Anti-static medical fabric and preparation method thereof

Abstract

The invention relates to the technical field of medical textile materials, in particular to an anti-static medical fabric and a preparation method thereof.The anti-static medical fabric comprises an outer layer, a middle layer, an inner layer and carbon fiber grids embedded into the outer layer and the inner layer, the outer layer is made of nanofibers prepared by electrostatic spinning and comprises polyvinylidene fluoride, an F-ZnO / TiO2 composite antibacterial agent, carboxylated carbon nanotubes and grafted quaternary ammonium salt; the middle layer is a chitosan enhanced polytetrafluoroethylene film, and the surface of the middle layer is sequentially coated with a chitosan / silk fibroin transition layer and a polypyrrole conducting layer; the inner layer is a blend fiber fabric and comprises hollow polyester fibers, chitosan microsphere modified cotton fibers and carbon nanotube grafted polyamide fibers; the carbon fiber grids are embedded into the outer layer and the inner layer in a warp knitting mode with the density of 20-24 pieces / cm. According to the antistatic fabric, a four-stage conductive network is formed by the outer-layer carbon nanotubes, the middle-layer polypyrrole, the inner-layer grafted carbon nanotubes and the carbon fiber grids, so that the antistatic performance of the fabric is greatly improved.

Description

Technical Field

[0001] This invention relates to the field of medical textile materials technology, specifically to an antistatic medical fabric and its preparation method. Background Technology

[0002] Medical protective fabrics need to block blood, body fluids, and pathogenic microorganisms while ensuring the comfort of medical staff during prolonged wear. Traditional fabrics such as polyester substrates, although strong, have many drawbacks: for example, insufficient antistatic properties, static electricity accumulation attracts pathogenic microorganisms, increasing the risk of infection; and the poor moisture wicking properties of round cross-section fibers, causing sweat retention and discomfort. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides an antistatic medical fabric and its preparation method, specifically achieved through the following technical solution: A method for preparing an antistatic medical fabric includes the following steps: S1. Prepare antistatic and antibacterial outer layer material: Take 100 parts of polyvinylidene fluoride, 8-15 parts of F-ZnO / TiO2, and 2-5 parts of carboxylated carbon nanotubes by weight and disperse them in DMAC / acetone mixed solvent. Then, after electrospinning and hot rolling, impregnate with 2wt%-4wt% CTAB ethanol solution for quaternary ammonium salt grafting. S2 prepares a chitosan-reinforced PTFE barrier interlayer material; after corona treatment, the PTFE membrane is alternately coated with N layers of chitosan and N-1 layers of silk fibroin, where N is an integer greater than or equal to 2. After coating, it is impregnated with a 0.5% volume fraction glutaraldehyde aqueous solution for cross-linking treatment to form a chitosan / silk fibroin layer on the surface of the PTFE membrane; then, a polypyrrole conductive layer is prepared by in-situ polymerization. S3 prepares a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material; by weight, take 55-60 parts of hollow polyester fiber, 12.5-25 parts of chitosan microsphere modified cotton fiber, and 15-27 parts of carbon nanotube-grafted nylon, and successively pass them through opening, carding, drawing, and air-jet vortex spinning to obtain composite cross-section fiber. S4 fabric composite: The outer layer fabric is spun using the material obtained from S1, and the inner layer fabric is spun using the material obtained from S3. Then, carbon fibers are embedded into the outer and inner layers fabrics at a mesh density of 22 fibers / cm using a warp knitting machine. Then, the outer layer fabric, the middle layer, and the inner layer fabric are sequentially stacked and rolled together. S5 post-processing: Waterproofing, softening, and UV curing are performed sequentially to obtain the finished fabric.

[0004] The specific method of grafting the quaternary ammonium salt is as follows: add CTAB ethanol solution to the reaction tank, immerse the hot-rolled fiber membrane in the solution to ensure complete immersion, heat in a 60°C water bath, stir at 100 rpm, and react for 3-5 hours. After the reaction is completed, take out the membrane, rinse it with ethanol 3 times, and dry it at 80°C.

