Antimicrobial resin, composition for forming antimicrobial resin, and molded article containing antimicrobial resin

Abstract

The present invention relates to an antibacterial resin, an antibacterial resin-forming composition, and a molded article containing the antibacterial resin.

Description

[Technical Field]

[0001] This specification relates to antimicrobial resins, compositions for forming antimicrobial resins, and molded articles containing antimicrobial resins.

[0002] This application claims the benefits as of the filing date of Korean Patent Application No. 10-2022-0131742, filed with the Korean Intellectual Property Office on 13 October 2022, and Korean Patent Application No. 10-2023-0135730, filed with the Korean Intellectual Property Office on 12 October 2023, and all of its contents are incorporated herein by reference. [Background technology]

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

[0004] The required degree of antibacterial properties and the requirements for materials to impart antibacterial properties vary depending on the materials used in a product where antibacterial properties are required, as well as the final state in which the product is used. For example, the properties of the materials used to impart antibacterial properties and the degree of antibacterial properties will differ depending on the amount of antibacterial material applied to the product and the materials used in conjunction with it.

[0005] However, when introducing antibacterial agents that suppress bacterial growth into resins, it is not easy to select and introduce antibacterial agent components that exhibit excellent bacterial growth suppression properties, are harmless to the human body, are economically viable, and do not degrade the basic physical properties of the polymer resin.

[0006] Therefore, there is a need to develop a highly antibacterial material that is suitable for application in various products, yet does not release antibacterial substances and is harmless to the human body. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Korean Patent Publication No. 10-2009-0131847 [Overview of the project]

Problems to be Solved by the Invention

[0008] The present invention provides an antibacterial resin, a composition for forming an antibacterial resin, and a molded article containing them.

Means for Solving the Problems

[0009] One embodiment of the present specification includes a first repeating unit derived from propylene; and a second repeating unit derived from a monomer represented by the following Chemical Formula 1, and provides an antibacterial resin in which the weight ratio of the first repeating unit and the second repeating unit is 1:0.005 or more.

[0010]

Chemical Formula

[0011] In Chemical Formula 1, L1 is an alkylene group, R1 to R3 are the same as or different from each other, and are each independently an alkyl group, R4 is hydrogen or an alkyl group.

[0012] Another embodiment of the present specification provides the aforementioned composition for forming an antibacterial resin.

[0013] Another embodiment of the present specification provides a molded article containing or produced from the aforementioned antibacterial resin.

Effects of the Invention

[0014] The antibacterial resin according to some embodiments of the present specification has hydrophilicity and hydrophobicity and is excellent in antibacterial properties.

[0015] The antibacterial resin according to some embodiments of the present specification can solve the problem of safety due to the outflow of antibacterial substances.

[0016] According to some embodiments of the present specification, the antibacterial resin can exhibit antibacterial properties within a short period of time.

[0017] According to some embodiments of the present specification, the antibacterial resin has little change in antibacterial power depending on the amount of the antibacterial material used. Therefore, when applied to a product, even if an unintentional variation in concentration occurs, it can exhibit antibacterial properties within a predicted range. Thus, the antibacterial property can be controlled within a specific range, and an antibacterial property with excellent safety can be imparted.

[0018] According to some embodiments of the present specification, the antibacterial resin has low toxicity, so that the problem of safety can be solved.

Brief Description of the Drawings

[0019] [Figure 1] It is a diagram showing the NMR measurement results of the antibacterial resin according to some embodiments of the present specification.

Mode for Carrying Out the Invention

[0020] Hereinafter, the present invention will be described in detail.

[0021] One embodiment of the present specification includes a first repeating unit derived from propylene; and a second repeating unit derived from a monomer represented by the following Chemical Formula 1, and provides an antibacterial resin in which the weight ratio of the first repeating unit and the second repeating unit is 1:0.005 or more.

[0022]

Chem.

[0023] In the Chemical Formula 1, L1 is an alkylene group, R1 to R3 are the same as or different from each other and are each independently an alkyl group, R4 is hydrogen or an alkyl group.

[0024] Conventionally, to impart antibacterial properties to materials, antibacterial agents were simply mixed with polymers, using either inorganic or organic antibacterial agents. Inorganic antibacterial agents are expensive, prone to causing discoloration of materials, and can degrade the physical properties of polymers during processing such as extrusion and injection molding. Furthermore, inorganic antibacterial agents have the disadvantage of low immediate antibacterial activity. Organic antibacterial agents themselves have poor stability to the human body and poor thermal stability, resulting in inferior antibacterial persistence.

