Antibacterial resin and molded body containing the same

Abstract

The present specification relates to an antibacterial resin and a molded article containing the same, the antibacterial resin including a copolymer containing a first unit derived from styrene and a second unit derived from a monomer represented by Chemical Formula 1, and the weight average molecular weight of the copolymer is 10,000 g / mol or more and 1,000,000 g / mol or less.

Description

[Technical field]

[0001] The present specification relates to an antibacterial resin and a molded article containing the same.

[0002] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0131728 filed with the Korean Intellectual Property Office on October 13, 2022, and Korean Patent Application No. 10-2023-0136278 filed with the Korean Intellectual Property Office on October 12, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

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

[0004] The required level of antibacterial properties and the requirements for materials to provide antibacterial properties vary depending on the material of the product for which antibacterial properties are required and the final state of use. For example, the nature of the material to provide antibacterial properties and the level of antibacterial properties vary depending on the amount of antibacterial material applied to the product and the materials used together.

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

[0006] For example, GPPS (general purpose polystyrene) is widely used because it is transparent and strong. In order to give GPPS antibacterial properties, inorganic antibacterial agents (Cu, Ag, etc.) are added, but in this case, the durability decreases depending on the addition method, and problems occur due to toxicity depending on the substance used.

[0007] Therefore, there is a need to develop highly antibacterial materials suitable for use in a variety of products, which do not release antibacterial substances and are harmless to the human body. [Prior art documents] [Patent documents]

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

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

[0010] One embodiment of the present invention is a copolymer comprising a first unit derived from styrene; and The copolymer includes a second unit derived from a monomer represented by the following chemical formula 1: The weight average molecular weight of the copolymer is from 10,000 g / mol to 1,000,000 g / mol.

[0011] [ka]

[0012] In the above Chemical Formula 1, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; X - is a monovalent anion.

[0013] Another embodiment herein provides a molded article comprising or made from the antimicrobial resin described above. Effect of the Invention

[0014] The antibacterial resin according to some embodiments of the present specification has hydrophilic and hydrophobic properties and has excellent antibacterial properties.

[0015] The antibacterial resin according to some embodiments of the present disclosure can solve the safety issue of antibacterial substance leakage.

[0016] The antimicrobial resins according to some embodiments herein can exhibit antimicrobial properties within a short period of time.

[0017] 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, even if the concentration of the antibacterial resin is unintentionally varied when applied to a product, the antibacterial activity can be controlled within a specific range, and antibacterial activity with excellent safety can be imparted.

[0018] The antimicrobial resin according to some embodiments of the present disclosure has low toxicity, which can solve the safety issue.

[0019] The antibacterial resin according to some embodiments of the present specification has excellent heat resistance and is characterized in that it can maintain its antibacterial activity even after high-temperature processing. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 shows the results of H NMR measurement of compound 14. [Diagram 2] FIG. 1 shows the results of F NMR measurement of compound 14. [Diagram 3] FIG. 1 shows the results of H NMR measurement of compound 15. [Figure 4] FIG. 1 shows the results of F NMR measurement of compound 15. [Diagram 5] FIG. 2 shows TGA results for antimicrobial resins according to some embodiments herein. [Figure 6] FIG. 2 shows the results of TGA measurements of a resin according to a comparative embodiment of the present specification. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] This specification will be explained in detail below.

[0022] One embodiment of the present disclosure includes a copolymer comprising a first unit derived from styrene; and a second unit derived from a monomer represented by formula 1: The weight average molecular weight of the copolymer is from 10,000 g / mol to 1,000,000 g / mol.

[0023] [ka]

[0024] In the above Chemical Formula 1, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; X - is a monovalent anion.

[0025] In the past, in order to impart antibacterial power to a material, an antibacterial agent was simply mixed with a polymer, and inorganic or organic antibacterial agents were used in this case. The inorganic antibacterial agents are expensive, tend to cause discoloration of the material, and can reduce the physical properties of the polymer during processing such as extrusion and injection. In addition, inorganic antibacterial agents have the disadvantage of low immediate antibacterial effect. The organic antibacterial agents themselves have the disadvantage of poor stability to the human body and poor thermal stability, resulting in poor antibacterial durability.

[0026] Meanwhile, the antibacterial resin according to the present specification does not contain an inorganic antibacterial agent, and thus overcomes drawbacks such as discoloration and reduced transparency, and has the advantage of excellent stability in the human body and maintaining antibacterial durability because the antibacterial substance is polymerized as a monomer rather than being contained as a separate substance. When an organic antibacterial agent is applied to the polymerization of a polymer, the polymerization efficiency or conversion rate is often reduced, and the inherent advantages of the polymer are often lost, but the present invention can also eliminate such drawbacks. Due to the above advantages, the antibacterial resin according to the present specification can exhibit excellent antibacterial durability. That is, the antibacterial resin according to the present specification has excellent antibacterial properties and antibacterial durability, while at the same time improving stability against antibacterial agent leakage.

