Antibacterial polymer and antibacterial polymer film containing the same

Abstract

The present invention relates to a crosslinked polymer containing an antibacterial polymer monomer, and an antibacterial polymer film containing the crosslinked polymer, which can exhibit improved bacterial growth inhibiting properties while maintaining the performance of an adhesive film.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0114960 dated August 30, 2021 and Korean Patent Application No. 10-2022-0097511 dated August 4, 2022, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to an antimicrobial polymer and an antimicrobial polymer film containing the same. [Background technology]

[0003] Recently, with the diversification of life, the improvement of living standards, and changes and improvements in consciousness, interest in promoting hygiene and comfort in personal living environments has increased. As a result, research on microorganisms that threaten these has been conducted, but the reality is that not only are there an extremely large number of types of microorganisms present in our daily living environments, but they are also distributed widely in the natural world, causing serious damage.

[0004] In particular, microorganisms such as bacteria and mold can inhabit various environments such as diet, living environment, clothing, and industrial products, and at this time, bacteria can cause various inflammations and food poisoning, while mold can cause problems such as bad odors and various skin diseases, respiratory diseases, allergies, atopic dermatitis, etc. Furthermore, microorganisms that inhabit the surfaces of electronic products and household goods can cause the performance of the products to deteriorate.

[0005] In particular, there has been an increasing trend recently to attach antibacterial films to parts of multipurpose facilities where contact with the human body is unavoidable due to the effects of the pandemic, etc. For this reason, various antibacterial substances have been developed to inhibit the growth of or kill microorganisms in order to prevent harm to humans caused by microorganisms.

[0006] In the case of antibacterial films, inorganic antibacterial agents are mainly used, which are manufactured by mixing inorganic particles (silver or copper, etc.) into the film to impart antibacterial properties. However, mixing inorganic particles has the advantage that antibacterial properties can be maintained even under high temperature conditions, but it has problems such as high cost, possibility of discoloration due to the metal ions contained after processing, and impaired basic physical properties due to increased viscosity and opacity of the film.

[0007] Meanwhile, organic antibacterial agents are another type of antibacterial substance that has been developed in the past. Organic antibacterial agents have the advantage of being cheaper than inorganic antibacterial agents and having excellent antibacterial effects even in small amounts, but they have the problem that they may dissolve after application to products and have poor antibacterial durability. Furthermore, although organic antibacterial agents can ensure product stability in terms of preventing and killing microbial proliferation, they are also toxic and can cause irritation to the skin of users.

[0008] For this reason, there is a demand for an antibacterial polymer composition that can be used as an antibacterial adhesive film, that does not elute from the film, that has sustained antibacterial properties, and that is safe, while maintaining the basic physical properties of the adhesive film. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention relates to an antibacterial polymer containing an antibacterial polymer monomer, and an antibacterial polymer film containing the same, which can exhibit improved bacterial growth inhibition properties while maintaining the performance of an adhesive film. [Means for solving the problem]

[0010] The present invention provides an antibacterial polymer, which is a crosslinked polymer of a polymerizable antibacterial monomer represented by the following chemical formula 1: a butyl-based rubber containing butylene-derived repeat units and isoprene repeat units; and a crosslinking agent:

[0011] [ka]

[0012] In the above 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; L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

[0013] The present invention also provides an antibacterial polymer film comprising the crosslinked polymer. Effect of the Invention

[0014] The antibacterial polymer of the present invention contains a polymerizable antibacterial monomer having antibacterial properties, and thus enables the production of a safe and stable antibacterial polymer film during the production into a film.

[0015] Specifically, the antibacterial polymer can be manufactured without any change in appearance when it is manufactured into a film because the polymerizable antibacterial monomer is cured during crosslinking of the monomer. As a result, while it exhibits antibacterial properties against at least one Gram-negative bacteria, the antibacterial monomer used does not remain in the resin, so there is no risk of human safety issues due to the elution of the antibacterial agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, the terms "include", "comprise", "have" or "have" are intended to specify the presence of an implemented feature, step, component, or combination thereof, and should be understood not to preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0017] In addition, in the present invention, when it is stated that each layer or element is formed "on" each other, it means that each layer or element is formed directly on each other, or that other layers or elements may be additionally formed between each layer, on the target body, or on the substrate.

