Antibacterial antiviral fiber and its preparation method and application

Abstract

The application discloses an antibacterial and antiviral fiber and a preparation method and application thereof, and belongs to the technical field of functionalized textiles. The preparation method comprises the following steps: mixing a high-molecular guanidine salt and a cationic antibacterial agent in an organic solvent to form an organic composite component liquid phase, mixing the organic composite component liquid phase with TiO2 and performing vacuum drying to form an organic-TiO2 composite functional component, then blending and granulating a first resin, an amino silane coupling agent and the organic-TiO2 composite functional component to form a functionalized master batch, and finally melt spinning a second resin and the functionalized master batch to obtain the antibacterial and antiviral fiber. The preparation method can not only endow the fiber with excellent antiviral performance and good appearance quality, but also greatly improve the antibacterial performance of the fiber.

Description

Technical Field

[0001] This application belongs to the field of functional textile technology, and in particular relates to an antibacterial and antiviral fiber, its preparation method and application. Background Technology

[0002] Utilizing antibacterial and antiviral functional ingredients combined with polymer matrices to prepare antibacterial and antiviral functionalized fibers is one of the effective methods for achieving functionalized antibacterial and antiviral properties in fiber materials. Specifically, to enhance the antibacterial and antiviral efficacy of the functional ingredients, related technologies can employ combinations of antibacterial and antiviral agents of different types / mechanisms.

[0003] For example, the prior art with application publication number CN 115323522 A discloses a method for preparing antibacterial polyamide fibers. It discloses that after dispersing acid-etched tourmaline in a solution of guanidine-containing organic polymer antibacterial agent, it is then mixed with benzotriazole powder and metal ions are introduced to form an antibacterial composite powder. Finally, an antibacterial functional polyamide masterbatch is prepared and melt-spun with polyamide resin, so that the antibacterial polyamide fiber can have a long-lasting antibacterial effect in an environment containing a large number of anions.

[0004] However, the existing technology has the following problems in practical applications: First, the modification process is lengthy, complex and costly, which is not conducive to industrial production; second, the modified fiber products do not have antiviral effects; and third, the average antibacterial performance of the modified fiber products is poor. Summary of the Invention

[0005] This application discloses an antibacterial and antiviral fiber, its preparation method, and its application, aiming to solve the technical problems of the lengthy modification process, complex operation, high cost, and lack of antiviral function of existing antibacterial functional fibers.

[0006] To achieve the above objectives, the technical solution of this application is:

[0007] The first aspect of this application provides a method for preparing antibacterial and antiviral fibers, the method comprising:

[0008] The high molecular weight guanidine salt and the cationic antibacterial agent are mixed in an organic solvent to form an organic composite liquid phase;

[0009] After mixing the organic composite component in liquid phase with TiO2, vacuum drying is performed to form an organic-TiO2 composite functional component.

[0010] The first polyamide resin, aminosilane coupling agent and the organic-TiO2 composite functional component are blended and granulated to form a functionalized masterbatch.

[0011] The second resin and the functionalized masterbatch are melt-spun to obtain antibacterial and antiviral polyamide fiber;

[0012] The first resin may be the same as or different from the second resin.

[0013] Preferably, in conjunction with the first aspect, the method further includes:

[0014] The antibacterial and antiviral fibers formed by melt spinning are immersed in an alcohol-containing aqueous solution for surface treatment, and the surface-treated product is dried.

[0015] Preferably, in conjunction with the first aspect, the polymeric guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate.

[0016] Preferably, in conjunction with the first aspect, the cationic antibacterial agent is one or more of quaternary ammonium salt antibacterial agents, chlorhexidine salt antibacterial agents, and haloamine salt antibacterial agents.

[0017] Preferably, in conjunction with the first aspect, the aminosilane coupling agent is one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane.

[0018] Preferably, in conjunction with the first aspect, it is one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin.

[0019] In conjunction with the first aspect, preferably, the mass ratio of the organic-TiO2 composite functional component to the first resin is 5-60:100.

[0020] Preferably, in conjunction with the first aspect, the mass ratio of the functionalized masterbatch to the second resin is 5-25:100.

[0021] The second aspect of this application provides antibacterial and antiviral fibers produced by the method described in the first aspect.

