Anti-virus nonwoven composite and method of manufacturing the same

Abstract

A nonwoven composite having antiviral performance and a method for manufacturing the same are disclosed. More specifically, a nonwoven composite is provided comprising: a nonwoven fabric comprising an α-olefin polymer; a tetravalent ammonium compound having a tetravalent ammonium functional group; and a moiety that connects the α-olefin polymer and the tetravalent ammonium compound by a covalent bond. The nonwoven composite having antiviral performance according to the present invention has low leaching of the tetravalent ammonium compound having antiviral performance, maintains antiviral properties even after washing, and can be reused multiple times.

Description

Technology Field

[0001] The present invention relates to a nonwoven fabric composite having antiviral performance and a method for manufacturing the same. Background Technology

[0002] Viruses can survive on plastic for 24 hours to up to 3 days, and on masks for up to 7 days or more. The long-term survival of viruses raises concerns about the spread of viruses accumulated by infected individuals and makes it difficult to identify infection routes and processes. Viruses accumulated on the surfaces of masks, air filters, and surfaces touched by hands can cause virus transmission through contact; in particular, masks worn for extended periods can become a medium of infection as viruses become distributed on the surface, potentially causing infection to the eyes, nose, and mouth.

[0003] Surface sterilization methods such as physical (ultraviolet, steam, microwave) and chemical (alcohol, hydrogen peroxide, surfactants) have been proposed to suppress vector-borne infections, but they are inefficient due to low accessibility, limitations in the performance of the materials themselves, and the inconvenience of performing protocols. Furthermore, some physical approaches to inactivate viruses may not be effective in the long term due to the flexibility and rapid movement of viral spikes. Additionally, masks coated with nanoscale porous structures, inorganic nanoparticles, and photosensitive nanocompounds for permanent damage to collected viruses have been introduced, but applying these measures requires toxicity and multiple processes for converting nanocompound production to the field.

[0004] Most additive-type antiviral substances added to personal protective equipment (PPE) utilize a release-based antiviral mechanism; consequently, their performance duration is short due to leaching and volatilization, and because they operate at concentrations above a certain level, they can also exhibit high cytotoxicity. Furthermore, their low durability makes them vulnerable to changes in usage environments, cleaning, and reuse.

[0005] Meanwhile, as of 2020, approximately 6.7 billion disposable masks were used domestically. Classified as general waste, about 3.8 billion were incinerated and about 2.1 billion were landfilled, causing environmental problems such as greenhouse gases and microplastics. Recycling is also practically impossible due to concerns about secondary infection during the collection process, and profitability is low due to the cost of removing wires and straps.

[0006] In addition, if antiviral nonwoven fabrics are used in clothing, surgical masks, and sanitary towels used in medical facilities, the risk of infection can be reduced, thereby reducing antibiotic use, infection treatment, labor costs, laundry costs, and medical waste.

[0007] Therefore, research is needed on nonwoven composites that can be reused after multiple washes and possess antiviral properties. The problem to be solved

[0008] The objective of the present invention is to solve the aforementioned problems by providing a surface-modified nonwoven fabric composite formed by forming a covalent bond through a non-catalytic CH insertion reaction between a polymer having antiviral performance and a nonwoven fabric.

[0009] Another objective of the present invention is to provide a nonwoven fabric composite that minimizes side reactions through a simple surface treatment process of the nonwoven fabric under relatively mild conditions, and minimizes the risk of cytotoxicity by utilizing a polymer used as a cosmetic ingredient as a component to impart antiviral properties.

[0010] Another objective of the present invention is to provide an antiviral nonwoven fabric composite that can be washed and reused by stabilizing organic matter and preventing leaching and volatility through the conversion of the nonwoven fabric composite into a covalently bonded, highly durable antiviral material. means of solving the problem

[0011] According to one aspect of the present invention, a nonwoven fabric comprising an α-olefin polymer; a tetravalent ammonium functional group and A nonwoven composite is provided comprising: a tetravalent ammonium compound having; and a moiety that connects the α-olefin polymer and the tetravalent ammonium compound by a covalent bond.

