Antibacterial polymers and antibacterial polymer films comprising the same

Abstract

Provided are a cross-linked polymer including a polymerizable antibacterial monomer and an antibacterial polymer film including the same, which is capable of exhibiting improved bacterial growth inhibition characteristics while maintaining adhesive film properties.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application Nos. 10-2021-0114960 and 10-2022-0097511, filed on August 30, 2021 and August 4, 2022, respectively, the disclosure of which is incorporated herein by reference in its entirety.

[0003] This invention relates to antimicrobial polymers and antimicrobial polymer films containing the same. Background Technology

[0004] Recently, with increasing biodiversity, improved living standards, and changing and heightened awareness, there has been a growing interest in improving hygiene and comfort in personal living environments. Consequently, research has been conducted on microorganisms that threaten these environments. However, many types of microorganisms exist in our daily lives, widely distributed in nature, and thus cause serious problems.

[0005] In particular, microorganisms such as bacteria and fungi can inhabit various environments, including food, living spaces, clothing, and industrial products. However, bacteria are problematic because they can cause various inflammations or food poisoning, and fungi can not only produce odors but also cause various skin diseases, respiratory illnesses, allergic reactions, and atopic dermatitis. Furthermore, microorganisms living on the surfaces of electronic and household products can lead to product performance degradation.

[0006] In particular, due to the recent surge in infectious diseases, there is an increasing number of cases where antimicrobial films are applied to products that people inevitably come into contact with in multipurpose facilities and other similar settings. Therefore, in order to prevent harm to humans caused by microorganisms, various antimicrobial substances have been developed to inhibit microbial growth or kill microorganisms.

[0007] Regarding antibacterial membranes, inorganic antibacterial agents are mainly used, which are prepared by mixing inorganic particles (such as silver or copper) into the membrane to impart antibacterial function. However, while mixing inorganic particles has the advantage of maintaining antibacterial properties even under high temperature conditions, it also presents the following problems: they are expensive, there is a possibility of discoloration due to the inclusion of metal ions after processing, and the basic physical properties of the membrane are compromised due to increased viscosity and opacity.

[0008] On the other hand, organic antimicrobial agents exist as another previously developed antimicrobial substance. Compared to inorganic antimicrobial agents, organic antimicrobial agents have the advantages of being inexpensive and having excellent antimicrobial effects even in small amounts, but they suffer from poor antimicrobial durability due to leaching after application to the product. Furthermore, while organic antimicrobial agents can ensure product stability in terms of inhibiting microbial growth and killing microorganisms, they are also toxic and can irritate the user's skin.

[0009] Therefore, there is a need for antimicrobial polymer compositions that can be used as antimicrobial adhesive films while maintaining antimicrobial properties and being safe without leaching out of the film, and while maintaining the basic physical properties of the adhesive film. Summary of the Invention

[0010] Technical issues

[0011] An antimicrobial polymer comprising a polymerizable antimicrobial monomer and an antimicrobial polymer film comprising the same are provided, the antimicrobial polymer film exhibiting improved bacterial growth inhibition properties while maintaining adhesive film properties.

[0012] Technical solution

[0013] An antimicrobial polymer is provided, which is a polymerizable antimicrobial monomer represented by the following chemical formula 1, a butyl-based rubber comprising butene-derived repeating units and isoprene repeating units, and a crosslinking agent:

[0014] [Chemical Formula 1]

[0015]

[0016] In chemical formula 1,

[0017] R1 to R3 are each independently hydrogen or methyl.

[0018] R4 and R5 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and

[0019] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0020] An antimicrobial polymer film comprising the crosslinked polymer is also provided.

[0021] Beneficial effects

[0022] The antimicrobial polymer of the present invention comprises polymerizable antimicrobial monomers with antimicrobial properties, and therefore, when made into a film, a safe and stable antimicrobial polymer film can be manufactured.

[0023] Specifically, because the polymerizable antimicrobial monomers cure together during monomer crosslinking, the antimicrobial polymer can be made into a film without any change in appearance. Therefore, it exhibits antimicrobial properties against at least one Gram-negative bacterium without causing human safety issues due to antimicrobial agent leaching, as the antimicrobial monomers used do not remain in the polymer. Detailed Implementation

[0024] The terminology used in this specification is for illustrative purposes only and is not intended to limit the invention. Singular expressions may include plural expressions unless the context otherwise requires. It must be understood that the terms “comprising,” “equipped,” or “having” in this specification are used only to indicate the presence of an effective feature, step, component, or combination thereof, and do not preclude the presence or possible addition of one or more different features, steps, components, or combinations thereof.

[0025] Furthermore, in this invention, when referring to layers or elements being formed "on" or "above" a layer or element, this means that the layers or elements are formed directly on the layer or element, or that other layers or elements may be formed between layers, objects, or substrates.

