Antibacterial resin, composition for forming antibacterial resin, and molded body containing antibacterial 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] The present specification relates to an antibacterial resin, an antibacterial resin-forming composition, and a molded article including the antibacterial resin.

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

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

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

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

[0006] Therefore, there is a need to develop highly antibacterial materials suitable for use in a variety of products, which do not release antibacterial substances and are harmless to the human body. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent Publication No. 10-2009-0131847 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides an antibacterial resin, an antibacterial resin-forming composition, and a molded article containing the same. [Means for solving the problem]

[0009] One embodiment of the present invention is a polymer comprising a first repeat unit derived from propylene; and The second repeating unit is derived from a monomer represented by the following chemical formula 1: The antibacterial resin has a weight ratio of the first repeating unit to the second repeating unit of 1:0.005 or more.

[0010] [ka]

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

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

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

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

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

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

[0017] The antibacterial resin according to some embodiments of the present specification exhibits little change in antibacterial activity depending on the amount of antibacterial material used, and therefore, even if the concentration of the antibacterial resin is unintentionally varied when applied to a product, the antibacterial activity can be controlled within a specific range, and antibacterial activity with excellent safety can be imparted.

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

[0019] [Figure 1] FIG. 2 shows NMR measurement results of an antibacterial resin according to some embodiments of the present specification. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention will be described in detail below.

[0021] One embodiment of the present invention is a polymer comprising a first repeat unit derived from propylene; and The antibacterial resin includes a second repeating unit derived from a monomer represented by the following chemical formula 1, and the weight ratio of the first repeating unit to the second repeating unit is 1:0.005 or more.

[0022] [ka]

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

[0024] Conventionally, in order to impart antibacterial power to a material, an antibacterial agent is simply mixed with a polymer, and inorganic or organic antibacterial agents are used in this case. The inorganic antibacterial agents are expensive, tend to cause discoloration of the material, and can reduce the physical properties of the polymer during processing such as extrusion and injection. In addition, inorganic antibacterial agents have the disadvantage of low immediate antibacterial effect. The organic antibacterial agents themselves have the disadvantage of poor stability to the human body and poor thermal stability, resulting in poor antibacterial durability.

[0025] Meanwhile, the antibacterial resin and antibacterial resin composition according to the present invention do not contain an inorganic antibacterial agent, and therefore, are able to overcome drawbacks such as discoloration and reduced transparency. In addition, since the antibacterial substance is not contained as a separate substance but is polymerized as a monomer, there are advantages in that the stability in the human body is excellent and antibacterial durability is maintained. When an organic antibacterial agent is applied to the polymerization of a polymer, the polymerization efficiency or conversion rate is often reduced, and the inherent advantages of the polymer are often lost, but the present invention can also solve such drawbacks. Due to the above advantages, the antibacterial resin of the present invention can exhibit excellent antibacterial durability. That is, the antibacterial resin of the present invention has excellent antibacterial properties and antibacterial durability, while at the same time improving stability against antibacterial agent leakage.

[0026] In addition, the antibacterial resin of 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 more, and when this range is satisfied, it has the effect of exhibiting excellent antibacterial properties and antibacterial durability.

[0027] According to one embodiment of the present 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 is said to "comprise" a certain component, this means that it may further include other components, rather than excluding other components, unless specifically stated to the contrary.

[0029] In the present specification, the term "derived from" means that a bond between at least two adjacent elements in a compound is broken or a new bond is generated by the detachment of hydrogen or a substituent, and the unit derived from the compound may mean a unit forming at least one of the main chain and the side chain of a polymer. The unit may be included in the main chain of the polymer to constitute the polymer.

[0030] In the present specification, the term "monomer" refers to a unit compound that can be converted into a polymeric compound by a polymerization reaction, and the structure derived therefrom can become a repeating unit in a polymer or copolymer. Specifically, this means that when the compound is polymerized and bound to a polymer, all or a part of two or more substituents are removed from the structure of the compound, and a radical for binding to other units of the polymer is located at the position. In this case, the compound may be included in a state of being bound to the polymer by polymerization in any order.