[0022] The third aspect of this application provides the use of the antimicrobial and antiviral fibers described in the second aspect in the manufacture of antimicrobial and antiviral fiber articles.

[0023] Compared with the prior art, the advantages or beneficial effects of the embodiments of this application include at least the following:

[0024] The preparation method provided in the first aspect of this application enables the organic-TiO2 composite functional component to be uniformly and stably dispersed in the resin for a long time, thereby giving the resin a highly efficient and long-lasting antibacterial and antiviral function. Specifically, the organic-TiO2 composite functional component is prepared by compounding a polymeric guanidine salt, a cationic antibacterial agent, and TiO2. An aminosilane coupling agent is introduced during the blending and granulation of the functionalized masterbatch and the resin. This process achieves several advantages: firstly, it allows for a strong synergistic effect among the polymeric guanidine salt, the cationic antibacterial agent, and TiO2, significantly improving the antibacterial and antiviral performance of the composite functional component; secondly, it enables interconnection between the components, effectively overcoming performance and mechanistic defects of each component and significantly improving the durability and drug resistance of the composite functional component's antibacterial and antiviral properties; thirdly, it allows the composite functional component to firmly bond with the resin surface, greatly improving the stability of the bond between the composite functional component and the resin, and also improving the dispersibility of the composite functional component on and within the resin surface; fourthly, it simplifies the modification process while greatly solving the problem of yellowing of the organic composite component during spinning, significantly improving the appearance quality of the finished antibacterial and antiviral fiber. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is an overall appearance view of the antibacterial and antiviral fiber αMPU1 provided in the embodiments of this application;

[0027] Figure 2 for Figure 1 The cross-sectional SEM image, where, Figure 2 A is Figure 1 SEM image of longitudinal section, Figure 2 B is Figure 1 Cross-sectional SEM image. Detailed Implementation

[0028] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0029] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0030] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0031] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0032] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0033] It should be noted that all raw materials and / or reagents in the embodiments of this application are purchased from the market or prepared according to conventional methods known to those skilled in the art. For example, various resins, high molecular weight guanidine salts, cationic antibacterial agents, TiO2 and aminosilane coupling agents are all purchased from the market.

[0034] In a first aspect, embodiments of this application provide an antibacterial and antiviral fiber, the preparation method of which includes:

[0035] The high molecular weight guanidine salt and the cationic antibacterial agent are mixed in an organic solvent to form an organic composite liquid phase;

[0036] After mixing the organic composite component in liquid phase with TiO2, vacuum drying is performed to form an organic-TiO2 composite functional component.

[0037] The first resin, aminosilane coupling agent and the organic-TiO2 composite functional component are blended and granulated to form a functionalized masterbatch.

[0038] The second resin and the functionalized masterbatch are melt-spun to obtain antibacterial and antiviral fibers.

[0039] The first resin may be the same as or different from the second resin.

[0040] It should be noted that the first resin and the second resin being the same or different in the embodiments of this application refers to the first resin and the second resin having the same or different material types. For example, when the first resin is polyamide 46, the second resin can be polyamide 46, or it can be polyamide 56, polyamide 66, or other common polyamide resin types.

[0041] Of course, the first resin can also be other common resins such as polylactic acid, polyester, polypropylene, polyethylene, and polyphenylene sulfide, and the corresponding second resin can also be common resins such as polylactic acid, polyester, polypropylene, polyethylene, and polyphenylene sulfide. The embodiments of this application do not impose any special restrictions on the specific models of the first resin and the second resin.

[0042] It should be noted that the organic solvent in this application embodiment is preferably ethanol with a volume concentration of less than 85%, so as to ensure that the polymeric guanidine salt can be uniformly and stably dispersed in the ethanol solvent, which is beneficial to improving the uniformity of the mixing of cationic antibacterial agent and polymeric guanidine salt, and effectively solving the problem of poor heat resistance of cationic antibacterial agent.

[0043] It should be noted that the vacuum drying in this application embodiment is preferably a two-stage drying process under vacuum. Specifically:

[0044] The preferred temperature for the first stage of drying is 65-78℃, the time is 0.5h-4h, and the pressure is 0.02-0.1Mpa;

[0045] The preferred temperature for the second stage of drying is 80-120℃, the time is 0.5-2h, and the pressure is 0.02-0.1Mpa;

[0046] The pressures for the first and second stages of drying may be the same or different.

