Preparation process of antibacterial fiber

Abstract

The invention relates to the field of textiles, and particularly discloses a preparation process of antibacterial fibers, which comprises the following steps: S1, respectively drying and preparing polymer slices and an antibacterial agent; s2, performing melt spinning on the polymer slices and an antibacterial agent, performing air cooling, and then performing traction and winding to obtain antibacterial fibers; wherein the antibacterial agent is prepared by mixing dodecyl trimethyl ammonium chloride, polyvinylpyrrolidone and core-shell type antibacterial particles according to the mass ratio of (0.4-0.5): (0.1-0.2): 1, the core-shell type antibacterial particles are prepared by loading nano-zinc oxide and nano-silver particles on intercalation modified montmorillonite and then forming a silicon dioxide coating layer through a sol-gel method, and the core-shell type antibacterial particles are prepared from the silicon dioxide coating layer through a sol-gel method. And carrying out spray drying to obtain the core-shell antibacterial particles. The preparation method has the characteristic of improving the antibacterial durability and uniformity of the antibacterial fiber.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of textiles, more particularly, it relates to a preparation process of antibacterial fiber. BACKGROUND

[0002] In the field of textile fiber manufacturing, antibacterial fiber as a functional material is widely used in medical, health, sports clothing and home supplies and other fields because it can effectively inhibit or kill bacteria, fungi and other microorganisms, thereby protecting the user from pathogenic bacteria. However, the traditional antibacterial fiber preparation technology has many limitations, which is difficult to meet the market demand for long-acting, uniform and environmentally friendly antibacterial fiber products.

[0003] At present, the preparation of most antibacterial fibers relies on the surface coating method, which coats the antibacterial agent on the surface of the fiber in the form of a coating to achieve antibacterial function. Although the surface coating method has the advantages of simple process and low cost, the bonding force between the coating and the fiber substrate is weak, and the coating is easy to fall off during long-term use or frequent washing, resulting in a significant reduction in antibacterial effect, and the distribution of the coating on the fiber surface is often uneven, which affects the stability and reliability of the antibacterial effect.

[0004] It is particularly important to develop a preparation process of antibacterial fiber that can achieve long-acting and uniform antibacterial effect. SUMMARY

[0005] In order to improve the antibacterial durability and uniformity of the antibacterial fiber, the present application provides a preparation process of antibacterial fiber.

[0006] The present application provides a preparation process of antibacterial fiber, which adopts the following technical scheme: A preparation process of antibacterial fiber, comprising the following steps: S1, dry the polymer chips and the antibacterial agent respectively, and prepare the materials; S2, melt spinning the polymer chips and the antibacterial agent, draw after air cooling, wind, and prepare the antibacterial fiber; Wherein, the antibacterial agent is prepared by mixing dodecyl trimethyl ammonium chloride, polyvinyl pyrrolidone and core-shell type antibacterial particles, the core-shell type antibacterial particles are prepared by loading nano zinc oxide and nano silver particles on intercalated modified montmorillonite, forming a silica coating layer by sol-gel method, and then spray drying.

[0007] By adopting the above technical scheme, the melt spinning method is adopted in the present application to blend the antibacterial agent with the polymer substrate, so that the antibacterial agent is uniformly dispersed in the fiber, forming a stable antibacterial structure. This integrated way not only enhances the bonding force between the antibacterial agent and the fiber substrate, improves the durability of the antibacterial effect, but also ensures the uniform distribution of the antibacterial agent in the fiber, thereby realizing the uniform and long-acting antibacterial performance.

[0008] On this basis, the antibacterial agent in the application is combined with the quaternary ammonium salt organic antibacterial agent, dodecyltrimethylammonium chloride is used as the organic antibacterial agent, has good spectrum, and synergistically acts with the nano-silver antibacterial particles to enhance the antibacterial effect. Meanwhile, the quaternary ammonium salt antibacterial agent contains long-chain alkane in the molecular structure, which can form a certain steric hindrance in the polymer matrix, and is helpful to the uniform dispersion of the antibacterial agent. Polyvinylpyrrolidone is used as a dispersant, the molecular chain of which is adsorbed between the antibacterial particles and the organic antibacterial components to form a protective film, preventing mutual aggregation and ensuring the uniform dispersion of the antibacterial agent in the polymer matrix.

[0009] In the application, the core-shell antibacterial particles use a mixed system of nano-silver particles and nano-zinc oxide as the matrix. The nano-zinc oxide generates hydroxyl radicals by photocatalysis to destroy the bacterial cell membrane, and the nano-silver releases silver ions to inactivate bacterial respiratory enzymes, thus having a spectrum of antibacterial effects. The synergistic effect of the two can significantly improve the antibacterial rate of Escherichia coli and Staphylococcus aureus. Moreover, the antibacterial activity of zinc oxide is significantly improved under visible light. In the application, the nano-zinc oxide and nano-silver particles are loaded in intercalation modified montmorillonite, and then a silica coating layer is formed, which can control the dissolution rate of nano-zinc oxide and nano-silver, thus realizing long-term antibacterial property and improving the durability of the antibacterial fiber. Moreover, the above operation can also improve the agglomeration of nano-silver particles and the like, and improve the dispersibility and compatibility in the polymer matrix, thereby improving the antibacterial performance.