[0018] Although the present invention can be modified in various ways and has various forms, specific embodiments are described in detail below. However, it is not intended to limit the present invention to the specific disclosed embodiments, and it should be understood that the present invention includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0019] Furthermore, the terminology used herein is for the purpose of referring to particular embodiments only and is not intended to limit the present invention, and the singular forms used herein include the plural forms unless the language clearly indicates otherwise.

[0020] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of the alkyl group 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, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like. Furthermore, in this specification, the above explanation regarding the alkyl group is applicable to the alkylene, except that the alkylene is a divalent group.

[0021] In general, in order to provide antibacterial properties to chemical products used in everyday living spaces such as homes, offices, and multipurpose facilities, antibacterial coatings capable of preventing and / or killing the growth of microorganisms such as bacteria are applied to the surfaces of such chemical products. In particular, due to the recent pandemic, there have been an increasing number of cases in multipurpose facilities where antibacterial films are additionally attached to items that are in contact with many people. In this case, the antibacterial agent contained in the antibacterial film damages the cell membrane or cell wall of microorganisms or induces the denaturation of these proteins, thereby inhibiting the growth of microorganisms and causing their growth and / or death.

[0022] There are more than 5,000 different types of bacteria that have been identified. Specifically, bacteria have a variety of cell shapes, including spherical, rod-shaped, and spiral, and the degree to which they require oxygen varies from bacteria to bacteria, and they are divided into aerobic, facultative, and anaerobic bacteria. Therefore, it is not easy for a single type of antibacterial agent to have a physical / chemical mechanism that can damage the cell membranes / cell walls of various bacteria or denature their proteins.

[0023] In addition, over time, the antibacterial agent used in the antibacterial coating may leach out, or if the user is exposed to persistent antibacterial agents, this may pose a threat to the user's health.

[0024] However, when an antibacterial polymer in which a polymerizable antibacterial monomer having a specific structure is cross-linked is used as an antibacterial polymer film, the antibacterial monomer does not leach out from the film, and the antibacterial polymer film exhibits antibacterial properties against gram-negative bacteria, and thus the present invention has been completed. When the amino group of the polymerizable antibacterial monomer represented by Chemical Formula 1 is positively charged by bonding with a proton, the interaction with the cell wall of the microorganism increases, and the alkyl group corresponding to the pendant group destabilizes the cell wall of the microorganism, inhibiting the growth of the microorganism, thereby exhibiting antibacterial properties.

[0025] The antibacterial polymer film contains the antibacterial monomer in a crosslinked form within the film by curing it together with the polymer (butyl rubber) that is the raw material of the film. Therefore, the appearance of the film does not change, and since the antibacterial monomer does not remain in the form of a compound within the antibacterial polymer film, there is no risk of the antibacterial agent leaching over time, and therefore the film can exhibit excellent safety and stability.

[0026] The antibacterial polymer and the antibacterial polymer film will be described in more detail below according to specific embodiments of the invention.

[0027] antibacterial polymer In one embodiment, the antibacterial polymer is a crosslinked polymer of a polymerizable antibacterial monomer represented by the following chemical formula 1: a butyl-based rubber containing butylene-derived repeat units and isoprene repeat units; and a crosslinker:

[0028] [ka]

[0029] In the above 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; L1 is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

[0030] Since most bacterial cell membranes are negatively charged, most antibacterial substances are positively charged. When a hydrogen cation (proton) is bonded to the amine of the compound represented by Chemical Formula 1, which exhibits cationicity, it is possible for the compound to interact with the bacterial cell membrane, and thus the compound represented by Chemical Formula 1 has antibacterial properties.

[0031] The polymerizable antibacterial monomer represented by Chemical Formula 1 is crosslinked with the butyl-based rubber described below to form the crosslinked polymer. The crosslinked polymer is formed by photopolymerization of the polymerizable antibacterial monomer, the butyl-based rubber, and the crosslinking agent, so the polymerizable antibacterial monomer also undergoes polymerization. In other words, the polymerizable antibacterial monomer does not exist as a separate compound in the antibacterial polymer film, but exists crosslinked with the butyl-based rubber, so it does not leak out over time, and is harmless to the human body while continuously maintaining the antibacterial properties of the film when it is manufactured into a polymer film.

[0032] In the above Chemical Formula 1, preferably, R1 and R2 are each hydrogen, and R3 may be methyl.