[0047] In this embodiment, the first stage of vacuum drying lowers the boiling point of the organic solvent, thereby efficiently and safely evaporating and removing most of the organic solvent in the liquid phase; the second stage of vacuum drying can fully remove the moisture in the organic-TiO2 composite functional component, thereby avoiding the problem that the high viscosity of the material due to water absorption by the polymer guanidine salt is not conducive to subsequent spinning, and greatly improving the processing performance of the modified fiber.

[0048] It should be noted that, unless otherwise specified, the blending granulation and melt spinning in the embodiments of this application are carried out in accordance with the general process requirements of the relevant fields. For example, blending granulation can be carried out using a twin-screw extruder at a process condition of 260±2℃ and then granulated; melt spinning can be carried out using a melt spinning machine at a process condition of 280±10℃ and a winding speed of 4000-5000m / min.

[0049] In summary, the preparation method of this application involves compounding a polymeric guanidine salt with a cationic antibacterial agent in an organic solvent to form an organic composite liquid phase, followed by mixing with TiO2 and vacuum drying to produce an organic-TiO2 composite functional component. This significantly improves the antibacterial and antiviral properties of the functional ingredients and enhances the appearance quality of the finished antibacterial and antiviral fiber product. Specifically:

[0050] By compounding high molecular weight guanidine salts with cationic antibacterial agents in organic solvents, the uniformity of the mixture between cationic antibacterial agents and high molecular weight guanidine salts can be significantly improved, thereby effectively overcoming the defect of poor heat resistance of single cationic antibacterial agents.

[0051] Organic-TiO2 composite functional components are prepared by mixing organic composite components with TiO2 in liquid phase and performing two-stage vacuum drying. Firstly, the surface electrostatic repulsion of TiO2 in the liquid phase promotes the stable, uniform, and interwoven distribution of polymeric guanidine salts on the surface of cationic antibacterial agents, which is beneficial for further improving the heat resistance of cationic antibacterial agents. Secondly, by introducing TiO2 to extend the antibacterial mechanism, not only is the antibacterial and antiviral effect synergistically enhanced, but the problem of decreased or even ineffective antibacterial performance of cationic antibacterial agents in environments containing a large number of anions can be effectively solved, allowing for efficient and long-lasting antibacterial and antiviral effects in such environments. Thirdly, the yellowing organic components induced by heating after TiO2 whitening can effectively improve the appearance quality of functionalized masterbatches and modified fiber products. Fourthly, the water absorption properties of TiO2 in air can promote the hydrolysis of polymeric guanidine salts and cationic antibacterial agents, thereby enabling the composite antibacterial and antiviral system to operate continuously and efficiently, which is beneficial for improving antibacterial efficiency.

[0052] Meanwhile, by introducing aminosilane during the preparation of functionalized masterbatch, the embodiments of this application can utilize aminosilane to bind organic functional groups and TiO2 on the resin surface, thereby further improving the dispersion performance of organic-TiO2 composite functional components on and inside the resin surface.

[0053] In addition, in this embodiment, resin chips are used as polymer matrix to combine with organic-TiO2 composite functional components containing high molecular weight guanidine salt. Since the high molecular weight resin and the high molecular weight guanidine salt have the same organic functional groups, they can be well compatible during the melting process. This not only improves the success rate of melt spinning, but also makes the surface and cross-section of the modified fiber product smooth and flat, thus improving the appearance quality of the modified fiber.

[0054] In a specific embodiment, the preparation method of this application preferably includes:

[0055] The antibacterial and antiviral fibers formed by melt spinning are immersed in an alcohol-containing aqueous solution for surface treatment, and the surface-treated product is then dried. The alcohol-containing aqueous solution refers to an aqueous solution containing one or more of the following solutes: methanol, ethanol, propanol, and butanol.

[0056] In this embodiment, the antibacterial and antiviral fibers formed by melt spinning are immersed in an alcohol-containing aqueous solution for surface treatment. This not only enables the silane grafts on the surface of the antibacterial and antiviral fibers to hydrolyze and form a stable film structure, but also inhibits the precipitation of the silane condensation, thereby significantly improving the film-forming efficiency and the stability of the film structure. This effectively solves the defect that the organic-TiO2 composite functional components are easily affected by the external anionic environment and fail, allowing the modified fibers to maintain a long-lasting and highly efficient antibacterial and antiviral function.