[0027] In addition, if the weight average molecular weight of the antibacterial resin is less than 10,000 g / mol, it exists in the form of a monomer rather than a polymer and may easily dissolve, and the low molecular weight may cause problems with absorption by the human body. If the weight average molecular weight of the antibacterial resin is more than 1,000,000 g / mol, the molecular weight becomes too large, resulting in high viscosity, making it difficult to apply, and reducing processability, which may lead to a decrease in antibacterial activity.

[0028] More preferably, the weight average molecular weight (Mw:g / mol) of the antibacterial resin is 15,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, or 40,000 g / mol or more, and 1,000,000 g / mol or less, 500,000 g / mol or less, 400,000 g / mol or less, 300,000 g / mol or less, 200,000 g / mol or less, or 150,000 g / mol or less.

[0029] 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 of 15,000 g / mol or more, 20,000 g / mol or more, 25,000 g / mol or more, 30,000 g / mol or more, 35,000 g / mol or more, or 40,000 g / mol or more, and 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less.

[0030] According to one embodiment of the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the antibacterial resin can be measured by gel permeation chromatography (GPC).

[0031] According to one embodiment of the present specification, the GPC is measured as follows.

[0032] The material to be analyzed is diluted in DMF (dimethylformamide) to a concentration of 5 mg / mL, dissolved at 50°C for 6 hours, and then filtered through a PVDF filter (pore size: 0.45 μm) to prepare a sample solution. The analysis program used was Agilent Technologies' ChemStation, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by comparing the elution time of the sample with a calibration curve. The GPC measurement conditions are as follows.

[0033] -Equipment: Agilent Technologies 1200 series -Stationary phase: 3x Agilent PLgel MIXED-C, 7.5 x 300mm, 5μm -Mobile phase A: 0.05M LiBr in DMF -Flow rate: 1.0mL / min -Stationary phase temperature: 40℃ -Injection volume: 100μL (0.45μm filter) -Standard sample: PS

[0034] According to one embodiment of the present specification, the antibacterial resin may have a molecular weight distribution (Mw / Mn) 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.

[0035] The weight average molecular weight, number average molecular weight and molecular weight distribution of the antibacterial resin can be determined by a copolymer including the first unit derived from the styrene; and the second unit derived from the monomer represented by Chemical Formula 1.

[0036] In this specification, when a part is said to "comprise" a certain component, this means that it may further include other components, rather than excluding other components, unless specifically stated to the contrary.

[0037] In the present specification, 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, this means that when the compound is polymerized and bound to a polymer, all or a part of two or more substituents are removed from the structure of the compound, and a radical for binding to other units of the polymer is located at the position. In this case, the compound may be included in a state of being bound to the polymer by polymerization in any order.

[0038] In the present 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 detachment of hydrogen or a substituent, and the unit derived from the compound may mean a unit forming at least one of the main chain and the side chain of a polymer. The unit may be included in the main chain of the polymer to constitute the polymer.

[0039] 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, by weight fraction, the molecular weights of component molecular species of a polymeric compound having a molecular weight distribution.

[0040] In this specification, among physical properties, those that are affected by temperature are physical properties measured at room temperature, unless otherwise specified.

[0041] In this specification, "room temperature" refers to a natural temperature that is neither heated nor cooled, and means, for example, any temperature within a range of about 10° C. to 30° C., such as 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.

[0042] In this specification, when pressure affects the results of a physical property, the physical property is measured at normal pressure, unless otherwise specified.

[0043] In this specification, "normal pressure" refers to the natural pressure that is neither increased nor decreased, and generally refers to approximately 1 atmosphere (approximately 700 to 800 mmHg).

[0044] In this specification, when humidity affects the results of a physical property, the physical property is measured at room temperature and pressure at unadjusted humidity, unless otherwise specified.

[0045] In the present specification, the "alkyl group" may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to 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, and a tridecyl group.

[0046] In this specification, the term "alkylene group" refers to an alkyl group having two bonding positions, i.e., a divalent group. The above description of the alkyl group can be applied to these groups, except that they are both divalent groups.

[0047] In the present specification, the "alkoxy group" may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferable that the number of carbon atoms is 1 to 30. Specifically, the alkoxy group may be, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, and the like.

[0048] In this specification, "*" means a bonding point in the copolymer. In this case, the bonding point may be a bonding point between the same units or a bonding point between different units. As an example, in the following chemical formula 2-1, * means both the bonding portion between the first units and the bonding portion between the first unit and the second unit.

[0049] In the present specification, the "antibacterial resin" may mean a copolymer itself containing the first unit derived from the styrene and the second unit derived from the monomer represented by Chemical Formula 1, or may mean a copolymer further containing an additional component.

[0050] According to one embodiment of the present specification, the first unit derived from styrene may have a structure in which a double bond of styrene is broken to form a repeating unit.

[0051] According to one embodiment of the present specification, the first unit is represented by the following chemical formula 2-1.

[0052] [ka]

[0053] In the above Chemical Formula 2-1, n1 is an integer from 1 to 10,000; * denotes a point of attachment within the copolymer.

[0054] According to one embodiment of the present specification, n1 is an integer from 3 to 10,000, an integer from 10 to 8,000, or an integer from 20 to 5,000.

[0055] According to one embodiment of the present specification, the copolymer contains 1 to 10,000 of the first unit, specifically, 3 to 10,000, 10 to 8,000, or 20 to 5,000.