[0033] Also, preferably, R4 may be a substituted or unsubstituted alkyl having 1 to 10 carbon atoms, more preferably, R4 may be tertiary butyl. In general, the more carbon atoms at the R4 position, the higher the affinity with the bilayer of the outer cell wall of a microorganism, and thus the stronger the antibacterial activity. In the case of an alkyl having 8 or more carbon atoms, it is important that it has an appropriate length so that it can exhibit strong bactericidal activity even in water.

[0034] Preferably, R5 may be hydrogen. When R5 is an alkyl group, as described above, it can play a role in interacting with the outer cell wall of microorganisms. However, when R4 and R5 are all alkyl groups, the inductive effect of electrons increases, but the steric effect negatively affects the interaction between the cell membrane and the positive charge. On the other hand, when R5 is hydrogen, the steric effect is reduced and it is more easily bonded with protons to become positively charged, so that it can exhibit a stronger interaction with the negatively charged cell wall of microorganisms. Therefore, even when R4 is a tertiary butyl having a relatively small number of carbons, it can exhibit excellent antibacterial performance.

[0035] Preferably, L1 may be a substituted or unsubstituted alkylene having 1 to 5 carbon atoms, and more preferably, L1 may be ethylene.

[0036] As an example, the polymerizable antibacterial monomer may be a compound represented by the following formula 1-1:

[0037] [ka]

[0038] Meanwhile, the polymerizable antibacterial monomer is contained in the antibacterial polymer in an amount of 5 to 20 parts by weight based on 100 parts by weight of the butyl rubber. When the polymerizable antibacterial monomer is contained in a small amount, the performance of the adhesive film is equal to or better than that of a conventional film, but the antibacterial monomer is insufficient to show sufficient antibacterial effect, and when the polymerizable antibacterial monomer is contained in a large amount, the antibacterial performance can be very excellent, but the adhesive performance of the adhesive film is relatively reduced and a yellowish problem may occur in which the appearance turns yellow. Therefore, when the polymerizable antibacterial monomer satisfies the above range, it is possible to have excellent effects in both the performance of the adhesive film and the antibacterial performance.

[0039] More specifically, the polymerizable antibacterial monomer is contained in the antibacterial polymer in an amount 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, per 100 parts by weight of the butyl-based rubber.

[0040] Meanwhile, the antibacterial polymer includes a butyl-based rubber. The butyl-based rubber includes a butylene-derived repeating unit and an isoprene repeating unit. When the polymerizable antibacterial monomer and the butyl-based rubber are polymerized, the isoprene repeating unit and the polymerizable antibacterial monomer can be crosslinked.

[0041] Preferably, in the butyl-based rubber, the butylene-derived repeating unit may be an isobutylene repeating unit.

[0042] Preferably, the butyl-based rubber may contain butylene-derived repeating units and isoprene repeating units in a weight ratio of 90:10 to 99:1. When the weight ratio of the butylene-derived repeating units and isoprene repeating units of the butyl-based rubber is within the above range, a pressure-sensitive adhesive composition with excellent moisture barrier properties can be obtained. This is presumably due to a stacking effect caused by the double bonds in the isoprene-derived skeleton. More preferably, the weight ratio of the butylene-derived repeating units and isobutylene repeating units is 92:8 or more, 95:5 or more, 97:3 or more, or 98:2 or more, and may be 99:1 or less.

[0043] The butyl-based rubber may have a weight average molecular weight (Mw) of 50,000 g / mol or more and 2,000,000 g / mol or less. If the weight average molecular weight of the butyl-based rubber is less than 50,000 g / mol, the composition for film production may not have sufficient viscosity, making it difficult to apply uniformly when coating the substrate surface, and may not have sufficient physical properties as a sealant after coating is completed. If the weight average molecular weight exceeds 2,000,000 g / mol, the viscosity is high when preparing a coating liquid, making it difficult to prepare a uniform coating liquid, and the high viscosity may make it difficult to coat uniformly during the coating process. More preferably, the weight average molecular weight of the antibacterial polymer is 100,000 g / mol or more, 200,000 g / mol or more, 300,000 g / mol or more, 400,000 g / mol or more, or 500,000 g / mol or more, and may be 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.

