An antibacterial and breathable yarn and its antibacterial and breathable socks

Abstract

The present invention relates to the field of textile materials, and provides an antibacterial and breathable yarn obtained by mixing and spinning polyester fibers, nylon fibers, cotton fibers and elastic fibers. The polyester fiber is prepared by a melt blending and spinning process, and contains polyethylene terephthalate chips, modified chitosan zinc oxide, antioxidant 1010, POE elastomer, polyether modified silicone oil and polyethylene glycol 200. The modified chitosan zinc oxide is made by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide. The chitosan cinnamaldehyde Schiff base is prepared by the Schiff base condensation reaction of chitosan and cinnamaldehyde, and the silane-modified zinc oxide is made by modifying nanorod-shaped zinc oxide particles with isocyanatopropyltriethoxysilane. The yarn has excellent antibacterial property, breathability and flexibility, and is further used for knitting antibacterial and breathable socks. The knitting density of the sock bottom part is reduced to enhance breathability, and the knitting density of the sock mouth part is increased to improve elasticity and fit, having wide application value.

Description

Technical Field

[0001] The present invention relates to the field of textile materials, and specifically relates to an antibacterial and breathable yarn and an antibacterial and breathable sock made therefrom. Background Art

[0002] With the continuous improvement of people's living standards and health needs, the functional requirements for textiles are gradually developing towards diversification and high performance. In daily life, as a textile that comes into long-term contact with the skin, the comfort and hygiene performance of socks are particularly important. Especially in sports, outdoor activities, and scenarios of long-term wear, the antibacterial and breathable properties of socks have become the core performance indicators that consumers focus on. On the one hand, the accumulation of sweat and skin secretions easily provides a breeding ground for bacteria, leading to the growth of unpleasant odors and even skin infections. Therefore, it is required that socks have persistent antibacterial properties to inhibit bacterial reproduction. On the other hand, the breathability of socks directly affects the wearing comfort and moisture emission ability, which can effectively reduce the accumulation of moisture on the feet, reduce discomfort, and extend the wearing life. In addition, these performance requirements also need to take into account the adaptability of socks in different scenarios, such as the antibacterial effect in high-humidity environments, the maintenance of breathability performance after long-term wear, and the durability after multiple washes. Therefore, the research and development of a yarn and sock material that simultaneously has excellent antibacterial properties and high breathability can not only significantly improve the functionality and comfort of textiles, but also promote the development of the textile industry towards a healthier and higher value-added direction, and has important application value and development prospects in the fields of sports, medical care, and daily wear.

[0003] At present, some functional yarns and sock products on the market attempt to improve antibacterial or breathable properties through modified materials, but there are still significant deficiencies in actual applications. For example, a Chinese patent with the publication number CN104611798A discloses a yarn made by blending wool and tree fibers, with breathable performance design such as fast absorption and dissipation of moisture, but does not involve antibacterial design, which limits its actual application scope. In addition, a Chinese patent with the publication number CN107299437A proposes an antibacterial yarn. Quaternary ammonium salts are used in the yarn to improve the yarn structure and breathability through optimized weaving processes, but it fails to solve the antibacterial requirements during the long-term use of the yarn and is difficult to meet the multi-functional performance requirements in high-humidity or special environments. The root cause of these problems is that existing technologies often cannot balance antibacterial properties and breathability in material design. The improvement of antibacterial effects usually comes at the cost of sacrificing breathability performance. At the same time, there is a lack of effective control over the uniform distribution and long-term stability of antibacterial components in the material, resulting in rapid performance degradation during actual use. Therefore, there is an urgent need for an innovative design of a yarn material that simultaneously has excellent antibacterial properties and high breathability to meet the increasingly diverse functional requirements of consumers for textiles and promote the application of functional yarns in a wider range of scenarios. Summary of the Invention

[0004] The object of the present invention is to provide an antibacterial and breathable yarn and a preparation process thereof, so as to solve the problem of insufficient antibacterial and breathable performance of current yarns.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] An antibacterial and breathable yarn, wherein the antibacterial and breathable yarn is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber;

[0007] The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber is (40-60):(20-30):(10-20):(5-10);

[0008] The polyester fiber is prepared from the following components in parts by weight: 85-90 parts of polyethylene terephthalate chips, 3.0-5.0 parts of modified chitosan zinc oxide, 0.3-0.5 part of antioxidant 1010, 1.0-2.0 parts of POE elastomer, 2.0-3.0 parts of polyether modified silicone oil, 1.0-2.0 parts of polyethylene glycol 200;

[0009] The modified chitosan zinc oxide is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide;

[0010] The chitosan cinnamaldehyde Schiff base is obtained by Schiff base condensation reaction of chitosan and cinnamaldehyde in acetic acid and absolute ethanol media;

[0011] The silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles;

[0012] Further, the preparation method of the modified chitosan zinc oxide is as follows: in parts by weight, 10.0-15.0 parts of chitosan cinnamaldehyde Schiff base are added to 500-600 parts of deionized water, and then the pH of the mixed solution is adjusted to 3.0-4.0 with a 3.0 wt.% acetic acid solution. After the adjustment, the mixture is stirred at a stirring rate of 200-250 rpm at 60-70 °C for 20-30 min. Then, 40.0-50.0 parts of silane-modified zinc oxide are added to the solution, and the mixed solution is first ultrasonicated for 20-30 min in an ultrasonic device, and then stirred for 30-45 min under a water bath condition of 50-60 °C. After the stirring is completed, the pH of the mixed solution is adjusted to 8.8-9.2 with a 5 wt.% sodium hydroxide solution. After the adjustment, flocculent precipitates are formed in the mixed solution. Then, the mixed solution is filtered and the precipitate is retained. The precipitate is washed 3 times with deionized water. After the washing is completed, it is dried in a vacuum drying oven at 50-60 °C for 8-12 h, and the dried product is ground to a particle size of 200 mesh to obtain modified chitosan zinc oxide.

[0013] Further, the preparation method of the silane-modified zinc oxide is as follows: by weight, 15.0 - 20.0 parts of ethyl glycolate and 40.0 - 50.0 parts of isocyanatopropyltriethoxysilane are added into a beaker, and then 0.20 - 0.40 part of dibutyltin dilaurate is added. At 40.0 - 45.0 °C, the mixture is stirred at a stirring rate of 300 - 350 rpm for 200 - 240 min to form a homogeneous mixture. Then, 100 - 150 parts of nanorod-shaped zinc oxide particles, 200 - 250 parts of absolute ethanol, and 150 - 160 parts of deionized water are successively added into the mixed solution. Then, the mixed solution is ultrasonicated for 30 - 45 min. After the ultrasonic treatment, the pH of the solution is adjusted to 9.8 - 10.2 with 5 wt.% sodium hydroxide solution. After adjusting the pH, the mixed solution is stirred in a water bath at 60 - 65 °C at a stirring rate of 300 - 400 rpm for 240 - 300 min. After the stirring is completed, the mixed solution is filtered and the precipitate is retained. Then, the precipitate is washed alternately with deionized water and absolute ethanol 3 - 5 times. The washed precipitate is dried at 50 - 60 °C for 6 - 10 h to obtain the silane-modified zinc oxide.

[0014] Further, the preparation method of the chitosan cinnamaldehyde Schiff base is as follows: by weight, 10.0 - 15.0 parts of chitosan are dissolved in 100 - 120 parts of 1 wt.% acetic acid solution to obtain a chitosan solution. Separately, 7.0 - 10.0 parts of cinnamaldehyde are dissolved in 300 - 400 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then, the cinnamaldehyde solution is added dropwise to the chitosan solution. After the addition is completed, the mixed solution is placed in an oil bath at 40 - 50 °C and stirred at a stirring rate of 350 - 400 rpm for 300 - 360 min. After the stirring is completed, 5 wt.% sodium hydroxide solution is slowly added dropwise to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then, the mixed solution is filtered and the precipitate is retained. The obtained precipitate is washed alternately with absolute ethanol and deionized water 3 times. Then, the precipitate is transferred to a vacuum drying oven and dried at 50 - 60 °C for 200 - 240 min. The dried product is ground to a particle size of 200 mesh to obtain the yellow powder of chitosan cinnamaldehyde Schiff base.

