Antibacterial resin and molded body containing the same

Abstract

The present specification relates to an antibacterial resin containing a copolymer including a first unit derived from a monomer represented by Chemical Formula 1 and a second unit derived from an alkyl acrylate or alkyl methacrylate, and a molded article containing the same.

Description

[Technical Field]

[0001] This application claims the benefit of the filing date 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 containing the same. [Background technology]

[0003] In recent years, with the diversification of lifestyles, improvements in living standards, and changes and improvements in awareness, there has been growing interest in improving hygiene and comfort in personal living environments. Accordingly, research into microorganisms that threaten these has been conducted, but the damage caused by microorganisms in everyday living environments is serious because there are many different types and they are widely distributed in nature.

[0004] In particular, microorganisms such as bacteria and mold can inhabit various environments such as diet, living environment, clothing, and industrial products, and in this case, bacteria can cause various inflammations and food poisoning, while mold can cause problems such as unpleasant odors and various skin diseases, respiratory diseases, allergies, etc. Furthermore, microorganisms that inhabit the surfaces of electronic products and household goods can cause a decrease in the performance of the products.

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

[0006] In this case, the level of antibacterial property required and the requirements for the material to impart antibacterial property will differ depending on the material of the product that requires antibacterial property and the state in which it will ultimately be used.

[0007] Conventionally developed antibacterial substances can be broadly divided into inorganic and organic antibacterial agents. Inorganic antibacterial agents contain metals such as silver or copper, and have the advantage of excellent thermal stability and maintaining antibacterial properties even under high temperature conditions, but have problems such as high cost and the possibility of discoloration due to the metal ions contained therein after processing. Organic antibacterial agents have the advantage of being cheaper than inorganic antibacterial agents and having excellent antibacterial effects even in small amounts, but have problems such as the possibility of leaching after application to products and poor antibacterial durability.

[0008] Thus, when introducing an antibacterial agent or the like that inhibits bacterial growth into a resin, it has not been very easy to select and introduce an antibacterial component that exhibits excellent bacterial growth inhibition properties, is harmless to the human body, is economical, and does not deteriorate the basic physical properties of the polymer resin.

[0009] For example, GPPS (general purpose polystyrene) is widely used because it is transparent and strong. To give GPPS antibacterial properties, inorganic antibacterial agents (Cu, Ag, etc.) are added, but the durability of the antibacterial agent decreases depending on the method of addition, and problems arise due to the toxicity of the substances used.

[0010] Therefore, there is a need to develop highly antibacterial materials that are suitable for use in a variety of products, but which do not release antibacterial substances and are harmless to the human body. Summary of the Invention [Problem to be solved by the invention]

[0011] The present specification provides an antibacterial resin and a molded article containing the same. [Means for solving the problem]

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

[0013] [ka]

[0014] 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 represent 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 each independently represents a hydrogen atom or a methyl group; X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0015] Other embodiments herein provide molded articles comprising or made from the aforementioned antimicrobial resins. [Effects of the Invention]

[0016] The antibacterial resin according to some embodiments of the present invention has excellent antibacterial properties.

[0017] The antimicrobial resin according to some embodiments of the present invention can exhibit antimicrobial properties in a short period of time.

[0018] The antibacterial resin according to some embodiments of the present specification exhibits little change in antibacterial activity depending on the amount of antibacterial material used, and therefore can exhibit antibacterial activity within a predicted range even if unintentional unevenness in concentration occurs when the resin is applied to a product. Therefore, the antibacterial activity can be controlled within a specific range, and excellent antibacterial activity can be imparted safely.

[0019] The antibacterial resins according to some embodiments of the present disclosure have low toxicity, which can solve safety issues.

[0020] The antibacterial resin according to some embodiments of the present disclosure can solve the safety issue of antibacterial substance leakage.

[0021] The antibacterial resin according to some embodiments of the present specification has excellent heat resistance and is characterized by being able to maintain antibacterial activity even after high-temperature processing. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 shows the results of NMR measurement of Monomer 1-1′ produced in Production Example 1. [Figure 2] FIG. 1 shows the results of TGA measurement for antibacterial resins 1, 2, and A produced in Production Examples 1 and 2 and Comparative Production Example 1, respectively. [Figure 3] (a) A diagram showing the appearance of antibacterial resins 1 and A produced in Production Example 1 and Comparative Production Example 1 after heat treatment at 180°C. (b) A diagram showing the appearance of antibacterial resins 1 and A produced in Production Example 1 and Comparative Production Example 1 after heat treatment at 220°C. DETAILED DESCRIPTION OF THE INVENTION

[0023] This specification will be explained in detail below.

[0024] One embodiment of the present specification provides an antibacterial resin comprising a 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 alkyl methacrylate.

[0025] [ka]

[0026] 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 represent 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 each independently represents a hydrogen atom or a methyl group; X - is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0027] There are over 5,000 different types of bacteria that have been identified. Specifically, bacteria are divided into aerobic, facultative, and anaerobic bacteria depending on the degree to which they require oxygen, and they are also divided into various shapes, such as ball-shaped, rod-shaped, and spiral-shaped. Therefore, it is not easy for a single antibacterial agent to have a physical and / or chemical mechanism that can damage or denature the cell membrane and / or cell wall of various bacteria.