[0056] According to one embodiment of the present specification, the monomer represented by Chemical Formula 1 is an antibacterial substance.

[0057] According to one embodiment of the present specification, the second unit is represented by the following chemical formula 1-1.

[0058] [ka]

[0059] In the above Chemical Formula 1-1, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; X - is a monovalent anion, n2 is an integer from 1 to 10,000; * denotes a point of attachment within the copolymer.

[0060] According to one embodiment of the present specification, n2 is an integer of 3 to 10,000, an integer of 10 to 8,000, or an integer of 20 to 5,000.

[0061] According to one embodiment of the present specification, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0062] According to one embodiment of the present specification, R4 is hydrogen or a methyl group.

[0063] According to one embodiment of the present specification, the L1 is an alkylene group having 1 to 10 carbon atoms.

[0064] According to one embodiment of the present specification, L1 is an alkylene group having 1 to 5 carbon atoms.

[0065] According to one embodiment of the present specification, L1 is a methylene group; an ethylene group; a propylene group; or a butylene group.

[0066] According to one embodiment of the present specification, R1 to R3 are the same or different and each independently represents an alkyl group having 1 to 30 carbon atoms.

[0067] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0068] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms.

[0069] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.

[0070] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0071] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms.

[0072] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.

[0073] According to one embodiment of the present specification, two or more of R1 to R3 are alkyl groups having 6 to 30 carbon atoms, or the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number among R1 to R3 is 4 or more.

[0074] Specifically, three of R1 to R3 are alkyl groups having 6 to 30 carbon atoms; two of R1 to R3 are alkyl groups having 6 to 30 carbon atoms and the remaining one is an alkyl group having 1 to 30 carbon atoms; or the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number among R1 to R3 is 4 or more. In this case, excellent antibacterial effect is exhibited.

[0075] According to one embodiment of the present specification, the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number being 4 or more means that the asymmetry is large, and the difference in carbon number may be 4 to 30, 5 to 30, or 5 to 10.

[0076] According to one embodiment of the present specification, the monomer represented by the above Chemical Formula 1 has any one of the following structures:

[0077] [ka]

[0078] In the above structure, X - is a monovalent anionic group.

[0079] According to one embodiment of the present specification, the second unit derived from the monomer represented by Chemical Formula 1 has any one of the following structures:

[0080] [ka] [ka]

[0081] In the above structure, X - is a monovalent anionic group, and * is a point of attachment within the copolymer.

[0082] According to one embodiment of the present specification, the copolymer contains 1 to 10,000 of the second units, specifically, 3 to 10,000, 10 to 8,000, or 20 to 5,000.

[0083] According to one embodiment of the present specification, the X - is one selected from Group 1 below.

[0084] [Group 1] Br - , Cl- , I - , F - , BF4 - , O.H. - , CF3COO - , CF3SO3 - , NO3 - , S.H. - ,

[0085] [ka]

[0086] In the group 1, R11 is hydrogen; deuterium; a hydroxy group; a substituted or unsubstituted alkoxy group; or a substituted or unsubstituted alkyl group; r11 is an integer of 1 to 5, and when r11 is 2 or more, the two or more R11's are the same or different.

[0087] According to one embodiment of the present specification, R11 is hydrogen; a hydroxyl group; or an alkoxy group.

[0088] According to one embodiment of the present specification, r11 is an integer of 1 to 3.

[0089] According to one embodiment of the present specification, the X - is one selected from Group 2 below.

[0090] [Group 2] Br - , Cl - , I - , F - , BF4 - , O.H. - , CF3COO - , CF3SO3 - , NO3 - , S.H. - ,

[0091] [ka]

[0092] According to one embodiment of the present specification, the molar ratio of the first unit to the second unit is 100:0.5 to 100:50. Specifically, it is 100:0.5 to 100:40, 100:0.5 to 100:30, or 100:0.5 to 100:10. When the molar ratio of the first unit to the second unit satisfies the above-mentioned range, the resin exhibits antibacterial properties, heat resistance, and mechanical properties (tensile strength, impact strength, bending properties, etc.) that are equal to or greater than those of a resin containing only the first unit and a resin containing only the second unit.

[0093] The antibacterial properties of the antibacterial resin are derived from the anionic and cationic functional groups contained in the second unit contained in the antibacterial resin. Generally, cell walls of bacteria and the like are often negatively charged, and the cationic functional groups can have a destructive effect on the cell walls.

[0094] According to 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.

[0095] According to one embodiment of the present specification, the first unit and the second unit are included in the main chain of the copolymer.

[0096] According to 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.

[0097] According to one embodiment of the present specification, the antibacterial resin includes a third unit represented by the following chemical formula 3.

[0098] [ka]

[0099] In the above Chemical Formula 3, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; X - is a monovalent anion, m1 and m2 are each an integer of 1 to 10,000; * denotes a point of attachment within the copolymer.

[0100] According to one embodiment of the present specification, m1 and m2 are each an integer of 3 to 10,000, an integer of 10 to 8,000, or an integer of 20 to 5,000.

[0101] According to one embodiment of the present specification, the copolymer including the first unit derived from styrene and the second unit derived from the monomer represented by Chemical Formula 1 is represented by Chemical Formula 3.

