Antibacterial DTY high stretch yarn and preparation method thereof

Abstract

The invention belongs to the technical field of DTY materials, and particularly discloses an antibacterial DTY high stretch yarn and a preparation method thereof. The antibacterial DTY high stretch yarn comprises a composite core yarn, a nanoparticle reinforcing layer and a polyurethane protective layer, and the composite core yarn comprises the following raw materials: nylon 6 slices, silicon carbide powder, an antioxidant 1010, a dispersing agent, a matting agent, an elastic agent, an antistatic agent and maleic anhydride grafted POE; the nano-particle reinforcing layer is prepared from the following raw materials: porous ceramic micro powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin and ethanol; the polyurethane protective layer is prepared from the following raw materials: polyurethane resin, lignin microspheres, nano silver, epoxidized natural rubber, dibromo neopentyl glycol and methanol. The composite core wire provides basic strength and elasticity, the nano-particle reinforcing layer provides additional strength, aging resistance and antibacterial performance, and the polyurethane protective layer provides good protection performance, strength and wear resistance.

Description

Technical Field

[0001] The present application relates to the technical field of DTY materials, and particularly relates to an antibacterial DTY high elastic yarn and a preparation method thereof. Background Art

[0002] DTY (Draw Textured Yarn) high elastic yarn is a synthetic fiber processed by a false twist texturing process. Usually, it uses polyester chips (PET) as raw materials, high-speed spins polyester pre-oriented yarn (POY), and then undergoes drawing and false twisting processing. It has excellent elasticity, anti-deformation property, and durability, and is widely used in the textile, household, and industrial fields.

[0003] Using DTY high elastic yarn to prepare stockings, through knitting, shaping, and dyeing, stockings are obtained. The stockings prepared from DTY high elastic yarn have high elasticity, enabling the stockings to closely fit the leg curves, showing good shaping effects. At the same time, the high elasticity also makes the stockings not easily deformed during wearing and can maintain their original shape and size.

[0004] However, if DTY high elastic yarn is exposed to sunlight for a long time or stored and used in a harsh environment, it will cause changes in the internal structure of DTY high elastic yarn, resulting in aging, a decrease in breaking strength, and thus affecting the durability of stockings. Summary of the Invention

[0005] In order to improve the problems of aging and decreasing breaking strength of DTY high elastic yarn, the present application provides an antibacterial DTY high elastic yarn and a preparation method thereof.

[0006] The present application provides an antibacterial DTY high elastic yarn, adopting the following technical solution: An antibacterial DTY high elastic yarn, comprising a composite core yarn, a nano-particle reinforcement layer, and a polyurethane protective layer. The composite core yarn comprises the following raw materials: nylon 6 chips, silicon carbide powder, antioxidant 1010, dispersant, delustering agent, elasticizer, antistatic agent, maleic anhydride grafted POE; the nano-particle reinforcement layer comprises the following raw materials: porous ceramic micro-powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin, ethanol; the polyurethane protective layer comprises the following raw materials: polyurethane resin, lignin microspheres, nano-silver, epoxidized natural rubber, dibromoneopentyl glycol, methanol.

[0007] By adopting the above technical solution, the composite core yarn is the core part of the DTY high elastic yarn, providing basic strength and elasticity. The nano-particle reinforcement layer is the middle layer of the DTY high elastic yarn, providing additional strength, aging resistance, and antibacterial properties. The polyurethane protective layer is the outer layer of the DTY high elastic yarn, providing good protection performance, strength, and wear resistance.

[0008] In the composite core filament raw materials, nylon 6 has high strength and wear resistance, which can provide basic mechanical property support for the high-elastic filament, making the high-elastic filament not easily break under external forces such as stretching and friction, and ensuring the service life and stability of the high-elastic filament. Silicon carbide increases the hardness and rigidity of the composite core filament, helps the composite core filament dissipate heat in time, and prevents adverse effects on the performance of the high-elastic filament caused by local overheating. Antioxidant 1010 can capture and neutralize free radicals, prevent the progress of oxidation reactions, and thus extend the service life of the composite core filament. The dispersant evenly disperses the silicon carbide powder in the nylon 6 chips, keeps the particles in good separation from each other, and ensures the uniform performance of the composite core filament. The matting agent changes the gloss of the high-elastic filament, can scatter light, and makes the surface gloss of the high-elastic filament soft. After stretching, the elasticizer can make the high-elastic filament quickly return to its original shape, and the antistatic agent prevents the high-elastic filament from generating static electricity during use.

[0009] In the nano-particle reinforcement layer, the porous ceramic micro-powder has high hardness and high porosity, provides a porous structure, adsorbs on the surface of the composite core filament, plays a role of skeleton support, and increases the strength and wear resistance of the core filament. Nano-zinc oxide particles have good antibacterial properties and can be loaded in the pores of the porous ceramic micro-powder to increase the antibacterial property, strength and wear resistance of the porous ceramic micro-powder. Illite powder has good lubrication performance, fills the pores of the system, makes the distribution of each component more uniform, and improves the strength and wear resistance of the system. Polyethylene glycol and ethanol help the porous ceramic micro-powder, nano-zinc oxide particles and illite powder to be evenly dispersed, improve the uniformity and stability of the nano-particle reinforcement layer, make the nano-particle reinforcement layer evenly load on the surface of the composite core filament, and improve the aging resistance of the high-elastic filament. Phenolic resin has good adhesion performance, not only makes the nano-particles firmly adhere to the surface of the composite core filament, but also makes the porous ceramic micro-powder, nano-zinc oxide particles and illite powder adhere tightly to each other, increasing the structural stability of the nano-particle reinforcement layer.