[0044] Here, the weight average molecular weight (Mw) of the butyl rubber can be measured by gel permeation chromatography (GPC) using polystyrene (PS) as a standard sample for calibration. More specifically, 200 mg of the antibacterial polymer is diluted with 200 ml of N,N-dimethylformamide (DMF) solvent to prepare a sample of about 1000 ppm, and then the weight average molecular weight can be measured by an RI detector at a flow rate of 1 ml / min using an Agilent 1200 series GPC instrument. Here, the molecular weight of the sample can be calculated based on a calibration curve prepared using eight types of standard PS standards.

[0045] The crosslinking agent may be any compound that allows the introduction of crosslinking bonds during polymerization of the antibacterial polymer composition. Preferably, the crosslinking agent may be one selected from the group consisting of multifunctional (meth)acrylate monomers, multifunctional urethane (meth)acrylate oligomers, and mixtures thereof, and a photocurable multifunctional (meth)acrylate monomer is preferably used as the crosslinking agent.Examples of the polyfunctional (meth)acrylate include 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, adipate) di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, di(meth)acryloxyethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, ethylene oxide modified hexahydrophthalic acid di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene and other bifunctional acrylates; trimethylolpropane tri(meth)acrylate, dipentaerythritol trifunctional acrylates such as tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trifunctional urethane (meth)acrylate or tris(meth)acryloxyethyl isocyanurate; tetrafunctional acrylates such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; pentafunctional acrylates such as dipentaerythritol penta(meth)acrylate; and hexafunctional acrylates such as dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate or urethane (meth)acrylate, a reaction product of an isocyanate monomer and trimethylolpropane tri(meth)acrylate.These may be used alone or in combination of two or more. More preferably, tricyclodecane dimethanol diacrylate (TCDDA) may be used as the crosslinking agent.

[0046] Preferably, the crosslinking agent can be used in an amount of 5 to 20 parts by weight per 100 parts by weight of the butyl 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, per 100 parts by weight of the butyl rubber.

[0047] Antibacterial polymer film In another embodiment of the present invention, there is provided an antimicrobial polymer film comprising the antimicrobial polymer described above.

[0048] The antibacterial polymer film including the antibacterial polymer can be easily applied to various fields and is suitable for mass production. In addition, the polymerizable antibacterial monomer represented by Chemical Formula 1, which has an antibacterial effect, is polymerized into the polymer and does not dissolve, so that the antibacterial effect can be sustained for a long time.

[0049] Meanwhile, according to one embodiment of the present invention, the antibacterial polymer film can be prepared by curing an antibacterial polymer composition including the polymerizable antibacterial monomer represented by Chemical Formula 1, a butyl-based rubber, and a crosslinking agent, and a solvent and other additives without any particular limitation within a range that does not reduce the effect of the present invention. The solvent is not limited as long as it is a commonly used solvent, and may be added when mixing each component included in the antibacterial polymer composition, or each component may be added in a state of being dispersed or mixed in the solvent and then included in the antibacterial polymer composition. For example, the antibacterial polymer composition may include a solvent such that the total solid concentration of the components included is 1 wt% to 80 wt%, or 2 wt% to 50 wt%.

[0050] Non-limiting examples of the organic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, or isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran or propylene glycol monomethyl ether; toluene; or a mixture of two or more thereof.

[0051] For example, the additives may include a tackifier, a photoinitiator, a buffer, a wetting agent, a neutralizing agent, a polymerization terminator, and the like, and any one or more of these may be additionally included.

[0052] The tackifier may preferably be a hydrogenated cyclic olefin polymer. For example, a hydrogenated petroleum resin obtained by hydrogenating a petroleum resin can be used. The hydrogenated petroleum resin may be partially or completely hydrogenated, or may be a mixture of these resins. Such a tackifier can be selected from those that have good compatibility with the substances constituting the antibacterial polymer composition described above, excellent moisture blocking properties, and low organic volatile components. Specific examples of hydrogenated petroleum resins include hydrogenated terpene resins, hydrogenated ester resins, and hydrogenated dicyclopentadiene resins. The content of the tackifier can be appropriately adjusted as necessary. Most preferably, a hydrogenated dicyclopentadiene resin can be used as the tackifier.

[0053] The photoinitiator may be, but is not limited to, an alpha-hydroxyketone type compound, a benzyl ketal type compound, or a mixture thereof.Preferably, the alpha-hydroxyketone type compound may be 1-hydroxycyclohexyl-phenyl-ketone, 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.

[0054] Additives such as buffers, wetting agents, neutralizing agents, and polymerization terminators can be used without restriction as long as they are commonly used in the art.