[0010] Optionally, the core-shell antibacterial particles are prepared by the following method: Nano-zinc oxide and nano-silver are added to an ethanol system, polyvinylpyrrolidone is added, and a suspension is prepared after ultrasonic treatment for 30-40 min; Intercalation modified montmorillonite is added to the suspension, and stirred at 60-65℃ for 2-3h. After the reaction is completed, suction filtration, freeze-drying are performed to prepare the composite particles; The composite particles are added to an ethanol solution, stirred, and then KH-560 is added. After ultrasonic treatment for 30-40 min, a mixture of tetraethyl orthosilicate and water is added, and then ammonia water is used to adjust the pH to 8-8.5. Cetyltrimethylammonium bromide is added, and reacted at 28-30℃ for 2-3h. After the reaction is completed, spray drying is performed, and then alcohol washing and drying are performed to prepare the core-shell antibacterial particles.

[0011] By adopting the technical scheme, the nano zinc oxide and nano silver are first added into the ethanol system, the polyvinyl pyrrolidone prevents the metal particles from agglomerating by the steric hindrance effect, and then the agglomeration is reduced by the charge complementation of the nano zinc oxide and nano silver, then the intercalation modified montmorillonite is added, the large specific surface area and the interlayer structure of the intercalation modified montmorillonite are used to provide good attachment points for the nano zinc oxide and nano silver particles, so that the nano zinc oxide and nano silver particles are embedded into the interlayer of the montmorillonite, then the montmorillonite embedded with the nano zinc oxide and nano silver is dispersed and then the KH-560 is added, the silicon hydroxyl of the silane coupling agent is chemically bonded with the surface hydroxyl of the montmorillonite, and the epoxy groups in the molecular structure of the silane coupling agent are condensed with the silanol groups generated by the hydrolysis of the tetraethyl orthosilicate to form a silicon oxygen covalent bond network, so that the inorganic particles and the organic silicon precursor are connected as a bridge when the silica coating layer is prepared, which is helpful to the uniformity and stability of the silica coating layer, the particles are in a spherical structure, which is more helpful to the dispersibility in the polymer, and the introduction of the epoxy groups is more helpful to the dispersion of the final antibacterial particles in the polymer matrix.

[0012] Optionally, when the core-shell type antibacterial particle is prepared, the mass ratio of the nano zinc oxide and the nano silver particles is (2-2.5):1, the ethanol system is obtained by mixing ethanol and water in a volume ratio of (7-8):(2-3), and the addition amount of the ethanol system is 4-5 times the mass of the nano zinc oxide, and the addition amount of the polyvinyl pyrrolidone is 0.5-0.8wt% of the nano zinc oxide. The addition mass ratio of the intercalation modified montmorillonite and the suspension is 1:(2-3), the ethanol solution is obtained by mixing ethanol and water in a volume ratio of (7-8):(2-3), the addition amount of the ethanol solution is 4-6 times the mass of the composite particles, and the addition amount of the KH-560 is 3-5wt% of the composite particles, the tetraethyl orthosilicate and water are mixed in a volume ratio of 10:(2-3), and the addition amount of the tetraethyl orthosilicate is 2-3 times the mass of the composite particles, and the addition amount of the cetyltrimethylammonium bromide is 5-10wt% of the tetraethyl orthosilicate.

[0013] By adopting the technical scheme, by controlling the addition amount of the above raw materials, the antibacterial effect and the antibacterial durability of the core-shell type antibacterial agent are better. The addition of the cetyltrimethylammonium bromide as a mesoporous template self-assembles into a micellar template in the solution, induces the growth of silica around the micelles when the silica is hydrolyzed and condensed under alkaline conditions, forms a mesoporous structure, realizes the slow release of the nano zinc oxide and nano silver particles as antibacterial active particles in the subsequent core material, plays a long-term antibacterial role, and after subsequent spray drying and alcohol washing to remove the cetyltrimethylammonium bromide, the mesoporous structure is more stable.

[0014] Optionally, when the core-shell type antibacterial particle is prepared, maleic anhydride grafted polypropylene is first added in the ethanol solution before the addition of the tetraethyl orthosilicate, and the addition amount of the maleic anhydride grafted polypropylene is 0.5-1wt% of the composite particles.

[0015] By adopting the technical scheme, the anhydride groups in the structure of the maleic anhydride grafted polypropylene react with the epoxy groups of KH-560, and the polypropylene segments thereof are compatible with the base polymer, thereby improving the compatibility and interface bonding of the antibacterial particles and the polymer base, and improving the antibacterial durability.