[0010] In the polyurethane protective layer, the polyurethane resin has good wear resistance and chemical resistance, serves as the outer protection of the high-elastic filament, and improves the wear resistance and chemical resistance of the fiber. Lignin microspheres have good strength and wear resistance, adhere to the outer layer of the high-elastic filament, and provide good mechanical properties. Nano-silver provides antibacterial properties and effectively inhibits the growth of bacteria. Epoxidized natural rubber has good adhesion performance, firmly adheres nano-silver and lignin microspheres to the surface of the high-elastic filament, and improves the strength, aging resistance and wear resistance of the high-elastic filament. Dibromoneopentyl glycol provides the flame retardant property of the high-elastic filament, and methanol serves as a solvent to help other components be evenly dispersed in the fiber, improving the uniformity and stability of the high-elastic filament.

[0011] Preferably, the composite core filament comprises the following raw materials: 60-65 parts of nylon 6 chips, 20-25 parts of silicon carbide powder, 2-4 parts of antioxidant 1010, 1-2 parts of dispersant, 1-2 parts of delustering agent, 10-14 parts of elasticizer, 4-5 parts of antistatic agent, and 1-2 parts of maleic anhydride grafted POE; the nano-particle reinforcement layer comprises the following raw materials: 30-36 parts of porous ceramic micro-powder, 10-12 parts of nano-zinc oxide particles, 7-10 parts of illite powder, 5-8 parts of polyethylene glycol, 2-5 parts of phenolic resin, and 50-55 parts of ethanol; the polyurethane protective layer comprises the following raw materials: 20-24 parts of polyurethane resin, 3-5 parts of nano-silver, 12-15 parts of lignin microspheres, 3-5 parts of epoxidized natural rubber, 1-3 parts of dibromoneopentyl glycol, and 35-40 parts of methanol.

[0012] By adopting the above technical solution, the dosages of the respective raw materials in the composite core filament, the nano-particle reinforcement layer, and the polyurethane protective layer are further defined. The obtained composite core filament has good strength and elasticity, the nano-particle reinforcement layer has good mechanical properties, aging resistance, and antibacterial properties, and the polyurethane protective layer has good mechanical properties, antibacterial properties, and wear resistance.

[0013] Preferably, the preparation method of the porous ceramic micro-powder comprises the following steps: (1) Disperse the ceramic micro-powder in an aqueous starch solution, add hydroxypropyl methylcellulose and boric acid, stir at a temperature of 60-65 °C for 1-2 h, filter, dry, and calcine at a temperature of 500-530 °C to obtain porous micro-powder; (2) Disperse the modal mixed fiber in deionized water, add the porous micro-powder, polyvinyl alcohol, and silane coupling agent obtained in step (1), ultrasonicate for 0.5-1 h, heat to 120-130 °C in nitrogen for 30-35 min, and the gas flow rate is 1-2 m / s to obtain porous ceramic micro-powder.

[0014] By adopting the above technical solution, the aqueous starch solution serves as a dispersion medium. The hydroxyl groups in the starch molecules adsorb on the surface of the ceramic micro-powder, enabling the ceramic micro-powder to be uniformly dispersed in the aqueous solution, preventing the micro-powder from agglomerating, and providing a stable dispersion system for subsequent processing. Hydroxypropyl methylcellulose further increases the viscosity of the system. Hydroxypropyl methylcellulose can coat the surface of the ceramic micro-powder, enhancing the stability of the ceramic micro-powder in the solution. Boric acid acts as a flux to lower the melting point of the ceramic micro-powder and promote the formation of a porous structure. When the ceramic micro-powder is calcined at a high temperature of 500-530 °C, organic components such as starch and hydroxypropyl methylcellulose will decompose and burn, leaving pores inside and on the surface of the ceramic micro-powder, thereby obtaining porous micro-powder.

[0015] Modal blended fiber has good mechanical properties, is soft and breathable. By adding porous micropowder, polyvinyl alcohol and silane coupling agent, the modal blended fiber can be adsorbed on the surface of the porous micropowder structure, adding a fiber structure to the final porous ceramic micropowder and improving its toughness and strength. Polyvinyl alcohol acts as an adhesive to help the porous micropowder and modal fiber bind together, improving the overall strength and density of the porous micropowder. The silane coupling agent improves the binding force between the porous micropowder and the modal fiber, enhancing the compatibility and comprehensive performance of the system.

[0016] Heating in nitrogen prevents oxidation reactions from occurring during the heating process, enabling the polyvinyl alcohol to undergo appropriate cross-linking reactions, further enhancing the strength and stability of the material, making the binding between the modal fiber and the porous micropowder firmer, and enabling the silane coupling agent to better play its coupling role. The obtained porous ceramic micropowder has a large specific surface area, improving its adsorption performance, and good binding force, which helps with the binding to the composite core wire, enhancing the mechanical properties, aging resistance and flexibility of the composite core wire.

[0017] Preferably, the mass ratio of the ceramic micropowder, modal blended fiber and polyvinyl alcohol is 1:0.5 - 0.6:0.1 - 0.2.

[0018] By adopting the above technical scheme, further limiting the mass ratio of the ceramic micropowder, modal blended fiber and polyvinyl alcohol within a certain range, the obtained porous ceramic micropowder has excellent comprehensive performance. The ceramic micropowder has high strength and hardness, and when added to the high-elastic yarn, it can improve the overall strength and wear resistance of the material, making the high-elastic yarn less likely to be worn and broken during use and increasing its service life. The modal blended fiber has softness, hygroscopicity, high elasticity and breathability, and when loaded on the surface of the ceramic micropowder structure, it increases the elasticity and tensile properties of the high-elastic yarn. Polyvinyl alcohol has good adhesiveness and can effectively bond the ceramic micropowder and the modal blended fiber together, making the structure of the high-elastic yarn more stable, the binding between the components firmer, and preventing phenomena such as delamination and shedding during use. The ceramic micropowder, modal blended fiber and polyvinyl alcohol cooperate with each other to have a synergistic effect, jointly improving the mechanical properties of the porous ceramic micropowder and helping to improve the mechanical properties, aging resistance and flexibility of the high-elastic yarn.

