WO2023130494A1

WO2023130494A1 - Nanofiber wrap yarn and preparation method therefor, and nanofiber wrap yarn strand and application thereof

Info

Publication number: WO2023130494A1
Application number: PCT/CN2022/071950
Authority: WO
Inventors: 樊威; 罗宇; 张瑶; 孙艳丽; 陈炜纯
Original assignee: 西安工程大学
Priority date: 2022-01-06
Filing date: 2022-01-14
Publication date: 2023-07-13
Also published as: CN114481392A

Abstract

A nanofiber wrap yarn and a preparation method therefor, and a nanofiber wrap yarn strand and an application thereof, relating to the technical field of antibacterial textiles. The nanofiber wrap yarn comprises a core yarn and an outer wrapping layer wrapping the surface of the core yarn; the core yarn is a polypyrrole-cotton yarn; the polypyrrole-cotton yarn comprises a cotton yarn and polypyrrole particles distributed on the surface of the cotton yarn; the outer wrapping layer is made of an antibacterial nanofiber; and the antibacterial nanofiber comprises a polyacrylonitrile nanofiber matrix and ketoconazole and nano zinc oxide which are distributed on the polyacrylonitrile nanofiber matrix. The nanofiber wrap yarn has a relatively good inhibition effect on fungi and bacteria, particularly has a certain treatment effect on tinea pedis, is relatively low in cost, safe and reliable, and has durability and sustained release performance.

Description

A kind of nanofiber covered yarn and its preparation method, nanofiber covered yarn strand and its application

This application is required to be submitted to the China Patent Office on January 06, 2022. The application number is CN202210007549.8, and the title of the invention is "a nanofiber-coated yarn and its preparation method, nanofiber-coated yarn strands and its application". The priority of the Chinese patent application, the entire content of which is incorporated in this application by reference.

technical field

The invention relates to the technical field of antibacterial textiles, in particular to a nanofiber-coated yarn and a preparation method thereof, a nanofiber-coated yarn strand and an application thereof.

Background technique

In daily life, people inevitably come into contact with various pathogenic microorganisms, which multiply and grow rapidly in a suitable environment. Due to its porous and loose structure, textiles are easy to absorb various impurities and become one of the main carriers of breeding and parasitic bacteria. When textiles are in contact with the human body, microorganisms will grow and multiply on the surface of the body, and once they multiply too much, they will cause skin diseases. Wherein tinea pedis is caused by fungal infection, and the incidence rate is high (the crowd incidence rate can reach 15-20%). In the later stage, along with the development of the disease or scratching, bacterial infection can be caused, and pustules etc. occur. At present, antibacterial textiles have been studied a lot, but there are few antifungal textiles, and there is no certain therapeutic effect for patients who have already suffered from tinea pedis. Therefore, it is very urgent to develop antibacterial textiles with high efficiency, low toxicity, inhibitory effect on fungi and bacteria, and certain therapeutic effect on tinea pedis.

At present, there are many designs and researches on antibacterial socks. Considering the convenience of production and processing, the sustainability of antibacterial properties and the comfort of fabrics, the modification of yarns used to make socks takes the largest proportion. At present, the main method of imparting antibacterial properties to yarns is the dipping method, which is simple to operate, but has a series of shortcomings such as not being washable, affecting the softness of yarns, and having a high burst release effect on antibacterial agents. Some products blend antibacterial agents with high polymers for melt spinning and wet spinning to make synthetic fibers, but such fibers have low antibacterial efficiency and no sustained release effect. For antibacterial materials, most antibacterial socks choose natural antibacterial fibers, such as bamboo fiber and hemp fiber, but their antibacterial effect is very limited, and they have no therapeutic effect on people who have already suffered from athlete's foot. In recent years, graphene and silver antibacterial socks have also appeared on the market, but the cost of these two materials is high, and silver is easy to oxidize, and graphene is black, which affects the appearance of the fabric. Ketoconazole (KCZ) is an imidazole antifungal drug, which has been widely used in medicine and has a good curative effect on various diseases such as tinea pedis, but its use is mostly limited to smearing at present.

