Efficient antibacterial polyester yarn and preparation method thereof

Abstract

The invention relates to the field of textile fibers, and particularly discloses an efficient antibacterial polyester yarn and a preparation method thereof.The polyester yarn is prepared by mixing polyester chips and a compound bacteriostatic agent according to the mass ratio of 1: (0.05-0.1) and then conducting melt spinning, the compound bacteriostatic agent is prepared by mixing nano-silver particles and plant essential oil, and the compound bacteriostatic agent is prepared by mixing nano-silver particles and plant essential oil. The addition mass ratio of the nano-silver to the plant essential oil is 1: (2-3), and the plant essential oil is selected from one or two of tea tree oil and lavender essential oil; the preparation method comprises the following steps: S1, mixing the nano-silver particles with the plant essential oil to prepare a composite bacteriostatic agent; s2, the composite bacteriostatic agent is mixed with polyester chips according to the proportion, then melt spinning is conducted, and the efficient bacteriostatic polyester yarn containing the bacteriostatic components is prepared, the bacteriostatic performance of the polyester yarn is improved, and meanwhile the polyester yarn is more natural and healthier.

Description

Technical Field

[0001] The present application relates to the field of textile fibers, and more specifically, to an efficient antibacterial polyester filament and a preparation method thereof. Background Art

[0002] With the improvement of people's requirements for health and quality of life, the demand for functional textiles is increasing day by day. Among them, antibacterial textiles have received wide attention because they can effectively inhibit the growth of bacteria, reduce odors and disease transmission. At present, the common antibacterial textiles on the market mainly achieve antibacterial functions through post-finishing technologies, such as soaking textiles in antibacterial liquids or coating antibacterial agents on textiles. However, the above methods have the disadvantages of easy shedding and non-persistent antibacterial effects.

[0003] Therefore, the development of antibacterial fibers has become a research hotspot. As a kind of synthetic fiber, polyester fiber is widely used in the textile industry due to its high strength, wear resistance and good dimensional stability. However, due to its hydrophobicity and chemical inertness, it lacks natural antibacterial properties. Ordinary polyester filaments on the market have obvious deficiencies in antibacterial performance, which limits their application potential in the fields of medical treatment and hygiene. Therefore, it is particularly important to develop polyester fibers with efficient antibacterial functions.

[0004] Although there are currently many chemical antibacterial agents on the market that can enhance the antibacterial performance of polyester filaments, these chemicals are often accompanied by health risks and environmental problems. For example, traditional chemical antibacterial agents may cause bacterial drug resistance and allergic reactions, making it difficult to balance antibacterial efficiency and safety, and the antibacterial persistence also needs to be solved. Therefore, it is of great significance to find safe natural substitutes to improve antibacterial properties. Summary of the Invention

[0005] In order to improve the antibacterial performance of polyester filaments and make them more natural and healthy, the present application provides an efficient antibacterial polyester filament and a preparation method thereof.

[0006] In the first aspect, the present application provides an efficient antibacterial polyester filament, adopting the following technical solution: An efficient antibacterial polyester filament is prepared by melt spinning after mixing polyester chips and a composite antibacterial agent in a mass ratio of 1:(0.05 - 0.1). Among them, the composite antibacterial agent is prepared by mixing nano silver particles and plant essential oils, and the added mass ratio of nano silver to plant essential oils is 1:(2 - 3), and the plant essential oil is selected from one or both of tea tree oil and lavender oil.

[0007] By adopting the above technical solution, tea tree oil contains the active ingredient terpinene-4-ol, which has broad-spectrum antibacterial properties and can inhibit Gram-positive bacteria (such as Staphylococcus aureus), Gram-negative bacteria (such as Escherichia coli) and fungi (such as Candida albicans). Lavender essential oil contains components such as linalool and linalyl acetate, which have antibacterial, anti-inflammatory and sedative effects and can inhibit common skin bacteria. In this application, tea tree oil and lavender essential oil are used as natural antibacterial components, which can play an antibacterial role by destroying the bacterial membrane structure or inhibiting enzyme activity. At the same time, they have natural fragrance and low toxicity. Combined with the antibacterial effect of nano silver, the obtained composite antibacterial agent has both natural health and antibacterial effects. Moreover, when the nano silver particles are ultrasonically dispersed in the plant extract antibacterial solution in this application, the cavitation effect formed by ultrasonic waves is used to break the nano silver aggregates, forming a uniformly dispersed liquid and melt-blending with polyester chips to prepare polyester fiber with antibacterial function, which can effectively prevent bacterial drug resistance, prolong the antibacterial persistence, be more healthy and natural, and reduce the side effects of chemical agents.

[0008] Optionally, the composite antibacterial agent is prepared by the following method: A plant extract antibacterial solution is prepared by mixing plant essential oil and an ethanol solution with a mass concentration of 5-10% according to a mass ratio of 1:(3-5), and then nano silver is added to the plant extract antibacterial solution and ultrasonically dispersed for 20-30 min to obtain the composite antibacterial agent.

[0009] By adopting the above technical solution, the nano silver is ultrasonically dispersed in the plant extract antibacterial solution. Ultrasonic dispersion helps to reduce the aggregation of nano silver. Moreover, after the plant essential oil is dissolved in ethanol and added, the addition of ethanol can dissolve tea tree oil and assist in the dispersion of nano silver, and it is easier to remove by using its volatile property in subsequent processing.