[0019] Preferably, the preparation method of the modal blended fiber includes the following steps: crushing the modal fiber into fiber particles, then dispersing them in sodium hydroxide solution, stirring for 20 - 25 minutes, washing with water, then dispersing in water, adding metal-organic framework (MOF) nanoparticles and Triton, and ball-milling until the particle size ≤ 5 μm to obtain a mixture; Spraying an aqueous solution of acrylate emulsion on the surface of the mixture and drying to obtain the modal blended fiber.

[0020] By adopting the above technical solution, the modal fiber is crushed to increase the specific surface area of the fiber and improve its binding ability with other materials. Treatment with sodium hydroxide solution can partially dissolve the fiber surface, increase the hydrophilicity of the fiber, remove impurities on the fiber surface at the same time, and improve the surface activity of the fiber.

[0021] Metal-organic framework (MOF) nanoparticles have a high specific surface area and a porous structure, which can improve the adsorption performance and mechanical strength of the fiber. Metal-organic framework (MOF) nanoparticles can be loaded in the pores on the surface of modal fiber to improve the adsorption and mechanical properties of modal fiber. Triton reduces the surface tension of water and helps the modal fiber and metal-organic framework (MOF) nanoparticles to disperse evenly. During the ball milling process, with the help of Triton, the modal fiber and metal-organic framework (MOF) nanoparticles can be further refined and mixed evenly, so that the metal-organic framework (MOF) nanoparticles can be evenly attached to the surface of modal fiber particles, while controlling the particle size within ≤5 μm to ensure that the mixture has good uniformity and performance stability.

[0022] Spray the aqueous solution of acrylate emulsion on the ball-milled mixture to bond the modal fiber and metal-organic framework (MOF) nanoparticles together, which plays a role in strengthening and stabilizing the fiber structure. The acrylate emulsion will form a continuous polymer film after drying, providing a certain flexibility and aging resistance for the modal hybrid fiber, enhancing the mechanical properties of the modal hybrid fiber, and subsequently helping with the adsorption and adhesion to other components.

[0023] Preferably, the preparation method of the lignin microspheres includes the following steps: (1) Disperse lignin in an aqueous ethylene glycol solution, add citric acid and choline chloride, stir at a temperature of 60-65 °C for 2-3 h, and spray dry to obtain microsphere particles; (2) Disperse the microsphere particles in step (1) in a potassium hydroxide solution, add glyoxal and hexamethylenediamine, and mix evenly to obtain a lignin solution; (3) Add mesoporous silica mixed particles and xanthan gum to the lignin solution in step (2), stir at a temperature of 60-65 °C for 30-40 min, and dry to obtain lignin microspheres.

[0024] By adopting the above technical solution, ethylene glycol is used as a solvent to help lignin disperse evenly. Citric acid is used as an acidic regulator to promote the dissolution and dispersion of lignin. Choline chloride, together with citric acid, etc., reduces the glass transition temperature of lignin, promotes the fluidity of lignin molecules, and improves the solubility of lignin. Spray drying can quickly dry the liquid into fine particles to form solid microsphere particles.

[0025] Disperse the microsphere particles in a potassium hydroxide solution. The potassium hydroxide causes the functional groups on the surface of the lignin microspheres to undergo a deprotonation reaction, increasing the negative charge on the surface of the microspheres, thereby improving the dispersibility and reactivity of the microspheres in the solution. Add glyoxal and hexamethylenediamine. Glyoxal and hexamethylenediamine achieve crosslinking modification of the lignin microspheres, forming a crosslinked network structure, and further enhancing the mechanical strength and stability of the lignin microspheres.

[0026] Mesoporous silica has a high specific surface area and an ordered mesoporous structure. When added to the lignin solution, it can adsorb on the surface of the lignin microspheres, increasing the specific surface area and adsorption performance of the lignin microspheres, and improving the mechanical strength and stability of the lignin microspheres. Xanthan gum has good thickening, viscosity and stability, enabling the mesoporous silica mixed particles to better adhere to the surface of the lignin microsphere particles, enhancing the stability of the system and the performance of the lignin microspheres. The interaction between the mesoporous silica mixed particles, xanthan gum and lignin microspheres enables them to bind together better. The obtained lignin microspheres have good mechanical properties and structural stability, thereby increasing the corresponding properties of the polyurethane outer layer.

[0027] Preferably, the mass ratio of the lignin, mesoporous silica mixed particles and xanthan gum is 1:0.4 - 0.5:0.2 - 0.3.

[0028] By adopting the above technical scheme, further limiting the mass ratio of the lignin, mesoporous silica mixed particles and xanthan gum within a certain range, the obtained lignin microspheres have excellent comprehensive properties. The lignin first forms microspheres with certain strength, toughness and adsorption properties. The mesoporous silica mixed particles have high hardness, adsorption properties and loading capacity, and can adsorb on the surface of the lignin microspheres, increasing the specific surface area and structural strength of the lignin microspheres. Xanthan gum increases the viscosity of the system, making the lignin microspheres and the mesoporous silica mixed particles adhere tightly, improving the corresponding properties of the system, and subsequent application in the polyurethane outer layer can improve the strength, flexibility and elasticity of the polyurethane outer layer.

[0029] Preferably, the preparation method of the mesoporous silica mixed particles includes the following steps: Disperse tetraethyl orthosilicate in deionized water, add cetyltrimethylammonium bromide and concentrated hydrochloric acid, stir in a water bath at 85 - 90 °C for 35 - 40 min, and calcine to obtain mesoporous silica particles; Disperse the mesoporous silica particles in deionized water, add multi-walled carbon nanotubes, (3-aminopropyl) dimethylethoxysilane and sodium alginate, heat in an oil bath at 70 - 75 °C for 2 - 3 h, and dry to obtain mesoporous silica mixed particles.

