Copolymer, antibacterial and deodorant composition containing the same, and method for producing the same

Abstract

The present specification relates to a copolymer containing a first unit derived from starch and a second unit derived from a compound represented by the following chemical formula 1, an antibacterial and deodorant composition containing the same, and a method for producing the same.

Description

[Technical Field]

[0001] The present specification relates to a copolymer, an antibacterial and deodorizing composition containing the copolymer, and a method for producing the same.

[0002] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0131942 filed with the Korean Intellectual Property Office on October 14, 2022, and Korean Patent Application No. 10-2023-0136164 filed with the Korean Intellectual Property Office on October 12, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] As damage caused by bacteria, mold, and other microorganisms that are harmful to the human body and cause odors increases in daily life, various antibacterial and deodorizing substances have been developed to inhibit the growth of or kill such microorganisms. In particular, there is a demand for antibacterial and deodorizing properties in polymeric materials used in products that we commonly use. For example, there is a demand for the development of antibacterial and deodorizing materials suitable for use in pet supplies (such as cat litter).

[0004] Previously, the main method for introducing antibacterial and deodorizing properties into polymers was to simply mix antibacterial and deodorizing substances into the polymer. However, this method poses the risk of antibacterial and deodorizing substances leaking out, so the safety of the antibacterial and deodorizing substances used must be guaranteed. Therefore, to fundamentally solve the problem of antibacterial and deodorizing substances leaking out, active research is being conducted on the development of antibacterial polymers that do not leak antibacterial substances by copolymerizing antibacterial and deodorizing substances into the polymer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2009-0131847 Summary of the Invention [Problem to be solved by the invention]

[0006] The present specification provides a copolymer, an antibacterial and deodorizing composition containing the copolymer, and a method for producing the copolymer. [Means for solving the problem]

[0007] One embodiment of the present invention provides a first unit derived from starch; and A copolymer including a second unit derived from a compound represented by the following Chemical Formula 1 is provided.

[0008] [ka]

[0009] In the above Chemical Formula 1, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group.

[0010] Another embodiment of the present specification provides an antibacterial and deodorizing composition comprising the above-described copolymer.

[0011] Another embodiment of the present invention provides an article of manufacture comprising or made from the antibacterial and deodorant composition described above.

[0012] Another embodiment of the present specification is a method for producing the above-mentioned copolymer, comprising: The present invention provides a method for producing a copolymer, which comprises reacting starch and the compound represented by Chemical Formula 1 at at least one temperature selected from the range of 80°C to 140°C. [Effects of the Invention]

[0013] Copolymers according to one embodiment of the present invention can provide improved antibacterial and deodorizing properties.

[0014] The copolymer according to one embodiment of the present invention can solve the safety issue of antibacterial substance leakage.

[0015] Copolymers according to some embodiments herein can exhibit antibacterial properties for a short period of time.

[0016] The copolymer according to one embodiment of the present invention exhibits little change in antibacterial activity depending on the amount of antibacterial material used, and therefore can exhibit antibacterial activity within a predicted range even when unintentional uneven concentration occurs when applied to a product. Therefore, the antibacterial activity can be controlled within a specific range, providing antibacterial activity with excellent safety.

[0017] The copolymer according to one embodiment of the present specification has low toxicity, which can solve the safety issue. DETAILED DESCRIPTION OF THE INVENTION

[0018] This specification will be explained in detail below.

[0019] Traditionally, to impart antibacterial and deodorizing properties to materials, antibacterial and deodorizing agents have been simply mixed with other substances, with either inorganic or organic antibacterial and deodorizing agents being used. Inorganic antibacterial and deodorizing agents are expensive, prone to discoloration of materials, and can degrade the physical properties of polymers during processing such as extrusion and injection. Inorganic antibacterial and deodorizing agents also have the disadvantage of not providing immediate antibacterial and deodorizing effects. Organic antibacterial and deodorizing agents have poor stability to the human body and poor thermal stability, resulting in poor durability of antibacterial and deodorizing effects.

[0020] In contrast, the copolymers of the present invention do not contain inorganic antibacterial and deodorizing agents, thereby overcoming drawbacks such as discoloration and loss of transparency. Furthermore, because the antibacterial and deodorizing substances are polymerized as monomers rather than contained as separate substances, they have the advantages of excellent stability to the human body and sustained antibacterial and deodorizing properties. Furthermore, while polymerizing organic antibacterial and deodorizing agents with other substances often results in reduced polymerization efficiency and conversion, or the properties of the polymerized substance are often impaired, the present invention overcomes these drawbacks. Due to the aforementioned advantages, the copolymers of the present invention can exhibit excellent antibacterial and deodorizing properties.

[0021] That is, the copolymer of the present invention has excellent antibacterial and deodorizing power and durability of the antibacterial and deodorizing properties, and can also improve stability against the leakage of the antibacterial and deodorizing agent.

[0022] Additionally, the copolymer of the present invention has the advantage of being environmentally friendly since it uses starch, a natural material.

[0023] In this specification, when a part is said to "comprise" a certain component, this does not mean that it excludes other components, but that it may further include other components, unless otherwise specified.

[0024] In this specification, "*" indicates a bonding point within the copolymer. For example, in the following chemical formula 2, * indicates both the bond between first units and the bond between the first unit and the second unit.

