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 deodorant composition containing the same, 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 suppress or kill the growth of such microorganisms. In particular, there is a demand for antibacterial and deodorizing properties in polymeric materials used in products that we commonly use. As an example, there is a demand for the development of antibacterial and deodorizing materials suitable for use in pet supplies (such as cat litter).

[0004] In the past, the main method of introducing antibacterial and deodorant properties into polymers was to simply mix antibacterial and deodorant substances into the polymer. However, since there is a possibility of the antibacterial and deodorant substances leaking out, the safety of the antibacterial and deodorant substances used must be guaranteed. Therefore, in order to fundamentally solve the problem of antibacterial and deodorant substances leaking out, active research is being conducted on the development of antibacterial polymers that do not leak out of antibacterial substances by copolymerizing antibacterial and deodorant 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 deodorant composition containing the same, and a method for producing the same. [Means for solving the problem]

[0007] One embodiment of the present invention provides a polymerizable composition comprising a first unit derived from starch; and The present invention provides a copolymer including a second unit derived from a compound represented by the following Chemical Formula 1:

[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 is an alkyl group having 1 to 30 carbon atoms; R4 is hydrogen or a methyl group.

[0010] Another embodiment of the present invention provides an antibacterial and deodorant 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 invention is a method for producing the copolymer described above, comprising the steps of: The present invention provides a method for producing a copolymer, comprising the step of 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. Effect of the Invention

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

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

[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 specification 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 the concentration is unintentionally non-uniform when applied to a product. Therefore, the antibacterial activity can be controlled within a specific range, and antibacterial activity with excellent safety can be imparted.

[0017] The copolymer according to one embodiment of the present specification has low toxicity, and therefore can solve the safety problem. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0019] In the past, in order to impart antibacterial and deodorizing power to materials, antibacterial and deodorizing agents were simply mixed with other substances, and inorganic or organic antibacterial and deodorizing agents were used. The inorganic antibacterial and deodorizing agents are expensive, tend to cause discoloration of materials, and may reduce the physical properties of polymers during processing such as extrusion and injection. In addition, inorganic antibacterial and deodorizing agents have the disadvantage of low immediate antibacterial and deodorizing effects. The organic antibacterial and deodorizing agents have the disadvantage of poor stability to the human body and poor thermal stability, resulting in poor antibacterial and deodorizing durability.

[0020] In contrast, the copolymer according to the present specification does not contain an inorganic antibacterial / deodorant agent, and thus overcomes the drawbacks of discoloration and reduced transparency, and has the advantage of being excellent in stability to the human body and maintaining antibacterial / deodorant durability because the antibacterial / deodorant substance is polymerized as a monomer rather than being contained as a separate substance. In addition, when an organic antibacterial / deodorant is polymerized with another substance, the polymerization efficiency and conversion rate are often reduced or the properties of the polymerized other substance are often impaired, but the present specification can also eliminate such drawbacks. Due to the above-mentioned advantages, the copolymer according to the present specification can exhibit excellent antibacterial / deodorant durability.

[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 improve stability against leakage of the antibacterial and deodorizing agent.

[0022] Additionally, the copolymers of the present invention have the advantage of being environmentally friendly since they use 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 specifically stated to the contrary.

[0024] In this specification, "*" denotes a bonding point in the copolymer. For example, in the following chemical formula 2, * denotes both the portion where the first units are bonded to each other and the portion where the first unit is bonded to the second unit.

[0025] In this 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 be 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 can be included in a state of being bound to the polymer by polymerization in any order.

[0026] 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 removing hydrogen or a substituent, and the unit derived from the compound may mean a unit forming 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 polymer 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 polymer compound having a molecular weight distribution.

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

[0029] 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, in this specification, the unit of temperature is ° C., unless otherwise specified.

[0030] In this specification, when pressure affects the results of a physical property, the physical property is 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 this specification, when a physical property is affected by humidity, the physical property is measured at room temperature and pressure at unadjusted humidity, unless otherwise specified.

[0033] 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. In one embodiment, the number of carbon atoms of the alkyl group is 1 to 30. Specific examples of the alkyl group include, but are not limited to, 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 the present 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 each of these is a divalent group.

[0035] In this specification, the term "starch" refers to starch as used in the art. Specifically, it is 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 represents -OH; or -O-*, and at least one of R10 to R12 is -O-*; n1 is 1 to 10 7 is an integer, * denotes attachment points within the copolymer.

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

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

[0046] [ka]

[0047] In the above structure, * is a bonding point in 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 Integer, 500~10 7 integer, 10 3 ~10 7 integer, 10 4 ~107 integer, 10 5 ~10 7 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 is 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 attachment points within the copolymer.

[0054] In one embodiment of the present specification, n2 is 1 to 10. 6 Integer, 1 to 10 5 Integer, 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 number and the alkyl group with the smallest carbon 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 number and the alkyl group with the smallest carbon 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 high asymmetry, 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 the chemical formula 1 exhibits cationicity and may exist in the form of a salt with a group exhibiting anionicity. In this case, the group exhibiting anionicity is not particularly limited, and any material known in the art may be used as long as it does not impair the purpose of antibacterial properties. For example, the group exhibiting anionicity 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 effect of exhibiting excellent deodorizing power, antibacterial power, deodorizing power and antibacterial power is obtained.