[0025] On the other hand, the antibacterial resin and antibacterial resin composition according to the present invention do not contain inorganic antibacterial agents, thus overcoming drawbacks such as discoloration and decreased transparency. Furthermore, since the antibacterial substance is polymerized as a monomer rather than being included as a separate substance, it has the advantage of excellent stability to the human body and sustained antibacterial properties. When organic antibacterial agents are applied to polymer polymerization, polymerization efficiency or conversion rate often decreases, or the inherent advantages of the polymer are impaired, but the present invention can eliminate such drawbacks. Due to the above advantages, the antibacterial resin according to this specification can exhibit excellent sustained antibacterial properties. In other words, the antibacterial resin according to this specification can have excellent antibacterial properties and sustained antibacterial properties while simultaneously improving stability due to the leaching of antibacterial agents.

[0026] Furthermore, the antibacterial resin according to the present invention is characterized in that the weight ratio of the first repeating unit to the second repeating unit is 1:0.005 or higher, and when this range is met, it exhibits excellent antibacterial properties and sustained antibacterial activity.

[0027] According to one embodiment of this specification, the weight ratio of the first repeating unit to the second repeating unit (first repeating unit:second repeating unit) is 1:0.005 to 1:0.5, and may be 1:0.005 to 1:0.3, or 1:0.005 to 1:0.1.

[0028] In this specification, when a part "includes" a component, this means, unless otherwise stated, that it may include other components rather than excluding them.

[0029] In this specification, “derived” means that a bond is broken between at least two adjacent elements in a compound, or a hydrogen atom or substituent is removed to form a new bond, and a unit derived from the compound can mean a unit that forms at least one of the main chain and side chains of a polymer. The unit can be included in the main chain of the polymer and constitute the polymer.

[0030] In this specification, "monomer" means a unit compound that can be converted into a polymer compound by a polymerization reaction, and whose derived structure can become a repeating unit within the polymer or copolymer. Specifically, this means that when the compound is polymerized and bonded within the polymer, all or some of two or more substituents are removed from the structure of the compound, and radicals for bonding with other units of the polymer are located in those positions. In this case, the compound may be included in a polymerized and bonded state in any order.

[0031] In this specification, "weight-average molecular weight" refers to one of the average molecular weights used as a reference when the molecular weights are not uniform, and is a value obtained by averaging the weight fractions of the molecular weights of the component molecular species of a polymer compound that has a molecular weight distribution.

[0032] In this specification, unless otherwise specified, physical properties that are affected by temperature are those measured at room temperature.

[0033] In this specification, "room temperature" means the natural temperature without heating or cooling, and refers to any temperature within the range of approximately 10°C to 30°C, for example, approximately 15°C, 18°C, 20°C, 23°C, or 25°C. Unless otherwise specified in this invention, the unit of temperature is °C.

[0034] In this specification, if pressure affects the results of a physical property, unless otherwise specified, the physical property is measured at normal pressure.

[0035] In this specification, "atmospheric pressure" refers to the natural pressure that is not pressurized or depressurized, and is usually defined as approximately 1 atmosphere (approximately 700-800 mmHg).

[0036] In this specification, if humidity affects the results of a physical property, unless otherwise specified, the physical property is the one measured at normal temperature and pressure with unadjusted humidity.

[0037] In this specification, the "alkyl group" may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. In one embodiment, the number of carbon atoms of the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl groups.

[0038] In this specification, "alkylene group" refers to an alkyl group with two bonding positions, i.e., a divalent group. The above description of alkyl groups can be applied to these groups, except that each of them is a divalent group.

[0039] In this specification, the term "antimicrobial resin" may mean the copolymer itself, which comprises a first repeating unit derived from propylene and a second repeating unit derived from the monomer represented by chemical formula 1, or it may mean a copolymer that further contains additional components in addition to the copolymer.

[0040] In this specification, * represents a bonding point within the antimicrobial resin. In this case, the bonding point may be a point where the same units bond with each other, or a point where different units bond with each other. For example, in the chemical formula 1-1 below, * represents both the part where the second repeating units bond with each other, and the part where the first repeating unit and the second repeating unit bond.

[0041] According to one embodiment of this specification, the monomer represented by chemical formula 1 is an antimicrobial material.

[0042] According to one embodiment of this specification, the second repeating unit is represented by the following chemical formula 1-1.

[0043] [ka]

[0044] In the above chemical formula 1-1, L1 is an alkylene group, R1 to R3 are either identical or different from each other, and each is an alkyl group independently. R4 is either hydrogen or an alkyl group. n² is an integer between 1 and 50,000. * indicates a bonding point within the antibacterial resin.

[0045] According to one embodiment of this specification, n2 is an integer between 2 and 40,000, an integer between 5 and 30,000, or an integer between 10 and 10,000.

[0046] According to one embodiment of this specification, R4 is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0047] According to one embodiment of this specification, R4 is a hydrogen atom or a methyl group.

[0048] According to one embodiment of this specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0049] According to one embodiment of this specification, L1 is an alkylene group having 1 to 5 carbon atoms.

[0050] According to one embodiment of this specification, L1 is a methylene group; an ethylene group; a propylene group; or a butylene group.