[0030] By adopting the above technical solution, tetraethyl orthosilicate hydrolyzes to produce silicic acid, and the silicic acid polycondenses to form a silica network structure. Through the condensation reaction, a mesoporous structure is formed. Octadecyltrimethylsilane reacts with the hydroxyl groups on the silica surface, introducing long-chain alkyl groups onto the silica surface to adjust the size and shape of the mesopores. The pore-forming agent creates pores during the formation of mesoporous silica, occupies a certain space in the silica network structure, and is removed during subsequent processing, thus leaving pores, making the mesoporous silica have a high porosity and specific surface area, which is beneficial to processes such as adsorption and diffusion of substances.

[0031] Mix mesoporous silica particles, multi-walled carbon nanotubes, (3-aminopropyl) dimethylethoxysilane, and sodium alginate. The multi-walled carbon nanotubes have good mechanical properties and antibacterial properties, can adsorb in the pore structure of mesoporous silica particles, increase the structural strength of mesoporous silica particles, and provide additional pore structures. (3-aminopropyl) dimethylethoxysilane reacts with the hydroxyl groups on the surface of mesoporous silica, introducing amino groups onto the surface of mesoporous silica particles. These amino groups can react with sodium alginate to enhance the mutual connection and stability between particles. Sodium alginate interacts with the amino group-bearing mesoporous silica particles to form a three-dimensional network structure, wrapping the multi-walled carbon nanotubes therein, further improving the stability and mechanical properties of the mesoporous silica composite particles, and subsequently improving the corresponding properties of the lignin microspheres.

[0032] In a second aspect, the present application also provides a method for preparing antibacterial DTY high-elastic yarn, including the following steps: (1) Mix nylon 6 chips, silicon carbide powder, antioxidant 1010, dispersant, delustering agent, elasticizer, antistatic agent, maleic anhydride grafted POE, and spin to obtain a composite core yarn; (2) Nanoparticle reinforcement layer: Mix porous ceramic micro powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin, and ethanol evenly to obtain a mixed liquid A; Rub the composite core yarn so that the surface of the composite core is microporous, and then spray with the mixed liquid A to obtain a nanoparticle reinforcement layer; (3) Twist the composite core yarn coated with the nanoparticle reinforcement layer to obtain a composite DTY high-elastic yarn; (4) Mix polyurethane resin, lignin microspheres, nano-silver, epoxidized natural rubber, dibromoneopentyl glycol, and methanol evenly, spray the composite DTY high-elastic yarn, and dry to obtain antibacterial DTY high-elastic yarn.

[0033] By adopting the above technical solution and the above preparation method, the operation is simple, the process time is short, and the obtained antibacterial DTY high-elastic yarn has good mechanical properties and antibacterial properties, improving the comprehensive performance of the antibacterial DTY high-elastic yarn.

[0034] Preferably, the spinning speed is 650 - 700 m / min and the spinning temperature is 280 - 290 °C.

[0035] By adopting the above technical solutions, specific parameters of the DTY process are defined, and the high-elastic yarn obtained has excellent comprehensive properties.

[0036] In summary, the present application has the following beneficial effects: 1. In the present application, the composite core filament provides basic strength and elasticity. The nano-particle reinforcement layer is the intermediate layer of the DTY high-elastic yarn, providing additional strength, aging resistance, and antibacterial properties. The polyurethane protective layer provides good protective properties, strength, and wear resistance.

[0037] 2. In the present application, the phenolic resin has good adhesion properties, which not only enables the nano-particles to firmly adhere to the surface of the composite core filament, but also makes the porous ceramic micro-powder, nano-zinc oxide particles, and illite powder adhere tightly to each other, increasing the structural stability of the nano-particle reinforcement layer.

[0038] 3. In the present application, the epoxidized natural rubber has good adhesion properties, firmly adhering the nano-silver and lignin microspheres to the surface of the high-elastic yarn, improving the strength, aging resistance, and wear resistance of the high-elastic yarn. Detailed Embodiments

[0039] The following further elaborates on the present application with reference to embodiments.

[0040] The raw materials used in the examples and comparative examples can all be obtained commercially.

[0041] Preparation Example of Porous Ceramic Micro-Powder Preparation Example 1 - 1 The preparation method of the porous ceramic micro-powder includes the following steps: (1) Disperse 42 kg of ceramic micro-powder in 60 L of an aqueous solution of 10% corn starch by mass, add 3 kg of hydroxypropyl methylcellulose and 2 kg of boric acid, stir at 62 °C for 1.5 h, filter, dry, and calcine at 520 °C for 2 h to obtain porous micro-powder; (2) Disperse the modal mixed fiber in 100 L of deionized water, add the porous micro-powder obtained in step (1), polyvinyl alcohol, and 3 kg of silane coupling agent kh550, ultrasonicate for 0.8 h, heat to 125 °C in nitrogen for 32 min, and the gas flow rate is 1.5 m / s to obtain the porous ceramic micro-powder.

[0042] The mass ratio of the ceramic micro-powder, modal mixed fiber, and polyvinyl alcohol is 1:0.5:0.2.

[0043] Preparation method of modal hybrid fiber, comprising the following steps: Crushing 30 kg of modal fiber into fiber particles with a mesh size of 500, then dispersing them in 56 L of sodium hydroxide solution with a mass fraction of 8%, stirring for 23 min, washing with water, then dispersing in 80 L of water, adding 10 kg of metal-organic framework (MOF) nanoparticles and 2 kg of Triton X-100, and ball-milling until the particle size is ≤5 μm to obtain a mixture; Spraying 1.5 kg of acrylate emulsion aqueous solution on the surface of the mixture, drying to obtain modal hybrid fiber; dispersing 5 kg of acrylate emulsion in 30 L of water to obtain acrylate emulsion aqueous solution.

[0044] The metal-organic framework (MOF) nanoparticles are ZIF-67, purchased from Henan Chenglongyi New Material Technology Co., Ltd.

[0045] Preparation Examples 1-2 The difference from Preparation Example 1-1 is that in step (2), no modal hybrid fiber is added.

