Elastic antibacterial polyurethane, its method of manufacture and articles containing same

Abstract

The present invention relates to an elastic antibacterial polyurethane polymer and a method for producing the same. The polyurethane polymer has excellent antibacterial properties, mechanical properties and heat resistance.

Description

[Technical Field]

[0001] Cross-reference to related applications(s) This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0110765, filed August 23, 2021, and Korean Patent Application No. 10-2022-0102689, filed August 17, 2022, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] Technical Field The present invention relates to an elastomeric antimicrobial polyurethane and a method for making the same. The present invention also relates to an article comprising the elastomeric antimicrobial polyurethane. [Background technology]

[0003] Polyurethane (PU), a type of engineering plastic, is used in a variety of fields, including synthetic fibers, paints, and vehicle interior materials. For example, polyurethane can be used with nylon to form a synthetic fiber called spandex, which can be used in underwear, socks, swimwear, and more. Polyurethane also has a three-dimensional foam structure, making it both elastic and firm, and is widely used in mattresses, textiles, and foam sponges.

[0004] On the other hand, when PU-related products are used for a long period of time, there is a problem that bacteria may grow, so it is necessary to ensure antibacterial properties. Summary of the Invention [Problem to be solved by the invention]

[0005] One object of the present invention is to provide a polyurethane having excellent elasticity and antibacterial properties.

[0006] Another object of the present invention is to provide a polyurethane having excellent heat resistance.

[0007] A further object of the invention relates to an article comprising a polyurethane of the above characteristics.

[0008] The above and other objects of the present invention can be achieved by the present invention, which will be described in detail below. [Means for solving the problem]

[0009] In an embodiment of the present invention, the present invention relates to an elastic antibacterial polyurethane polymer and a method for producing the same. The polyurethane polymer of the present invention has excellent antibacterial properties, heat resistance (durability), tensile properties, etc.

[0010] Unless otherwise defined herein, the term "alkyl group" may be an alkyl group having 1 to 40 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. In this case, the alkyl group may be a linear, branched, or cyclic alkyl group. In addition, the alkyl group may be optionally substituted with one or more substituents.

[0011] Unless otherwise defined, the term "haloalkyl group" used herein refers to a compound in which a hydrogen atom of an alkyl group is substituted with a halogen atom. In this case, the alkyl group may be used in the same sense as defined above.

[0012] Unless otherwise defined, the term "alkenyl group" used herein may refer to an alkenyl group having 2 to 40 carbon atoms. For example, the alkenyl group may be an alkenyl group having 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. In this case, the alkenyl group may be a linear, branched, or cyclic alkenyl group. In addition, the alkenyl group may be optionally substituted with one or more substituents.

[0013] Unless otherwise defined herein, the term "alkynyl group" may refer to an alkynyl group having 2 to 40 carbon atoms. For example, the alkynyl group may be an alkynyl group having 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. In this case, the alkynyl group may be a straight-chain, branched-chain, or cyclic alkynyl group. In addition, the alkynyl group may be optionally substituted with one or more substituents.

[0014] Unless otherwise defined, the term "aryl group" used herein refers to a monovalent residue derived from a compound or derivative thereof that includes a benzene ring structure, or a structure in which two or more benzene rings are linked by sharing one or two carbon atoms, or are linked by an optional linker. For example, the aryl group may be an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the aryl group may be optionally substituted with one or more substituents.

[0015] Unless otherwise defined, the term "heteroaryl group" used herein refers to an aryl group containing one or more of O, N, Si, and S. For example, the aryl group in the heteroaryl group may have the same meaning as defined above. The heteroaryl group may have 2 to 30 carbon atoms.

[0016] In this specification, unless otherwise defined, the term "aryloxy group" refers to a group RO- in which R is an aryl group, and in this case, the aryl group may be used in the same sense as defined above.

[0017] Unless otherwise defined herein, an "alkoxy group" may be an alkoxy group having 1 to 40 carbon atoms. For example, the alkoxy group may be an alkoxy group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group may be a linear, branched, or cyclic alkoxy group. Furthermore, the alkoxy group may be optionally substituted with one or more substituents.

[0018] In this specification, unless otherwise defined, the term "alicyclic structure" refers to a compound that is a cyclic hydrocarbon structure that is not an aromatic ring structure and is represented by -Y. The alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms, unless otherwise defined. The alicyclic structure may be optionally substituted with one or more substituents.

[0019] In this specification, unless otherwise defined, a "heteroalicyclic structure" refers to an alicyclic structure containing one or more of O, N, Si, and S. For example, an alicyclic structure can be used in the same sense as described above.

[0020] In this specification, unless otherwise defined, the term "alkylthio group" refers to RS-, where R is an alkyl group. In this case, the alkyl group can be used in the same sense as defined above.

[0021] In this specification, unless otherwise defined, the term "arylthio group" refers to RS- in which R is an aryl group, and the aryl group may have the same meaning as defined above.

[0022] In this specification, unless otherwise defined, a "direct bond" means that there is no atom at a position that can form a direct bond.

[0023] Unless otherwise defined herein, an "alkylene group" may be an alkylene group having 1 to 40 carbon atoms. For example, the alkylene group may be an alkylene group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be a linear, branched, or cyclic alkylene group. Furthermore, the alkylene group may be optionally substituted with one or more substituents.

[0024] Unless otherwise defined, in this specification, a "heteroalkylene group" may be an alkylene group containing one or more of O, N, Si, and S. In this case, the alkylene group may be used in the same sense as defined above.

[0025] Unless otherwise defined herein, a "cycloalkylene group" is a divalent functional group derived from a cycloalkane and may have 3 to 20 carbon atoms. For example, the cycloalkylene group may be a cycloalkylene group having 3 to 15 carbon atoms, 3 to 10 carbon atoms, or 3 to 5 carbon atoms. In addition, the cycloalkylene group may be optionally substituted with one or more substituents.