[0025] As used herein, 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 part of two or more substituents are removed from the compound structure, leaving radicals in their place for bonding to other units of the polymer. In this case, the compound can be polymerized in any order and included in the polymer in a bound state.

[0026] In this 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 removing hydrogen or a substituent, and a unit derived from the compound may refer to a unit that forms one or more of the main chain and side chain of a polymer. The unit may be included in the main chain of the polymer to constitute the polymer.

[0027] 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 the molecular weights of component molecular species of a polymeric compound having a molecular weight distribution, by weight fraction.

[0028] In this specification, physical properties that are affected by temperature are measured at room temperature unless otherwise specified.

[0029] As used herein, "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 a temperature of about 15°C, about 18°C, about 20°C, about 23°C, or about 25°C. Unless otherwise specified, the unit of temperature used in this specification is °C.

[0030] In this specification, when pressure affects the results of physical properties, the physical properties are measured at normal pressure unless otherwise specified.

[0031] In this specification, "normal pressure" refers to natural pressure that is neither pressurized nor reduced, and generally refers to approximately 1 atmosphere (approximately 700 mmHg to 800 mmHg).

[0032] In the present specification, when humidity affects the results of physical properties, the physical properties are measured at room temperature and pressure without any particular adjustment of humidity, unless otherwise specified.

[0033] In this specification, the "alkyl group" may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably is 1 to 60. In one embodiment, the number of carbon atoms in 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.

[0034] 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 may be applied, except that these are both divalent groups.

[0035] As used herein, "starch" refers to starch as used in the art, specifically a polysaccharide in which multiple glucose units are linked by glycosidic bonds, and has the following structure:

[0036] [ka]

[0037] In the above structure:

[0038] [ka]

[0039] means the moiety that binds to other units in starch.

[0040] In one embodiment of the present invention, the molecular weight of the starch is 10 5 g / mol~10 9 g / mol, or 10 6 g / mol~10 8 g / mol.

[0041] In one embodiment of the present specification, the first unit derived from starch includes a unit represented by the following chemical formula 2:

[0042] [ka]

[0043] In the above Chemical Formula 2, R10 to R12 are the same or different and each independently represent -OH or -O-*, and at least one of R10 to R12 is -O-*; n1 is 1 to 10 7 is an integer, * denotes a point of attachment within the copolymer.

[0044] Specifically, the unit represented by Chemical Formula 2 may mean that a portion of the first unit derived from the starch is grafted, or in some cases, it may mean that all of the first unit is grafted.

[0045] In one embodiment of the present specification, Chemical Formula 2 is represented by any one of the following structures:

[0046] [ka]

[0047] In the above structure, * is a bonding point within the copolymer, and n1 is 1 to 10. 7 is an integer.

[0048] Specifically, in the first units, * denotes a portion where first units are bonded to each other, or a portion where a first unit is bonded to a second unit.

[0049] In one embodiment of the present specification, n1 is 100 to 10 7 Integers, 500 to 10 7 integer, 10 3 ~10 7 integer, 10 4 ~107 integer, 10 5 ~10 7 an integer, or 10 5 ~10 6 is an integer.

[0050] In one embodiment of the present specification, the compound represented by Chemical Formula 1 is an antibacterial and deodorant substance.

[0051] In one embodiment of the present specification, the second unit is represented by the following chemical formula 3.

[0052] [ka]

[0053] In the above Chemical Formula 3, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group; n2 is 1 to 10 6 is an integer, * denotes a point of attachment within the copolymer.

[0054] In one embodiment of the present specification, n2 is 1 to 10 6 Integers, 1 to 10 5 Integers, 1 to 10 4 or an integer between 1 and 5000.

[0055] In one embodiment of the present specification, L1 is an alkylene group having 1 to 10 carbon atoms.

[0056] In one embodiment of the present specification, L1 is an alkylene group having 1 to 5 carbon atoms.

[0057] In one embodiment of the present specification, L1 is a methylene group; an ethylene group; a propylene group; or a butylene group.

[0058] In 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.

[0059] In 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.

[0060] In 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.

[0061] In 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.

[0062] In one embodiment of the present specification, two or more of R1 to R3 are alkyl groups having 5 to 30 carbon atoms, or the difference in carbon number between the alkyl group with the largest carbon atom number and the alkyl group with the smallest carbon atom number among R1 to R3 is 4 or more.

[0063] Specifically, three of R1 to R3 are alkyl groups having 5 to 30 carbon atoms; two of R1 to R3 are alkyl groups having 5 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 atom number and the alkyl group with the smallest carbon atom number among R1 to R3 is 4 or more. In this case, excellent antibacterial effect is exhibited.

[0064] In one embodiment of the present specification, the difference in carbon number between the alkyl group with the largest carbon number and the alkyl group with the smallest carbon number being 4 or more means that asymmetry is high, and the difference in carbon number may be 4 to 30, 5 to 30, or 5 to 10.

[0065] In one embodiment of the present specification, the compound represented by Chemical Formula 1 has any one of the following structures:

[0066] [ka]

[0067] In one embodiment of the present specification, the second unit derived from the compound represented by Chemical Formula 1 has any one of the following structures:

[0068] [ka] [ka]

[0069] In the above structure, * is the point of attachment within the copolymer.