Contents of the invention

The object of the present invention is to provide a kind of nanofiber coated yarn and preparation method thereof, nanofiber coated yarn strand and application thereof, the nanofiber coated yarn provided by the present invention has good inhibitory effect on fungus and bacteria, especially It has a certain therapeutic effect on tinea pedis, is low in cost, safe and reliable, and has durability and sustained release.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a nanofiber covered yarn, comprising a core yarn and an outer cladding covered on the surface of the core yarn; the core yarn is polypyrrole-cotton yarn; the polypyrrole-cotton yarn comprises cotton yarn and is distributed on the Polypyrrole particles on the surface of the cotton yarn;

The outer cladding is an antibacterial nanofiber; the antibacterial nanofiber includes a polyacrylonitrile nanofiber matrix and ketoconazole and nano zinc oxide distributed on the polyacrylonitrile nanofiber matrix.

Preferably, the mass ratio of the outer cladding layer to the core yarn is 0.5-1:1.

Preferably, the density of the nanofiber-coated yarn is 0.0495-0.066 g/m; the average diameter of the nanofiber-coated yarn is 410-470 μm.

Preferably, based on the mass of the polypyrrole-cotton yarn as 100%, the mass content of polypyrrole particles in the polypyrrole-cotton yarn is 0.05-0.1%;

Based on the mass of the outer cladding layer as 100%, the mass content of the ketoconazole is 1-10%, and the mass content of the nano zinc oxide is 1-7%.

The present invention provides a preparation method of the nanofiber covered yarn described in the above technical solution, comprising the following steps:

placing the cotton yarn in the aqueous dispersion of pyrrole monomer to obtain a solution of pyrrole soaked in the cotton yarn;

Adding FeCl ₃ -p-toluenesulfonic acid solution dropwise to the pyrrole solution soaked in cotton yarn, performing in-situ oxidation polymerization reaction to obtain polypyrrole-cotton yarn;

The polyacrylonitrile-ketoconazole solution is used as the positive electrode electrospinning solution, the polyacrylonitrile-nano zinc oxide solution is used as the negative electrode electrospinning solution, and the polypyrrole-cotton yarn is rotated and coated by double-electrode electrospinning , to obtain nanofiber-coated yarn.

Preferably, the temperature of the in-situ oxidation polymerization reaction is 0-5°C.

Preferably, the conditions of the two-electrode electrospinning include: a voltage of 10-12V; a rotational speed of 200-600r/min; a moving speed of the polypyrrole-cotton yarn of 0.05-0.3mm/s; a positive electrode electrospinning liquid and a negative electrode The jet flow rate of the electrospinning solution is independently 0.1-0.5 mL/h.

The invention provides a strand of nanofiber-coated yarn, which is obtained by plying polypyrrole-cotton yarn and nanofiber-coated yarn; The nanofiber covered yarn prepared by the preparation method described in the scheme.

Preferably, S twist is adopted during the plying, and the twist is 50-150 twists/10cm.

The present invention provides the application of the nanofiber-coated yarn strands described in the above technical solution in antibacterial fabrics.

The invention provides a nanofiber covered yarn, comprising a core yarn and an outer cladding covered on the surface of the core yarn; the core yarn is polypyrrole-cotton yarn; the polypyrrole-cotton yarn comprises cotton yarn and is distributed on the The polypyrrole particles on the surface of the cotton yarn; the outer cladding is an antibacterial nanofiber; the antibacterial nanofiber includes a polyacrylonitrile nanofiber matrix and ketoconazole and nano-zinc oxide distributed on the polyacrylonitrile nanofiber matrix. The present invention selects cotton yarn with good hygroscopicity and abrasion resistance as raw material, uniformly adheres polypyrrole particles on the surface of cotton yarn, and obtains polypyrrole-cotton yarn with electrothermal performance, which is low in cost, safe, reliable, reusable, and electrothermal With excellent performance, it can quickly reach the comfortable temperature of the human body (37°C) at low voltage (1.5V), which has a warming effect on the human body; at 4.5V, it can reach 88°C, which can destroy the permeability of the bacterial cell membrane and cause damage to the bacterial structure , thereby killing bacteria. Therefore, it not only has a warming effect on the human body in an extremely cold environment, but also has a synergistic antibacterial effect, which can reduce the dosage of ketoconazole, thereby slowing down the emergence of drug resistance. The present invention adopts polypyrrole-cotton yarn coated with antibacterial nanofibers comprising ketoconazole and nano-zinc oxide, wherein ketoconazole is a class of broad-spectrum antifungal drugs, and it inhibits by interacting with enzyme 14-a demethylase Biosynthesis of ergosterol (cell membrane sterol of many fungi), ketoconazole can be used for local treatment of all superficial mycoses and seborrheic dermatitis; nano-zinc oxide is effective against Escherichia coli, Staphylococcus aureus, Salmonella, etc. The fungus has a strong inhibitory or killing effect, and the nanofiber-coated yarn provided by the invention has better inhibitory effects on both fungi and bacteria, with a bacteriostatic rate as high as 99%, and has a certain therapeutic effect on tinea pedis. The present invention uses antibacterial nanofibers as the outer cladding, and the antibacterial nanofibers include a polyacrylonitrile nanofiber matrix and ketoconazole and nano-zinc oxide distributed on the polyacrylonitrile nanofiber matrix, which can improve the sustained release of antibacterial agents Effect. Moreover, the nanofiber covered yarn provided by the invention has better strength, abrasion resistance and washing resistance, and has a longer service life.