[0102] According to one embodiment of the present specification, the end group of the copolymer has any one of the following structures:

[0103] [ka]

[0104] In the above structure, L1, R1 to R4 and X - is the same as defined in Chemical Formula 1,

[0105] [ka]

[0106] is the moiety that binds to the copolymer.

[0107] According to one embodiment of the present specification, the antibacterial resin has antibacterial properties.

[0108] In this specification, having antibacterial properties means that the antibacterial activity measured based on the following method 1, that is, the bacteriostatic reduction rate, is 90% or more.

[0109] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 90% or more against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by the following method 1.

[0110] [Method 1] 0.2 g of the antibacterial resin was placed in a 50 mL conical tube, and then 2 × 10 5 10 mL of phosphate buffered saline inoculated with CFU / mL of bacterial strain is poured and cultured for 1 hour in a shaking incubator maintained at 35°C. The culture liquid is diluted 1x, 10x, and 100x, respectively, 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 according to the following formula 1 based on the number of CFU (Colony Forming Unit) of each of the samples diluted 1x, 10x, and 100x.

[0111]

number

[0112] When the antibacterial activity of the antibacterial resin according to the present specification was evaluated by the above-mentioned method 1, the antibacterial activity was observed only in cases where it was 90% or more. As a result, it was confirmed that the antibacterial resin according to the present specification has excellent antibacterial activity.

[0113] In other examples, the antibacterial activity may be 92% or more, 95% or more, 99% or more, 99.8% or more, or 99.9% or more. The upper limit of the antibacterial activity is not particularly limited, and may be, for example, 100% or less or less than 100%.

[0114] In this specification, gram-positive bacteria is a general term for bacteria that are stained purple when stained by the gram staining method. The cell walls of gram-positive bacteria are composed of multiple layers of peptidoglycan, and after staining with a basic dye such as crystal violet, the color does not fade and remains purple even when treated with ethanol.

[0115] According to 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 one selected from the above-mentioned examples, but is not limited thereto.

[0116] 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 that has 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.

[0117] According to 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 one selected from the above-mentioned examples, but is not limited thereto.

[0118] According to one embodiment of the present specification, the fungus may be, but is not limited to, Candida albicans.

[0119] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 90% or more against Gram-positive bacteria as measured by the method 1.

[0120] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity against gram-negative bacteria measured by the method 1 above of 90% or more.

[0121] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity against fungi measured by the method 1 above of 90% or more.

[0122] According to one embodiment of the present specification, the bacterium used in the antibacterial activity measurement is Escherichia coli.

[0123] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 90% or more against gram-positive bacteria, gram-negative bacteria, and fungi as measured by the method 1. Since the strains of gram-positive bacteria, gram-negative bacteria, and fungi may not only cause various diseases upon contact, but may also cause secondary infections, it is preferable to use one antibacterial agent that exhibits antibacterial properties against all of the gram-positive bacteria, gram-negative bacteria, and fungi.

[0124] One embodiment of the present specification provides an antibacterial resin-forming composition for forming the above-mentioned antibacterial resin.

[0125] According to one embodiment of the present specification, the antibacterial resin-forming composition includes styrene; a monomer represented by Chemical Formula 1; and an initiator.

[0126] According to one embodiment of the present specification, the styrene is 55 parts by weight to 99.7 parts by weight with respect to 100 parts by weight of the antibacterial resin forming composition. Specifically, the styrene is included in an amount of 65 parts by weight to 99.5 parts by weight, or 70 parts by weight to 99.5 parts by weight. When the content of styrene satisfies the above range, the composition can exhibit excellent strength while being transparent.

[0127] According to one embodiment of the present specification, the content of the monomer represented by Chemical Formula 1 is 0.2 to 40 parts by weight relative to 100 parts by weight of the antibacterial resin forming composition. Specifically, the content of the monomer represented by Chemical Formula 1 is 0.5 to 35 parts by weight, or 0.5 to 30 parts by weight. When the content of the monomer represented by Chemical Formula 1 satisfies the above range, the composition has an effect of exhibiting excellent antibacterial properties and antibacterial durability.

[0128] According to one embodiment of the present specification, the initiator is included in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the antibacterial resin forming composition. As an example, the initiator is included in an amount of 0.1 to 5 parts by weight, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight relative to 100 parts by weight of the antibacterial resin forming composition. In this case, if the content of the initiator is less than 0.1 parts by weight, the polymerization reaction time may be extended, the polymerization conversion efficiency may be reduced, and the productivity may be reduced. Specifically, there is a drawback that the polymerization conversion efficiency is reduced and a large amount of residual monomers and decomposition products are generated. On the other hand, if the content exceeds 5 parts by weight, the initiator is not completely consumed during the polymerization process and may remain in the final polymer to be produced, thereby reducing the physical properties of the polymer, especially the thermal stability.

