Antibacterial textile yarn and preparation method thereof

Abstract

The invention relates to the technical field of textiles, in particular to an antibacterial textile yarn and a preparation method thereof, and the antibacterial textile yarn is formed by blending nano copper ion modified polyester fibers, anti-yellowing regenerated cellulose fibers, electrostatic spinning nanofibers and cepharanthine-nano zinc oxide composite antibacterial fibers. Wherein the nano-copper ion modified polyester fiber is impregnated and modified through a copper ion solution, the anti-yellowing regenerated cellulose fiber is crosslinked with beta-cyclodextrin through an anti-yellowing finishing agent to load copper sulfate, and the electrostatic spinning nano-fiber is combined with ZnO / SiO2 nano-particles and a halamine-GO composite material. The cepharanthine-nano zinc oxide composite antibacterial fiber is integrated with natural antibacterial components and inorganic nano particles through electrostatic spinning. The preparation method comprises independent preparation of each functional fiber and a four-component blending process, synergistic antibiosis among the fibers is realized by controlling the copper ion loading capacity, cross-linking reaction and electrostatic spinning parameters, and the preparation method has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the field of textile technology, and particularly to an antibacterial textile yarn and a preparation method thereof. Background Art

[0002] In modern life, textiles are extremely closely related to people's daily life. They are everywhere, from the clothes worn next to the skin, bedding, to the sofa covers and curtains used in public places. However, these textiles are extremely likely to become a breeding ground for microorganisms such as bacteria and germs. When microorganisms multiply in large numbers on textiles, not only will the textiles produce unpleasant odors, seriously affecting the use experience, but also may pose a direct threat to human health. For example, in a hospital environment, the bacteria and viruses on textiles may cause cross-infection, prolong the recovery time of patients, and even endanger lives. In daily life, wearing contaminated clothes may also cause skin allergies, respiratory infections and other diseases, bringing many inconveniences and troubles to people's lives.

[0003] At present, there are various preparation technologies for antibacterial textiles, but each method has certain limitations. For example, in the existing technology, antibacterial materials are mainly loaded on the surface of textiles through physical or chemical means, such as common surface coating, graft modification and other methods. Although this method can endow textiles with antibacterial properties to a certain extent, there are many problems that cannot be ignored. On the one hand, the amount of antibacterial agent used is often large, which not only increases the production cost, but also may lead to excessive release of the antibacterial agent during use, causing potential harm to the environment and human health. On the other hand, after multiple washes or long-term use, the antibacterial agent is likely to fall off, resulting in a significant decline in the antibacterial effect, unable to meet people's demand for long-lasting antibacterial properties of textiles. Moreover, some chemical reagents used in the process may have a negative impact on the physical strength and feel of textiles, reducing the quality and comfort of textiles.

[0004] The fibrillation method is another common preparation technology for antibacterial textiles. It is to incorporate natural antibacterial fibers into textiles or add antibacterial materials during the preparation process of chemical fibers. Although this method solves the problem of easy shedding of antibacterial components to a certain extent, and the consumption of chemical reagents is relatively small, which is convenient for secondary processing, it also has obvious deficiencies. For example, this method has extremely strict requirements for the selection of antibacterial materials, and the types of available antibacterial materials are limited, which greatly restricts its application scope. At the same time, the preparation process is relatively complex, requiring precise control of multiple links, increasing the production difficulty and cost. In addition, the phenomenon of embedding antibacterial components inside the fibers is relatively common, which will seriously affect the contact between antibacterial components and external microorganisms, thereby reducing the antibacterial efficiency and making it difficult to achieve efficient antibacterial protection.

[0005] From the perspective of antibacterial agents, different types of antibacterial agents also have their own defects. Among inorganic antibacterial agents, silver antibacterial agents, although having the characteristics of broad-spectrum and high-efficiency antibacterial, and being non-toxic and low-allergy, have high production costs, which greatly limits their large-scale application. At the same time, silver antibacterial agents have certain cytotoxicity, and long-term use will cause their antibacterial effect to gradually weaken. Moreover, organic antibacterial agents have relatively high toxicity and poor heat resistance, and are easily decomposed and inactivated in high-temperature environments, which also limits their application in some special environments.

[0006] In summary, the existing antibacterial textile preparation technologies have obvious deficiencies in aspects such as the durability of antibacterial effect, the diversity of antibacterial types, and the maintenance of the original performance of fabrics, and cannot meet the needs of people for high-quality antibacterial textiles.

[0007] Therefore, according to the relevant technologies described above, it is urgent to develop an antibacterial textile yarn and its preparation method. Summary of the Invention

[0008] In view of this, the purpose of the present invention is to provide an antibacterial textile yarn and its preparation method, which has high-efficiency and long-lasting antibacterial properties against a variety of bacteria and viruses, and at the same time maintains good air permeability, mechanical properties and color stability.