[0057] In specific embodiments, the polymeric guanidine salts used in this application are preferably one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate. These polymeric guanidine salts are highly efficient, non-toxic, and easy to prepare. Furthermore, the antibacterial active ingredient of these polymeric guanidine salts is a guanidine group, and the combined use of several types will not affect the effect; several types can be used in combination.

[0058] In specific embodiments, the cationic antibacterial agents in this application are one or more of quaternary ammonium salt antibacterial agents, chlorhexidine salt antibacterial agents, or haloamine salt antibacterial agents. For example, quaternary ammonium salt antibacterial agents can be benzalkonium chloride; chlorhexidine salt antibacterial agents can be chlorhexidine acetate, chlorhexidine gluconate, etc.; and haloamine salt antibacterial agents can be trichloroisocyanuric acid, 5,5-dimethylhydantoin, etc. These cationic antibacterial agents possess the characteristics of high efficiency, low toxicity, and minimal susceptibility to pH changes. Furthermore, both the cationic antibacterial agents and the high molecular weight guanidine salts are hydrolyzable cationic systems. When combined, they do not interfere with each other's antibacterial effects while introducing a new antibacterial system, thereby significantly enhancing the antibacterial range, efficiency, and drug resistance of the composite antibacterial system.

[0059] In specific embodiments, the aminosilane coupling agent used in this application is preferably one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane. These aminosilane coupling agents can simultaneously bind to the organic functional groups and inorganic TiO2 on the resin sheet surface, thereby further improving the dispersion performance of the organic-TiO2 composite functional components on and within the resin surface.

[0060] In a specific embodiment, the first resin and the second resin are the same as or different from one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin. These polymeric resins possess organic functional groups that are the same as or have an affinity for polymeric guanidine salts, thus allowing for good compatibility during blending, granulation, and melt spinning. This results in a smooth and flat fiber surface and cross-section, significantly improving the success rate of melt spinning. Furthermore, this type of fiber can be widely used in textiles, military applications, environmental protection, medical and health fields, and construction.

[0061] In a specific embodiment, the preferred mass ratio of the organic-TiO2 composite functional component to the first resin in this application is 5-60:100. When the mass ratio is lower than 5:100, to achieve the desired antibacterial and antiviral effects, it is usually necessary to increase the amount of functionalized masterbatch added during melt spinning, which significantly affects the continuity of spinning. Conversely, a mass ratio higher than 60:100 can easily lead to excessive pressure on the equipment components during the granulation process, which is detrimental to industrial production. Therefore, this application preferably uses a mass ratio of 5-60:100 for the organic-TiO2 composite functional component to the first resin, thereby improving granulation performance while achieving the desired antibacterial and antiviral effects.

[0062] In a specific embodiment, the preferred mass ratio of the functionalized masterbatch to the second resin in this application is 5-25:100. When the mass ratio is less than 5:100, the modified fiber exhibits weak antibacterial and antiviral effects, making it difficult to achieve the desired results. Conversely, when the mass ratio is greater than 25:100, it can easily lead to excessive pressure on the equipment components during the spinning process, affecting the fiber's spinnability. Therefore, the preferred mass ratio of the functionalized masterbatch to the second resin is 5-25:100, thereby improving spinning performance while achieving good antibacterial and antiviral effects.

[0063] Secondly, embodiments of this application also provide antibacterial and antiviral fibers prepared by the method described in the first aspect.

[0064] The preparation method based on the first aspect enables the polymeric guanidine salt, cationic antibacterial agent, and TiO2 to achieve a sufficient synergistic effect, thereby improving the appearance quality of the finished antibacterial and antiviral fiber. Therefore, the antibacterial and antiviral fiber prepared in the embodiments of this application possesses excellent antibacterial and antiviral properties and superior appearance quality.

[0065] The test results of the examples show that the antibacterial and antiviral fibers of this application have an antibacterial rate of over 99% against Escherichia coli, Staphylococcus aureus and Candida albicans; an antiviral rate of over 99.9% against H1N1 influenza virus; and the surface and cross-section of the antibacterial and antiviral fibers are smooth and flat.