[0028] Conventionally, to impart antibacterial properties to materials, antibacterial agents have been simply mixed with polymers, and inorganic or organic antibacterial agents have been used. The inorganic antibacterial agents are expensive, easily cause discoloration of the material, and can deteriorate the physical properties of the polymer during processing such as extrusion or injection. Furthermore, inorganic antibacterial agents have the disadvantage of low immediate antibacterial efficacy.

[0029] The organic antibacterial agents themselves have the drawback of poor stability to the human body, poor thermal stability, etc., resulting in low antibacterial durability. Furthermore, when polymerizable organic antibacterial agents are used in polymer polymerization, there are problems such as a decrease in polymerization efficiency or conversion rate, and the inherent advantages of the polymer are often lost.

[0030] On the other hand, the antibacterial resin of the present invention does not contain an inorganic antibacterial agent, thereby overcoming drawbacks such as discoloration and loss of transparency. Furthermore, since the antibacterial substance is not contained as a separate substance in the antibacterial resin itself, but is polymerized as a monomer and contained as a repeating unit forming the main chain of the polymer, there is no risk of leaching, and there are advantages in that it is stable in the human body and maintains its antibacterial durability. In other words, the antibacterial resin of the present invention exhibits the effects of having excellent antibacterial properties and antibacterial durability.

[0031] While polymers typically undergo high-temperature molding processes such as injection or extrusion during application, and many known antibacterial polymers suffer from the problem of their antibacterial properties being reduced or lost during these processes, the antibacterial resin of the present invention can maintain its antibacterial properties even after undergoing such high-temperature molding processes by incorporating a specific anion.

[0032] In this specification, when a part is said to "comprise" a certain component, this does not mean that it may further include other components, unless specifically stated to the contrary, but rather that it does not exclude other components.

[0033] As used herein, the term "monomer" refers to a unit compound that can be converted into a polymeric compound by a polymerization reaction, and the structure derived therefrom can become a repeating unit in a polymer or copolymer. Specifically, when the compound is polymerized and bound to a polymer, all or part of two or more substituents are removed from the compound structure, and a radical for binding to other units of the polymer is located in their place. In this case, the compound can be polymerized in any order and contained in the polymer in a bound state.

[0034] In this specification, the term "derived from" means that a bond between at least two adjacent elements in a compound is broken or a new bond is generated by the removal of hydrogen or a substituent, and a unit derived from the compound may refer to 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 constitute the polymer.

[0035] In this specification, the term "weight average molecular weight" refers to one of the average molecular weights in which the molecular weight of a polymeric 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 polymeric compound having a molecular weight distribution, by weight fraction.

[0036] In this specification, terms such as "first" and "second" are used to describe various components, and such terms are used only to distinguish one component from another.

[0037] As used herein, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise.

[0038] In this specification, among physical properties, physical properties that are affected by temperature are physical properties measured at room temperature unless otherwise specified.

[0039] As used herein, "room temperature" refers to a natural temperature that is neither heated nor cooled, and means, for example, any temperature within a range of about 10°C to 30°C, such as a temperature of about 15°C, about 18°C, about 20°C, about 23°C, or about 25°C. Unless otherwise specified in this specification, the unit of temperature is °C.

[0040] In this specification, when pressure affects the results of a physical property, the physical property is measured at normal pressure unless otherwise specified.

[0041] In this specification, "normal pressure" refers to the natural pressure that is neither pressurized nor reduced, and generally refers to about 1 atmosphere (about 700 to 800 mmHg).

[0042] In this specification, when humidity affects the results of physical properties, the physical properties are measured at room temperature and pressure at unadjusted humidity, unless otherwise specified.

[0043] In this specification, the "alkyl group" may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably is 1 to 60. In one embodiment of the specification, the number of carbon atoms in the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group.

[0044] In this specification, the term "alkylene group" refers to an alkyl group having two bonding positions, i.e., a divalent group. The same explanation as for the alkyl group above can be applied to these groups, except that they are both divalent groups.

[0045] In this specification, "*" refers to an attachment point within a copolymer. In this case, the attachment point may be a point where the same units are attached to each other, or a point where different units are attached to each other. For example, in the following chemical formula 1-A, * refers to both the portion where first units are attached to each other and the portion where the first unit is attached to a second unit.

[0046] In one embodiment of the present specification, the first unit is represented by the following chemical formula 1-A.

[0047] [ka]

[0048] 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 represent 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 each independently represents a hydrogen atom or a methyl group; X- is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate; n1 is an integer from 1 to 10,000, * denotes attachment points within the copolymer.

[0049] In one embodiment of the present specification, the quaternary ammonium cation contained in the first unit has a linker (L1) connected to the main chain and three terminal groups (R1 to R3).

[0050] In one embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0051] In one embodiment of the present specification, L1 is a linear alkylene group having 1 to 10 carbon atoms.

[0052] In one embodiment of the present specification, L1 is an alkylene group having 1 to 4 carbon atoms.