[0046] Preparation Example 1-3 The difference from Preparation Example 1-1 is that in step (2), no polyvinyl alcohol is added.

[0047] Preparation Example 1-4 The difference from Preparation Example 1-1 is that the mass ratio of ceramic micro-powder, modal hybrid fiber and polyvinyl alcohol is 1:0.6:0.1.

[0048] Preparation Example 1-5 The difference from Preparation Example 1-1 is that the mass ratio of ceramic micro-powder, modal hybrid fiber and polyvinyl alcohol is 1:0.1:0.7.

[0049] Preparation Example 1-6 The difference from Preparation Example 1-1 is that in the preparation method of modal hybrid fiber, no metal-organic framework (MOF) nanoparticles are added.

[0050] Preparation Example 1-7 The difference from Preparation Example 1-1 is that in the preparation method of modal hybrid fiber, no acrylate emulsion aqueous solution is added.

[0051] Preparation Examples of Lignin Microspheres Preparation Example 2-1 Preparation method of lignin microspheres, comprising the following steps: (1) Disperse 20 kg of lignin in 50 L of ethylene glycol aqueous solution with a mass fraction of 30%, add 1 kg of citric acid and 6 kg of choline chloride, stir at a temperature of 62 °C for 2.5 h, and spray-dry (inlet temperature 170 °C, outlet temperature 75 °C, feeding rate 10 mL / min) to obtain microsphere particles; (2) Disperse the microsphere particles in step (1) in 30 L of a potassium hydroxide solution with a mass fraction of 3%, add 7 kg of glyoxal and 5.5 kg of hexamethylenediamine, and mix at 50 °C for 2 h to obtain a lignin solution; (3) Add mesoporous silica mixed particles and xanthan gum to the lignin solution in step (2), stir at a temperature of 63 °C for 35 min, and dry to obtain lignin microspheres.

[0052] The mass ratio of lignin, mesoporous silica mixed particles, and xanthan gum is 1:0.5:0.2.

[0053] The preparation method of the mesoporous silica mixed particles includes the following steps: Disperse 12 kg of tetraethyl orthosilicate in 35 L of deionized water, add 3.5 kg of cetyltrimethylammonium bromide and 1 L of concentrated hydrochloric acid (mass fraction 36%), stir in a water bath at 86 °C for 38 min, and calcine at 550 °C for 4 h to obtain mesoporous silica particles; Disperse the mesoporous silica particles in 45 L of deionized water, add 6 kg of multi-walled carbon nanotubes, 2 kg of (3-aminopropyl) dimethylethoxysilane, and 2 kg of sodium alginate, heat in an oil bath at 74 °C for 2.8 h, and dry to obtain mesoporous silica mixed particles.

[0054] Preparation Example 2-2 The difference from Preparation Example 2-1 is that in step (3), mesoporous silica mixed particles are not added.

[0055] Preparation Example 2-3 The difference from Preparation Example 2-1 is that in step (3), xanthan gum is not added.

[0056] Preparation Example 2-4 The difference from Preparation Example 2-1 is that the mass ratio of lignin, mesoporous silica mixed particles, and xanthan gum is 1:0.4:0.3.

[0057] Preparation Example 2-5 The difference from Preparation Example 2-1 is that the mass ratio of lignin, mesoporous silica mixed particles, and xanthan gum is 1:0.08:0.85.

[0058] Preparation Example 2-6 The difference from Preparation Example 2-1 is that in the preparation method of the mesoporous silica mixed particles, multi-walled carbon nanotubes are not added.

[0059] Preparation Example 2-7 The difference from Preparation Example 2-1 is that in the preparation method of the mesoporous silica mixed particles, sodium alginate is not added. Example

[0060] Example 1 An antibacterial DTY high elastic yarn, comprising a composite core yarn, a nano-particle reinforcement layer and a polyurethane protective layer. The composite core yarn comprises the following raw materials: 65 kg of nylon 6 chips, 12 kg of silicon carbide powder, 4 kg of antioxidant 1010, 2 kg of dispersant (polyethylene glycol), 1 kg of delustering agent (titanium dioxide), 9 kg of elasticizer (polyether ester elastomer), 0.5 kg of antistatic agent (alkali copper brightener), 1 kg of maleic anhydride grafted POE; The nano-particle reinforcement layer comprises the following raw materials: 30 kg of porous ceramic micro-powder, 12 kg of nano-zinc oxide particles, 10 kg of illite powder, 8 kg of polyethylene glycol, 10 kg of phenolic resin, 55 kg of ethanol; The polyurethane protective layer comprises the following raw materials: 24 kg of polyurethane resin, 5 kg of nano-silver, 15 kg of lignin microspheres, 5 kg of epoxidized natural rubber, 3 kg of dibromoneopentyl glycol, 35 kg of methanol; The polyether ester elastomer is purchased from Hengtai Plastic Raw Material Business Department in Zhangmutou, Dongguan City, the alkali copper brightener is purchased from Jinan Zhendong Chemical Co., Ltd., the epoxidized natural rubber is purchased from Shandong Kepler Biotechnology Co., Ltd., and the polyurethane resin is purchased from Jining Fangyu Chemical Co., Ltd.

[0061] The preparation method of the above antibacterial DTY high elastic yarn comprises the following steps: (1) Mix nylon 6 chips, silicon carbide powder, antioxidant 1010, dispersant, delustering agent, elasticizer, antistatic agent, maleic anhydride grafted POE, and then carry out spinning to obtain a composite core yarn; Among them, the temperature of the double-screw extruder is controlled in sections: the feeding section is 200 °C, the mixing section is 240 °C, the head is 220 °C, and the screw speed is 300 rpm; (2) Nano-particle reinforcement layer: Mix porous ceramic micro-powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin, and ethanol evenly to obtain a mixed solution A; Rub the composite core yarn to make the surface of the composite core porous, and then spray it with the mixed solution A and dry it at 160 °C to obtain a nano-particle reinforcement layer; (3) Twist the composite core yarn coated with the nano-particle reinforcement layer (using S-Z bidirectional alternating twisting (S twist 800 twists / m → Z twist 600 twists / m)) to obtain a composite DTY high elastic yarn; (4) Mix polyurethane resin, lignin microspheres, nano-silver, epoxidized natural rubber, dibromoneopentyl glycol, and methanol evenly, spray the composite DTY high elastic yarn, and dry it at 60 °C to obtain an antibacterial DTY high elastic yarn.