[0005] The specific preparation method of the chitosan / silk fibroin layer is as follows: a chitosan solution with pH 5.0 and a concentration of 0.032–0.04 kg / L is prepared using a 1% (w / w) acetic acid aqueous solution; a silk fibroin solution with a concentration of 0.008–0.028 kg / L is prepared using deionized water; the pretreated PTFE membrane is first immersed in the chitosan solution for 5 min, then removed, centrifuged, and dried; then immersed in the silk fibroin solution for 5 min, and centrifuged and dried again; this process is repeated until the predetermined number of layers is reached; then immersed in an aqueous solution containing 0.5% glutaraldehyde and reacted at 80°C for 20 min.

[0006] The preparation of the polypyrrole conductive layer is as follows: A 0.02–0.025 kg / L sodium dodecylbenzenesulfonate solution is prepared using deionized water. Then, pyrrole monomer is added to the sodium dodecylbenzenesulfonate solution at a volume ratio of deionized water to pyrrole monomer of 150:1–1.25, and stirred until dissolved. A PTFE membrane coated with a chitosan / silk fibroin layer is then immersed in the solution, completely submerged, and placed in an ice-water bath while nitrogen is introduced to purge air. Finally, a 0.4–0.5 kg / L ammonium persulfate aqueous solution is added dropwise to the reactor through a constant-pressure dropping funnel, and ultrasonic polymerization is performed for 10–14 hours. The dropping time is 1–3 hours.

[0007] The chitosan microsphere-modified cotton fiber was prepared by the following method: the cotton fiber was fully wetted in deionized water, and then chitosan microspheres were added at a mass ratio of cotton fiber to chitosan microspheres of 15:1. After stirring evenly, the pH value was adjusted to 5.0 with 1% acetic acid, and the reaction was carried out at a constant temperature of 30°C for 2 hours. After the reaction was completed, the cotton fiber was washed with deionized water until neutral and dried at 80°C.

[0008] The carbon nanotube-grafted nylon was prepared by the following method: after plasma pretreatment, the nylon was immersed in a 4wt% acidified carbon nanotube dispersion, and shaken in a water bath at 150 rpm and 60°C for 6 hours. The nylon was then removed, washed with deionized water until neutral, and dried at 80°C.

[0009] Before use, the carbon fiber is immersed in a 2wt% KH560 ethanol solution, soaked at 60°C for 1 hour, and then dried at 80°C.

[0010] The chitosan microspheres were prepared by the following method: a 5 g / L chitosan solution was prepared by taking chitosan with a degree of deacetylation of 90% and 1% acetic acid aqueous solution. Span-80 was added at a mass ratio of 1:1 to chitosan. The mixture was sheared at 10,000 rpm for 30 min to form an emulsion. One-tenth the volume of 10% glutaraldehyde solution was added to the 1% acetic acid aqueous solution. The mixture was reacted at 30°C for 2 h. After centrifugation, the mixture was washed with deionized water until neutral and dried at 60°C to obtain chitosan microspheres.

[0011] The waterproofing treatment specifically involves mixing fluorocarbon resin and deionized water at a volume ratio of 13-15:85-87, then immersing the fabric obtained by roller pressing in the mixture and letting it stand for 12 minutes. After removal, the fabric is placed in a roller press and then dried with hot air.

[0012] An antistatic medical fabric is prepared using the above-mentioned method for preparing antistatic medical fabric.

[0013] The technical solution of the present invention has the following advantages: 1. High specific surface area antibacterial system: Electrospun PVDF nanofibers are loaded with F-ZnO / TiO2 (photocatalytic antibacterial) and quaternary ammonium salts to form multi-level antibacterial effect. The antibacterial rate is still ≥92% after 100 washes. 2. Quadruple conductive network: outer layer carbon nanotubes + middle layer polypyrrole + inner layer grafted carbon nanotubes + carbon fiber mesh, with a surface resistivity stable at 10. 6 ~10 7 Ω·m, electrostatic half-life < 0.6s; 3. Interface-enhanced structure: The chitosan / silk fibroin transition layer is connected by covalent and hydrogen bonds, and the peel strength is increased to ≥65N / cm. No delamination occurs after 100 water washes. 4. Composite irregular cross section optimization: The inner Y-shaped hollow groove structure combined with the electrospun outer porous network improves the moisture permeability to 3800g / m²·24h and the moisture wicking speed ≤5s. Detailed Implementation

[0014] The technical solution of the present invention will be clearly and completely described below through specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0015] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0016] The national standards used in the following examples are all current standards.

[0017] Example 1 S1 is used to prepare an antistatic and antibacterial outer layer material.