[0015] The design of the present invention using modified chitosan zinc oxide is mainly used to enhance the antibacterial and breathable properties of materials. Through the composite effect of chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide, the synergistic effect between multi-component materials is achieved. Chitosan cinnamaldehyde Schiff base is prepared by the Schiff base condensation reaction of chitosan and cinnamaldehyde in acetic acid and absolute ethanol media. The conjugate system of cinnamaldehyde is introduced into its molecular structure, which not only enhances the antibacterial property of chitosan but also improves its chemical stability in the composite material. Silane-modified zinc oxide is prepared by functionalizing the surface of nanorod-shaped zinc oxide particles with isocyanatopropyltriethoxysilane, endowing it with excellent dispersibility and interfacial compatibility, and further enhancing the breathability and antibacterial activity of the material through the nanorod structure. During the preparation of modified chitosan zinc oxide, chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide are fully compounded by ultrasonic dispersion and water bath stirring. The spatial network structure of chitosan molecular chains and the surface activity of nano-zinc oxide act synergistically, making the composite material have a uniform distribution of antibacterial components and stable physical properties. In addition, during the composite preparation process, the formation process of flocculent precipitation is further optimized by adjusting the pH condition and stirring rate to ensure the structural integrity and functionality of the composite product. Generally speaking, the present invention constructs a composite material system with significantly enhanced antibacterial and breathable properties through the biological activity provided by chitosan cinnamaldehyde Schiff base and the nano-effect of silane-modified zinc oxide, meeting the dual requirements of antibacterial and breathable properties in multi-scenario applications, and providing new ideas and technical support for the development of functional materials.

[0016] Further, the preparation method of the polyester fiber is as follows: Add polyethylene terephthalate chips, antioxidant 1010, and POE elastomer into a high-speed mixer, and mix at 300 - 500 rpm for 5 - 10 min at room temperature to obtain uniformly dispersed raw materials. Then add the uniformly dispersed filler into a twin-screw co-blending extruder, and melt-blend at 250 - 280 °C for 30 - 45 min with a melt-blending rate of 300 - 500 rpm. During the blending process, gradually add modified chitosan zinc oxide and polyether-modified silicone oil into it, and then obtain fiber masterbatch by extrusion. Then add the fiber masterbatch into a melt spinning device and spin at 260 - 280 °C to form polyester fiber.

[0017] Further, the preparation method of the nanorod-shaped zinc oxide particles is as follows: by weight, 0.5-1.0 parts of zinc nitrate and 0.5-1.0 parts of urea are dissolved in 100-200 parts of deionized water, and stirred at a stirring rate of 300-500 rpm for 10-20 min to form a mixed solution; the mixed solution is transferred to a hydrothermal reaction kettle, sealed and reacted at 90-95 °C for 240-360 min. After the reaction is completed, it is naturally cooled to room temperature, the reaction solution is filtered and the solid powder is retained, and the solid powder is washed with deionized water 3-5 times, with each washing time being 5-10 min. The washed solid powder is placed in a vacuum drying oven at 50-60 °C and dried for 6-10 h to obtain nanorod-shaped zinc oxide particles.

[0018] Further, the average diameter of the nanorod-shaped zinc oxide particles is 50-100 nm, and the average length is 500-1000 nm.

[0019] The design of the present invention using nanorod-shaped zinc oxide particles is mainly used to enhance the flexibility and antibacterial properties of materials, and realizes the synergistic optimization of various properties through a fine preparation process and a unique nanostructure. First, the nanorod-shaped zinc oxide particles are prepared by zinc nitrate and urea under hydrothermal reaction conditions. Their one-dimensional nanorod-shaped morphology ensures a high specific surface area and good dispersibility, providing an abundant contact interface for the antibacterial activity of the material, and at the same time significantly enhancing the physical coupling effect of the particles in the composite system. By strictly controlling the reaction conditions, including the ratio of zinc nitrate to urea, reaction temperature and time, the size uniformity and morphological integrity of the zinc oxide particles are ensured, and finally a nanorod-shaped structure with an average diameter of 50-100 nm and a length of 500-1000 nm is formed. This special geometric shape not only endows the particles with stronger antibacterial activity, but also enhances the flexibility of the material through its physical filling effect in the composite material. The high aspect ratio structure of the nanorod-shaped zinc oxide can form a uniform distribution state in the composite material, and improve the flexibility through physical intercalation with the matrix material. At the same time, the high surface activity brought by its specific surface area enables the particles to quickly contact with microorganisms, thus achieving the purpose of efficient antibacterial. The present invention realizes the synergistic improvement of flexibility and antibacterial properties by optimizing the structure and preparation process of nanorod-shaped zinc oxide, providing an important technical support for the development of high-performance functional materials.

[0020] Furthermore, the preparation method of the antibacterial and breathable yarn is as follows: Polyester fiber, polyamide fiber, cotton fiber and elastic fiber are spun by air-jet spinning. The spinning tension is set at 8-15 cN, the twist is 300-500 turns / m, and the spinning speed is 100-200 m / min. The spun yarn is subjected to drafting treatment, and the draft ratio is controlled at 1.05-1.2. Subsequently, twisting is carried out, and the twist coefficient is controlled at 3.5-4.5. The yarn is wound into a bobbin, and the winding tension is controlled at 5-10 cN, thereby preparing the antibacterial and breathable yarn.

[0021] Furthermore, the elastic fiber is Lycra fiber or Spandex fiber.

[0022] The design of the antibacterial and breathable yarn in the present invention is mainly used to enhance the air permeability and antibacterial properties of textiles. Through the scientific combination of various fiber materials and precise process control, the synergistic optimization of the functional and mechanical properties of the yarn is achieved. In the process of preparing the yarn, polyester fiber, polyamide fiber, cotton fiber and elastic fiber are spun by air-jet spinning. The reasonable proportion of each component endows the yarn with good mechanical properties and functional basis. The precise control of spinning tension, twist and spinning speed ensures the tight combination between fibers and the uniformity of yarn structure. Subsequently, the strength and elasticity of the yarn are further improved through drafting and twisting processes. The adjustment of the draft ratio and twist coefficient optimizes the flexibility and tensile properties of the yarn, while the reasonable setting of the winding tension ensures the stability of the yarn in subsequent processing. Polyester fiber serves as a reinforcing matrix for mechanical properties in the yarn. It is prepared by the melt blending of polyethylene terephthalate chips with antioxidant 1010 and POE elastomer, endowing the fiber with excellent strength and flexibility. During the blending process, the gradually added modified chitosan zinc oxide and polyether modified silicone oil further enhance the antibacterial and breathable properties of the fiber. The modified chitosan zinc oxide is uniformly dispersed in the fiber, providing a long-lasting antibacterial effect through its biological activity. At the same time, the polyether modified silicone oil improves the softness and moisture permeability of the fiber through its lubricity and hydrophilicity. In addition, the high abrasion resistance of polyamide fiber and the moisture absorption and air permeability of cotton fiber in the yarn synergistically act with the elastic recovery of elastic fiber (such as Lycra fiber or Spandex fiber), further optimizing the comprehensive performance of the yarn in antibacterial and breathable properties. Finally, through precise process design and the synergistic effect of each component, the antibacterial and breathable yarn prepared in the present invention can not only effectively inhibit the growth of microorganisms, but also maintain high air permeability while taking into account high flexibility and durability, providing technical support for the development of high-performance textile materials.

[0023] The present invention also discloses an antibacterial and breathable sock, which is woven from the antibacterial and breathable yarn.

[0024] The preparation method of the antibacterial and breathable socks is as follows: Using the antibacterial and breathable yarn, according to the design requirements of sock weaving, the socks are knitted and formed by a knitting machine. The stitch density of the knitting machine is 12 - 18 stitches per inch, the weaving tension is 5 - 15 cN, and the weaving speed is 20 - 40 rpm. Adjust the knitting density according to the functional requirements of different parts of the socks. The knitting density of the sock bottom part is appropriately reduced, and the knitting density is controlled at 150 - 180 stitches per square inch to enhance breathability. While the knitting density of the sock mouth part is appropriately increased, and the knitting density is controlled at 200 - 240 stitches per square inch to improve elasticity and fit. After knitting and forming, the socks are seamed. The seaming process adopts the chain stitch method, and the sewing thread tension is controlled at 4 - 8 cN. Then, the socks are shaped. The shaping temperature is 80 - 100 °C, and the shaping time is 3 - 8 min. The shaped socks are heat-set. The heat-setting temperature is 120 - 150 °C, and the setting time is 5 - 15 min. Finally, the antibacterial and breathable socks are prepared.

[0025] The design of using antibacterial and breathable yarn in the present invention is mainly used to enhance the antibacterial performance and comfort of antibacterial and breathable socks. By optimizing the combination of yarn and weaving process, the overall improvement of the socks in terms of functionality and wearing experience is realized. In the present invention, the antibacterial and breathable socks are woven from antibacterial and breathable yarn. Through reasonable component matching and precise process control, the yarn has excellent antibacterial and breathable properties, laying the foundation for the performance of the socks. During the knitting and forming process of the socks, through the precise control of the stitch density, weaving tension and weaving speed of the knitting machine, the overall structure of the socks is uniform and has good mechanical properties. In order to meet the functional requirements of different parts, a lower knitting density is adopted for the sock bottom part to enhance breathability, effectively remove foot moisture, and improve the dry feeling during wearing. For the sock mouth part, the elasticity and fit are enhanced by increasing the knitting density, ensuring that the socks are more comfortable and not easy to slip during wearing. After knitting and forming, through the chain stitch seaming process and strictly controlled sewing thread tension, the discomfort of the seamed part of the socks is avoided, and at the same time, the durability and overall aesthetics of the product are improved. In addition, after the socks are formed, appropriate shaping and heat-setting treatment processes are adopted. The optimization of the shaping temperature and time can further stabilize the size and shape of the socks, while the heat-setting treatment improves the washability and durability of the socks through structure curing under high temperature conditions. The synergistic effect of each process link enables the socks to take into account breathability, elasticity and durability while meeting the antibacterial requirements, providing high-quality guarantee for daily wearing, sports and special environments. Through the precise design of yarn performance and weaving process, the present invention realizes the organic combination of functionality and comfort, providing technical support and market competitiveness for the development and promotion of antibacterial and breathable socks.