The nanofiber-coated yarn provided by the invention has excellent antibacterial activity, certain durability and sustained release, and still has 97% antibacterial performance under 10 washing cycles, which can provide protection for people with foot diseases; electric heating It can promote the release of drugs, has a certain effect on wound healing, and can be used for antibacterial protection in low temperature environments.

The present invention also provides a preparation method of the nanofiber-coated yarn described in the above technical solution. The preparation method provided by the present invention is simple to operate, and the parameters are easy to control. The prepared nanofiber-coated yarn has good microscopic appearance, excellent antibacterial properties and Electrothermal performance.

The invention also provides a nanofiber-coated yarn strand, which has sufficient strength and wear resistance, and can be woven into antibacterial fabrics, such as socks and the like.

Instructions attached

Fig. 1 is the schematic flow chart of the preparation of polypyrrole-cotton yarn of the embodiment of the present invention;

Fig. 2 is the schematic flow chart of the preparation process of the nanofiber covered yarn of the embodiment of the present invention;

Fig. 3 is the schematic flow chart of the preparation process of the nanofiber coated yarn strand of the embodiment of the present invention;

Fig. 4 is the surface SEM figure of the nanofiber coated yarn strand prepared by embodiment 4;

Fig. 5 is the surface SEM figure of the polypyrrole-cotton yarn prepared by embodiment 4;

Fig. 6 is the surface SEM picture of the nanofiber covered yarn prepared by embodiment 4;

Fig. 7 is the abrasion resistance test figure of cotton yarn, polypyrrole-cotton yarn, nanofiber-coated yarn and nanofiber-coated yarn strand in embodiment 4;

Fig. 8 is the electrical heating performance test figure of the nanofiber coated yarn strand prepared in embodiment 4;

Fig. 9 is the antibacterial performance test figure of the nanofiber coated yarn strands prepared in Examples 1 to 4 to Escherichia coli and Staphylococcus aureus;

Figure 10 is a graph of the release rate of antibacterial drugs in the release medium.

Detailed ways

The nanofiber covered yarn provided by the invention includes a core yarn. In the present invention, the core yarn is polypyrrole-cotton yarn; the polypyrrole-cotton yarn includes cotton yarn and polypyrrole particles distributed on the surface of the cotton yarn. In the present invention, based on the weight of the polypyrrole-cotton yarn as 100%, the mass content of polypyrrole particles in the polypyrrole-cotton yarn is preferably 0.05-0.1%, more preferably 0.07-0.09%. In the present invention, the cotton yarn is preferably 40-count twisted cotton yarn. In the present invention, the color of the polypyrrole-cotton yarn is black.

The nanofiber covered yarn provided by the invention includes an outer cladding layer covering the surface of the core yarn. In the present invention, the outer cladding is an antibacterial nanofiber; the antibacterial nanofiber includes a polyacrylonitrile nanofiber matrix and ketoconazole and nano zinc oxide distributed on the polyacrylonitrile nanofiber matrix. In the present invention, the mass ratio of the outer cladding layer to the core yarn is preferably 0.5-1:1, more preferably 0.6-0.7:1. In the present invention, the mass content of the ketoconazole is preferably 1-10%, more preferably 5-8% based on the mass of the outer cladding layer as 100%; the mass content of the nano zinc oxide is preferably 1-7%, more preferably 2-5%; the balance is polyacrylonitrile nanofiber matrix. In the present invention, the diameter of the nano zinc oxide is preferably 20-100 nm.

In the present invention, the density of the nanofiber-coated yarn is preferably 0.0495-0.066 g/m, more preferably 0.056-0.060 g/m; the average diameter of the nanofiber-coated yarn is preferably 410-470 μm, more preferably Preferably it is 440-460 micrometers.