[0070] In one embodiment of the present specification, the compound represented by Chemical Formula 1 exhibits cationic properties and may exist in the form of a salt with a group exhibiting anionic properties. In this case, the group exhibiting anionic properties is not particularly limited, and materials well known in the art may be used as long as the antibacterial purpose is not impaired. For example, the group exhibiting anionic properties may be a halogen-based anion or a sulfonate-based anion, specifically, Br - It may be, but is not limited to these.

[0071] In one embodiment of the present specification, the weight ratio of the first unit to the second unit is 100:0.5 to 100:10. Specifically, it is 100:1 to 100:5, or 100:1 to 100:3. When the weight ratio of the first unit to the second unit satisfies the above-mentioned range, the composition exhibits excellent deodorizing power, antibacterial power, and sustained deodorizing power and antibacterial power.

[0072] The deodorizing and antibacterial properties of the copolymer are derived from the second unit contained in the copolymer. Generally, cell walls of bacteria and the like are often negatively charged, and the second unit can have a destructive effect on the cell walls.

[0073] In one embodiment of the present specification, the first unit and the second unit are copolymerized. Specifically, one embodiment of the present specification provides a copolymer including a first unit derived from starch; and a second unit derived from the compound represented by Chemical Formula 1 and copolymerized with the first unit. When the first unit and the second unit are copolymerized in this manner, the antibacterial substance is not contained as a separate substance but is polymerized as a monomer, which has the advantage of excellent stability to the human body and maintaining antibacterial durability. As an example, one embodiment of the present specification provides a copolymer in which the first unit and the second unit are grafted.

[0074] In one embodiment of the present specification, the copolymer includes a third unit represented by the following chemical formula 4:

[0075] [ka]

[0076] In the above Chemical Formula 4, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group; m1 is 1 to 10 7 is an integer, m2 is 1 to 10 6 is an integer, * denotes a point of attachment within the copolymer.

[0077] In one embodiment of the present specification, the copolymer comprising the first unit derived from starch; and the second unit derived from the compound represented by Chemical Formula 1 is represented by Chemical Formula 4.

[0078] According to one embodiment of the present specification, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer.

[0079] In one embodiment of the present specification, the third unit represented by Chemical Formula 4 is a unit in which the first unit and the second unit are grafted.

[0080] In one embodiment of the present specification, the copolymer comprises a third unit represented by Chemical Formula 4. Specifically, the copolymer includes a structure in which a plurality of third units are repeatedly bonded.

[0081] In one embodiment of the present specification, in the grafted copolymer, the first repeating unit may be the main chain, and the second repeating unit may be grafted to the main chain in the form of a side chain.

[0082] In one embodiment of the present specification, the weight average molecular weight (Mw) of the copolymer is 10 5 g / mol~10 9 g / mol. Specifically, the weight average molecular weight of the copolymer is 10 6 g / mol~10 8 g / mol.

[0083] In one embodiment of the present specification, the weight average molecular weight (Mw) of the copolymer can be measured using gel permeation chromatography (GPC).

[0084] In one embodiment of the present specification, the copolymer has a deodorizing ability.

[0085] In this specification, having deodorizing power means that the deodorizing power measured based on the following method 1 is 70% or more.

[0086] In one embodiment of the present specification, when the copolymer is evaluated for deodorizing ability by the following method 1, the copolymer has a deodorizing power against ammonia of 70% or more.

[0087] [Method 1] 2.5 mL of artificial urine inoculated with 3000±30 CFU / mL of bacteria and 1 g of the copolymer were placed in a cell culture flask, and then cultured at 35° C. for 12 hours to prepare a test culture solution.

[0088] A control culture medium is prepared in the same manner as the test culture medium, except that a compressed sample of starch and glycerol is used instead of the copolymer.

[0089] The amount of ammonia collected in the test culture medium and the control culture medium is measured using an ammonia detector tube, and the deodorizing power is calculated using the following formula 1.

[0090]

number

[0091] In Method 1 and Scheme 1, the test culture medium contains a copolymer according to an embodiment of the present invention, and the control culture medium does not contain the copolymer.

[0092] As used herein, CFU (Colony Forming Unit) means colony forming unit, and CFU / mL means the number of CFU per mL.

[0093] When the deodorizing power of the copolymer according to the present specification was evaluated by the above-mentioned method 1, only cases where the deodorizing power was 70% or more were observed. As a result, it was confirmed that the copolymer according to the present specification has excellent deodorizing power.

[0094] As another example, the deodorizing power may be 80% or more, 85% or more, or 90% or more. The upper limit of the deodorizing power is not particularly limited, and for example, the deodorizing power may be 100% or less, or less than 100%.

[0095] In one embodiment of the present specification, the copolymer has antibacterial properties.

[0096] In this specification, having antibacterial properties means that the antibacterial activity, ie, bacteriostatic performance, measured according to the following method 1 is 90% or more.

[0097] In one embodiment of the present specification, the copolymer has an antibacterial activity of 90% or more against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by the following method 2.

[0098] [Method 2] 2.5 mL of artificial urine inoculated with 3000 ± 30 CFU / mL of bacteria and 1 g of the copolymer were placed in a cell culture flask and incubated at 35°C for 12 hours to prepare a test culture. Ammonia was collected from the test culture using an ammonia detector. After ammonia collection was completed, 7.5 mL of saline solution (0.9 wt%) was added to the test culture and mixed to dilute the bacterial solution. This was then serially diluted with the saline solution to enable colony counting, and smeared on a nutrient agar plate. The smeared nutrient agar plate was incubated at 35°C for 18 hours to prepare a test sample.

