An antibacterial and wear-resistant fiber and its preparation method

Abstract

This invention relates to the field of nylon fiber technology and discloses an antibacterial and wear-resistant fiber filament and its preparation method, comprising the following preparation steps: drying nylon chips, mixing them with a composite wear-resistant filler, stirring to obtain a blend; melting, drawing, and winding the blend to obtain wear-resistant fiber filaments; surface-treating the wear-resistant fiber filaments with silane, then immersing them in an antibacterial finishing agent, adding an initiator, reacting at 70-80℃ for 1-2 hours, filtering, washing, and drying to obtain the antibacterial and wear-resistant fiber filaments. The introduction of amide groups on the surface of the wear-resistant filler improves the wear resistance of the fiber filaments by creating a tight bond between the filler and the nylon fiber filaments; the antibacterial finishing agent polymerizes on the surface of the wear-resistant fiber filaments to form an antibacterial coating with excellent antibacterial activity and wear resistance.

Description

Technical Field

[0001] This invention relates to the field of nylon fiber technology, specifically to an antibacterial and abrasion-resistant fiber and its preparation method. Background Technology

[0002] Nylon, also known as nylon or nylon fiber, is a general term for thermoplastic resins containing repeating amide groups in their molecular backbone. It includes aliphatic PA, aliphatic-aromatic PA, and aromatic PA. It is one of the earliest synthetic fibers to be industrialized and has now become the second largest synthetic fiber for clothing after polyester. Nylon fiber is usually produced by melt spinning a mixture of nylon chips, abrasion-resistant fillers, and auxiliaries. It has good mechanical properties, lubricity, corrosion resistance, oil resistance, and barrier properties, and is lightweight and soft, making it widely used in the clothing industry.

[0003] However, traditional nylon fibers have poor antibacterial and abrasion resistance properties, so existing nylon needs to be improved. By mixing nylon chips and abrasion-resistant fillers and then melt spinning, nylon fibers with excellent abrasion resistance can be prepared. However, the inorganic abrasion-resistant fillers have poor compatibility with nylon chips, which affects the abrasion resistance of nylon fibers. By forming an antibacterial coating on the surface of nylon fibers, the antibacterial activity of nylon fibers can be effectively improved. However, the bonding force between the antibacterial coating and nylon fibers is weak, which leads to the antibacterial coating easily falling off and resulting in the loss of antibacterial performance. Summary of the Invention

[0004] This invention provides an antibacterial and wear-resistant fiber and its preparation method, which solves the problem of poor antibacterial and wear-resistant properties of traditional nylon fiber.

[0005] The technical solution of the present invention:

[0006] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0007] S1. After drying nylon chips at 70-90℃ for 10-12h, mix them with composite wear-resistant fillers and stir at 500-600r / min for 30-40min to obtain a blend.

[0008] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0009] S3. After surface treatment of wear-resistant fiber filaments with silane, the fiber filaments are immersed in an antibacterial finishing agent, an initiator is added, and the reaction is carried out at 70-80℃ for 1-2 hours. After filtration, washing and drying, antibacterial wear-resistant fiber filaments are obtained.

[0010] The antibacterial finishing agent is obtained by mixing and reacting 4-vinylphenyl glycidyl ether, a compound antibacterial agent and boron trifluoride ethyl ether, and then mixing it with curcumin and tannic acid.

[0011] The composite antibacterial agent is obtained by modifying antibacterial nanoparticles with oleic acid and then intercalating them into the interlayer of montmorillonite modified with chlorhexidine acetate.

[0012] The composite wear-resistant filler is obtained by mixing and reacting ferulic acid and pretreated wear-resistant filler.

[0013] Furthermore, in step S1, the nylon chips are selected from nylon 6 chips or nylon 66 chips.

[0014] Further, in step S1, the mass ratio of nylon chips to composite wear-resistant filler is (50-60):(8-10).

[0015] Furthermore, in step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 260-280℃, with a spinneret micro-orifice diameter of 0.18-0.22mm and an aspect ratio of 3:1.

[0016] Furthermore, in step S2, the stretching is carried out on a parallel stretching machine at a temperature of 60-90℃, a stretching speed of 300-400m / min, and a stretching ratio of 5.5-6.5.

[0017] Furthermore, in step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0018] The wear-resistant fiber filaments were added to ethanol and deionized water and stirred evenly. Silane was then added and stirred at 65-75℃ for 1-2 hours. After cooling to room temperature, the fibers were filtered, washed, and dried to obtain silane-surface-treated wear-resistant fiber filaments.