[0055] The antibacterial polymer film can exhibit antibacterial properties against gram-negative bacteria. Gram-negative bacteria are a collective term for bacteria that are stained red by gram staining. Gram-negative bacteria have a cell wall with a relatively small amount of peptidoglycan compared to gram-positive bacteria, but have an outer membrane made of lipid polysaccharides, lipid proteins, and other complex polymeric substances. As a result, they are decolorized when stained with a basic dye such as crystal violet and then treated with ethanol, and show red color when counterstained with a red dye such as safranin. Examples of bacteria classified as gram-negative bacteria include Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae.

[0056] Preferably, the antibacterial polymer film is capable of exhibiting antibacterial properties against Escherichia coli (E. coli).

[0057] Specifically, the antibacterial property of the antibacterial polymer film against Escherichia coli (E. coli) can be evaluated using the antibacterial evaluation method of JIS Z 2081, and the bacterial growth inhibition rate can be confirmed by calculating using the following Equation 1. The E. coli growth inhibition rate of the antibacterial polymer composition measured in this manner is 70% or more, 72% or more, 80% or more, 84% or more, 90% or more, 92% or more, 95% or more, 96% or more, or 96.43% or more, and may be 100% or less, or 99.89% or less.

[0058] Specifically, the antibacterial properties can be measured by the following method: 4 400μl of PBS buffer solution inoculated with a concentration of CFU / ml is applied to an antibacterial polymer film measuring 5cm x 5cm. To prevent evaporation of water on the film surface, the film is covered with a PET film that has been disinfected with alcohol and dried, and then cultured for 24 hours. The bacteria cultured for 24 hours are sequentially diluted and smeared on solid agar medium to confirm and measure the number of bacteria based on the resulting clusters. The measurement can be carried out once or more than twice, and the results can be averaged.

[0059] On the other hand, the bacterial growth inhibition rate can be confirmed by calculating using the following mathematical formula 1.

[0060] [Formula 1] Bacterial suppression rate (%)=(1-S 24hrs / R 24hrs ) x 100

[0061] S 24hrs is the number of bacteria in the community confirmed by smearing on an agar medium after culturing the antibacterial treated sample for which the bacterial inhibition rate is to be confirmed for 24 hours, and R 24hrs means the number of bacteria in the colony confirmed by smearing on an agar medium after culturing the comparative example that was not subjected to antibacterial treatment for 24 hours.

[0062] The antibacterial polymer film of the present invention can have glass adhesion and viscosity at the same level as conventional materials that do not contain a polymerizable antibacterial monomer.

[0063] Preferably, the glass adhesion of the antibacterial polymer film may be 2300gf / 25mm or more and 2500gf / 25mm or less, more preferably 2350gf / 25mm or more, 2400gf / 25mm or more, or 2420gf / 25mm or more, and 2480gf / 25mm or less, or 2450gf / 25mm or less.

[0064] The glass adhesive strength of the antibacterial polymer film can be measured by the following method. After removing the release film from the antibacterial polymer film, the Cu side of the copper foil and PET film are laminated and attached to an adhesive film. The attached film is cut to a width of 25 mm and a length of 150 mm, and the prepared test piece is laminated and attached to a 90 mm x 150 mm glass plate at a temperature of 50°C. The glass plate of the prepared test piece is fixed, the film part is peeled off, and the low-speed peel strength is measured using the TA Tension mode of the TA.XTplus Textureanalyser. The low-speed peel strength measurement is carried out under the conditions of a speed of 5 mm / sec, a trigger force of 5.0 g, and a distance of 80 mm.

[0065] Preferably, the viscosity of the antibacterial polymer film may be 70,000 Pa·s or more and 90,000 Pa·s or less, more preferably 72,000 Pa·s or more, 75,000 Pa·s or more, 77,000 Pa·s or more, or 78,000 Pa·s or more, 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.

[0066] The viscosity of the antibacterial polymer film can be measured by the following method. First, the protective film (release film) of two identical adhesive film samples is removed, and the two sides are laminated to match the size of each side. Part of the periphery is removed, and the film is divided into two equal parts, one of the release films is removed, and the film is laminated again. This process is repeated until the thickness of the adhesive film is within the range of 500 to 800 μm. After measuring the exact thickness, the film is cut into a square size of 15 mm x 15 mm and measured using an ARES-G2 Rheometer. The measurement is performed in frequency sweep mode under conditions of strain 5% and temperature 27°C, and the complex viscosity at 1 Hz is measured.

