decomposition temperature (℃) Glass transition temperature (℃) Experimental example 2-1 Antibacterial resin 1 Tetrafluoroborate (BF4 - )30098.7 Experimental Example 2-2 Antibacterial resin 2-trifluoromethanesulfonate (CF3SO3 - )35081.7 Experimental Example 2-3 Antibacterial resin 3-methanesulfonate (CH3SO3 - )35080.5 Experimental Example 2-4 Antibacterial resin 9-hexafluorophosphate (PF6) - )420103 Comparative Example 2-1 Antibacterial Resin ABr - 18663.2 Comparative Example 2-2 PMMA-248105 Comparative Example 2-3 Antibacterial Resin B Toluenesulfonate ( )35085.6 Comparative Example 2-4 Antibacterial resin C phosphate (Na2PO4) -)37088.2 Comparative Example 2-5 Antibacterial Resin D Acetate (CH3COO - )19047.2 Comparative Example 2-6 Antibacterial resin E-phenyl acetate ( )19656.3 Comparative Example 2-7 Antibacterial resin F salicylate ( )19545.8 Comparative Example 2-8 Antibacterial Resin G-Benzoate ( )19053.2 Comparative Example 2-9 Antibacterial resin H-benzyl phosphate ( )380101.8

[0302] According to Table 1 and Figure 2, Br as anion - In the case of Comparative Example 2-1 (antibacterial resin A) containing, it can be confirmed that the primary thermal decomposition temperature is low at less than 200°C, and the glass transition temperature is also less than 80°C. From this, it can be predicted that when a halogen group is included as an anion, heat resistance may be reduced, resulting in decomposition or color change.

[0303] In addition, according to Tables 1 and 2, in the case of antibacterial resins containing anions different from those of the present invention, it can be confirmed that the antibacterial activity is less than 99%, or the first thermal decomposition temperature is low as less than 200°C and the glass transition temperature is also less than 80°C. Specifically, when the anion is toluenesulfonate, phosphate, or benzyl phosphate, the antibacterial activity is less than 99% (Comparative Examples 1-3, 1-4, 1-9), and when the anion is acetate, benzyl acetate, salicylate, or benzoate, the first thermal decomposition temperature is low as less than 200°C and the glass transition temperature is also less than 80°C (Comparative Examples 2-5 to 2-8). Through this, it can be confirmed that the type of anion affects the antibacterial activity and heat resistance.

[0304] Meanwhile, according to Tables 1 and 2, it can be confirmed that the antibacterial resin of the present invention has an antibacterial activity exceeding 99.9%, a primary thermal decomposition temperature of 200°C or higher, and a glass transition temperature of 80°C or higher. From this, it can be predicted that the antibacterial resin of the present invention has excellent antibacterial activity, excellent processability, and improved heat resistance.

[0305] <Experimental Example 4> Visual evaluation after heat treatment

[0306] Antibacterial resin 1 and antibacterial resin A manufactured in the above manufacturing example were heat-treated at 180°C and 220°C, respectively, and changes were confirmed visually.

[0307] In Fig. 3, (a) is after heat treatment at 180°C, and (b) is after heat treatment at 220°C. '1' refers to antibacterial resin 1, and 'A' refers to antibacterial resin A.

[0308] According to Figure 3, Br as anion - In the case of antibacterial resin A containing BF4, it can be confirmed that the color changes after heat treatment at 220℃. On the other hand, BF4 as anion - In the case of antibacterial resin 1 including , it can be confirmed that there is no change even when heat-treated at 220°C. Through this, it can be confirmed that the antibacterial resin according to one embodiment of the present invention is more thermally stable.

[0309] In summary, through the above Table 1, Table 2, Figures 2 and 3, it can be confirmed that the antibacterial resin according to the present specification has excellent antibacterial properties while also exhibiting heat resistance and excellent processability.

Claims

1. A first unit derived from a monomer represented by the following chemical formula 1; and A second unit derived from alkyl acrylate or alkyl methacrylate; Antibacterial resin comprising a copolymer comprising: [Chemical Formula 1] In the above chemical formula 1, L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms, R4 to R6 are the same or different and are each independently hydrogen or a methyl group, X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

2. In claim 1, An antibacterial resin wherein two of the above R1 to R3 are the same or different, each independently a methyl group or an ethyl group, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

3. In claim 1, An antibacterial resin wherein the above L1 is a methylene group; an ethylene group; or a propylene group.

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

5. In claim 1, An antibacterial resin wherein the first unit is represented by the following chemical formula 1-A. [Chemical Formula 1-A] In the above chemical formula 1-A, L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms, R4 to R6 are the same or different and are each independently hydrogen or a methyl group, X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tetratrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate, n1 is an integer from 1 to 10,000, * is the attachment point within the copolymer.

6. In claim 1, The above chemical formula 1 is an antibacterial resin having one of the following structures: .

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

8. In claim 1, An antibacterial resin wherein the copolymer comprises a third unit represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, Two of R1 to R3 are the same or different, and each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the remaining one represents a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms, R11 is an alkyl group, R4 and R12 are the same or different and are each independently hydrogen or methyl group, X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methylsulfate, malate, tetratrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate, n1 and n2 are integers from 1 to 10,000, respectively, * is the attachment point within the copolymer.

9. In claim 1, An antibacterial resin wherein the molar ratio of the first unit and the second unit in the copolymer is 10:90 to 80:

20.

10. In claim 1, The above antibacterial resin is an antibacterial resin having a primary thermal decomposition temperature of 200°C or higher.

11. In claim 1, The above antibacterial resin is an antibacterial resin that exhibits antibacterial properties against at least one of gram-positive bacteria, gram-negative bacteria, and fungi.

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

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