[0018] S1.1 Raw material preparation.

[0019] Weigh out 14 kg of PVDF (polyvinylidene fluoride), 1.2 kg of F-ZnO / TiO2, 0.4 kg of carboxylated carbon nanotubes, 60 L of DMAC (dimethylacetamide), 40 L of acetone, 0.5 kg of CTAB (cetyltrimethylammonium bromide), and 10 L of anhydrous ethanol. Prepare the S1.2 spinning solution. Add 60 L of DMAC and 40 L of acetone sequentially to a 100 L stainless steel reactor, start stirring, and maintain a speed of 300 rpm. Then add 14 kg of PVDF particles to the reactor and stir until completely dissolved.

[0020] After the PVDF is completely dissolved, add 1.2 kg F-ZnO / TiO2 and 0.4 kg carboxylated carbon nanotubes, and start the ultrasonic device at 800 W for 6 h. During the dispersion process, stop the machine every 1 h to observe the dispersion state and ensure that there is no obvious agglomeration.

[0021] After dispersion, turn off the stirring and let it stand at room temperature for 12 hours to remove bubbles, then set aside for later use.

[0022] S1.3 electrospinning.

[0023] Inspect the high-voltage power supply, feed pump, and receiving device of the electrospinning machine. Install a 0.2mm orifice stainless steel spinneret and cover the receiving roller with aluminum foil. Set the parameters: voltage 28kV, distance between spinneret and receiving roller 18cm, receiving roller speed 500rpm. Pour the spinning solution into the storage tank, start the equipment, and spin nanofibers.

[0024] S1.4 Hot rolling treatment.

[0025] Nanofibers were placed in a hot roller press, with the temperature set at 120℃, the pressure at 0.3MPa, and the roller speed at 2m / min. The density of the treated nanofibers increased by 20%, and the breaking strength increased from 3.5cN / dtex to 4.2cN / dtex.

[0026] S1.5 quaternary ammonium salt grafting.

[0027] Add a 3wt% CTAB ethanol solution to the reaction vessel, immerse the hot-pressed fiber in the solution to ensure complete submersion, heat in a 60°C water bath, stir at 100 rpm, and react for 4 hours. After the reaction is complete, remove the membrane, rinse it three times with ethanol to remove unreacted CTAB, and dry it at 80°C for 2 hours.

[0028] The porous structure of electrospun nanofibers results in a high specific surface area and a stronger loading capacity for F-ZnO / TiO2. Under ultraviolet light, the photocatalytic inhibition rate against Staphylococcus aureus can reach over 99%.

[0029] After grafting with quaternary ammonium salts, the zeta potential on the surface of the fiber membrane changes from negative to positive, enhancing its ability to adsorb negatively charged bacteria and effectively improving the efficiency of contact sterilization.

[0030] Hot rolling treatment makes the fibers bond more tightly, preventing breakage during subsequent lamination, while retaining some pores so that the material still has good air permeability.

[0031] The photocatalytic effect of F-ZnO / TiO2 synergizes with the physical adsorption and sterilization of quaternary ammonium salts, and the antibacterial rate can be further improved under light conditions. Carboxylated carbon nanotubes and PVDF molecular chains are bonded by hydrogen bonds and are evenly distributed during ultrasonic dispersion, which not only enhances the conductivity of the fiber, but also improves the fiber strength through bridging effect.

[0032] S2 is used to prepare chitosan-reinforced PTFE (polytetrafluoroethylene) barrier interlayer material.

[0033] S2.1 Raw material preparation.

[0034] 100 m² of PTFE membrane with a thickness of 8 μm, a pore size of 1.0 μm, and a porosity of 85%; 2 kg of chitosan with a degree of deacetylation of 90%; 1.5 kg of silk fibroin; 50 L of 1% acetic acid aqueous solution (volume fraction, the same below); 0.5 L of glutaraldehyde; 1 L of pyrrole monomer; 3 kg of sodium dodecylbenzenesulfonate; 2 kg of ammonium persulfate; and deionized water.

[0035] S2.2PTFE membrane pretreatment.

[0036] Fix the PTFE membrane on the worktable of the corona treatment machine, set the power to 150W, and the treatment time to 2 minutes (5cm away from the membrane surface).

[0037] This treatment is used to reduce the surface contact angle of the membrane and increase the oxygen group content.