[0099] A control sample is prepared in the same manner as the test sample, except that a compressed sample of starch and glycerol is used instead of the copolymer.

[0100] The microbial concentrations of the test sample and the control sample were measured, and the antibacterial activity (%) was calculated according to the following formula 2.

[0101]

number

[0102] In Method 2 and Formula 2 above, the test sample comprises a copolymer according to an embodiment of the present invention, and the control sample does not comprise said copolymer.

[0103] When the antibacterial activity of the copolymer according to the present specification was evaluated by the above-mentioned method 2, only cases where the antibacterial activity was 90% or more were observed. As a result, it was confirmed that the antibacterial resin according to the present specification has excellent antibacterial activity.

[0104] As another example, the antibacterial activity may be 92% or more, 93% or more, or 94% or more. The upper limit of the antibacterial activity is not particularly limited, and for example, the antibacterial activity may be 100% or less, or less than 100%.

[0105] In this specification, Gram-positive bacteria is a general term for bacteria that stain 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, they retain their purple color even when treated with ethanol without being decolorized.

[0106] In 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 may be any one selected from the above-mentioned examples, but is not limited thereto.

[0107] 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 with relatively less peptidoglycan than Gram-positive bacteria, but instead have an outer membrane made up of lipopolysaccharides, lipoproteins, and / or other complex polymeric substances.

[0108] In 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, it is any one selected from the above-mentioned examples, but is not limited thereto.

[0109] In one embodiment of the present specification, the fungus may be, but is not limited to, Candida albicans.

[0110] In one embodiment of the present specification, the copolymer has an antibacterial activity of 90% or more against Gram-positive bacteria as measured by the method 2 above.

[0111] In one embodiment of the present specification, the copolymer has an antibacterial activity of 90% or more against Gram-negative bacteria as measured by the method 2 above.

[0112] In one embodiment of the present specification, the copolymer has an antibacterial activity against mold of 90% or more as measured by the method 2 above.

[0113] In one embodiment of the present specification, the copolymer has an antibacterial activity of 90% or more against gram-positive bacteria, gram-negative bacteria, and fungi as measured by the method 2. Since the gram-positive bacteria, gram-negative bacteria, and fungi strains can not only cause various diseases upon contact but also secondary infections, it is preferable that a single antibacterial agent exhibits antibacterial activity against all of the gram-positive bacteria, gram-negative bacteria, and fungi.

[0114] According to one embodiment of the present specification, the bacterium used for measuring the antibacterial activity is a gram-negative bacterium. Specifically, the bacterium used for evaluating the antibacterial activity is Proteus mirabilis.

[0115] Another embodiment of the present specification provides an antibacterial and deodorizing composition comprising the above-described copolymer.

[0116] In one embodiment of the present specification, the antibacterial and deodorant composition may further comprise one or more of activated carbon; bentonite; superabsorbent polymer (SAP); polyethylene (PE); polypropylene (PP); polystyrene (PS); polyamide (PA); polyimide (PI); polyethylene terephthalate (PET); polyvinyl chloride (PVC); acryloyl-butadiene-styrene (ABS); and polyacrylic acid (PA).

[0117] In one embodiment of the present specification, the antibacterial deodorant composition further comprises 1 to 5, 1 to 3, 2, or 1 of the additional components described above.

[0118] In one embodiment of the present specification, the antibacterial and deodorant composition may be in a state where the compound and additional ingredients are simply mixed together.

[0119] One embodiment of the present specification provides a molded article containing or produced from the antibacterial and deodorizing composition described above. The molded article may be, but is not limited to, cat litter, refrigerator vegetable boxes, automobile parts, blown-film molded articles, inflation-molded articles, cast-molded articles, extrusion-laminated molded articles, extrusion-molded articles, foam-molded articles, injection-molded articles, sheets, films, fibers, monofilaments, or nonwoven fabrics. The automobile parts may be automobile interior / exterior materials, etc.

[0120] One embodiment of the present specification provides a copolymer-forming composition for forming the above-described copolymer.

[0121] In one embodiment of the present specification, the copolymer-forming composition includes starch; a compound represented by Chemical Formula 1; and an initiator.

[0122] In one embodiment of the present specification, the starch is contained in an amount of 55 to 99.7 parts by weight relative to 100 parts by weight of the copolymer-forming composition. Specifically, the starch is contained in an amount of 65 to 99.5 parts by weight, or 70 to 99.5 parts by weight. When the starch content satisfies the above range, excellent antibacterial activity and malodor suppression effects can be exhibited.

[0123] In one embodiment of the present specification, the compound represented by Chemical Formula 1 is contained in an amount of 0.2 to 40 parts by weight relative to 100 parts by weight of the copolymer-forming composition. Specifically, the compound represented by Chemical Formula 1 is contained in an amount of 0.5 to 35 parts by weight, or 0.5 to 30 parts by weight. When the content of the compound represented by Chemical Formula 1 is within the above-mentioned range, excellent antibacterial properties and antibacterial durability are exhibited.