[0009] Based on the above purpose, the present invention provides an antibacterial textile yarn and its preparation method.

[0010] An antibacterial textile yarn, the antibacterial textile yarn comprises the following components: nano-copper ion modified polyester fiber, anti-yellowing regenerated cellulose fiber, electrospun nanofiber, cepharanthine-nano-zinc oxide composite antibacterial fiber.

[0011] Preferably, the preparation process of the nano-copper ion modified polyester fiber is as follows:

[0012] Put polyacrylonitrile fibers into a copper ion solution. Keep the solution temperature at 70 °C by heating and stirring. The stirring speed is 250 r / min, and the reaction lasts for 2.5 h. After the reaction, take out the fibers, rinse them repeatedly with deionized water, and then dry them to a constant weight in an oven at 70 °C to make nano-copper ion modified polyester fibers. Control the copper ion content to be 39298.2 mg / kg. Copper ions have excellent antibacterial properties. They can bind to biological macromolecules such as proteins and nucleic acids of bacteria, destroy the cell structure and physiological functions of bacteria, and thus achieve the purpose of inhibiting and killing bacteria. The amount of copper ions in the fibers directly affects their antibacterial ability. Only by controlling the copper ion content within a suitable range can the fibers have efficient and lasting antibacterial effects on a variety of bacteria and viruses. If the copper ion content is too low, it may not be able to effectively inhibit the growth and reproduction of microorganisms; while if the content is too high, it will not only increase the cost but also may have an adverse impact on other properties of the fibers. For example, too many copper ions may reduce the strength of the fibers and make the flexibility worse, affecting the spinnability and subsequent processing performance of the fibers.

[0013] The copper ion solution is prepared by dissolving copper sulfate in deionized water, and the copper ion concentration in the copper ion solution is 0.8 mol / L.

[0014] Preferably, the preparation process of the anti-yellowing regenerated cellulose fiber is as follows:

[0015] Step A1. Preparation of the anti-yellowing finishing agent: Mix 2,6-di-tert-butyl-p-cresol and triphenyl phosphite, add ethanol, and stir evenly to obtain the anti-yellowing finishing agent;

[0016] Step A2. Fiber modification treatment: Immerse the regenerated cellulose yarn in the anti-yellowing finishing agent for 45 min, and then dry it at 90 °C to obtain the modified yarn;

[0017] Step A3. β-cyclodextrin crosslinking treatment: Prepare a β-cyclodextrin solution with a β-cyclodextrin concentration of 1.5 wt%, and add epichlorohydrin with a dosage of 8% of the mass of β-cyclodextrin. Immerse the modified yarn in the β-cyclodextrin solution for 1.5 h, and then rinse it with deionized water;

[0018] Step A4. Loading copper sulfate antibacterial agent: Prepare a copper sulfate solution with a copper sulfate concentration of 0.3 mol / L. Immerse the crosslinked yarn in the copper sulfate solution for 1.5 h, and then rinse it with deionized water to obtain the anti-yellowing regenerated cellulose fiber.

[0019] Preferably, the dosage ratio of 2,6-di-tert-butyl-p-cresol, triphenyl phosphite and ethanol in Step A1 is 10 g:15 g:125 mL.

[0020] Preferably, the regenerated cellulose yarn in step A2 is natural cellulose, and the natural cellulose is any one of cotton linter, wood, bamboo, and reed. As a base material, after being modified by an anti-yellowing finishing agent, the anti-yellowing performance of the regenerated cellulose yarn is significantly improved. At the same time, it can also be blended with other fibers (such as nano-copper ion modified polyester fiber, electrospun nanofiber, etc.), so that the final antibacterial textile yarn can maintain good hygroscopicity, softness and other properties on the basis of having antibacterial properties, and improve the comprehensive quality of textiles.

[0021] Preferably, the preparation process of the electrospun nanofiber is as follows:

[0022] Step B1. Preparation of ZnO / SiO2 / PU nanofiber: Mix ZnO nanoparticles and SiO2 nanoparticles according to a mass ratio of 1:1.5, add them to DMF solvent, and ultrasonically disperse for 1.5 h. Then add polyurethane to the above solution, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 h. Load the spinning solution into a syringe, and use an electrospinning device for electrospinning. The electrospinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h to obtain ZnO / SiO2 / PU nanofiber;

[0023] Step B2. Preparation of haloamine-GO composite material: Disperse graphene oxide in deionized water and ultrasonically treat for 1.5 h. Then add polyethyleneimine, and the mass ratio of polyethyleneimine to graphene oxide is 1:1.5. Stir and react for 18 h. Then, add 3-chloro-1,2-propanediol, and the mass ratio of 3-chloro-1,2-propanediol to graphene oxide is 1:1.5. React at pH = 9 for 18 h. Centrifuge and separate the composite material, wash it 3 times with deionized water, and then dry it to constant weight in an oven at 70 °C to obtain the haloamine-GO composite material;

[0024] Step B3. Mixing of electrospun nanofibers: Mix ZnO / SiO2 / PU nanofibers and haloamine-GO composite materials according to a mass ratio of 1:1.5, add DMF solvent, control the solid content ratio in the solution to be 10%-20%, ultrasonically disperse for 1.5 h, then load the mixed solution into a syringe, and use an electrospinning device for electrospinning. The electrospinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h to obtain electrospun nanofibers.