[0019] Furthermore, during the above reaction process, the silanol groups generated by the hydrolysis of silane can chemically bond with the active groups on the surface of the wear-resistant fiber, allowing silane to be grafted onto the surface of the wear-resistant fiber, providing reactive functional groups for the wear-resistant fiber, which is beneficial for applying an antibacterial coating to the surface of the wear-resistant fiber.

[0020] Furthermore, the ratio of abrasion-resistant fiber filaments, ethanol, deionized water, and silane is (55-65)g:(280-320)mL:(90-110)mL:(13-17)g.

[0021] Furthermore, the antibacterial finishing agent is prepared by the following steps:

[0022] A1. Oleic acid and antibacterial nanoparticles were added to ethanol and stirred until homogeneous. Sulfuric acid was added, and the mixture was stirred at 70-80℃ for 8-12 minutes. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain oleic acid-modified antibacterial nanoparticles.

[0023] A2. Add montmorillonite modified with chlorhexidine acetate and antibacterial nanoparticles modified with oleic acid to deionized water, heat to 50-60℃, sonicate at 40-60KHz for 5-6 hours, filter, wash and dry to obtain a composite antibacterial agent.

[0024] A3. Add 4-vinylphenyl glycidyl ether to chloroform, stir evenly, add composite antibacterial agent and boron trifluoride ethyl ether, stir and react at 25-35℃ for 20-30 min, filter, wash and dry to obtain modified composite antibacterial agent;

[0025] A4. Add the modified composite antibacterial agent, curcumin and tannic acid to acetone, stir well to obtain the antibacterial finishing agent.

[0026] Furthermore, during the A1 reaction process described above, the hydroxyl groups on the surface of the antibacterial nanoparticles react with the carboxyl groups of oleic acid, causing oleic acid to be grafted onto the surface of the nano zinc oxide, resulting in oleic acid-modified antibacterial nanoparticles.

[0027] Furthermore, in the A2 reaction process described above, the long-chain alkane structure contained in the oleic acid-modified antibacterial nanoparticles can interact with the montmorillonite modified with chlorhexidine acetate through hydrophobic chains, allowing the oleic acid-modified antibacterial nanoparticles to intercalate into the montmorillonite modified with chlorhexidine acetate, thereby achieving montmorillonite loading of oleic acid-modified antibacterial nanoparticles and obtaining a composite antibacterial agent.

[0028] Furthermore, in the above A3 reaction process, boron trifluoride ether acts as a catalyst in chloroform, causing the epoxy groups of 4-vinylphenyl glycidyl ether to react with the hydroxyl groups on the surface of montmorillonite in the composite antibacterial agent, thereby grafting 4-vinylphenyl glycidyl ether onto the composite antibacterial agent to obtain a modified composite antibacterial agent.

[0029] Furthermore, in the A4 reaction process described above, the modified composite antibacterial agent is chemically bonded to the oxygen-containing functional groups contained in curcumin and tannic acid, serving as an antibacterial finishing agent.

[0030] Further, in step A1, the ratio of oleic acid, antibacterial nanoparticles, ethanol and sulfuric acid is (1.5-1.9)g:(5-6)g:(80-120)mL:(0.1-0.3)mL.

[0031] Further, in step A2, the ratio of the amount of montmorillonite modified with chlorhexidine acetate, the antibacterial nanoparticles modified with oleic acid, and deionized water is (5-6) g:(2.2-2.4) g:(90-110) mL.

[0032] Further, in step A3, the ratio of the amounts of 4-vinylphenyl glycidyl ether, chloroform, the composite antibacterial agent and boron trifluoride ether is (3.2-3.4)g:(45-55)mL:(7-8)g:(0.1-0.3)g.

[0033] Further, in step A4, the ratio of the modified composite antibacterial agent, curcumin, tannic acid and acetone is (9-11)g:(5.1-5.5)g:(4-5)g:(90-110)mL.

[0034] Furthermore, the antibacterial nanoparticles are selected from nano-silver or nano-zinc oxide.

[0035] Furthermore, the composite wear-resistant filler is prepared by the following steps:

[0036] B1. Add the wear-resistant filler to ethanol and deionized water, stir evenly, add γ-aminopropyltriethoxysilane, stir and react at 65-75℃ for 1-2 hours, cool to room temperature, filter, wash and dry to obtain the pretreated wear-resistant filler.