[0026] Unless otherwise defined, the term "arylene group" used herein refers to a divalent aromatic hydrocarbon group. For example, the arylene group refers to a divalent residue derived from a compound or derivative thereof containing one benzene ring structure, or a structure in which two or more benzene rings are linked by sharing one or two carbon atoms, or are linked by an optional linker. For example, the arylene group may be an arylene group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the arylene group may be optionally substituted with one or more substituents.

[0027] Unless otherwise defined herein, the term "heteroarylene group" may refer to an arylene group containing one or more of O, N, Si, and S. For example, the heteroarylene group may have the same meaning as defined above. The heteroarylene group may have 2 to 30 carbon atoms.

[0028] Although not particularly limited, the aforementioned groups may be substituted or unsubstituted. As used herein, the term "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, hydroxy, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, aryloxy, alkylthioxy, arylthioxy, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamine, aralkylamine, heteroarylamine, arylamine, arylphosphine, or heteroaryl containing one or more N, O, and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked together. For example, a "substituent linked to two or more substituents" may be a biphenyl group. In other words, a biphenyl group may be an aryl group or may be interpreted as a substituent linked to two phenyl groups.

[0029] In this specification, unless otherwise specified, the carbon number of the aforementioned group means the carbon number related to the length of the main chain or the carbon number of the main skeleton.

[0030] As used herein, the term "elastomeric antimicrobial polyurethane polymer contains a specific unit" means that the compound is polymerized into a polymer structure (main chain or side chain) formed by the reaction of one or more compounds, and the unit derived from the compound is included in the polymer structure.

[0031] In this specification, unless otherwise defined, the "molecular weight" may be a weight average molecular weight (e.g., g / mol) measured by GPC in terms of polystyrene.

[0032] The present invention will now be described in more detail.

[0033] In one embodiment, the present invention relates to an elastic antibacterial polyurethane. The polyurethane described below has excellent antibacterial properties, mechanical properties (e.g., tensile strength, tensile strain), and heat resistance.

[0034] Specifically, the elastic antibacterial polyurethane of the present invention comprises (A) an isocyanate compound; and (B) a unit derived from a polyol containing a polyether glycol and a diol represented by the following Chemical Formula 1, wherein the polyol (B) contains 0.01 to 40 mol % of the diol represented by Chemical Formula 1:

[0035] [ka]

[0036] In the above Chemical Formula 1, R1 and R2 are each independently a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, an alkylthio group, or an arylthio group; L1 and L2 each independently represent an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; L3 is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; A is an alkylene group having more than 6 carbon atoms; X - means an anion.

[0037] In this case, the number of carbon atoms in A in the above formula 1 means the number of carbon atoms in the main chain.

[0038] As described above, the elastic antibacterial polyurethane of the present invention may be prepared by reacting an isocyanate compound with at least two different polyols, i.e., a polyol component including a polyether glycol and a compound of Formula 1 (quaternary ammonium diol).

[0039] The type of the (A) isocyanate compound is not particularly limited, and the isocyanate compound may be selected, for example, in consideration of the physical properties of the polymer (e.g., processability, heat resistance, etc.) and the reactivity between the polymer-forming components.

[0040] In an embodiment of the present invention, the isocyanate compound used to form the polyurethane may be an aromatic isocyanate, which can complement the low heat resistance of the ammonium diol represented by Chemical Formula 1.

[0041] In one example, the isocyanate compound contained in the polyurethane may be toluene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate (MDI), or an aromatic isocyanate compound having a skeleton of any of the compounds listed above. However, the aromatic isocyanate used in preparing the polymer of the present invention is not limited to those listed above.

[0042] The (B) polyol refers to an alcohol compound containing two or more hydroxyl groups. In the present invention, the polyol includes (b1) a polyether glycol and (b2) a diol represented by Chemical Formula 1.

[0043] The polyether glycol (b1) is the main component that ensures the elastic properties of the polyurethane of the present invention.

[0044] The type of polyether glycol used is not particularly limited as long as it does not contradict the achievement of the technical object of the present invention. For example, polytetramethylene glycol (PTMG) or polypropylene glycol (PPG) may be used.

[0045] In one example, the polyether glycol may have a weight average molecular weight in the range of 500 to 3,000. Specifically, the lower limit of the molecular weight may be 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 1100 or more, 1200 or more, 1300 or more, 1400 or more, 1500 or more, 1600 or more, 1700 or more, 1800 or more, 1900 or more, 2000 or more, 2100 or more, 2200 or more, 2300 or more, 2400 or more, or 2500 or more, and the upper limit may be, for example, 2900 or less, 2800 or less, 2700 or less, 2600 or less, 2500 or less, 2400 or less, 2300 or less, 2200 or less, 2100 or less, 2000 or less, 1900 or less, 1800 or less, 1700 or less, 1600 or less, or 1500 or less. In a specific example of the present invention, the polyether glycol may have a weight average molecular weight of 1000 or more or 1500 or more and 2500 or less or 2000 or less. When the molecular weight of the polyether glycol is appropriately adjusted within the above range, it is advantageous to ensure mechanical properties (e.g., elasticity or tensile properties).

[0046] The diol component (b2) represented by the above chemical formula 1 can impart antibacterial properties to polyurethane.

[0047] In one example, R1 in Chemical Formula 1 may be, except for hydrogen, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, an alkylthio group, or an arylthio group. Polyurethanes containing units derived from diol-type quaternary ammonium monomers (or diol-based quaternary ammonium monomers) are more advantageous in providing excellent antibacterial properties.