[0124] In one embodiment of the present specification, the initiator is included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the copolymer-forming composition. Specifically, the initiator is included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the antibacterial resin-forming composition. In this case, if the content of the initiator is less than 0.1 parts by weight, the polymerization reaction time may be prolonged, the polymerization conversion rate may be low, and productivity may be reduced. Specifically, there are drawbacks such as a low polymerization conversion rate and the generation of large amounts of residual monomers and decomposition products. On the other hand, if the content is more than 5 parts by weight, the initiator may not be completely consumed during the polymerization process and may remain in the final polymer, potentially reducing the physical properties of the polymer, particularly its thermal stability.

[0125] In one embodiment of the present specification, examples of the initiator include peroxide-based compounds such as dicumyl peroxide, dipentyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, and dilauryl peroxide; peroxydicarbonate-based compounds such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and di-2-ethylhexyl peroxydicarbonate; peroxyester-based compounds such as t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, and t-butyl peroxyneodecanoate; azo-based compounds such as azobisbutyronitrile (AIBN) and azobis-2,4-dimethylvaleronitrile; hydroperoxide-based compounds such as t-butyl hydroperoxide; and sulfate-based compounds such as sodium persulfate (SPS), potassium persulfate, and ammonium persulfate. These may be used alone or in combination, but are not limited to these examples.

[0126] In one embodiment of the present specification, the copolymer-forming composition further includes a plasticizer. The plasticizer may be any substance commonly used in the art, such as, but not limited to, glycerol.

[0127] In one embodiment of the present specification, the plasticizer is contained in an amount of 0.5 to 50 parts by weight relative to 100 parts by weight of the copolymer-forming composition. Specifically, the plasticizer is contained in an amount of 5 to 40 parts by weight. When the content of the plasticizer satisfies the above range, the processability of the copolymer is improved.

[0128] In one embodiment of the present specification, the copolymer-forming composition further includes a solvent, which may be included in an amount excluding the above-mentioned materials, based on 100 parts by weight of the copolymer-forming composition.

[0129] In one embodiment of the present specification, the type of the solvent is not limited, and for example, water, methanol, ethyl alcohol, isopropyl alcohol, etc. may be used.

[0130] One embodiment of the present specification provides a method for producing the aforementioned copolymer, comprising step (a) of reacting starch and the monomer represented by Chemical Formula 1 at at least one temperature selected from the range of 80°C to 140°C.

[0131] In one embodiment of the present specification, the specific explanations regarding the starch and the monomer represented by Chemical Formula 1 mentioned in the preparation method are the same as those explained for the copolymer.

[0132] In one embodiment of the present specification, the reaction may be performed under temperature conditions where at least one temperature selected from the range of 80°C to 140°C is changed within the range of 80°C to 140°C, or at any temperature selected from the aforementioned temperature range. For example, the reaction may be performed at 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, or 140°C. Alternatively, the reaction may be performed while increasing the temperature from 80°C to 140°C.

[0133] In one embodiment of the present specification, the reaction time in the reaction step may vary depending on the reaction temperature and reactants. For example, when the reaction is carried out at 80°C, the reaction time may be 10 minutes to 24 hours. Specifically, the reaction time may be 10 minutes to 16 hours, 10 minutes to 10 hours, 10 minutes to 5 hours, 10 minutes to 3 hours, or 10 minutes to 1 hour. Furthermore, when the reaction temperature or reactants differ from those in the production examples described below, the reaction time may vary.

[0134] In one embodiment of the present specification, the reacting step may include the step (a1) of preparing a mixture of the starch and the monomer represented by Chemical Formula 1; and the step (a2) of reacting the mixture.

[0135] In one embodiment of the present specification, the reaction time in step (a2) of reacting the mixture is as described above.

[0136] In one embodiment of the present specification, the step (a1) of preparing the mixture may include the steps of: preparing starch and a monomer represented by Chemical Formula 1; mixing the starch with a solvent to prepare a mixture A (a1-2); and mixing the mixture A and the monomer represented by Chemical Formula 1 to prepare a mixture B (a1-3).

[0137] In one embodiment of the present specification, step (a1-3) of preparing mixture B may include a process of mixing under pressure. The method of mixing under pressure may be any method known in the art, and may use, for example, an intermixer.

[0138] In one embodiment of the present specification, the step (a1-3) of preparing the mixture B may be carried out at 10 rpm to 500 rpm for 5 minutes to 5 hours.

[0139] In one embodiment of the present specification, the method for preparing the copolymer may further include step (b) of washing the reactants. Specifically, the reactants may be washed with one or more organic solvents such as water, ethanol, and acetone.

[0140] In one embodiment of the present specification, the method for producing the copolymer may further include step (c) of drying the reaction product. Specifically, the reaction product may be dried at 25°C to 140°C for 1 hour to 48 hours.

[0141] In one embodiment of the present specification, the method for producing the copolymer may further include step (d) of pulverizing the reactants. The pulverization may be performed by a method commonly used in the art, and the reactants may be obtained in a sand-like form by the pulverization.

[0142] In one embodiment of the present specification, the method for producing the copolymer may further include one or more of the steps of (b) washing the reactants; (c) drying the reactants; and (d) grinding the reactants.

[0143] In one embodiment of the present specification, the method for producing the copolymer may include one or more of a reacting step (a); and a washing step (b) of the reactants, a drying step (c) of the reactants, and a pulverizing step (d) of the reactants. [Example]

[0144] Hereinafter, the present specification will be described in detail with reference to examples. However, the examples of the present specification may be modified in various different forms, and the scope of the present specification should not be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to those skilled in the art.