[0025] Preferably, the preparation process of the cepharanthine-nano zinc oxide composite antibacterial fiber is as follows:

[0026] Cepharanthine, nano-zinc oxide, and rare earth composite antibacterial materials are mixed in a mass ratio of 1:1:1.5 and added to DMAc solvent, followed by ultrasonic dispersion for 1.5 h. Then, polyurethane is added, with a mass fraction of 15%, and stirred to dissolve for 18 h. The spinning solution is loaded into a syringe and electrospun using an electrospinning device. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h.

[0027] Preferably, the particle size of the nano-zinc oxide is 20 - 80 nm.

[0028] The rare earth antibacterial composite material is any one of cerium nitrate, lanthanum, and gadolinium.

[0029] A method for preparing an antibacterial textile yarn includes the following steps:

[0030] The nano-copper ion modified polyester fiber, anti-yellowing regenerated cellulose fiber, electrospun nanofiber, and cepharanthine-nano-zinc oxide composite antibacterial fiber are blended in a ratio of 40%, 30%, 15%, and 15% to obtain the antibacterial textile yarn.

[0031] Advantages of the present invention:

[0032] The present invention provides an antibacterial textile yarn and its preparation method, which breaks through the single antibacterial mechanism and durability bottleneck of traditional antibacterial textiles. Through multi-component synergy and structural design, it realizes efficient, durable, and safe antibacterial performance, and also has additional functions such as anti-yellowing and far-infrared, showing broad application prospects:

[0033] The present invention integrates multiple antibacterial components such as nano-copper ions, haloamine compounds, cepharanthine, and ZnO / SiO2 nanoparticles to form a synergistic antibacterial effect, which is significantly superior to textiles finished with traditional single antibacterial agents. Among them, copper ions achieve rapid sterilization by destroying the bacterial cell membrane and DNA structure, the haloamine-GO composite material continuously inactivates viruses by releasing active chlorine (N-Cl bond), and nano-zinc oxide damages bacteria through reactive oxygen species (ROS). The multi-mechanism synergy ensures efficient antibacterial;

[0034] The nano-copper ions are bonded to the fiber molecules through covalent bonds. The β-cyclodextrin cross-linking and electrospun nanofiber wrapping technologies reduce the loss of antibacterial components. The antibacterial rate still remains above 95% after 50 washes. Moreover, the haloamine compound can also restore the active chlorine content through chlorination regeneration, realizing the recycling of antibacterial performance and extending the service life;

[0035] The anti-yellowing regenerated cellulose fiber is finished by compounding a phenolic oxidant and a phosphite ester, effectively inhibiting yellowing caused by high temperature and light, and solving the common color stability problem of copper ion antibacterial agents; ZnO / SiO2 nanoparticles endow the yarn with far-infrared emission performance (emissivity in the 8-15μm band is 0.896), promoting blood circulation and expanding the application scenarios of medical and health care; using natural polymers (chitosan, β-cyclodextrin) and renewable materials (regenerated cellulose) to avoid the cytotoxicity and environmental risks of traditional antibacterial agents (such as silver ions), and controlling the copper ion content within the safety threshold (≤6mg / g), meeting the food contact grade standard; the electrospinning process reduces solvent consumption, and environmentally friendly catalysts (citric acid, epichlorohydrin) are used in the cross-linking reaction, with low pollution in the production process.

[0036] The blending process adopted in the present invention optimizes the bonding force between fibers, enabling the yarn to maintain flexibility and weavability comparable to those of pure cotton yarns, and is suitable for various weaving methods such as weaving and knitting. Specific embodiments

[0037] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments.

[0038] Example 1: A method for preparing an antibacterial textile yarn, comprising the following steps:

[0039] S1. Put polyacrylonitrile fibers into a copper ion solution, keep the solution temperature at 70°C by heating and stirring, with a stirring speed of 250r / min, and continuously react for 2.5h. After the reaction, take out the fibers, rinse them repeatedly with deionized water, and then dry them to constant weight in an oven at 70°C to make nano-copper ion modified polyester fibers. Control the copper ion content to be 39298.2mg / kg. Copper ions have excellent antibacterial properties and can bind to biological macromolecules such as proteins and nucleic acids of bacteria, destroying the cell structure and physiological functions of bacteria, thereby achieving the purpose of inhibiting and killing bacteria. The amount of copper ions in the fiber directly affects its antibacterial ability. Only by controlling the copper ion content within a suitable range can the fiber have efficient and lasting antibacterial effects on various bacteria and viruses. If the copper ion content is too low, it may not be able to effectively inhibit the growth and reproduction of microorganisms; while too high a content will not only increase costs, but may also have an adverse impact on other properties of the fiber. For example, excessive copper ions may reduce the strength and flexibility of the fiber, affecting the spinnability and subsequent processing performance of the fiber. The copper ion solution is prepared by dissolving copper sulfate in deionized water, and the copper ion concentration in the copper ion solution is 0.8mol / L;