[0026] Beneficial technical effects

[0027] 1. Through the design of modified chitosan zinc oxide, the present invention is significantly superior to the prior art in terms of antibacterial performance and breathability. The conjugated system of chitosan cinnamaldehyde Schiff base enhances antibacterial performance and chemical stability, and the surface functionalization of silane-modified zinc oxide enhances the dispersibility and breathability of the material. The two achieve a synergistic effect between components through uniform compounding, making the antibacterial components evenly distributed and the performance long-lasting. The present invention not only solves the technical pain point of the difficulty in balancing antibacterial properties and breathability in existing materials, but also ensures the structural integrity of the material by optimizing process conditions, is applicable to fields such as medical treatment and textiles, promotes the industry to develop towards high performance and environmental protection, and shows broad application prospects.

[0028] 2. The present invention adopts the design of nanorod-shaped zinc oxide particles. Through its high aspect ratio structure and excellent dispersibility, the synergistic improvement of flexibility and antibacterial performance is achieved. Compared with the prior art, it has higher antibacterial efficiency and mechanical properties. The special morphology and high surface area of the particles enhance antibacterial activity, and at the same time improve the flexibility of the material through physical embedding, solving the pain point of the difficulty in balancing antibacterial and mechanical properties in traditional materials. Strict control of the preparation process ensures the uniformity of particle size and functional stability, is applicable to fields such as medical treatment and textiles, provides an innovative solution for the industry development and shows broad application prospects.

[0029] 3. Through the design of antibacterial breathable yarn, the present invention innovatively realizes the synergistic optimization of breathability, antibacterial property and flexibility. Compared with the prior art, the comprehensive performance of the yarn is significantly improved. Through the synergistic effect of the strength enhancement of polyester fiber, the wear resistance of nylon fiber, the moisture absorption and breathability of cotton fiber and the recovery of elastic fiber, combined with the antibacterial activity of modified chitosan zinc oxide and the softness of polyether-modified silicone oil, the yarn has the advantages of uniform structure and stable function, solves the pain point of the difficulty in balancing antibacterial and comfort in traditional textiles, is applicable to fields such as medical treatment, sports and household, provides new technical support and application prospects for the development of the textile industry towards high performance and multi-function.

[0030] 4. Through the collaborative design of antibacterial breathable yarn and precise weaving process, the present invention significantly improves the antibacterial property, breathability and wearing comfort of socks. Compared with the prior art, the present invention realizes function optimization in the sock bottom and sock mouth areas, can efficiently discharge moisture and keep dry, and also enhances elasticity and fit, solving the problems of easy slipping and poor breathability of traditional socks. Through reasonable ratio and process control of each component, it performs excellently in durability, dimensional stability and antibacterial persistence, is applicable to daily, sports and special environments, provides a reliable solution for the upgrade of functional socks, and promotes the industry to develop towards high performance and comfort. Brief Description of the Drawings

[0031] Figure 1 It is the SEM morphology diagram of the nanorod-shaped zinc oxide particles prepared in Example 1 of the present invention.

[0032] Figure 2 Infrared Fourier spectrum of the nanorod-shaped zinc oxide particles prepared in Example 1 of the present invention.

[0033] Figure 3 Infrared Fourier spectrum of the silane-modified zinc oxide prepared in Example 1 of the present invention.

[0034] Figure 4 Infrared Fourier spectrum of the chitosan cinnamaldehyde Schiff base prepared in Example 1 of the present invention.

[0035] Figure 5 Infrared Fourier spectrum of the modified chitosan zinc oxide prepared in Example 1 of the present invention. Detailed implementation manners

[0036] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0037] Under the condition that specific conditions are not specified, the operations in the embodiments are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments used, if the manufacturer is not indicated, they are all common products on the market. For the parts not mentioned in the technical content of the present invention, reference will be made to the prior art for handling. Unless otherwise specified, the following examples and comparative examples will be carried out in parallel tests and the same treatment steps and parameters will be adopted. Table 1 shows the reagents required for the examples and comparative examples and the corresponding purchasing companies.

[0038] Table 1 Reagents required for the examples and comparative examples and the corresponding purchasing companies

[0039]

[0040]

[0041] Example 1

[0042] An antibacterial and breathable yarn. The antibacterial and breathable yarn of this embodiment is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber;

[0043] The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber in this embodiment is 40:20:10:5;

[0044] The polyester fiber in this embodiment is prepared from the following components in parts by weight: 85 parts of polyethylene terephthalate chips, 3.0 parts of modified chitosan zinc oxide, 0.3 part of antioxidant 1010, 1.0 part of POE elastomer, 2.0 parts of polyether-modified silicone oil, and 1.0 part of polyethylene glycol 200;

[0045] The modified chitosan zinc oxide of this embodiment is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide; the chitosan cinnamaldehyde Schiff base is obtained by the Schiff base condensation reaction of chitosan and cinnamaldehyde in an acetic acid and absolute ethanol medium; the silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles.

[0046] The preparation method of the modified chitosan zinc oxide of this embodiment is as follows: by weight, 10.0 parts of chitosan cinnamaldehyde Schiff base are added to 500 parts of deionized water, and then the pH of the mixed solution is adjusted to 3.0 with a 3.0 wt.% acetic acid solution. After the adjustment, the mixture is stirred at a stirring rate of 200 rpm at 60 °C for 20 min. Then, 40.0 parts of silane-modified zinc oxide are added to the solution, and the mixed solution is first ultrasonicated for 20 min in an ultrasonic device, and then stirred in a water bath at 50 °C for 30 min. After the stirring is completed, the pH of the mixed solution is adjusted to 8.8 with a 5 wt.% sodium hydroxide solution. After the adjustment, flocculent precipitates are formed in the mixed solution. Then, the mixed solution is filtered and the precipitate is retained. The precipitate is washed 3 times with deionized water. After the washing is completed, it is dried in a vacuum drying oven at 50 °C for 8 h, and the dried product is ground to a particle size of 200 mesh to obtain the modified chitosan zinc oxide.

[0047] The preparation method of the silane-modified zinc oxide of this embodiment is as follows: by weight, 15.0 parts of ethyl glycolate and 40.0 parts of isocyanatopropyltriethoxysilane are added to a beaker, and 0.20 part of dibutyltin dilaurate is further added. At 40.0 °C, the mixture is stirred at a stirring rate of 300 rpm for 200 min to form a homogeneous mixture. Then, 100 parts of nanorod-shaped zinc oxide particles, 200 parts of absolute ethanol and 150 parts of deionized water are successively added to the mixed solution. Then, the mixed solution is ultrasonicated for 30 min. After the ultrasonic treatment is completed, the pH of the solution is adjusted to 9.8 with a 5 wt.% sodium hydroxide solution. After the pH is adjusted, the mixed solution is stirred in a water bath at 60 °C at a stirring rate of 300 rpm for 240 min. After the stirring is completed, the mixed solution is filtered and the precipitate is retained. Then, the precipitate is washed alternately 3 times with deionized water and absolute ethanol, and the washed precipitate is dried at 50 °C for 6 h to obtain the silane-modified zinc oxide.

[0048] The preparation method of the chitosan cinnamaldehyde Schiff base in this example is as follows: By weight, 10.0 parts of chitosan are dissolved in 100 parts of 1 wt.% acetic acid solution to obtain a chitosan solution, and another 7.0 parts of cinnamaldehyde are dissolved in 300 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then, the cinnamaldehyde solution is added dropwise to the chitosan solution. After the addition is completed, the mixed solution is placed under an oil bath condition at 40 °C and stirred and reacted for 300 min at a stirring rate of 350 rpm. After the stirring is completed, 5 wt.% sodium hydroxide solution is slowly added dropwise to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then, the mixed solution is filtered and the precipitate is retained. The obtained precipitate is washed alternately with absolute ethanol and deionized water 3 times, and then the precipitate is transferred to a vacuum drying oven and dried at 50 °C for 200 min. The dried product is ground to a particle size of 200 mesh to obtain the chitosan cinnamaldehyde Schiff base in the form of a yellow powder.

[0049] The preparation method of the polyester fiber in this example is as follows: Polyethylene terephthalate chips, antioxidant 1010, and POE elastomer are added to a high-speed mixer and mixed at 300 rpm for 5 min at room temperature to obtain uniformly dispersed raw materials. Then, the uniformly dispersed filler is added to a twin-screw co-mixing extruder and melt-blended at 250 °C for 30 min at a melt-blending rate of 300 rpm. During the co-mixing process, modified chitosan zinc oxide and polyether-modified silicone oil are gradually added thereto, and then fiber masterbatch is obtained by extrusion. Then, the fiber masterbatch is added to a melt spinning device and spun at 260 °C to form polyester fiber.