[0051] According to one embodiment of this specification, R1 to R3 are identical or different from each other and are each an alkyl group having 1 to 30 carbon atoms.

[0052] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 30 carbon atoms.

[0053] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 20 carbon atoms.

[0054] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 10 carbon atoms.

[0055] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 30 carbon atoms.

[0056] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 20 carbon atoms.

[0057] According to one embodiment of this specification, one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the remaining ones are identical or different from each other, and each is an alkyl group having 1 to 10 carbon atoms.

[0058] According to one embodiment of this specification, two or more of R1 to R3 are alkyl groups having 6 to 30 carbon atoms, or the difference in the number of carbon atoms between the alkyl group with the most carbon atoms and the alkyl group with the fewest carbon atoms among R1 to R3 is 5 or more.

[0059] Specifically, three of R1 to R3 are alkyl groups with 6 to 30 carbon atoms; two of R1 to R3 are alkyl groups with 6 to 30 carbon atoms and the remaining one is an alkyl group with 1 to 30 carbon atoms; or the difference in the number of carbon atoms between the alkyl group with the most carbon atoms and the alkyl group with the fewest carbon atoms among R1 to R3 is 5 or more. In this case, it shows excellent antibacterial activity.

[0060] According to one embodiment of this specification, a difference of 5 or more carbon atoms between the alkyl group with the most carbon atoms and the alkyl group with the fewest carbon atoms signifies a large asymmetry, and the difference in carbon atoms may be 5 to 30 or 5 to 10.

[0061] According to one embodiment of this specification, the monomer represented by chemical formula 1 has one of the following structures.

[0062] [ka]

[0063] According to one embodiment of this specification, the second repeating unit derived from the monomer represented by chemical formula 1 is one of the following structures.

[0064] [ka] [ka]

[0065] In the above configuration, * represents a bonding point within the antibacterial resin.

[0066] In one embodiment of the present specification, the copolymer contains 1 to 50,000 of the second repeating units. Specifically, it contains 2 to 40,000, 5 to 30,000, 10 to 10,000 or 20 to 5,000.

[0067] According to one embodiment of the present specification, since the monomer represented by Chemical Formula 1 exhibits cationicity, it may exist in the form of forming a salt together with a group exhibiting anionicity. Further, since the second repeating unit derived from the monomer represented by Chemical Formula 1 exhibits cationicity, it can exist in the form of forming a salt together with a group exhibiting anionicity. At this time, the group exhibiting anionicity is not particularly limited, and materials known in the art may be used as long as the purpose of antibacterial property is not impaired. For example, the group exhibiting anionicity may be a halogen-based anion, a sulfonate-based anion, a salicylate-based anion, a benzoate-based anion, a citrate-based anion, a tetrafluoroborate-based anion, a sorbate-based anion or a lactate-based anion.

[0068] Specifically, the group exhibiting anionicity is Br

[0071] , , , , Cl - , I - , F - , BF4 - , OH - , CF3COO - , CF3SO3 - , NO3 - , SH - ,

[0069]

Chemical formula

[0070] and may be, but are not limited to, these.

[0071] According to one embodiment of this specification, the second repeating unit is an antibacterial unit. That is, the second repeating unit enables the antibacterial resin to exhibit antibacterial properties. Specifically, the antibacterial properties of the antibacterial resin are derived from the aforementioned anionic and cationic functional groups contained in the antibacterial resin. Generally, the cell walls of bacteria and other organisms are often negatively charged, and the cationic functional groups can exert a destructive effect on these cell walls.

[0072] According to one embodiment of this specification, the first repeating unit derived from propylene is represented by the following chemical formula 2.

[0073] [ka]

[0074] In the aforementioned chemical formula 2, n1 is an integer between 1 and 50,000. * indicates a bonding point within the antibacterial resin.

[0075] According to one embodiment of this specification, n1 is an integer between 2 and 40,000, an integer between 5 and 30,000, or an integer between 10 and 10,000.

[0076] According to one embodiment of this specification, the first repeating unit undergoes desorption of hydrogen contained in the first repeating unit and combines with the second repeating unit, or the * portion combines with the second repeating unit.

[0077] According to one embodiment of this specification, the first repeating unit derived from the propylene monomer may be polypropylene.

[0078] According to one embodiment of this specification, the first repeating unit and the second repeating unit are graft polymerized. That is, one embodiment of this specification provides an antimicrobial resin comprising a polymer in which the first repeating unit and the second repeating unit are grafted. Specifically, one embodiment of this specification provides an antimicrobial resin comprising a first repeating unit derived from propylene; and a second repeating unit derived from the monomer represented by chemical formula 1 and grafted onto the first repeating unit. In this way, when the first repeating unit and the second repeating unit are graft polymerized, the antimicrobial substance is polymerized as a monomer rather than being included as a separate substance, which has the advantage of excellent biocompatibility and sustained antimicrobial properties.