[0010] Optionally, the plant essential oil is added after being loaded on modified silica aerogel. The modified silica aerogel is prepared by first impregnating silica aerogel in a mixed solution of zinc nitrate and EDTA, drying, then impregnating with hydrochloric acid, and then impregnating in an amino silane solution.

[0011] By adopting the above technical solution, since the plant essential oil decomposes at high temperature during the melt spinning process, resulting in the loss of active ingredients and affecting the antibacterial effect, in this application, the plant essential oil is added after being loaded on the modified silica aerogel. The nano-porous network structure of the silica aerogel physically confines the essential oil molecules in the pores through physical adsorption and capillary action, reducing the direct contact with the high-temperature environment. Moreover, the low thermal conductivity of the aerogel delays the heat transfer to the essential oil molecules in the pores, reducing the decomposition of the essential oil. In this way, the loss of the plant essential oil can be reduced. In this application, the silica aerogel is first impregnated in a mixed solution of zinc nitrate and EDTA, so that Zn2 + can be introduced on the surface of the silica aerogel. Then, it is treated in a hydrochloric acid solution to expose more hydroxyl functional groups in the silica aerogel. After that, it is treated in an amino silane solution, so that amino groups are also introduced into the silica aerogel. The introduction of Zn2 + and amino groups in the silica aerogel utilizes the negatively charged ester groups in lavender essential oil to electrostatically adsorb with the amino-modified silica aerogel, while Zn2 + can form coordination bonds with the phenolic hydroxyl groups in tea tree oil, so that the silica aerogel significantly improves the loading effect on the plant essential oil after the above modification treatment, while improving the thermal stability, reducing the loss of decomposition at high temperature, and improving the antibacterial effect.

[0012] Optionally, the modified silica aerogel is prepared by the following method: 1) Mix zinc nitrate, EDTA and water, and adjust the pH value to 5-6 with acetic acid to prepare an impregnating solution. Then add the silica aerogel to the impregnating solution, and carry out impregnation treatment at 55-65 °C and 0.2-0.3 MPa for 2-3 h. After that, centrifuge, wash and dry to obtain a pretreated silica aerogel; 2) Then, the obtained pretreated silica aerogel is first activated at room temperature in a 5 wt% hydrochloric acid solution for 20-30 min, washed with water and dried to obtain an activated silica aerogel; 3) Immerse the obtained activated silica aerogel in a mixed solution of 3-aminopropyltriethoxysilane and ethanol solution for 1-2 h, and the impregnation temperature is 55-65 °C. Then wash with alcohol and dry to obtain the modified silica aerogel.

[0013] Optionally, during the preparation of the modified silica aerogel, in step 1), the mass ratio of zinc nitrate, EDTA and water added is 1:(0.2-0.3):(4-5), and the mass ratio of the silica aerogel to the impregnating solution added is 1:(6-8); In step 2), the mass ratio of the pretreated silica aerogel to the hydrochloric acid solution added is 1:(6-8); In step 3), the concentration of the ethanol solution is 30-45 wt%, the added mass ratio of 3-aminopropyltriethoxysilane to the ethanol solution is 1:(3-4), and the added mass ratio of the activated silica aerogel to the mixed solution is 1:(4-6).

[0014] By adopting the above technical solution, ethylenediaminetetraacetic acid (EDTA) forms a stable complex with Zn2+ under acidic conditions as a complexing agent, inhibits the hydrolysis of Zn2+, avoids the formation of Zn(OH)2 precipitation, and then through high-temperature and high-pressure impregnation treatment, promotes the diffusion of the Zn2+ complex to the silica aerogel, and forms zinc loading in the pores of the silica aerogel through physical pore adsorption and the binding of hydroxyl groups to complex ions. Then, through hydrochloric acid treatment, on the one hand, the number of hydroxyl groups is increased, and on the other hand, the complex acid in the complexed zinc is protonated to release zinc ions and form coordination with hydroxyl groups to achieve the anchoring of zinc ions. Then, it is impregnated in an amino silane coupling agent, and the hydrolysis of the hydroxyl groups in the amino silane coupling agent condenses with the hydroxyl groups on the silica surface to introduce amino groups into the silica aerogel, and finally realizes the introduction of amino groups and zinc ions on the silica aerogel, improving the loading effect on plant essential oils.

[0015] Optionally, the specific operation of loading the plant essential oil on the modified silica aerogel is as follows: Dissolve the plant essential oil in 8-10 times the mass of ethanol, and prepare an essential oil impregnation solution after stirring at room temperature for 20-30 min; Mix the modified silica aerogel and the essential oil impregnation solution according to a mass ratio of 1:(6-8), perform oscillation impregnation treatment at room temperature for 2-4 h, and then perform centrifugation and drying treatment to obtain a plant essential oil-modified silica aerogel composite.

[0016] By adopting the above technical solution, the porous structure of the modified silica aerogel is used to adsorb and load the plant essential oil through capillary action, and at the same time, its amino groups and zinc ions form a combination with the plant essential oil to achieve its loading.

[0017] Optionally, after loading the plant essential oil on the modified silica aerogel to obtain a plant essential oil-modified silica aerogel composite, microencapsulation treatment is also carried out. During the microencapsulation treatment, the plant essential oil-modified silica aerogel composite is used as the core material, and a mixture of a modified polyacrylic resin and polyvinylpyrrolidone K30 is used as the coating layer; Among them, the modified polyacrylic resin is prepared from 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N,N'-methylenebisacrylamide, L-phenylalanine, and N-hydroxysuccinimide-modified polyacrylic resin.