[0050] The preparation method of the nanorod-shaped zinc oxide particles in this example is as follows: By weight, 0.5 part of zinc nitrate and 0.5 part of urea are dissolved in 100 parts of deionized water and stirred at a stirring rate of 300 rpm for 10 min to form a mixed solution. The mixed solution is transferred to a hydrothermal reaction kettle, sealed and reacted at 90 °C for 240 min. After the reaction is completed, it is naturally cooled to room temperature. The reaction solution is filtered and the solid powder is retained, and the solid powder is washed with deionized water 3 times, with each washing time being 5 min. The washed solid powder is placed in a vacuum drying oven at 50 °C and dried for 6 h to obtain nanorod-shaped zinc oxide particles.

[0051] The average diameter of the nanorod-shaped zinc oxide particles in this example is 50 nm, and the average length is 500 nm.

[0052] The preparation method of the antibacterial and breathable yarn in this embodiment is as follows: Polyester fiber, nylon fiber, cotton fiber and elastic fiber are spun by air-jet spinning. The spinning tension is set at 8 cN, the twist is 300 turns / m, and the spinning speed is 100 m / min. The spun yarn is subjected to drafting treatment. In this embodiment, the drafting ratio is controlled at 1.05, and then twisting is carried out. In this embodiment, the twist coefficient is controlled at 3.5, and the yarn is wound into a bobbin. In this embodiment, the winding tension is controlled at 5 cN, thereby preparing the antibacterial and breathable yarn.

[0053] The elastic fiber in this embodiment is Lycra fiber.

[0054] The present invention also discloses an antibacterial and breathable sock. The antibacterial and breathable sock in this embodiment is woven from the antibacterial and breathable yarn in this embodiment;

[0055] The preparation method of the antibacterial and breathable sock in this embodiment is as follows: Using the antibacterial and breathable yarn in this embodiment, according to the design requirements of sock weaving, the sock is knitted and formed by a knitting machine. In this embodiment, the stitch density of the knitting machine is 12 stitches per inch, the weaving tension is 5 cN, and the weaving speed is 20 rpm; The knitting density is adjusted according to the functional requirements of different parts of the sock. Among them, the knitting density of the sock bottom part is appropriately reduced, and the knitting density is controlled at 150 stitches per square inch to enhance breathability, while the knitting density of the sock mouth part is appropriately increased, and the knitting density is controlled at 200 stitches per square inch to improve elasticity and fit; After knitting and forming, the sock is subjected to seaming treatment. In this embodiment, the seaming process adopts the chain stitch method, and the sewing thread tension is controlled at 4 cN. Then, the sock is subjected to shaping treatment. In this embodiment, the shaping temperature is 80 °C and the shaping time is 3 min; The shaped sock is subjected to heat setting treatment. In this embodiment, the heat setting temperature is 120 °C and the setting time is 5 min; Finally, the antibacterial and breathable sock is prepared.

[0056] Combined with Figures 1 to 5 the characterization results, the following conclusions can be drawn: The present invention successfully prepared nanorod-shaped zinc oxide particles through Example 1, and verified its surface characteristics through the infrared Fourier spectrum ( Figure 2 ). Among them, the broadband absorption peak at 3388 cm -1 is attributed to the O-H stretching vibration of hydroxyl groups on the ZnO surface or adsorbed water molecules, while the characteristic peak at 869 cm -1 is caused by the bending vibration of Zn-O-Zn. Further, through silane modification ( Figure 3 ), the surface grafting of nanorod-shaped zinc oxide was successfully achieved, and changes in characteristic peaks were observed in the infrared spectrum, including the stretching vibration peaks of N-H and Si-X at 3369 cm -1 , the -CH2 doublets at 2926 cm -1 and 2856 cm -1 , and 1716 cm-1 and 869 cm -1 correspond to the characteristic peaks of amide groups and the superposition of Zn-O and Si-O respectively, proving that IPTS has been successfully grafted onto the surface of zinc oxide. At the same time, through Figure 4 it can be confirmed that the chitosan cinnamaldehyde Schiff base of the present invention has been successfully prepared. The C=N stretching vibration absorption peak at 1632 cm in the infrared spectrum indicates that the -NH2 in chitosan and the -CHO in cinnamaldehyde form a Schiff base structure through a condensation reaction. In addition, -1 the Figure 5 further indicates that the composite modification of chitosan cinnamaldehyde Schiff base and zinc oxide has been successfully achieved. The vibration peaks of benzene ring C-H and olefins at 749 cm -1 and 688 cm -1 clearly characterize the formation of the modified structure. In summary, through multi-step functionalization modification, the present invention has successfully constructed a modified chitosan composite based on nanorod-shaped zinc oxide, and the chemical modifications at each stage have been fully verified.

[0057] Example 2

[0058] An antibacterial and breathable yarn. The antibacterial and breathable yarn of this example is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber;

[0059] The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber in this example is 46:23:13:7;

[0060] The polyester fiber of this example is prepared from the following components in parts by weight: 87 parts of polyethylene terephthalate chips, 3.6 parts of modified chitosan zinc oxide, 0.4 part of antioxidant 1010, 1.3 parts of POE elastomer, 2.3 parts of polyether-modified silicone oil, 1.3 parts of polyethylene glycol 200;

[0061] The modified chitosan zinc oxide of this example is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide; the chitosan cinnamaldehyde Schiff base is obtained by the Schiff base condensation reaction of chitosan and cinnamaldehyde in an acetic acid and absolute ethanol medium; the silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles;

[0062] The preparation method of the modified chitosan zinc oxide in this example is as follows: by weight, add 11.5 parts of chitosan cinnamaldehyde Schiff base to 530 parts of deionized water, then adjust the pH of the mixed solution to 3.3 with 3.0 wt.% acetic acid solution. After the adjustment, stir the solution at a stirring rate of 215 rpm at 63 °C for 23 min. Then add 43.0 parts of silane-modified zinc oxide to the solution, place the mixed solution in an ultrasonic device and ultrasonicate for 23 min first, then stir for 35 min under the condition of a 53 °C water bath. After stirring, adjust the pH of the mixed solution to 9.0 with 5 wt.% sodium hydroxide solution. After the adjustment, flocculent precipitates are formed in the mixed solution. Then filter the mixed solution and retain the precipitate, wash the precipitate 3 times with deionized water. After washing, dry the precipitate in a vacuum drying oven at 53 °C for 9 h, and grind the dried product to a particle size of 200 mesh to obtain the modified chitosan zinc oxide.

[0063] The preparation method of the silane-modified zinc oxide in this example is as follows: by weight, add 16.5 parts of ethyl glycolate and 43.0 parts of isocyanatopropyltriethoxysilane to a beaker, and then add 0.26 parts of dibutyltin dilaurate. At 41.5 °C, stir at a stirring rate of 315 rpm for 212 min to form a homogeneous mixture. Then, sequentially add 115 parts of nanorod-shaped zinc oxide particles, 215 parts of absolute ethanol, and 153 parts of deionized water to the mixed solution. Then ultrasonicate the mixed solution for 35 min. After the ultrasonic treatment, adjust the pH of the solution to 9.9 with 5 wt.% sodium hydroxide solution. After adjusting the pH, place the mixed solution in a water bath at 61.5 °C and stir at a stirring rate of 330 rpm for 258 min. After stirring, filter the mixed solution and retain the precipitate. Then wash the precipitate alternately with deionized water and absolute ethanol 4 times. Dry the washed precipitate at 53 °C for 7 h to obtain the silane-modified zinc oxide.

[0064] The preparation method of the chitosan cinnamaldehyde Schiff base in this example is as follows: by weight, dissolve 11.5 parts of chitosan in 106 parts of 1 wt.% acetic acid solution to obtain a chitosan solution. Separately, dissolve 7.9 parts of cinnamaldehyde in 330 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then add the cinnamaldehyde solution drop by drop to the chitosan solution. After the addition, place the mixed solution under the condition of a 43 °C oil bath and stir at a stirring rate of 365 rpm for 318 min for reaction. After stirring, slowly add 5 wt.% sodium hydroxide solution to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then filter the mixed solution and retain the precipitate. Wash the obtained precipitate alternately with absolute ethanol and deionized water 3 times. Then transfer the precipitate to a vacuum drying oven and dry at 53 °C for 212 min. Grind the dried product to a particle size of 200 mesh to obtain the chitosan cinnamaldehyde Schiff base in the form of a yellow powder.