[0079] According to one embodiment of this specification, the antimicrobial resin comprises a third repeating unit represented by the following chemical formula 3.

[0080] [ka]

[0081] In the aforementioned chemical formula 3, m1 and m2 are integers between 1 and 50,000, L1 is an alkylene group, R1 to R3 are either identical or different from each other, and each is an alkyl group independently. R4 is either hydrogen or an alkyl group. * represents a connection point within a repeating unit.

[0082] According to one embodiment of this specification, m1 and m2 are integers from 2 to 40,000, from 5 to 30,000, or from 10 to 10,000, respectively.

[0083] According to one embodiment of this specification, the third repeating unit represented by chemical formula 3 is a unit in which the first repeating unit and the second repeating unit are grafted.

[0084] According to one embodiment of this specification, the antimicrobial resin comprises a third repeating unit represented by the chemical formula 3.

[0085] According to one embodiment of this specification, in the grafted polymer, the first repeating unit is the main chain, and the second repeating unit is grafted to the main chain in the form of side chains.

[0086] In this specification, "having antibacterial properties" means having antibacterial activity, or in other words, a bacteriostatic reduction rate of 99% or more, as measured according to Method 1 below. This antibacterial activity may be 99% or more or 99.8% or more in other examples. There is no particular upper limit to this antibacterial activity; for example, the bacteriostatic reduction rate may be 100% or less or less than 100%.

[0087] According to one embodiment of this specification, the specific method for measuring the antibacterial activity, i.e., the bacteriostatic reduction rate, is the same as that of Method 1 described later.

[0088] According to one embodiment of this specification, the antimicrobial resin has an antimicrobial activity of 99% or more against any bacterial strain selected from the group consisting of Gram-positive bacteria, Gram-negative bacteria, and fungi, as measured by the method 1 described below.

[0089] [Method 1] The strain was divided into 1.6 × 10 5 Dilute the solution in 1XPBS to a concentration of CFU / mL. Place the antimicrobial resin and bacterial suspension in a 50mL conical tube (ratio = 0.1g / 5mL) and shake in a shaking incubator at 37°C for 1 hour to allow contact between the antimicrobial resin and bacterial suspension. Dilute this solution and spread it onto an agar medium plate. Perform serial dilution to enable colony counting, using 1XPBS in this process. The bacteriostatic performance should be determined by considering the initial microbial concentration (C) based on the dilution concentration. Reference After calculating the CFU / mL, the calculation is performed using the following formula.

[0090]

number

[0091] When the antibacterial activity of the antibacterial resin according to the present invention was evaluated using Method 1 described above, antibacterial activity was observed only when the antibacterial activity was 99% or higher. As a result, it was confirmed that the antibacterial resin according to the present invention has excellent antibacterial activity.

[0092] In this specification, Gram-positive bacteria are a general term for bacteria that stain purple when stained using the Gram staining method. The cell walls of Gram-positive bacteria are composed of multiple layers of peptidoglycan, and after staining with a basic dye such as crystal violet, they retain their purple color even after being treated with ethanol.

[0093] According to one embodiment of this specification, the Gram-positive bacteria are selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, it is one of the examples described above, but is not limited to these.

[0094] In this specification, Gram-negative bacteria are a general term for bacteria that stain red when stained using the Gram staining method, and instead of having a cell wall containing relatively small amounts of peptidoglycan compared to Gram-positive bacteria, they have an outer membrane composed of lipid polysaccharides, lipid proteins and / or other complex macromolecules.

[0095] According to one embodiment of this specification, the Gram-negative bacteria are selected from among Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, it is one of the examples described above, but is not limited to these.

[0096] According to one embodiment of this specification, the mold, or fungus, may be, but is not limited to, Candida albicans.

[0097] In the antibacterial resin having antibacterial properties, the strains of Gram-positive bacteria, Gram-negative bacteria, and fungi can not only induce various diseases upon contact but also potentially cause secondary infections. Therefore, it is preferable to use a single antibacterial agent that exhibits antibacterial activity against all of the Gram-positive bacteria, Gram-negative bacteria, and fungi.

[0098] According to one embodiment of this specification, the antibacterial resin has an antibacterial activity of 99% or more against Gram-positive bacteria as measured by Method 1.

[0099] According to one embodiment of this specification, the antibacterial resin has an antibacterial activity of 99% or more against Gram-negative bacteria as measured by Method 1.

[0100] According to one embodiment of this specification, the antibacterial resin has an antibacterial activity of 99% or more against fungi as measured by Method 1.

[0101] In the above method 1, "containing a bacteriostatic substance" may mean "containing a second repeating unit."