[0018] By adopting the above technical solution, a mixture of a modified polyacrylic acid resin and povidone K30 is used as a coating layer in the present application to form a high-temperature resistant barrier. During the modification process of the polyacrylic acid resin in the present application, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are combined to activate the carboxyl groups in the polyacrylic acid resin, enabling it to react with the amino groups in L-phenylalanine to form chemical bonds, thereby introducing L-phenylalanine onto the polyacrylic acid resin chain. The introduction of the rigid benzene ring group further improves the heat resistance of the polyacrylic acid resin. And N,N'-methylenebisacrylamide, as a bifunctional crosslinking agent, can also form a crosslinked structure with the polyacrylic acid resin, further improving its heat resistance. Finally, the coating layer serves as a high-temperature resistant barrier to prevent the internal plant essential oil from decomposing and inactivating at high temperatures during the melt spinning process, improving the final antibacterial effect.

[0019] Optionally, the modified polyacrylic acid resin is prepared by the following method: Dissolve the polyacrylic acid resin in N,N-dimethylformamide, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, stir at room temperature for 1-2 h to obtain an activated polyacrylic acid resin solution, then dropwise add L-phenylalanine, stir and react at room temperature for 50-80 min, finally add N,N'-methylenebisacrylamide and azobisisobutyronitrile, react at 60-80 °C for 2-3 h, cool to room temperature, then add methanol to precipitate, and then dry the precipitate to obtain the modified polyacrylic acid resin.

[0020] Optionally, the added mass ratio of the polyacrylic acid resin, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1:(0.1-0.2):(0.05-0.1), and the added amount of L-phenylalanine is 5-8 wt% of the polyacrylic acid resin, the added amount of N,N'-methylenebisacrylamide is 3-5 wt% of the polyacrylic acid resin, the added amount of azobisisobutyronitrile is 0.5-2 wt% of the polyacrylic acid resin, and the added amount of N,N-dimethylformamide is 4-6 mass times the added amount of the polyacrylic acid resin.

[0021] Optionally, the specific operation for microencapsulating the plant essential oil-modified silica aerogel composite is as follows: Step 1: Mix the modified polyacrylic acid resin and povidone K30 in a mass ratio of (3-5):1 as a coating mixture, and dissolve it in a mixed solvent with a volume ratio of (2-3):1 of dichloromethane and acetone. The added mass ratio of the coating mixture to the mixed solvent is 1:(3-5) to form a coating solution; Step 2: Add polyethylene glycol to the coating solution. The addition amount of polyethylene glycol is 2-5% of the added mass of the coating mixture. After ultrasonic treatment for 5-20 min, it is sprayed on the plant essential oil-modified silica aerogel composite and dried to obtain plant essential oil microcapsules. The added mass ratio of the coating mixture to the plant essential oil-modified silica aerogel composite is 1:(1.2-1.5).

[0022] By adopting the above technical solution, the above method realizes the coating of the plant essential oil after loading with a mixture of modified polyacrylic resin and povidone K30 as the coating layer, significantly reducing its high-temperature loss during the melt spinning process and retaining more active ingredients to play an antibacterial role subsequently. The addition of povidone K30 will not affect subsequent operations such as dyeing in the production of polyester filaments by mixing the plant essential oil microcapsules and polyester chips. Alternatively, the antibacterial polyester filaments prepared in this application can be directly washed with water to remove povidone K30 to form a pore structure, thus realizing the slow release of the antibacterial component fabric essential oil in the microcapsules, with better antibacterial effects and more persistent antibacterial effects.

[0023] In the second aspect, the present application provides a method for preparing highly antibacterial polyester filaments, adopting the following technical solution: A method for preparing highly antibacterial polyester filaments includes the following steps: S1: Mix nano silver particles and plant essential oils to obtain a composite antibacterial agent; S2: Mix the composite antibacterial agent with polyester chips in proportion, and then perform melt spinning to obtain highly antibacterial polyester filaments containing antibacterial components.

[0024] By adopting the above technical solution, the method provided in the present application is simple, convenient, and easy to industrialize. Moreover, the antibacterial components in this application are a mixture of plant extracts and nano silver, which is more natural and safe, while ensuring excellent antibacterial performance and antibacterial persistence.