[0012] In addition, the above moiety can be represented by the structural formula 1 below.

[0013] [Structural Formula 1]

[0014]

[0015] In addition, one of the nitrogens of the above moiety may be substituted with a hydrogen of the CH bond of the α-olefin polymer to form a covalent bond, and another nitrogen of the above moiety may be substituted with a hydrogen of the CH bond of the tetravalent ammonium compound to form a covalent bond.

[0016] In addition, the above structural formula 1 can be represented by the following structural formula 2.

[0017] [Structural Formula 2]

[0018]

[0019] In the above structural formula 2,

[0020] R 1 is a C1-C6 alkylene, and

[0021] n is an integer from 1 to 30.

[0022] In addition, the α-olefin polymer can be modified by grafting the tetravalent ammonium compound onto the α-olefin polymer.

[0023] In addition, the above α-olefin polymer may be a polymer of an α-olefin monomer represented by the structural formula 3 below.

[0024] [Structural Formula 3]

[0025]

[0026] In the above structural formula 3,

[0027] R 2is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded.

[0028] In addition, the α-olefin polymer may include one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene.

[0029] In addition, the tetravalent ammonium compound may include one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride.

[0030] In addition, the above nonwoven fabric composite may have antiviral and antibacterial properties.

[0031] According to another aspect of the present invention, an antiviral mask comprising the nonwoven fabric composite is provided.

[0032] According to another aspect of the present invention, (a) azidoformate groups at both ends ( A method for manufacturing a nonwoven fabric composite is provided, comprising the steps of: (a) preparing a solution by mixing an azidoformate compound having ), a tetravalent ammonium compound, and a solvent; (b) bringing a nonwoven fabric containing an α-olefin polymer into contact with the solution to produce a nonwoven fabric impregnated with the solution; (c) drying the nonwoven fabric impregnated with the solution to produce a nonwoven fabric coated with an azidoformate compound and a tetravalent ammonium compound; and (d) irradiating the nonwoven fabric coated with the azidoformate compound and the tetravalent ammonium compound with light to react the azidoformate compound, the tetravalent ammonium compound, and the α-olefin polymer of the nonwoven fabric to produce a nonwoven fabric composite.

[0033] In addition, the contact in step (b) above can be performed by a spray method.

[0034] In addition, the solution may comprise 100 parts by weight of the azidoformate compound; 5 to 50 parts by weight of the tetravalent ammonium compound; and 100 to 3,000 parts by weight of the solvent.

[0035] In addition, the solvent may contain water and ethanol, and the weight ratio (e / w) of ethanol (e) to water (w) may be 1 to 5.

[0036] In addition, the above reaction of step (d) is carried out as a CH insertion reaction, and the CH insertion reaction is such that the nitrogen of the azidoformate group becomes a singlet nitrene as shown in Reaction Scheme 1 below, and the singlet nitrene can be covalently bonded by substituting the hydrogen of the CH bond of the α-olefin polymer and / or the hydrogen of the CH bond of the tetravalent ammonium compound.

[0037] [Reaction Equation 1]

[0038]

[0039] In addition, the method for manufacturing the nonwoven fabric composite may further include, after step (d), step (e) washing and drying the nonwoven fabric composite with an aqueous ethanol solution containing ethanol and water.

[0040] Additionally, in step (d) above, light irradiation can be performed by irradiating with ultraviolet light.

[0041] In addition, the above α-olefin polymer can be polymerized from an α-olefin monomer represented by the structural formula 3 below.

[0042] [Structural Formula 3]

[0043]

[0044] In the above structural formula 3,

[0045] R 2 is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded.

[0046] In addition, the α-olefin polymer may include one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene.

[0047] In addition, the tetravalent ammonium compound may include one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride. Effects of the invention

[0048] The nonwoven fabric of the present invention has excellent antiviral performance.

[0049] In addition, the present invention connects a polymer with antiviral properties to the surface of a nonwoven fabric via covalent bonding, resulting in low leaching and allowing for multiple reuses even after washing.