[0067] The antibacterial polymer film may function as an adhesive or bonding film by itself by including a tackifier and curing it, or the antibacterial polymer composition may be coated on a substrate and then photo-cured to be used.

[0068] Specifically, according to one embodiment of the present invention, there is provided an antibacterial article comprising one or more substrates; and a coating layer provided on at least one surface of the substrate, the coating layer being formed by curing an antibacterial polymer composition including the above-mentioned antibacterial polymer.

[0069] The substrate may be, but is not limited to, a polymer film such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), polyimide (PI), polyethylene terephthalate (PET), polyvinyl chloride (PVC), etc.; a woven fabric; glass; a plastic foam such as urethane foam or polystyrene; raw wood; plywood; or a metal substrate.

[0070] In addition, the antibacterial article may be any of a variety of household chemical products, automobile parts, building materials, organic electronic devices, etc., which require antibacterial properties. For example, when the antibacterial polymer film is used in an organic electronic device, it can be used as a sealing film.

[0071] Specifically, the antibacterial article may be one or more selected from freshness-preserving materials, fabric products, agricultural films, organic electronic devices, various office supplies, and various packaging materials.

[0072] For example, the products may be packaging materials such as food packaging materials, vegetable packaging materials, grain packaging materials, fruit packaging materials, meat packaging materials, seafood packaging materials, and processed food packaging materials; freshness-preserving materials such as containers for vegetables, grains, fruits, meat, seafood, and processed foods; food tray mats; fabric products such as table mats, tablecloths, carpets, and seat covers; agricultural films; organic electronic devices; masks; office supplies such as tape, adhesive tape, masking tape, and masking film; flower packaging materials, plastic envelopes, easy-open packaging envelopes, shopping bags, standing bags, transparent packaging boxes, automatic packaging films, electronic component packaging materials, and machine component packaging materials.

[0073] The coating layer may have a thickness of, for example, 10 μm or more, 20 μm or more, 50 μm or more, 80 μm or more, 100 μm or more, or 150 μm or more 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. Such a coating layer may be formed by applying the antibacterial polymer composition to at least one surface of the substrate and then drying at a temperature of 40° C. to 80° C. for 60 minutes to 240 minutes to form a thin film coating.

[0074] The antibacterial polymer composition may be applied by any method and device that is commonly used, without particular limitation. For example, a bar coating method such as a Meyer bar, a gravure coating method, a two-roll reverse coating method, a vacuum slot die coating method, a two-roll coating method, etc. may be used.

[0075] The thickness of the antibacterial polymer film can be determined depending on the final use of the film. For example, the antibacterial polymer composition is coated to a thickness of 1 μm to 1,000 μm, or is manufactured into a single adhesive film.

[0076] In the step of photocuring the antibacterial polymer composition, ultraviolet rays or visible light having a wavelength of 200 to 400 nm may be irradiated, and the exposure dose during irradiation is 50 to 2,000 mJ / cm. 2 The exposure time is not particularly limited either, and can be appropriately changed depending on the exposure device used, the wavelength of the irradiated light, or the exposure dose.

[0077] In addition, in the step of photocuring the antibacterial polymer coating composition, nitrogen purging may be performed to apply nitrogen atmosphere conditions.

[0078] The present invention will be described in more detail below for a better understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[0079] [Example: Production of antibacterial polymer film] Comparative Example 1 A polymer composition was obtained by dissolving 99g of a solution of butyl rubber (weight average molecular weight 500,000g / mol, product name: BR268, ExxonMobil Chemical), a copolymer of 98% by weight of isobutene and 2% by weight of isoprene, in toluene to a solid content of 16% by weight, 20g of dicyclopentadiene hydrogenated resin (SU500, Kolon, solid content 70% by weight) dissolved in toluene as a tackifier, 1.6g of TCDDA (tricyclodecane dimethanol diacrylate) as a crosslinker, and 0.3g of Irgacure651 (2,2-dimethoxy-2-phenylacetophenone) as a photoinitiator in toluene and mixing them so that the total solid content was 22% by weight.