[0016] Optionally, the core-shell antibacterial particles are first added after low-temperature plasma treatment, the plasma treatment power is 50-100 W, the treatment time is 2-5 min, and the plasma gas is oxygen, and the gas flow is 50-100 sccm.

[0017] By adopting the technical scheme, the core-shell antibacterial particles are etched after plasma treatment, oxygen-containing functional groups are introduced, the surface roughness is increased, the density of polar functional groups is improved, and the adhesion to the polymer base is improved, the interface adhesion is improved, and the antibacterial durability is improved.

[0018] Optionally, the intercalation modified montmorillonite is prepared by the following method: The chitosan quaternary ammonium salt and the montmorillonite are prepared according to a mass ratio of 1:(0.6-0.8), then the chitosan quaternary ammonium salt is dissolved in a 0.1M acetic acid solution to prepare a chitosan quaternary ammonium salt solution with a mass concentration of 1-3wt%; The sodium-based montmorillonite is dispersed in water to prepare a montmorillonite suspension with a mass concentration of 0.5-2wt%; The montmorillonite suspension is ultrasonically treated for 20-30min, then the chitosan quaternary ammonium salt solution is added dropwise, stirred at 60-65℃ for 3-4h, centrifuged, washed with water, dried, and ground to prepare the intercalation modified montmorillonite.

[0019] By adopting the technical scheme, the quaternary ammonium salt is intercalated into the interlayer of the montmorillonite by the above method, the interlayer spacing is expanded, and it is more conducive to the subsequent loading of nano-zinc oxide and nano-silver antibacterial components, and the slow-release antibacterial agent is used to improve the durability.

[0020] Optionally, in step S2, the antibacterial agent is first melt-extruded with 5-10% of the total amount of polymer chips at 180-200℃, pelletized to prepare a master batch, then the master batch is mixed with the remaining polymer chips, and melt-spun again.

[0021] By adopting the technical scheme, the antibacterial agent is pre-melt-blended with a small amount of polymer chips to prepare a master batch, and then mixed with the remaining polymer chips for spinning, which avoids uneven dispersion of the antibacterial agent caused by direct addition, and improves the dispersion uniformity of the antibacterial agent.

[0022] Optionally, the polymer chips in step S1 are polyester chips or polyamide chips.

[0023] Optionally, in the melt spinning process in step S2, the polymer chips and the antibacterial agent are melt blended at 220-280℃, the melted polymer melt is extruded through a spinneret to form a primary fiber, the spinning speed is 3000-5000m / min, and the spinneret hole diameter is 0.1-0.5mm.

[0024] Optionally, in the air cooling in step S2, the air temperature is 20-40℃, and the air speed is 0.5-1m / s.

[0025] Optionally, in the drawing in step S2, the draw ratio is 3-5, and the drawing temperature is 80-120℃.

[0026] Optionally, the amount of the antibacterial agent added is 3-5wt% of the polyester chips.

[0027] In summary, the present application has the following beneficial effects: 1. In the present application, melt spinning is used to blend the antibacterial agent with the polymer substrate, so that the antibacterial agent is uniformly dispersed in the fiber, forming a stable antibacterial structure. This integrated way not only enhances the bonding force between the antibacterial agent and the fiber substrate, improves the durability of the antibacterial effect, but also ensures the uniform distribution of the antibacterial agent in the fiber, thereby achieving uniform and long-acting antibacterial performance. 2. In the present application, the antibacterial agent is a combination of core-shell type antibacterial particles and quaternary ammonium salt organic antibacterial agent. Dodecyltrimethylammonium chloride is used as an organic antibacterial agent, which has good spectral properties and synergistic effect with nano-silver antibacterial particles to enhance the antibacterial effect. At the same time, the quaternary ammonium salt antibacterial agent contains long-chain alkanes in its molecular structure, which can form a certain steric hindrance in the polymer matrix, helping to uniformly disperse the antibacterial agent. Polyvinylpyrrolidone is used as a dispersant, and its molecular chain is adsorbed between the antibacterial particles and the organic antibacterial components to form a protective film, preventing mutual aggregation and ensuring uniform dispersion of the antibacterial agent in the polymer matrix. 3. In the present application, the core-shell type antibacterial particles use a mixed system of nano-silver particles and nano-zinc oxide as the matrix. Nano-zinc oxide generates hydroxyl radicals through photocatalysis to destroy bacterial cell membranes, and nano-silver releases silver ions to inactivate bacterial respiratory enzymes, achieving spectral antibacterial effect. The synergistic effect of the two significantly improves the antibacterial rate of Escherichia coli and Staphylococcus aureus. Moreover, the antibacterial activity of zinc oxide is significantly improved under visible light. In the present application, nano-zinc oxide and nano-silver particles are loaded in intercalated modified montmorillonite, and then a silica coating layer is formed, which can control the dissolution rate of nano-zinc oxide and nano-silver, thereby achieving long-term antibacterial property and improving the durability of the antibacterial fiber. Moreover, the above operation can also improve the agglomeration of nano-silver particles and the like, improve the dispersibility and compatibility in the polymer matrix, and further improve the antibacterial performance. DETAILED DESCRIPTION

[0028] The application will be further described in detail in connection with the following examples. It is particularly pointed out that the following examples were prepared under conventional conditions or the conditions recommended by the manufacturer, and the raw materials used in the following examples can be obtained from ordinary commercial sources unless otherwise specified.