[0050] In addition, the present invention has the effect of maintaining excellent antiviral performance even when reused multiple times by covalently bonding a polymer having antiviral properties to the surface of a nonwoven fabric. Brief explanation of the drawing

[0051] These drawings are for reference to explain exemplary embodiments of the present invention, and therefore, the technical concept of the present invention should not be interpreted as being limited to the attached drawings. Figure 1 is a diagram showing the manufacturing process of the nonwoven fabric composite of Example 1 of the present invention and the bonding structure between compounds within the nonwoven fabric composite. Figure 2a shows the FT-IR analysis results of GDAF prepared according to Preparation Example 1. FIG. 2b is of the GDAF prepared according to Preparation Example 1. 1 This shows the results of the H-NMR analysis. Figure 2c shows the Q-TOF MS analysis results of the GDAF prepared according to Preparation Example 1. Figure 3 shows the FT-IR analysis results of PQ-11 used in an embodiment of the present invention. Figure 4a shows the FT-IR analysis results for the nonwoven fabric composites of Example 1, Examples 2-1, 2-2, 2-3 and Comparative Example 1 of the present invention. FIG. 4b is an optical microscope image showing the surface of the nonwoven fabric composite of Comparative Example 1 of the present invention. FIG. 4c is an optical microscope image showing the surface of the nonwoven fabric composite of Example 1 of the present invention. FIG. 4d is an optical microscope image showing the surface of the nonwoven fabric composite of Example 2-3 of the present invention. FIG. 5 is a diagram showing the antiviral performance of the nonwoven fabric composites of Examples 2-3 and Comparative Example 1 of the present invention. Specific details for implementing the invention

[0052] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0053] However, the following description is not intended to limit the present invention to specific embodiments, and detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions could obscure the essence of the present invention.

[0054] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to indicate the presence of the features, numbers, steps, actions, components, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, or combinations thereof.

[0055] Additionally, terms including ordinal numbers, such as "first," "second," etc., used below may be used to describe various components, but said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0056] Furthermore, when it is stated that a component is "formed" or "laminated" on another component, it should be understood that while it may be formed or laminated by being directly attached to the entire surface or one surface of the other component, there may also be other components present in between.

[0057] Hereinafter, the nonwoven fabric composite having antiviral performance and the method for manufacturing the same according to the present invention will be described in detail. However, this is presented as an example and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims set forth below.

[0058] Figure 1 is a diagram showing the manufacturing process of the nonwoven fabric composite of Example 1 of the present invention and the bonding structure between compounds within the nonwoven fabric composite.

[0059] Referring to FIG. 1, the present invention comprises a nonwoven fabric comprising an α-olefin polymer; a tetravalent ammonium functional group and A nonwoven composite is provided comprising: a tetravalent ammonium compound having; and a moiety that connects the α-olefin polymer and the tetravalent ammonium compound by a covalent bond.

[0060] In addition, the above moiety can be represented by the structural formula 1 below.

[0061] [Structural Formula 1]

[0062]

[0063] In addition, one of the nitrogens of the above moiety may be substituted with a hydrogen of the CH bond of the α-olefin polymer to form a covalent bond, and another nitrogen of the above moiety may be substituted with a hydrogen of the CH bond of the tetravalent ammonium compound to form a covalent bond.

[0064] In addition, the above structural formula 1 can be represented by the following structural formula 2.

[0065] [Structural Formula 2]

[0066]

[0067] In the above structural formula 2,

[0068] R 1 is a C1-C6 alkylene, and

[0069] n is an integer from 1 to 30.

[0070] In addition, the α-olefin polymer can be modified by grafting the tetravalent ammonium compound onto the α-olefin polymer.

[0071] In addition, the above α-olefin polymer may be a polymer of an α-olefin monomer represented by the structural formula 3 below.

[0072] [Structural Formula 3]

[0073]

[0074] In the above structural formula 3,

[0075] R 2 is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded.

[0076] In addition, the α-olefin polymer may include one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene.