[0080] The prepared composition solution was filtered through a 400 mesh nylon filter, then coated on the release surface of a release PET film using a bar coater and dried in a dryer at 120°C for 4 minutes, and an additional release PET film was laminated on the release surface of the upper surface of the dried polymer film. A polymer film was prepared so that the thickness of the polymer film layer after drying was 30 to 40 μm. The polymer film was irradiated with ultraviolet rays at a total of 2 J / cm 2 It was cured by irradiation.

[0081] Reference example 1 An antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that the polymer composition further contained 3 parts by weight of 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer based on 100 parts by weight of butyl rubber in addition to the polymer composition of Comparative Example 1.

[0082] Reference example 2 An antibacterial polymer film was prepared in the same manner as in Comparative Example 1, except that the polymer composition further contained 25 parts by weight of 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer based on 100 parts by weight of butyl rubber in addition to the polymer composition of Comparative Example 1.

[0083] Example 1 An antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that the polymer composition further contained 13 parts by weight of 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer based on 100 parts by weight of butyl rubber in addition to the polymer composition of Comparative Example 1.

[0084] Example 2 An antibacterial polymer film was prepared in the same manner as in Comparative Example 1, except that the polymer composition further contained 19 parts by weight of 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer based on 100 parts by weight of butyl rubber in addition to the polymer composition of Comparative Example 1.

[0085] Example 3 An antibacterial polymer film was manufactured in the same manner as in Comparative Example 1, except that the polymer composition further contained 7 parts by weight of 2-(tert-butylamino)ethyl methacrylate (Sigma-Aldrich) as a polymerizable antibacterial monomer based on 100 parts by weight of butyl rubber in addition to the polymer composition of Comparative Example 1.

[0086] [Experimental Example] (1) Evaluation of antibacterial properties of antibacterial polymer films against Escherichia coli (E. coli) The antibacterial adhesive films prepared in the Examples and Comparative Examples were each subjected to an antibacterial evaluation.

[0087] Specifically, the number of bacteria was confirmed using the antibacterial evaluation method of JIS Z 2081 for antibacterial testing. 4 400μl of PBS buffer solution inoculated with a concentration of CFU / ml was applied to an antibacterial polymer film measuring 5cm x 5cm. To prevent evaporation of water from the film surface, the film was covered with a PET film that had been disinfected with alcohol and dried, and then cultured for 24 hours. The bacteria cultured for 24 hours were serially diluted and smeared on solid agar medium to count the number of bacteria based on the resulting clusters, and the results are shown in Table 1. The experiment was carried out twice, and the number of bacteria was counted each time and the average was calculated.

[0088] On the other hand, the bacterial growth inhibition rate was calculated as follows, and the results are shown in Table 1.

[0089] [Formula 1] Bacterial suppression rate (%)=(1-S 24hrs / R 24hrs ) x 100

[0090] S 24hrs is the number of bacteria in the community confirmed by smearing the example (antibacterial treated sample) on an agar medium after culturing for 24 hours, and R 24hrs means the number of bacteria in the colony confirmed by smearing the comparative example on an agar medium after culturing for 24 hours.

[0091] [Table 1]

[0092] Referring to Table 1, it can be seen that when an antibacterial film is manufactured using the antibacterial polymer composition of the Examples, it shows an excellent bacterial growth inhibition rate of 95% or more against Escherichia coli (E. coli), a gram-negative bacterium, unlike the antibacterial film of Comparative Example 1 which does not contain an antibacterial polymer. When the content of the antibacterial monomer is low as in Reference Example 1, it is determined that the antibacterial performance does not exceed the standard value and the antibacterial function is not expressed. In the case of Reference Example 2, it was confirmed that the content of the antibacterial monomer is high and therefore high antibacterial performance is expressed.

[0093] (2) Measurement of adhesion of antibacterial polymer film to glass After removing the release film from the antibacterial polymer film manufactured in the examples and comparative examples, the Cu side of the copper foil and PET film was laminated and attached to an adhesive film. The attached film was cut to a width of 25 mm and a length of 150 mm. The prepared test piece was attached to a 90 mm x 150 mm glass plate by lamination at a temperature of 50°C. The glass plate of the prepared test piece was fixed, the film part was peeled off, and the low-speed peel force was measured using the TA Tension mode of a TA.XTplus Texture Analyzer (Stable micro systems). The measurement of the low-speed peel force was carried out under the conditions of a speed of 5 mm / sec, a trigger force of 5.0 g, and a distance of 80 mm, and the results are shown in Table 2 below.