[0031] In this specification, the term "weight average molecular weight" refers to one of the average molecular weights in which the molecular weight of a polymeric substance is not uniform and is used as a standard, and is a value obtained by averaging, by weight fraction, the molecular weights of component molecular species of a polymeric compound having a molecular weight distribution.

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

[0033] In this specification, "room temperature" refers to a natural temperature that is neither heated nor cooled, and means, for example, any temperature within a range of about 10° C. to 30° C., such as about 15° C., about 18° C., about 20° C., about 23° C., or about 25° C. In addition, unless otherwise specified in the present invention, the unit of temperature is ° C.

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

[0035] In this specification, "normal pressure" refers to the natural pressure that is neither increased nor decreased, and generally refers to approximately 1 atmosphere (approximately 700 to 800 mmHg).

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

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

[0038] In this specification, the term "alkylene group" refers to an alkyl group having two bonding positions, i.e., a divalent group. The above description of the alkyl group can be applied to these groups, except that they are both divalent groups.

[0039] In the present specification, the "antibacterial resin" may mean a copolymer itself including the first repeating unit derived from the propylene and the second repeating unit derived from the monomer represented by Chemical Formula 1, or may mean a copolymer further including additional components.

[0040] In this specification, * means a bonding point in the antibacterial resin. In this case, the bonding point may be a bonding point between the same units or a bonding point between different units. As an example, in the following chemical formula 1-1, * means both the bonding portion between the second repeating units and the bonding portion between the first repeating unit and the second repeating unit.

[0041] According to one embodiment of the present specification, the monomer represented by Chemical Formula 1 is an antibacterial material.

[0042] According to one embodiment of the present 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 the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; n2 is an integer from 1 to 50,000; * denotes binding points within the antibacterial resin.

[0045] According to one embodiment of the present specification, n2 is an integer from 2 to 40,000, an integer from 5 to 30,000, or an integer from 10 to 10,000.

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

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

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

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

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

[0051] According to one embodiment of the present specification, R1 to R3 are the same or different and each independently represents an alkyl group having 1 to 30 carbon atoms.

[0052] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0053] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms.

[0054] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 30 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.

[0055] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 30 carbon atoms.

[0056] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 20 carbon atoms.

[0057] According to one embodiment of the present specification, any one of R1 to R3 is an alkyl group having 5 to 20 carbon atoms, and the rest are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.

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

[0059] Specifically, three of R1 to R3 are alkyl groups having 6 to 30 carbon atoms; two of R1 to R3 are alkyl groups having 6 to 30 carbon atoms and the remaining one is an alkyl group having 1 to 30 carbon atoms; or the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number among R1 to R3 is 5 or more, in which case excellent antibacterial effect is exhibited.

[0060] According to one embodiment of the present specification, the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number being 5 or more means that the asymmetry is large, and the difference in carbon number may be 5 to 30, or 5 to 10.

[0061] According to one embodiment of the present specification, the monomer represented by the above Chemical Formula 1 has any one of the following structures:

[0062] [ka]

[0063] According to one embodiment of the present specification, the second repeating unit derived from the monomer represented by Chemical Formula 1 has any one of the following structures:

[0064] [ka] [ka]

[0065] In the above configuration, * is a binding 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, 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, the monomer represented by Chemical Formula 1 exhibits cationicity and may exist in the form of a salt together with a group exhibiting anionicity. In addition, the second repeating unit derived from the monomer represented by Chemical Formula 1 exhibits cationicity and may exist in the form of a salt together with a group exhibiting anionicity. In this case, the group exhibiting anionicity is not particularly limited, and materials known in the art may be used as long as they do not impair the purpose of antibacterial properties. 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 anionic group is Br - , Cl - , I - , F - , BF4 - , O.H. - , CF3COO - , CF3SO3 - , NO3 - , S.H. - ,

[0069] [ka]

[0070] It may be, but is not limited to these.