[0026] This invention can be modified in various ways and has various forms, and specific exemplary embodiments are illustrated and described in detail in the following description. However, it is not intended to limit the invention to the specific exemplary embodiments, and it must be understood that the invention includes every modification, equivalent, and alternative included within the spirit and technical scope of the invention.

[0027] Furthermore, the technical terminology used in this specification is for illustrative purposes only and is not intended to limit the invention. Unless the context otherwise requires, singular expressions used herein may include plural expressions.

[0028] Furthermore, in this specification, the alkyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably 1 to 20. According to one embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups may include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc. Furthermore, in this specification, the above description of alkyl groups may also apply to alkylene groups, the difference being that alkylene groups are divalent groups.

[0029] To impart antimicrobial properties to household chemical products commonly used in everyday living spaces such as homes, offices, and multi-purpose facilities, an antimicrobial coating is formed on the surface of these products to inhibit the growth of microorganisms and / or kill microorganisms such as bacteria. In particular, due to the recent impact of infectious diseases, there is an increasing number of cases where antimicrobial films are additionally attached to products that come into contact with many people in multi-purpose facilities and the like. In this regard, the antimicrobial agent contained in the antimicrobial film disrupts the cell membrane or cell wall of microorganisms or induces protein denaturation, thus inhibiting microbial growth, thereby causing inhibition of microbial reproduction and / or microbial death.

[0030] More than 5,000 species of bacteria have been identified. Specifically, bacteria exhibit diverse cell morphologies, such as spherical, rod-shaped, and spiral, and their oxygen requirements also differ, thus classifying them into aerobic, facultative, and anaerobic bacteria. Therefore, it is generally not easy for a single type of antibacterial agent to possess a physical / chemical mechanism that disrupts the cell membrane / cell wall or denatures the proteins of various bacteria.

[0031] In addition, there are concerns that the antimicrobial agents used in antimicrobial coatings may leach out over time, or that users' health may be threatened by the antimicrobial agents when they are continuously exposed to them.

[0032] However, it was discovered that when an antimicrobial polymer prepared by cross-linking and polymerization of a polymerizable antimicrobial monomer with a specific structure is used as an antimicrobial polymer membrane, the antimicrobial polymer membrane can exhibit antimicrobial properties against Gram-negative bacteria without the leaching of the antimicrobial monomer from the membrane, thus completing the present invention. When the amino group of the polymerizable antimicrobial monomer represented by Formula 1 combines with a positively charged proton, the interaction with the microbial cell wall increases, and the alkyl group corresponding to the side group destabilizes the microbial cell wall and inhibits microbial growth, thereby exhibiting antimicrobial properties.

[0033] Antimicrobial polymer membranes are made by curing antimicrobial monomers together with a polymer (butyl-based rubber) that serves as the raw material for the membrane, thus containing the antimicrobial monomers in a cross-linked form. Therefore, since the appearance of the membrane remains unchanged and the antimicrobial monomers do not remain in the antimicrobial polymer membrane as compounds, there are no concerns about antimicrobial leaching even after a period of time, resulting in excellent safety and stability.

[0034] The antimicrobial polymer and antimicrobial polymer film according to specific embodiments of the present invention will be described in more detail below.

[0035] Antibacterial polymers

[0036] One embodiment of the antimicrobial polymer is a crosslinked polymer comprising: a polymerizable antimicrobial monomer represented by the following chemical formula 1; a butyl-based rubber comprising butene-derived repeating units and isoprene repeating units; and a crosslinking agent:

[0037] [Chemical Formula 1]

[0038]

[0039] In chemical formula 1,

[0040] R1 to R3 are each independently hydrogen or methyl.

[0041] R4 and R5 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and

[0042] L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0043] Since most bacterial cell membranes are negatively charged, most antibacterial substances are positively charged. When a hydrogen cation (proton) combines with the amine group of a compound represented by Formula 1 to exhibit cationic properties, it can interact with the bacterial cell membrane, and thus the compound represented by Formula 1 possesses antibacterial properties.

[0044] The polymerizable antimicrobial monomer, represented by Formula 1, is crosslinked with a butyl-based rubber, described later, to form a crosslinked polymer. Since the crosslinked polymer is formed through photopolymerization of the polymerizable antimicrobial monomer, the butyl-based rubber, and the crosslinking agent, polymerization of the polymerizable antimicrobial monomer also occurs. In other words, the polymerizable antimicrobial monomer does not exist as a separate compound in the antimicrobial polymer film, but is crosslinked with the butyl-based rubber, and therefore does not leach out over time. Therefore, when the polymerizable antimicrobial monomer is made into a polymer film, the antimicrobial properties of the film can be maintained continuously while remaining harmless to the human body.