[0062] The spinning speed is 680 m / min, and the spinning temperature is 285 °C.

[0063] Method for preparing lignin microspheres, comprising the following steps: Disperse 20 kg of lignin in 50 L of an aqueous ethylene glycol solution with a mass fraction of 10%, stir at a temperature of 62 °C for 2.5 h, and perform spray drying (inlet temperature 170 °C, outlet temperature 75 °C, feed rate 10 mL / min) to obtain lignin microspheres.

[0064] The porous ceramic micro-powder was purchased from Shijiazhuang Yuanjing Mineral Products Co., Ltd.

[0065] Example 2 An antibacterial DTY high-elastic yarn, different from Example 1, in terms of weight, the composite core yarn comprises the following raw materials: 60 kg of nylon 6 chips, 14 kg of silicon carbide powder, 2 kg of antioxidant 1010, 1 kg of dispersant, 2 kg of delustering agent, 7 kg of elasticizer, 0.1 kg of antistatic agent, 2 kg of maleic anhydride grafted POE; the nano-particle reinforcement layer comprises the following raw materials: 36 kg of porous ceramic micro-powder, 10 kg of nano-zinc oxide particles, 7 kg of illite powder, 5 kg of polyethylene glycol, 12 kg of phenolic resin, 50 kg of ethanol; the polyurethane protective layer comprises the following raw materials: 20 kg of polyurethane resin, 3 kg of nano-silver, 12 kg of lignin microspheres, 3 kg of epoxidized natural rubber, 1 kg of dibromoneopentyl glycol, 40 kg of methanol.

[0066] Example 3 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-1.

[0067] Example 4 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-2.

[0068] Example 5 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-3.

[0069] Example 6 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-4.

[0070] Example 7 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-5.

[0071] Example 8 An antibacterial DTY high-elastic yarn, different from Example 1, in that the lignin microspheres are prepared by Preparation Example 2-6.

[0072] Example 9 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that the lignin microspheres are prepared by Preparation Examples 2-7.

[0073] Example 10 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that the porous ceramic micropowder is prepared by Preparation Example 1-1.

[0074] Example 11 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that the porous ceramic micropowder is prepared by Preparation Example 1-2.

[0075] Example 12 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that the porous ceramic micropowder is prepared by Preparation Example 1-3.

[0076] Example 13 An antibacterial DTY high elastic yarn, which is different from that of Example 4 in that the porous ceramic micropowder is prepared by Preparation Example 1-4.

[0077] Example 14 An antibacterial DTY high elastic yarn, which is different from that of Example 4 in that the porous ceramic micropowder is prepared by Preparation Example 1-5.

[0078] Example 15 An antibacterial DTY high elastic yarn, which is different from that of Example 4 in that the porous ceramic micropowder is prepared by Preparation Example 1-6.

[0079] Example 16 An antibacterial DTY high elastic yarn, which is different from that of Example 4 in that the porous ceramic micropowder is prepared by Preparation Example 1-7.

[0080] Comparative Example Comparative Example 1 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that no porous ceramic micropowder is added.

[0081] Comparative Example 2 An antibacterial DTY high elastic yarn, which is different from that of Example 1 in that no lignin microspheres are added.

[0082] Performance Detection Test Perform performance tests on the antibacterial DTY high elastic yarns prepared in Examples 1-16 and Comparative Examples 1-2; Determine the breaking strength and breaking elongation according to GB / T14344-2022 "Test Method for Tensile Properties of Chemical Fiber Filaments"; The aging method is as follows: Place the DTY elastic yarn in an air oven at 180 °C for 6 days, and then determine the breaking strength retention rate and breaking elongation retention rate according to GB / T14344-2022; The DTY high-elastic yarn is woven into silk stockings with a mass per unit area of 60 g / m 2 , and a sample is obtained. The sample (with a size of 9*9 in) is placed in a conical flask containing 500 mL of deionized water, the stopper is tightened, and it is oscillated at 350 rpm for 8 min. 5 mL of the oscillated solution is taken and diluted to 200 mL with distilled water, filtered by suction using a mesh filter membrane, the filter membrane is dried at 45 °C, observed and counted under a microscope, and the number of fibers with a length above 60 μm is recorded.

[0083] Calculation of the fiber shedding rate: Number of fibers / cm 2 =(F t )(V b ) / (V a )(A) where: F t Total number of fibers, V b Volume of the solution used to soak the sample, V a Volume of the solution used for testing, A Area of the sample, and the result is taken to two significant figures.

[0084] The sample is taken and tested for abrasion resistance according to the method of "FZ / T 01121-2014 Textiles - Test method for abrasion resistance - Flat abrasion method". The number of frictions accumulated before the breakage of each specimen is recorded as the abrasion resistance number, and the average value of 5 specimens is calculated; the test results are shown in Table 1.

[0085] Table 1 Test data of the examples and comparative examples As can be seen from Table 1, the antibacterial DTY high-elastic yarns prepared in Examples 1-2 of the present application have good mechanical properties, mechanical stability, abrasion resistance and adhesion. Among them, the breaking strength of Example 1 is 7.52 cN / dtex, the breaking elongation is 28.65%, the retention rate of the breaking strength after aging is 88%, the retention rate of the breaking elongation is 86%, and the fiber shedding rate is 49 cm 2 , and the abrasion resistance number is 8530. It shows that the DTY high-elastic yarn prepared in the present application has good mechanical properties. The composite core yarn provides basic strength and elasticity, the nanoparticle reinforcement layer provides additional strength and antibacterial properties, and the polyurethane protective layer provides good protective properties, strength and abrasion resistance.