[0065] The preparation method of the polyester fiber in this embodiment is as follows: Add polyethylene terephthalate chips, antioxidant 1010, and POE elastomer into a high-speed mixer, and mix at 360 rpm for 7 min at room temperature to obtain uniformly dispersed raw materials. Then add the uniformly dispersed filler into a twin-screw co-mixing extruder, and carry out melt blending at 259 °C for 35 min with a melt blending rate of 360 rpm. During the co-mixing process, modified chitosan zinc oxide and polyether-modified silicone oil are gradually added thereto. Then, fiber masterbatch is obtained through extrusion. Next, the fiber masterbatch is added into a melt spinning device, and spun at 266 °C to form polyester fiber.

[0066] The preparation method of the nanorod-shaped zinc oxide particles in this embodiment is as follows: By weight, dissolve 0.65 parts of zinc nitrate and 0.65 parts of urea in 130 parts of deionized water, and stir at a stirring rate of 360 rpm for 13 min to form a mixed solution; transfer the mixed solution to a hydrothermal reaction kettle, seal it, and react at 92 °C for 276 min. After the reaction is completed, naturally cool it to room temperature, filter the reaction solution and retain the solid powder, and wash the solid powder 4 times with deionized water, with each washing time being 6.5 min. Place the washed solid powder in a vacuum drying oven at 53 °C and dry it for 7 h to obtain nanorod-shaped zinc oxide particles.

[0067] The average diameter of the nanorod-shaped zinc oxide particles in this embodiment is 65 nm, and the average length is 650 nm.

[0068] The preparation method of the antibacterial and breathable yarn in this embodiment is as follows: Spin polyester fiber, nylon fiber, cotton fiber, and elastic fiber by air-jet spinning, set the spinning tension to 10 cN, the twist to 360 turns / m, and the spinning speed to 130 m / min; carry out drawing treatment on the spun yarn. The drawing ratio in this embodiment is controlled at 1.1. Subsequently, twist is added, and the twist coefficient in this embodiment is controlled at 3.8. Then wind the yarn into a bobbin, and the winding tension in this embodiment is controlled at 6.5 cN, thereby preparing the antibacterial and breathable yarn.

[0069] The elastic fiber in this embodiment is spandex fiber.

[0070] The present invention also discloses an antibacterial and breathable sock. The antibacterial and breathable sock in this embodiment is woven from the antibacterial and breathable yarn in this embodiment;

[0071] The preparation method of the antibacterial and breathable socks in this embodiment is as follows: Using the antibacterial and breathable yarn of this embodiment, according to the design requirements of sock weaving, the sock is knitted and formed by a knitting machine. The stitch density of the knitting machine in this embodiment is 14 stitches per inch, the weaving tension is 8 cN, and the weaving speed is 26 rpm; The knitting density is adjusted according to the functional requirements of different parts of the sock. Among them, the knitting density of the sock bottom part is appropriately reduced, and the knitting density is controlled within 159 stitches per square inch to enhance breathability, while the knitting density of the sock mouth part is appropriately increased, and the knitting density is controlled within 212 stitches per square inch to improve elasticity and fit; After knitting and forming, the sock is seamed. The seaming process in this embodiment uses a chain stitch method, and the sewing thread tension is controlled at 5.2 cN. Then, the sock is shaped. The shaping temperature in this embodiment is 86 °C, and the shaping time is 4.5 min; The shaped sock is heat-set. The heat-setting temperature in this embodiment is 129 °C, and the setting time is 8 min; Finally, the antibacterial and breathable socks are prepared.

[0072] Example Three

[0073] An antibacterial and breathable yarn. The antibacterial and breathable yarn of this embodiment is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber;

[0074] The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber in this embodiment is 53:26:14:7;

[0075] The polyester fiber of this embodiment is prepared from the following components in parts by weight: 88 parts of polyethylene terephthalate chips, 4.2 parts of modified chitosan zinc oxide, 0.4 part of antioxidant 1010, 1.6 parts of POE elastomer, 2.6 parts of polyether-modified silicone oil, and 1.6 parts of polyethylene glycol 200;

[0076] The modified chitosan zinc oxide of this embodiment is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide; Chitosan cinnamaldehyde Schiff base is obtained by the Schiff base condensation reaction of chitosan and cinnamaldehyde in acetic acid and absolute ethanol media; The silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles;

[0077] The preparation method of the modified chitosan zinc oxide in this example is as follows: by weight, 13 parts of chitosan cinnamaldehyde Schiff base are added to 560 parts of deionized water. Then, the pH of the mixed solution is adjusted to 3.6 with 3.0 wt.% acetic acid solution. After the adjustment, the mixture is stirred at a stirring rate of 230 rpm at 66 °C for 26 min. Then, 46 parts of silane-modified zinc oxide are added to the solution. The mixed solution is first ultrasonicated for 26 min in an ultrasonic device, and then stirred in a water bath at 56 °C for 39 min. After the stirring is completed, the pH of the mixed solution is adjusted to 9.0 with 5 wt.% sodium hydroxide solution. After the adjustment, flocculent precipitates are formed in the mixed solution. Then, the mixed solution is filtered and the precipitate is retained. The precipitate is washed 3 times with deionized water. After the washing is completed, it is dried in a vacuum drying oven at 56 °C for 10 h. The dried product is ground to a particle size of 200 mesh to obtain the modified chitosan zinc oxide.

[0078] The preparation method of the silane-modified zinc oxide in this example is as follows: by weight, 18 parts of ethyl glycolate and 46 parts of isocyanatopropyltriethoxysilane are added to a beaker. Then, 0.32 part of dibutyltin dilaurate is added. At 43 °C, the mixture is stirred at a stirring rate of 330 rpm for 224 min to form a homogeneous mixture. Then, 130 parts of nanorod-shaped zinc oxide particles, 230 parts of absolute ethanol, and 156 parts of deionized water are successively added to the mixed solution. Then, the mixed solution is ultrasonicated for 39 min. After the ultrasonic treatment is completed, the pH of the solution is adjusted to 10.1 with 5 wt.% sodium hydroxide solution. After the pH is adjusted, the mixed solution is stirred in a water bath at 63 °C at a stirring rate of 360 rpm for 276 min. After the stirring is completed, the mixed solution is filtered and the precipitate is retained. Then, the precipitate is washed alternately 4 times with deionized water and absolute ethanol. The washed precipitate is dried at 56 °C for 8 h to obtain the silane-modified zinc oxide.

[0079] The preparation method of the chitosan cinnamaldehyde Schiff base in this example is as follows: by weight, 13 parts of chitosan are dissolved in 112 parts of 1 wt.% acetic acid solution to obtain a chitosan solution. Separately, 8.6 parts of cinnamaldehyde are dissolved in 360 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then, the cinnamaldehyde solution is added dropwise to the chitosan solution. After the addition is completed, the mixed solution is placed in an oil bath at 46 °C and stirred at a stirring rate of 380 rpm for a reaction of 336 min. After the stirring is completed, 5 wt.% sodium hydroxide solution is slowly added dropwise to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then, the mixed solution is filtered and the precipitate is retained. The obtained precipitate is washed alternately 3 times with absolute ethanol and deionized water. Then, the precipitate is transferred to a vacuum drying oven and dried at 56 °C for 224 min. The dried product is ground to a particle size of 200 mesh to obtain the chitosan cinnamaldehyde Schiff base in the form of a yellow powder.

[0080] The preparation method of the polyester fiber in this embodiment is as follows: Add polyethylene terephthalate chips, antioxidant 1010, and POE elastomer into a high-speed mixer, and mix at 420 rpm for 8 min at room temperature to obtain uniformly dispersed raw materials. Then add the uniformly dispersed filler into a twin-screw co-blending extruder, and conduct melt blending at 268 °C for 39 min with a melt blending rate of 420 rpm. During the blending process, modified chitosan zinc oxide and polyether-modified silicone oil are gradually added thereto. Then, fiber masterbatch is obtained through extrusion. Subsequently, the fiber masterbatch is added into a melt spinning device, and spun at 272 °C to form polyester fiber.

[0081] The preparation method of the nanorod-shaped zinc oxide particles in this embodiment is as follows: By weight, dissolve 0.8 parts of zinc nitrate and 0.8 parts of urea in 160 parts of deionized water, and stir at a stirring rate of 420 rpm for 16 min to form a mixed solution; transfer the mixed solution to a hydrothermal reaction kettle, seal it, and react at 93 °C for 316 min. After the reaction is completed, naturally cool it to room temperature, filter the reaction solution and retain the solid powder, and wash the solid powder 4 times with deionized water, with each washing time being 8 min. Place the washed solid powder in a vacuum drying oven at 56 °C and dry it for 8 h to obtain nanorod-shaped zinc oxide particles.

[0082] The average diameter of the nanorod-shaped zinc oxide particles in this embodiment is 80 nm, and the average length is 800 nm.

[0083] The preparation method of the antibacterial and breathable yarn in this embodiment is as follows: Spin polyester fiber, polyamide fiber, cotton fiber, and elastic fiber by air-jet spinning, set the spinning tension to 12 cN, the twist to 420 turns / m, and the spinning speed to 160 m / min; conduct stretching treatment on the spun yarn. In this embodiment, the stretching ratio is controlled at 1.15, and then twisting is carried out. In this embodiment, the twist coefficient is controlled at 4.1, and the yarn is wound into a bobbin. In this embodiment, the winding tension is controlled at 8 cN, thereby preparing the antibacterial and breathable yarn.