[0145] <Preparation Example 1> Preparation of a monomer represented by chemical formula 1 Preparation Example 1-1. Synthesis of Compound 1 Step 1 (1) 0.1 mol of 2-(dibutylamino)ethanol (DBAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of acryloyl chloride was added dropwise onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After filtering to remove triethylamine salts, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0146] Step 2 (1) The product of Step 1 and 1-bromooctane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 to a concentration of 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 reaction mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (5) Compound 1 was produced by vacuum drying at 45°C.

[0147] Preparation Example 1-2. Synthesis of Compounds 2 and 3 Compounds 2 and 3 were prepared in the same manner as in Preparation Example 1-1, except that 1-bromodecane (preparation of compound 2) or 1-bromododecane (preparation of compound 3) was used instead of 1-bromooctane in Step 2(1) of Preparation Example 1-1.

[0148] Preparation Example 1-3. Synthesis of Compound 4 Compound 4 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dioctylamino)ethanol (DOAE) was used instead of 2-(dibutylamino)ethanol in Step 1(1) of Preparation Example 1-1.

[0149] Preparation Example 1-4. Synthesis of Compound 5 Step 1 (1) 0.1 mol of 2-(dihexylamino)ethanol (DHAE), 0.1 mol of trimethylamine, and 0.001 mol of hydroquinone were added to 100 mL of THF (solvent). (2) While stirring the materials, 0.1 mol of methacryloyl chloride was added dropwise onto the reaction solution (room temperature). (3) Stirred for 2 hours. (4) After filtering to remove triethylamine salts, the solvent was removed using a rotary evaporator. (5) Vacuum dried at 83°C to 87°C.

[0150] Step 2 (1) The product of Step 1 and 1-bromodecane were dissolved in acrylonitrile (solvent) at a molar ratio of 1:1 to a concentration of 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 reaction mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (5) Compound 5 was produced by vacuum drying at 45°C.

[0151] Preparation Example 1-5. Synthesis of Compound 6 Compound 6 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butylhexylamino)ethanol (BHAE, 2-butylhexylamino)ethanol) was used instead of 2-(dihexylamino)ethanol in Step 1(1) of Preparation Example 1-4.

[0152] Preparation Example 1-6. Synthesis of Compound 7 Compound 7 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyloctylamino)ethanol (BOAE) was used instead of 2-(dihexylamino)ethanol in Step 1(1) of Preparation Example 1-4.

[0153] Preparation Example 1-7. Synthesis of Compound 8 Compound 8 was prepared in the same manner as in Preparation Example 1-4, except that 2-(butyldecylamino)ethanol (BOAE, 2-butyldecylamino)ethanol was used instead of 2-(dihexylamino)ethanol in Step 1(1) of Preparation Example 1-4.

[0154] Preparation Example 1-8. Synthesis of Compound 9 Compound 9 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dibutylamino)butanol (DBAB) was used instead of 2-(dibutylamino)ethanol in Step 1(1) of Preparation Example 1-1.

[0155] Preparation Example 1-9. Synthesis of Compound 10 Compound 10 was prepared in the same manner as in Preparation Example 1-1, except that 2-(dioctylamino)butanol (DOAB) was used instead of 2-(dibutylamino)ethanol in Step 1(1) of Preparation Example 1-1.

[0156] Preparation Example 1-10. Synthesis of Compound 11 (1) 1-bromooctane (production of Compound 11), 2-(dimethylamino)ethyl methacrylate, 4-methoxyphenol, and acetonitrile were sequentially placed in a two-neck round bottom flask (RBF). (2) The reaction was carried out at 60°C for 6 hours. (3) The reaction mixture was precipitated in methyl t-butyl ether (MTBE) (MTBE: reaction solution = 15:1 (volume ratio)) and then filtered. (4) Vacuum dried at 45°C.

[0157] Preparation Example 1-11. Synthesis of Compounds 12 and 13 Compounds 12 and 13 were prepared in the same manner as in Preparation Example 1-10, except that 1-bromodecane (preparation of compound 12) or 1-bromododecane (preparation of compound 13) was used instead of 1-bromooctane.

[0158] In Preparation Examples 1-1 to 1-11, a forward precipitation method was used in which the reactants were added to a nonsolvent, but a reverse precipitation method in which the nonsolvent is added to the reactants may also be used. In addition, the ratio of MTBE to the reaction solution may be other than 15:1, such as 12:1 or 26:1.

[0159] The structures of compounds 1 to 13 prepared in the above Preparation Examples 1-1 to 1-11 are as follows.

[0160] [ka]

[0161] <Production Example 2> Production of copolymer Manufacturing Example 2-1 28.44 g of glycerol and 14.39 g of water were added to 100 g of corn starch (control), and then 2 g of Compound 12 and 1.33 g of SPS were added and mixed uniformly. The mixture was placed in an internal mixer heated to 100°C and reacted at 50 rpm for 40 minutes to obtain a kneaded sample. The sample was dried at 80°C for 16 hours and then crushed to obtain Sample 1 in a sandy state.

[0162] Manufacturing Example 2-(Comparative Manufacturing Example) A sandy sample 2 was obtained in the same manner as in Preparation Example 2-1, except that compound 12 and SPS were not added.