[0045] In chemical formula 1, R1 and R2 can each preferably be hydrogen, and R3 can be methyl.

[0046] Furthermore, preferably, R4 can be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably, R4 can be tert-butyl. Generally, the greater the number of carbon atoms at the R4 position, the higher the affinity for the outer cell wall of microorganisms, thus exhibiting strong antibacterial activity. In the case of alkyl groups having 8 or more carbon atoms, having an appropriate length is important because it exhibits strong bactericidal properties even in water.

[0047] Preferably, R5 can be hydrogen. When R5 is an alkyl group, it can function in the interaction with the outer cell wall of microorganisms as described above. However, when both R4 and R5 are alkyl groups, the electron-induced effect is not increased, but the alkyl group negatively affects the interaction between the cell membrane and the positively charged microorganism due to steric effects. In contrast, when R5 is hydrogen, the steric effect becomes smaller, and it is more likely to bind to protons and become positively charged, thus exhibiting a stronger interaction with the negatively charged microbial cell wall. Therefore, even when R4 is a tert-butyl group with a relatively small number of carbon atoms, it can still exhibit excellent antibacterial properties.

[0048] Preferably, L1 is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, and more preferably, L1 can be an ethylene group.

[0049] For example, polymerizable antimicrobial monomers can be compounds represented by the following chemical formula 1-1:

[0050] [Chemical Formula 1-1]

[0051]

[0052] Meanwhile, relative to 100 parts by weight of butyl-based rubber, the polymerizable antimicrobial monomer is included in the antimicrobial polymer in an amount of 5 parts by weight or more and 20 parts by weight or less. When the polymerizable antimicrobial monomer is included in small amounts, the performance of the adhesive film is comparable to or better than that of conventional films, but it is difficult to exhibit sufficient antimicrobial effect due to the lack of antimicrobial monomer. When the polymerizable antimicrobial monomer is included in large amounts, its antimicrobial performance can be excellent, but the adhesive performance of the adhesive film is relatively reduced, and yellowing may occur. Therefore, when the polymerizable antimicrobial monomer meets the above range, it can have excellent effects in both adhesive film performance and antimicrobial performance.

[0053] More specifically, relative to 100 parts by weight of butyl-based rubber, the polymerizable antimicrobial monomer may be included in the antimicrobial polymer in amounts of 5 parts by weight or more, 7 parts by weight or more, 9 parts by weight or more, 11 parts by weight or more, or 13 parts by weight or more, and 20 parts by weight or less, or 19 parts by weight or less.

[0054] Meanwhile, the antimicrobial polymer includes a butyl-based rubber. The butyl-based rubber comprises butene-derived repeating units and isoprene repeating units. During the polymerization of the aforementioned polymerizable antimicrobial monomer and the butyl-based rubber, the isoprene repeating units and the polymerizable antimicrobial monomer can be crosslinked.

[0055] Preferably, in butyl-based rubber, the butene-derived repeating unit can be an isobutylene repeating unit.

[0056] Preferably, the butyl-based rubber may comprise butene-derived repeating units and isoprene repeating units in a weight ratio of 90:10 to 99:1. When the weight ratio of butene-derived repeating units to isoprene repeating units in the butyl-based rubber is within the above range, an adhesive composition with excellent water-blocking properties can be obtained. This is presumably due to the stacking effect caused by the double bonds in the isoprene-derived backbone. More preferably, the weight ratio of butene-derived repeating units to isoprene repeating units may be 92:8 or greater, 95:5 or greater, 97:3 or greater, or 98:2 or greater, and 99:1 or less.

[0057] The weight-average molecular weight (Mw) of butyl-based rubber can be 50,000 g / mol or greater and 2,000,000 g / mol or less. When the weight-average molecular weight of butyl-based rubber is less than 50,000 g / mol, the composition used to manufacture the film has almost insufficient viscosity, and therefore it is difficult to apply the composition uniformly when coating the substrate surface, and it is difficult to have sufficient physical properties as an encapsulant when the coating is completed. When the weight-average molecular weight of butyl-based rubber is greater than 2,000,000 g / mol, it is difficult to prepare a uniform coating solution due to the high viscosity, and it may be difficult to achieve uniform coating even during the coating process due to the high viscosity. More preferably, the weight-average molecular weight of the antimicrobial polymer may be 100,000 g / mol or greater, 200,000 g / mol or greater, 300,000 g / mol or greater, 400,000 g / mol or greater, or 500,000 g / mol or greater, and 1,500,000 g / mol or less, 1,200,000 g / mol or less, 1,000,000 g / mol or less, 900,000 g / mol or less, 800,000 g / mol or less, 700,000 g / mol or less, or 600,000 g / mol or less.