[0102] According to one embodiment of this specification, the weight-average molecular weight (Mw) of the antimicrobial resin is between 10,000 g / mol and 1,000,000 g / mol. If the weight-average molecular weight of the antimicrobial resin is less than 10,000 g / mol, it may exist in monomeric form rather than polymeric form and be easily eluted, and due to its low molecular weight, problems may arise with absorption into the human body. Furthermore, if the weight-average molecular weight of the antimicrobial resin exceeds 1,000,000 g / mol, the molecular weight becomes large and the viscosity becomes high, which may make application impossible or prevent dissolution in water. More preferably, the weight-average molecular weight (Mw: g / mol) of the antibacterial resin is 15,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, or 40,000 g / mol or more, while being 500,000 g / mol or less, 400,000 g / mol or less, 300,000 g / mol or less, 200,000 g / mol or less, or 150,000 g / mol or less.

[0103] According to one embodiment of this specification, the antimicrobial resin has a number average molecular weight (Mn) of 20,000 g / mol to 200,000 g / mol. More preferably, the number average molecular weight of the antimicrobial resin is 25,000 g / mol or more, 30,000 g / mol or more, 35,000 g / mol or more, or 40,000 g / mol or more, or 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less.

[0104] According to one embodiment of this specification, the weight-average molecular weight and the number-average molecular weight can be measured by high-temperature GPC (Gel Premeation Chromatography). The high-temperature GPC can be any method used in the art without limitation.

[0105] According to one embodiment of this specification, the antimicrobial resin may have a molecular weight distribution (Mw / Mn) in the range of 1 to 3. In other examples, the molecular weight distribution is 1.1 or more, 1.2 or more, 1.3 or more or 1.4 or more, or 2.8 or less, 2.6 or less, 2.4 or less, 2.2 or less, 2.0 or less, 1.8 or less or 1.6 or less.

[0106] In one embodiment of this specification, the end groups of the antimicrobial resin are

[0107] [ka]

[0108] Therefore, L1 and R1-R4 are defined similarly to those in Chemical Formula 1.

[0109] [ka]

[0110] This refers to the portion that is connected to the main chain or side chain of the antimicrobial resin.

[0111] One embodiment of this specification provides the aforementioned antimicrobial resin-forming composition.

[0112] According to one embodiment of this specification, the antimicrobial resin-forming composition comprises polypropylene; a monomer represented by chemical formula 1; and an initiator.

[0113] According to one embodiment of this specification, the polypropylene is included in an amount of 70 to 99.5 parts by weight per 100 parts by weight of the antimicrobial resin-forming composition. Specifically, it is included in an amount of 80 to 99.5 parts by weight, 90 to 99.5 parts by weight, or 95 to 99.5 parts by weight.

[0114] According to one embodiment of this specification, the monomer represented by chemical formula 1 is contained in an amount of 0.4 to 20 parts by weight per 100 parts by weight of the antibacterial resin-forming composition. Specifically, it is contained in an amount of 0.5 to 15 parts by weight, 0.5 to 10 parts by weight, or 0.5 to 5 parts by weight. When the content of the monomer represented by chemical formula 1 satisfies the above range, it exhibits excellent antibacterial properties and sustained antibacterial activity.

[0115] According to one embodiment of this specification, the initiator may be a peroxide compound such as dicumyl peroxide, dipentyl peroxide, di-3,5,5-trimethylhexanoyl peroxide or dilauryl peroxide; a peroxydicarbonate compound such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate or di-2-ethylhexyl peroxydicarbonate; a peroxyester compound such as t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate or t-butyl peroxyneodecanoate; an azo compound such as azobis-2,4-dimethylvaleronitrile; a hydroperoxide compound such as t-butyl hydroperoxide; or a sulfate compound such as potassium persulfate or ammonium persulfate. One or more of these may be used, but are not limited to the above examples.

[0116] According to one preferred embodiment of this specification, the initiator is dicumyl peroxide (DCP).

[0117] According to one embodiment of this specification, the initiator is included in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the antibacterial resin-forming composition. Specifically, it is included in amounts of 0.01 to 4 parts by weight, 0.01 to 3 parts by weight, 0.01 to 2 parts by weight, 0.01 to 1 part by weight, or 0.01 to 0.5 parts by weight. In this case, if the amount of the initiator is less than 0.01 parts by weight, the polymerization reaction time will be prolonged, the polymerization conversion efficiency will be low, and productivity may decrease. Specifically, the polymerization conversion efficiency will be low, and there is a disadvantage in that a large amount of residual monomers and decomposition products will be generated. On the other hand, if it exceeds 10 parts by weight, the initiator may not be completely consumed during the polymerization process and may remain in the final polymer produced, potentially degrading the polymer's physical properties, especially its thermal stability.