[0066] Thirdly, based on the antibacterial and antiviral properties of the antibacterial and antiviral fibers described above and their role in improving the appearance quality of modified fibers, this application also provides applications of the aforementioned antibacterial and antiviral fibers. Specifically, these applications are made using the antibacterial and antiviral fibers of this application as raw materials in the production of daily necessities such as textiles, environmentally friendly products, medical products, and building products. Based on the characteristics and effects of these antibacterial and antiviral fibers, the textiles, environmentally friendly products, medical products, and building products made using these fibers possess excellent antibacterial and antiviral properties and good appearance quality.

[0067] The technical solution of this application will be further described below with reference to specific embodiments.

[0068] Example 1

[0069] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU1, specifically including:

[0070] S101: Dissolve 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride in 100mL of 75% vv ethanol, and stir thoroughly to obtain the liquid phase of the organic composite component;

[0071] S102: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 2:1, a two-stage vacuum drying process is carried out with a vacuum pressure of 0.1 MPa. The first stage of drying is carried out at a temperature of 75℃ for 2 hours, and the second stage of drying is carried out at a temperature of 100℃ for 1 hour to obtain the organic-TiO2 composite functional component.

[0072] S103: The organic-TiO2 composite functional component is blended with polyamide 56 resin and aminopropyltriethoxysilane in a mass ratio of 11.5:100:6 and granulated to obtain a functionalized masterbatch;

[0073] S104: Under nitrogen protection, functionalized masterbatch and polyamide 56 resin are melt-spun at a mass ratio of 10:100, and then immediately immersed in a 5% vv ethanol aqueous solution for surface treatment. After treatment, they are dried to obtain antibacterial and antiviral fiber αMPU1.

[0074] Example 2

[0075] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU2, specifically including:

[0076] S201: Dissolve 30.2g of polyhexamethylene biguanide hydrochloride, 20.3g of polyhexamethylene biguanide hydrochloride and 40.3g of benzalkonium chloride in 150mL of 65% vv ethanol and stir thoroughly to obtain the liquid phase of the organic composite component;

[0077] S202: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 4:1, a two-stage vacuum drying process is carried out. The first stage of drying is carried out at a temperature of 65℃ for 0.5h and a pressure of 0.02MPa. The second stage of drying is carried out at a temperature of 90℃ for 0.1h and a pressure of 0.1MPa to obtain the organic-TiO2 composite functional component.

[0078] S203: Organic-TiO2 composite functional components are blended with polylactic acid resin and aminopropyltriethoxysilane in a mass ratio of 5:100:6 and granulated to obtain functionalized masterbatch.

[0079] S204: Under nitrogen protection, functionalized masterbatch and polylactic acid resin are melt-spun at a mass ratio of 25:100, and then immediately immersed in a 5% vv methanol aqueous solution for surface treatment. After treatment, they are dried to obtain antibacterial and antiviral fiber αMPU2.

[0080] Example 3

[0081] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU3, specifically including:

[0082] S301: Dissolve 45.5g of polyhexamethylene biguanide hydrochloride, 37.6g of benzalkonium chloride and 22.4g of chlorhexidine gluconate in 120mL of 85% vv ethanol and stir thoroughly to obtain the liquid phase of the organic composite component.

[0083] S302: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 5:1, a two-stage vacuum drying process is carried out with a vacuum pressure of 0.05 MPa. The first stage of drying is carried out at a temperature of 72℃ for 2 hours, and the second stage of drying is carried out at a temperature of 80℃ for 2 hours to obtain the organic-TiO2 composite functional component.

[0084] S303: The organic-TiO2 composite functional component is blended with polypropylene resin and aminopropylmethyldimethoxysilane in a mass ratio of 20:100:6 and granulated to obtain a functionalized masterbatch.

[0085] S304: Under nitrogen protection, functionalized masterbatch and polypropylene resin are melt-spun at a mass ratio of 10:100, and then immediately immersed in a 5% vv ethanol aqueous solution for surface treatment. After the treatment is completed, it is dried to obtain antibacterial and antiviral fiber αMPU3.

[0086] Example 4

[0087] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU4, specifically including:

[0088] S401: Dissolve 55.2g of polyhexamethylene guanidine phosphate, 26.5g of chlorhexidine citrate and 35.5g of chloramine salt in 300mL of 80% vv ethanol and stir thoroughly to obtain the liquid phase of the organic composite component.