[0072] The deodorant 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 is 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 attachment points 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 the 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 is composed of 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 by gel permeation chromatography (GPC).

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

[0085] In this specification, having a 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 deodorization 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 are 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 according to the following formula 1.

[0090]

number

[0091] In the above method 1 and formula 1, the test culture comprises a copolymer according to an embodiment of the present invention, and the control culture does not comprise said copolymer.

[0092] In this specification, CFU (Colony Forming Unit) means colony forming unit, and CFU / mL means the number of CFU per mL.

[0093] When the copolymer according to the present specification was evaluated for deodorizing power 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, i.e., bacteriostatic performance, measured based on 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 are placed in a cell culture flask and cultured at 35°C for 12 hours to produce a test culture solution. Ammonia is collected from the test culture solution using an ammonia detector. After ammonia collection is completed, 7.5 mL of salt solution (0.9 wt%) is added to the test culture solution and mixed to dilute the bacteria solution, which is then serially diluted with the salt solution for colony counting and smeared on a nutrient agar plate. The smeared nutrient agar plate is cultured at 35°C for 18 hours to produce 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 when preparing the test sample.

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

[0101]

number

[0102] In Method 2 and Scheme 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 remain purple 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, it is any one selected from the above-mentioned examples, but is not limited thereto.

[0107] As used herein, gram-negative bacteria is a collective term for bacteria that stain red when stained with the gram staining method, and which have a cell wall with relatively little peptidoglycan compared to gram-positive bacteria, but instead have an outer membrane composed 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 mold may be, but is not limited to, Candida albicans.

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

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

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

[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 mold bacteria, as measured by the method 2. The gram-positive bacteria, gram-negative bacteria, and mold strains can not only cause various diseases upon contact, but also cause secondary infections, so it is preferable that one antibacterial agent exhibits antibacterial properties against all of the gram-positive bacteria, gram-negative bacteria, and mold bacteria.

[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 invention provides an antibacterial and deodorant 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 contains 1 to 5 types, 1 to 3 types, 2 types, or 1 type of the additional components described above.

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

[0119] One embodiment of the present specification provides a molded article comprising or produced from the antibacterial and deodorant composition described above. The molded article may be, but is not limited to, cat litter, vegetable boxes for refrigerators, automobile parts, blow molded articles, inflation molded articles, cast molded articles, extrusion laminate molded articles, extrusion molded articles, foam molded articles, injection molded articles, sheets, films, fibers, monofilaments, nonwoven fabrics, etc. The automobile parts may be automobile interior and exterior materials, etc.

[0120] One embodiment of the present disclosure 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 content of starch satisfies the above-mentioned range, excellent antibacterial activity and odor 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 falls within the above-mentioned range, it has the effect of exhibiting excellent antibacterial properties and antibacterial durability.

[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 extended, the polymerization conversion rate may be reduced, and the productivity may be reduced. Specifically, there is a drawback that the polymerization conversion rate is reduced and a large amount of residual monomers and decomposition products are generated. On the other hand, if the content is more than 5 parts by weight, the initiator cannot be completely consumed during the polymerization process and may remain in the final polymer, which may reduce the physical properties of the polymer, especially the thermal stability.

[0125] In 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 azobisbutyronitrile (AIBN) or azobis-2,4-dimethylvaleronitrile; a hydroperoxide-based compound such as t-butyl hydroperoxide; or a sulfate-based compound such as sodium persulfate (SPS), potassium persulfate, or ammonium persulfate; or the like, and any one or a mixture of two or more of these may be used, but is not limited to the above examples.

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

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

[0128] In one embodiment of the present specification, the copolymer-forming composition further includes a solvent. The solvent 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, but for example, water, methanol, ethyl alcohol, isopropyl alcohol, and the like may be used.

[0130] One embodiment of the present specification provides a method for producing the above-mentioned copolymer, comprising step (a) of reacting starch and a monomer represented by Chemical Formula 1 at at least one temperature selected from 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 in which at least one temperature selected from 80° C. to 140° C. is changed within the temperature range of 80° C. to 140° C., or may be performed at any temperature selected from the above-mentioned 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. The reaction may also 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. In addition, when the reaction temperature or reactants are different from those in the production examples described below, the reaction time may be different.

[0134] In one embodiment of the present specification, the reacting step may include the steps of: (a1) preparing a mixture of the starch and a monomer represented by Chemical Formula 1; and (a2) 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 (a1-1); 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, the step (a1-3) of preparing the mixture B may include a process of mixing under pressure. The method of mixing under pressure may be any method used in the art without limitation, and may, for example, be 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 a 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 a 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 a step (d) of pulverizing the reactants. The pulverization may be performed by a method 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 grinding step (d) of the reactants. EXAMPLES

[0144] Hereinafter, the present specification will be described in detail with reference to examples in order to specifically explain the present specification. However, the examples according to the present specification may be modified in various different 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 specification to those having average knowledge in the art.