[0025] In summary, the present application has the following beneficial effects: 1. In the present application, tea tree oil and lavender essential oil are used as natural antibacterial components, which can play an antibacterial role by destroying the bacterial membrane structure or inhibiting enzyme activity. At the same time, they have a natural fragrance and low toxicity. Combining with the antibacterial effect of nano silver, the obtained composite antibacterial agent has both natural health and antibacterial effects. Moreover, when the nano silver particles are ultrasonically dispersed in the plant extract antibacterial solution in this application, the cavitation effect formed by ultrasonic waves is used to break the nano silver aggregates, forming a uniform dispersion and melt-blending with polyester chips to obtain polyester filament fibers with antibacterial functions. It can effectively prevent bacterial drug resistance, extend the antibacterial persistence, and is more healthy and natural, reducing the side effects of chemical agents; 2. In this application, the plant essential oil is loaded and then added after being loaded on the modified silica aerogel. The nano-porous network structure of the silica aerogel physically confines the essential oil molecules in the pores through physical adsorption and capillary action, reducing the direct contact with the high-temperature environment. Moreover, the low thermal conductivity of the aerogel delays the heat transfer to the essential oil molecules in the pores, reducing the decomposition of the essential oil. In this way, the loss of the plant essential oil can be reduced. In this application, the silica aerogel is first impregnated in a mixed solution of zinc nitrate and EDTA, so that Zn2+ can be introduced on the surface of the silica aerogel. + , and then treated in a hydrochloric acid solution to expose more hydroxyl functional groups in the silica aerogel. After that, it is treated in an amino silane solution, so that amino groups are also introduced into the silica aerogel. The introduction of Zn2+ + and amino groups in the silica aerogel. Utilizing the negatively charged ester groups in lavender essential oil, electrostatic adsorption occurs with the amino-modified silica aerogel, while Zn2+ + can form a coordination bond with the phenolic hydroxyl groups in tea tree oil, making the silica aerogel significantly improve the loading effect on the plant essential oil after the above-mentioned modification treatment, while improving the thermal stability, reducing the loss of high-temperature decomposition, and improving the antibacterial effect. 3. In this application, a mixture of modified polyacrylic resin and povidone K30 is used as the coating layer to form a high-temperature resistant barrier. During the modification process of the polyacrylic resin in this application, 1-ethyl-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide are combined to activate the carboxyl groups in the polyacrylic resin, enabling it to react with the amino groups in L-phenylalanine to form a chemical bond, thereby introducing L-phenylalanine on the polyacrylic resin chain. The introduction of the rigid benzene ring group further improves the heat resistance of the polyacrylic resin. And N,N'-methylenebisacrylamide, as a bifunctional cross-linking agent, can also form a cross-linked structure with the polyacrylic resin, further improving its heat resistance. Finally, the coating layer serves as a high-temperature resistant barrier to prevent the internal plant essential oil from being decomposed and inactivated at high temperature during the melt spinning process, and improves the final antibacterial effect. Detailed Embodiments

[0026] The following further elaborates on this application with reference to the embodiments. It should be specifically noted that: for those not indicating specific conditions in the following embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. All raw materials used in the following embodiments can be obtained from ordinary commercial sources unless otherwise specified.

[0027] In the following embodiments, the tea tree oil is selected from the Australian tea tree oil of Guangzhou Puyifeng Biotechnology Co., Ltd.; The lavender essential oil is selected from the lavender essential oil of Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.; The silica aerogel is the hydrophilic nano-silica aerogel powder from Senat (Guangdong) New Materials Technology Co., Ltd.; the polyacrylic resin is the polyacrylic resin from Shanghai Changwei Pharmaceutical Excipient Technology Co., Ltd., with the specific specification and grade being RL PODMF#1242, which is prepared from the copolymer of ethyl acrylate, methyl methacrylate, and trimethylaminoethyl methacrylate chloride; The nano-silver is nano-silver with a particle size of 50 - 100 nm.

[0028] The following preparation examples are for the preparation of modified silica aerogel Preparation Example 1 A method for preparing modified silica aerogel includes the following steps: 1), Mix zinc nitrate, EDTA, and water according to a mass multiple ratio of 1:0.2:4, and adjust the pH value to 5.5 with acetic acid to obtain an impregnation solution. Then add the silica aerogel to the impregnation solution, and perform impregnation treatment at 60 °C and 0.2 MPa for 2.5 h. The addition mass ratio of the silica aerogel to the impregnation solution is 1:7. Then, after centrifugal washing and drying, a pretreated silica aerogel is obtained; 2), Then, first subject the obtained pretreated silica aerogel to activation treatment in a 5 wt% hydrochloric acid solution at room temperature for 25 min, and then wash and dry it to obtain an activated silica aerogel. The addition mass ratio of the pretreated silica aerogel to the hydrochloric acid solution is 1:7; 3), Immerse the obtained activated silica aerogel in a mixed solution of 3-aminopropyltriethoxysilane and an ethanol solution (mass concentration of 35 wt%) for 1 - 2 h, with the impregnation temperature being 60 °C. Then, after alcohol washing and drying, a modified silica aerogel is obtained. The addition mass ratio of 3-aminopropyltriethoxysilane to the ethanol solution is 1:3.5, and the addition mass ratio of the activated silica aerogel to the mixed solution is 1:5.

[0029] Preparation Example 2 A method for preparing modified silica aerogel includes the following steps: 1), Mix zinc nitrate, EDTA, and water according to a mass multiple ratio of 1:0.2:4, and adjust the pH value to 5 with acetic acid to obtain an impregnation solution. Then add the silica aerogel to the impregnation solution, and perform impregnation treatment at 55 °C and 0.2 MPa for 3 h. The addition mass ratio of the silica aerogel to the impregnation solution is 1:6. Then, after centrifugal washing and drying, a pretreated silica aerogel is obtained; 2), Then, first subject the obtained pretreated silica aerogel to activation treatment in a 5 wt% hydrochloric acid solution at room temperature for 20 min, and then wash and dry it to obtain an activated silica aerogel. The addition mass ratio of the pretreated silica aerogel to the hydrochloric acid solution is 1:6; 3), impregnate the prepared activated silica aerogel in a mixed solution of 3-aminopropyltriethoxysilane and an ethanol solution (mass concentration of 30 wt%) for 1 h at an impregnation temperature of 65°C, then wash with alcohol and dry to obtain a modified silica aerogel. The added mass ratio of 3-aminopropyltriethoxysilane to the ethanol solution is 1:3, and the added mass ratio of the activated silica aerogel to the mixed solution is 1:4.