[0089] S402: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 5:2, a two-stage vacuum drying process is carried out. The first stage of drying is performed at a temperature of 78℃ for 3 hours and a pressure of 0.1 MPa. The second stage of drying is performed at a temperature of 120℃ for 1.5 hours and a pressure of 0.04 MPa to obtain the organic-TiO2 composite functional component.

[0090] S403: The organic-TiO2 composite functional component is blended with polyester resin and aminopropyltriethoxysilane in a mass ratio of 20:100:6 and granulated to obtain a functionalized masterbatch.

[0091] S404: Under nitrogen protection, functionalized polyester masterbatch and polyester resin are melt-spun at a mass ratio of 10:100, and then immediately immersed in a 5% vv ethanol aqueous solution for surface treatment. After the treatment is completed, they are dried to obtain antibacterial and antiviral fiber αMPU4.

[0092] Example 5

[0093] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU5, specifically including:

[0094] S501: Dissolve 48.5g of polyhexamethylene guanidine phosphate, 30.5g of polyhexamethylene biguanide hydrochloride and 60.2g of chloramine salt in 200mL of 70% vv ethanol and stir thoroughly to obtain the liquid phase of the organic composite component;

[0095] S502: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 2:1, a two-stage vacuum drying process is carried out. The first stage of drying is performed at a temperature of 70℃ for 1 hour and a pressure of 0.04 MPa. The second stage of drying is performed at a temperature of 100℃ for 0.5 hours and a pressure of 0.08 MPa to obtain the organic-TiO2 composite functional component.

[0096] S503: The organic-TiO2 composite functional component is blended with polyethylene resin and aminopropylmethyldiethoxysilane in a mass ratio of 10:100:6 and granulated to obtain a functionalized masterbatch.

[0097] S504: Under nitrogen protection, functionalized masterbatch and polyethylene resin are melt-spun at a mass ratio of 5:100, then immersed in a 5% vv propanol aqueous solution for surface treatment. After treatment, they are dried to obtain antibacterial and antiviral fiber αMPU5.

[0098] Example 6

[0099] This embodiment provides a method for preparing antibacterial and antiviral fiber αMPU6, specifically including:

[0100] S601: Dissolve 35.5g of polyhexamethylene guanidine phosphate, 15.5g of polyhexamethylene guanidine hydrochloride, 5g of polyhexamethylene biguanide hydrochloride, 10.9g of ammonium bromide, 12.5g of benzalkonium bromide, and 15.3g of chlorhexidine gluconate in 180mL of 75% vv ethanol, and stir thoroughly to obtain the liquid phase of the organic composite component;

[0101] S602: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 10:3, a two-stage vacuum drying process is performed. The first stage of drying is carried out at a temperature of 68℃ for 4 hours and a pressure of 0.08 MPa. The second stage of drying is carried out at a temperature of 110℃ for 0.8 hours and a pressure of 0.02 MPa to obtain the organic-TiO2 composite functional component.

[0102] S603: The organic-TiO2 composite functional component is blended with polyphenylene sulfide resin and phenylaminomethyltriethoxysilane in a mass ratio of 15:100:6 and granulated to obtain a functionalized masterbatch.

[0103] S604: Under nitrogen protection, functionalized masterbatch and polyphenylene sulfide 6 resin are melt-spun at a mass ratio of 20:100, then immersed in a 5% vv butanol aqueous solution for surface treatment. After treatment, the fibers are dried to obtain antibacterial and antiviral fiber αMPU6.

[0104] To verify the appearance quality of the antibacterial and antiviral fibers prepared in the embodiments of this application, the appearance of the antibacterial and antiviral fiber αMPU1 prepared in Example 1 was characterized, and the results were as follows: Figures 1 to 2 As shown. Among them, Figure 1 This is an overall appearance diagram of the antibacterial and antiviral fiber αMPU1; Figure 2 A is Figure 1 SEM image of longitudinal section, Figure 2 B is Figure 1 Cross-sectional SEM image.

[0105] according to Figures 1 to 2 It is known that the organic-TiO2 composite functional components of the antibacterial and antiviral fiber prepared in this application are uniformly dispersed inside the fiber without obvious particulate boundaries, and a uniform substance is formed on the fiber surface, which can effectively encapsulate the organic-TiO2 composite functional components inside, resulting in good appearance and melt spinning passability, and excellent industrial production prospects.