[0118] One embodiment of this specification provides a molded article containing or manufactured from the aforementioned antimicrobial resin. The molded article may, but is not limited to, automotive parts, blow-molded articles, blow-molded articles, cast articles, extruded laminate articles, extruded articles, foamed articles, injection-molded articles, sheets, films, fibers, monofilaments, or nonwoven fabrics. The automotive parts may include interior and exterior materials for automobiles. [Examples]

[0119] The present invention will be described in detail below with reference to examples. However, the examples of the present invention can be modified in various other forms, and the scope of this specification should not be construed as being limited to the examples described below. The examples of this specification are provided to give a more complete explanation of the present invention to a person of average skill in the art.

[0120] <Manufacturing Example 1> Manufacturing of monomers represented by chemical formula 1 Manufacturing Example 1-1. Synthesis of Compound 1, Compound 2, and Compound 3 Step 1. (1) 0.1 mol of 2-(dibutylamino)ethanol (DBAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of acryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0121] Step 2. (1) The product from Step 1 was dissolved in acrylonitrile (solvent) at a 50 wt% concentration in a 1:1 molar ratio with 1-bromooctane (1-boromooctane, for the production of compound 1), 1-bromodecane (1-boromodecane, for the production of compound 2), or 1-bromododecane (1-boromododecane, for the production of compound 3). (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0122] Manufacturing Example 1-2. Synthesis of Compound 4 Step 1 (1) 0.1 mol of 2-(Dioctylamino)ethanol (DOAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of acryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0123] Step 2 (1) The product from Step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0124] Manufacturing Example 1-3. Synthesis of Compound 5 Step 1. (1) 0.1 mol of 2-(dihexylamino)ethanol (DHAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0125] Step 2. (1) The product from Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0126] Production Example 1-4. Synthesis of Compound 6 Step 1. (1) 0.1 mol of 2-(butylhexylamino)ethanol (BHAE, 2-(butylhexylamino)ethanol), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0127] Step 2. (1) The product from Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0128] Manufacturing Example 1-5. Synthesis of Compound 7 Step 1. (1) 0.1 mol of 2-(butyloctylamino)ethanol (BOAE, 2-(butyloctylamino)ethanol), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0129] Step 2. (1) The product from Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0130] Production Example 1-6. Synthesis of Compound 8 Step 1. (1) 0.1 mol of 2-(butyldecylamino)ethanol (BOAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0131] Step 2. (1) The product from Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0132] Production Example 1-7. Synthesis of Compound 9 Step 1. (1) 0.1 mol of 2-(dibutylamino)butanol (DBAB), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of acryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

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

[0134] Production Example 1-8. Synthesis of Compound 10 Step 1. (1) 0.1 mol of 2-(Dioctylamino)butanol (DOAB), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of acryloyl chloride was added dropwise to the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After filtering to remove the triethylamine salt, the solvent was removed using a rotary evaporator. (5) Vacuum-dried at 83°C to 87°C.

[0135] Step 2. (1) The product from Step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 at a concentration of 50 wt%. (2) Next, p-methoxyphenol, a polymerization inhibitor, was added (in a ratio of 1:0.001 (eq) to the reactants). (3) The reaction was carried out at 50°C for 20 hours. (4) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1 (volume ratio)), and then the mixture was filtered. (5) Vacuum-dried at 45°C.

[0136] Production Example 1-9. Synthesis of Compound 11 (1) Acetonitrile (30 mL) was placed in a two-neck RBF (Round Bottom Flask), and 7.86 g of 2-(dimethylamino)ethyl methacrylate (0.05 mol), 11.1 g of bromodecane (0.05 mol), and 4-methoxyphenol (4 mg) were added. (2) The reaction was carried out at 45°C for 16 hours with stirring. (3) Static precipitation was performed on methyl t-butyl ether (MTBE) (MTBE:reaction solution = 15:1), and then the mixture was filtered.

[0137] Production Examples 1-10. Synthesis of Compound 12 Compound 12 was prepared in the same manner as the synthesis method in Production Example 9, except that bromododecane was used instead of bromodecane in Production Example 9.

[0138] In the above production examples 1-1 to 1-10, a static precipitation method was used in which the reactants were added to a nonsolvent. However, a reverse precipitation method, in which the nonsolvent is added to the reactants, can also be used. In addition, the ratio of MTBE to the reaction solution may be other than 15:1; for example, 12:1 or 26:1 may be used.

[0139] The structures of compounds 1 to 12 produced in the above production examples 1-1 to 1-10 are as follows.

[0140] [ka] [ka]

[0141] <Manufacturing Example 2> Manufacturing of antibacterial resin Manufacturing Example 2-1. When the internal temperature of the internal mixer reached 160°C, polypropylene (PP, LG Chem, MH1700) was added and melted. After 5 minutes, compound 1 (1 wt% of PP) produced in Production Example 1 and the initiator DCP (0.1 wt% of total) were added, and a graft reaction was carried out with stirring for 30 minutes. After the reaction was complete, the internal mixer was disassembled to obtain a lump-shaped sample. This was finely ground into a powder, washed (H2O, 50°C, 24 hours) to remove unreacted monomers, and dried to obtain sample 1.