[0053] In one embodiment of the present specification, L1 is a methylene group; an ethylene group; or a propylene group.

[0054] In one embodiment of the present specification, L1 is an ethylene group.

[0055] In one embodiment of the present specification, two of R1 to R3 are the same or different and each independently represent an alkyl group having 1 to 4 carbon atoms, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

[0056] In one embodiment of the present specification, any one of R1 to R3 is a linear 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 the copolymer does not exhibit antibacterial properties, and if 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 producing the copolymer is not soluble in a solvent, making synthesis impossible.

[0057] In one embodiment of the present specification, two of R1 to R3 are the same or different and each independently represent a methyl group or an ethyl group, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

[0058] In one 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.

[0059] 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.

[0060] In one embodiment of the present specification, R2 and R3 are the same or different and each independently represent an alkyl group having 1 to 4 carbon atoms, and R1 is an alkyl group having 5 to 20 carbon atoms.

[0061] 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.

[0062] In one embodiment of the present specification, R4 to R6 are the same or different and each independently represents hydrogen or a methyl group.

[0063] In one embodiment of the present specification, R5 and R6 are each hydrogen.

[0064] In one embodiment of the present specification, R4 is hydrogen or a methyl group.

[0065] In one embodiment of the present specification, the chemical formula 1 is the following chemical formula 1-1 or 1-2.

[0066] [ka]

[0067] 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, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate.

[0068] In one embodiment of the present specification, the first unit is represented by the following chemical formula 1-A-1 or 1-A-2.

[0069] [ka]

[0070] In the above chemical formulas 1-A-1 and 1-A-2, 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, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate; n1 is an integer from 1 to 10,000, * denotes attachment points within the copolymer.

[0071] In one embodiment of the present specification, the trifluoromethanesulfonate is CF3SO3 - or

[0072] [ka]

[0073] It is expressed as:

[0074] In one embodiment of the present specification, the methanesulfonate is CH3SO3 - or

[0075] [ka]

[0076] It is expressed as:

[0077] In one embodiment of the present specification, the tetrafluoroborate is BF4 - or

[0078] [ka]

[0079] It is shown as follows.

[0080] In one embodiment of the present specification, the methylsulfate is CH3OSO3 - or

[0081] [ka]

[0082] It is shown as follows.

[0083] In one embodiment of the present specification, the maleate is

[0084] [ka]

[0085] It is shown as follows.

[0086] In one embodiment of the present specification, the tartrate is

[0087] [ka]

[0088] It is shown as follows.

[0089] In one embodiment of the present specification, the vanillate is

[0090] [ka]

[0091] It is shown as follows.

[0092] In one embodiment of the present specification, the syringe gate (syringate) is

[0093] [ka]

[0094] It is shown as follows.

[0095] In one embodiment of the present specification, the hexafluorophosphate is PF6 - or

[0096] [ka]

[0097] It is shown as follows.

[0098] In one embodiment of the present specification, the thiocyanate is SCN. - or

[0099] [ka]

[0100] It is displayed as:

[0101] In one embodiment of the present specification, the trifluoroacetate is CF3COO - or

[0102] [ka]

[0103] It is expressed as:

[0104] In one embodiment of the present specification, Chemical Formula 1 has any of the following structures:

[0105] [ka] [ka] [ka] [ka] [ka] [ka]

[0106] In one embodiment of the present specification, n1 is an integer of 3 to 10,000. Specifically, it is an integer of 10 to 8,000, an integer of 20 to 5,000, an integer of 20 to 1,000, or an integer of 20 to 500.

[0107] In one 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 bacteria (at least one of gram-positive bacteria, gram-negative bacteria, and Escherichia coli) by including the first unit. More specifically, the cell walls of bacteria and the like are generally negatively charged. A quaternary ammonium cation having an alkyl group with a specific carbon number attached from the first unit electrostatically adsorbs to the bacterial cell wall, and then interacts with the hydrophobic alkyl groups (R1 to R3) of the quaternary ammonium salt to coat and / or destroy the bacterial cell surface structure, thereby exhibiting antibacterial properties.

[0108] In one embodiment of the present specification, the second unit derived from the alkyl acrylate or alkyl methacrylate may have a structure in which the double bond of the acrylate group is broken to form a repeating unit.

[0109] In one embodiment of the present specification, the alkyl acrylate or alkyl methacrylate may be 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, lauryl methacrylate, cetyl methacrylate, or stearyl methacrylate.Preferably, it may be methyl methacrylate.

[0110] In one embodiment of the present specification, the second unit is represented by the following chemical formula 2.

[0111] [ka]

[0112] In the above Chemical Formula 2, R11 is an alkyl group; R12 is hydrogen or a methyl group; n2 is an integer between 1 and 10,000; * denotes attachment points within the copolymer.

[0113] In one embodiment of the present specification, n2 is an integer of 3 to 10,000. Specifically, it is an integer of 10 to 8,000, an integer of 20 to 5,000, an integer of 20 to 1,000, or an integer of 20 to 500.