[0030] Preparation Example 3 A method for modifying silica aerogel, comprising the following steps: 1), mix zinc nitrate, EDTA, and water in a mass multiple ratio of 1:0.3:5, adjust the pH value to 6 with acetic acid to obtain an impregnation solution, then add the silica aerogel to the impregnation solution, and impregnate at 65°C and 0.3 MPa for 2 h. The added mass ratio of the silica aerogel to the impregnation solution is 1:8, then centrifuge, wash, and dry to obtain a pretreated silica aerogel; 2), then first activate the obtained pretreated silica aerogel in a 5 wt% hydrochloric acid solution at room temperature for 30 min, wash with water and dry to obtain an activated silica aerogel. The added mass ratio of the pretreated silica aerogel to the hydrochloric acid solution is 1:8; 3), impregnate the prepared activated silica aerogel in a mixed solution of 3-aminopropyltriethoxysilane and an ethanol solution (mass concentration of 45 wt%) for 2 h at an impregnation temperature of 55°C, then wash with alcohol and dry to obtain a modified silica aerogel. The added mass ratio of 3-aminopropyltriethoxysilane to the ethanol solution is 1:4, and the added mass ratio of the activated silica aerogel to the mixed solution is 1:6.

[0031] Preparation Example 4 A preparation method of modified silica aerogel is carried out according to the method in Preparation Example 1, except that step 1) is not carried out.

[0032] The following preparation examples are for the preparation of modified polyacrylic resin Preparation Example 5 A preparation method of modified polyacrylic resin, comprising the following method: Dissolve the polyacrylic resin in N,N-dimethylformamide, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, stir at room temperature for 1.5 h to obtain an activated polyacrylic resin solution, then dropwise add L-phenylalanine, stir and react at room temperature for 60 min, finally add N,N'-methylenebisacrylamide and azobisisobutyronitrile, react at 70°C for 2.5 h, cool to room temperature, then add methanol to precipitate, and then dry the precipitate to obtain a modified polyacrylic resin; Among them, the mass ratio of polyacrylic resin, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1:0.1:0.08, and the addition amount of L-phenylalanine is 6 wt% of the polyacrylic resin, the addition amount of N,N'-methylenebisacrylamide is 4 wt% of the polyacrylic resin, the addition amount of azobisisobutyronitrile is 1 wt% of the polyacrylic resin, and the addition amount of N,N-dimethylformamide is 5 times the mass of the polyacrylic resin addition amount.

[0033] Preparation Example 6 A preparation method of a modified polyacrylic resin, comprising the following method: Dissolve the polyacrylic resin in N,N-dimethylformamide, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, stir at room temperature for 1 h to obtain an activated polyacrylic resin solution, then dropwise add L-phenylalanine, stir and react at room temperature for 50 min, finally add N,N'-methylenebisacrylamide and azobisisobutyronitrile, react at 60 °C for 3 h, cool to room temperature, then add methanol for precipitation, and then dry the precipitate to obtain the modified polyacrylic resin; among them, the mass ratio of polyacrylic resin, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1:0.1:0.05, and the addition amount of L-phenylalanine is 5 wt% of the polyacrylic resin, the addition amount of N,N'-methylenebisacrylamide is 3 wt% of the polyacrylic resin, the addition amount of azobisisobutyronitrile is 0.5 wt% of the polyacrylic resin, and the addition amount of N,N-dimethylformamide is 4 times the mass of the polyacrylic resin addition amount.

[0034] Preparation Example 7 A preparation method of a modified polyacrylic resin, comprising the following method: Dissolve the polyacrylic resin in N,N-dimethylformamide, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, stir at room temperature for 2 h to obtain an activated polyacrylic resin solution, then dropwise add L-phenylalanine, stir and react at room temperature for 80 min, finally add N,N'-methylenebisacrylamide and azobisisobutyronitrile, react at 80 °C for 2 h, cool to room temperature, then add methanol for precipitation, and then dry the precipitate to obtain the modified polyacrylic resin; among them, the mass ratio of polyacrylic resin, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1:0.2:0.1, and the addition amount of L-phenylalanine is 8 wt% of the polyacrylic resin, the addition amount of N,N'-methylenebisacrylamide is 5 wt% of the polyacrylic resin, the addition amount of azobisisobutyronitrile is 2 wt% of the polyacrylic resin, and the addition amount of N,N-dimethylformamide is 6 times the mass of the polyacrylic resin addition amount.

[0035] Example 1 A preparation method of highly efficient antibacterial polyester filaments includes the following steps: S1. Mix nano silver particles and plant essential oils to obtain a composite antibacterial agent. The specific operation is as follows: First, mix plant essential oils (specifically, tea tree oil and lavender essential oil are mixed according to a mass ratio of 1:0.5) with an ethanol solution with a mass concentration of 8% according to a mass ratio of 1:4 to obtain a plant extract antibacterial solution. Then, add nano silver to the plant extract antibacterial solution and ultrasonically disperse for 25 min to obtain a composite antibacterial agent. The added mass ratio of nano silver to plant essential oils is 1:2.5; S2. Mix the composite antibacterial agent and polyester chips according to a mass ratio of 1:0.1, and then perform melt spinning at 260 °C to obtain highly efficient antibacterial polyester filaments containing antibacterial components.