[0084] The elastic fiber in this embodiment is Lycra fiber.

[0085] The present invention also discloses an antibacterial and breathable sock. The antibacterial and breathable sock in this embodiment is woven from the antibacterial and breathable yarn in this embodiment;

[0086] The preparation method of the antibacterial and breathable socks in this embodiment is as follows: Using the antibacterial and breathable yarn of this embodiment, according to the design requirements of sock weaving, the sock is knitted and formed by a knitting machine. The stitch density of the knitting machine in this embodiment is 16 stitches per inch, the weaving tension is 11 cN, and the weaving speed is 32 rpm; The knitting density is adjusted according to the functional requirements of different parts of the sock. Among them, the knitting density of the sock bottom part is appropriately reduced, and the knitting density is controlled within 168 stitches per square inch to enhance breathability, while the knitting density of the sock mouth part is appropriately increased, and the knitting density is controlled within 224 stitches per square inch to improve elasticity and fit; After knitting and forming, the sock is subjected to seaming treatment. The seaming process in this embodiment adopts the chain stitch method, and the sewing thread tension is controlled at 6.4 cN. Then, the sock is subjected to shaping treatment. The shaping temperature in this embodiment is 92 °C, and the shaping time is 6 min; The shaped sock is subjected to heat setting treatment. The heat setting temperature in this embodiment is 138 °C, and the setting time is 11 min; Finally, the antibacterial and breathable socks are prepared.

[0087] Example 4

[0088] An antibacterial and breathable yarn. The antibacterial and breathable yarn of this embodiment is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber;

[0089] The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber in this embodiment is 60:30:20:10;

[0090] The polyester fiber of this embodiment is prepared from the following components in parts by weight: 90 parts of polyethylene terephthalate chips, 5.0 parts of modified chitosan zinc oxide, 0.5 part of antioxidant 1010, 2.0 parts of POE elastomer, 3.0 parts of polyether modified silicone oil, 2.0 parts of polyethylene glycol 200;

[0091] The modified chitosan zinc oxide of this embodiment is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide; Chitosan cinnamaldehyde Schiff base is obtained by the Schiff base condensation reaction of chitosan and cinnamaldehyde in an acetic acid and absolute ethanol medium; The silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles;

[0092] The preparation method of the modified chitosan zinc oxide in this example is as follows: by weight, 15.0 parts of chitosan cinnamaldehyde Schiff base are added to 600 parts of deionized water. Then, the pH of the mixed solution is adjusted to 4.0 with 3.0 wt.% acetic acid solution. After the adjustment, the mixture is stirred at a stirring rate of 250 rpm at 70 °C for 30 min. Then, 50.0 parts of silane-modified zinc oxide are added to the solution. The mixed solution is first ultrasonicated for 30 min in an ultrasonic device, and then stirred in a water bath at 60 °C for 45 min. After the stirring is completed, the pH of the mixed solution is adjusted to 9.2 with 5 wt.% sodium hydroxide solution. After the adjustment, flocculent precipitates are formed in the mixed solution. Then, the mixed solution is filtered and the precipitate is retained. The precipitate is washed 3 times with deionized water. After the washing is completed, it is dried in a vacuum drying oven at 60 °C for 12 h. The dried product is ground to a particle size of 200 mesh to obtain the modified chitosan zinc oxide.

[0093] The preparation method of the silane-modified zinc oxide in this example is as follows: by weight, 20.0 parts of ethyl glycolate and 50.0 parts of isocyanatopropyltriethoxysilane are added to a beaker. Then, 0.40 part of dibutyltin dilaurate is added. At 45.0 °C, the mixture is stirred at a stirring rate of 350 rpm for 240 min to form a homogeneous mixture. Then, 150 parts of nanorod-shaped zinc oxide particles, 250 parts of absolute ethanol and 160 parts of deionized water are successively added to the mixed solution. Then, the mixed solution is ultrasonicated for 45 min. After the ultrasonic treatment is completed, the pH of the solution is adjusted to 10.2 with 5 wt.% sodium hydroxide solution. After the pH is adjusted, the mixed solution is stirred in a water bath at 65 °C at a stirring rate of 400 rpm for 300 min. After the stirring is completed, the mixed solution is filtered and the precipitate is retained. Then, the precipitate is washed alternately 5 times with deionized water and absolute ethanol. The washed precipitate is dried at 60 °C for 10 h to obtain the silane-modified zinc oxide.

[0094] The preparation method of the chitosan cinnamaldehyde Schiff base in this example is as follows: by weight, 15.0 parts of chitosan are dissolved in 120 parts of 1 wt.% acetic acid solution to obtain a chitosan solution. Separately, 10.0 parts of cinnamaldehyde are dissolved in 400 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then, the cinnamaldehyde solution is added dropwise to the chitosan solution. After the addition is completed, the mixed solution is placed in an oil bath at 50 °C and stirred at a stirring rate of 400 rpm for 360 min for reaction. After the stirring is completed, 5 wt.% sodium hydroxide solution is slowly added dropwise to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then, the mixed solution is filtered and the precipitate is retained. The obtained precipitate is washed alternately 3 times with absolute ethanol and deionized water. Then, the precipitate is transferred to a vacuum drying oven and dried at 60 °C for 240 min. The dried product is ground to a particle size of 200 mesh to obtain the chitosan cinnamaldehyde Schiff base in the form of a yellow powder.

[0095] The preparation method of the polyester fiber in this embodiment is as follows: Add polyethylene terephthalate chips, antioxidant 1010, and POE elastomer into a high-speed mixer, mix at 500 rpm for 10 min at room temperature to obtain uniformly dispersed raw materials. Then add the uniformly dispersed filler into a twin-screw co-blending extruder, melt and blend at 280 °C for 45 min, with a melt blending rate of 500 rpm. During the blending process, modified chitosan zinc oxide and polyether-modified silicone oil are gradually added. Then fiber masterbatch is obtained through extrusion. Next, the fiber masterbatch is added into a melt spinning device and spun at 280 °C to form polyester fiber.

[0096] The preparation method of the nanorod-shaped zinc oxide particles in this embodiment is: By weight, dissolve 1.0 part of zinc nitrate and 1.0 part of urea in 200 parts of deionized water, stir at a stirring rate of 500 rpm for 20 min to form a mixed solution; transfer the mixed solution to a hydrothermal reaction kettle, seal it and react at 95 °C for 360 min. After the reaction is completed, naturally cool it to room temperature, filter the reaction solution and retain the solid powder, wash the solid powder 5 times with deionized water, with each washing time being 10 min. Place the washed solid powder in a vacuum drying oven at 60 °C and dry it for 10 h to obtain nanorod-shaped zinc oxide particles.

[0097] The average diameter of the nanorod-shaped zinc oxide particles in this embodiment is 100 nm, and the average length is 1000 nm.

[0098] The preparation method of the antibacterial and breathable yarn in this embodiment is: Spin polyester fiber, nylon fiber, cotton fiber, and elastic fiber by air-jet spinning, set the spinning tension to 15 cN, the twist to 500 turns / m, and the spinning speed to 200 m / min; perform drawing treatment on the spun yarn. The drawing ratio in this embodiment is controlled at 1.2. Subsequently, twist is added. The twist coefficient in this embodiment is controlled at 4.5, and the yarn is wound into a bobbin. The winding tension in this embodiment is controlled at 10 cN, thereby preparing the antibacterial and breathable yarn.

[0099] The elastic fiber in this embodiment is spandex fiber.

[0100] The present invention also discloses an antibacterial and breathable sock. The antibacterial and breathable sock in this embodiment is woven from the antibacterial and breathable yarn in this embodiment;

[0101] The preparation method of the antibacterial and breathable socks in this embodiment is as follows: Using the antibacterial and breathable yarn of this embodiment, according to the requirements of sock weaving design, the socks are knitted and formed by a knitting machine. The stitch density of the knitting machine in this embodiment is 18 stitches per inch, the weaving tension is 15 cN, and the weaving speed is 40 rpm; The knitting density is adjusted according to the functional requirements of different parts of the socks. Among them, the knitting density of the sock bottom part is appropriately reduced, and the knitting density is controlled within 180 stitches per square inch to enhance breathability, while the knitting density of the sock mouth part is appropriately increased, and the knitting density is controlled within 240 stitches per square inch to improve elasticity and fit; After knitting and forming, the socks are seamed. In this embodiment, the seaming process uses the chain stitch method, and the sewing thread tension is controlled at 8 cN. Then, the socks are shaped. The shaping temperature in this embodiment is 100 °C, and the shaping time is 8 min; The shaped socks are heat-set. The heat-setting temperature in this embodiment is 150 °C, and the setting time is 15 min; Finally, the antibacterial and breathable socks are prepared.