[0048] In one example, A may be an alkylene group having more than 6 and not more than 20 carbon atoms, more specifically, 8 to 20, 8 to 18, 8 to 16, 8 to 14, 8 to 12, or 8 to 10. When A in Chemical Formula 1 is an alkylene group satisfying the above carbon number, it is advantageous in imparting excellent antibacterial properties and low toxicity to the polyurethane polymer.

[0049] In one example, A may be a linear alkylene group. In the monomer represented by Chemical Formula 1, the ammonium cation adsorbs to the anionic membrane of bacteria, and the linear alkylene group, i.e., A in Chemical Formula 1, which is a hydrophobic group, advantageously functions to exert an antibacterial effect by destroying the cell membrane structure of bacteria and releasing proteins and enzymes.

[0050] The antibacterial effect due to the disruption of the cell membrane structure is more effective when A has a structure that is advantageous for penetration into the bacterial cell membrane while maintaining a certain degree of hydrophobicity. In consideration of this, in a specific example of the present invention, A may have a structure represented by the following chemical formula 2:

[0051] [ka]

[0052] In the above Chemical Formula 2, n is a number of 4 or more (for example, n is 4 or more, 5 or more, or 6 or more), and L3 and R2 may be bonded to both ends represented by the *, respectively. However, when L3 is a direct bond, one end represented by the * is bonded to a N atom.

[0053] If n in Chemical Formula 2 is too large, the toxicity of the polymer may increase. In consideration of this, the upper limit of n may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.

[0054] In one example, R1 and / or R2 in Formula 1 may be a linear alkyl group.

[0055] The antibacterial activity of the monomer of Formula 1 is initiated by the adsorption of ammonium cations to the anionic membrane of bacteria. However, if R1 and / or R2 have a large number of carbon atoms (e.g., if the chain is long), adsorption may be hindered due to a steric hindrance, and the antibacterial properties of the polymer may not be fully exhibited. In consideration of this, in a specific example of the present invention, R1 and / or R2 of Formula 1 may be an alkyl group having 12 or less, 8 or less, or 4 or less carbon atoms. Specifically, R1 and / or R2 may be a propyl group, an ethyl group, or a methyl group.

[0056] In one example, R1 and R2 in Formula 1 may be the same.

[0057] In one example, L1 and / or L2 may be a straight-chain alkylene group.

[0058] As described above, the antibacterial activity of the monomer of Formula 1 is initiated by the adsorption of ammonium cations to the anionic membrane of bacteria. However, if L1 and / or L2 have a large number of carbon atoms, adsorption may be hindered due to a steric hindrance, and the antibacterial properties of the polymer may not be fully exhibited. In consideration of this, in a specific example of the present invention, L1 and / or L2 of Formula 1 may be an alkylene group having 12 or less, 8 or less, or 4 or less carbon atoms. For example, L1 and / or L2 may be a propylene group, an ethylene group, or a methylene group.

[0059] In consideration of ensuring antibacterial properties and yield regarding monomer production, in an embodiment of the present invention, L1 and L2 may be the same.

[0060] In one example, L3 may be a linear alkylene group.

[0061] As described above, the number of carbon atoms in L3 may be determined in consideration of the degree of antibacterial activity exhibited by the monomer of Chemical Formula 1. In a specific example of the present invention, L3 may be an alkylene group having 12 or less carbon atoms, 8 or less carbon atoms, or 4 or less carbon atoms. For example, L3 may be a propylene group, an ethylene group, or a methylene group.

[0062] In relation to Chemical Formula 1, the X - is not particularly limited. For example, - is F - , Cl - , Br - , I - , NO3 - , (CN)2N - , BF4 - , ClO4 - , RSO3 - (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), RCOO - (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), PF6 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , (CF3SO3 - )2, (CF2CF2SO3 - )2, (C2F5SO2)2N - , (CF3SO3)2N - , (CF3SO2)(CF3CO)N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3(CF2)7SO3 - , CF3COO - , C3F7COO - , CF3SO3 - , or C4F9SO3 - may be.

[0063] The molecular weight of the monomer represented by Chemical Formula 1 may be adjusted in consideration of antibacterial properties. For example, if the molecular weight is too large because the number of carbon atoms in the group bonded to the N atom constituting the ammonium in Chemical Formula 1 is too large, it may be toxic to the human body. On the other hand, if the molecular weight is too small because the number of carbon atoms in the group bonded to the N atom constituting the ammonium is too small, it may be difficult to ensure sufficient antibacterial activity.

[0064] In consideration of the above, in an embodiment of the present invention, the compound represented by Chemical Formula 1, i.e., the diol-form ammonium monomer, may have a weight-average molecular weight of 300 or more. Specifically, the lower limit of the weight-average molecular weight of the diol-form ammonium monomer may be 310 or more, 320 or more, 330 or more, 340 or more, 350 or more, 360 or more, 370 or more, 380 or more, 390 or more, or 400 or more. The upper limit may be 500 or less. Specifically, the upper limit of the weight-average molecular weight of the diol-form ammonium monomer may be, for example, 490 or less, 480 or less, 470 or less, 460 or less, 450 or less, 440 or less, 430 or less, 420 or less, 410 or less, 400 or less, 390 or less, 380 or less, 370 or less, 360 or less, or 350 or less.

[0065] In a specific example of the present invention, the (B) polyol contains 0.01 to 40 mol % of the diol represented by Chemical Formula 1.

[0066] Specifically, the content of the diol represented by Chemical Formula 1 in the (B) polyol is, for example, 0.05 mol% or more, 0.1 mol% or more, or 0.5 mol% or more, specifically 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, or 14 mol% or more. , 15 mol% or more, 16 mol% or more, 17 mol% or more, 18 mol% or more, 19 mol% or more, 20 mol% or more, 21 mol% or more, 22 mol% or more, 23 mol% or more, 24 mol% or more, 25 mol% or more, 26 mol% or more, 27 mol% or more, 28 mol% or more, 29 mol% or more, 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, or 35 mol% or more. The upper limit may be, for example, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less.