[0106] Meanwhile, to verify the antibacterial and antiviral properties of the antibacterial and antiviral fibers αMPU1-αMPU6 prepared in the above embodiments, this application provides the following comparative examples 1-3 for detailed description.

[0107] Comparative Example 1

[0108] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU1, specifically including:

[0109] S701: Mix 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride and stir thoroughly to obtain a composite antibacterial component;

[0110] S702: The composite antibacterial component is blended with polyamide 56 resin at a mass ratio of 1:9 and granulated to obtain a functionalized masterbatch.

[0111] S703: Under nitrogen protection, functionalized masterbatch and polyamide 56 resin are melt-spun at a mass ratio of 1:9 to obtain antibacterial and antiviral fiber βMPU1.

[0112] Comparative Example 2

[0113] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU2, specifically including:

[0114] S801: Dissolve 100g of polyhexamethylene monoguanidine hydrochloride in 100mL of 75% vv ethanol and stir thoroughly to obtain an antibacterial solution.

[0115] S802: After mixing the antibacterial solution and TiO2 at a mass ratio of 2:1, a two-stage vacuum drying process is performed with a vacuum pressure of 0.1 MPa. The first stage of drying is carried out at a temperature of 75℃ for 2 hours, and the second stage is carried out at a temperature of 100℃ for 1 hour to obtain the composite antibacterial component.

[0116] S803: The composite antibacterial component is blended with polyamide 56 resin at a mass ratio of 1:9 and granulated to obtain a functionalized masterbatch.

[0117] S804: Under nitrogen protection, functionalized masterbatch and polyamide 56 resin are melt-spun at a mass ratio of 1:9 to obtain antibacterial and antiviral fiber βMPU2.

[0118] Comparative Example 3

[0119] This comparative example provides a method for preparing antibacterial and antiviral fiber βMPU3, specifically including:

[0120] S901: Dissolve 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride in 100mL of 75% vv ethanol, and stir thoroughly to obtain the liquid phase of the organic composite component;

[0121] S902: The organic composite component liquid phase is subjected to a two-stage vacuum drying process at a vacuum pressure of 0.1 MPa. The first stage of drying is carried out at a temperature of 75℃ for 2 hours, and the second stage is carried out at a temperature of 100℃ for 1 hour to obtain the composite antibacterial component.

[0122] S903: The composite antibacterial component is blended with polyamide 56 resin at a mass ratio of 1:9 and granulated to obtain a functionalized masterbatch.

[0123] S904: Under nitrogen protection, functionalized masterbatch and polyamide 56 resin are melt-spun at a mass ratio of 1:9 to obtain antibacterial and antiviral fiber βMPU2.

[0124] The antibacterial and antiviral properties of the antibacterial and antiviral fibers αMPU1-αMPU6 prepared in Examples 1-6 and the antibacterial and antiviral fibers βMPU1-βMPU3 prepared in Comparative Examples 1-3 were tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties - Part 3: Oscillation method" and ISO 18184 "Textiles - Test for antiviral properties". The test results are shown in Table 1.

[0125] Table 1: Antibacterial and antiviral performance tests of αMPU1-αMPU6 and βMPU1-βMPU3

[0126]

[0127]

[0128] As shown in Table 1, the embodiments of this application, by compounding polymeric guanidine salts, cationic antibacterial agents, and TiO2 to prepare organic-TiO2 composite functional components and incorporating them into resin fibers, significantly enhance both the antibacterial and antiviral properties of the fibers. This indicates that polymeric guanidine salt antibacterial agents, cationic antibacterial agents, and TiO2 antibacterial agents have a significant synergistic effect. Furthermore, comparing Comparative Example 1 and Comparative Example 3 reveals that the composite powder of polymeric guanidine salts and cationic antibacterial agents exhibits significantly different antibacterial and antiviral properties compared to the composite liquid phase formed by polymeric guanidine salts and cationic antibacterial agents in organic solvents. The difference in antiviral properties is particularly pronounced, indicating that improving the uniformity of the mixing of cationic antibacterial agents and polymeric guanidine salts is crucial for enhancing the antibacterial and antiviral properties of the product.