[0129] According to one embodiment of the present specification, the initiator may be a peroxide-based compound such as dicumyl peroxide, dipentyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, or dilauryl peroxide; a peroxydicarbonate-based compound such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, or di-2-ethylhexyl peroxydicarbonate; a peroxyester-based compound such as t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, or t-butyl peroxyneodecanoate; an azo-based compound such as azobisbutyronitrile (AIBN) or azobis-2,4-dimethylvaleronitrile; a hydroperoxide-based compound such as t-butyl hydroperoxide; or a sulfate-based compound such as potassium persulfate or ammonium persulfate. Any one of these or a mixture of two or more of these may be used, but is not limited to the above examples.

[0130] One embodiment of the present specification provides a molded article containing or produced from the antibacterial resin described above. The molded article may be, but is not limited to, a refrigerator vegetable box, an automobile part, 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. The automobile part may be an interior or exterior material for an automobile. EXAMPLES

[0131] Hereinafter, the present specification will be described in detail with reference to examples in order to specifically explain the present specification. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to those having average knowledge in the art.

[0132] <Preparation Example 1> Preparation of monomer represented by formula 1 Preparation Example 1-1. Synthesis of Compound 1 Step 1. (1) 0.1 mol of 2-(dibutylamino)ethanol (DBAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0133] Step 2. (1) The product of Step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at 50 wt %. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (ratio to reactants: 1:0.001 (eq)). (3) The reaction was carried out at 50°C for 20 hours. (4) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE:reaction solution=15:1 (volume ratio)) and then filtered. (5) Compound 1 was produced by vacuum drying at 45°C.

[0134] Preparation Example 1-2. Synthesis of Compounds 2 and 3 Compounds 2 and 3 were prepared in the same manner as in Preparation Example 1-1, except that in step 2(1) of Preparation Example 1-1, 1-bromodecane (1-boromodecane, preparation of compound 2) or 1-bromododecane (1-boromododecane, preparation of compound 3) was used instead of 1-bromooctane.

[0135] Preparation Example 1-3. Synthesis of Compound 4 Compound 4 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dioctylamino)ethanol (DOAE) was used instead of 2-(dibutylamino)ethanol in step 1(1) of Preparation Example 1-1.

[0136] Preparation Example 1-4. Synthesis of Compound 5 Step 1. (1) 0.1 mol of 2-(dihexylamino)ethanol (DHAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0137] Step 2. (1) The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (ratio to reactants: 1:0.001 (eq)). (3) The reaction was carried out at 50°C for 20 hours. (4) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE:reaction solution=15:1 (volume ratio)) and then filtered. (5) Compound 5 was produced by vacuum drying at 45°C.

[0138] Preparation Example 1-5. Synthesis of Compound 6 Compound 6 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butylhexylamino)ethanol (BHAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0139] Preparation Example 1-6. Synthesis of Compound 7 Compound 7 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyloctylamino)ethanol (BOAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0140] Preparation Example 1-7. Synthesis of Compound 8 Compound 8 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyldecylamino)ethanol (BOAE) was used instead of 2-(dihexylamino)ethanol in step 1(1) of Preparation Example 1-4.

[0141] Preparation Example 1-8. Synthesis of Compound 9 Compound 9 was prepared in the same manner as in Preparation Example 1-1, except that in step 1(1) of Preparation Example 1-1, 2-(dibutylamino)butanol (DBAB) was used instead of 2-(dibutylamino)ethanol.

[0142] Preparation Example 1-9. Synthesis of Compound 10 Compound 10 was prepared in the same manner as in Preparation Example 1-1, except that in step 1(1) of Preparation Example 1-1, 2-(dioctylamino)butanol (DOAB) was used instead of 2-(dibutylamino)ethanol.

[0143] Preparation Example 1-10. Synthesis of Compound 11 (1) 1-bromooctane (production of compound 11), 2-(dimethylamino)ethylmethacrylate, 4-methoxyphenol, and acetonitrile were sequentially placed in a two-neck round bottom flask (RBF). (2) The reaction was carried out at 60°C for 6 hours. (3) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (4) Vacuum dried at 45°C.

[0144] Preparation Example 1-11. Synthesis of Compounds 12 and 13 Compounds 12 and 13 were prepared in the same manner as in Preparation Example 1-10, except that 1-bromodecane (1-boromodecane, preparation of compound 12) or 1-bromododecane (1-boromododecane, preparation of compound 13) was used instead of 1-bromooctane in Preparation Example 1-10.

[0145] Preparation Example 1-12. Synthesis of Compound 14 Compound 13 prepared in Preparation Example 1-11 is dissolved in water, sodium tetrafluoroborate is dissolved in water, and the mixture is mixed together. When stirred, the product precipitates as a solid, which is filtered and rinsed several times with water to produce compound 14.

[0146] Preparation Example 1-13. Synthesis of Compound 15 Compound 15 was prepared in the same manner as in Preparation Example 1-12, except that sodium trifluoromethanesulfonate was used instead of sodium tetrafluoroborate.

[0147] In the above Preparation Examples 1-1 to 1-12, a static precipitation method was used in which the reactants were added to a nonsolvent, but a reverse precipitation method in which the nonsolvent is added to the reactants may also be used. In addition, the ratio of MTBE to the reaction solution may be other than 15:1, for example, 12:1 or 26:1.

[0148] The structures of compounds 1 to 15 produced in the above Production Examples 1-1 to 1-13 are as follows.