[0058] In this regard, the weight-average molecular weight (Mw) of butyl-based rubber can be measured using gel permeation chromatography (GPC) with polystyrene (PS) as a standard sample for calibration. More specifically, 200 mg of the antimicrobial polymer is diluted with 200 ml of N,N-dimethylformamide (DMF) solution to prepare a sample of approximately 1000 ppm, which can then be measured using an Agilent 1200 series GPC instrument at a flow rate of 1 ml / min through an RI detector. The molecular weight of the sample can then be calculated based on a calibration curve obtained using eight PS standards.

[0059] As a crosslinking agent, any compound can be used, as long as it can introduce crosslinking during the polymerization of the antibacterial polymer composition. Preferably, the crosslinking agent can be any of the polyfunctional (meth)acrylate monomers, polyfunctional urethane (meth)acrylate oligomers, and mixtures thereof. As a crosslinking agent, a photocurable polyfunctional (meth)acrylate monomer is preferably used. Polyfunctional (meth)acrylates may include: difunctional acrylates, such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, di(meth)acryloyloxyethyl isocyanurate, allylated di(meth)acrylate, tricyclodecanediethanol (meth)acrylate, dihydroxymethyldicyclopentane di(meth)acrylate, ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate, or 9,9-bis[4-(2-propanediol)meth]acrylate. [Fluorene, etc.]; trifunctional acrylates, such as trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trifunctional carbamate (meth)acrylate, or tri(meth)acryloyloxyethyl isocyanurate, etc.; tetrafunctional acrylates, such as diglycerol tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate, etc.; pentafunctional acrylates, such as dipentaerythritol penta(meth)acrylate, etc.; and hexafunctional acrylates, such as dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, or carbamate (meth)acrylate (reaction product of isocyanate monomer and trimethylolpropane tri(meth)acrylate), etc., but not limited thereto. These compounds can be used alone or in mixtures of two or more thereof. More preferably, tricyclodecanediethanol diacrylate (TCDDA) can be used as a crosslinking agent.

[0060] Preferably, the crosslinking agent can be used in an amount of 5 to 20 parts by weight relative to 100 parts by weight of butyl-based rubber. More preferably, the crosslinking agent can be used in an amount of 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, and 18 parts by weight or less, 16 parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, or 11 parts by weight or less relative to 100 parts by weight of butyl-based rubber.

[0061] Antibacterial polymer film

[0062] According to another embodiment of the present invention, an antimicrobial polymer film comprising the above-described antimicrobial polymer is provided.

[0063] The antimicrobial polymer film containing the aforementioned antimicrobial polymer is easy to apply in various fields, suitable for mass production, and can maintain its antimicrobial effect for a long time because the polymerizable antimicrobial monomer represented by chemical formula 1 with antimicrobial effect is polymerized into a polymer and does not leach out.

[0064] Furthermore, according to an exemplary embodiment of the present invention, the antimicrobial polymer film can be manufactured by curing an antimicrobial polymer composition comprising a polymerizable antimicrobial monomer represented by Formula 1, a butyl-based rubber, and a crosslinking agent, and without particular limitation including solvents and other additives to the extent that the effects of the present invention are not impaired. The solvent is not limited, as long as it is a commonly used solvent, and the solvent can be added when mixing the components contained in the antimicrobial polymer composition, or can be included in the antimicrobial polymer composition while adding the components dispersed or mixed in the solvent. For example, the antimicrobial polymer composition may contain a solvent such that the total solids content of the components contained in the antimicrobial polymer composition is from 1% to 80% by weight, or from 2% to 50% by weight.

[0065] Non-limiting examples of organic solvents may include: ketones, such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, or isobutyl ketone; alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or tert-butanol; acetates, such as ethyl acetate, isopropyl acetate, or polyethylene glycol monomethyl ether acetate; ethers, such as tetrahydrofuran or propylene glycol monomethyl ether; toluene; or mixtures of two or more thereof.

[0066] For example, additives may include tackifiers, photoinitiators, buffers, wetting agents, neutralizers, polymerization terminators, etc., and may include any or more of them.

[0067] The tackifier is preferably a hydrogenated cycloolefin-based polymer. For example, hydrogenated petroleum resins obtained by hydrogenating petroleum resins can be used. The hydrogenated petroleum resins can be partially or fully hydrogenated, and the tackifier can be a mixture of such resins. Such tackifiers can be selected from those that have good compatibility with the materials constituting the above-described antibacterial polymer composition and possess excellent moisture barrier properties and low volatile organic components. Specific examples of hydrogenated petroleum resins may include hydrogenated terpene-based resins, hydrogenated ester-based resins, or hydrogenated dicyclopentadiene resins. The tackifier content can be appropriately adjusted as needed. Most preferably, hydrogenated dicyclopentadiene resins can be used as the tackifier.