[0086] In Example 3, lignin microspheres were prepared. As can be seen from Table 1, the breaking strength of Example 3 is 12.35 cN / dtex, the breaking elongation is 37.54%, the retention rate of the breaking strength after aging is 94%, the retention rate of the breaking elongation is 92%, and the fiber shedding rate is 30 cm 2, the number of wear-resistant cycles is 8,900. This indicates that the lignin microspheres prepared in this application have excellent mechanical properties, wear resistance, and structural stability, thereby improving the corresponding properties of DTY high-elastic yarn.

[0087] In the preparation methods of the lignin microspheres in Examples 4-5, mesoporous silica mixed particles and xanthan gum were not added respectively. In Examples 6-7, the mass ratios of lignin, mesoporous silica mixed particles, and xanthan gum were changed. As can be seen from Table 1, the test results of the breaking strength, breaking elongation, retention rate of breaking strength after aging, retention rate of breaking elongation, chipping rate, and number of wear-resistant cycles in Examples 4-5 were significantly worse than those in Examples 3 and 6, but better than those in Examples 1-2. The test results of the corresponding properties in Example 7 were better than those in Examples 4-5 but worse than those in Example 3. This indicates that the mesoporous silica mixed particles have high hardness, adsorption capacity, and loading capacity, can be adsorbed on the surface of the lignin microspheres, increase the specific surface area and structural strength of the lignin microspheres, and xanthan gum makes the lignin microspheres and mesoporous silica mixed particles adhere tightly, improving the corresponding properties of the system. When applied to the polyurethane outer layer subsequently, it can improve the strength, flexibility, and elasticity of the polyurethane outer layer.

[0088] In the preparation methods of the mesoporous silica mixed particles in Examples 8-9, multi-walled carbon nanotubes and sodium alginate were not added respectively. As can be seen from Table 1, the test results of the breaking strength, breaking elongation, retention rate of breaking strength after aging, retention rate of breaking elongation, chipping rate, and number of wear-resistant cycles in Examples 8-9 were significantly better than those in Example 4 but worse than those in Example 3. This indicates that sodium alginate interacts with the mesoporous silica particles with amino groups to form a three-dimensional network structure, encapsulating the multi-walled carbon nanotubes therein, further improving the stability and mechanical properties of the mesoporous silica mixed particles, and subsequently improving the corresponding properties of the lignin microspheres.

[0089] In Example 10, porous ceramic micro-powder was prepared. As can be seen from Table 1, the breaking strength of Example 10 was 16.23 cN / dtex, the breaking elongation was 42.35%, the retention rate of breaking strength after aging was 99%, the retention rate of breaking elongation was 98%, and the chipping rate was 20 cm 2 . This indicates that the porous ceramic micro-powder prepared in this application has excellent mechanical properties and structural stability, thereby improving the corresponding properties of DTY high-elastic yarn.

[0090] In the preparation methods of Example 11 - 12 of porous ceramic micro - powder, modal blended fiber and polyvinyl alcohol are not added respectively. In Example 13 - 14, the mass ratios of ceramic micro - powder, modal blended fiber and polyvinyl alcohol are changed. It can be seen from Table 1 that the test results of breaking strength, elongation at break, retention rate of breaking strength after aging, retention rate of elongation at break, and chipping rate in Example 11 - 12 are significantly worse than those in Example 10 and 13, but better than those in Example 1 - 2. And the test results of the corresponding properties of Example 12 are better than those of Example 11 - 12, but worse than those of Example 10. It shows that modal blended fiber has softness, hygroscopicity, high elasticity and air permeability. Loaded on the surface of the ceramic micro - powder structure, it increases the elasticity and tensile properties of the high - elastic yarn. Polyvinyl alcohol has good adhesiveness and can effectively bond ceramic micro - powder and modal blended fiber together, making the structure of the high - elastic yarn more stable, the combination between components more firm, and preventing phenomena such as delamination and shedding during use.

[0091] In the preparation methods of Example 15 - 16 of modal blended fiber, metal - organic framework (MOF) nanoparticles and aqueous acrylate emulsion are not added respectively. It can be seen from Table 1 that the test results of breaking strength, elongation at break, retention rate of breaking strength after aging, retention rate of elongation at break, and chipping rate in Example 15 - 16 are significantly worse than those in Example 10, but better than those in Example 11. It shows that modal fiber and metal - organic framework (MOF) nanoparticles are bonded together, playing a role in strengthening and stabilizing the fiber structure. The acrylate emulsion will form a continuous polymer film after drying, providing a certain flexibility and wear resistance for the modal blended fiber, enhancing the mechanical properties of the modal blended fiber, and being helpful for the adsorption and adhesion with other components subsequently.

[0092] In Comparative Example 1 - 2, porous ceramic micro - powder and lignin micro - spheres are not added respectively. It can be seen from Table 1 that the test results of breaking strength, elongation at break, retention rate of breaking strength after aging, retention rate of elongation at break, chipping rate, and number of abrasion resistance times in Comparative Example 1 - 2 are significantly worse than those in Example 1 - 2. It shows that lignin micro - spheres have good strength and wear resistance, adhere to the outer layer of the high - elastic yarn, providing good mechanical properties and wear resistance; porous ceramic micro - powder has high hardness and high porosity, provides a porous structure, adsorbs on the surface of the composite core yarn, plays a role of skeleton support, increases the strength and adhesiveness of the core yarn, and thus improves the corresponding properties of the DTY high - elastic yarn.