[0114] In one embodiment of the present specification, the copolymer exhibits a glass transition temperature (Tg) by containing the second unit, which improves processability in processing steps such as extrusion and injection molding, and also improves miscibility with other polymers such as polyethylene and polypropylene.

[0115] In one embodiment of the present invention, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer. Specifically, the copolymer is a random copolymer.

[0116] In one embodiment of the present specification, the first unit and the second unit are contained in the main chain of the copolymer.

[0117] In one embodiment of the present specification, the first unit is contained in the main chain of the copolymer, and the second unit is contained in the side chain of the copolymer.

[0118] In one embodiment of the present specification, the first unit is contained in a side chain of the copolymer, and the second unit is contained in the main chain of the copolymer.

[0119] In one embodiment of the present specification, the copolymer includes a third unit represented by the following chemical formula 3:

[0120] [ka]

[0121] 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 represent 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 each independently represent a hydrogen atom or a methyl group; 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, * denotes attachment points within the copolymer.

[0122] In one embodiment of the present specification, a copolymer including a first unit derived from a monomer represented by Chemical Formula 1 and a second unit derived from an alkyl acrylate or alkyl methacrylate is represented by Chemical Formula 3.

[0123] In one embodiment of the present specification, R11 is an alkyl group having 1 to 10 carbon atoms.

[0124] In one embodiment of the present specification, R11 is a linear alkyl group having 1 to 10 carbon atoms.

[0125] In one embodiment of the present specification, R11 is a methyl group; an ethyl group; or a propyl group.

[0126] 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 leach out. Furthermore, the low molecular weight may cause problems with absorption by the human body. Furthermore, if the weight-average molecular weight of the copolymer exceeds 1,000,000 g / mol, problems may occur with processability.

[0127] 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.

[0128] According to one embodiment of the present specification, the antibacterial resin has a number average molecular weight (Mn) of 10,000 g / mol to 800,000 g / mol. More preferably, the antibacterial resin has a number average molecular weight (Mn; g / mol) of 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 may have a number average molecular weight (Mn; g / mol) of 150,000 or less, 100,000 or less, 90,000 or less, or 80,000 or less.

[0129] In one embodiment of the present specification, the weight-average molecular weight (Mw) of the copolymer can be measured using gel permeation chromatography (GPC) with polymethyl methacrylate (PMMA) as a calibration standard. More specifically, 200 mg of the copolymer can be diluted with 200 mL of N,N-dimethylformamide (DMF) to prepare a sample of approximately 1000 ppm. The weight-average molecular weight can then be measured using an Agilent 1200 series GPC instrument at a flow rate of 1 mL / min via an RI detector. The molecular weight of the sample can be calculated based on a calibration curve prepared using eight PMMA standards.

[0130] According to one embodiment of the present specification, the molecular weight distribution (Mw / Mn) of the copolymer may be in the 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.

[0131] In one embodiment of the present specification, the copolymer is an antibacterial copolymer that exhibits antibacterial activity.

[0132] 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.

[0133] In one embodiment of the present specification, the molar ratio of the first unit to the second unit in the copolymer is 10:90 to 80:20.

[0134] In one embodiment of the present specification, the first units are contained in an amount of 10 mol % to 80 mol % based on the total number of moles of the first units and the second units in the copolymer. If the content of the first units is less than 10 mol %, it is difficult to exert a sufficient antibacterial effect, and if the content of the first units is more than 80 mol %, there is a problem that processability is reduced and it is difficult to apply to practical use.

[0135] More specifically, the first units are contained in an amount of 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, based on the total mass of the first units and second units in the copolymer.

[0136] In one embodiment of the present specification, the antibacterial resin exhibits antibacterial activity against at least one of gram-positive bacteria, gram-negative bacteria, and molds.

[0137] In this specification, Gram-positive bacteria is a general term for bacteria that stain purple when stained with the Gram staining method. The cell walls of Gram-positive bacteria are composed of multiple layers of peptidoglycan, and after staining with a basic dye such as crystal violet, they retain their purple color even when treated with ethanol without decolorizing.

[0138] In one embodiment of the present specification, the Gram-positive bacterium is selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, the Gram-positive bacterium is any bacterium selected from the aforementioned examples, but is not limited thereto.

[0139] As used herein, Gram-negative bacteria are a collective term for bacteria that stain red when stained with the Gram staining method, and have a cell wall with a relatively small amount of peptidoglycan compared to Gram-positive bacteria, but instead have an outer membrane composed of lipid polysaccharides, lipid proteins, and / or other complex polymeric substances.

[0140] In one embodiment of the present specification, the Gram-negative bacterium is selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, the Gram-negative bacterium is any bacterium selected from the aforementioned examples, but is not limited thereto.

[0141] In one embodiment of the present specification, the fungus may be, but is not limited to, Candida albicans.

[0142] The antibacterial activity of the copolymer against bacteria can be evaluated according to JIS Z 2801 (Measurement of antibacterial activity on plastic and non-porous surfaces) or ASTM E2149 (Determining the antimicrobial activity of immobilized antimicrobial agents under dynamic contact conditions).