The present invention also provides a preparation method of the nanofiber covered yarn described in the above technical solution, comprising the following steps:

In the invention, the cotton yarn is placed in the aqueous dispersion liquid of the pyrrole monomer to obtain the pyrrole solution soaked in the cotton yarn. In the present invention, the cotton yarn preferably includes pretreatment before soaking; the pretreatment method preferably includes: washing the cotton yarn with ethanol, washing with water and drying in sequence. In the present invention, the washing liquid used in the ethanol washing is preferably absolute ethanol; the ethanol washing method is preferably soaking; the soaking time is preferably 30min; the washing liquid used in the washing with water is preferably deionized water ; The drying is preferably natural air drying. The invention utilizes pretreatment to remove impurities attached to the surface of the cotton yarn.

In the present invention, the preparation method of the aqueous dispersion of the pyrrole monomer preferably comprises: adding the pyrrole monomer dropwise into water, stirring while adding the dropwise, to obtain the aqueous dispersion of the pyrrole monomer. In the present invention, the water is preferably deionized water. In the present invention, the concentration of the aqueous dispersion of the pyrrole monomer is preferably 0.3-0.7 mol/L, more preferably 0.45-0.60 mol/L.

In the present invention, the mass ratio of the cotton yarn to water in the aqueous dispersion of pyrrole monomer is preferably 1:60.

In the present invention, the cotton yarn is preferably placed in the aqueous dispersion of pyrrole monomer, followed by stirring and standing in order to obtain the pyrrole solution soaked in cotton yarn. In the present invention, the stirring time is preferably 3-5 minutes; the standing time is preferably 30 minutes. In the invention, the pyrrole monomer is fully adsorbed on the cotton yarn by stirring and standing still.

After obtaining the pyrrole solution impregnated with cotton yarn, the present invention adds FeCl ₃ -p-toluenesulfonic acid solution dropwise to the pyrrole solution impregnated with cotton yarn to carry out in-situ oxidation polymerization reaction to obtain polypyrrole-cotton yarn. In the present invention, the mass ratio of FeCl ₃ to pyrrole monomer in the FeCl ₃ -p-toluenesulfonic acid solution is preferably 1 to 2:1, more preferably 3:2; the FeCl ₃ -p-toluenesulfonic acid The mass ratio of p-toluenesulfonic acid to pyrrole monomer in the solution is preferably 2 to 4:1, more preferably 3:1; the total mass concentration of FeCl and p-toluenesulfonic acid in the _FeCl3 _- p-toluenesulfonic acid solution Preferably it is 17 to 24%, more preferably 20 to 22%. In the present invention, the solvent of the FeCl ₃ -p-toluenesulfonic acid solution is preferably water, more preferably deionized water. In the present invention, the preparation method of the FeCl ₃ -p-toluenesulfonic acid solution preferably includes: mixing FeCl ₃ , p-toluenesulfonic acid and water to obtain a FeCl ₃ -p-toluenesulfonic acid solution. In the present invention, the mixing is preferably magnetic stirring; the time of magnetic stirring is preferably 30 min. In the present invention, the FeCl ₃ plays an oxidation role, and p-toluenesulfonic acid is a stabilizer for in-situ polymerization.

In the present invention, the method of adding the FeCl ₃ -p-toluenesulfonic acid solution dropwise to the pyrrole solution soaked in cotton yarn preferably includes: placing the pyrrole solution soaked in cotton yarn in an ice bath, and immersing 10~ 15mL FeCl ₃ -p-toluenesulfonic acid solution was added dropwise to the pyrrole solution soaked in cotton gauze. In the present invention, the dropping speed is preferably 15 mL/min. In a specific embodiment of the present invention, the total time of the dropping is within 120 minutes. In the present invention, during the dropping process, it is preferred to stir once every 10 min. In the present invention, during the dropping process, the pyrrole monomer undergoes an in-situ oxidative polymerization reaction to obtain polypyrrole.

In the present invention, the temperature of the in-situ oxidative polymerization reaction is preferably 0-5°C. In the present invention, in the in-situ oxidation polymerization reaction, the polypyrrole is evenly covered on the cotton yarn to obtain the polypyrrole-cotton yarn.