[0040] S2. Preparation of anti-yellowing finishing agent: Mix 2,6-di-tert-butyl-p-cresol and triphenyl phosphite, add ethanol, and stir evenly to obtain the anti-yellowing finishing agent. Immerse the cotton linter regenerated cellulose yarn in the anti-yellowing finishing agent for 45 min, and then dry it at 90 °C to obtain the modified yarn. The dosage ratio of 2,6-di-tert-butyl-p-cresol, triphenyl phosphite and ethanol is 10 g: 15 g: 125 mL;

[0041] S3. β-cyclodextrin cross-linking treatment: Prepare a β-cyclodextrin solution with a β-cyclodextrin concentration of 1.5 wt%, and add epichlorohydrin. The dosage of epichlorohydrin is 8% of the mass of β-cyclodextrin. Immerse the modified yarn in the β-cyclodextrin solution for 1.5 h, then rinse it with deionized water. Load copper sulfate antibacterial agent: Prepare a copper sulfate solution with a copper sulfate concentration of 0.3 mol / L. Immerse the cross-linked yarn in the copper sulfate solution for 1.5 h, and then rinse it with deionized water to obtain anti-yellowing regenerated cellulose fibers. As a basic material, the regenerated cellulose yarn has significantly improved anti-yellowing performance after being modified with the anti-yellowing finishing agent. At the same time, it can also be blended with other fibers (such as nano-copper ion modified polyester fibers, electrospun nanofibers, etc.), so that the final antibacterial textile yarn can maintain good hygroscopicity, softness and other properties while having antibacterial properties, improving the comprehensive quality of textiles;

[0042] S4. Preparation of ZnO / SiO2 / PU nanofibers: Mix ZnO nanoparticles and SiO2 nanoparticles according to a mass ratio of 1:1.5, add them to the DMF solvent, and ultrasonically disperse for 1.5 h. Then add polyurethane to the above solution, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 h. Load the spinning solution into a syringe and use an electrospinning device for electrospinning. The electrospinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding rate is 0.8 mL / h to obtain ZnO / SiO2 / PU nanofibers. Preparation of haloamine-GO composite: Disperse graphene oxide in deionized water and ultrasonically treat for 1.5 h. Then add polyethyleneimine, and the mass ratio of polyethyleneimine to graphene oxide is 1:1.5. Stir and react for 18 h. Then, add 3-chloro-1,2-propanediol, and the mass ratio of 3-chloro-1,2-propanediol to graphene oxide is 1:1.5. React at pH = 9 for 18 h. Centrifuge and separate the composite material, wash it 3 times with deionized water, and then dry it to constant weight in an oven at 70 °C to obtain the haloamine-GO composite;

[0043] S5. Mixing of electrospun nanofibers: Mix ZnO / SiO2 / PU nanofibers and haloamine-GO composite materials according to a mass ratio of 1:1.5, add DMF solvent, control the proportion of solid components in the solution to be 10%-20%, ultrasonically disperse for 1.5 h, then load the mixed solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the advancing speed is 0.8 mL / h to obtain electrospun nanofibers;

[0044] S6. Mix cepharanthine, nano-zinc oxide, and cerium nitrate according to a mass ratio of 1:1:1.5, add them to DMAc solvent, ultrasonically disperse for 1.5 h, then add polyurethane, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 h, load the spinning solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the advancing speed is 0.8 mL / h. The particle size of nano-zinc oxide is 20-80 nm to obtain cepharanthine-nano-zinc oxide composite antibacterial fibers;

[0045] S7. Blending nano-copper ion modified polyester fibers, anti-yellowing regenerated cellulose fibers, electrospun nanofibers, and cepharanthine-nano-zinc oxide composite antibacterial fibers in a ratio of 40%, 30%, 15%, and 15% to obtain antibacterial textile yarns.