[0143] Specifically, the antibacterial property can be measured according to ASTM E2149 as follows.

[0144] 1 g of antibacterial resin was placed in a 250 mL Erlenmeyer flask, and then 2 × 10 5 50 mL of phosphate buffered saline (PBS) inoculated with E. coli ATCC 25922 strain (CFU / mL) is poured into the sample and cultured in a shaking incubator maintained at 35°C for 1 hour. The culture medium is diluted 10-fold and 100-fold and smeared on an agar medium plate. The smeared agar medium plate is cultured statically at 37°C for 24 to 48 hours. The antibacterial activity is calculated using the following formula 1 based on the CFU count of the diluted sample.

[0145]

number

[0146] In this specification, "exhibiting antibacterial properties" means that the antibacterial activity measured based on the above method, that is, the bacteriostatic reduction rate, is 99% or more.

[0147] Specifically, the antibacterial resin has a bacteriostatic reduction rate of bacteria measured according to ASTM E2149 of 99.1% or more, 99.5% or more, or 99.9% or more, and may be 100% or less.

[0148] In one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 99% or more against Gram-positive bacteria as measured according to ASTM E2149.

[0149] In one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 99% or more against gram-negative bacteria as measured according to ASTM E2149.

[0150] In one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 99% or more against mold as measured according to ASTM E2149.

[0151] As used herein, "CFU (Colony Forming Unit)" means colony forming unit, and CFU / mL means the number of CFU per mL.

[0152] In one embodiment of the present specification, the CFU value measured by the method 1 is introduced as the A value (microorganism concentration) in the mathematical formula 1.

[0153] Since contact with the above strains of gram-positive bacteria, gram-negative bacteria and fungi can cause various illnesses as well as secondary infections, it is preferable to use a single compound that exhibits antibacterial activity against all of the above gram-positive bacteria, gram-negative bacteria and fungi.

[0154] In one embodiment of the present specification, the antibacterial resin has a primary thermal decomposition temperature of 200°C or higher.

[0155] 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.

[0156] In this specification, the thermal decomposition temperature can be measured using a TGA (thermogravimetric analyzer).

[0157] Specifically, the thermal decomposition temperature can be determined by measuring the TGA in a nitrogen atmosphere with the following temperature ranges set as follows:

[0158] Step 1) Heat from 30°C to 110°C at a rate of 10°C / min Step 2) Hold at 110°C for 10 minutes Step 3) Cool from 110°C to 50°C at a rate of 10°C / min Step 4) Heat from 50°C to 600°C at a rate of 10°C / min

[0159] The first temperature decrease section of the four-stage mass loss curve in this section was defined as the primary pyrolysis temperature. Specifically, the pyrolysis temperature was defined as the extrapolated intersection point between the initial mass reference line and the tangent line of the maximum gradient point in the first mass loss section of the mass loss curve measured by TGA.

[0160] In one embodiment of the present specification, the upper limit of the primary pyrolysis temperature is not particularly limited, and may be, for example, 500°C or lower, 480°C or lower, or 450°C or lower.

[0161] According to one embodiment of the present specification, the antibacterial resin has a glass transition temperature (Tg) of 80°C or higher.

[0162] In this specification, the glass transition temperature can be measured using DSC (Differential Scanning Calorimetry).

[0163] Specifically, the glass transition temperature can be determined by measuring DSC under the following temperature ranges:

[0164] Step 1) Heat from 30°C to 200°C at a rate of 10°C / min Step 2) Hold at 200°C for 5 minutes Step 3) Cool from 200°C to -50°C at a rate of -10°C / min Step 4) Hold at -50°C for 5 minutes Step 5) Heat from -50°C to 200°C at a rate of 10°C / min

[0165] 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 lower, 140°C or lower, or 130°C or lower.

[0166] The antibacterial resin has the above-mentioned thermal decomposition temperature and glass transition temperature, which has the effect of improving processability in processes such as extrusion and injection.

[0167] In one embodiment of the present specification, the antibacterial resin may be prepared by copolymerizing a monomer represented by Chemical Formula 1 (hereinafter referred to as a first monomer) and an alkyl acrylate or alkyl methacrylate (hereinafter referred to as a second monomer).

[0168] In one embodiment of the present specification, the antibacterial resin may be polymerized in the presence of a polymerization initiator. Such a polymerization initiator can be appropriately selected depending on the polymerization method. For example, a thermal polymerization initiator can be used when a thermal polymerization method is used, a photopolymerization initiator can be used when a photopolymerization method is used, and both a thermal polymerization initiator and a photopolymerization initiator can be used when a hybrid polymerization method (a method using both heat and light) is used. However, even in the photopolymerization method, a certain amount of heat is generated by light irradiation such as ultraviolet irradiation, and a certain amount of heat is also generated as the polymerization reaction, which is an exothermic reaction, progresses. Therefore, a thermal polymerization initiator can also be used in addition.