[0071] According to one embodiment of the present specification, the second repeating unit is a unit exhibiting antibacterial properties. That is, the second repeating unit allows the antibacterial resin to exhibit antibacterial properties. Specifically, the antibacterial properties of the antibacterial resin are derived from the anionic functional group and cationic functional group contained in the antibacterial resin. In general, cell walls of bacteria and the like are often negatively charged, and the cationic functional group can have a destructive effect on the cell walls.

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

[0073] [ka]

[0074] In the above Chemical Formula 2, n1 is an integer from 1 to 50,000, * denotes binding points within the antibacterial resin.

[0075] According to one embodiment of the present specification, n1 is an integer from 2 to 40,000, an integer from 5 to 30,000, or an integer from 10 to 10,000.

[0076] According to one embodiment of the present specification, the first repeating unit is such that hydrogen contained in the first repeating unit is released and bonds to the second repeating unit, or the * portion bonds to the second repeating unit.

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

[0078] According to one embodiment of the present specification, the first repeating unit and the second repeating unit are graft-polymerized. That is, one embodiment of the present specification provides an antibacterial resin including a polymer to which the first repeating unit and the second repeating unit are grafted. Specifically, one embodiment of the present specification provides an antibacterial resin including a first repeating unit derived from propylene; and a second repeating unit derived from a monomer represented by Chemical Formula 1 and grafted to the first repeating unit. In this way, when the first repeating unit and the second repeating unit are graft-polymerized, the antibacterial substance is not contained as a separate substance but is polymerized as a monomer, which has the advantage of excellent stability in the human body and maintaining antibacterial durability.

[0079] According to one embodiment of the present specification, the antibacterial resin includes a third repeating unit represented by the following chemical formula 3.

[0080] [ka]

[0081] In the above Chemical Formula 3, m1 and m2 are each an integer of 1 to 50,000; L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; * indicates the point of attachment within the repeat unit.

[0082] According to one embodiment of the present specification, m1 and m2 are each an integer of 2 to 40,000, an integer of 5 to 30,000, or an integer of 10 to 10,000.

[0083] According to one embodiment of the present specification, the third repeating unit represented by the 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 the present specification, the antibacterial resin comprises a third repeating unit represented by the chemical formula 3.

[0085] According to one embodiment of the present specification, in the grafted polymer, the first repeat unit may be the main chain and the second repeat unit may be grafted to the main chain in the form of a side chain.

[0086] In this specification, having antibacterial properties means that the antibacterial activity measured based on the following method 1, in other words, the bacteriostatic reduction rate is 99% or more. In other examples, the antibacterial activity may be 99% or more or 99.8% or more. There is no particular upper limit to the antibacterial activity, and for example, the bacteriostatic reduction rate may be 100% or less or less than 100%.

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

[0088] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity of 99% or more against any strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by the following method 1.

[0089] [Method 1] The strain was 1.6 × 10 5 Dilute in 1XPBS solution at a concentration of CFU / mL. Place antibacterial resin and bacterial liquid in a 50mL conical tube (ratio = 0.1g / 5mL) and agitate in a shaking incubator at 37℃ for 1 hour to bring the antibacterial resin into contact with the bacterial liquid. Dilute this solution and smear it on an agar medium plate. Serial dilutions are performed to enable colony counting, and 1XPBS is used in this process. Bacteriostatic performance is calculated by taking into account the dilution concentration and the initial microbial concentration (C Reference , CFU / mL), then calculate using the following formula:

[0090]

number

[0091] When the antibacterial activity of the antibacterial resin according to the present invention was evaluated by the above-mentioned method 1, the antibacterial activity was observed only in cases where it was 99% or more. 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 is a general term for bacteria that are stained purple when stained by the gram staining method. The cell walls of gram-positive bacteria are composed of multiple layers of peptidoglycan, and after staining with a basic dye such as crystal violet, the color does not fade and remains purple even when treated with ethanol.