[0077] Meanwhile, although α-olefin polymers were cited as examples of the nonwoven fabric material of the present invention, any type of polymer material capable of being used as a nonwoven fabric material is possible. For example, polyester, nylon, viscose rayon, polyethylene terephthalate, polyetherimide, polylactide, and poly(methyl methacrylate) can also be used as the nonwoven fabric material of the present invention.

[0078] In addition, the above moiety may include not only azidoformate groups at both ends but also 1,3-benzene disulfonylazide (BDSA) or glycidyl diazide groups having sulfonyl azide groups at both ends, and any of the functional groups having antiviral properties having functional groups at both ends may be covalently connected to a nonwoven fabric containing an α-olefin polymer.

[0079] In addition, the tetravalent ammonium compound may include one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride.

[0080] In addition, any compound that includes not only tetravalent ammonium compounds but also functional groups having antiviral functions and can covalently bond to an α-olefin polymer nonwoven fabric by a CH insertion reaction through the moiety may be used in the present invention.

[0081] In addition, the above nonwoven fabric composite may have antiviral and antibacterial properties.

[0082] According to another aspect of the present invention, an antiviral mask comprising the nonwoven fabric composite is provided.

[0083] According to another aspect of the present invention, (a) azidoformate groups at both ends ( A method for manufacturing a nonwoven fabric composite is provided, comprising the steps of: (a) preparing a solution by mixing an azidoformate compound having ), a tetravalent ammonium compound, and a solvent; (b) bringing a nonwoven fabric containing an α-olefin polymer into contact with the solution to produce a nonwoven fabric impregnated with the solution; (c) drying the nonwoven fabric impregnated with the solution to produce a nonwoven fabric coated with an azidoformate compound and a tetravalent ammonium compound; and (d) irradiating the nonwoven fabric coated with the azidoformate compound and the tetravalent ammonium compound with light to react the azidoformate compound, the tetravalent ammonium compound, and the α-olefin polymer of the nonwoven fabric to produce a nonwoven fabric composite.

[0084] In addition, the contact in step (b) above can be performed by a spray method.

[0085] In addition, the solution may comprise 100 parts by weight of the azidoformate compound; 5 to 50 parts by weight of the tetravalent ammonium compound; and 100 to 3,000 parts by weight of the solvent.

[0086] In addition, the solvent may contain water and ethanol, and the weight ratio (e / w) of ethanol (e) to water (w) may be 1 to 5.

[0087] In addition, the above reaction of step (d) is carried out as a CH insertion reaction, and the CH insertion reaction is such that the nitrogen of the azidoformate group becomes a singlet nitrene as shown in Reaction Scheme 1 below, and the singlet nitrene can be covalently bonded by substituting the hydrogen of the CH bond of the α-olefin polymer and / or the hydrogen of the CH bond of the tetravalent ammonium compound.

[0088] [Reaction Equation 1]

[0089]

[0090] In addition, the method for manufacturing the nonwoven fabric composite may further include, after step (d), step (e) washing and drying the nonwoven fabric composite with an aqueous ethanol solution containing ethanol and water.

[0091] Additionally, in step (d) above, light irradiation can be performed by irradiating with ultraviolet light.

[0092] In addition, the above α-olefin polymer can be polymerized from an α-olefin monomer represented by the structural formula 3 below.

[0093] [Structural Formula 3]

[0094]

[0095] In the above structural formula 3,

[0096] R 2 is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded.

[0097] In addition, the α-olefin polymer may include one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene.

[0098] Figure 3 shows the FT-IR analysis results of PQ-11 used in an embodiment of the present invention.

[0099] In addition, the tetravalent ammonium compound may include one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride.

[0100] In addition, any compound that includes not only tetravalent ammonium compounds but also functional groups having antiviral functions and can covalently bond to an α-olefin polymer nonwoven fabric by a CH insertion reaction through the moiety may be used in the present invention.

[0101] The nonwoven fabric composite of the present invention connects a polymer compound containing a tetravalent ammonium compound having antiviral performance to the surface of an α-olefin polymer nonwoven fabric composite via covalent bonding, so there is no leaching and it can be reused even after multiple washes.