After obtaining the polypyrrole-cotton yarn, the present invention uses the polyacrylonitrile-ketoconazole solution as the positive electrode electrospinning liquid, and the polyacrylonitrile-nano zinc oxide solution as the negative electrode electrospinning liquid, adopts double-electrode electrospinning, and the The above polypyrrole-cotton yarn is rotated and covered to obtain a nanofiber covered yarn. In the present invention, the solvent of the polyacrylonitrile-ketoconazole solution is preferably N,N-dimethylformamide (DMF); the polyacrylonitrile (PAN) in the polyacrylonitrile-ketoconazole solution The mass fraction is preferably 10-15%, more preferably 13%; the mass fraction of ketoconazole (KCZ) in the polyacrylonitrile-ketoconazole solution is preferably 1-10%, more preferably 5%.

In the present invention, the solvent of the polyacrylonitrile-nanometer zinc oxide solution is preferably DMF; the mass fraction of PAN in the polyacrylonitrile-nanometer zinc oxide solution is preferably 10 to 15%, more preferably 13%; The mass fraction of nano zinc oxide in the polyacrylonitrile-nanometer zinc oxide solution is preferably 1-7%, more preferably 3-5%. In the present invention, the diameter of the nano zinc oxide is preferably 20-100 nm.

In the present invention, before performing the double-electrode electrospinning, preferably, the polyacrylonitrile-ketoconazole solution and the polyacrylonitrile-nanometer zinc oxide solution are homogenized respectively; the polyacrylonitrile-ketoconazole solution The homogeneous treatment method is preferably: the polyacrylonitrile-ketoconazole solution is treated in a water bath at 65°C for 4h; the homogeneous treatment method of the polyacrylonitrile-nanometer zinc oxide solution is preferably: Treated in a water bath for 4h, and then ultrasonicated for 180min at 25°C.

In the present invention, the conditions of the electrospinning include: the voltage is preferably 10-12V; the rotational speed is preferably 200-600r/min, more preferably 300-500r/min; the moving speed of the polypyrrole-cotton yarn is preferably 0.05- 0.3 mm/s, more preferably 0.1 mm/s; the jet flow rates of the positive electrospinning solution and the negative electrospinning solution are independently preferably 0.1-0.5 mL/h, more preferably 0.3 mL/h. In the present invention, the injection flow rates of the positive electrode electrospinning solution and the negative electrode electrospinning solution are preferably the same.

The invention adopts the rotating covering, so that the nanofiber covering yarn has a certain orientation arrangement, which is beneficial to improving the mechanical properties of the nanofiber covering yarn.

The present invention also provides a strand of nanofiber-coated yarn, which is obtained by plying polypyrrole-cotton yarn and nanofiber-coated yarn; The nanofiber covered yarn prepared by the preparation method described in the technical solution. In the present invention, the composition of the polypyrrole-cotton yarn is consistent with that of the core yarn described above, and will not be repeated here. In the present invention, the mass ratio of the polypyrrole-cotton yarn to the nanofiber-coated yarn is preferably 1:0.5-1, more preferably 1:0.7. In the present invention, S twist is preferably used in the plying, and the twist is preferably 50-150 twists/10cm, more preferably 80 twists/10cm. In the present invention, the plying is preferably performed on a spinning frame.

In the present invention, the average diameter of the nanofiber-coated yarn strands is preferably 630-710 μm, more preferably 658 μm.

In a specific embodiment of the present invention, the abrasion resistance of the nanofiber-coated yarn strands is as high as 430 times, and it still maintains a good shape after 200 times of friction; the yarn breaking strength is 613cN, which is higher than the cotton yarn strength of 411cN. The nanofiber-coated yarn strand provided by the invention has good microscopic appearance, excellent antibacterial performance, electric heating performance, sufficient strength and wear resistance.

The present invention also provides the application of the nanofiber-coated yarn strand in the above technical solution in antibacterial fabrics. In the present invention, the antibacterial fabric preferably includes socks. In the present invention, the mass content of the nanofiber-coated yarn strand in the antibacterial fabric is preferably 30-70%, more preferably 40-60%. In the present invention, there is no special limitation on the application method, and methods known to those skilled in the art can be used.

The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Example 1

Step (1): Weigh 30g of cotton yarn, soak it in absolute ethanol for 30min, rinse it with deionized water, and let it dry naturally.

Step (2): According to the bath ratio of cotton yarn and deionized water as 1:60, measure 1800mL of deionized water, add 54.27g of pyrrole monomer dropwise, stir until it is evenly dispersed in deionized water, and then put the cotton yarn into the above-mentioned pyrrole monomer aqueous dispersion, stirred for 5 minutes and soaked for 30 minutes to obtain the pyrrole solution soaked in cotton yarn.