[0142] Manufacturing examples 2-2 to 2-12. Samples 2 to 12 were prepared in the same manner as in Production Example 2-1, except that the compounds listed in Table 1 below were used instead of compound 1.

[0143] [Table 1]

[0144] Manufacturing example 2-13. Sample 13 was prepared in the same manner as in Production Example 2-1, except that compound 11 (5 wt% of PP) was used instead of compound 1 (1 wt% of PP) and DCP (0.5 wt% of total) was used instead of DCP (0.1 wt% of total).

[0145] Manufacturing example 2-14. Sample 14 was prepared in the same manner as in Production Example 2-1, except that compound 11 (0.3 wt% of PP) was used instead of compound 1 (1 wt% of PP) and DCP (0.01 wt% of total) was used instead of DCP (0.1 wt% of total).

[0146] 1 The production of samples 1 to 14 was confirmed by measuring 1H NMR. Specifically, the NMR measurement method is as follows:

[0147] - Experimental equipment: Bruker 600MHz NMR - Solvent: TCE-d2 (1,1,2,2-Tetrachloroethane-d2) - Experimental temperature: 120℃ - Sample preparation: Place 10 mg of the sample into a vial at room temperature, add 0.7 mL of TCE-d2, and then completely dissolve the sample using a heat gun. After that, transfer to an NMR tube and sample.

[0148] Figure 1 and Table 2 show the results for samples 11, 13, and 14. 1 The results of the 1H NMR measurement are shown.

[0149] In Figure 1, (a) is sample 13. 1 The 1H NMR measurement results are shown, and (b) is for sample 11. 1 The 1H NMR measurement results are shown, and (c) is for sample 14. 1 The results of the 1H NMR measurement are shown.

[0150] [Table 2]

[0151] Table 2 and Figure 1 confirm that an antimicrobial resin containing a first repeating unit derived from propylene and a second repeating unit derived from the monomer represented by chemical formula 1 was produced.

[0152] Manufacturing example 2-15. Compound 11, produced in Production Examples 1-9, was added at a concentration of 1 wt% to PP (LG Chem, MH1700) and simply mixed. After washing (H2O, 50°C, 24 hours), the mixture was dried to obtain sample 15.

[0153] Manufacturing example 2-16. Compound 12, produced in Production Examples 1-10, was added at a concentration of 1 wt% to PP (LG Chem, MH1700) and simply mixed. After washing (H2O, 50°C, 24 hours), the mixture was dried to obtain sample 16.

[0154] <Example> Antimicrobial activity measurement Example 1. Standard strain of E. coli ATCC 25922: 1.6 × 10⁶ 5 Dilute the sample in 1XPBS solution to a concentration of CFU / mL. Place sample 1 and the bacterial suspension in a 50mL conical tube (ratio = 0.1g / 5mL) and shake in a shaking incubator at 37°C for 1 hour to allow the sample 1 and bacterial suspension to come into contact. Dilute this solution and spread it onto an agar medium plate. Perform serial dilution to enable colony counting, using 1XPBS in this process. The antimicrobial activity is determined by considering the dilution concentration and the initial microbial concentration (C). Referenece After calculating the CFU / mL, use the following formula to perform the calculation.

[0155]

number

[0156] Examples 2-12. The antibacterial activity was measured in the same manner as in the manufacturing method of Example 1, except that the samples in Table 3 below were used instead of Sample 1 in Example 1.

[0157] Comparative Examples 1-3. The antibacterial activity was measured in the same manner as in the manufacturing method of Example 1, except that the samples in Table 3 below were used instead of Sample 1 in Example 1.

[0158] Comparative Example 4. In Example 1 described above, antibacterial activity was measured using PP (LG Chem, MH1700) instead of Sample 1.

[0159] The antibacterial activity calculated in Examples 1-12 and Comparative Examples 1-4 is shown in Table 3 below.

[0160] In Table 3 below, the control is a bacterial inoculation culture without the added sample, and it serves as a measure to determine whether or not the bacteria grew properly. Examples 1-12 and Comparative Examples 1-4 were conducted after confirming the reliability of the experiment using the control in Table 3 below.

[0161] [Table 3]

[0162] As shown in Table 3 above, when polypropylene alone is included (Comparative Example 4) and when polypropylene is simply blended with the monomer represented by chemical formula 1 (antimicrobial monomer) (Comparative Examples 1 and 2), the antimicrobial monomer is washed away with water during the sample manufacturing process, resulting in a low antimicrobial activity of 5% or less. From this, it can be confirmed that when polypropylene and the antimicrobial monomer are simply blended, even if the antimicrobial monomer is added, it can be separated by physical methods such as washing, washed away and removed, and does not exhibit sustained antimicrobial activity, as in the case where only polypropylene is included (Comparative Example 4).