[0102] Comparative Example 1

[0103] It is basically the same as Example 1, except that an equal amount of rod-shaped nano-zinc oxide particles are used to replace the modified chitosan zinc oxide. Therefore, the rod-shaped nano-zinc oxide is not treated with chitosan cinnamaldehyde Schiff base and silane.

[0104] Comparative Example 2

[0105] It is basically the same as Example 1, except that an equal amount of rod-shaped nano-zinc oxide particles are not treated with silane.

[0106] Comparative Example 3

[0107] It is basically the same as Example 1, except that commercial nano-zinc oxide particles are used to replace the rod-shaped nano-zinc oxide particles. The commercial nano-zinc oxide particles are usually spherical particles and are purchased from Shijiazhuang Jixin Zinc Industry Co., Ltd.

[0108] Comparative Example 4

[0109] It is basically the same as Example 1, except that POE elastomer is not added during the preparation of polyester fiber, and the other components remain unchanged.

[0110] Comparative Example 5

[0111] It is basically the same as Example 1, except that polyether modified silicone oil is not added during the preparation of polyester fiber, and the proportions of other components remain unchanged.

[0112] Comparative Example 6

[0113] It is basically the same as Example 1, except that POE elastomer is not added during the preparation of polyester fiber, and the other components remain unchanged.

[0114] Performance test:

[0115] Mechanical properties: The mechanical properties of the yarn were tested using a YG061 electronic single yarn strength tester (Laizhou Electronic Instrument Co., Ltd.) in accordance with the standard of GB / T 3916-2013 "Determination of breaking strength and elongation at break of single yarns in packages of textiles". The test parameters were set as follows: test gauge length 500 mm, tensile speed 500 mm / min, and pre-tension 0.5±0.1 cN / tex. Each group of blended yarns was tested 60 times repeatedly, and the breaking strength data were recorded and averaged. Combining the measured yarn linear density, the breaking tenacity and elongation at break were calculated.

[0116] Air permeability: According to the fabric air permeability test standard, the air permeability of the sock samples was measured. Before the test, the samples were conditioned to equilibrium in a standard environment. Using a fabric air permeability tester, the air permeability was characterized by measuring the air flow rate through a unit area of the fabric per unit time under a specified pressure difference. During the test, the sample was flatly fixed on the test head of the tester, a standard pressure difference was applied, and the air flow rate was recorded. The test results were expressed in units of milliliters per square centimeter per second (mL / cm 2 ·s). Each sample was repeatedly tested at different positions, and the average value was taken as the final air permeability. The larger the air permeability value, the better the air permeability of the fabric and the stronger the wearing comfort.

[0117] Antibacterial property: The antibacterial property of the yarn was tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method". The experimental steps were carried out in accordance with Standard 4.3.2.2, including details such as the preparation of the culture medium, the cultivation and dilution of the bacterial solution, etc., which were strictly in accordance with the standard requirements. After the test specimens were oscillated in an air-bath constant temperature shaker at 24℃±1℃ and a rotation speed of 150 r / min for 18 h, 1 mL of the solution was taken and diluted 10 2 、10 3 、104 times and then plated for cultivation, and cultivated at 37℃±1℃ for 24 h. The concentration of the bacterial solution was adjusted to 1×109~5×109 CFU / mL by the turbidimetric method. Finally, the viable bacteria concentration in the conical flask of the test specimen was calculated according to the formula, and the antibacterial effect of the yarn was quantitatively expressed by the antibacterial rate.

[0118] The properties of the yarns and antibacterial breathable socks of Examples 1 to 4 and Comparative Examples 1 to 6 are summarized in Table 2.

[0119] Table 2 Summary of the properties of the yarns and antibacterial breathable socks of Examples 1 to 4 and Comparative Examples 1 to 6

[0120]

[0121] The main difference between Comparative Example 1 and Example 1 is that an equal amount of rod-shaped nano-zinc oxide particles are used to replace the modified chitosan zinc oxide. Therefore, the rod-shaped nano-zinc oxide is not treated with chitosan cinnamaldehyde Schiff base and silane. As can be seen from Table 2, the antibacterial rate of Comparative Example 1 is significantly reduced, only 85.0%, while that of Example 1 reaches 99.5%. This indicates that the unmodified zinc oxide particles have poor dispersibility and insufficient binding ability with the polyester matrix, resulting in a decline in antibacterial effect. At the same time, the mechanical properties slightly decrease (16.0 cN / tex), and the air permeability also decreases from 320 mL / cm 2 ·s in Example 1 to 310 mL / cm 2 ·s, which may be due to the uneven dispersion of the particles, resulting in a certain impact on the fiber pore structure.

[0122] The main difference between Comparative Example 2 and Example 1 is that an equal amount of rod-shaped nano-zinc oxide particles are not treated with silane. As can be seen from Table 2, the antibacterial rate of Comparative Example 2 slightly increases (91.0%), but is still significantly lower than 99.5% of Example 1. This is because although the rod-shaped nano-zinc oxide has a good morphology, the lack of silane modification will lead to insufficient surface activity of the particles and weak interfacial interaction with the fiber matrix, affecting the release efficiency of antibacterial substances. In addition, the mechanical properties (15.8 cN / tex) and air permeability (318 mL / cm 2 ·s) are slightly lower than those of Example 1, indicating that the interfacial properties of the particles have a certain impact on the comprehensive properties of the yarn.

[0123] The main difference between Comparative Example 3 and Example 1 is that commercial nano-zinc oxide particles (spherical) are used to replace the rod-shaped nano-zinc oxide particles. As can be seen from Table 2, the antibacterial rate of Comparative Example 3 is significantly reduced, only 80.0%, far lower than 99.5% of Example 1. This is because the commercial spherical particles have a smaller specific surface area and fewer active sites, resulting in a significant decline in antibacterial effect. The mechanical properties (15.5 cN / tex) also decrease, which may be due to the weak enhancement effect of the spherical particles on the fiber cohesion. At the same time, the air permeability decreases significantly, only 290 mL / cm 2 ·s, indicating that the spherical particles may affect the pore distribution between fibers and hinder air circulation.

[0124] The main difference between Comparative Example 4 and Example 1 is that no POE elastomer is added during the preparation of the polyester fiber. As can be seen from Table 2, the antibacterial rate of Comparative Example 4 (98.5%) is close to 99.5% of Example 1, indicating that the absence of the POE elastomer has little effect on the antibacterial performance. However, the mechanical properties (16.0 cN / tex) are slightly lower than 16.2 cN / tex of Example 1, because the POE elastomer can enhance the flexibility and tensile strength of the fiber. The air permeability is similar to that of Example 1, 315 mL / cm 2·s, indicating that the POE elastomer has limited impact on the air permeability of the fiber.

[0125] The main difference between Comparative Example 5 and Example 1 lies in that polyether-modified silicone oil was not added during the preparation of the polyester fiber. As can be seen from Table 2, the antibacterial rate of Comparative Example 5 (98.0%) is slightly lower than that of Example 1 (99.5%), indicating that the absence of polyether-modified silicone oil has a certain impact on the antibacterial performance, probably because the uniform coating formed on the fiber surface helps the distribution and release of antibacterial substances. The mechanical properties (15.8 cN / tex) are slightly lower than those of Example 1, indicating that the lubricating effect of the silicone oil contributes to the fiber strength to a certain extent. The air permeability decreases significantly, only being 280 mL / cm 2 ·s, probably because the absence of the silicone oil results in a decrease in the smoothness of the fiber surface, affecting air flow.

[0126] The main difference between Comparative Example 6 and Example 1 lies in that the POE elastomer was not added during the preparation of the polyester fiber. As can be seen from Table 2, the antibacterial rate of Comparative Example 6 (97.0%) is lower than that of Example 1 (99.5%), indicating that the absence of the POE elastomer may indirectly affect the uniform distribution of antibacterial substances. The mechanical properties (15.8 cN / tex) are significantly lower than those of Example 1 because the POE elastomer can improve the flexibility and strength of the fiber. The air permeability (312 mL / cm 2 ·s) is slightly lower than 320 mL / cm of Example 1 2 ·s, but still higher than some of the comparative examples, indicating that its impact on the pore structure of the fiber is small.

[0127] In summary, through the performance comparison of Examples 1 to 4 and Comparative Examples 1 to 6, it can be seen that the synergy of component design has a crucial impact on the comprehensive performance of the yarn and antibacterial breathable socks. The introduction of modified chitosan zinc oxide, under the synergistic modification of chitosan cinnamaldehyde Schiff base and silane, significantly improves the antibacterial rate, ensuring the persistence and stability of the antibacterial effect; while the unmodified or replacement with other morphologies of zinc oxide particles will weaken the dispersibility and interfacial action of the antibacterial agent, resulting in a significant decrease in antibacterial performance. In addition, the addition of POE elastomer and polyether-modified silicone oil plays a key role in the mechanical properties and air permeability of the yarn respectively, and they form a good synergistic effect in improving the flexibility, strength and air circulation of the fiber. Especially the presence of the POE elastomer not only enhances the breaking strength of the fiber, but also improves the wearing comfort and durability of the yarn to a certain extent. These results indicate that the excellent performance of the yarn and socks is not the result of a single component, but the result of the mutual synergy of each component in aspects such as chemical modification, physical dispersion and performance reinforcement. Reasonable component design and optimization can achieve a balance among hygroscopicity, mechanical properties, air permeability and antibacterial properties, and ultimately endow the product with excellent comprehensive performance to meet the multi-functional requirements.