[0046] Example 2: A method for preparing antibacterial textile yarns, comprising the following steps:

[0047] S1. Put polyacrylonitrile fibers into a copper ion solution, keep the solution temperature at 70 °C by heating and stirring, the stirring speed is 250 r / min, and react for 2.5 h. After the reaction, take out the fibers, rinse them repeatedly with deionized water, and then dry them to constant weight in an oven at 70 °C to make nano-copper ion modified polyester fibers. Control the copper ion content to be 39298.2 mg / kg. Copper ions have excellent antibacterial properties and can bind to biological macromolecules such as proteins and nucleic acids of bacteria, destroying the cell structure and physiological functions of bacteria, thereby achieving the purpose of inhibiting and killing bacteria. The amount of copper ions in the fibers directly affects their antibacterial ability. Only by controlling the copper ion content within a suitable range can the fibers have efficient and lasting antibacterial effects on a variety of bacteria and viruses. If the copper ion content is too low, it may not be able to effectively inhibit the growth and reproduction of microorganisms; while too high content will not only increase costs but also may have adverse effects on other properties of the fibers. For example, too many copper ions may reduce the strength and flexibility of the fibers, affecting the spinnability and subsequent processing performance of the fibers. The copper ion solution is prepared by dissolving copper sulfate in deionized water, and the copper ion concentration in the copper ion solution is 0.8 mol / L;

[0048] S2. Preparation of anti-yellowing finishing agent: Mix 2,6-di-tert-butyl-p-cresol and triphenyl phosphite, add ethanol, and stir evenly to obtain the anti-yellowing finishing agent. Immerse the wood regenerated cellulose yarn in the anti-yellowing finishing agent for 45 minutes, and then dry it at 90 °C to obtain the modified yarn. The dosage ratio of 2,6-di-tert-butyl-p-cresol, triphenyl phosphite and ethanol is 10 g: 15 g: 125 mL;

[0049] S3. β-cyclodextrin cross-linking treatment: Prepare a β-cyclodextrin solution with a β-cyclodextrin concentration of 1.5 wt%, and add epichlorohydrin with a dosage of 8% of the mass of β-cyclodextrin. Immerse the modified yarn in the β-cyclodextrin solution for 1.5 hours, and then rinse it with deionized water. Load copper sulfate antibacterial agent: Prepare a copper sulfate solution with a copper sulfate concentration of 0.3 mol / L. Immerse the cross-linked yarn in the copper sulfate solution for 1.5 hours, and then rinse it with deionized water to obtain anti-yellowing regenerated cellulose fibers. As a basic material, the regenerated cellulose yarn has significantly improved anti-yellowing performance after being modified with the anti-yellowing finishing agent. At the same time, it can also be blended with other fibers (such as nano-copper ion modified polyester fibers, electrospun nanofibers, etc.), so that the final antibacterial textile yarn can maintain good moisture absorption, softness and other properties on the basis of antibacterial performance, improving the comprehensive quality of textiles;

[0050] S4. Preparation of ZnO / SiO2 / PU nanofibers: Mix ZnO nanoparticles and SiO2 nanoparticles according to a mass ratio of 1:1.5, add them to DMF solvent, and ultrasonically disperse for 1.5 hours. Then add polyurethane with a mass fraction of 15% to the above solution, stir and dissolve for 18 hours. Load the spinning solution into a syringe and use an electrospinning device for electrospinning. The electrospinning voltage is 20 kV, the receiving distance is 15 cm, and the pushing speed is 0.8 mL / h to obtain ZnO / SiO2 / PU nanofibers. Preparation of haloamine-GO composite: Disperse graphene oxide in deionized water and ultrasonically treat for 1.5 hours. Then add polyethyleneimine with a mass ratio of polyethyleneimine to graphene oxide of 1:1.5, and stir and react for 18 hours. Then, add 3-chloro-1,2-propanediol with a mass ratio of 3-chloro-1,2-propanediol to graphene oxide of 1:1.5, and react at pH = 9 for 18 hours. Centrifuge and separate the composite material, wash it 3 times with deionized water, and then dry it in an oven at 70 °C to constant weight to obtain the haloamine-GO composite;

[0051] S5. Mixing of electrospun nanofibers: Mix ZnO / SiO2 / PU nanofibers and haloamine-GO composite materials in a mass ratio of 1:1.5, add DMF solvent, control the solid content ratio in the solution to be 10%-20%, ultrasonically disperse for 1.5 h, then load the mixed solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the advancing speed is 0.8 mL / h to obtain electrospun nanofibers;

[0052] S6. Mix cepharanthine, nano-zinc oxide, and lanthanum in a mass ratio of 1:1:1.5, add them to DMAc solvent, ultrasonically disperse for 1.5 h, then add polyurethane, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 h, load the spinning solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the advancing speed is 0.8 mL / h. The particle size of nano-zinc oxide is 20-80 nm to obtain cepharanthine-nano-zinc oxide composite antibacterial fibers;

[0053] S7. Blend nano-copper ion modified polyester fibers, anti-yellowing regenerated cellulose fibers, electrospun nanofibers, and cepharanthine-nano-zinc oxide composite antibacterial fibers in a ratio of 40%, 30%, 15%, and 15% to obtain antibacterial textile yarns.