[0102] According to another aspect of the present invention, medical clothing such as masks, spunbond nonwoven fabrics, and protective clothing, carpets, packaging materials, reusable wipers, patient beds, bedding covers, and living materials may be included, but are not limited thereto, comprising the nonwoven fabric composite.

[0103] In step (c) above, the drying time can be 1 to 60 minutes, preferably 25 to 35 minutes.

[0104] In addition, in step (d) above, the light irradiation may be performed by exposing to UV for 1 minute to 2 hours, preferably 3 minutes to 1 hour, and more preferably 5 minutes to 30 minutes. If the exposure time is less than 1 minute, the conversion rate to nitrene may be low and is undesirable, and if it exceeds 2 hours, the physical properties of the nonwoven fabric itself may deteriorate due to the light irradiation and are undesirable.

[0105] The nonwoven fabric composite of the present invention connects a polymer compound containing a tetravalent ammonium functional group having antiviral performance to the surface of a polypropylene nonwoven fabric composite via covalent bonding, so there is no leaching and it can be reused even after multiple washes.

[0106] [Example]

[0107] Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only and does not limit the scope of the present invention.

[0108] Preparation of diazide compounds having azide groups at both ends

[0109] Preparation Example 1: Preparation of tri(ethylene glycol) diazidoformate (GDAF)

[0110] A solution of sodium azide (2.0 g, 0.031 mol) dissolved in 65.0 mL of deionized water was added to a solution of tri(ethylene glycol) bis(chloroformate) (4.0 g, 0.015 mol) dissolved in 120.0 mL of acetone, and the reaction was carried out in an ice bath for 2 hours. The reaction mixture was extracted with DCM (100 mL × 2), and the organic layer was dried with MgSO4. After filtering the MgSO4, the solvent was evaporated by vacuum distillation at low temperature to prevent decomposition. A pale yellow oil-like GDAF was obtained (3.5 g, 87.1%).

[0111] The structure of the GDAF prepared according to the above Preparation Example 1 is shown in Structural Formula 4 below.

[0112] [Structural Formula 4]

[0113]

[0114] Example 1: Preparation of a modified nonwoven composite (nonwoven composite modified by CH insertion reaction of GDAF)

[0115] The commercially available chemical poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (PQ-11, Sigma-Aldrich, Mw < 10), a tetravalent ammonium compound represented by structural formula 5 6 PQ-11 (g / mol, 20 wt.% in H2O) was purchased. PQ-11 in aqueous solution was used without undergoing a separate dehydration process. A stock solution was prepared by adding 0.2684 g of the above PQ-11 and 0.9153 g of GDAF prepared according to Preparation Example 1 to an aqueous solution containing 4.290 g of water and 11.525 g of ethanol. The polypropylene nonwoven fabric was cut into a square shape (2 cm x 2 cm).

[0116] [Structural Formula 5]

[0117]

[0118] The prepared stock solution was sprayed onto polypropylene using a spray method and dried in a shaded area at room temperature for about 30 minutes to remove water and ethanol. The dried PP was reacted under UV (254 nm) for 15 minutes to induce a CH insertion reaction of GDAF, thereby finally producing a nonwoven composite.

[0119] Reaction Scheme 2 below shows that through the CH insertion reaction, the nitrogen atom of the azidoformate group becomes a singlet nitrene and / or triplet nitrene, and the singlet nitrene and / or triplet nitrene is substituted with the hydrogen of the CH bond of the polypropylene and the tetravalent ammonium compound to form a covalent bond.

[0120] [Reaction Equation 2]

[0121]

[0122] Example 2: Nonwoven composite washed after modification

[0123] Example 2-1: Nonwoven fabric composite washed once

[0124] The nonwoven fabric composite prepared according to Example 1 was washed once by shaking it in an aqueous ethanol solution (0.25 mol ethanol and 0.25 mol water) for about 3 minutes and dried to remove water and ethanol.