[0037] B2. Ferulic acid and pretreated wear-resistant filler are added to N,N-dimethylformamide and stirred evenly. Then, N,N'-dicyclohexylcarbodiimide is added and stirred at 80-100℃ for 1-2 hours. After filtration, washing, and drying, the composite wear-resistant filler is obtained.

[0038] Furthermore, during the B1 reaction process described above, the silanol groups generated by the hydrolysis of γ-aminopropyltriethoxysilane can be chemically bonded to the hydroxyl groups on the surface of the wear-resistant filler, thereby grafting γ-aminopropyltriethoxysilane onto the surface of the wear-resistant filler to obtain a pretreated wear-resistant filler. This facilitates the introduction of amide groups onto the surface of the wear-resistant filler, allowing the wear-resistant filler to be uniformly dispersed in the nylon fiber matrix.

[0039] Furthermore, in the B2 reaction process described above, N,N'-dicyclohexylcarbodiimide acts as a catalyst, enabling the carboxyl groups contained in ferulic acid to undergo an amidation reaction with the amino groups on the surface of the pretreated wear-resistant filler, thereby introducing amide groups onto the surface of the wear-resistant filler and making it a composite wear-resistant filler.

[0040] Further, in step B1, the ratio of the amount of wear-resistant filler, ethanol, deionized water and γ-aminopropyltriethoxysilane is (4-6)g:(25-35)mL:(8-12)mL:(1-2)g.

[0041] Further, in step B2, the ratio of ferulic acid, pretreated wear-resistant filler, N,N-dimethylformamide and N,N'-dicyclohexylcarbodiimide is (3-4)g:(3-5)g:(90-110)mL:(1.1-1.3)g.

[0042] Furthermore, the wear-resistant filler is selected from one of nano-zirconia, nano-calcium silicate, nano-alumina, nano-calcium carbonate, nano-silicon carbide, and nano-silica.

[0043] The present invention has the following beneficial effects:

[0044] (1) In the technical solution of the present invention, ferulic acid reacts with pretreated wear-resistant filler, thereby introducing amide groups on the surface of wear-resistant filler. On the one hand, the amide groups on the surface of the composite wear-resistant filler can form hydrogen bonds with the amide groups in the nylon chips. These hydrogen bonds play a cross-linking role between molecular chains, making the wear-resistant filler and nylon fiber filaments tightly bonded to form wear-resistant fiber filaments with excellent wear resistance. On the other hand, the hydrogen bonds play a cross-linking role between molecular chains, increasing the cross-linking density of the fiber filaments and improving the mechanical strength of the fiber filaments.

[0045] (2) In the technical solution of this invention, the double bonds contained in the silane-treated wear-resistant fiber can copolymerize with the double bonds of 4-vinylphenyl glycidyl ether in the antibacterial finishing agent, so that the antibacterial finishing agent polymerizes on the surface of the wear-resistant fiber to form an antibacterial coating, giving the fiber excellent antibacterial activity and wear resistance. The montmorillonite intercalated with chlorhexidine acetate in the antibacterial coating serves as the first antibacterial defense line for the wear-resistant fiber, improving the antibacterial activity of the wear-resistant fiber. Among them, after the montmorillonite is intercalated with chlorhexidine acetate, the interlayer spacing of the montmorillonite is expanded, giving the montmorillonite excellent antibacterial properties. Moreover, chlorhexidine acetate is hydrophobic in the interlayer of montmorillonite, which is conducive to the intercalation of oleic acid modified antibacterial nanoparticles into the interlayer of montmorillonite. In addition, montmorillonite also has good wear resistance, improving the wear resistance of the fiber.

[0046] (3) In the technical solution of this invention, the oleic acid-modified antibacterial nanoparticles intercalated between the montmorillonite layers in the antibacterial coating serve as the second antibacterial defense line for the wear-resistant fiber filaments, thereby improving the antibacterial activity of the wear-resistant fiber filaments. Specifically, the antibacterial nanoparticles, such as zinc oxide nanoparticles, generate superoxide radicals on their surface under light irradiation. These radicals combine with hydrogen to generate hydrogen peroxide, which can penetrate the cell membrane, causing cell peroxidation and achieving antibacterial properties. The oleic acid-modified antibacterial nanoparticles make the zinc oxide nanoparticles hydrophobic, which is beneficial for the intercalation of the antibacterial nanoparticles between the montmorillonite layers. Furthermore, oleic acid, as a fatty acid, can penetrate the surface of bacteria, causing the loss of nutrients inside the bacteria, thus also exhibiting good antibacterial properties. In addition, the combination of oleic acid-modified antibacterial nanoparticles with chlorhexidine acetate intercalated montmorillonite significantly improves the antibacterial properties of the wear-resistant fiber filaments.