Step (3): According to the amount of pyrrole, FeCl _{3 is weighed according to the mass ratio of FeCl 3} _and pyrrole as 3:2, and 171.198g of p-toluenesulfonic acid is calculated and weighed, and FeCl ₃ and p-toluenesulfonic acid are poured into 1800mL In deionized water, stir magnetically for 30 min until completely dissolved to obtain FeCl ₃ -p-toluenesulfonic acid solution.

Step (4): Place the pyrrole solution soaked in cotton yarn in step (2) in an ice bath at 0°C, and add 15 mL of the FeCl ₃ -p-toluenesulfonic acid solution prepared in step (3) dropwise to the In the pyrrole solution soaked in cotton yarn, carry out in-situ oxidative polymerization reaction. During this period, stir the ice bath regularly every 10 minutes to ensure that the FeCl ₃ -p-toluenesulfonic acid solution is added within 120 minutes. The solution gradually turns black, and a large amount of polypyrrole is evenly covered On the cotton yarn, polypyrrole-cotton yarn is obtained, and the schematic diagram of the preparation process of the polypyrrole-cotton yarn is shown in Figure 1.

Step (5): PAN and KCZ are dissolved in DMF, obtain PAN-KCZ solution; The mass fraction of PAN is 13% in the described PAN-KCZ solution, and the mass fraction of KCZ is 5%; PAN and nanometer ZnO are dissolved in In DMF, a PAN-nano-ZnO solution is obtained; the mass fraction of PAN in the PAN-nano-ZnO solution is 13%, and the mass fraction of nano-ZnO is 1%. Both the PAN-KCZ solution and the PAN-nano-ZnO solution were placed in a 65°C water bath for 4h, and then the PAN-nano-ZnO solution was ultrasonically treated at 25°C for 180min.

Step (6): The polypyrrole-cotton yarn obtained in step (4) is used as the core yarn, the PAN-KCZ solution obtained in step (5) is used as the positive electrode electrospinning liquid, and the PAN-nano ZnO solution is used as the negative electrode electrospinning liquid. Two-electrode electrospinning technology, adjust the electrospinning parameters, and rotate and coat the polypyrrole-cotton yarn through a conventional nozzle-type electrospinning device to obtain nanofiber-coated yarn; the parameters of the electrospinning are: the voltage is 12V ; The rotation speed is 300r/min; the moving speed of polypyrrole-cotton yarn is 0.1mm/s; The schematic diagram of the preparation process of the nanofiber-coated yarn is shown in FIG. 2 .

Step (7): The polypyrrole-cotton yarn obtained in step (4) and the nanofiber-coated yarn obtained in step (6) are carried out S-twisting and plying with a spinning frame, and the twist is 80 twists/10cm to obtain nanofiber-coated yarn strands The schematic diagram of the preparation process of the nanofiber-coated yarn strand is shown in Figure 3.

Example 2

Step (3): According to the amount of pyrrole, FeCl ₃ is weighed according to the mass ratio of FeCl ₃ and pyrrole as 3:2, and 171.198g of p-toluenesulfonic acid is calculated and weighed, and FeCl ₃ and p-toluenesulfonic acid are poured into 1800mL In deionized water, stir magnetically for 30 min until completely dissolved to obtain FeCl ₃ -p-toluenesulfonic acid solution.

Step (5): PAN and KCZ are dissolved in DMF, obtain PAN-KCZ solution; The mass fraction of PAN is 13% in the described PAN-KCZ solution, and the mass fraction of KCZ is 5%; PAN and nanometer ZnO are dissolved in In DMF, a PAN-nano-ZnO solution is obtained; the mass fraction of PAN in the PAN-nano-ZnO solution is 13%, and the mass fraction of nano-ZnO is 3%. Both the PAN-KCZ solution and the PAN-nano-ZnO solution were placed in a 65°C water bath for 4h, and then the PAN-nano-ZnO solution was ultrasonically treated at 25°C for 180min.

Example 3

Step (5): PAN and KCZ are dissolved in DMF, obtain PAN-KCZ solution; The mass fraction of PAN is 13% in the described PAN-KCZ solution, and the mass fraction of KCZ is 5%; PAN and nanometer ZnO are dissolved in In DMF, a PAN-nano-ZnO solution is obtained; the mass fraction of PAN in the PAN-nano-ZnO solution is 13%, and the mass fraction of nano-ZnO is 5%. Both the PAN-KCZ solution and the PAN-nano-ZnO solution were placed in a 65°C water bath for 4h, and then the PAN-nano-ZnO solution was ultrasonically treated at 25°C for 180min.