[0067] When the content of the diol represented by Chemical Formula 1 satisfies the above range, it is advantageous to ensure excellent heat resistance, elasticity, and antibacterial properties, which are the technical objectives of the present invention.

[0068] The content of the polyether glycol in the (B) polyol may be, for example, the amount remaining after subtracting the content (mol %) of the diol represented by Chemical Formula 1 in the polyol.

[0069] For example, the content of polyether glycol in the (B) polyol may be 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, or 95 mol% or more, and the upper limit may be, for example, 99.99 mol% or less, 99.95 mol% or less, 99.9 mol% or less, or 99.5 mol% or less, specifically 99 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, or 65 mol% or less.

[0070] When the polyether glycol content satisfies the above range, it is advantageous to ensure excellent heat resistance, elasticity, and antibacterial properties, which are the technical objectives of the present invention.

[0071] In one example, the molar ratio of the (A) isocyanate to the (B) polyol may be in the range of 1.0 to 2.0, where the molar ratio means the number of moles of the isocyanate compound used in the production of the polymer divided by the total number of moles of the polyol.

[0072] For example, the lower limit of the molar ratio of the (A) isocyanate to the (B) polyol may be 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, or 1.9 or more, and the upper limit may be 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, or 1.2 or less.

[0073] In a specific example of the present invention, the polyurethane polymer may include methylene diphenyl diisocyanate (MDI), which is an isocyanate compound; polytetramethylene glycol (PTMG), which is a polyether glycol; and a unit derived from the compound of Chemical Formula 1. In this case, the polyurethane polymer may include a structure represented by the following formula:

[0074] [ka]

[0075] In the above structural formula, n may be an integer that satisfies the molecular weight of the polyether glycol described above.

[0076] In the structural formula, m may be an integer that satisfies the molecular weight of the urethane polymer described below, and may be, for example, 3 to 100.

[0077] In another example, the polyurethane polymer may further include units containing methylene diphenyl diisocyanate (MDI), an isocyanate compound, and polytetramethylene glycol (PTMG), a polyether glycol, in addition to the units of Formula 1 (i.e., units that do not include units derived from the compound of Formula 1). These units are those in Formula 1 that do not include units derived from Formula 1, and in these units, the integer m may be 3 to 100 or even greater than 100.

[0078] In one example, the elastic antibacterial polyurethane polymer may further include units derived from a diamine compound. Specifically, the elastic antibacterial polyurethane polymer may include (A) an isocyanate compound; (B) a polyol including a polyether glycol and a diol represented by the following Chemical Formula 1; and (C) units derived from a diamine compound. More specifically, the elastic antibacterial polyurethane polymer may be produced by further reacting a diamine compound with a polymer (e.g., a prepolymer) of (A) the isocyanate compound and (B) the polyol including a polyether glycol and a diol represented by the following Chemical Formula 1.

[0079] The diamine compound can function as a chain extender. The type of diamine that can be used is not particularly limited, but for example, compounds such as ethylenediamine, 1,2'-propylenediamine, hexamethylenediamine, xylenediamine, 4,4'-diphenylmethanediamine, or hydrazine may be used in the present invention. Alternatively, one or more of the compounds listed above may be used.

[0080] In one example, the molar ratio of the (C) diamine compound to the (B) polyol may be less than 1.0. For example, the molar ratio of the (C) diamine compound to the (B) polyol may be 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, or 0.4 or less. The lower limit may be, for example, 0.1 mol or more, 0.2 mol or more, 0.3 mol or more, or 0.4 mol or more. Within this range, the aforementioned function of ethylenediamine can be adequately ensured.

[0081] Although not particularly limited, in a specific example of the present invention, the polyurethane may have a molecular weight of 10,000 or more. Specifically, the molecular weight of the polyurethane may be 50,000 or more or 100,000 or more. The upper limit may be, for example, 300,000 or less, 250,000 or less, 200,000 or less, 150,000 or less, or 100,000 or less. Satisfying the above ranges is advantageous for ensuring mechanical properties (e.g., tensile properties), and is particularly advantageous for exhibiting elasticity in fiber applications.

[0082] The antimicrobial elastomeric polyurethane polymer can exhibit certain properties.

[0083] In one example, the polyurethane polymer of the present invention can exhibit an antibacterial rate (bacteriostatic reduction rate) of 90% or more when measured according to JIS Z 2801. For example, the antibacterial rate can be 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 99.9% or more. In a specific example of the present invention, the polyurethane polymer can exhibit an antibacterial rate of substantially 100%. If the antibacterial rate is less than the above value, it is difficult to consider the polyurethane polymer to have excellent antibacterial properties.

[0084] In one example, the polyurethane polymer of the present invention may have a thermal decomposition temperature (Td) of 280°C or higher. The thermal decomposition temperature refers to the temperature (Td) at which the weight loss of the polymer reaches 10% when the temperature is increased to 700°C at a rate of 10°C / min under N2, as in the experiment shown in FIG. 1 (thermal decomposition onset temperature). The thermal decomposition temperature may be, for example, 285°C or higher, 290°C or higher, 295°C or higher, 300°C or higher, 305°C or higher, or 310°C or higher. The upper limit of the thermal decomposition temperature may be, for example, 350°C or lower, 345°C or lower, 340°C or lower, 335°C or lower, 330°C or lower, 325°C or lower, 320°C or lower, 315°C or lower, 310°C or lower, 305°C or lower, or 300°C or lower. Within this range, the polymer may exhibit excellent processability and heat resistance and durability.