[0036] Example 2 A preparation method of highly efficient antibacterial polyester filaments includes the following steps: S1. Mix nano silver particles and plant essential oils to obtain a composite antibacterial agent. The specific operation is as follows: First, mix plant essential oils (specifically, lavender essential oil) with an ethanol solution with a mass concentration of 5% according to a mass ratio of 1:3 to obtain a plant extract antibacterial solution. Then, add nano silver to the plant extract antibacterial solution and ultrasonically disperse for 20 min to obtain a composite antibacterial agent. The added mass ratio of nano silver to plant essential oils is 1:2; S2. Mix the composite antibacterial agent and polyester chips according to a mass ratio of 1:0.05, and then perform melt spinning at 260 °C to obtain highly efficient antibacterial polyester filaments containing antibacterial components.

[0037] Example 3 A preparation method of highly efficient antibacterial polyester filaments includes the following steps: S1. Mix nano silver particles and plant essential oils to obtain a composite antibacterial agent. The specific operation is as follows: First, mix plant essential oils (specifically, tea tree oil) with an ethanol solution with a mass concentration of 10% according to a mass ratio of 1:5 to obtain a plant extract antibacterial solution. Then, add nano silver to the plant extract antibacterial solution and ultrasonically disperse for 30 min to obtain a composite antibacterial agent. The added mass ratio of nano silver to plant essential oils is 1:3; S2. Mix the composite antibacterial agent and polyester chips according to a mass ratio of 1:0.1, and then perform melt spinning at 280 °C to obtain highly efficient antibacterial polyester filaments containing antibacterial components.

[0038] Example 4 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 1, with the difference that: The plant essential oil in step S1 is processed by microencapsulation after being loaded to obtain microencapsulated plant essential oil, and then the microencapsulated plant essential oil is mixed with nano silver to obtain a composite antibacterial agent. The specific operation is as follows: S1-1: Take the same amount of plant essential oil as in Example 1, dissolve the plant essential oil in 9 times the mass of ethanol, and stir at room temperature for 25 min to obtain an essential oil impregnation solution; S1-2: Mix the modified silica aerogel prepared in Preparation Example 1 with the essential oil impregnation solution according to a mass ratio of 1:7, perform oscillation impregnation treatment at room temperature for 3 h, then centrifuge and dry to obtain a plant essential oil-modified silica aerogel composite, realizing the loading of the plant essential oil on the modified silica aerogel; S1-3: Then mix the modified polyacrylic resin and povidone K30 prepared in Preparation Example 5 according to a mass ratio of 4:1 as a coating mixture, and dissolve it in a mixed solvent of dichloromethane and acetone mixed according to a volume ratio of 2:1. The addition mass ratio of the coating mixture to the mixed solvent is 1:4 to form a coating solution; S1-4: Add polyethylene glycol PEG-400 to the coating solution. The addition amount of polyethylene glycol is 3% of the addition mass of the coating mixture. After ultrasonic treatment for 10 min, spray (realized by fluidized bed spray embedding) on the plant essential oil-modified silica aerogel composite and dry to obtain plant essential oil microcapsules. The addition mass ratio of the coating mixture to the plant essential oil-modified silica aerogel composite is 1:1.3; S1-5: Directly mix the plant essential oil microcapsules prepared in step S1-4 with nano silver to obtain a composite antibacterial agent, and then perform step S2 treatment.

[0039] Example 5 A preparation method of a highly antibacterial polyester filament is carried out according to the method in Example 1, the difference is that: The plant essential oil in step S1 is processed by microencapsulation after being loaded to obtain microencapsulated plant essential oil, and then the microencapsulated plant essential oil is mixed with nano silver to obtain a composite antibacterial agent. The specific operation is as follows: S1-1: Take the same amount of plant essential oil as in Example 1, dissolve the plant essential oil in 8 times the mass of ethanol, and stir at room temperature for 20 min to obtain an essential oil impregnation solution; S1-2: Mix the modified silica aerogel prepared in Preparation Example 2 with the essential oil impregnation solution according to a mass ratio of 1:6, perform oscillation impregnation treatment at room temperature for 2 h, then centrifuge and dry to obtain a plant essential oil-modified silica aerogel composite, realizing the loading of the plant essential oil on the modified silica aerogel; S1-3. Then, the modified polyacrylic resin obtained in Preparation Example 6 and povidone K30 were mixed at a mass ratio of 3:1 as the coating mixture, and dissolved in a mixed solvent of dichloromethane and acetone with a volume ratio of 2:1. The added mass ratio of the coating mixture to the mixed solvent was 1:3 to form a coating solution. S1-4. Polyethylene glycol PEG-400 was added to the coating solution, and the addition amount of polyethylene glycol was 2% of the added mass of the coating mixture. After ultrasonic treatment for 5 min, it was sprayed (achieved by fluidized bed spray embedding) onto the plant essential oil-modified silica aerogel composite and dried to obtain plant essential oil microcapsules. The added mass ratio of the coating mixture to the plant essential oil-modified silica aerogel composite was 1:1.2. S1-5. The plant essential oil microcapsules obtained in step S1-4 were directly mixed with nano silver to obtain a composite bacteriostatic agent, and then step S2 was carried out.