[0047] (4) In the technical solution of this invention, curcumin and tannic acid in the antibacterial coating serve as the third antibacterial defense line for the wear-resistant fiber, thereby improving the antibacterial activity of the wear-resistant fiber. Among them, curcumin and tannic acid are organic antibacterial materials. Curcumin can inhibit the activity of bacterial enzymes, and tannic acid can change the bacterial structure and destroy the cell membrane. When used together, they have a synergistic effect in antibacterial properties, enhancing the antibacterial performance of the wear-resistant fiber. Furthermore, the hydroxyl groups contained in the 4-vinylphenyl glycidyl ether polymer in the antibacterial coating can chemically bond with the oxygen-containing functional groups contained in curcumin and tannic acid, increasing the polymer crosslinking density and forming a dense antibacterial coating, thereby enhancing the antibacterial performance of the fiber. Detailed Implementation

[0048] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0049] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0050] The nylon chips were selected from nylon 6 chips, grade BL2340, and purchased from Dongguan Dongshuo Plastic Raw Materials Co., Ltd.; the silane was KH570; and the initiator was azobisisobutyronitrile.

[0051] The antibacterial nanoparticles are made of silver nanoparticles with a particle size of 10 nm.

[0052] The wear-resistant filler is nano-zirconia with a particle size of 100nm.

[0053] Montmorillonite is sodium-based montmorillonite with a particle size of 2.5 μm.

[0054] The montmorillonite modified with chlorhexidine acetate is prepared by the following steps:

[0055] 3.3 g of chlorhexidine acetate and 4.8 g of montmorillonite were added to 100 mL of deionized water and stirred at 80 °C for 3 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 110 °C for 10 min to obtain montmorillonite modified with chlorhexidine acetate.

[0056] Example 1

[0057] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0058] S1. After drying nylon 6 chips at 70℃ for 10h, mix them with composite wear-resistant filler and stir at 500r / min for 30min to obtain a blend.

[0059] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0060] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 70℃ for 1h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0061] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 50:8.

[0062] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 260°C, with a spinneret micro-orifice diameter of 0.18 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 60°C, a drawing speed of 300 m / min, and a drawing ratio of 5.5.

[0063] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0064] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0065] The antibacterial finishing agent is prepared by the following steps:

[0066] A1. Add 1.5g of oleic acid and 5g of nano-silver to 90mL of ethanol, stir well, add 0.1mL of 36% sulfuric acid, stir and react at 70℃ for 8min, cool to room temperature, filter, wash with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0067] A2. Add 5g of chlorhexidine acetate-modified montmorillonite and 2.2g of oleic acid-modified nano-silver to 90mL of deionized water, heat to 50℃, sonicate at 40KHz for 5h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0068] A3. Add 3.2g of 4-vinylphenyl glycidyl ether to 45mL of chloroform, stir well, then add 7g of composite antibacterial agent and 0.1g of boron trifluoride ether, stir and react at 25℃ for 20min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0069] A4. Add 9g of modified composite antibacterial agent, 5.1g of curcumin and 4g of tannic acid to 90mL of acetone and stir well to obtain antibacterial finishing agent.

[0070] The composite wear-resistant filler is prepared by the following steps:

[0071] B1. Add 4g of nano-zirconia to 25mL of ethanol and 8mL of deionized water, stir well, add 1g of γ-aminopropyltriethoxysilane, stir and react at 65℃ for 1h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0072] B2. Add 3g ferulic acid and 3g pretreated nano-zirconia to 90mL N,N-dimethylformamide, stir evenly, add 1.1g N,N'-dicyclohexylcarbodiimide, stir and react at 80℃ for 1h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0073] Example 2

[0074] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0075] S1. After drying nylon 6 chips at 80℃ for 11h, mix them with composite wear-resistant filler and stir at 550r / min for 35min to obtain a blend.

[0076] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0077] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 75℃ for 1.5h. After filtration, it is washed three times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0078] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 55:9.

[0079] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 270°C, with a spinneret micro-orifice diameter of 0.2 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 75°C, a drawing speed of 350 m / min, and a drawing ratio of 6.