[0038] S2.3 Chitosan / silk fibroin layer coating.

[0039] Chitosan solution preparation: Add 2 kg of chitosan to 50 L of 1% acetic acid aqueous solution, stir for 3 h until completely dissolved, and adjust the pH value to 5.0 with 10% NaOH.

[0040] Preparation of silk fibroin solution: Dissolve 1.5 kg of silk fibroin in 100 L of deionized water, stir at 60 °C for 1 h, and filter to remove insoluble matter.

[0041] Layer-by-layer self-assembly: The pretreated PTFE membrane is first immersed in chitosan solution for 5 minutes, then centrifuged at 2000 rpm for 1 minute and dried at 80°C for 5 minutes; then immersed in silk fibroin solution for 5 minutes, and centrifuged and dried in the same way; the chitosan-silk fibroin coating is repeated 3 times to finally form a transition layer of 3 chitosan layers + 2 silk fibroin layers.

[0042] Crosslinking treatment: Glutaraldehyde was prepared into a 0.5% (v / v) aqueous solution; the membrane was immersed in the 0.5% glutaraldehyde aqueous solution and reacted at 80°C for 20 min to allow the amino groups of chitosan to crosslink with the hydroxyl groups of silk fibroin, thereby enhancing the stability of the membrane layer.

[0043] Preparation of S2.4 polypyrrole conductive layer.

[0044] Preparation of polymerization solution: Add 150L of deionized water to a 200L reactor, then add 1L of pyrrole monomer and 3Kg of sodium dodecylbenzenesulfonate, and stir until dissolved.

[0045] Membrane impregnation: Immerse the PTFE membrane coated with chitosan / silk fibroin into the solution. After complete immersion, place it in an ice-water bath at 0-5°C and purge with nitrogen for 30 minutes to remove air.

[0046] In-situ polymerization: Weigh 2 kg of ammonium persulfate, dissolve it in 5 L of deionized water, and add it dropwise into the reactor through a constant pressure dropping funnel over 1.5 hours. After the addition is complete, turn on the sonicator at 700 W and allow the polymerization reaction to proceed for 12 hours.

[0047] Post-processing: Remove the membrane, wash it three times with deionized water, and dry it at 60℃ for 2 hours to form a polypyrrole layer with a thickness of 70±10nm.

[0048] The chitosan / silk fibroin transition layer can be firmly bonded to the PTFE membrane and is not easily detached during water washing.

[0049] The amino groups of chitosan bind to the phospholipids of bacterial cell membranes, which can effectively inhibit fungi; Polypyrrole forms covalent bonds with the amino groups of chitosan, which improves the water resistance of the conductive layer.

[0050] The hydrophilicity of chitosan and the hydrophobicity of PTFE form a gradient wetting effect, which not only retains the barrier properties of PTFE, but also enhances the interception of viruses through the micropores of the transition layer; the conductivity of polypyrrole and the antibacterial properties of chitosan work synergistically at the interface, inhibiting bacterial growth on the membrane surface while dissipating charge.

[0051] S3 was used to prepare a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material.

[0052] S3.1 Raw material preparation.

[0053] 55 kg of hollow polyester fiber with a length of 38 mm and a hollow rate of 25%; 1 kg of chitosan microspheres with a particle size of 1-3 μm; 15 kg of cotton fiber; 30 kg of nylon; 20 L of acidified carbon nanotube dispersion with a carboxylation degree of 5.5 mmol / g and a mass concentration of 4 wt%; and 1% acetic acid aqueous solution.

[0054] S3.2 Preparation of cotton fiber modified with chitosan microspheres.

[0055] Chitosan microspheres were prepared by the following method: 50 g of chitosan with a degree of deacetylation of 90% was dissolved in 10 L of 1% acetic acid aqueous solution and stirred until completely dissolved. 50 g of Span-80 was added, and the mixture was sheared at 10000 rpm for 30 min using a high-speed shear mill to form an emulsion. 500 ml of 10% glutaraldehyde solution was added, and the mixture was reacted at 30 °C for 2 h. The mixture was then centrifuged at 5000 rpm to obtain chitosan microspheres, washed with deionized water until neutral, dried at 60 °C, and sieved to obtain microspheres of 1–3 μm.