[0029] In the following preparation examples, the chitosan quaternary ammonium salt is selected from chitosan quaternary ammonium salt of YC-1027 type from Wuhan Yuancheng Chemical Co., Ltd. The maleic anhydride grafted polypropylene is selected from maleic anhydride grafted polypropylene (PP-g-MAH) of PO1015 type from YuCheng (HongJi) Plastic Co., Ltd.

[0030] In the following examples, the polyester chip is selected from polyester chip of CR-8863 type from Dongguan Shenghua Plastic Raw Material Co., Ltd.

[0031] The following preparation example is a preparation example of the core-shell type antibacterial particle. A preparation method of a core-shell type antibacterial particle, comprising the following steps: 1) Preparation of intercalation modified montmorillonite: raw materials are prepared according to the mass ratio of chitosan quaternary ammonium salt to montmorillonite of 1:0.7, then the chitosan quaternary ammonium salt is dissolved in 0.1M acetic acid solution to prepare a chitosan quaternary ammonium salt solution with a mass concentration of 2wt%; The sodium-based montmorillonite is dispersed in water to obtain a montmorillonite suspension with a mass concentration of 1wt%; The montmorillonite suspension is ultrasonically treated for 25min, then the chitosan quaternary ammonium salt solution is added dropwise, stirred at 60℃ for 3.5h, centrifuged, washed with water, dried and ground to obtain the intercalation modified montmorillonite; 2) Taking 1kg of nano-silver as a treatment reference, ethanol and water are mixed in a volume ratio of 7.5:2.5 to obtain an ethanol system, then nano-zinc oxide and nano-silver are mixed in a mass ratio of 2.2:1 and added to the ethanol system, the addition amount of the ethanol system (i.e. the sum of the addition mass of ethanol and water) is 4.5 times the mass of the nano-zinc oxide, then polyvinylpyrrolidone is added, the addition amount of the polyvinylpyrrolidone is 0.6wt% of the nano-zinc oxide, and the suspension is prepared after ultrasonic treatment (ultrasonic power is 300W) for 35min; 3) The intercalation modified montmorillonite prepared in step 1) is added to the suspension in step 2), the addition mass ratio of the intercalation modified montmorillonite to the suspension is 1:2.5, and the mixture is stirred at 60℃ for 2.5h, then the reaction is completed, the mixture is filtered, and the composite particles are obtained by freeze-drying; 4), ethanol and water are mixed in a volume ratio of 7.5:2.5 to obtain an ethanol solution, then the composite particles prepared in step 3) are added to the ethanol solution, the ethanol solution is added in an amount of 5 times the mass of the composite particles, after stirring, KH-560 is added, the amount of KH-560 added is 4wt% of the composite particles, after ultrasonic treatment (ultrasonic power is 200W) for 35min, the initial mixed solution is prepared; tetraethyl orthosilicate is added in an amount of 2.5 times the mass of the composite particles, then the tetraethyl orthosilicate and water are mixed in a volume ratio of 10:2 to obtain a mixed solution, then the mixed solution is added to the initial mixed solution, then the pH is adjusted to 8 with ammonia water, cetyltrimethylammonium bromide is added, the amount of cetyltrimethylammonium bromide added is 8wt% of the tetraethyl orthosilicate, and the reaction is carried out at 30°C for 2.5h, after the reaction is completed, spray drying is carried out, then alcohol washing and drying are carried out, and the core-shell antibacterial particles are prepared.