[0093] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. An antibacterial DTY high elastic yarn, characterized in that, It includes a composite core filament, a nano-particle reinforcement layer, and a polyurethane protective layer. The composite core filament comprises the following raw materials: nylon 6 chips, silicon carbide powder, antioxidant 1010, dispersant, matting agent, elasticizer, antistatic agent, maleic anhydride grafted POE; the nano-particle reinforcement layer comprises the following raw materials: porous ceramic micro-powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin, ethanol; the polyurethane protective layer comprises the following raw materials: polyurethane resin, lignin microspheres, nano-silver, epoxidized natural rubber, dibromoneopentyl glycol, methanol.

2. The antibacterial DTY high elastic yarn according to claim 1, wherein The composite core filament comprises the following raw materials: 60 - 65 parts of nylon 6 chips, 12 - 14 parts of silicon carbide powder, 2 - 4 parts of antioxidant 1010, 1 - 2 parts of dispersant, 1 - 2 parts of matting agent, 7 - 9 parts of elasticizer, 0.1 - 0.5 parts of antistatic agent, 1 - 2 parts of maleic anhydride grafted POE; the nano-particle reinforcement layer comprises the following raw materials: 30 - 36 parts of porous ceramic micro-powder, 10 - 12 parts of nano-zinc oxide particles, 7 - 10 parts of illite powder, 5 - 8 parts of polyethylene glycol, 10 - 12 parts of phenolic resin, 50 - 55 parts of ethanol; the polyurethane protective layer comprises the following raw materials: 20 - 24 parts of polyurethane resin, 3 - 5 parts of nano-silver, 12 - 15 parts of lignin microspheres, 3 - 5 parts of epoxidized natural rubber, 1 - 3 parts of dibromoneopentyl glycol, 35 - 40 parts of methanol.

3. An antibacterial DTY high elastic yarn according to claim 1, characterized in that, The preparation method of the porous ceramic micro-powder comprises the following steps: (1) Disperse ceramic micro-powder in an aqueous starch solution, add hydroxypropyl methylcellulose and boric acid, stir at a temperature of 60 - 65 °C for 1 - 2 h, filter, dry, and calcine at a temperature of 500 - 530 °C to obtain porous micro-powder; (2) Disperse modal mixed fiber in deionized water, add the porous micro-powder obtained in step (1), polyvinyl alcohol, and silane coupling agent, ultrasonicate for 0.5 - 1 h, heat to 120 - 130 °C in nitrogen for 30 - 35 min, with an air flow rate of 1 - 2 m / s, to obtain porous ceramic micro-powder.

4. The antibacterial DTY high elastic yarn according to claim 3, characterized in that, The mass ratio of the ceramic micro-powder, modal mixed fiber, and polyvinyl alcohol is 1:0.5 - 0.6:0.1 - 0.

2.

5. An antibacterial DTY high elastic yarn according to claim 3, characterized in that The preparation method of the modal mixed fiber comprises the following steps: Crush modal fiber into fiber particles, then disperse them in a sodium hydroxide solution, stir for 20 - 25 min, wash with water, then disperse in water, add metal-organic framework nano-particles and Triton, and ball mill until the particle size ≤ 5 μm to obtain a mixture; Spray an aqueous acrylate emulsion solution on the surface of the mixture, and dry to obtain modal mixed fiber.

6. An antibacterial DTY high elastic yarn according to claim 1, characterized in that, The preparation method of the lignin microspheres comprises the following steps: (1) Disperse lignin in an aqueous ethylene glycol solution, add citric acid and choline chloride, stir at a temperature of 60 - 65 °C for 2 - 3 h, and spray dry to obtain microsphere particles; (2) Disperse the microsphere particles obtained in step (1) in a potassium hydroxide solution, add glyoxal and hexamethylenediamine, and mix evenly to obtain a lignin solution; (3) Add mesoporous silica mixed particles and xanthan gum to the lignin solution in step (2), stir at 60 - 65 °C for 30 - 40 min, and dry to obtain lignin microspheres.

7. An antibacterial DTY high elastic yarn according to claim 6, characterized in that, The mass ratio of the lignin, mesoporous silica mixed particles and xanthan gum is 1:0.4 - 0.5:0.2 - 0.

3.

8. An antibacterial DTY high elastic yarn according to claim 6, characterized in that, The preparation method of the mesoporous silica mixed particles includes the following steps: Disperse tetraethyl orthosilicate in deionized water, add cetyltrimethylammonium bromide and concentrated hydrochloric acid, stir in a water bath at 85 - 90 °C for 35 - 40 min, and calcine to obtain mesoporous silica particles; Disperse the mesoporous silica particles in deionized water, add multi-walled carbon nanotubes, (3-aminopropyl) dimethylethoxysilane and sodium alginate, heat in an oil bath at 70 - 75 °C for 2 - 3 h, and dry to obtain mesoporous silica mixed particles.

9. The preparation method of an antibacterial DTY high elastic yarn according to claim 1, characterized in that, It includes the following steps: (1) Mix nylon 6 chips, silicon carbide powder, antioxidant 1010, dispersant, matting agent, elasticizer, regulator, softener, antistatic agent, maleic anhydride grafted POE, and spin to obtain a composite core filament; (2) Nanoparticle reinforcement layer: Mix porous ceramic micro-powder, nano-zinc oxide particles, illite powder, polyethylene glycol, phenolic resin, and ethanol evenly to obtain mixture A; Rub the composite core filament to make the surface of the composite core microporous, and then spray with mixture A to obtain a nanoparticle reinforcement layer; (3) Twist the composite core filament coated with the nanoparticle reinforcement layer to obtain a composite DTY high elastic filament; (4) Mix polyurethane resin, lignin microspheres, nano-silver, epoxidized natural rubber, dibromoneopentyl glycol, and methanol evenly, spray on the composite DTY high elastic filament, and dry to obtain an antibacterial DTY high elastic filament.

10. The preparation method of an antibacterial DTY high elastic yarn according to claim 9, characterized in that, The spinning speed is 650 - 700 m / min, and the spinning temperature is 280 - 290 °C.

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