[0163] Manufacturing Example 2-(Comparative Manufacturing Example) 28.44 g of glycerol and 14.39 g of water were added to 100 g of cellulose (Sigma-Aldrich, 40230854), and then 2 g of compound 12 and 1.33 g of SPS were added and mixed uniformly. The mixture was placed in an internal mixer heated to 100°C and reacted at 50 rpm for 40 minutes, but the cellulose did not gelatinize, resulting in a sample that remained as powder.

[0164] Manufacturing Example 2-4 (Comparative Manufacturing Example) Sandy sample 3 was prepared in the same manner as in Preparation Example 2-1, except that the following monomer A was used instead of compound 12 in Preparation Example 2-1.

[0165] [ka]

[0166] The preparation of Samples 1 and 3 was confirmed by HPLC analysis. Specifically, 0.2 g of the target sample was placed in 10 mL of saline and shaken at room temperature for 24 hours, and the resulting eluate was subjected to HPLC analysis. The HPLC analysis showed that no residual monomer was detected, confirming that the target samples were prepared.

[0167] <Experimental Example 1> Measurement of deodorizing power Experimental Example 1-1 2.5 mL of artificial urine inoculated with 3000±30 CFU / mL of Proteus mirabilis bacteria and 1 g of Sample 1 prepared in Preparation Example 2-1 were placed in a cell culture flask and cultured at 35°C for 12 hours to prepare a test culture medium.

[0168] A control culture medium was prepared in the same manner as the test culture medium, except that Sample 2 prepared in Preparation Example 2-2 was used instead of Sample 1.

[0169] The amount of ammonia collected in the test culture medium and the control culture medium was measured using an ammonia detector tube, and the deodorizing power was calculated using the following formula 1.

[0170]

number

[0171] Comparative Example 1-1 The deodorizing power was calculated in the same manner as in Experimental Example 1-1, except that Sample 3 prepared in Preparation Example 2-4 was used instead of Sample 1 in Experimental Example 1-1.

[0172] The measured ammonia capture amounts and calculated deodorizing powers in Experimental Example 1-1 and Comparative Example 1-1 are shown in Table 1 below.

[0173] Comparative Example 1-2 2.5 mL of artificial urine inoculated with 3000±30 CFU / mL of Proteus mirabilis bacteria and 1 g of Sample 2 prepared in Preparation Example 2-2 were placed in a cell culture flask and cultured at 35°C for 12 hours to prepare a test culture medium.

[0174] The amount of ammonia collected in the test culture solution was measured using an ammonia detector tube, and the results are shown in Table 1 below.

[0175] [Table 1]

[0176] In Table 1, the amount of ammonia detected (ppm) was measured repeatedly for the same sample, and the first measurement result is listed as #1 and the second measurement result as #2. The average is the average value of the ammonia detected in #1 and #2.

[0177] From Table 1, it can be seen that the copolymer according to one embodiment of the present invention (Sample 1, Experimental Example 1-1) has a low ammonia detection amount of less than 100. In contrast, it can be seen that the copolymer using a compound in which R1 to R3 are all methyl groups (Sample 3, Comparative Example 1-1) and the polymer consisting only of starch (Comparative Example 1-2) both have high ammonia detection amounts of 500 or more.

[0178] Furthermore, it can be seen from Table 1 that the copolymer according to one embodiment of the present invention (Sample 1, Experimental Example 1-1) exhibits a deodorizing power of 70% or more compared to a polymer consisting only of starch (Sample 2, control culture medium).In contrast, it can be seen that the polymer using a compound in which R1 to R3 are all methyl groups (Sample 3, Comparative Example 1-1) exhibits a low deodorizing power of 20% or less.

[0179] Therefore, it can be seen from Table 1 that the copolymer according to one embodiment of the present invention has excellent deodorizing power.

[0180] <Experimental Example 2> Antibacterial activity measurement Experimental Example 2-1 2.5 mL of artificial urine inoculated with 3000 ± 30 CFU / mL of Proteus mirabilis bacteria and 1 g of Sample 1 prepared in Preparation Example 2-1 were placed in a cell culture flask and incubated at 35°C for 12 hours to prepare a test culture solution. Ammonia was collected from the test culture solution using an ammonia detector tube. After ammonia collection, 7.5 mL of saline solution (0.9 wt%) was added to the test culture solution and mixed to dilute the bacterial solution. Serial dilutions were then made using saline solution to enable colony counting, and the diluted solution was smeared onto nutrient agar plates. The smeared nutrient agar plates were incubated at 35°C for 18 hours to prepare test samples.

[0181] A control sample was prepared in the same manner as the test sample, except that Sample 2 prepared in Preparation Example 2-2 was used instead of Sample 1 in the preparation of the test sample.

[0182] The microbial concentrations of the test samples and the control samples were measured, and the antibacterial activity (%) was calculated according to the following formula 2.

[0183]

number

[0184] Comparative Example 2-1 The antibacterial activity was calculated in the same manner as in Experimental Example 2-1, except that Sample 3 prepared in Preparation Example 2-4 was used instead of Sample 1 in Experimental Example 2-1.

[0185] The log CFU values ​​and antibacterial activity calculated from the microbial concentrations measured in Experimental Example 2-1 and Comparative Example 2-1 are shown in Table 2 below.