[0032] Preparation Example 2 A preparation method of a core-shell antibacterial particle, comprising the following steps: 1), preparation of intercalation modified montmorillonite: raw materials are prepared according to a mass ratio of chitosan quaternary ammonium salt to montmorillonite of 1:0.6, then the chitosan quaternary ammonium salt is dissolved in 0.1M acetic acid solution to prepare a chitosan quaternary ammonium salt solution with a mass concentration of 1wt%; Sodium-based montmorillonite is dispersed in water to prepare a montmorillonite suspension with a mass concentration of 0.5wt%; The montmorillonite suspension is ultrasonically treated for 20min, then the chitosan quaternary ammonium salt solution is added dropwise, stirring is carried out at 60°C for 4h, after centrifugal separation, water washing and drying, the intercalation modified montmorillonite is prepared by grinding; 2), taking 1kg of nano-silver as a treatment reference, ethanol and water are mixed in a volume ratio of 7:3 to obtain an ethanol system, then nano-zinc oxide and nano-silver are mixed in a mass ratio of 2:1 and added to the ethanol system, the amount of ethanol system (that is, the sum of the added mass of ethanol and water) is 4 times the mass of nano-zinc oxide, then polyvinylpyrrolidone is added, the amount of polyvinylpyrrolidone added is 0.5wt% of nano-zinc oxide, after ultrasonic treatment (ultrasonic power is 300W) for 30min, a suspension is prepared; 3), the intercalation modified montmorillonite prepared in step 1) is added to the suspension in step 2), the mass ratio of intercalation modified montmorillonite to suspension is 1:2, and stirring is carried out at 60°C for 3h, after the reaction is completed, suction filtration and freeze-drying are carried out, and the composite particles are prepared; 4), ethanol and water are mixed in a volume ratio of 7:3 to obtain an ethanol solution, then the composite particles prepared in step 3) are added to the ethanol solution, the amount of ethanol solution added is 4 times the mass of the composite particles, after stirring, KH-560 is added, the amount of KH-560 added is 3wt% of the composite particles, after ultrasonic treatment (ultrasonic power is 200W) for 30min, the initial mixed solution is prepared; According to the addition amount of tetraethyl orthosilicate being 2 mass times of the composite particles, the tetraethyl orthosilicate was added, the tetraethyl orthosilicate and water were mixed in a volume ratio of 10:2 to obtain a mixed solution, then the mixed solution was added to the preliminary mixed solution, then the pH was adjusted to 8 with ammonia water, cetyltrimethylammonium bromide was added, the addition amount of cetyltrimethylammonium bromide was 5wt% of the tetraethyl orthosilicate, and the reaction was carried out at 28°C for 3h, after the reaction was completed, spray drying was carried out, then alcohol washing and drying were carried out, and the core-shell type antibacterial particles were prepared.

[0033] Preparation Example 3 A preparation method of a core-shell type antibacterial particle, comprising the following steps: 1) Preparation of intercalation modified montmorillonite: raw materials were prepared according to the mass ratio of chitosan quaternary ammonium salt to montmorillonite being 1:0.8, then the chitosan quaternary ammonium salt was dissolved in 0.1M acetic acid solution to prepare a chitosan quaternary ammonium salt solution with a mass concentration of 3wt%; Sodium-based montmorillonite was dispersed in water to obtain a montmorillonite suspension with a mass concentration of 2wt%; The montmorillonite suspension was ultrasonically treated for 30min, then the chitosan quaternary ammonium salt solution was added dropwise, and stirred at 65°C for 3h, after centrifugal separation, water washing and drying, the intercalation modified montmorillonite was prepared by grinding; 2) Taking 1kg of nano-silver as a treatment reference, ethanol and water were mixed in a volume ratio of 8:2 to obtain an ethanol system, then nano-zinc oxide and nano-silver were mixed in a mass ratio of 2.5:1 and added to the ethanol system, the addition amount of the ethanol system (that is, the sum of the addition mass of ethanol and water) was 5 mass times of the nano-zinc oxide, then polyvinylpyrrolidone was added, the addition amount of polyvinylpyrrolidone was 0.8wt% of the nano-zinc oxide, and after ultrasonic treatment (ultrasonic power was 300W) for 40min, a suspension was prepared; 3) The intercalation modified montmorillonite prepared in step 1) was added to the suspension in step 2), the addition mass ratio of the intercalation modified montmorillonite to the suspension was 1:3, and stirring was carried out at 65°C for 2h, after the reaction was completed, suction filtration and freeze-drying were carried out, and the composite particles were prepared; 4) Ethanol and water were mixed in a volume ratio of 8:2 to obtain an ethanol solution, then the composite particles prepared in step 3) were added to the ethanol solution, the addition amount of the ethanol solution was 6 mass times of the composite particles, after stirring, KH-560 was added, the addition amount of KH-560 was 5wt% of the composite particles, and after ultrasonic treatment (ultrasonic power was 200W) for 40min, a preliminary mixed solution was prepared; According to the addition amount of 3 mass times of the composite particles, tetraethyl orthosilicate was added, and tetraethyl orthosilicate and water were mixed in a volume ratio of 10:3 to obtain a mixed solution, then the mixed solution was added to the initial mixed solution, then the pH was adjusted to 8.5 with ammonia water, and hexadecyl trimethyl ammonium bromide was added, the addition amount of hexadecyl trimethyl ammonium bromide was 10wt% of tetraethyl orthosilicate, and the reaction was carried out at 30℃ for 2h, then spray drying was carried out after the reaction was completed, then alcohol washing and drying were carried out, and the core-shell type antibacterial particles were prepared.

[0034] Preparation Example 4 A preparation method of core-shell type antibacterial particles was carried out according to the method in Preparation Example 1, except that in step 4), before adding tetraethyl orthosilicate, maleic anhydride grafted polypropylene was first added to the initial mixed solution, and after ultrasonic treatment (200W) for 25min, the mixed solution of tetraethyl orthosilicate and water was added, and the addition amount of maleic anhydride grafted polypropylene was 0.8wt% of the composite particles.