[0149] [ka]

[0150] It was confirmed by NMR measurement that the compounds 1 to 15 were synthesized.

[0151] Representatively, the NMR measurement results of compounds 14 and 15 are shown in FIGS.

[0152] FIG. 1 shows the results of H NMR measurement of compound 14.

[0153] FIG. 2 shows the results of F NMR measurement of compound 14.

[0154] FIG. 3 shows the results of H NMR measurement of compound 15.

[0155] FIG. 4 shows the results of F NMR measurement of compound 15.

[0156] <Production Example 2> Production of antibacterial resin Manufacturing Example 2-1. Styrene (10 g, Aldrich), compound 1 (0.36 g) prepared in Preparation Example 1, AIBN (azobisisobutyronitrile) (0.08 g, Aldrich), and acetonitrile (10 mL) were sequentially added to a flask. After reacting at 80° C. for 16 hours, precipitation was performed using isopropyl alcohol (Duksan), and after precipitation, only solids were selectively obtained through a filter. The remaining solvent was completely removed by drying in a vacuum oven to obtain sample 1.

[0157] It was confirmed by GPC measurement that samples 1 to 15 were produced.

[0158] Representatively, the GPC measurement results of Samples 14 and 15 are shown.

[0159] (Sample 14) Mn: 87,080, Mw: 160,635, PDI: 1.8 (Sample 15) Mn: 86,161, Mw: 153,204, PDI: 1.8

[0160] Manufacturing Examples 2-2 to 2-15. Samples 2 to 15 were obtained in the same manner as in Production Example 2-1, except that the compounds shown in Table 1 below were used instead of Compound 1 in Production Example 2-1.

[0161] [Table 1]

[0162] Manufacturing Example 2-16. Sample 16 was obtained in the same manner as in Preparation Example 2-1, except that the polymerization was carried out without using Compound 1.

[0163] Manufacturing Example 2-17. Sample 17 was obtained by simply mixing compound 13 with styrene.

[0164] Manufacturing Example 2-18. A flask was charged with styrene (10 g, Aldrich), the compound 12 (0.36 g), AIBN (azobisisobutyronitrile) (0.16 g, Aldrich), dodecyl mercaptane (0.20 g, Aldrich), and acetonitrile (90 mL) in that order.

[0165] After reacting at 80°C for 4 hours, precipitation was performed with isopropyl alcohol (Duksan), and after precipitation, only the solid was selectively obtained through a filter. The remaining solvent was completely removed by drying in a vacuum oven to obtain sample 18.

[0166] Manufacturing Example 2-19. Styrene (10 g, Aldrich), the compound 12 (0.36 g), and AIBN (azobisisobutyronitrile) (0.01 g, Aldrich) were sequentially placed in a flask.

[0167] After reacting at 70° C. for 16 hours, the mixture was dissolved in acetonitrile (10 mL).

[0168] The solution was precipitated with isopropyl alcohol (Duksan), and the solid was selectively collected through a filter after precipitation. The remaining solvent was completely removed by drying in a vacuum oven to obtain sample 19.

[0169] The GPC measurement results of samples 18 and 19 are shown below.

[0170] (Sample 18) Mn: 5,432, Mw: 8,329, PDI: 1.5 (Sample 19) Mn: 382,786, Mw: 1,014,872, PDI: 2.7

[0171] <Experimental Example 1> Antibacterial activity measurement Example 1-1. 0.2 g of sample 12 was placed in a 50 mL conical tube, and then 2 × 10 510 mL of phosphate buffered saline inoculated with CFU / mL E. coli strain was poured and cultured for 1 hour in a shaking incubator maintained at 35°C. The culture solutions were diluted 1x, 10x, and 100x and smeared on agar medium plates. The smeared agar medium plates were cultured statically at 37°C for 24 to 48 hours. Based on the number of CFU of each of the samples diluted 1x, 10x, and 100x, the antibacterial activity was calculated using the following formula 1.

[0172]

number

[0173] Examples 1-2 to 1-4, Comparative Examples 1-1 to 1-4. The antibacterial activity was determined in the same manner as in Example 1-1, except that the samples in Table 2 below were used instead of Sample 12 in Example 1-1.

[0174] In the above Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4, the antibacterial activity calculated by the above Formula 1 is shown in Table 2 below.

[0175] [Table 2]

[0176] From Table 2, it can be seen that the antibacterial resin according to one embodiment of the present specification (Examples 1-1 to 1-4) has superior antibacterial activity compared to the resin obtained by homopolymerizing only styrene (Comparative Example 1-1).

[0177] <Experimental Example 2> Antibacterial Stability Measurement Example 2-1. Sample 12 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare sample 12-1. 0.2 g of sample 12-1 was placed in a 50 mL conical tube and diluted with 2×10 510 mL of phosphate buffered saline inoculated with the strain of CFU / mL was poured and cultured for 1 hour in a shaking incubator maintained at 35°C. The culture solution was diluted 1x, 10x, and 100x and smeared on an agar medium plate. The smeared agar medium plate was cultured statically at 37°C for 24 to 48 hours. Based on the number of CFU of each of the samples diluted 1x, 10x, and 100x, the antibacterial activity was calculated according to Equation 1.