[0054] Example 3: A method for preparing antibacterial textile yarns, comprising the following steps:

[0055] S1. Put polyacrylonitrile fibers into a copper ion solution, keep the solution temperature at 70 °C by heating and stirring, the stirring speed is 250 r / min, and react for 2.5 h. After the reaction, take out the fibers, rinse them repeatedly with deionized water, and then dry them to constant weight in an oven at 70 °C to make nano-copper ion modified polyester fibers. Control the copper ion content to be 39298.2 mg / kg. Copper ions have excellent antibacterial properties and can bind to biological macromolecules such as proteins and nucleic acids of bacteria to destroy the cell structure and physiological functions of bacteria, thereby achieving the purpose of inhibiting and killing bacteria. The amount of copper ions in the fibers directly affects their antibacterial ability. Only by controlling the copper ion content within a suitable range can the fibers have efficient and lasting antibacterial effects on a variety of bacteria and viruses. If the copper ion content is too low, it may not be able to effectively inhibit the growth and reproduction of microorganisms; while too high a content will not only increase costs but also may have adverse effects on other properties of the fibers. For example, too many copper ions may reduce the strength and flexibility of the fibers, affecting the spinnability and subsequent processing performance of the fibers. The copper ion solution is prepared by dissolving copper sulfate in deionized water, and the copper ion concentration in the copper ion solution is 0.8 mol / L;

[0056] S2. Preparation of anti-yellowing finishing agent: Mix 2,6-di-tert-butyl-p-cresol and triphenyl phosphite, add ethanol, and stir evenly to obtain the anti-yellowing finishing agent. Immerse the regenerated cellulose yarn of bamboo in the anti-yellowing finishing agent for 45 minutes, and then dry it at 90 °C to obtain the modified yarn. The dosage ratio of 2,6-di-tert-butyl-p-cresol, triphenyl phosphite and ethanol is 10 g: 15 g: 125 mL;

[0057] S3. β-cyclodextrin cross-linking treatment: Prepare a β-cyclodextrin solution with a concentration of 1.5 wt% of β-cyclodextrin, and add epichlorohydrin. The dosage of epichlorohydrin is 8% of the mass of β-cyclodextrin. Immerse the modified yarn in the β-cyclodextrin solution for 1.5 hours, then rinse it with deionized water. Load copper sulfate antibacterial agent: Prepare a copper sulfate solution with a concentration of 0.3 mol / L. Immerse the cross-linked yarn in the copper sulfate solution for 1.5 hours, and then rinse it with deionized water to obtain anti-yellowing regenerated cellulose fibers. As a basic material, the regenerated cellulose yarn has significantly improved anti-yellowing performance after being modified by the anti-yellowing finishing agent. At the same time, it can also be blended with other fibers (such as nano-copper ion modified polyester fibers, electrospun nanofibers, etc.), so that the final antibacterial textile yarn can maintain good moisture absorption, softness and other properties on the basis of antibacterial performance, and improve the comprehensive quality of textiles;

[0058] S4. Preparation of ZnO / SiO2 / PU nanofibers: Mix ZnO nanoparticles and SiO2 nanoparticles according to a mass ratio of 1:1.5, add them to DMF solvent, and ultrasonically disperse for 1.5 hours. Then add polyurethane to the above solution, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 hours. Load the spinning solution into a syringe and use an electrospinning device for electrospinning. The electrospinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h to obtain ZnO / SiO2 / PU nanofibers. Preparation of haloamine-GO composite: Disperse graphene oxide in deionized water and ultrasonically treat for 1.5 hours. Then add polyethyleneimine, and the mass ratio of polyethyleneimine to graphene oxide is 1:1.5. Stir and react for 18 hours. Then, add 3-chloro-1,2-propanediol, and the mass ratio of 3-chloro-1,2-propanediol to graphene oxide is 1:1.5. React at pH = 9 for 18 hours. Centrifuge and separate the composite material, wash it 3 times with deionized water, and then dry it in an oven at 70 °C to constant weight to obtain the haloamine-GO composite;

[0059] S5. Mixing of electrospun nanofibers: Mix ZnO / SiO2 / PU nanofibers and haloamine-GO composite materials according to a mass ratio of 1:1.5, add DMF solvent, control the proportion of solid components in the solution to be 10%-20%, ultrasonically disperse for 1.5 h, then put the mixed solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h to obtain electrospun nanofibers;

[0060] S6. Mix cepharanthine, nano-zinc oxide, and gadolinium according to a mass ratio of 1:1:1.5, add them to DMAc solvent, ultrasonically disperse for 1.5 h, then add polyurethane, and the mass fraction of polyurethane is 15%. Stir and dissolve for 18 h, put the spinning solution into a syringe, and use an electrospinning device for spinning. The spinning voltage is 20 kV, the receiving distance is 15 cm, and the feeding speed is 0.8 mL / h. The particle size of nano-zinc oxide is 20-80 nm to obtain cepharanthine-nano-zinc oxide composite antibacterial fibers;

[0061] S7. Blending nano-copper ion modified polyester fibers, anti-yellowing regenerated cellulose fibers, electrospun nanofibers, and cepharanthine-nano-zinc oxide composite antibacterial fibers in a ratio of 40%, 30%, 15%, and 15% to obtain antibacterial textile yarns.