[0186] Comparative Example 2-2 2.5 mL of artificial urine inoculated with 3000 ± 30 CFU / mL of Proteus mirabilis bacteria and 1 g of Sample 2 prepared in Preparation Example 2-2 were placed in a cell culture flask and incubated at 35°C for 12 hours to prepare a test culture medium. 7.5 mL of saline solution (0.9 wt%) was added to the test culture medium and mixed to dilute the bacterial solution, which was then serially diluted with saline solution to enable colony counting and smeared on nutrient agar plates. The smeared nutrient agar plates were incubated at 35°C for 18 hours to prepare test samples.

[0187] The microbial concentrations of the test samples were measured and the log CFU values ​​were calculated and are shown in Table 2 below.

[0188] [Table 2]

[0189] Table 2 shows the CFU values ​​measured repeatedly for the same sample. The log CFU value for the first measurement is listed as #1, and the log CFU value for the second measurement is listed as #2. The average is the log CFU value of the CFU values ​​measured in #1 and #2. Table 2 shows that the copolymer according to one embodiment of the present invention (Sample 1, Experimental Example 2-1) has excellent antibacterial activity of 90% or more. In contrast, the polymer consisting only of starch (Sample 2, Comparative Example 2-1) and the copolymer using a compound in which R1 to R3 of Chemical Formula 1 are all methyl groups (Sample 3, Comparative Example 2-2) have no antibacterial activity or a low antibacterial activity of less than 30%.

Claims

1. A first unit derived from starch; and A second unit derived from a compound represented by the following chemical formula 1: A copolymer comprising: 【Chemical 1】 In the above Chemical Formula 1, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group.

2. 2. The copolymer of claim 1, wherein the first unit derived from starch comprises a unit represented by the following chemical formula 2: 【Chemistry 2】 In the above Chemical Formula 2, R10 to R12 are the same or different and each independently represent -OH or -O-*, and at least one of R10 to R12 is -O-*; n1 is 1 to 10 ７ is an integer, * denotes a point of attachment within the copolymer.

3. The copolymer according to claim 1 , wherein the second unit derived from the compound represented by Chemical Formula 1 is represented by the following Chemical Formula 3: 【Chemistry 3】 In the above Chemical Formula 3, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group; n2 is 1 to 10 ６ is an integer, * denotes a point of attachment within the copolymer.

4. The copolymer of claim 1, wherein the compound represented by Chemical Formula 1 has any one of the following structures: 【Chemistry 4】

5. The copolymer of claim 1 , comprising a third unit represented by the following chemical formula 4: 【Chemistry 5】 In the above Chemical Formula 4, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group; m1 is 1 to 10 ７ is an integer, m2 is 1 to 10 ６ is an integer, * denotes a point of attachment within the copolymer.

6. 2. The copolymer according to claim 1, wherein the weight ratio of the first unit to the second unit is 100:0.5 to 100:

10.

7. The copolymer according to claim 1, wherein when the copolymer is subjected to an odor-eliminating evaluation by the following method 1, the copolymer has an odor-eliminating power against ammonia of 70% or more. [Method 1] 2.5 mL of artificial urine inoculated with 3000±30 CFU / mL of bacteria and 1 g of the copolymer were placed in a cell culture flask, and then cultured at 35° C. for 12 hours to prepare a test culture solution. A control culture medium is prepared in the same manner as the test culture medium, except that a compressed sample of starch and glycerol is used instead of the copolymer. The amount of ammonia collected in the test culture medium and the control culture medium is measured using an ammonia detector tube, and the deodorizing power is calculated using the following formula 1. [Equation 1]

8. The copolymer according to claim 1, wherein the copolymer has an antibacterial activity of 90% or more against at least one strain selected from the group consisting of gram-positive bacteria, gram-negative bacteria, and fungi, as measured by the following method 2: [Method 2] 2.5 mL of artificial urine inoculated with 3000±30 CFU / mL of bacteria and 1 g of the copolymer were placed in a cell culture flask and incubated at 35°C for 12 hours to prepare a test culture. Ammonia was collected from the test culture using an ammonia detector. After ammonia collection was completed, 7.5 mL of salt solution (0.9 wt%) was added to the test culture and mixed to dilute the bacterial solution. The diluted solution was then serially diluted with salt solution to enable colony counting, and smeared on a nutrient agar plate. The smeared nutrient agar plate was incubated at 35°C for 18 hours to prepare a test sample. A control sample is prepared in the same manner as the test sample, except that a compressed sample of starch and glycerol is used instead of the copolymer. The microbial concentrations of the test sample and the control sample were measured, and the antibacterial activity (%) was calculated according to the following formula 2. [Equation 2]

9. An antibacterial and deodorizing composition comprising the copolymer according to any one of claims 1 to 8.

10. 10. The antibacterial and deodorizing composition of claim 9, further comprising one or more of activated carbon; bentonite; superabsorbent polymer; polyethylene; polypropylene; polystyrene; polyamide; polyimide; polyethylene terephthalate; polyvinyl chloride; acryloyl-butadiene-styrene; and polyacrylic acid.

11. 10. An article of manufacture comprising or made from the antibacterial and deodorant composition of claim 9.

12. A method for producing the copolymer according to any one of claims 1 to 8, comprising the steps of: A method for producing a copolymer, comprising reacting starch and a compound represented by the following formula 1 at at least one temperature selected from 80°C to 140°C: 【Chemistry 6】 In the above Chemical Formula 1, L1 is an alkylene group, 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; R4 is hydrogen or a methyl group.

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