[0178] Example 2-2. Sample 13 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 13-1. The antibacterial activity of Sample 13-1 was evaluated in the same manner as in Example 2-1.

[0179] Example 2-3. Sample 14 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 14-1. The antibacterial activity of Sample 14-1 was evaluated in the same manner as in Example 2-1.

[0180] Example 2-4. Sample 15 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 15-1. The antibacterial activity of Sample 15-1 was evaluated in the same manner as in Example 2-1.

[0181] Comparative Example 2-1. Sample 17 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 17-1. The antibacterial activity of Sample 17-1 was evaluated in the same manner as in Example 2-1.

[0182] Comparative Example 2-2. Sample 18 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 18-1. The antibacterial activity of Sample 18-1 was evaluated in the same manner as in Example 2-1.

[0183] Comparative Example 2-3. Sample 19 was stored in water at room temperature for 24 hours, and the remaining solid was collected to prepare Sample 19-1. The antibacterial activity of Sample 19-1 was evaluated in the same manner as in Example 2-1.

[0184] In the above Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3, the antibacterial activity calculated by the above Formula 1 is shown in Table 3 below.

[0185] [Table 3]

[0186] From Table 3, it can be seen that the antibacterial resin according to one embodiment of the present specification maintains its antibacterial activity even after a certain period of time has passed. On the other hand, in the case of a resin in which a compound and styrene are simply mixed (Comparative Example 2-1) and a resin having a weight average molecular weight of 10,000 g / mol or less (Comparative Examples 2-2 and 2-3), it can be seen that the antibacterial activity decreases after a certain period of time has passed. This confirms that the antibacterial resin according to one embodiment of the present specification is excellent in both antibacterial activity and antibacterial durability.

[0187] <Experimental Example 3> Heat resistance measurement Example 3-1. The thermal decomposition temperature was measured using a TGA (Thermogravimetric Analyzer, TA Instruments, DISCOVERY TGA 550 W / MFC&AUTO) for Sample 12. More specifically, the initial temperature decrease section in the mass reduction curve under normal pressure and temperature conditions of heating from 50°C to 600°C at a rate of 10°C / min was determined as the thermal decomposition temperature.

[0188] Example 3-2. The thermal decomposition temperature was measured in the same manner as in Example 3-1, except that Sample 14 was used instead of Sample 12 in Example 3-1.

[0189] Example 3-3. The thermal decomposition temperature was measured in the same manner as in Example 3-1, except that Sample 15 was used instead of Sample 12 in Example 3-1.

[0190] Comparative Example 3-1. The thermal decomposition temperature was measured in the same manner as in Example 3-1, except that Sample 16 (styrene homopolymer) was used instead of Sample 12 in Example 3-1.

[0191] The results of thermal decomposition measured in Examples 3-1 to 3-3 are shown in FIG. 5, and the results of thermal decomposition measured in Comparative Example 3-1 are shown in FIG.

[0192] A higher thermal decomposition temperature means improved heat resistance. From Fig. 5, it can be seen that all of the antibacterial resins according to an embodiment of the present specification exhibit a thermal decomposition temperature of 150°C or higher. In particular, when the resins contain anions other than halogen groups (Examples 3-2 and 3-3), they exhibit a thermal decomposition temperature (300°C or higher) similar to that of polystyrene (Comparative Example 3-1, Fig. 6).

[0193] From the above-mentioned embodiment, it can be confirmed that the antibacterial resin of the present invention has heat resistance while exhibiting antibacterial properties and antibacterial durability. In particular, it can be confirmed that the heat resistance is further improved when substituted with a specific anion.

[0194] <Experimental Example 4> Antibacterial activity measurement after extrusion Manufacturing Example 4-1. Into a 3000 mL flask, styrene (1000 g, Aldrich), the compound 12 (360 g), AIBN (azobisisobutyronitrile) (80 g, Aldrich), and acetonitrile (1000 mL) were sequentially placed.

[0195] After reacting at 80° C. for 16 hours, the mixture was precipitated with isopropyl alcohol (Duksan), and the precipitate was filtered to selectively collect only the solid.

[0196] Sample 20 was reserved after drying in a vacuum oven to completely remove residual solvent.

[0197] The preparation of Sample 20 was confirmed by GPC measurement.

[0198] (Sample 20) Mn: 87,451, Mw: 162,400, PDI: 1.9

[0199] Manufacturing Example 4-2. A 3000 mL flask was charged with styrene (1000 g, Aldrich), the compound 12 (360 g), and AIBN (azobisisobutyronitrile) (10 g, Aldrich) in that order.

[0200] After reacting at 70° C. for 16 hours, the mixture was dissolved in acetonitrile (1000 mL).

[0201] The solution was precipitated with isopropyl alcohol (Duksan), and after precipitation, the solid was selectively collected through a filter.

[0202] Sample 21 was reserved after drying in a vacuum oven to completely remove residual solvent.

[0203] The preparation of sample 21 was confirmed by GPC measurement.