[0080] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0081] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0082] The antibacterial finishing agent is prepared by the following steps:

[0083] A1. Add 1.7g of oleic acid and 5.5g of nano-silver to 100mL of ethanol, stir well, add 0.2mL of 36% sulfuric acid, stir and react at 75℃ for 10min, cool to room temperature, filter, wash with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0084] A2. Add 5.5g of chlorhexidine acetate-modified montmorillonite and 2.3g of oleic acid-modified nano-silver to 100mL of deionized water, heat to 55℃, sonicate at 50KHz for 5.5h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0085] A3. Add 3.3g of 4-vinylphenyl glycidyl ether to 50mL of chloroform, stir well, then add 7.5g of composite antibacterial agent and 0.2g of boron trifluoride ether. Stir and react at 30℃ for 25min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0086] A4. Add 10g of modified composite antibacterial agent, 5.3g of curcumin and 4.6g of tannic acid to 100mL of acetone and stir well to obtain antibacterial finishing agent.

[0087] The composite wear-resistant filler is prepared by the following steps:

[0088] B1. Add 5g of nano-zirconia to 30mL of ethanol and 10mL of deionized water, stir well, add 1.5g of γ-aminopropyltriethoxysilane, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0089] B2. Add 3.5g ferulic acid and 4g pretreated nano-zirconia to 100mL N,N-dimethylformamide, stir evenly, add 1.2g N,N'-dicyclohexylcarbodiimide, stir and react at 90℃ for 1.5h, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0090] Example 3

[0091] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0092] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0093] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0094] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0095] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0096] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0097] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0098] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0099] The antibacterial finishing agent is prepared by the following steps:

[0100] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0101] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0102] A3. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0103] A4. Add 11g of modified composite antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0104] The composite wear-resistant filler is prepared by the following steps:

[0105] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0106] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0107] Comparative Example 1

[0108] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0109] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0110] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0111] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0112] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0113] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0114] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0115] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0116] The antibacterial finishing agent is prepared by the following steps:

[0117] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0118] A2. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of oleic acid-modified nano-silver and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0119] A3. Add 11g of modified composite antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0120] The composite wear-resistant filler is prepared by the following steps:

[0121] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0122] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0123] Comparative Example 2

[0124] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0125] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0126] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0127] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0128] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0129] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0130] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0131] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0132] The antibacterial finishing agent is prepared by the following steps:

[0133] A1. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of nano silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0134] A2. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether, stir and react at 35℃ for 30min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0135] A3. Add 11g of modified composite antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0136] The composite wear-resistant filler is prepared by the following steps:

[0137] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0138] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0139] Comparative Example 3

[0140] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0141] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0142] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0143] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0144] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0145] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0146] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0147] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0148] The antibacterial finishing agent is prepared by the following steps:

[0149] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0150] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0151] A3. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0152] A4. Add 11g of modified composite antibacterial agent and 10.5g of curcumin to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0153] The composite wear-resistant filler is prepared by the following steps:

[0154] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0155] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0156] Comparative Example 4

[0157] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0158] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0159] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0160] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0161] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0162] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0163] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0164] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0165] The antibacterial finishing agent is prepared by the following steps:

[0166] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0167] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0168] A3. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0169] A4. Add 11g of modified composite antibacterial agent and 10.5g of tannic acid to 110mL of acetone, stir well, and obtain antibacterial finishing agent.

[0170] The composite wear-resistant filler is prepared by the following steps:

[0171] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0172] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0173] Comparative Example 5

[0174] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0175] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0176] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0177] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0178] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0179] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0180] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0181] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0182] The antibacterial finishing agent is prepared by the following steps:

[0183] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0184] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0185] A3. Add 11g of compound antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0186] The composite wear-resistant filler is prepared by the following steps:

[0187] B1. Add 6g of nano-zirconia to 35mL of ethanol and 12mL of deionized water, stir well, add 2g of γ-aminopropyltriethoxysilane, stir and react at 75℃ for 2h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0188] B2. Add 4g ferulic acid and 5g pretreated nano-zirconia to 110mL N,N-dimethylformamide, stir evenly, add 1.3g N,N'-dicyclohexylcarbodiimide, stir and react at 100℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain composite wear-resistant filler.

[0189] Comparative Example 6

[0190] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0191] S1. After drying nylon 6 chips at 90℃ for 12h, mix them with composite wear-resistant filler and stir at 600r / min for 40min to obtain a blend.