[0085] In one example, the polyurethane polymer of the present invention may have a tensile strain of 900% or more as measured by the ASTM D882 tensile test method. In this case, the tensile strain may be measured, for example, on an elastic antibacterial polyurethane polymer sample having a width-to-length ratio (width:length) of 1:1 to 100, 1:1 to 50, 1:1 to 30, or 1:1 to 10. Specifically, the tensile strain may be, for example, 910% or more, 920% or more, 930% or more, 940% or more, 950% or more, 960% or more, 970% or more, 980% or more, 990% or more, 1000% or more, or 1010% or more. The upper limit may be, for example, 1100% or less, 1090% or less, 1080% or less, 1070% or less, 1060% or less, 1050% or less, 1040% or less, 1030% or less, 1020% or less, 1010% or less, or 1000% or less. As confirmed by experiments described below, the polymer of the present invention can maintain a high tensile strain even while incorporating the diol of Chemical Formula 1 to ensure antibacterial properties.

[0086] In one example, the polyurethane polymer of the present invention may have a tensile strength of 30 MPa or more as measured by the ASTM D882 tensile test method. In this case, the tensile strength may be measured, for example, on an elastic antibacterial polyurethane polymer sample having a width-to-length ratio (width:length) of 1:1 to 100, 1:1 to 50, 1:1 to 30, or 1:1 to 10. Specifically, the tensile strength may be, for example, 35 MPa or more, 40 MPa or more, 45 MPa or more, 50 MPa or more, 55 MPa or more, or 60 MPa or more. The upper limit may be, for example, 65 MPa or less, 60 MPa or less, 55 MPa or less, 50 MPa or less, 45 MPa or less, 40 MPa or less, or 35 MPa or less. As confirmed by the experiments described below, the polymer of the present invention can maintain high tensile strength even when incorporating a diol of Formula 1 to ensure antibacterial properties.

[0087] In one example, the polyurethane polymer of the present invention may have a content of unreacted diol represented by Chemical Formula 1 of 1,000 ppm or less relative to the entire polymer. The unreacted content can be determined using High Performance Liquid Chromatography (HPLC). Specifically, the content of unreacted diol represented by Chemical Formula 1 relative to the entire polymer may be 950 ppm or less, 900 ppm or less, 850 ppm or less, 800 ppm or less, 750 ppm or less, 700 ppm or less, 650 ppm or less, 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, or 50 ppm or less. If the content of unreacted monomer increases or exceeds the above range, the mechanical properties (tensile properties) may be reduced due to the monomer of Formula 1 that has not been chemically bonded.

[0088] The uses of the polyurethane polymer are not particularly limited, and for example, the polymer can be used as a raw material for fibers (e.g., elastic yarns such as spandex), fabrics, clothing (e.g., underwear, swimwear, socks, etc.), paints, vehicle interior materials, mattresses, foams, etc.

[0089] In another aspect, the present invention relates to a method for producing an elastomeric antimicrobial polyurethane polymer, which produces an elastomeric antimicrobial polyurethane polymer of the above-described configuration.

[0090] Specifically, the method includes a step (S1) of mixing and reacting (A) an isocyanate compound and (B) a polyol containing a polyether glycol and a diol represented by the following Chemical Formula 1. Here, the (B) polyol contains 0.01 to 40 mol % of the diol represented by Chemical Formula 1.

[0091] [ka]

[0092] In the above Chemical Formula 1, R1 and R2 are each independently a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, an alkylthio group, or an arylthio group; L1 and L2 each independently represent an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; L3 is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; A is an alkylene group having more than 6 carbon atoms; X - means an anion.

[0093] Here, the number of carbon atoms in the formula 1A means the number of carbon atoms in the main chain.

[0094] The components forming the polyurethane of the present invention, i.e., the polymerization components used in the production of the polyurethane and their contents, and the properties of the produced polyurethane polymer are the same as those described above, and therefore will not be described further.

[0095] In one example, the reaction may be carried out at a temperature of 100°C or less. If the reaction temperature is higher than 100°C, the diisocyanate may produce a dimer through a side reaction, which may hinder polymer synthesis. Specifically, the reaction temperature may be 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, or 60°C or less. The lower limit may be, for example, 50°C or more, 55°C or more, 60°C or more, 65°C or more, or 70°C or more.

[0096] In one example, the reaction may be carried out for several tens of minutes to several tens of hours. Specifically, the reaction may be carried out for, for example, 30 minutes or more, 60 minutes or more, or 90 minutes or more. The upper limit of the reaction time may be, for example, 30 hours or less, 25 hours or less, 20 hours or less, 15 hours or less, 10 hours or less, or 5 hours or less. Within this time range, the molecular weight of the polymer can be appropriately controlled, and the occurrence of side reactions can be controlled.

[0097] In one example, the method may further include a step (S2) of further reacting a prepolymer obtained by reacting (A) an isocyanate compound and (B) a polyol including a polyether glycol and a diol represented by the following Chemical Formula 1 with (C) a diamine compound:

[0098] Specifically, the prepolymer or its solution is diluted with a solvent to prepare a dilute solution. The type of solvent used to prepare the dilute solution is not particularly limited, and for example, DMAc (dimethylacetamide) may be used. The concentration of the dilute solution may be adjusted so that the prepolymer content is about 10 to 40 or 20 to 30 wt% of the total weight of the dilute solution. A diamine compound is then added to the prepolymer dilute solution prepared as described above. According to an embodiment of the present invention, the temperature at which the diamine compound is added to the prepolymer dilute solution may be adjusted to 10°C or less, for example, about 0 to 4°C, to prevent a rapid reaction from occurring. After the addition of the diamine compound, the reaction may be carried out for several hours, for example, 1 to 2 hours.

[0099] As described above, the antibacterial elastic polyurethane of the present invention can be prepared by reacting the diamine compound, which is a chain extender, with the prepolymer.