[0125] Example 2-2: Nonwoven fabric composite washed twice

[0126] The nonwoven fabric composite prepared according to Example 1 was washed by shaking it in an aqueous ethanol solution (0.25 mol ethanol and 0.25 mol water) for about 3 minutes, and this was repeated twice and dried to remove water and ethanol.

[0127] Example 2-3: Nonwoven fabric composite washed three times

[0128] The nonwoven fabric composite prepared according to Example 1 was washed by shaking it in an aqueous ethanol solution (0.25 mol ethanol and 0.25 mol water) for about 3 minutes, and this was repeated 3 times and dried to remove water and ethanol.

[0129] Comparative Example 1: Nonwoven composite manufactured without adding GDAF (nonwoven composite before modification)

[0130] A nonwoven composite was prepared in the same manner as in Example 1, except that the GDAF prepared according to Preparation Example 1 was not included.

[0131] Table 1 below summarizes the types of compounds and the number of washes used in the nonwoven fabric composites according to Preparation Example 1, Examples 1 to 2-3 and Comparative Example 1.

[0132] division azide compounds Washing frequency Preparation Example 1 GDAF - Example 1 GDAF - Example 2-1 GDAF 1 time Example 2-2 GDAF 2nd time Examples 2-3 GDAF 3 times Comparative Example 1 - -

[0133] [Test Example]

[0134] Test Example 1: Confirmation of GDAF Synthesis

[0135] FIG. 2a shows the FT-IR analysis results of the GDAF prepared according to Preparation Example 1, and FIG. 2b shows the GDAF prepared according to Preparation Example 1. 1 Figure 2a shows the H-NMR analysis results, and Figure 2c shows the Q-TOF MS analysis results of the GDAF prepared according to Preparation Example 1. Referring to Figures 2a to 2c, it was confirmed that the GDAF was successfully synthesized according to Preparation Example 1.

[0136] Referring to Fig. 2a, 2160 cm -1 At [location], stretching vibrations corresponding to N=N=N(azide) of GDAF appeared, and at 1700 cm -1 Strong stretching vibrations corresponding to C=O(carbonyl) could be observed.

[0137] Referring to Fig. 2b, 1 It was confirmed that the chemical shift position, the integral value of the proton peak, and the split pattern in H-NMR matched the expected compound.

[0138] Referring to Fig. 2c, it was confirmed that the molecular weight of the GDAF prepared according to Preparation Example 1 was 289.089 g / mol, indicating that the GDAF was successfully synthesized.

[0139] Test Example 2: Analysis of the amount of compounds present in the nonwoven composite washed after modification

[0140] The amount of the compound (mixture of PQ-11 and GDAF) present on the nonwoven fabric composite of Example 1, which was not washed after modification, and the nonwoven fabric composite of Examples 2-3, which was washed three times after modification, was measured three times by weight, and the grafting efficiency of the compound into the nonwoven fabric was calculated and shown in Table 2.

[0141] Example 1 (before washing) Example 2-3 (after 3 washes) grafting efficiency(%) 0.0099 ± 0.0012 0.0074 ± 0.0002 74.855 ± 7.5504

[0142] Referring to Table 2 above, it was confirmed that a significant amount of the PQ-11 and GDAF mixture remained on the surface of the nonwoven fabric composite even after three washes (Examples 2-3) compared to before washing (Example 1). Through this, it was confirmed that the nonwoven fabric composite of the present invention has low leaching and can be reused even after multiple washes by covalently bonding a polymer compound containing a tetravalent ammonium functional group with antiviral performance to the surface of the polypropylene nonwoven fabric composite.

[0143] Test Example 3: FT-IR analysis of nonwoven composites before modification, after modification, and after washing.

[0144] Figure 4a shows the FT-IR analysis results for the nonwoven fabric composites of Example 1, Examples 2-1, 2-2, 2-3 and Comparative Example 1 of the present invention.

[0145] Referring to FIG. 4a, in Examples 2-1, 2-2, and 2-3 washed after modification, 3100 to 3700 cm -1 A stretching vibration corresponding to the polyquaternium peak of PQ-11 was observed at 2720 cm⁻¹. -1 Based on the intensity of the CH stretch peak of polypropylene, 3100 to 3700 cm⁻¹ -1 It was confirmed that the polyquaternium peak intensity also remained significantly strong even after 3 washes.