[0068] The photoinitiator can be an α-hydroxy ketone compound, a benzyl ketal compound, or a mixture thereof, but is not limited thereto. Preferably, as an α-hydroxy ketone compound, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc., can be used.

[0069] Additives such as buffers, wetting agents, neutralizing agents, polymerization terminators, etc., can also be used without limitation, as long as they are commonly used in the field.

[0070] Antimicrobial polymer membranes can exhibit antimicrobial properties against Gram-negative bacteria. Gram-negative bacteria are bacteria that stain red using the Gram staining method and, compared to Gram-positive bacteria, possess an outer membrane composed of lipopolysaccharides, lipoproteins, and other complex polymeric materials, rather than a cell wall with a relatively small amount of peptidoglycan. Therefore, after staining with a basic dye such as crystal violet, Gram-negative bacteria will decolorize even when treated with ethanol, and will appear red when counterstained with a red dye such as safranin. Bacteria classified as Gram-negative can include *Proteus mirabilis*, *Escherichia coli*, *Salmonella typhi*, *Pseudomonas aeruginosa*, or *Vibrio cholerae*, among others.

[0071] Preferably, the antimicrobial polymer film can exhibit antimicrobial properties against Escherichia coli (E. coli).

[0072] Specifically, the antimicrobial properties of the antimicrobial polymer film against Escherichia coli (E. coli) can be evaluated according to the antimicrobial activity test method JIS Z 2081, and the bacterial growth inhibition rate can be calculated using Equation 1 described below. The E. coli growth inhibition rate of the antimicrobial polymer composition thus measured can be 70% or greater, 72% or greater, 80% or greater, 84% or greater, 90% or greater, 92% or greater, 95% or greater, 96% or greater, or 96.43% or greater, and 100% or less, or 99.89% or less.

[0073] Specifically, the antibacterial properties can be measured using the following method: 400 μl of the sample is divided into 2 × 10⁻⁶ samples. 4 A PBS buffer solution of E. coli, used as an inoculum, was applied to an antimicrobial polymer membrane measuring 5 cm × 5 cm at a concentration of CFU / ml. To prevent moisture evaporation from the membrane surface, the antimicrobial polymer membrane was covered with a dry PET membrane sterilized with alcohol and incubated for 24 hours. The bacteria incubated for 24 hours were serially diluted and spread on solid agar medium. The bacterial count was determined by examining the colonies that appeared. One, two, or more measurements could be performed, and the average of the results could be obtained.

[0074] Meanwhile, the bacterial growth inhibition rate can be determined by calculation according to the following Equation 1.

[0075] [Equation 1]

[0076] Bacterial inhibition rate (%) = (1-S) 24小时 / R 24小时 )*100

[0077] S 24小时 This indicates the number of bacteria in colonies determined by culturing the antimicrobial-treated sample (with the bacterial inhibition rate to be tested) for 24 hours and then dispersing it on agar medium, along with R. 24小时 This indicates the number of bacteria in the colonies determined by culturing untreated comparative examples for 24 hours and then spreading them on agar medium.

[0078] The glass bonding strength and viscosity of the antibacterial polymer film of the present invention are comparable to those of conventional materials without polymerizable antibacterial monomers.

[0079] Preferably, the glass bonding strength of the antibacterial polymer film can be 2300gf / 25mm or greater and 2500gf / 25mm or less, more preferably 2350gf / 25mm or greater, 2400gf / 25mm or greater, or 2420gf / 25mm or greater, and 2480gf / 25mm or less, or 2450gf / 25mm or less.

[0080] The glass adhesion strength of the antibacterial polymer film can be measured using the following method. After removing the release film of the antibacterial polymer film, the Cu side of the film with attached copper foil and PET is joined to the adhesive film layer. The attached film is cut into pieces 25 mm wide and 150 mm long, and the prepared sample is attached by laminating it to a 90 mm * 150 mm glass plate at a temperature of 50 °C. The glass plate of the prepared sample is fixed, and the film portion is peeled off to measure the low-speed peel force in T.A.Tension mode on a TA.XTplus texture analyzer. The low-speed peel force is measured at a speed of 5 mm / s, a trigger force of 5.0 g, and a distance of 80 mm.

[0081] Preferably, the viscosity of the antibacterial polymer film can be 70,000 Pa·s or greater and 90,000 Pa·s or less, more preferably 72,000 Pa·s or greater, 75,000 Pa·s or greater, 77,000 Pa·s or greater, or 78,000 Pa·s or greater, and 85,000 Pa·s or less, 83,000 Pa·s or less, 81,000 Pa·s or less, 80,000 Pa·s or less, or 79,000 Pa·s or less.