[0100] The antibacterial elastomeric polyurethane produced by the above method satisfies the above-mentioned properties (e.g., antibacterial rate, tensile strain, tensile strength, and unreacted diol content).

[0101] In yet another embodiment of the present invention, the present invention relates to an engineering plastic comprising the antibacterial elastomeric polyurethane polymer.

[0102] The engineering plastics are plastics used as materials for parts of industrial machines, tools, etc., and their specific uses are not particularly limited.

[0103] In yet another aspect of the present invention, the present invention relates to an article comprising the antimicrobial elastomeric polyurethane polymer.

[0104] In one example, the article may be a fiber (e.g., elastic yarn such as spandex), a fabric, a garment (e.g., underwear, swimwear, socks, etc.), a paint, a vehicle interior material, a mattress, or foam. According to an embodiment of the present invention, the article may be a spandex fiber containing the antimicrobial elastomeric polymer described above, or a fabric or garment containing the fiber.

[0105] In yet another embodiment, the present invention relates to a spinning composition (or spinning solution) for producing elastic yarn, which comprises at least the elastic polymer described above.

[0106] In yet another embodiment of the present invention, the present invention relates to a method for preparing the spinning composition (or spinning solution) for producing the elastic yarn. The method includes all of the methods and steps for producing the elastic antibacterial polyurethane polymer.

[0107] In yet another embodiment, the present invention relates to an elastic yarn (e.g., spandex) comprising the antimicrobial elastic polyurethane polymer.

[0108] The elastic yarn contains a polyurethane polymer having the above-described properties, and therefore can provide antibacterial properties without reducing tensile properties or heat resistance. Such elastic yarn can be used in hygiene or medical textiles.

[0109] The form of the elastic yarn is not particularly limited and may be monofilament or multifilament. The fineness of the elastic yarn is also not particularly limited and may be appropriately adjusted depending on the application of the fiber.

[0110] The explanation regarding the polyurethane polymer is the same as that described above, and therefore will be omitted.

[0111] In yet another embodiment of the present invention, the present invention relates to a method for producing the elastic yarn. Specifically, the method includes a step (S1) of producing a spinning solution and a step (S2) of spinning the spinning solution.

[0112] In a specific example of the present invention, step (S1) includes step (S11) of mixing and reacting (A) an isocyanate compound and (B) a polyol containing a polyether glycol and the diol represented by Chemical Formula 1; and step (S12) of further reacting (C) a diamine compound with a prepolymer obtained by reacting (A) an isocyanate compound and (B) a polyol containing a polyether glycol and the diol represented by Chemical Formula 1. In this case, the (B) polyol contains 0.01 to 40 mol % of the diol represented by Chemical Formula 1.

[0113] In addition, in relation to the step of preparing the spinning solution, the details of preparing the elastic antibacterial polyurethane, which is the main component of the spinning solution (e.g., prepolymer preparation, reaction of prepolymer with diamine, etc.) are the same as those described for the elastic antibacterial polyurethane and its preparation method, so they will be omitted here.

[0114] Regarding step (S2), the spinning process for producing fibers is not particularly limited. For example, a spinning device equipped with a spinneret may be used, and the temperature during spinning may be adjusted to, for example, a level of 200°C or higher or 250°C or higher.

[0115] After spinning, cooling with air or liquid (e.g., water or other liquid containing a solvent) may be performed.

[0116] In one example, the method may further include a winding step (S3). The spun or cooled fiber after spinning may be wound using a known method or device, such as a winding roller. [Effects of the Invention]

[0117] According to an embodiment of the present invention, a polyurethane having excellent antibacterial properties, mechanical properties (eg, tensile strength and tensile strain), and heat resistance can be provided. [Brief explanation of the drawings]

[0118] [Figure 1a] FIG. 1a is a graph showing the experimental results regarding the heat resistance of Comparative Example 1. [Figure 1b] FIG. 1b is a graph showing the experimental results regarding the heat resistance of Example 1. [Figure 1c] FIG. 1c is a graph showing the experimental results regarding the heat resistance of Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0119] The functions and effects of the present invention will be explained in more detail below through specific examples of the present invention, but these are presented as examples of the present invention and do not limit the scope of the invention in any way.

[0120] Polymer production Example 1 11.6 g of MDI (Methylene diphenyl diisocyanate) (Mw molecular weight 250.25), 52.3 g of PTMG (Poly(tetramethylene ether)glycol) (Mw molecular weight 2000.0), and 1.1 g of a quaternary ammonium diol (Mw molecular weight 368.00) having the structure shown below in Formula 1-1 were placed in a reactor, and the atmosphere inside the reactor was replaced with N2. DMAc solvent was then placed in the reactor, and the reactor was heated to 90°C and reacted for 90 minutes to produce a polyurethane prepolymer.

[0121] [ka]

[0122] The prepared polyurethane prepolymer solution was then mixed with DMAc solvent to prepare a prepolymer solution diluted to a concentration of about 25% by weight, and 0.9 g of ethylenediamine (Mw 60.10) was added at a temperature range of about 0 to 4°C. After the addition of ethylenediamine, the reaction was carried out for about 1.5 hours to prepare a polyurethane polymer.

[0123] Example 2 Polyurethane was prepared in the same manner as in Example 1, except that 11.2 g of MDI (methylene diphenyl diisocyanate) (MW 250.25), 53.3 g of PTMG (poly(tetramethylene ether) glycol) (MW 2000.0), 0.5 g of the quaternary ammonium diol having the structure of [Chemical Formula 1-1] (MW 368.00), and 0.9 g of ethylene diamine (MW 60.10) were added to the reactor.