[0093] According to one embodiment of the present specification, the Gram-positive bacterium is selected from Enterococcus faecalis, Staphylococcus aureus, Streptococcus pneumoniae, Enterococcus faecium, and Lactobacillus lactis. Specifically, the Gram-positive bacterium is any one selected from the above-mentioned examples, but is not limited thereto.

[0094] As used herein, gram-negative bacteria are a collective term for bacteria that stain red when stained with the gram staining method, and have a cell wall that has a relatively small amount of peptidoglycan compared to gram-positive bacteria, but instead have an outer membrane composed of lipid polysaccharides, lipid proteins and / or other complex polymeric substances.

[0095] According to one embodiment of the present specification, the Gram-negative bacterium is selected from Proteus mirabilis, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Vibrio cholerae. Specifically, the Gram-negative bacterium is any one selected from the above-mentioned examples, but is not limited thereto.

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

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

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

[0099] According to one embodiment of the present specification, the antibacterial resin has an antibacterial activity against gram-negative bacteria measured by the method 1 above of 99% or more.

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

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

[0102] According to one embodiment of the present specification, the antibacterial resin has a weight average molecular weight (Mw) of 10,000 g / mol to 1,000,000 g / mol. If the antibacterial resin has a weight average molecular weight of less than 10,000 g / mol, it may be present in the form of a monomer rather than a polymer and may be easily dissolved, and the low molecular weight may cause a problem of absorption by the human body. In addition, if the antibacterial resin has a weight average molecular weight of more than 1,000,000 g / mol, the molecular weight becomes large and the viscosity becomes high, so that it may be impossible to apply or may not dissolve 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, and 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 the present specification, the antibacterial resin has a number average molecular weight (Mn) of 20,000 g / mol to 200,000 g / mol, more preferably 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 the present 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 any restrictions.

[0105] According to one embodiment of the present specification, the antibacterial resin may have a molecular weight distribution (Mw / Mn) in the range of 1 to 3. In other examples, the molecular weight distribution 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 the present specification, the end group of the antibacterial resin is

[0107] [ka]

[0108] L1 and R1 to R4 are defined as in Chemical Formula 1.

[0109] [ka]

[0110] means a moiety that is linked to the main chain or side chain of the antibacterial resin.

[0111] One embodiment of the present specification provides the antibacterial resin-forming composition described above.

[0112] According to one embodiment of the present specification, the antibacterial resin-forming composition includes polypropylene; a monomer represented by Chemical Formula 1; and an initiator.

[0113] According to one embodiment of the present specification, the polypropylene is contained in an amount of 70 parts by weight to 99.5 parts by weight, specifically, 80 parts by weight to 99.5 parts by weight, 90 parts by weight to 99.5 parts by weight, or 95 parts by weight to 99.5 parts by weight, based on 100 parts by weight of the antibacterial resin forming composition.

[0114] According to one embodiment of the present specification, the monomer represented by Chemical Formula 1 is contained in an amount of 0.4 to 20 parts by weight relative to 100 parts by weight of the antibacterial resin forming composition. Specifically, the monomer represented by Chemical Formula 1 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, the composition has an effect of exhibiting excellent antibacterial properties and antibacterial durability.

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

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

[0117] According to one embodiment of the present specification, the initiator is included in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the antibacterial resin forming composition. Specifically, the initiator is included in an amount 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 content of the initiator is less than 0.01 parts by weight, the polymerization reaction time may be extended, the polymerization conversion efficiency may be reduced, and the productivity may be reduced. Specifically, there is a drawback that the polymerization conversion efficiency is reduced and a large amount of residual monomers and decomposition products are generated. On the other hand, if the content exceeds 10 parts by weight, the initiator is not completely consumed during the polymerization process and may remain in the final polymer to reduce the physical properties of the polymer, especially the thermal stability.

[0118] One embodiment of the present specification provides a molded article containing or produced from the antibacterial resin. The molded article may be, but is not limited to, an automobile part, a blow molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, a foam molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric. The automobile part may be an interior or exterior material for an automobile. EXAMPLES

[0119] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the present invention. However, the examples of the present invention can be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present invention to those having average knowledge in the art.