[0082] The viscosity of the antibacterial polymer film can be measured using the following method. First, the protective film (release film) is removed from two samples of the same adhesive film, and then laminated and attached by ensuring good dimensional matching on both sides. A portion of the circumference is removed, and the film is divided into two parts to remove the release film from each side, and then laminated again. This method is repeated until the thickness of the adhesive film falls within the range of 500 μm to 800 μm. After measuring the exact thickness, the film is cut into 15 mm × 15 mm squares and measured using an ARES-G2 rheometer. Measurements are performed in frequency sweep mode under conditions of 5% strain and 27 °C, with the complex viscosity measured at 1 Hz.

[0083] The antimicrobial polymer film can be cured by including an adhesive that can itself be used as an adhesive film, or the antimicrobial polymer composition can be applied to a substrate and the resulting product can be used after photocuring.

[0084] Specifically, according to an exemplary embodiment of the present invention, an antimicrobial article is provided, the antimicrobial article comprising one or more substrates; and a coating disposed on at least one surface of the substrate, wherein the coating is formed by curing an antimicrobial polymer composition comprising the aforementioned antimicrobial polymer.

[0085] The substrate can be a polymer film, such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), polyimide (PI), polyethylene terephthalate (PET), polyvinyl chloride (PVC), etc.; fabric; glass; plastic foam, such as polyurethane foam and polystyrene foam (styrofoam); solid wood; plywood; or a metal substrate, but is not limited thereto.

[0086] Furthermore, antimicrobial products are not limited to any particular type; for example, they can be used in various household chemical products, automotive parts, building materials, and organic electronic devices that require antimicrobial properties. For instance, when used in organic electronic devices, antimicrobial polymer films can be used as encapsulation films.

[0087] Specifically, antimicrobial products can be selected from one or more of the following: preservation materials, textile products, agricultural films, organic electronic devices, various office supplies, and various packaging materials.

[0088] For example, antimicrobial products can be packaging materials such as food packaging materials, vegetable packaging materials, grain packaging materials, fruit packaging materials, meat packaging materials, aquatic product packaging materials, processed food packaging materials, and preservation materials (e.g., containers for vegetables, grains, fruits, meat, aquatic products, processed foods, etc.); tray mats for food; textile products such as placemats, tablecloths, carpets, seat covers, etc.; agricultural films; organic electronic devices; face masks; office supplies such as tapes, adhesive tapes, masking tapes, and masking films, etc.; and various packaging materials such as flower packaging materials, plastic bags, easy-open packaging bags, shopping bags, stand-up pouches, transparent packaging boxes, automatic packaging films, electronic component packaging materials, and mechanical component packaging materials, etc.

[0089] Furthermore, the coating can be set with thicknesses of, for example, 10 μm or greater, 20 μm or greater, 50 μm or greater, 80 μm or greater, 100 μm or greater, or 150 μm or greater, and 1 mm or less, 800 μm or less, 600 μm or less, 500 μm or less, 300 μm or less, 250 μm or less, or 200 μm or less. The coating can be formed by thin-film coating, wherein an antimicrobial polymer composition is applied to at least one surface of a substrate and then dried at a temperature of 40°C to 80°C for 60 minutes to 240 minutes.

[0090] There are no particular limitations on the methods and apparatus commonly used for applying antimicrobial polymer compositions. For example, bar coating such as Meyer bars, gravure coating, two-roll reverse coating, vacuum slot die coating, two-roll coating, etc., can be used.

[0091] The thickness of the antimicrobial polymer film can be determined according to the intended use of the final manufactured film. For example, the antimicrobial polymer composition can be coated (applied) with a thickness of 1 μm to 1,000 μm, or made into a single adhesive film.

[0092] In the step of photocuring the antibacterial polymer composition, ultraviolet or visible light with a wavelength of 200 nm to 400 nm can be used for irradiation, and the exposure dose is preferably 50 mJ / cm². 2 Up to 2,000 mJ / cm 2 There are no particular restrictions on exposure time, but it can be adjusted appropriately depending on the exposure device used, the wavelength of the light to be emitted, or the amount of exposure.

[0093] In addition, nitrogen purging can be performed to apply nitrogen atmosphere conditions during the step of photocuring the antibacterial polymer composition.

[0094] In the following description, for better understanding, the invention will be described in more detail. However, the following exemplary embodiments are for illustrative purposes only, and the scope of the invention is not limited to the following exemplary embodiments.