Example 4

Step (5): PAN and KCZ are dissolved in DMF, obtain PAN-KCZ solution; The mass fraction of PAN is 13% in the described PAN-KCZ solution, and the mass fraction of KCZ is 5%; PAN and nanometer ZnO are dissolved in In DMF, a PAN-nano-ZnO solution is obtained; the mass fraction of PAN in the PAN-nano-ZnO solution is 13%, and the mass fraction of nano-ZnO is 7%. Both the PAN-KCZ solution and the PAN-nano-ZnO solution were placed in a 65°C water bath for 4h, and then the PAN-nano-ZnO solution was ultrasonically treated at 25°C for 180min.

test case 1

Fig. 4 is the surface SEM image of the nanofiber-coated yarn strand prepared in Example 4. It can be seen from Fig. 4 that the structure and shape of the nanofiber-coated yarn strand prepared by the present invention is good.

Figure 5 is a scanning electron microscope image of the polypyrrole-cotton yarn prepared in Example 4. It can be seen from Figure 5 that a large amount of polypyrrole is evenly covered on the cotton yarn. The structure of the polypyrrole-cotton yarn prepared in Examples 1-3 is similar to that of Example 4.

Figure 6 is the surface SEM image of the nanofiber-coated yarn prepared in Example 4. It can be seen from Figure 6 that nano-ZnO and KCZ have good spinnability and can be evenly coated on the core yarn.

Fig. 7 is the abrasion resistance test figure of cotton yarn, polypyrrole-cotton yarn, nanofiber-coated yarn and nanofiber-coated yarn strand in embodiment 4, as can be seen from Fig. 7, the nanofiber-coated yarn after ply twisting The wear resistance of the covered yarn is obviously improved, and it still maintains a good shape and structure after 200 friction tests.

FIG. 8 is a graph showing the electric heating performance test of the nanofiber-coated yarn strand prepared in Example 4. FIG. It can be seen from Figure 8 that the nanofiber-coated yarn strands prepared by the present invention have excellent electrothermal properties, and can quickly heat up at low voltage (1.5V) to reach the comfortable temperature of the human body (37°C); 4.5V can reach 88.1°C, which can Kills most bacteria.

Fig. 9 is the antibacterial performance test chart of the nanofiber-coated yarn strands prepared in Examples 1 to 4 to Escherichia coli and Staphylococcus aureus; the detection method is GB/T 20944.3-2008 "Evaluation of the Antibacterial Performance of Textiles Part 3 Oscillation For details, see Table 1.

Table 1 Antibacterial properties of nanofiber-coated yarn strands against Escherichia coli and Staphylococcus aureus

实施例Example	大肠杆菌抑菌率/％Escherichia coli inhibition rate/%	金黄色葡萄球抑菌率/％Staphylococcus aureus antibacterial rate/%
实施例1Example 1	74.2274.22	96.1633396.16333
实施例2Example 2	91.5791.57	99.5933399.59333
实施例3Example 3	91.5666791.56667	98.4898.48
实施例4Example 4	97.7633397.76333	99.6133399.61333

It can be seen from Table 1 that the nanofiber-covered yarn provided by the present invention has a better inhibitory effect on bacteria.

test case 2

The nanofiber coated yarn strand prepared by the embodiment is woven into an antibacterial fabric, and 0.08g of the antibacterial fabric is immersed in 50mL of 0.01mol/L phosphate buffered saline (PBS, PH= 4.5) in the solution, shake gently, and measure the concentration of ketoconazole by ultraviolet spectrophotometer, record the concentration change of KCZ within a certain period of time. Replace 1 mL of soaking solution with 1 mL of fresh PBS at regular intervals. Through the release behavior of the antibacterial drug KCZ in the release medium, the effect of temperature on the sustained release rate, the durability of the antibacterial fabric, and the effect of twisting on the sustained release of the drug were evaluated, as shown in Figure 10 and Table 2.

Table 2 The release rate results of antibacterial drugs in the release medium

It can be seen from Figure 10 and Table 2 that the release of KCZ in the antibacterial fabric shows a two-stage release behavior. At the beginning, due to the dissolution of KCZ adsorbed on the surface of the nanofiber-coated yarn, a certain amount of KCZ will be quickly provided to the environment. The release was rapid in the first few hours; in the subsequent time, the release rate was much slower than that of the first stage, which was the result of KCZ diffusion from the interior of the fiber into the solution as the sample degraded. And it can be seen that increasing the temperature can promote the release rate of KCZ.