[0145] <Preparation Example 1> Preparation of monomer represented by 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 (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.

[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 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 solution 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 produced in the same manner as in Production Example 1-1, except that in Step 2(1) of Production Example 1-1, 1-bromodecane (production of compound 2) or 1-bromododecane (production of compound 3) was used instead of 1-bromooctane.

[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 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.

[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 obtain 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 solution 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) 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 in Step 1(1) of Preparation Example 1-1, 2-(dibutylamino)butanol (DBAB) was used instead of 2-(dibutylamino)ethanol.

[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 solution 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 in Preparation Example 1-10.

[0158] In the above Preparation Examples 1-1 to 1-11, a normal 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, for example, 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 28.44g of glycerol and 14.39g of water were added to 100g of corn starch (control), and 2g of the compound 12 and 1.33g of SPS were further added thereto 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 sand-like sample 1.

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

[0163] Production Example 2-(Comparative Production Example) 28.44g of glycerol and 14.39g of water were added to 100g of cellulose (Sigma-Aldrich, 40230854), and 2g of the compound 12 and 1.33g of SPS were further added thereto 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 and the sample obtained was in the form of powder.

[0164] Manufacturing Example 2-4 (Comparative Manufacturing Example) A sand-like 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] It was confirmed by HPLC measurement that the samples 1 and 3 were prepared. 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 eluate was then subjected to HPLC measurement. As a result of the HPLC measurement, it was confirmed that no residual monomer was detected, and thus 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 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 solution.

[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 according to 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 2.5mL of artificial urine inoculated with 3000±30CFU / mL of Proteus mirabilis and 1g 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 solution.

[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, the first measurement result is recorded as #1 and the second measurement result as #2, and 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) all have a high ammonia detection amount of 500 or more.

[0178] Also, from Table 1, it can be seen 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 of only starch (Sample 2, control culture medium).In contrast, it can be seen that the polymer (Sample 3, Comparative Example 1-1) to which a compound in which R1 to R3 are all methyl groups is applied exhibits a deodorizing power of 20% or less, which is low.

[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 2.5mL of artificial urine inoculated with 3000±30CFU / mL of Proteus mirabilis bacteria and 1g 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 solution. Ammonia was collected from the test culture solution using an ammonia detector. After ammonia collection was completed, 7.5mL of salt solution (0.9wt%) was added to the test culture solution and mixed to dilute the bacteria solution, which was then serially diluted with salt solution for colony counting and smeared on a nutrient agar plate. The smeared nutrient agar plate was cultured at 35°C for 18 hours to prepare a test sample.

[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 2.5mL of artificial urine inoculated with 3000±30 CFU / mL of Proteus mirabilis bacteria and 1g 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 solution. 7.5mL of salt solution (0.9wt%) was added to the test culture solution and mixed to dilute the bacterial solution, which was then serially diluted with salt solution for colony counting and smeared on a nutrient agar plate. The smeared nutrient agar plate was cultured at 35°C for 18 hours to prepare a test sample.

[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] In Table 2, the CFU value of the same sample is repeatedly measured, and the log CFU value of the first measurement is recorded as #1, and the log CFU value of the second measurement is recorded as #2, and the average is the log CFU value of the average of the CFU values ​​measured in #1 and #2. From Table 2, it can be seen that the copolymer according to one embodiment of the present invention (sample 1, experimental example 2-1) has an excellent antibacterial activity of 90% or more. In contrast, it can be seen that the polymer made of only 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 30% or less.

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: 【Chemistry 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 is an alkyl group having 1 to 30 carbon atoms; R4 is hydrogen or a methyl group.

2. The copolymer of claim 1 , wherein the first unit derived from starch comprises a unit represented by the following 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 attachment points 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 is 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 attachment points within the copolymer.

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

5. The copolymer according to claim 1 , comprising a third unit represented by the following 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 is 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 attachment points within the copolymer.

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

10.

7. The copolymer according to claim 1, wherein the copolymer has a deodorizing power against ammonia of 70% or more when the copolymer is subjected to a deodorizing evaluation by the following method 1: [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 according to the following formula 1. [0010]

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 are placed in a cell culture flask and incubated at 35° C. for 12 hours to prepare a test culture. Ammonia is collected from the test culture through an ammonia detector. After ammonia collection is completed, 7.5 mL of salt solution (0.9 wt%) is added to the test culture and mixed to dilute the bacteria solution, which is then serially diluted with salt solution for colony counting and smeared on a nutrient agar plate. The smeared nutrient agar plate is 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 when preparing the test sample. 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. [0025]

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

10. The antibacterial and deodorizing composition of claim 9, further comprising one or more of activated carbon; bentonite; superabsorbent resin; 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 is an alkyl group having 1 to 30 carbon atoms; R4 is hydrogen or a methyl group.

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