[0120] <Preparation Example 1> Preparation of monomer represented by chemical formula 1 Production 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 onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0122] Preparation 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 onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0124] Preparation 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 acryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0126] Preparation Example 1-4. Synthesis of Compound 6 Step 1. (1) 0.1 mol of 2-(butylhexylamino)ethanol (BHAE), 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 onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0128] Preparation Example 1-5. Synthesis of Compound 7 Step 1. (1) 0.1 mol of 2-(butyloctylamino)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 acryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0130] Preparation 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 acryloyl chloride was added dropwise onto the reaction solution (at room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0132] Preparation 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 onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0134] Preparation 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 onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After removing the triethylamine salt by filtration, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

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

[0136] Preparation Example 1-9. Synthesis of Compound 11 (1) Acetonitrile (30 mL) was placed in a two-neck round bottom flask (RBF), 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 thereto. (2) The reaction was carried out at 45°C for 16 hours with stirring. (3) The mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE:reaction solution=15:1) and then filtered.

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

[0138] In the above Preparation Examples 1-1 to 1-10, a static precipitation method was used in which the reactants were added to a nonsolvent, but a reverse precipitation method in which the nonsolvent is added to the reactants 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.

[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] <Production Example 2> Production 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) prepared in Preparation Example 1 and initiator DCP (0.1 wt% of total) were added and grafted for 30 minutes with stirring. After the reaction was completed, the internal mixer was disassembled to obtain a lump sample. This was finely crushed into powder, washed (H2O, 50°C, 24 hours) to remove unreacted monomer, and dried to obtain sample 1.

[0142] Manufacturing Examples 2-2 to 2-12. Samples 2 to 12 were obtained in the same manner as in Production Example 2-1, except that the compounds shown in Table 1 below were used instead of Compound 1 in Production Example 2-1.

[0143] [Table 1]

[0144] Manufacturing Example 2-13. Sample 13 was produced 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 produced 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 1 H NMR. Specifically, the NMR measurement method is as follows.

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

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

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

[0150] [Table 2]

[0151] From Table 2 and FIG. 1, it can be seen that an antibacterial resin was produced that contains a first repeat unit derived from propylene and a second repeat unit derived from the monomer represented by Chemical Formula 1.

[0152] Manufacturing Example 2-15. Compound 11 prepared in Preparation Example 1-9 was added to PP (LG Chemical, MH1700) at 1 wt % 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 prepared in Preparation Example 1-10 was added to PP (LG Chemical, MH1700) at 1 wt % and simply mixed. After washing (H2O, 50°C, 24 hours), the mixture was dried to obtain sample 16.

[0154] <Example> Antibacterial activity measurement Example 1. Standard strain of E. coli ATCC 25922 was used at 1.6 × 10 5 Dilute in 1XPBS solution at a concentration of CFU / mL. Place sample 1 and the bacterial solution in a 50mL conical tube (ratio = 0.1g / 5mL) and stir in a shaking incubator at 37℃ for 1 hour to allow sample 1 to come into contact with the bacterial solution. Dilute this solution and smear on an agar medium plate. Serial dilutions are performed to enable colony counting, and 1XPBS is used in this process. Antibacterial activity is calculated by multiplying the initial concentration of microorganisms (C Referenece , CFU / mL) and then calculate using the following formula.

[0155]

number

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

[0157] Comparative Examples 1 to 3. The antibacterial activity was measured in the same manner as in 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, PP (LG Chemical, MH1700) was used instead of Sample 1 to measure the antibacterial activity.

[0159] The antibacterial activities calculated in the above Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Table 3 below.

[0160] In the following Table 3, the control is a bacterial inoculated culture solution to which no sample was added, and is a measure of whether or not the bacteria grew properly. In the above-mentioned Examples 1 to 12 and Comparative Examples 1 to 4, the reliability of the experiment was confirmed through the control in the following Table 3, and then the experiment was carried out.