[0169] In one embodiment of the present specification, the photopolymerization initiator can be any compound capable of forming radicals upon exposure to light such as ultraviolet light, and its structure is not limited. For example, the photopolymerization initiator may be one or more selected from the group consisting of benzoin ether, dialkyl acetophenone, hydroxyl alkyl ketone, phenyl glyoxylate, benzyl dimethyl ketal, acyl phosphine, and α-aminoketone. Specific examples of acyl phosphines include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate. A wider variety of photoinitiators are clearly described in "UV Coatings: Basics, Recent Developments and New Applications" by Reinhold Schwalm (Elsevier 2007), p. 115, and are not limited to the examples mentioned above.

[0170] 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 total of the first and second monomers. If the content of the photopolymerization initiator is less than 0.001 part by weight, the polymerization rate may be slow. If the content of the photopolymerization initiator is more than 1 part by weight, the molecular weight of the polymer may be small and the physical properties may be non-uniform. More specifically, the photopolymerization 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 0.5 parts by weight or less, or 0.3 parts by weight or less based on 100 parts by weight of the total of the monomers.

[0171] In one embodiment of the present specification, the thermal polymerization initiator may be one or more selected from the group consisting of persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid. Specific examples of persulfate initiators include sodium persulfate (NaSO), potassium persulfate (KSO), and ammonium persulfate ((NHSO). Examples of azo initiators include azobisisobutyronitrile, 2,2-azobis(2-amidinopropane) dihydrochloride, and 2,2-azobis(N,N-dimethylene)isobutyramidine dihydrochloride. dihydrochloride, 2-(carbamoylazo)isobutylonitrile, 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, and 4,4-azobis-(4-cyanovaleric acid). A wider variety of thermal polymerization initiators are described in Odian's book "Principle of Polymerization" (Wiley, 1981), p. 203, and are not limited to the examples mentioned above.

[0172] 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 total of the first and second monomers. If the content of the thermal polymerization initiator is less than 0.001 part by weight, additional thermal polymerization hardly occurs, and the effect of adding the thermal polymerization initiator is negligible. If the content of the thermal polymerization initiator is more than 3 parts by weight, the molecular weight of the polymer may be small and the physical properties may be inconsistent. 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, but not more than 3 parts by weight, 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.

[0173] According to one embodiment of the present specification, the end group of the copolymer may have a structure derived from the first unit, the second unit, and the initiator used in producing the copolymer. Specifically, the first unit and the second unit may have one bonding position or a structure corresponding to half of the initiator used.

[0174] For example, the end group of the copolymer has one of the following structures:

[0175] [ka]

[0176] In the above structure, L1, R1 to R6, R11, R12 and X - corresponds to the definition in Chemical Formulas 1 and 2, and * is the moiety attached to the copolymer.

[0177] The first monomer, the second monomer and the polymerization initiator may be prepared in the form of a solution dissolved in a solvent.

[0178] In one embodiment of the present specification, the solvent may be any solvent that can dissolve the above-mentioned components, and may be used without any particular constitutional limitations. For example, one or more solvents selected from the group consisting of 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.

[0179] In one embodiment of the present specification, the copolymerization of the first monomer and the second monomer can be carried out by a commonly known method without any particular structural limitations. 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. After the reaction is completed, the produced polymer can be extracted and dried to finally obtain the desired copolymer.

[0180] One embodiment of the present specification provides a molded article comprising or made from the antibacterial resin.

[0181] In this specification, a molded article refers to a material containing the antibacterial resin, a material made from the antibacterial resin, or a product containing the antibacterial resin.

[0182] Specifically, the molded article is one or more selected from freshness-preserving materials, fabric products, agricultural films, automobile parts, various office supplies, various packaging materials, and medical supplies.

[0183] More specifically, the molded article may be packaging materials such as food packaging materials, vegetable packaging materials, grain packaging materials, fruit packaging materials, meat packaging materials, seafood packaging materials, and processed food packaging materials, as well as freshness-preserving materials such as containers for vegetables, grains, fruits, meat, seafood, 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 tape, adhesive tape, masking tape, and masking film; 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 machine component packaging materials; and medical supplies such as medical films, medical tapes, and cell culture packs.

[0184] The molded article may be a blow molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, a foam molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric, but is not limited to the above examples. [Example]

[0185] Hereinafter, in order to specifically explain the present specification, a detailed description will be given using examples. However, the examples according to the present specification can be modified into various other forms, and the scope of the present specification should not be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to those skilled in the art.

[0186] Manufacturing Example 1: Manufacturing of antibacterial resin 1 (1) Preparation of Monomer 1

[0187] [ka]

[0188] A 2L round-bottom flask was charged with 70mL of acetonitrile, 2mol of 2-(dimethylamino)ethyl methacrylate, 2mol of 1-bromododecane, and 0.32g of p-methoxyphenol. The mixture was stirred at 45°C using a magnetic bar for 16 hours to convert the amino group to an alkyl group and produce a quaternary ammonium salt. The reaction solution was then extracted with 10L of methyl tert-butyl ether (MTBE). The reaction mixture was then filtered using a vacuum filter, and the remaining MTBE was completely removed to produce antibacterial monomer 1-1'.

[0189] FIG. 1 shows the results of NMR measurement of Monomer 1-1′.