[0129] To verify the antibacterial and antiviral properties of the antibacterial and antiviral fibers αMPU1-αMPU6 prepared in the above embodiments under anionic conditions, this application provides the following comparative example 4 for detailed description.

[0130] Comparative Example 4

[0131] This embodiment provides a method for preparing antibacterial and antiviral fiber βMPU4, specifically including:

[0132] S101: Dissolve 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride in 100mL of 75% vv ethanol, and stir thoroughly to obtain the liquid phase of the organic composite component;

[0133] S102: After mixing the organic composite liquid phase with TiO2 at a mass ratio of 2:1, a two-stage vacuum drying process is carried out with a vacuum pressure of 0.1 MPa. The first stage of drying is carried out at a temperature of 75℃ for 2 hours, and the second stage of drying is carried out at a temperature of 100℃ for 1 hour to obtain the organic-TiO2 composite functional component.

[0134] S103: The organic-TiO2 composite functional component is blended with polyamide 56 resin and aminopropyltriethoxysilane in a mass ratio of 11.5:100:6 and granulated to obtain a functionalized masterbatch;

[0135] S104: Under nitrogen protection, functionalized masterbatch and polyamide 56 resin are melt-spun at a mass ratio of 10:100 to obtain antibacterial and antiviral fiber γMPU1.

[0136] Antibacterial and antiviral fibers αMPU1 and γMPU1 were anionicly dyed using black acid dye at 95°C for 30 minutes. The antibacterial and antiviral properties of the dyed samples were then tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties - Part 3: Shaking method" and ISO 18184 "Textiles - Antiviral testing". The results are shown in Table 2.

[0137] Table 2: Antibacterial and antiviral properties of αMPU1 and γMPU1 under anionic conditions

[0138]

[0139] As shown in Table 2, in this embodiment of the application, after immersing the melt-spun antibacterial and antiviral fibers in an alcohol-containing aqueous solution for surface treatment, the durability and effectiveness of the antibacterial and antiviral fibers in an anionic environment can be significantly improved. This indicates that the treatment with the alcohol-containing aqueous solution can not only hydrolyze the silane grafted on the surface of the antibacterial and antiviral fibers to form a stable film structure, but also inhibit the precipitation of the silane condensation, thereby greatly improving the film-forming efficiency and the stability of the film structure, so that the modified fibers can maintain a durable and efficient antibacterial and antiviral function.

[0140] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0141] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.

Claims

1. A method for preparing antibacterial and antiviral fibers, characterized in that, The method includes: The high molecular weight guanidine salt and the cationic antibacterial agent are mixed in an organic solvent to form an organic composite liquid phase; After mixing the organic composite component in liquid phase with TiO2, vacuum drying is performed to form an organic-TiO2 composite functional component. The first resin, aminosilane coupling agent and the organic-TiO2 composite functional component are blended and granulated to form a functionalized masterbatch. The second resin and the functionalized masterbatch are melt-spun to obtain antibacterial and antiviral fibers. The antibacterial and antiviral fibers formed by melt spinning are immersed in an alcohol-containing aqueous solution for surface treatment, and the surface-treated product is dried to obtain the final product. The first resin may be the same as or different from the second resin.

2. The preparation method according to claim 1, characterized in that, The polymeric guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and polyhexamethylene guanidine phosphate.

3. The preparation method according to claim 1, characterized in that, The cationic antibacterial agent is one or more of the following: quaternary ammonium salt antibacterial agents, chlorhexidine salt antibacterial agents, and haloamine salt antibacterial agents.

4. The preparation method according to claim 1, characterized in that, The aminosilane coupling agent is one of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and aminoethylaminoethylaminopropyltrimethoxysilane.

5. The preparation method according to claim 1, characterized in that, The first resin is the same as or different from the second resin, and is one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resin.

6. The preparation method according to claim 1, characterized in that, The mass ratio of the organic-TiO2 composite functional component to the first resin is 5-60:

100.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the functionalized masterbatch to the second resin is 5-25:

100.

8. Antibacterial and antiviral fine denier monofilaments, multifilaments, and profiled fibers prepared by the method according to any one of claims 1-7.

9. The use of antimicrobial and antiviral fibers produced by any one of claims 1-7 in the manufacture of antimicrobial and antiviral fiber products.

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