The nanofiber coated yarn prepared by the embodiment is woven into an antibacterial fabric without twisting, and the above-mentioned same method is used to evaluate the influence of temperature on the slow-release rate, and the slow-release result is basically consistent with Fig. 10 and table 2, which proves that twisting has an Drug release has no effect.

This shows that both the nanofiber-coated yarn and the nanofiber-coated yarn strand provided by the present invention have good slow-release properties.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

A nanofiber covered yarn, comprising a core yarn and an outer cladding covered on the surface of the core yarn; the core yarn is a polypyrrole-cotton yarn; the polypyrrole-cotton yarn includes a cotton yarn and the Polypyrrole particles;

The outer cladding is an antibacterial nanofiber; the antibacterial nanofiber includes a polyacrylonitrile nanofiber matrix and ketoconazole and nano zinc oxide distributed on the polyacrylonitrile nanofiber matrix.
The nanofiber covered yarn according to claim 1, characterized in that the mass ratio of the outer covering layer to the core yarn is 0.5-1:1.
The nanofiber-covered yarn according to claim 1, characterized in that, the density of the nanofiber-covered yarn is 0.0495-0.066 g/m; the average diameter of the nanofiber-covered yarn is 410-470 μm.
The nanofiber-coated yarn according to claim 1, characterized in that, based on the mass of the polypyrrole-cotton yarn as 100%, the mass content of polypyrrole particles in the polypyrrole-cotton yarn is 0.05-0.1%;

Based on the mass of the outer cladding layer as 100%, the mass content of the ketoconazole is 1-10%, and the mass content of the nano zinc oxide is 1-7%.
The nanofiber covered yarn according to claim 1, characterized in that the diameter of the nano-zinc oxide is 20-100 nm.
The preparation method of the nanofiber covered yarn described in any one of claims 1 to 5, comprising the following steps:

placing the cotton yarn in the aqueous dispersion of pyrrole monomer to obtain a solution of pyrrole soaked in the cotton yarn;

Adding FeCl 3 -p-toluenesulfonic acid solution dropwise to the pyrrole solution soaked in cotton yarn, performing in-situ oxidation polymerization reaction to obtain polypyrrole-cotton yarn;

The polyacrylonitrile-ketoconazole solution is used as the positive electrode electrospinning solution, the polyacrylonitrile-nano zinc oxide solution is used as the negative electrode electrospinning solution, and the polypyrrole-cotton yarn is rotated and coated by double-electrode electrospinning , to obtain nanofiber coated yarn.
The preparation method according to claim 6, characterized in that, the mass ratio of FeCl 3 to pyrrole monomer in the FeCl 3 -p-toluenesulfonic acid solution is 1 to 2:1; the FeCl 3 -p -toluenesulfonic acid solution The mass ratio of p-toluenesulfonic acid to pyrrole monomer in the acid solution is 2-4:1.
The preparation method according to claim 6 or 7, characterized in that the temperature of the in-situ oxidation polymerization reaction is 0-5°C.
The preparation method according to claim 6, characterized in that the mass fraction of ketoconazole in the polyacrylonitrile-ketoconazole solution is 1-10%.
The preparation method according to claim 6, characterized in that the mass fraction of nano-zinc oxide in the polyacrylonitrile-nanometer zinc oxide solution is 1-7%.
The preparation method according to claim 6, characterized in that, the conditions of the two-electrode electrospinning include: the voltage is 10-12V; the rotational speed is 200-600r/min; the moving speed of the polypyrrole-cotton yarn is 0.05-0.3 mm/s; the jet flow rates of the positive electrospinning solution and the negative electrospinning solution are independently 0.1-0.5 mL/h.
A nanofiber-covered yarn strand, which is obtained by plying polypyrrole-cotton yarn and nanofiber-covered yarn; the nanofiber-covered yarn is the nanofiber-covered yarn or claim The nanofiber covered yarn prepared by the preparation method described in any one of 6 to 11 is required.
The nanofiber-coated yarn strand according to claim 12, characterized in that S twist is used during the plying, and the twist is 50-150 twists/10cm.
The application of the nanofiber covered yarn strand in any one of claims 12 to 13 in antibacterial fabrics.
The application according to claim 14, characterized in that the mass content of the nanofiber-coated yarn strand in the antibacterial fabric is 30-70%.