[0190] (2) Manufacture of antibacterial resin 1 A 500 mL round-bottom flask was charged with 188 mL of ethanol, 50 g of methyl methacrylate (0.5 M), 60.9 g of monomer 1-1', and 2 mol% azobisisobutyronitrile. The mixture was stirred at 65°C for 16 hours using a stir bar to carry out the polymerization reaction. After the reaction was completed at room temperature, the solution was diluted with 50 mL of acetonitrile and added to 2 L of a 50 wt% aqueous solution of sodium tetrafluoroborate to cause precipitation. The solid polymer was then filtered using a vacuum filter and vacuum dried to completely remove any remaining solvent, producing antibacterial resin 1.

[0191] Production example 2. Antibacterial resin 2 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium trifluoromethanesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0192] Production example 3. Antibacterial resin 3 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium methanesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0193] Production example 4. Antibacterial resin 4 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium methyl sulfate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0194] Production example 5. Antibacterial resin 5 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium maleate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0195] Production example 6. Antibacterial resin 6 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium tartrate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0196] Production Example 7. Antibacterial resin 7 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium vanillate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0197] Production example 8. Antibacterial resin 8 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium syringate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0198] Production example 9. Antibacterial resin 9 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium hexafluorophosphate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0199] Production example 10. An antibacterial resin 10 was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium thiocyanate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0200] Production Example 11. An antibacterial resin 11 was produced in the same manner as in Production Example 1, except that in Production Example 1 (2), an aqueous solution of sodium trifluoroacetate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0201] Comparative manufacturing example 1. An antibacterial resin A was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, water was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0202] Comparative manufacturing example 2. A 500 mL round-bottom flask was charged with 188 mL of ethanol, 50 g of methyl methacrylate (0.5 M), and 2 mol% azobisisobutyronitrile. The mixture was stirred at 65°C with a stir bar for 16 hours to carry out the polymerization reaction. After the reaction was completed at room temperature, the solution was diluted with 50 mL of acetonitrile and added to 2 L of water to precipitate. The solid polymer was then filtered using a vacuum filter and vacuum dried to completely remove any remaining solvent, producing a homopolymer PMMA.

[0203] Comparative manufacturing example 3. Antibacterial resin B was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium toluenesulfonate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0204] Comparative manufacturing example 4. Antibacterial resin C was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium phosphate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0205] Comparative Manufacturing Example 5. Antibacterial resin D was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium acetate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0206] Comparative Manufacturing Example 6. An antibacterial resin E was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous solution of sodium phenylacetate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0207] Comparative Manufacturing Example 7. Antibacterial resin F was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium salicylate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0208] Comparative Manufacturing Example 8. Antibacterial resin G was produced in the same manner as in Production Example 1, except that in (2) of Production Example 1, an aqueous sodium benzoate solution was used instead of the aqueous sodium tetrafluoroborate solution during precipitation.

[0209] Comparative Manufacturing Example 9. Antibacterial resin H was produced in the same manner as in Production Example 1, except that in Production Example 1 (2), an aqueous solution of sodium benzyl phosphate was used instead of the aqueous solution of sodium tetrafluoroborate during precipitation.

[0210] The anion types of the antibacterial resins produced in Production Examples 1 to 11 and Comparative Production Examples 1 to 9 are shown in Table 1 below.

[0211] <Experimental Example 1> Antibacterial activity measurement The antibacterial activity of each of the antibacterial resins 1 to 11, antibacterial resins A to H, and PMMA produced in Production Examples 1 to 11 and Comparative Production Examples 1 to 9 was measured in accordance with ASTM E 2179. The specific measurement method is as follows.

[0212] 1 g of antibacterial resin was placed in a 250 mL Erlenmeyer flask and diluted to 2 × 10 5 50 mL of phosphate-buffered saline (PBS) inoculated with E. coli ATCC 25922 strain (CFU / mL) was poured into the sample and cultured for 1 hour in a shaking incubator maintained at 35°C. The culture medium was diluted 10-fold and 100-fold and smeared on an agar medium plate. The smeared agar medium plate was cultured statically at 37°C for 24 to 48 hours. The antibacterial activity was calculated using the following formula 1 based on the CFU count of the diluted sample.

[0213]

number

[0214] The measured antibacterial activity is shown in Table 1 below.

[0215] [Table 1A] [Table 1B]

[0216] According to Table 1, it can be seen that the antibacterial activity of Comparative Example 1-2, which is a methyl methacrylate homopolymer, is 0.

[0217] 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 activity is excellent, exceeding 99.9%.

[0218] <Experimental Example 2> Pyrolysis temperature measurement The thermal decomposition temperatures 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 a TGA (Thermogravimetric Analyzer, TA Instrument, DISCOVERY TGA 550 W / MFC & AUTO).