[0040] Example 6 A preparation method of a highly bacteriostatic polyester filament was carried out according to the method in Example 1, except that: The plant essential oil in step S1 was processed by loading and microencapsulation to obtain microencapsulated plant essential oil, and then the microencapsulated plant essential oil was mixed with nano silver to obtain a composite bacteriostatic agent. The specific operation was as follows: S1-1. Take the same amount of plant essential oil as in Example 1, and dissolve the plant essential oil in 10 times the mass of ethanol. After stirring at room temperature for 30 min, an essential oil impregnation solution was obtained. S1-2. The modified silica aerogel obtained in Preparation Example 3 and the essential oil impregnation solution were mixed at a mass ratio of 1:8, and subjected to room temperature oscillation impregnation treatment for 4 h, and then centrifuged and dried to obtain a plant essential oil-modified silica aerogel composite, realizing the loading of the plant essential oil on the modified silica aerogel. S1-3. Then, the modified polyacrylic resin obtained in Preparation Example 7 and povidone K30 were mixed at a mass ratio of 5:1 as the coating mixture, and dissolved in a mixed solvent of dichloromethane and acetone with a volume ratio of 3:1. The added mass ratio of the coating mixture to the mixed solvent was 1:5 to form a coating solution. S1-4. Polyethylene glycol PEG-400 was added to the coating solution, and the addition amount of polyethylene glycol was 5% of the added mass of the coating mixture. After ultrasonic treatment for 20 min, it was sprayed (achieved by fluidized bed spray embedding) onto the plant essential oil-modified silica aerogel composite and dried to obtain plant essential oil microcapsules. The added mass ratio of the coating mixture to the plant essential oil-modified silica aerogel composite was 1:1.5. S1-5. The plant essential oil microcapsules obtained in step S1-4 were directly mixed with nano silver to obtain a composite bacteriostatic agent, and then step S2 was carried out.

[0041] Example 7 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 4, the difference is that: in step S1-2, the modified silica aerogel is the modified silica aerogel prepared in Preparation Example 4.

[0042] Example 8 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 4, the difference is that the modified silica aerogel in step S1-2 is equally replaced by silica aerogel.

[0043] Example 9 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 4, the difference is that the modified polyacrylic acid resin in step S1-3 is equally replaced by polyacrylic acid resin.

[0044] Example 10 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 4, the difference is that the operations of steps S1-3 and S1-4 are not carried out, and the plant essential oil-modified silica aerogel composite prepared in step S1-2 is directly mixed with nano silver to prepare a composite antibacterial agent.

[0045] Comparative Example 1 A preparation method of highly efficient antibacterial polyester filaments is carried out according to the method in Example 1, the difference is that no plant essential oil is added in step S1.

[0046] Performance detection The polyester filaments prepared in the examples and comparative examples are washed with water and then dried as test samples. Referring to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", the antibacterial properties of the polyester filaments prepared in the examples, comparative examples and blank control group of this application against Candida albicans are measured. In addition, the polyester filaments prepared in the examples and comparative examples of this application are washed 30 times with water and then the above antibacterial test is carried out, and the reduction rate of antibacterial rate before and after washing is counted. The statistical results are shown in Table 1 below.

[0047] Table 1: Antibacterial performance detection results Referring to the test results in Table 1 above, the polyester filaments prepared in this application have good antibacterial properties. Referring to the test results of Example 1 and Examples 4-6, it can be seen that after the plant essential oil is loaded and microencapsulated in Example 4, its high-temperature loss during the melt spinning process is low. While the antibacterial property is significantly improved, its antibacterial rate retention effect after washing is better, and its antibacterial persistence is better. Combining with the test results in Example 10, it can be seen that when the plant essential oil is only loaded without microencapsulation, its antibacterial property and antibacterial persistence are improved compared with Example 1, but it is still much weaker than the test results in Example 4. Combining with the test results in Example 7, when only amino groups are introduced and zinc ions are not introduced during the modification of the plant essential oil-loaded carrier silica aerogel in Example 7, its antibacterial property and antibacterial persistence are also reduced compared with Example 4. This is only because the introduction of zinc ions helps to improve the binding strength between the plant essential oil and the silica aerogel, can improve its thermal stability, and reduce the loss of active ingredients. Referring to the test results in Examples 8 and 9, when the silica aerogel or the wall material polyacrylic resin is directly applied without modification treatment, its antibacterial property and antibacterial persistence are significantly reduced. The above modification treatment not only helps to improve the thermal stability and reduce the high-temperature loss, but also has an impact on the slow-release effect.

[0048] In addition, the antibacterial rates and antibacterial persistences of the polyester filaments prepared in Examples 1 and 4 against Staphylococcus aureus and Escherichia coli were detected respectively according to the above method, and the test results are shown in Table 2 below.

[0049] Table 2: Referring to the test results in Table 2 above, the polyester filaments prepared in this application have excellent antibacterial properties against Staphylococcus aureus, Escherichia coli and Candida albicans.

[0050] This specific embodiment is only an explanation of this application, and it is not a limitation of this application. Those skilled in the art can make modifications without creative contributions to this embodiment after reading this specification, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

Claims

1. A highly efficient antibacterial polyester yarn, characterized in that: The method is prepared by mixing polyester slices and a composite antibacterial agent in a mass ratio of 1: (0.05-0.1) and then melt-spinning the mixture. The composite antibacterial agent is prepared by mixing nanosilver particles and plant essential oil. The mass ratio of nanosilver to plant essential oil is 1: (2-3), and the plant essential oil is selected from one or both of tea tree oil and lavender essential oil.