[0161] [Table 3]

[0162] From Table 3, it can be seen that in the case where only polypropylene was included (Comparative Example 4) and in the case where polypropylene and the monomer (antibacterial monomer) represented by Chemical Formula 1 were simply blended (Comparative Examples 1 and 2), the antibacterial monomer was washed away with water during the sample preparation process, resulting in low antibacterial activity of 5% or less. From this, it can be seen that in the case where polypropylene and the antibacterial monomer were simply blended, even if the antibacterial monomer was added, it can be separated by a physical method such as washing and can be washed away and removed, and thus does not exhibit sustained antibacterial activity, as in the case where only polypropylene was included (Comparative Example 4).

[0163] In addition, when the content of the antibacterial monomer in the PP resin was 0.3 wt% (Comparative Example 3), it was confirmed that when the weight ratio of the repeating unit derived from the propylene monomer (first repeating unit) to the repeating unit derived from the antibacterial monomer (second repeating unit, the antibacterial monomer is represented by chemical formula 1) was outside the range of 1:0.005 or more, the antibacterial activity was significantly reduced to 98%.

[0164] Meanwhile, the antibacterial resin (example group) according to the embodiments of the present specification uses a polymer in which a repeating unit (first repeating unit) derived from a propylene monomer and a repeating unit (second repeating unit) derived from an antibacterial monomer are grafted, and it has been confirmed that the resin cannot be separated by physical methods, there is no risk of leakage, and the resin exhibits an antibacterial activity of 99% or more.

[0165] In particular, when two or more of R1 to R3 in the chemical formula of the antibacterial monomer are alkyl groups having 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 largest carbon number and the alkyl group with the smallest carbon number among R1 to R3 is 5 or more (i.e., when the structure of the antibacterial monomer is highly asymmetry) (Examples 2, 3, 6, 11 and 12), it was confirmed that the antibacterial activity was excellent, at 99.99% or more. In addition, it was confirmed that the antibacterial resin according to the embodiment of the present specification has an antibacterial activity of 99% or more because the weight ratio of the first repeating unit to the second repeating unit falls within the range of 1:0.005 or more.

Claims

1. a first repeat unit derived from propylene; and The polymerizable composition includes a second repeating unit derived from a monomer represented by the following chemical formula 1: The weight ratio of the first repeat unit and the second repeat unit is 1:0.005 or more. 【Chemistry 1】 In the above Chemical Formula 1, L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group.

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

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

5.

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

5. The antibacterial resin according to claim 1 , wherein the first repeating unit is represented by the following chemical formula 2: 【Chemistry 3】 In the above Chemical Formula 2, n1 is an integer from 1 to 50,000; * denotes a binding point within the antibacterial resin.

6. The antibacterial resin according to claim 1, further comprising a third repeating unit represented by the following chemical formula 3: 【Chemistry 4】 In the above Chemical Formula 3, m1 and m2 each represent an integer from 1 to 50,000; L1 is an alkylene group; R1 to R3 are the same or different and each independently represents an alkyl group; R4 is hydrogen or an alkyl group; * denotes a binding point within the antibacterial resin.

7. 2. The antibacterial resin of claim 1, wherein the weight average molecular weight of the antibacterial resin is from 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 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 strain was 1.6 × 10 ５ The solution is diluted in 1X PBS solution at a concentration of CFU / mL. The antibacterial resin and the bacterial solution are placed in a 50 mL conical tube (ratio = 0.1 g / 5 mL), and the antibacterial resin and the bacterial solution are brought into contact with each other by stirring in a shaking incubator at 37°C for 1 hour. The solution is diluted and smeared on an agar medium plate. Serial dilution is performed to enable colony counting, and 1X PBS is used in this process. The antibacterial activity is calculated by taking into account the dilution concentration and the initial microbial concentration (C Ｒｅｆｅｒｅｎｃｅ , CFU / mL) is calculated using the following formula: [0010]

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

10. 9. The antimicrobial resin of claim 8, wherein the Gram-negative bacteria is selected from among 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 produced from the antibacterial resin according to any one of claims 1 to 10.

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