[0219] The TGA was measured in a nitrogen atmosphere, and the temperature conditions for each section were set as follows:

[0220] Step 1) Heat from 30°C to 110°C at a rate of 10°C / min Step 2) Hold at 110°C for 10 minutes Step 3) Cool from 110°C to 50°C at a rate of 10°C / min Step 4) Heat from 50°C to 600°C at a rate of 10°C / min

[0221] The first temperature decrease section of the four-stage mass loss curve in this section was defined as the primary pyrolysis temperature. Specifically, the pyrolysis temperature was defined as the extrapolated intersection point between the initial mass reference line and the tangent line of the maximum gradient point in the first mass loss section of the mass loss curve measured by TGA.

[0222] The measured primary pyrolysis temperatures are shown in Table 2 below.

[0223] Figure 2 shows the TGA measurement results for antibacterial resins 1, 2 and A.

[0224] <Experimental Example 3> Glass transition temperature measurement The glass transition temperatures 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 DSC (Differential Scanning Calorimetry, TA Instrument, DISCOVER TGA 550W / MFC&AUTO).

[0225] During the DSC measurement, the temperature conditions were set as follows:

[0226] Step 1) Heat from 30°C to 200°C at a rate of 10°C / min Step 2) Hold at 200°C for 5 minutes Step 3) Cool from 200°C to -50°C at a rate of -10°C / min Step 4) Hold at -50°C for 5 minutes Step 5) Heat from -50°C to 200°C at a rate of 10°C / min

[0227] The measured glass transition temperatures are listed in Table 2 below.

[0228] [Table 2]

[0229] According to Table 2 and Figure 2, Br is used as the anion. - In the case of Comparative Example 2-1 (antibacterial resin A) containing a halogen group, the primary thermal decomposition temperature was low at less than 200° C., and the glass transition temperature was also confirmed to be less than 80° C. From this, it can be predicted that when a halogen group is contained as an anion, the heat resistance may decrease, leading to decomposition or color change.

[0230] Furthermore, Tables 1 and 2 confirm that antibacterial resins containing anions different from those of the present invention have antibacterial activity of less than 99%, a low primary thermal decomposition temperature of less than 200°C, and a glass transition temperature of 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, and 1-9), and when the anion is acetate, benzyl acetate, salicylate, or benzoate, the low primary thermal decomposition temperature is less than 200°C and a glass transition temperature is less than 80°C (Comparative Examples 2-5 to 2-8). This confirms that the type of anion affects antibacterial activity and heat resistance.

[0231] On the other hand, Tables 1 and 2 confirm that the antibacterial resin of the present invention has an antibacterial activity of 99.9% or more, a primary thermal decomposition temperature of 200°C or more, and a glass transition temperature of 80°C or more. From these results, it can be predicted that the antibacterial resin of the present invention has excellent antibacterial activity, excellent processability, and improved heat resistance.

[0232] <Experimental Example 4> Visual evaluation after heat treatment Antibacterial resin 1 and antibacterial resin A produced in the above Production Examples were heat treated at 180°C and 220°C, respectively, and changes were visually confirmed.

[0233] 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.

[0234] According to Figure 3, Br is the anion. - In the case of antibacterial resin A containing BF4 as an anion, a color change can be confirmed after heat treatment at 220°C. - It can be seen that the antibacterial resin 1 containing the compound (I) remains unchanged even after heat treatment at 220° C. This confirms that the antibacterial resin according to one embodiment of the present invention is more thermally stable.

[0235] That is, it can be seen from Tables 1 and 2, and Figures 2 and 3 that the antibacterial resin according to the present specification has excellent antibacterial activity, heat resistance, and processability.

Claims

1. A first unit derived from a monomer represented by the following chemical formula 1; and a second unit derived from an alkyl acrylate or alkyl methacrylate; an antimicrobial resin comprising a copolymer comprising: 【Chemistry 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 represent 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 each independently represents a hydrogen atom or a methyl group; 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 and each independently represent a methyl group or an ethyl group, and the remaining one is an alkyl group having 5 to 20 carbon atoms.

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

4. The antibacterial resin according to claim 1, wherein the chemical formula 1 is the following chemical formula 1-1 or 1-2: 【Chemistry 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 － teeth 、 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: 【Transformation 3】 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 represent 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 each independently represents a hydrogen atom or a methyl group; X － is trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, methyl sulfate, maleate, tartrate, vanillate, syringate, hexafluorophosphate, thiocyanate, or trifluoroacetate; n1 is an integer from 1 to 10,000, * denotes attachment points within the copolymer.

6. 2. The antibacterial resin of claim 1, wherein the chemical formula 1 is any one of the following structures: 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】

7. The antibacterial resin according to claim 1 , wherein the second unit is represented by the following chemical formula 2: 【Chemistry 10】 In the above Chemical Formula 2, R11 is an alkyl group, R12 is hydrogen or a methyl group; n2 is an integer from 1 to 10,000, * denotes attachment points within the copolymer.

8. The antibacterial resin according to claim 1 , wherein the copolymer comprises a third unit represented by the following chemical formula 3: 【Chemistry 11】 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 represent 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, R and R are the same or different and each independently represent a hydrogen atom or a methyl group; 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, * denotes attachment points within 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 10:90 to 80:

20.

10. The antibacterial resin according to claim 1 , wherein the antibacterial resin has a primary thermal decomposition temperature of 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 mold.

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

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