[0094] (3) Viscosity measurement of antibacterial polymer film First, the protective film (release film) of two identical adhesive film samples was removed, and the two sides were laminated to match the size of each side. Part of the periphery was removed, and the film was divided into two equal parts, one of the release films was removed, and the film was laminated again. This process was repeated until the thickness of the adhesive film was within the range of 500 to 800 μm, and the exact thickness was measured. The film was then cut into a square of 15 mm x 15 mm and measured using an ARES-G2 Rheometer (TA Instruments). The measurement was performed in frequency sweep mode under conditions of strain 5% and temperature 27°C, and the complex viscosity was measured at 1 Hz. The results are shown in Table 2 below.

[0095] [Table 2]

[0096] As shown in Table 2, it was confirmed that there was not much difference in adhesive strength between a film prepared by co-polymerizing an antibacterial monomer and a film that did not contain an antibacterial monomer. It was also confirmed that there was not much difference in viscosity, even in the examples having an antibacterial function, just like the adhesive strength to glass. Based on these results, it was confirmed that in the case of a polymerizable antibacterial substance, up to a certain content level, there is no significant effect on adhesive properties. However, as in Reference Example 2, it was confirmed that when the content of the antibacterial monomer was high, both the adhesive strength and viscosity decreased. This is believed to be due to the effect on the existing adhesive strength caused by the high copolymerization ratio of the antibacterial monomer.

Claims

1. A crosslinked polymer of a polymerizable antibacterial monomer represented by the following chemical formula 1; a butyl-based rubber containing butylene-derived repeating units and isoprene repeating units; and a crosslinking agent, An antimicrobial polymeric film comprising an antimicrobial polymer, including a tackifier: 【Chemistry 1】 In the above Chemical Formula 1, R １ ~R ３ are each independently hydrogen or methyl; R ４ and R ５ are each independently hydrogen or a substituted or unsubstituted alkyl having 1 to 20 carbon atoms; L １ is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

2. R １ and R ２ are hydrogen, R ３ is methyl, The antimicrobial polymeric film of claim 1 .

3. R ４ is tertiary butyl, The antimicrobial polymeric film of claim 1 .

4. R ５ is hydrogen, The antimicrobial polymeric film of claim 1 .

5. L １ is ethylene, The antimicrobial polymeric film of claim 1 .

6. The polymerizable antibacterial monomer represented by the formula 1 is represented by the following formula 1-1: The antibacterial polymeric film of claim 1 : 【Chemistry 2】

7. The polymerizable antibacterial monomer is used in an amount of 5 to 20 parts by weight per 100 parts by weight of the butyl rubber. The antimicrobial polymeric film of claim 1 .

8. The butylene-derived repeat unit is an isobutylene repeat unit. The antimicrobial polymeric film of claim 1 .

9. The butyl-based rubber contains butylene-derived repeating units and isoprene repeating units in a weight ratio of 90:10 or more and 99:1 or less. The antimicrobial polymeric film of claim 1 .

10. The weight average molecular weight of the butyl rubber is 50,000 g / mol or more and 2,000,000 g / mol or less. The antimicrobial polymeric film of claim 1 .

11. The crosslinking agent is any one selected from the group consisting of a multifunctional (meth)acrylate monomer, a multifunctional urethane (meth)acrylate oligomer, and a mixture thereof; The antimicrobial polymeric film of claim 1 .

12. The tackifier is a hydrogenated dicyclopentadiene (DCPD) resin. The antimicrobial polymeric film of claim 1 .

13. The antibacterial polymer film exhibits antibacterial properties against gram-negative bacteria. The antimicrobial polymeric film of claim 1 .

14. The gram-negative bacterium is Escherichia coli. The antimicrobial polymeric film of claim 13.

15. The antibacterial polymer composition is formed by curing an antibacterial polymer composition comprising: a polymerizable antibacterial monomer represented by the following chemical formula 1; a butyl-based rubber containing butylene-derived repeating units and isoprene repeating units; and a crosslinking agent. including a tackifier, Antibacterial polymer film: 【Chemistry 3】 In the above Chemical Formula 1, R １ ~R ３ are each independently hydrogen or methyl; R ４ and R ５ are each independently hydrogen or a substituted or unsubstituted alkyl having 1 to 20 carbon atoms; L １ is a substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

16. One or more substrates; and The antimicrobial polymer film according to claim 1 is provided on at least one surface of the substrate. Antibacterial articles.

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