[0062] Comparative Example 1:

[0063] Compared with Example 1, in this comparative example, electrospun nanofibers were not added during the preparation of antibacterial textile yarns. The remaining three fibers were directly blended in a ratio of 40%:30%:30%, that is, 40% of nano-copper ion modified polyester fibers, 30% of anti-yellowing regenerated cellulose fibers, and 30% of cepharanthine-nano-zinc oxide composite antibacterial fibers. The remaining steps and parameters are the same. This comparative example will not be repeated here. Finally, antibacterial textile yarns were obtained.

[0064] Comparative Example 2:

[0065] The difference between this comparative example and Example 1 is that only nano-copper ion modified polyester fibers (100%) were used, and anti-yellowing regenerated cellulose fibers, electrospun nanofibers, and cepharanthine-nano-zinc oxide composite antibacterial fibers were removed. The remaining steps and parameters are the same. This comparative example will not be repeated here. Finally, antibacterial textile yarns were obtained.

[0066] Comparative Example 3:

[0067] The difference between this comparative example and Example 1 is that:

[0068] Reduce the proportion of anti-yellowing regenerated cellulose fiber from 30% to 10%, increase the proportion of nano-copper ion modified polyester fiber to 60% (i.e., 60%:10%:15%:15%), and keep the proportions of other fibers unchanged.

[0069] Comparative Example 4:

[0070] Basically the same as Example 1, the difference is that the β-cyclodextrin cross-linking treatment is omitted, and the yarn after anti-yellowing finishing is directly immersed in copper sulfate solution.

[0071] Comparative Example 5:

[0072] Basically the same as Example 1, the difference is that: nano-silver ion modified polyester fiber is used to replace nano-copper ion modified polyester fiber (proportion 40%), and the other fiber components remain unchanged.

[0073] Performance Test: The following performance tests are carried out on the samples prepared in Examples 1 - 3 and Comparative Examples 1 - 5:

[0074] I. Test Methods:

[0075] 1. Antibacterial Performance Test: Bacterial strains: Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), Candida albicans (C. albicans). Refer to GB / T20944.3 - 2008 "Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method". The inoculated bacteria concentration is 10 5 CFU / mL. After 18h of oscillation treatment, calculate the antibacterial rate according to the following formula:

[0076]

[0077] 2. Wash Fastness Test: Refer to AATCC61 - 2017 "Colorfastness to Washing: Home and Commercial Laundering". After 50 washing cycles, repeat the antibacterial performance test;

[0078] 3. Mechanical Property Test - Tensile Strength: Refer to GB / T3916 - 2013 "Determination of Breaking Strength and Elongation at Break of Single Yarns of Textiles". Use an electronic tensile testing machine with a clamping length of 50mm and a tensile speed of 50mm / min. Elongation at Break: Simultaneously record the elongation at break;

[0079] 4. Anti-Yellowing Performance Test: Refer to AATCC16 - 2018 "Colorfastness to Light: Xenon-Arc Lamp". After 100h of light aging, measure the ΔE value with a color difference meter (the smaller the ΔE, the better the anti-yellowing performance);

[0080] 5. Far-Infrared Emissivity Test: Use an infrared emissivity tester to measure the far-infrared emissivity of the sample in the 8 - 15μm band;

[0081] The results are shown in Table 1-3 below:

[0082] Table 1

[0083] Item Bacteriostasis rate (E. coli) / % Bacteriostasis rate (S. aureus) / % Bacteriostasis rate (C. albicans) / % Example 1 99.98 99.95 98.5 Example 2 99.97 99.93 98.3 Example 3 99.96 99.90 98.0 Comparative Example 1 95.2 94.8 85.0 Comparative Example 2 90.5 89.2 75.0 Comparative Example 3 99.5 99.2 95.0 Comparative Example 4 98.0 97.5 90.0 Comparative Example 5 99.90 99.80 97.0

[0084] Table 2

[0085] Item Bacteriostasis rate after washing (E. coli) / % Bacteriostasis rate after washing (S. aureus) / % Example 1 95.2 94.8 Example 2 95.0 94.5 Example 3 94.8 94.2 Comparative Example 1 80.5 78.3 Comparative Example 2 60.0 55.0 Comparative Example 3 85.0 82.0 Comparative Example 4 70.0 65.0 Comparative Example 5 75.0 72.0

[0086] Table 3

[0087]

[0088]

[0089] Data analysis:

[0090] Antibacterial performance: Examples 1-3: The antibacterial rate is >98% for all, due to the synergistic effect of nano-copper ions, haloamine-GO composite materials, and nano-zinc oxide. Multiple mechanisms destroy the bacterial cell membrane, DNA, and generate ROS, which is significantly better than a single antibacterial component (such as Comparative Example 2). Comparative Example 1: After omitting the electrospun nanofibers, the antibacterial rate decreased by about 5%-10%, indicating that the loading of electrospun nanofibers improves the dispersibility and contact area of the antibacterial component. Comparative Example 5: Using nano-silver ions to replace copper ions, the initial antibacterial rate is high but the wash resistance is poor (decreases by 25% after 50 washes), reflecting that silver ions are easily lost, while copper ions are more stable through covalent bonding.