[0128] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that any equivalent structural transformation made under the concept of the present invention by using the content of the specification and drawings of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. An antibacterial and breathable yarn, characterized in that, The described antibacterial and breathable yarn is obtained by spinning polyester fiber, nylon fiber, cotton fiber and elastic fiber; The mass ratio of the polyester fiber, nylon fiber, cotton fiber and elastic fiber is (40~60):(20~30):(10~20):(5~10); The polyester fiber is prepared from the following components in parts by weight: 85~90 parts of polyethylene terephthalate chips, 3.0~5.0 parts of modified chitosan zinc oxide, 0.3~0.5 parts of antioxidant 1010, 1.0~2.0 parts of POE elastomer, 2.0~3.0 parts of polyether modified silicone oil, 1.0~2.0 parts of polyethylene glycol 200; The modified chitosan zinc oxide is prepared by compounding chitosan cinnamaldehyde Schiff base and silane-modified zinc oxide; The chitosan cinnamaldehyde Schiff base is obtained by the Schiff base condensation reaction of chitosan and cinnamaldehyde in acetic acid and absolute ethanol media; The silane-modified zinc oxide is isocyanatopropyltriethoxysilane-modified nanorod-shaped zinc oxide particles.

2. The antibacterial and breathable yarn according to claim 1, characterized in that, The preparation method of the modified chitosan zinc oxide is as follows: in parts by weight, add 10.0~15.0 parts of chitosan cinnamaldehyde Schiff base to 500~600 parts of deionized water, then adjust the pH of the mixed solution to 3.0~4.0 with 3.0wt.% acetic acid solution. After adjustment, stir at a stirring rate of 200~250 rpm at 60~70 °C for 20~30 min. Then add 40.0~50.0 parts of silane-modified zinc oxide to the solution, place the mixed solution in an ultrasonic device and ultrasonicate for 20~30 min first, then stir for 30~45 min under the condition of a water bath at 50~60 °C. After stirring, adjust the pH of the mixed solution to 8.8~9.2 with 5wt.% sodium hydroxide solution. After adjustment, flocculent precipitates are formed in the mixed solution. Then filter the mixed solution and retain the precipitate. Wash the precipitate 3 times with deionized water. After washing, dry it in a vacuum drying oven at 50~60 °C for 8~12 h. Grind the dried product to a particle size of 200 mesh to obtain modified chitosan zinc oxide.

3. The antibacterial and breathable yarn according to claim 1 or 2, characterized in that, The preparation method of the silane-modified zinc oxide is as follows: in parts by weight, add 15.0~20.0 parts of ethyl glycolate and 40.0~50.0 parts of isocyanatopropyltriethoxysilane to a beaker, continue to add 0.20~0.40 parts of dibutyltin dilaurate, and stir at a stirring rate of 300~350 rpm at 40.0~45.0 °C for 200~240 min to form a uniform mixed solution. Then continue to add 100~150 parts of nanorod-shaped zinc oxide particles, 200~250 parts of absolute ethanol and 150~160 parts of deionized water to the mixed solution in sequence. Then, the mixed solution was ultrasonically treated for 30 - 45 min. After the ultrasonic treatment, the pH of the solution was adjusted to 9.8 - 10.2 with 5 wt.% sodium hydroxide solution. After adjusting the pH, the mixed solution was stirred in a water bath at 60 - 65 °C at a stirring rate of 300 - 400 rpm for 240 - 300 min. After stirring, the mixed solution was filtered and the precipitate was retained. Then, the precipitate was washed alternately with deionized water and absolute ethanol 3 - 5 times. The washed precipitate was dried at 50 - 60 °C for 6 - 10 h to obtain silane - modified zinc oxide.

4. The antibacterial and breathable yarn according to claim 3, wherein The preparation method of the chitosan cinnamaldehyde Schiff base is as follows: By weight, 10.0 - 15.0 parts of chitosan are dissolved in 100 - 120 parts of 1 wt.% acetic acid solution to obtain a chitosan solution. Separately, 7.0 - 10.0 parts of cinnamaldehyde are dissolved in 300 - 400 parts of absolute ethanol to obtain a cinnamaldehyde solution. Then, the cinnamaldehyde solution is added drop - by - drop to the chitosan solution. After the addition, the mixed solution is placed in an oil bath at 40 - 50 °C and stirred at a stirring rate of 350 - 400 rpm for 300 - 360 min. After stirring, 5 wt.% sodium hydroxide solution is slowly added drop - by - drop to the solution to adjust the pH of the solution to 10 until flocculent precipitates are formed in the solution. Then, the mixed solution is filtered and the precipitate is retained. The obtained precipitate is washed alternately with absolute ethanol and deionized water 3 times. Then, the precipitate is transferred to a vacuum drying oven and dried at 50 - 60 °C for 200 - 240 min. The dried product is ground to a particle size of 200 mesh to obtain the yellow - powder - shaped chitosan cinnamaldehyde Schiff base.

5. The antibacterial and breathable yarn according to claim 1, characterized in that, The preparation method of the polyester fiber is as follows: Polyethylene terephthalate chips, antioxidant 1010, and POE elastomer are added to a high - speed mixer and mixed at 300 - 500 rpm for 5 - 10 min at room temperature to obtain a uniformly dispersed raw material. Then, the uniformly dispersed filler is added to a twin - screw co - mixing extruder and melt - blended at 250 - 280 °C for 30 - 45 min at a melt - blending rate of 300 - 500 rpm. During the co - blending process, modified chitosan zinc oxide and polyether - modified silicone oil are gradually added thereto. Then, fiber masterbatch is obtained by extrusion. Then, the fiber masterbatch is added to a melt - spinning device and spun at 260 - 280 °C to form polyester fiber.

6. The antibacterial and breathable yarn according to claim 3, wherein, The preparation method of the nanorod - shaped zinc oxide particles is as follows: By weight, 0.5 - 1.0 part of zinc nitrate and 0.5 - 1.0 part of urea are dissolved in 100 - 200 parts of deionized water and stirred at a stirring rate of 300 - 500 rpm for 10 - 20 min to form a mixed solution. The mixed solution is transferred to a hydrothermal reaction kettle, sealed, and reacted at 90 - 95 °C for 240 - 360 min. After the reaction is completed, it is naturally cooled to room temperature. The reaction solution is filtered and the solid powder is retained. The solid powder is washed with deionized water 3 - 5 times, with each washing time being 5 - 10 min. The washed solid powder is placed in a vacuum drying oven at 50 - 60 °C and dried for 6 - 10 h to obtain nanorod - shaped zinc oxide particles.

7. The antibacterial and breathable yarn according to claim 6, characterized in that, The average diameter of the nanorod-shaped zinc oxide particles is 50-100 nm, and the average length is 500-1000 nm.

8. The antibacterial and breathable yarn according to claim 1, characterized in that, The preparation method of the antibacterial breathable yarn is as follows: Polyester fiber, nylon fiber, cotton fiber and elastic fiber are spun by air-jet spinning. The spinning tension is set to 8-15 cN, the twist is 300-500 turns / m, and the spinning speed is 100-200 m / min. The spun yarn is subjected to draft treatment, and the draft ratio is controlled at 1.

2. Then, twisting is carried out, and the twist coefficient is controlled at 3.5-4.

5. The yarn is wound into a bobbin, and the winding tension is controlled at 5-10 cN, thereby preparing the antibacterial breathable yarn. The elastic fiber is Lycra fiber or Spandex fiber.

9. An antibacterial and breathable sock, characterized in that The antibacterial breathable socks are woven with the antibacterial breathable yarn according to any one of claims 1-8. The preparation method of the antibacterial breathable socks is as follows: Using the antibacterial breathable yarn, according to the design requirements of sock weaving, the socks are knitted and formed by a knitting machine. The stitch density of the knitting machine is 12-18 stitches per inch, the weaving tension is 5-15 cN, and the weaving speed is 20-40 rpm. The knitting density is adjusted according to the functional requirements of different parts of the socks. The knitting density of the sock bottom part is appropriately reduced to 150-180 stitches per square inch to enhance breathability, while the knitting density of the sock mouth part is appropriately increased to 200-240 stitches per square inch to improve elasticity and fit. After knitting and forming, the socks are seamed. The seaming process adopts the chain stitch method, and the sewing thread tension is controlled at 4-8 cN. Then, the socks are shaped, and the shaping temperature is 80-100 °C, and the shaping time is 3-8 min. The shaped socks are heat-set, and the heat-setting temperature is 120-150 °C, and the setting time is 5-15 min. Finally, the antibacterial breathable socks are prepared.

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