[0163] Furthermore, when the antibacterial monomer content in the PP resin was 0.3 wt% (Comparative Example 3), it was confirmed that when the weight ratio of repeating units derived from propylene monomer (first repeating units) to repeating units derived from antibacterial monomer (second repeating units, the antibacterial monomer is represented by chemical formula 1) fell outside the range of 1:0.005 or greater, the antibacterial activity decreased to 98%, a significant decrease in antibacterial activity.

[0164] On the other hand, the antimicrobial resin according to the embodiments of this specification (group of examples) uses a polymer grafted with repeating units derived from propylene monomers (first repeating units) and repeating units derived from antimicrobial monomers (second repeating units), and it can be confirmed that it does not separate by physical means, there is no risk of leakage, and it exhibits antimicrobial activity of 99% or more.

[0165] In particular, when the chemical formula of the antimicrobial monomer shows that two or more of R1 to R3 are alkyl groups with 6 or more carbon atoms (Examples 4, 5, 7, 8, and 10), or when the difference in the number of carbon atoms between the alkyl group with the most carbon atoms and the alkyl group with the fewest carbon atoms among R1 to R3 is 5 or more (i.e., when there is a large asymmetry in the structure of the antimicrobial monomer) (Examples 2, 3, 6, 11, and 12), it can be confirmed that the antimicrobial activity is excellent, at 99.99% or more. Furthermore, in the antimicrobial resin according to the embodiments of this specification, the weight ratio of the first repeating unit to the second repeating unit falls within the range of 1:0.005 or more, thus confirming that the antimicrobial activity is 99% or more.

Claims

1. A first repeating unit derived from propylene; and It contains a second repeating unit derived from the monomer represented by the chemical formula 1 below, The weight ratio of the first repeating unit and the second repeating unit is 1:0.005 or greater, antibacterial resin: 【Chemistry 1】 In the aforementioned chemical formula 1, L1 is an alkylene group, Three of R1 to R3 are alkyl groups having 6 to 30 carbon atoms; or two of R1 to R3 are alkyl groups having 6 to 30 carbon atoms, and the remaining one is an alkyl group having 1 to 30 carbon atoms. R4 is either hydrogen or an alkyl group.

2. The antimicrobial resin according to claim 1, wherein the first repeating unit and the second repeating unit are graft polymerized.

3. The antibacterial resin according to claim 1, wherein the weight ratio of the first repeating unit and the second repeating unit is 1:0.005 to 1:0.

5.

4. The antibacterial resin according to claim 1, wherein the monomer represented by the chemical formula 1 has any of the following structures: 【Chemistry 2】

5. The first repeating unit is the antibacterial resin according to claim 1, represented by the following chemical formula 2: 【Transformation 3】 In the aforementioned chemical formula 2, n1 is an integer between 1 and 50,000. * indicates a bonding point within the antibacterial resin.

6. The antibacterial resin according to claim 1, comprising a third repeating unit represented by the following chemical formula 3: 【Chemistry 4】 In the aforementioned chemical formula 3, m1 and m2 are integers between 1 and 50,000, L1 is an alkylene group, R1 to R3 are either identical or different from each other, and each is independently an alkyl group. R4 is hydrogen or an alkyl group. * indicates a bonding point within the antibacterial resin.

7. The antibacterial resin according to claim 1, wherein the weight-average molecular weight of the antibacterial resin is 10,000 g / mol to 1,000,000 g / mol.

8. The antibacterial resin according to claim 1, which has an antibacterial activity of 99% or more against any bacterial strain selected from the group consisting of Gram-positive bacteria, Gram-negative bacteria, and fungi, as measured by the following method 1: [Method 1] The bacterial strain was divided into 1.6 x 10 ５ Dilute the antimicrobial resin with 1XPBS solution at a concentration of CFU / mL. Place the antimicrobial resin and bacterial suspension in a 50 mL conical tube (ratio = 0.1 g / 5 mL) and shake in a shaking incubator at 37°C for 1 hour to bring the antimicrobial resin and bacterial suspension into contact. Dilute this solution and spread it onto an agar medium plate. Perform serial dilution to enable colony counting, using 1XPBS in this process. Antimicrobial activity is determined by considering the dilution concentration and the initial microbial concentration (C Ｒｅｆｅｒｅｎｃｅ After calculating the CFU / mL, the calculation is performed using the following formula. [Math 1]

9. The antimicrobial resin according to claim 8, wherein the Gram-positive bacteria are selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis.

10. The antimicrobial resin according to claim 8, wherein the Gram-negative bacteria are selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae.

11. The antibacterial resin-forming composition according to any one of claims 1 to 10.

12. The antibacterial resin-forming composition according to claim 11, comprising polypropylene; a monomer represented by the chemical formula 1; and an initiator.

13. A molded article comprising or manufactured therefrom the antimicrobial resin described in any one of claims 1 to 10.

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