[0192] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0193] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0194] In step S1, the mass ratio of nylon 6 chips to composite wear-resistant filler is 60:10.

[0195] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0196] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0197] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0198] The antibacterial finishing agent is prepared by the following steps:

[0199] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0200] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0201] A3. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0202] A4. Add 11g of modified composite antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0203] The composite wear-resistant filler is prepared by the following steps:

[0204] 4g ferulic acid and 5g nano-zirconia were added to 110mL of N,N-dimethylformamide and stirred until homogeneous. Then, 1.3g of N,N'-dicyclohexylcarbodiimide was added and stirred at 100℃ for 2h. After filtration, the mixture was washed three times with deionized water and dried in an oven at 70℃ for 10min to obtain the composite wear-resistant filler.

[0205] Comparative Example 7

[0206] A method for preparing antibacterial and wear-resistant fiber filaments includes the following preparation steps:

[0207] S1. After drying nylon 6 chips at 90℃ for 12h, they are mixed with pretreated nano-zirconia and stirred at 600r / min for 40min to obtain a blend.

[0208] S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament;

[0209] S3. After surface treatment of wear-resistant fiber with silane, it is immersed in 200mL of antibacterial finishing agent, 0.8g of azobisisobutyronitrile is added, and the mixture is stirred and reacted at 80℃ for 2h. After filtration, it is washed 3 times with deionized water and dried in an oven at 70℃ for 10min to obtain antibacterial wear-resistant fiber.

[0210] In step S1, the mass ratio of nylon 6 chips to pretreated nano-zirconia is 60:10.

[0211] In step S2, melt spinning is carried out on a spinning machine at a spinning temperature of 280°C, with a spinneret micro-orifice diameter of 0.22 mm and an aspect ratio of 3:1; drawing is carried out on a parallel drawing machine at a temperature of 90°C, a drawing speed of 400 m / min, and a drawing ratio of 6.5.

[0212] In step S3, the silane-surface-treated wear-resistant fiber filaments are specifically prepared by the following steps:

[0213] Add 60g of wear-resistant fiber to 300mL of ethanol and 100mL of deionized water, stir well, add 15g of KH570, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain silane surface-treated wear-resistant fiber.

[0214] The antibacterial finishing agent is prepared by the following steps:

[0215] A1. Add 1.9g of oleic acid and 6g of nano-silver to 120mL of ethanol, stir well, add 0.3mL of 36% sulfuric acid, stir and react at 80℃ for 12min, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 20min to obtain oleic acid modified nano-silver.

[0216] A2. Add 6g of chlorhexidine acetate-modified montmorillonite and 2.4g of oleic acid-modified nano-silver to 110mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 15min to obtain a composite antibacterial agent.

[0217] A3. Add 3.4g of 4-vinylphenyl glycidyl ether to 55mL of chloroform, stir well, then add 8g of composite antibacterial agent and 0.3g of boron trifluoride ether. Stir and react at 35℃ for 30min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified composite antibacterial agent.

[0218] A4. Add 11g of modified composite antibacterial agent, 5.5g of curcumin and 5g of tannic acid to 110mL of acetone and stir well to obtain antibacterial finishing agent.

[0219] Pretreated nano-zirconia is prepared by the following steps:

[0220] 6g of nano-zirconia was added to 35mL of ethanol and 12mL of deionized water and stirred until homogeneous. Then, 2g of γ-aminopropyltriethoxysilane was added and stirred at 75℃ for 2h. After cooling to room temperature, the mixture was filtered, washed three times with ethanol and three times with deionized water, and dried in an oven at 70℃ for 10min to obtain pretreated nano-zirconia.

[0221] The antibacterial and abrasion-resistant fiber filaments prepared in Examples 1-3 and Comparative Examples 1-7 were tested for performance.

[0222] Monofilament fineness: Tested according to GB / T 14344-2008.

[0223] Mechanical performance testing: The breaking strength of the prepared antibacterial and wear-resistant fiber filaments was tested according to GB / T14344-2022 standard, with a clamping distance of 250 mm and a tensile speed of 200 mm / min; the breaking elongation of the prepared antibacterial and wear-resistant fiber filaments was tested using a multifilament tensile tester, with a pre-tension of 3 cN, a tensile speed of 200 mm / min, and a clamping distance of 200 mm.