[0035] Preparation Example 5 A preparation method of core-shell type antibacterial particles was carried out according to the method in Preparation Example 1, except that in step 4), before adding tetraethyl orthosilicate, maleic anhydride grafted polypropylene was first added to the initial mixed solution, and after ultrasonic treatment (200W) for 20min, the mixed solution of tetraethyl orthosilicate and water was added, and the addition amount of maleic anhydride grafted polypropylene was 0.5wt% of the composite particles.

[0036] Preparation Example 6 A preparation method of core-shell type antibacterial particles was carried out according to the method in Preparation Example 1, except that in step 4), before adding tetraethyl orthosilicate, maleic anhydride grafted polypropylene was first added to the initial mixed solution, and after ultrasonic treatment (200W) for 30min, the mixed solution of tetraethyl orthosilicate and water was added, and the addition amount of maleic anhydride grafted polypropylene was 1wt% of the composite particles.

[0037] Comparative Preparation Example 1 A preparation method of core-shell type antibacterial particles was carried out according to the method in Preparation Example 1, except that the nano zinc oxide was replaced by nano silver particles.

[0038] Comparative Preparation Example 2 A preparation method of core-shell type antibacterial particles was carried out according to the method in Preparation Example 1, except that the nano silver particles were replaced by nano zinc oxide.

[0039] Comparative Preparation Example 3 A preparation method of antibacterial particles was carried out according to the method in Preparation Example 1, except that step 4) was not carried out, and the composite particles in step 3) were directly used as antibacterial particles.

[0040] Example 1 A process for preparing an antibacterial fiber includes the following steps: S1. Dry the polyester chips at 60℃ for 6 hours and set aside. Dodecyltrimethylammonium chloride, polyvinylpyrrolidone, and the core-shell antibacterial particles prepared in Preparation Example 1 were mixed in a mass ratio of 0.5:0.1:1 to prepare an antibacterial agent. The antibacterial agent was then dried at 50°C for 3 hours before use. S2. Take dried polyester chips and antibacterial agent. The amount of antibacterial agent added is 4 wt% of the total amount of polyester chips. First, melt extrude the dried antibacterial agent with 8 wt% of the total amount of polyester chips at 200℃, and then pelletize it to obtain masterbatch. Then, mix the masterbatch with the remaining polyester chips and add it back into the screw extruder. Melt blend it at 250℃ to form a melt by mixing the polyester chips and antibacterial agent. The screw speed is 80 r / min. Then, it is extruded through a spinneret to form nascent fibers. The spinning speed is 4000 m / min and the spinneret orifice diameter is 0.3 mm. The extruded nascent fibers enter the cooling air system for air cooling at a temperature of 4000 m / min and a spinneret orifice diameter of 0.2 mm to solidify the fibers. The cooled and cured fibers are then stretched, with a stretch ratio controlled at 4 and a stretching temperature of 100℃. The stretched fibers are then wound through a winding device to obtain antibacterial fibers with a winding tension of 0.3N.

[0041] Example 2 A process for preparing an antibacterial fiber includes the following steps: S1. Dry the polyester chips at 60℃ for 6 hours and set aside. Dodecyltrimethylammonium chloride, polyvinylpyrrolidone, and the core-shell antibacterial particles prepared in Preparation Example 2 were mixed in a mass ratio of 0.4:0.1:1 to prepare an antibacterial agent. The antibacterial agent was then dried at 50°C for 3 hours before use. S2. Take dried polyester chips and antibacterial agent. The amount of antibacterial agent added is 3 wt% of the total amount of polyester chips. First, melt extrude the dried antibacterial agent with 5 wt% of the total amount of polyester chips at 180°C, and then pelletize it to obtain masterbatch. Then, mix the masterbatch with the remaining polyester chips and add it back into the screw extruder. Melt blend it at 220°C so that the polyester chips and antibacterial agent are mixed to form a melt. The screw speed is 50 r / min. Then, it is extruded through a spinneret to form nascent fibers. The spinning speed is 3000 m / min and the spinneret orifice diameter is 0.1 mm. The extruded nascent fibers enter the cooling air system for air cooling at a temperature of 3000 m / min and a spinneret orifice diameter of 0.1 mm, so that the fibers solidify. The cooled and cured fibers are then stretched, with a stretch ratio controlled at 3 and a stretching temperature of 80°C. The stretched fibers are then wound through a winding device to obtain antibacterial fibers with a winding tension of 0.1N.