[0146] Through this, the present invention was able to confirm that a significant portion of the compound having antiviral properties remains even after multiple washes and reuse by covalently bonding a polymer having antiviral properties to the surface of a polypropylene nonwoven fabric composite.

[0147] Test Example 4: Surface analysis of nonwoven composites before modification, after modification, and after washing.

[0148] FIG. 4b is an optical microscope image showing the surface of the nonwoven fabric composite of Comparative Example 1 of the present invention, FIG. 4c is an optical microscope image showing the surface of the nonwoven fabric composite of Example 1 of the present invention, and FIG. 4d is an optical microscope image showing the surface of the nonwoven fabric composite of Examples 2-3 of the present invention.

[0149] Referring to Figures 4b to 4d, it was confirmed that PQ-11 was evenly sprayed and bonded without damaging the physical properties of the surface of the existing nonwoven composite.

[0150] Test Example 5: Confirmation of Antiviral Performance of Nonwoven Fabric Composite

[0151] FIG. 5 is a diagram showing the antiviral performance of the nonwoven fabric composites of Examples 2-3 and Comparative Example 1 of the present invention.

[0152] Referring to Fig. 5, the antiviral performance of the polypropylene nonwoven fabric composite before and after modification using PQ-11 and GDAF was compared. For the modified nonwoven fabric composite, the nonwoven fabric composite of Examples 2-3, which had undergone three washes, was used for the antiviral test, and all specimens were tested in a square shape (2 cm x 2 cm). On each specimen, a high concentration (~10 8After loading a virus (MS2 bacteriophage) solution of PFU / mL, the surface was covered with a clear film to ensure the film adhered closely to the surface loaded with the virus. Subsequently, the virus was cultured for 24 hours at a temperature of 37°C under appropriate humidity, and then washed with a phosphate buffer solution to analyze the virus inactivation efficiency. When comparing the number of viruses before culture (N0) and the number of viruses after 24 hours of culture (N) as a function of log(N / N0), the nonwoven fabric composite before modification (Comparative Example 1) yielded a value of approximately -0.06, while the nonwoven fabric composite after modification (Example 2-3) yielded a value of -1.99. When converted into the percentage of viruses inactivated after culture / viruses before culture, the nonwoven fabric composite before modification (Comparative Example 1) showed approximately 13.4%, indicating almost no antiviral performance, whereas the nonwoven fabric composite after modification (Example 2-3) showed approximately 99.0% antiviral performance.

[0153] Through this, it was confirmed that the present invention provides an effect of excellent antiviral performance even when reused multiple times by covalently bonding a polymer with antiviral properties to the surface of a polypropylene nonwoven fabric composite.