[0224] Abrasion resistance test: Referring to the FZ / T01058-1999 standard, the abrasion resistance of the antibacterial abrasion-resistant fiber was tested using a reciprocating abrasion tester. The tension weight used was 35g, and the sandpaper was 400 grit. The number of frictions at the point of breakage was recorded to evaluate its abrasion resistance.

[0225] Antibacterial performance testing: The antibacterial performance of the prepared antibacterial and wear-resistant fiber filaments was tested by the oscillation method according to GB / T 20944.3-2008 standard.

[0226] As shown in Table 1 below.

[0227] Table 1. Performance tests of antibacterial and abrasion-resistant fibers prepared in Examples 1-3 and Comparative Examples 1-7

[0228]

[0229]

[0230] As can be seen from the data in Table 1, the antibacterial and wear-resistant fiber filaments prepared in Examples 1-3 have high antibacterial and wear-resistant properties.

[0231] In Comparative Example 1, when the composite antibacterial agent was replaced with an antibacterial finishing agent prepared by oleic acid-modified nano-silver and applied to the surface of the wear-resistant fiber, its antibacterial performance decreased. This proves that montmorillonite intercalated with chlorhexidine acetate serves as the first line of antibacterial defense for the wear-resistant fiber, improving the antibacterial activity of the wear-resistant fiber. Furthermore, montmorillonite also has good wear resistance and thermal stability, further enhancing the wear resistance of the fiber.

[0232] In Comparative Example 2, when the oleic acid-modified nano-silver was replaced with an antibacterial finishing agent prepared from nano-silver and applied to the surface of the wear-resistant fiber, its antibacterial properties decreased. This demonstrates that the oleic acid-modified antibacterial nanoparticles serve as a second line of antibacterial defense for the wear-resistant fiber, improving its antibacterial properties. Furthermore, oleic acid makes the nano-zinc oxide hydrophobic, which is beneficial for the intercalation of antibacterial nanoparticles into the montmorillonite layers modified with chlorhexidine acetate. In addition, oleic acid also has good antibacterial properties.

[0233] Comparative Example 3 used only curcumin and Comparative Example 4 used only tannic acid to prepare antibacterial finishing agents. When these were applied to the surface of abrasion-resistant fibers, their antibacterial properties decreased. This proves that curcumin and tannic acid serve as the third line of antibacterial defense for abrasion-resistant fibers. Curcumin can inhibit the activity of bacterial enzymes, while tannic acid can change the bacterial structure and destroy the cell membrane. When used together, they have a synergistic effect in antibacterial properties, enhancing the antibacterial performance of abrasion-resistant fibers.

[0234] In Comparative Example 5, when the modified composite antibacterial agent was replaced with an antibacterial finishing agent prepared from the composite antibacterial agent and applied to the surface of the wear-resistant fiber, its antibacterial performance decreased. This proves that the double bonds contained in the silane-treated wear-resistant fiber can copolymerize with the double bonds of 4-vinylphenyl glycidyl ether in the antibacterial finishing agent, thereby forming an antibacterial coating on the surface of the wear-resistant fiber with excellent antibacterial activity. Furthermore, the 4-vinylphenyl glycidyl ether polymer can chemically bond with the oxygen-containing functional groups contained in curcumin and tannic acid, increasing the polymer crosslinking density and forming a dense antibacterial coating, thereby enhancing the antibacterial performance of the fiber.

[0235] Comparative Example 6 showed that when pretreated nano-zirconia was replaced with a composite wear-resistant filler prepared from nano-zirconia and added to the fiber, its wear resistance decreased. This proved that γ-aminopropyltriethoxysilane grafting onto the surface of nano-zirconia is beneficial for introducing amide groups onto the surface of nano-zirconia, so that nano-zirconia is uniformly dispersed in the nylon fiber matrix, thereby improving the wear resistance of the fiber.

[0236] Comparative Example 7 showed that replacing the composite wear-resistant filler with pretreated nano-zirconia added to the fiber filaments resulted in a decrease in wear resistance. This demonstrates that the reaction between ferulic acid and pretreated nano-zirconia can introduce amide groups on the surface of nano-zirconia, which can form hydrogen bonds with the amide groups in the nylon chips. This results in a tight bond between the nano-zirconia and the nylon fiber filaments, exhibiting excellent wear resistance. Furthermore, the hydrogen bonds act as cross-linking agents between molecular chains, increasing the cross-linking density of the fiber filaments and improving their mechanical strength.