[0042] Example 3 A process for preparing an antibacterial fiber includes the following steps: S1. Dry the polyester chips at 60℃ for 6 hours and set aside. Dodecyltrimethylammonium chloride, polyvinylpyrrolidone, and the core-shell antibacterial particles prepared in Preparation Example 1 were mixed in a mass ratio of 0.5:0.2:1 to prepare an antibacterial agent. The antibacterial agent was then dried at 50°C for 3 hours before use. S2. Take dried polyester chips and antibacterial agent. The amount of antibacterial agent added is 5 wt% of the total amount of polyester chips. First, melt extrude the dried antibacterial agent with 10 wt% of the total amount of polyester chips at 200℃, and then pelletize it to obtain masterbatch. Then, mix the masterbatch with the remaining polyester chips and add it back into the screw extruder. Melt blend it at 280℃ so that the polyester chips and antibacterial agent are mixed to form a melt. The screw speed is 100 r / min. Then, it is extruded through a spinneret to form nascent fibers. The spinning speed is 5000 m / min and the spinneret orifice diameter is 0.5 mm. The extruded nascent fibers enter the cooling air system for air cooling at a temperature of 5000 m / min and a spinneret orifice diameter of 0.5 mm, so that the fibers solidify. The cooled and cured fibers are then stretched, with a stretch ratio controlled at 5 and a stretching temperature of 120°C. The stretched fibers are then wound through a winding device to obtain antibacterial fibers with a winding tension of 0.5N.

[0043] Example 4 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that in step S2, the dried polyester chips and antibacterial agent are directly added to the screw extruder and melt-blended at 250°C.

[0044] Examples 5-7 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that the core-shell antibacterial particles in the antibacterial agent in step S1 are selected from the core-shell antibacterial particles prepared in Examples 4-6.

[0045] Example 8 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that the core-shell antibacterial particles in step S1 are first added after being treated with low-temperature plasma. The plasma treatment power is 80W, the treatment time is 3min, and the plasma gas is oxygen with a flow rate of 80sccm.

[0046] Example 9 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that the core-shell antibacterial particles in step S1 are first added after being treated with low-temperature plasma. The plasma treatment power is 50W, the treatment time is 2min, and the plasma gas is oxygen with a flow rate of 50sccm.

[0047] Example 10 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that the core-shell antibacterial particles in step S1 are first added after being treated with low-temperature plasma. The plasma treatment power is 100W, the treatment time is 5min, and the plasma gas is oxygen with a flow rate of 100sccm.

[0048] Comparative Examples 1-2 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that the core-shell antibacterial particles in step S1 are selected from the core-shell antibacterial particles in Comparative Preparation Example 1 and Comparative Preparation Example 2, respectively.

[0049] Comparative Example 3 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that in step S1, the core-shell antibacterial particles are replaced in equal amounts with the antibacterial particles prepared in Comparative Preparation Example 3.

[0050] Comparative Example 4 A process for preparing an antibacterial fiber is carried out according to the method in Example 1, except that in step S1, the core-shell antibacterial particles are replaced in equal amounts with a mixture of nano zinc oxide and nano silver particles, and the reasonable mass ratio of nano zinc oxide to nano silver is 2.2:1.

[0051] Performance testing The antibacterial properties of the textiles made from the antibacterial fibers obtained in the above embodiments and comparative examples were tested. The vibration method of GB / T2099.3 was used as the reference standard. First, the inhibition rate of Candida albicans was tested. Then, the textiles made from the antibacterial fibers were washed 50 times and the inhibition rate was tested. The reduction rate of inhibition rate before and after washing was statistically analyzed. The statistical results are shown in Table 1 below.

[0052] Table 1: Referring to the test results in Table 1 above, the antibacterial fibers prepared in the embodiments of this application have excellent antibacterial properties and antibacterial durability. Combining the test results of Examples 1 and 4, pre-melting the antibacterial agent with the polyester chips and then mixing the masterbatch with the remaining polyester chips helps to achieve uniform distribution of the antibacterial agent, resulting in fabrics with better antibacterial properties and antibacterial durability. Combining the test results of Examples 5-7, in Examples 5-7, when forming the silica coating layer using the sol-gel method, maleic anhydride-grafted polypropylene was added, which chemically linked the maleic anhydride with the antibacterial particles, resulting in better compatibility between the polypropylene groups and the polyester particles. This improves the compatibility between the core-shell antibacterial particles and the polyester matrix, helps to achieve uniform dispersion of the antibacterial particles, and improves antibacterial performance. Combining the test results of Examples 8-10, plasma treatment of the core-shell antibacterial particles helps to improve their roughness and polar functional group density, thereby improving their compatibility with the polyester matrix and enhancing antibacterial performance.

[0053] Based on the test results of Example 1 and Comparative Examples 1 and 2, the antibacterial performance was reduced when only single nano-zinc oxide or nano-silver particles were used in Comparative Examples 1 and 2. Based on the test results of Comparative Example 3, the antibacterial durability was significantly reduced compared to Example 1 when nano-zinc oxide and nano-silver particles were directly loaded onto montmorillonite. Based on the test results of Comparative Example 4, the agglomeration of nano-zinc oxide and nano-silver in the polymer matrix was weak and the antibacterial performance was ultimately reduced when nano-zinc oxide and nano-silver were directly added in Comparative Example 4.