[0095] [Example: Manufacturing of an antibacterial polymer film]

[0096] Comparative Example 1

[0097] A polymer composition was obtained by dissolving 99 g of butyl rubber (weight average molecular weight 500,000 g / mol, product name: BR268, ExxonMobil Chemical) containing 98 wt% isobutylene-derived units and 2 wt% isoprene-derived units in toluene, 20 g of dicyclopentadiene hydrogenated resin (SU500, Kolon, 70 wt%) dissolved in toluene as a tackifier, 1.6 g of tricyclodecanediethanol diacrylate (TCDDA) as a crosslinking agent, and 0.3 g of Irgacure 651 (2,2-dimethoxy-2-phenylacetophenone) as a photoinitiator in toluene and mixing them to a total solid content of 22 wt%.

[0098] The prepared composition solution was filtered through a 400-mesh nylon filter and applied to the release surface of a release PET using a bar coater. It was dried in a desiccator at 120°C for 4 minutes, and then another release PET was laminated onto the release surface of the dried polymer film. The polymer film was manufactured such that the thickness of the polymer film layer after drying was 30 μm to 40 μm. A total of 2 J / cm was applied during irradiation. 2 The ultraviolet light causes the polymer film to solidify.

[0099] Reference example 1

[0100] The antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that, in addition to the polymer composition of Comparative Example 1, the polymer composition also contained 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer in an amount of 3 parts by weight relative to 100 parts by weight of butyl rubber.

[0101] Reference example 2

[0102] The antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that, in addition to the polymer composition of Comparative Example 1, the polymer composition also contained 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer in an amount of 25 parts by weight relative to 100 parts by weight of butyl rubber.

[0103] Example 1

[0104] The antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that, in addition to the polymer composition of Comparative Example 1, the polymer composition also contained 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer in an amount of 13 parts by weight relative to 100 parts by weight of butyl rubber.

[0105] Example 2

[0106] The antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that, in addition to the polymer composition of Comparative Example 1, the polymer composition also contained 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer in an amount of 19 parts by weight relative to 100 parts by weight of butyl rubber.

[0107] Example 3

[0108] The antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that, in addition to the polymer composition of Comparative Example 1, the polymer composition also contained 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer in an amount of 7 parts by weight relative to 100 parts by weight of butyl rubber.

[0109] [Experimental Example]

[0110] (1) Evaluation of the antibacterial properties of antimicrobial polymer films against E. coli

[0111] The antimicrobial properties of the antimicrobial polymer films manufactured in the Examples and Comparative Examples were evaluated respectively.

[0112] Specifically, as an antibacterial test, the bacterial count was checked using the antibacterial activity test method JIS Z 2081. 400 μl of the sample was prepared at a concentration of 2 × 10⁻⁶. 4 A PBS buffer solution of E. coli, used as inoculum, was applied to an antimicrobial polymer membrane measuring 5 cm × 5 cm at a concentration of CFU / ml. To prevent moisture evaporation from the membrane surface, the antimicrobial polymer membrane was covered with a dry PET membrane sterilized with alcohol and incubated for 24 hours. The bacteria incubated for 24 hours were serially diluted and spread on solid agar medium, and the bacterial count was determined by examining the colonies that appeared. The results are shown in Table 1. Two experiments were performed, and the bacterial count was examined and averaged.

[0113] Meanwhile, the bacterial growth inhibition rate was calculated as follows, and the results are shown in Table 1.

[0114] [Equation 1]

[0115] Bacterial inhibition rate (%) = (1-S) 24小时 / R 24小时 )*100

[0116] S 24小时 This indicates the number of bacteria in the colonies determined by culturing the example (antimicrobial treated sample) for 24 hours and then dispersing it on agar medium, and R 24小时 This indicates the number of bacteria in the colonies determined by culturing the comparative example for 24 hours and then spreading it on agar medium.

[0117] [Table 1]

[0118]

[0119]

[0120] Referring to Table 1, unlike the antimicrobial film of Comparative Example 1 which did not contain an antimicrobial polymer, the antimicrobial films manufactured using the antimicrobial polymer compositions of the examples exhibited excellent bacterial growth inhibition rates of 95% or greater against Gram-negative bacteria E. coli. As in Comparative Example 1, when the content of the antimicrobial monomer was low, it was considered that no antimicrobial function was exhibited because the antimicrobial performance did not exceed the reference value. Comparative Example 2 was confirmed to exhibit high antimicrobial performance due to its high antimicrobial monomer content.

[0121] (2) Measurement of the glass bonding strength of the antibacterial polymer film

[0122] After removing the release film from the antibacterial polymer films manufactured in the Examples and Comparative Examples, the Cu side of the film with attached copper foil and PET was joined to the adhesive film layer. The attached film was cut into pieces 25 mm wide and 150 mm long, and the prepared samples were attached by laminating them to a 90 mm * 150 mm glass plate at 50 °C. The glass plate of the prepared sample was fixed, and the film was partially peeled off to measure the low-speed peel force in TA Tension mode on a TA.XTplus texture analyzer. The low-speed peel force was measured at a speed of 5 mm / s, a trigger force of 5.0 g, and a distance of 80 mm. The results are shown in Table 2 below.