[0124] Example 3 Polyurethane was prepared in the same manner as in Example 1, except that 10.9 g of MDI (methylene diphenyl diisocyanate) (MW 250.25), 54.0 g of PTMG (poly(tetramethylene ether) glycol) (MW 2000.0), 0.1 g of the quaternary ammonium diol having the structure of [Chemical Formula 1-1] (MW 368.00), and 0.9 g of ethylene diamine (MW 60.10) were added to the reactor.

[0125] Comparative Example 1 Polyurethane was produced in the same manner as in Example 1, except that 10.8 g of MDI (methylene diphenyl diisocyanate) (MW 250.25), 54.2 g of PTMG (poly(tetramethylene ether) glycol) (MW 2000.0), and 0.9 g of ethylene diamine (MW 60.10) were added to the reactor.

[0126] Comparative Example 2 Polyurethane was prepared using the same amounts of PTMG, MDI, and [Chemical Formula 1-1] as used in Example 3. However, unlike Example 3 in which PTMG, MDI, and [Chemical Formula 1-1] were reacted together, PTMG and MDI were reacted first (until the NCO conversion rate of MDI reached about 99%), and then [Chemical Formula 1-1] was added to a chain extender to react with the remaining -NCO groups.

[0127] Among the components used in the production of each polymer in the Examples and Comparative Examples, the molar ratios between MDI, PTMG and the component [Chemical Formula 1-1] are as shown in Table 1 below.

[0128] [Table 1]

[0129] evaluation (1) Content of unreacted [Chemical Formula 1-1] The amount of the monomer of formula 1-1 remaining in the polyurethane after polymerization was quantitatively measured using an HPLC (High Performance Liquid Chromatography) analyzer. More specifically, the produced resin pellets were first placed in a certain amount of solvent (saline) and stirred for 24 hours, and the extract was then filtered to extract unreacted components from the resin. The resulting solution was then analyzed by HPLC, and the amount of the compound of formula 1 remaining in the resin was determined by comparing it with the HPLC analysis results of the copolymer monomer measured previously. Based on the experimental results described below, the unreacted monomer of formula 1-1 remaining in the polymerized polyurethane is believed to be the cause of the deterioration of mechanical properties.

[0130] (2) Antibacterial evaluation The antibacterial activity of each polymer in Examples 1-3 and Comparative Examples 1-2 was evaluated. Specifically, a 20 wt% polymer solution prepared using DMF (dimethylformamide) as a solvent was subjected to solvent casting to prepare a film (5 cm x 5 cm), and the antibacterial activity was evaluated according to the JIS Z 2801 method.

[0131] (3) Durability (heat resistance) evaluation The heat resistance of each polymer in Examples 1-2 and Comparative Example was evaluated. Specifically, the weight loss of the polymers was compared while the temperature was increased to 700°C at a rate of 10°C / min under N2. The results are shown in Figure 1a (Comparative Example 1), Figure 1b (Example 1), and Figure 1c (Example 2).

[0132] FIG. 1 confirms that the heat resistance of polyurethane does not decrease even when the unit of the compound of Chemical Formula 1 (or Chemical Formula 1-1) is introduced during polyurethane polymerization as in the examples.

[0133] (4) Tensile property evaluation The tensile properties of each polymer in Examples 1-3 and Comparative Examples 1-2 were evaluated. Specifically, the tensile strength and tensile strain of the samples were measured using the tensile test method of ASTM D882. For reference, ASTM D882 relates to tensile testing of thin films (thickness less than about 1 mm), and the sample size used in the experiments for the present invention was 5 mm x 50 mm (width x length) (thickness: about 200 to 300 μm).

[0134] For reference, tensile strength means the maximum stress a material can withstand before breaking under tensile load, and is calculated by dividing the maximum load by the cross-sectional area of ​​the material. Tensile strain means the strain when a material is deformed by tensile stress, and is expressed as the ratio of the change in length from the initial length.

[0135] [Table 2]

[0136] As shown in Table 1, Example 1-3 has a higher tensile strength than Comparative Example 1-2. In terms of tensile strain, Example 1-3, which further ensures antibacterial properties, exhibits a tensile strain similar to that of Comparative Example 1. In other words, Example 1-3 exhibits excellent elasticity (despite the additional reaction of Chemical Formula 1-1).

[0137] On the other hand, in Comparative Example 2, in which the diol of Formula 1-1 was used as a chain extender, unlike the process for preparing the polyurethane polymer of the present invention, it was confirmed that the mechanical properties (tensile strength, tensile strain) were poor due to the presence of excess unreacted monomer.

Claims

1. (A) an isocyanate compound; and (B) a unit derived from a polyol containing a polyether glycol and a diol represented by the following Chemical Formula 1: (C) contains a unit derived from a diamine compound which is a chain extender, the molar ratio of the diamine compound (C) to the polyol (B) is 0.4 or more and 0.6 or less; The polyol (B) contains 4 to 40 mol % of a diol represented by Chemical Formula 1, When measured according to JIS Z 2801, it exhibits an antibacterial rate of 90% or more. The content of the unreacted diol represented by Chemical Formula 1 is 1,000 ppm or less based on the entire polymer. Elastic antibacterial polyurethane polymer. 【Chemistry 1】 (However, in the above chemical formula 1, R １ and R ２ each independently represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, an alkylthio group, or an arylthio group; L １ and L ２ are each independently an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group, L ３ is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; A is an alkylene group having more than 6 carbon atoms; X － means an anion.)

2. The tensile strain measured by the ASTM D882 tensile test method is 900% or more.

10. The elastomeric antimicrobial polyurethane polymer of claim 1. (However, the tensile strain is measured on an elastic antibacterial polyurethane polymer sample having a width to length ratio (width:length) of 1:1 to 100.)

3. The tensile strength measured by the ASTM D882 tensile test method is 30 MPa or more.

10. The elastomeric antimicrobial polyurethane polymer of claim 1. (However, the tensile strength is measured on elastic antibacterial polyurethane polymer samples having a width to length ratio (width:length) of 1:1 to 100.)