[0054] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A process for preparing antibacterial fibers, characterized in that, Includes the following steps: S1. Dry the polymer chips and antibacterial agent separately and prepare the materials; S2. The polymer chips and antibacterial agent are melt-spun together, cooled by air, drawn and wound to obtain antibacterial fibers. The antibacterial agent is prepared by mixing dodecyltrimethylammonium chloride, polyvinylpyrrolidone and core-shell antibacterial particles in a mass ratio of (0.4-0.5):(0.1-0.2):

1. The core-shell antibacterial particles are prepared by loading nano-zinc oxide and nano-silver particles onto intercalated modified montmorillonite, forming a silica coating layer by sol-gel method, and then spray drying.

2. The preparation process of an antibacterial fiber according to claim 1, characterized in that: Core-shell antibacterial particles are prepared by the following method: A suspension was prepared by adding nano zinc oxide and nano silver to an ethanol system, adding polyvinylpyrrolidone, and ultrasonically treating for 30-40 minutes. Intercalated modified montmorillonite was added to the suspension and stirred at 60-65℃ for 2-3 hours. After the reaction was completed, the mixture was filtered and freeze-dried to obtain composite particles. The composite particles were added to an ethanol solution, stirred, and then KH-560 was added. After ultrasonic treatment for 30-40 minutes, a mixture of tetraethyl orthosilicate and water was added. The pH was then adjusted to 8-8.5 with ammonia, and hexadecyltrimethylammonium bromide was added. The mixture was reacted at 28-30℃ for 2-3 hours. After the reaction was completed, the mixture was spray-dried, washed with alcohol, and then dried to obtain core-shell antibacterial particles.

3. The preparation process of an antibacterial fiber according to claim 2, characterized in that: When preparing core-shell antibacterial particles, the mass ratio of added nano-zinc oxide to nano-silver particles is (2-2.5):1, and the ethanol system is obtained by mixing ethanol and water in a volume ratio of (7-8):(2-3). The amount of ethanol added is 4-5 times the mass of nano-zinc oxide, and the amount of polyvinylpyrrolidone added is 0.5-0.8 wt% of nano-zinc oxide. The mass ratio of intercalated modified montmorillonite to suspension is 1:(2-3). The ethanol solution is obtained by mixing ethanol and water in a volume ratio of (7-8):(2-3). The amount of ethanol solution added is 4-6 times the mass of the composite particles, and the amount of KH-560 added is 3-5 wt% of the composite particles. Ethyl orthosilicate and water are mixed in a volume ratio of 10:(2-3). The amount of ethyl orthosilicate added is 2-3 times the mass of the composite particles, and the amount of hexadecyltrimethylammonium bromide added is 5-10 wt% of ethyl orthosilicate.

4. The preparation process of an antibacterial fiber according to claim 2, characterized in that: When preparing core-shell antibacterial particles, before adding tetraethyl orthosilicate, maleic anhydride-grafted polypropylene is first added to an ethanol solution, and the amount of maleic anhydride-grafted polypropylene added is 0.5-1 wt% of the composite particles.

5. The preparation process of an antibacterial fiber according to claim 1, characterized in that: The core-shell antibacterial particles are first added after being treated with low-temperature plasma. The plasma treatment power is 50-100W, the treatment time is 2-5min, and the plasma gas is oxygen with a flow rate of 50-100sccm.

6. The preparation process of an antibacterial fiber according to claim 1, characterized in that: Intercalated modified montmorillonite was prepared by the following method: Prepare chitosan quaternary ammonium salt and montmorillonite in a mass ratio of 1:(0.6-0.8), then dissolve chitosan quaternary ammonium salt in 0.1M acetic acid solution to prepare a chitosan quaternary ammonium salt solution with a mass concentration of 1-3wt%. Sodium-based montmorillonite was dispersed in water to prepare a montmorillonite suspension with a mass concentration of 0.5-2 wt%. The montmorillonite suspension was sonicated for 20-30 minutes, then chitosan quaternary ammonium salt solution was added dropwise, and the mixture was stirred at 60-65℃ for 3-4 hours. After centrifugation, the mixture was washed with water, dried, and ground to obtain intercalated modified montmorillonite.

7. The preparation process of an antibacterial fiber according to claim 1, characterized in that: In step S2, the antibacterial agent and 5-10% of polymer chips are first melt-extruded at 180-200°C, granulated to obtain masterbatch, and then the masterbatch is mixed with the remaining polymer chips and melt-spun again.

8. The preparation process of an antibacterial fiber according to claim 1, characterized in that: The polymer chips in step S1 are polyester chips or polyamide chips.

9. The preparation process of an antibacterial fiber according to claim 1, characterized in that: In step S2, during the melt spinning process, polymer chips and antibacterial agents are melt-blended at 220-280℃. The melted polymer melt is extruded through a spinneret to form nascent fibers. The spinning speed is 3000-5000 m / min, and the spinneret orifice diameter is 0.1-0.5 mm.

10. The preparation process of an antibacterial fiber according to claim 1, characterized in that: In step S2, the air temperature during air cooling is 20-40℃, and the air velocity is 0.5-1m / s; In step S2, the draw ratio is 3-5 and the draw temperature is 80-120℃.

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