[0237] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0238] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing antibacterial and wear-resistant fiber filaments, characterized in that, The preparation steps include the following: S1. After drying nylon chips at 70-90℃ for 10-12h, mix them with composite wear-resistant fillers and stir at 500-600r / min for 30-40min to obtain a blend. S2. The blended material is melt-spun, drawn, and wound to form a wear-resistant fiber filament; S3. After surface treatment of wear-resistant fiber filaments with silane, they are then immersed in an antibacterial finishing agent, an initiator is added, and the reaction is carried out at 70-80℃ for 1-2 hours. After filtration, washing and drying, antibacterial wear-resistant fiber filaments are obtained. The antibacterial finishing agent is obtained by mixing and reacting 4-vinylphenyl glycidyl ether, a compound antibacterial agent and boron trifluoride ethyl ether, and then mixing it with curcumin and tannic acid. The composite antibacterial agent is obtained by modifying antibacterial nanoparticles with oleic acid and then intercalating them into the interlayer of montmorillonite modified with chlorhexidine acetate. The composite wear-resistant filler is obtained by mixing and reacting ferulic acid and pretreated wear-resistant filler. The pretreated wear-resistant filler is obtained by grafting γ-aminopropyltriethoxysilane onto the surface of the wear-resistant filler.

2. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 1, characterized in that, The antibacterial finishing agent is prepared by the following steps: A1. Oleic acid and antibacterial nanoparticles were added to ethanol and stirred until homogeneous. Sulfuric acid was added, and the mixture was stirred at 70-80℃ for 8-12 minutes. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain oleic acid-modified antibacterial nanoparticles. A2. Add montmorillonite modified with chlorhexidine acetate and antibacterial nanoparticles modified with oleic acid to deionized water, heat to 50-60℃, sonicate at 40-60 kHz for 5-6 hours, filter, wash and dry to obtain a composite antibacterial agent; A3. Add 4-vinylphenyl glycidyl ether to chloroform, stir evenly, add composite antibacterial agent and boron trifluoride ethyl ether, stir and react at 25-35℃ for 20-30 min, filter, wash and dry to obtain modified composite antibacterial agent; A4. Add the modified composite antibacterial agent, curcumin and tannic acid to acetone, stir well to obtain the antibacterial finishing agent.

3. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 2, characterized in that, In step A1, the ratio of oleic acid, antibacterial nanoparticles, ethanol and sulfuric acid is (1.5-1.9)g:(5-6)g:(80-120)mL:(0.1-0.3)mL.

4. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 2, characterized in that, In step A2, the ratio of the amount of montmorillonite modified with chlorhexidine acetate, the antibacterial nanoparticles modified with oleic acid, and deionized water is (5-6)g:(2.2-2.4)g:(90-110)mL.

5. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 2, characterized in that, In step A3, the ratio of the amounts of 4-vinylphenyl glycidyl ether, chloroform, the compound antibacterial agent and boron trifluoride ether is (3.2-3.4)g:(45-55)mL:(7-8)g:(0.1-0.3)g.

6. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 2, characterized in that, In step A4, the ratio of the modified composite antibacterial agent, curcumin, tannic acid and acetone is (9-11)g:(5.1-5.5)g:(4-5)g:(90-110)mL.

7. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 1, characterized in that, The composite wear-resistant filler is prepared by the following steps: B1. Add the wear-resistant filler to ethanol and deionized water, stir evenly, add γ-aminopropyltriethoxysilane, stir and react at 65-75℃ for 1-2 hours, cool to room temperature, filter, wash and dry to obtain the pretreated wear-resistant filler. B2. Ferulic acid and pretreated wear-resistant filler are added to N,N-dimethylformamide and stirred evenly. Then, N,N'-dicyclohexylcarbodiimide is added and stirred at 80-100℃ for 1-2 hours. After filtration, washing, and drying, the composite wear-resistant filler is obtained.

8. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 7, characterized in that, In step B1, the ratio of the amount of wear-resistant filler, ethanol, deionized water and γ-aminopropyltriethoxysilane is (4-6)g:(25-35)mL:(8-12)mL:(1-2)g.

9. The method for preparing an antibacterial and wear-resistant fiber filament according to claim 7, characterized in that, In step B2, the ratio of ferulic acid, pretreated wear-resistant filler, N,N-dimethylformamide and N,N'-dicyclohexylcarbodiimide is (3-4)g:(3-5)g:(90-110)mL:(1.1-1.3)g.

10. An antibacterial and abrasion-resistant fiber filament prepared by the method of any one of claims 1-9.

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