[0154] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

Claim 1 Nonwoven fabric comprising an α-olefin polymer; tetravalent ammonium functional group and A nonwoven composite comprising: a tetravalent ammonium compound having; and a moiety that covalently links the α-olefin polymer and the tetravalent ammonium compound, wherein the moiety is represented by the following structural formula 1. [Structural Formula 1] Claim 2 delete Claim 3 A nonwoven composite according to claim 1, characterized in that one of the nitrogen atoms of the moiety is substituted with a hydrogen atom of the CH bond of the α-olefin polymer and covalently bonded, and another nitrogen atom of the moiety is substituted with a hydrogen atom of the CH bond of the tetravalent ammonium polymer and covalently bonded. Claim 4 A nonwoven fabric composite according to claim 1, characterized in that the above structural formula 1 is represented by the following structural formula 2. [Structural Formula 2] In the above structural formula 2, R 1 is a C1-C6 alkylene, and n is an integer from 1 to 30. Claim 5 A nonwoven composite according to claim 1, characterized in that the α-olefin polymer is modified by grafting the tetravalent ammonium compound onto the α-olefin polymer. Claim 6 A nonwoven composite according to claim 1, characterized in that the α-olefin polymer is polymerized from an α-olefin monomer represented by the structural formula 3 below. [Structural Formula 3] In the above structural formula 3, R 2 is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded. Claim 7 A nonwoven composite according to claim 6, characterized in that the α-olefin polymer comprises one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene. Claim 8 A nonwoven composite according to claim 1, characterized in that the tetravalent ammonium compound comprises one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride. Claim 9 A nonwoven fabric composite according to claim 1, characterized in that the nonwoven fabric has antiviral and antibacterial properties. Claim 10 Antiviral and antibacterial mask comprising a nonwoven fabric composite according to paragraph 1. Claim 11 (a) Azidoformate groups at both ends ( A method for manufacturing a nonwoven fabric composite comprising: (a) a step of preparing a solution by mixing an azidoformate compound having ), a tetravalent ammonium compound, and a solvent; (b) a step of producing a nonwoven fabric impregnated with the solution by contacting a nonwoven fabric containing an α-olefin polymer with the solution; (c) a step of producing a nonwoven fabric coated with an azidoformate compound and a tetravalent ammonium compound by drying the nonwoven fabric impregnated with the solution; and (d) a step of producing a nonwoven fabric composite by light irradiating the nonwoven fabric coated with the azidoformate compound and the tetravalent ammonium compound to react the azidoformate compound, the tetravalent ammonium compound, and the α-olefin polymer of the nonwoven fabric. Claim 12 A method for manufacturing a nonwoven composite, characterized in that, in claim 11, the contact of step (b) is performed by a spray method. Claim 13 A method for manufacturing a nonwoven composite according to claim 11, characterized in that the solution comprises 100 parts by weight of the azidoformate compound; 5 to 50 parts by weight of the tetravalent ammonium compound; and 100 to 3,000 parts by weight of the solvent. Claim 14 A method for manufacturing a nonwoven composite according to claim 13, characterized in that the solvent comprises water and ethanol, and the weight ratio (e / w) of ethanol (e) to water (w) is 1 to 5. Claim 15 A method for manufacturing a nonwoven fabric composite according to claim 11, wherein the reaction of step (d) is performed as a CH insertion reaction, and the CH insertion reaction is characterized in that the nitrogen of the azidoformate group becomes a singlet nitrene as shown in Reaction Scheme 1 below, and the singlet nitrene is substituted with and covalently bonded with a hydrogen of the CH bond of an α-olefin polymer and / or a hydrogen of the CH bond of a tetravalent ammonium compound. [Reaction Scheme 1] Claim 16 A method for manufacturing a nonwoven fabric composite according to claim 11, characterized in that, after step (d), the method for manufacturing the nonwoven fabric composite further comprises the step (e) of washing and drying the nonwoven fabric composite with an aqueous ethanol solution containing ethanol and water. Claim 17 A method for manufacturing a nonwoven composite according to claim 11, characterized in that the light irradiation in step (d) above is performed by irradiating ultraviolet light. Claim 18 A method for manufacturing a nonwoven fabric composite according to claim 11, characterized in that the α-olefin polymer is polymerized from an α-olefin monomer represented by the structural formula 3 below. [Structural Formula 3] In the above structural formula 3, R 2 is a hydrogen atom, a C1-C18 alkyl, a C2-C18 alkenyl, a C6-C20 aryl, a C3-C20 heteroaryl, a C5-C20 cycloalkyl, a C3-C20 heterocycloalkyl, a C7-C20 aralkyl, a C7-C20 alkaryl, or a combination thereof covalently bonded. Claim 19 A method for manufacturing a nonwoven composite according to claim 18, wherein the α-olefin polymer comprises one or more selected from the group consisting of polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, and polydiene. Claim 20 A method for manufacturing a nonwoven fabric composite according to claim 11, characterized in that the tetravalent ammonium compound comprises one or more selected from the group consisting of Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)], benzalkonium chloride, benzethonium chloride, polyoxyethylene trimethyl ammonium chloride, polyoxyalkyl trialkyl ammonium chloride, polydiallyldimethylammonium chloride, and [(Acryloyloxy)ethyl]trimethylammonium chloride.

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