[0123] (3) Measurement of viscosity of antibacterial polymer film

[0124] First, the protective film (release film) was removed from two samples of the same adhesive film, and then lamination and attachment were performed by ensuring good dimensional matching on both sides. A portion of the circumference was removed and the film was divided into two parts to remove the release film from each side, and then the films were laminated again. This method was repeated until the thickness of the adhesive film fell within the range of 500 μm to 800 μm. After measuring the exact thickness, the film was cut into 15 mm × 15 mm squares and measured using an ARES-G2 rheometer (TA Instruments). Measurements were performed in frequency sweep mode at 5% strain and 27 °C, and the complex viscosity was measured at 1 Hz. The results are shown in Table 2 below.

[0125] [Table 2]

[0126]

[0127] As shown in Table 2, it was determined that there was no significant difference in adhesive strength between films manufactured by polymerizing antimicrobial monomers together and films without antimicrobial monomers. It was also confirmed that, similar to the adhesive strength of glass, there was no significant difference in viscosity between the antimicrobial examples. Based on these results, it was determined that polymerizable antimicrobial materials did not significantly affect adhesive properties up to a certain content level. However, as in Reference Example 2, it was determined that both adhesive strength and viscosity decreased when the content of antimicrobial monomers was high. This is considered to be due to the increased copolymerization ratio of the antimicrobial monomers, which affects the existing adhesive strength.

Claims

1. An antimicrobial polymer, said antimicrobial polymer being a polymerizable antimicrobial monomer represented by the following chemical formula 1, a butyl-based rubber comprising butene-derived repeating units and isoprene repeating units, and a crosslinking agent, comprising a crosslinking polymer. The polymerizable antimicrobial monomer is used in an amount of 5 to 20 parts by weight relative to 100 parts by weight of the butyl-based rubber, and The butyl-based rubber has a weight-average molecular weight of 50,000 g / mol or greater and 2,000,000 g / mol or less. [Chemical Formula 1] In chemical formula 1, R1 to R3 are each independently hydrogen or methyl. R4 and R5 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

2. The antibacterial polymer according to claim 1, wherein... R1 and R2 are both hydrogen, and R3 is a methyl group.

3. The antibacterial polymer according to claim 1, wherein... R4 is tert-butyl.

4. The antibacterial polymer according to claim 1, wherein... R5 is hydrogen.

5. The antibacterial polymer according to claim 1, wherein... L1 is ethylene.

6. The antimicrobial polymer according to claim 1, wherein the polymerizable antimicrobial monomer represented by chemical formula 1 is represented by the following chemical formula 1-1: [Chemical Formula 1-1] 。 7. The antibacterial polymer according to claim 1, wherein... The butene-derived repeating unit is an isobutene repeating unit.

8. The antibacterial polymer according to claim 1, wherein... The butyl-based rubber comprises the butene-derived repeating unit and the isoprene repeating unit in a weight ratio of 90:10 or greater and 99:1 or less.

9. The antibacterial polymer according to claim 1, wherein... The crosslinking agent is selected from any of the polyfunctional (meth)acrylate monomers, polyfunctional urethane (meth)acrylate oligomers, and mixtures thereof.

10. An antimicrobial polymer film comprising the antimicrobial polymer according to any one of claims 1 to 9.

11. The antimicrobial polymer film according to claim 10, further comprising a tackifier.

12. The antibacterial polymer film according to claim 11, wherein... The tackifier is a hydrogenated dicyclopentadiene resin.

13. The antibacterial polymer film according to claim 10, wherein... The antimicrobial polymer membrane exhibits antimicrobial properties against Gram-negative bacteria.

14. The antibacterial polymer film according to claim 13, wherein... The Gram-negative bacterium mentioned is Escherichia coli.

15. An antimicrobial polymer film, said antimicrobial polymer film being manufactured by curing an antimicrobial polymer composition comprising: a polymerizable antimicrobial monomer represented by chemical formula 1; a butyl-based rubber comprising butene-derived repeating units and isoprene repeating units; and a crosslinking agent. The polymerizable antimicrobial monomer is used in an amount of 5 to 20 parts by weight relative to 100 parts by weight of the butyl-based rubber, and The butyl-based rubber has a weight-average molecular weight of 50,000 g / mol or greater and 2,000,000 g / mol or less. [Chemical Formula 1] In chemical formula 1, R1 to R3 are each independently hydrogen or methyl. R4 and R5 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and L1 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

16. An antibacterial product, comprising: One or more substrates; and The antimicrobial polymer film according to claim 10 is disposed on one or more surfaces of the substrate.

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