4. the molar ratio of the isocyanate compound (A) to the polyol (B) is in the range of 1.0 to 2.0; 10. The elastomeric antimicrobial polyurethane polymer of claim 1.

5. A is an alkylene group having more than 6 and not more than 20 carbon atoms.

10. The elastomeric antimicrobial polyurethane polymer of claim 1.

6. The A has a structure represented by the following chemical formula 2:

10. The elastomeric antimicrobial polyurethane polymer of claim 1. 【Chemistry 2】 (In the above Chemical Formula 2, n is a number of 4 or more, and both ends represented by * are ３ and R ２ may be combined with each other. ３ is a direct bond, one end represented by the * is bonded to the N atom.

7. The X － Is F － , Cl － ,Br － , I － , NO ３ － , (CN) ２ N － , B.F. ４ － , ClO ４ － , RSO ３ － (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), RCOO － (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), PF ６ － , (CF ３ ) ２ PF ４ － , (CF ３ ) ３ PF ３ － , (CF ３ ) ４ PF ２ － , (CF ３ ) ５ PF － , (CF ３ ) ６ P － , (CF ３ SO ３ － ) ２ , (CF ２ CF ２ SO ３ － ) ２ , (C ２ F ５ SO ２ ) ２ N － , (CF ３ SO ３ ) ２ N － , (CF ３ SO ２ ) (CF ３ CO)N － , C.F. ３ CF ２ (CF ３ ) ２ CO － , (CF ３ SO ２ ) ２ CH － , (SF ５ ) ３ C － , (CF ３ SO ２ ) ３ C － , C.F. ３ (CF ２ ) ７ SO ３ － , C.F. ３ COO － , C ３ F ７ COO － , C.F. ３ SO ３ － , or C ４ F ９ SO ３ － That is, 10. The elastomeric antimicrobial polyurethane polymer of claim 1.

8. (A) an isocyanate compound; and (B) a step of reacting a polyol including a polyether glycol and a diol represented by the following Chemical Formula 1: The method includes the step of further reacting a prepolymer obtained by reacting (A) an isocyanate compound and (B) a polyol including a polyether glycol and a diol represented by the following Chemical Formula 1 with (C) a diamine compound as a chain extender, the molar ratio of the diamine compound (C) to the polyol (B) is 0.4 or more and 0.6 or less; The polyol (B) contains 4 to 40 mol % of a diol represented by Chemical Formula 1.

1. A method for producing an elastomeric antimicrobial polyurethane polymer, comprising: The elastic antibacterial polyurethane polymer exhibits an antibacterial rate of 90% or more when measured according to JIS Z 2801; The elastic antibacterial polyurethane polymer has an unreacted diol content of 1,000 ppm or less based on the total polymer. 【Transformation 3】 (In the above Chemical Formula 1, R １ and R ２ each independently represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkoxy group, an alicyclic structure, a heteroalicyclic structure, an alkylthio group, or an arylthio group; L １ and L ２ are each independently an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group, L ３ is a direct bond, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group; A is an alkylene group having more than 6 carbon atoms; X － means an anion.)

9. mixing and reacting the (B) polyol with the (A) isocyanate compound so that the molar ratio of the (A) isocyanate compound to the (B) polyol is in the range of 1.0 to 2.0; 9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8.

10. The reaction is carried out at a temperature of 100°C or less.

9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8.

11. A is an alkylene group having more than 6 and not more than 20 carbon atoms.

9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8.

12. The A has a structure represented by the following chemical formula 2:

9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8. 【Chemistry 4】 (In the above Chemical Formula 2, n is a number of 4 or more, and both ends represented by * are ３ and R ２ may be combined with each other. ３ is a direct bond, one end represented by the * is bonded to the N atom.

13. The X － Is F － , Cl － ,Br － , I － , NO ３ － , (CN) ２ N － , B.F. ４ － , ClO ４ － , RSO ３ － (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), RCOO － (wherein R is an alkyl group having 1 to 9 carbon atoms or a phenyl group), PF ６ － , (CF ３ ) ２ PF ４ － , (CF ３ ) ３ PF ３ － , (CF ３ ) ４ PF ２ － , (CF ３ ) ５ PF － , (CF ３ ) ６ P － , (CF ３ SO ３ － ) ２ , (CF ２ CF ２ SO ３ － ) ２ , (C ２ F ５ SO ２ ) ２ N － , (CF ３ SO ３ ) ２ N － , (CF ３ SO ２ ) (CF ３ CO)N － , C.F. ３ CF ２ (CF ３ ) ２ CO － , (CF ３ SO ２ ) ２ CH － , (SF ５ ) ３ C － , (CF ３ SO ２ ) ３ C － , C.F. ３ (CF ２ ) ７ SO ３ － , C.F. ３ COO － , C ３ F ７ COO － , C.F. ３ SO ３ － , or C ４ F ９ SO ３ － That is, 9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8.

14. The elastic antibacterial polyurethane polymer has a tensile strain of 900% or greater as measured by the ASTM D882 tensile test method.

9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8. (However, the tensile strain is measured on an elastic antibacterial polyurethane polymer sample having a width to length ratio (width:length) of 1:1 to 100.)

15. The elastic antibacterial polyurethane polymer has a tensile strength of 30 MPa or more as measured by the ASTM D882 tensile test method.

9. A method for producing the elastomeric antimicrobial polyurethane polymer of claim 8. (However, the tensile strength is measured on elastic antibacterial polyurethane polymer samples having a width to length ratio (width:length) of 1:1 to 100.)

16. 10. An article comprising the polyurethane polymer of claim 1, The article is a fiber, a fabric, a garment, a paint, a vehicle interior, a mattress, or a foam.

Images