[0204] (Sample 21) Mn: 364,809, Mw: 1,026,020, PDI: 2.8

[0205] Manufacturing Example 5-1 Sample 20 was extruded using a 16mm extruder (16mm Twin Screw Extruder LTE16, LAB TECH). More specifically, extrusion was performed at a screw speed of 160 RPM under isothermal conditions of 200°C to obtain a long cylindrical sample with a diameter of 1 to 2 mm, which was then cooled and cut into a length of about 2 mm to obtain pellet-shaped sample 20-1. At this time, the pressure at the discharge port was 15 bar on average.

[0206] Manufacturing Example 5-2 Except for using Sample 21 instead of Sample 20, extrusion was performed in the same manner as in Preparation Example 5-1 to obtain pellet-shaped Sample 21-1, at an average pressure of 20 bar at the discharge port.

[0207] Example 4-1 The sample 20 (0.2 g) was placed in a 50 mL conical tube and then diluted with 2 × 10 5 Ten milliliters of phosphate-buffered saline inoculated with CFU / mL of the bacterial strain was poured into the wells, and the wells were incubated for 24 hours in a shaking incubator maintained at 35°C.

[0208] The culture solutions were diluted 1-fold, 10-fold, and 100-fold, and then smeared on agar medium plates. The smeared agar medium plates were statically cultured at 37° C. for 24 to 48 hours. Based on the CFU counts of the samples diluted 1-fold, 10-fold, and 100-fold, the antibacterial activity was calculated according to Equation 1.

[0209] Example 4-2. The antibacterial activity was determined in the same manner as in Example 4-1, except that Sample 20-1 was used instead of Sample 20 in Example 4-1.

[0210] Comparative Example 4-1. The antibacterial activity was determined in the same manner as in Example 4-1, except that Sample 21 was used instead of Sample 20 in Example 4-1.

[0211] Comparative Example 4-2. The antibacterial activity was determined in the same manner as in Example 4-1, except that Sample 21-1 was used instead of Sample 20 in Example 4-1.

[0212] The antibacterial activities of the above Examples 4-1, 4-2, and Comparative Examples 4-1 and 4-2 are shown in Table 4 below.

[0213] [Table 4]

[0214] According to Table 4, it can be seen that the antibacterial resin according to the present specification, when the weight average molecular weight is in the range of 10,000 g / mol to 1,000,000 g / mol, maintains high antibacterial activity even after the extrusion process (Example 4-2) compared to before the extrusion process (Example 4-1). On the other hand, when the weight average molecular weight is out of the range of 10,000 g / mol to 1,000,000 g / mol, it can be seen that the antibacterial activity is high before the extrusion process (Comparative Example 4-1) but is inferior after the extrusion process (Comparative Example 4-2).

[0215] It is believed that these results are due to the fact that when a resin with an excessively high molecular weight is applied to processing steps such as extrusion, the resin has high viscosity and low fluidity, so it remains under high temperature and pressure conditions for a long time, leading to a decrease in antibacterial activity.

Claims

1. a first unit derived from styrene; and A second unit derived from a monomer represented by the following chemical formula 1: The copolymer comprises The weight average molecular weight of the copolymer is 10,000 g / mol or more and 1,000,000 g / mol or less. 【Chemistry 1】 In the above Chemical Formula 1, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; X － is a monovalent anion.

2. The X － is any one selected from the following Group 1: [Group 1] Br － 、Cl － 、I － 、F － 、BF ４ － 、OH － 、CF ３ COO － 、CF ３ SO ３ － 、NO ３ － 、SH － 、 【Chemistry 2】 In the group 1, R11 is hydrogen; deuterium; a hydroxy group; a substituted or unsubstituted alkoxy group; or a substituted or unsubstituted alkyl group; r11 is an integer of 1 to 5, and when r11 is 2 or more, the two or more R11's are the same or different.

3. The antibacterial resin according to claim 1, wherein a molar ratio of the first unit to the second unit is from 100:0.5 to 100:

50.

4. The antibacterial resin according to claim 1 , wherein the copolymer is a random copolymer.

5. The antibacterial resin according to claim 1, wherein any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently is an alkyl group having 1 to 30 carbon atoms.

6. The monomer represented by the formula 1 is the antibacterial resin according to claim 1, which has any one of the following structures: 【Chemistry 3】 In the above structure, X － is as defined in claim 1.

7. The antibacterial resin according to claim 1, which has an antibacterial activity of 90% or more against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by the following method 1: [Method 1] 0.2 g of the antibacterial resin was placed in a 50 mL conical tube, and then 2 × 10 ５ 10 mL of phosphate buffered saline inoculated with 100 CFU / mL of bacterial strain is poured into each well and incubated for 1 hour in a shaking incubator maintained at 35° C. The culture solutions are diluted 1x, 10x, and 100x and smeared on agar medium plates. The smeared agar medium plates are incubated at 37° C. for 24 to 48 hours. Based on the number of CFU in each of the samples diluted 1x, 10x, and 100x, the antibacterial activity is calculated according to the following formula 1. [0010]

8. 8. The antimicrobial resin of claim 7, wherein the Gram-positive bacteria is selected from among Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis.

9. 8. The antimicrobial resin of claim 7, wherein the Gram-negative bacteria is selected from among Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae.

10. A molded article comprising or produced from the antibacterial resin according to any one of claims 1 to 9.

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