[0091] Wash resistance: For Examples 1-3, the antibacterial rate is still >94% after 50 washes, attributed to the β-cyclodextrin crosslinking and electrospinning encapsulation techniques that reduce the loss of antibacterial components; in Comparative Example 4, after omitting the crosslinking treatment, the antibacterial rate dropped sharply to 70%, proving that the crosslinking process is crucial for durability.

[0092] Mechanical properties: The breaking strength of the examples is >16 cN / tex, comparable to that of pure cotton yarn. The blending process optimizes the cohesion between fibers; the strength of the single fiber in Comparative Example 2 is relatively low (14.0 cN / tex), indicating that multi-component blending improves the mechanical properties.

[0093] Anti-yellowing and far-infrared properties: For the examples, ΔE < 1.5, with excellent anti-yellowing performance. The phenolic antioxidants in the anti-yellowing regenerated cellulose fibers effectively inhibit yellowing; in Comparative Example 3, after reducing the proportion of anti-yellowing fibers, ΔE increased to 2.0, verifying the necessity of the anti-yellowing component. The far-infrared emissivity of the examples is >0.88, due to SiO2 / ZnO nanoparticles, which is suitable for healthcare applications; in Comparative Examples 1-5, the emissivity decreased due to component absence or proportion change.

[0094] Conclusion: Through the multi-component synergy (nano copper ions, haloamine-GO, nano zinc oxide) and structural design (β-cyclodextrin crosslinking, electrospinning) in the examples, high-efficiency antibacterial property (bacteriostatic rate > 98%), durability ( > 94% after 50 washes), good mechanical properties, and anti-yellowing / far-infrared functions are achieved. The comparative examples verify the necessity of key components (such as electrospun nanofibers, crosslinking process) and multi-component compounding. Simplification of a single component or process will lead to performance degradation.

[0095] Those of ordinary skill in the art should understand that the discussion of any above embodiments is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

[0096] The present invention aims to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. An antibacterial textile yarn, characterized in that, The antibacterial textile yarn comprises the following components: nano copper ion modified polyester fiber, anti-yellowing regenerated cellulose fiber, electrospun nanofiber, and cepharanthine-nano zinc oxide composite antibacterial fiber.

2. The antibacterial textile yarn according to claim 1, characterized in that, The nano copper ion modified polyester fiber is prepared by immersing polyacrylonitrile fiber in a copper ion solution. The copper ion solution is prepared by dissolving copper sulfate in deionized water, and the concentration of copper ions in the copper ion solution is 0.8 mol / L.

3. The antibacterial textile yarn according to claim 1, wherein The anti-yellowing regenerated cellulose fiber is obtained by subjecting regenerated cellulose yarn to anti-yellowing finishing agent, β-cyclodextrin, and copper sulfate modification in sequence.

4. The antibacterial textile yarn according to claim 1, wherein The electrospun nanofiber is prepared by electrospinning a modified polyurethane nanofiber and a haloamine composite material. The mass ratio of the modified polyurethane nanofiber to the haloamine composite material is 1:1.

5.

5. The antibacterial textile yarn according to claim 4, characterized in that, The modified polyurethane nanofiber is obtained by modifying polyurethane with ZnO nanoparticles and SiO2 nanoparticles. The haloamine composite material is prepared from graphene oxide, polyethyleneimine, and 3-chloro-1,2-propanediol.

6. The antibacterial textile yarn according to claim 1, wherein The cepharanthine-nano zinc oxide composite antibacterial fiber is prepared by electrospinning cepharanthine, nano zinc oxide, a rare earth composite antibacterial material, and polyurethane.

7. The antibacterial textile yarn according to claim 6, characterized in that, The particle size of the nano zinc oxide is 20 - 80 nm. The rare earth composite antibacterial material is obtained by mixing cerium nitrate, lanthanum, and gadolinium in a mass ratio of 1:1:1.

5.

8. The preparation method of the antibacterial textile yarn according to any one of claims 1-7, characterized in that, It includes the following steps: Mix the nano copper ion modified polyester fiber, anti-yellowing regenerated cellulose fiber, electrospun nanofiber, and cepharanthine-nano zinc oxide composite antibacterial fiber in a ratio of 40%, 30%, 15%, and 15% respectively to obtain the antibacterial textile yarn.

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