2. The high-efficiency antibacterial polyester yarn according to claim 1, characterized in that: The composite antibacterial agent is prepared by the following method: The plant essential oil and the ethanol solution with a mass concentration of 5-10% are mixed in a mass ratio of 1: (3-5) to prepare a plant extract antibacterial solution, and then nanosilver is added to the plant extract antibacterial solution and ultrasonically dispersed for 20-30 minutes to prepare a composite antibacterial agent.

3. The high-efficiency antibacterial polyester yarn according to claim 1, characterized in that: The plant essential oil is added after being loaded on the modified silica aerogel, and the modified silica aerogel is prepared by firstly immersing the silica aerogel in a mixed solution of zinc nitrate and EDTA, then drying it, then immersing it in hydrochloric acid, and then immersing it in an aminosilane solution.

4. The high-efficiency antibacterial polyester yarn according to claim 3, characterized in that: The modified silica aerogel is prepared by the following method: 1) Mix zinc nitrate, EDTA and water, and adjust the pH value to 5-6 with acetic acid to prepare an impregnation solution, then add silica aerogel to the impregnation solution, and impregnate for 2-3 hours at 55-65°C and 0.2-0.3MPa, then centrifuge and wash, and then dry to obtain pretreated silica aerogel; 2) The obtained pretreated silica aerogel is first activated in a 5wt% hydrochloric acid solution at room temperature for 20-30 minutes, and then washed and dried to obtain activated silica aerogel; 3) The prepared activated silica aerogel is immersed in a mixed solution of 3-aminopropyltriethoxysilane and ethanol solution for 1-2 hours at a temperature of 55-65° C., and then washed with alcohol and dried to obtain the modified silica aerogel.

5. The high-efficiency antibacterial polyester yarn according to claim 4, characterized in that: In the preparation process of modified silica aerogel, the mass ratio of zinc nitrate, EDTA and water added in step 1) is 1:(0.2-0.3):(4-5), and the mass ratio of silica aerogel to impregnation liquid added is 1:(6-8); In step 2), the mass ratio of the pretreated silica aerogel to the hydrochloric acid solution is 1:(6-8); In step 3), the concentration of the ethanol solution is 30-45wt%, the mass ratio of 3-aminopropyltriethoxysilane to the ethanol solution is 1:(3-4), and the mass ratio of activated silica aerogel to the mixed solution is 1:(4-6).

6. The high-efficiency antibacterial polyester yarn according to claim 3, characterized in that: The specific operation of loading plant essential oil on modified silica aerogel is as follows: Dissolve the plant essential oil in 8-10 times the mass of ethanol, and stir at room temperature for 20-30 minutes to obtain an essential oil impregnation solution; The modified silica aerogel and the essential oil impregnation solution are mixed in a mass ratio of 1:(6-8), and the mixture is subjected to an oscillating impregnation treatment at room temperature for 2-4 hours, followed by a centrifugal and drying treatment to obtain a plant essential oil-modified silica aerogel composite.

7. The high-efficiency antibacterial polyester yarn according to claim 3, characterized in that: The plant essential oil is loaded on the modified silica aerogel to obtain the plant essential oil-modified silica aerogel composite, and then microencapsulation is performed. During the microencapsulation, the plant essential oil-modified silica aerogel composite is used as the core material, and a mixture of modified polyacrylic acid resin and povidone K30 is used as the coating layer; The modified polyacrylic acid resin is prepared by modifying the polyacrylic acid resin with 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N,N'-methylenebisacrylamide, L-phenylalanine and N-hydroxysuccinimide.

8. The high-efficiency antibacterial polyester yarn according to claim 7, characterized in that: The modified polyacrylic acid resin is prepared by the following method: The polyacrylic acid resin is dissolved in N,N-dimethylformamide, and then 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are added, and the mixture is stirred at room temperature for 1-2 hours to obtain an activated polyacrylic acid resin solution. Then L-phenylalanine is added dropwise, and the mixture is stirred at room temperature for reaction for 50-80 minutes. Finally, N,N'-methylenebisacrylamide and azobisisobutyronitrile are added, and the mixture is reacted at 60-80°C for 2-3 hours. The mixture is cooled to room temperature, and then methanol is added for precipitation. The precipitate is then dried to obtain a modified polyacrylic acid resin.

9. The high-efficiency antibacterial polyester yarn according to claim 7, characterized in that: The specific operation of microencapsulation of plant essential oil-modified silica aerogel composite is as follows: Step 1: Mix the modified polyacrylic acid resin and povidone K30 in a mass ratio of (3-5):1 as a coating mixture, and dissolve the mixture in a mixed solvent of dichloromethane and acetone in a volume ratio of (2-3):1, wherein the added mass ratio of the coating mixture to the mixed solvent is 1:(3-5), to form a coating solution; Step 2: Add polyethylene glycol to the coating solution, the amount of polyethylene glycol added is 2-5% of the mass of the coating mixture, and after ultrasonic treatment for 5-20 minutes, spray it on the plant essential oil-modified silica aerogel composite and dry it to obtain plant essential oil microcapsules. The mass ratio of the coating mixture to the plant essential oil-modified silica aerogel composite is 1: (1.2-1.5).

10. A method for preparing a highly efficient antibacterial polyester yarn according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1, mixing nano silver particles with plant essential oil to prepare a composite antibacterial agent; S2. The composite antibacterial agent is mixed with polyester chips in proportion, and then melt-spinned to obtain high-efficiency antibacterial polyester yarn containing antibacterial ingredients.

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