[0056] Cotton fiber modification: Add 50L of deionized water to the reaction tank, add 15Kg of cotton fiber, and soak for 30min to fully wet it. Add 1Kg of chitosan microspheres, stir evenly, adjust the pH to 5.0 with 1% acetic acid, and react at 30℃ for 2h. After the reaction is complete, remove the cotton fiber, wash it with deionized water until neutral, and dry it at 80℃ to obtain chitosan microsphere-modified cotton fiber.

[0057] Preparation of S3.3 carbon nanotube grafted nylon.

[0058] Plasma pretreatment: 30 kg of nylon was placed in the plasma treatment chamber, Ar gas was introduced, the power was set to 80 W, and the treatment time was 5 min. This treatment is used to generate free radicals on the surface of the nylon.

[0059] Grafting reaction: The pretreated nylon was immersed in 20L of 4wt% acidified carbon nanotube dispersion and shaken in a water bath at 150rpm and 60℃ for 6h. The carboxyl groups of the carbon nanotubes reacted with the free radicals on the surface of the nylon to form covalent bonds.

[0060] Remove the nylon and wash it with deionized water until neutral, then dry it at 80℃ for 3 hours.

[0061] S3.4 Blended fiber preparation.

[0062] Cleaning: Hollow polyester fiber, chitosan modified cotton fiber, and carbon nanotube grafted nylon are respectively put into the cleaning machine, and the machine is operated at a speed of 850 rpm for 12 minutes to remove impurities.

[0063] Carding: Hollow polyester fiber, chitosan modified cotton fiber, and carbon nanotube grafted nylon are fed into the carding machine at a cylinder speed of 320 rpm and a flat plate speed of 110 mm / min to form a single-fiber cotton web.

[0064] Drawing: The three types of cotton web are fed into the drawing frame at a mass ratio of 55:30:15, the roller speed is 220m / min, and the blending uniformity CV value after three drawing passes is ≤2.8%.

[0065] Jet vortex spinning: The drawn fiber sliver is fed into the spinning machine, a Y-type hollow-groove composite spinneret is installed, the spinning speed is set to 450 m / min, the hot air temperature is 245℃, and the spinning pressure is 0.4 MPa to obtain composite cross-section fibers.

[0066] The surface resistivity of carbon nanotube-grafted nylon is much lower than that of nylon, and the graft bonds are covalent, so washing will not significantly affect the surface resistivity; the Y-shaped hollow-groove structure enhances the capillary effect. The blend ratio balances strength and comfort, making it suitable for long-term wear.

[0067] After the hydrophilic groups of chitosan microspheres adsorb sweat, it is quickly discharged through the capillary action of the Y-shaped grooves, and the air layer of hollow polyester fiber reduces the stuffiness; carbon nanotube grafted nylon is evenly distributed in the blended fiber, forming a continuous channel with the conductive materials of the outer and middle layers, avoiding the accumulation of static electricity in local areas.

[0068] S4 fabric composite.

[0069] S4.1 Raw Material Preparation 100m² of outer fabric made of antistatic and antibacterial outer layer material; 100m² of chitosan-reinforced PTFE barrier middle layer material; 100m² of inner fabric made of carbon nanotube-grafted moisture-wicking and comfortable inner layer material; 5Kg of polyacrylonitrile-based carbon fiber; 0.1Kg of coupling agent KH560.

[0070] The outer fabric is made of antistatic and antibacterial material obtained from S1 and woven into a plain weave fabric using a rapier loom (model GA747) at a speed of 320 rpm, with a warp density of 22 yarns / cm and a weft density of 20 yarns / cm.

[0071] The inner layer fabric is made of carbon nanotubes grafted with S3 to create a moisture-wicking and comfortable inner layer material in a twill weave. The machine speed is 300 rpm, the warp density is 20 threads / cm, and the weft density is 18 threads / cm.

[0072] S4.2 carbon fiber embedding.

[0073] Carbon fiber pretreatment: 0.1 kg KH560 was prepared into a 2 wt% ethanol solution; 5 kg of carbon fiber was immersed in the prepared KH560 ethanol solution, soaked at 60℃ for 1 hour, and dried at 80℃ to enhance the bonding force with the fiber.

[0074] Warp knitting embedding: Carbon fibers are embedded into the outer and inner fabrics at a mesh density of 22 fibers / cm using a warp knitting machine at a knitting speed of 220 rpm, ensuring that the number of carbon fibers per 10cm² deviates by ≤1 fiber.

[0075] S4.3 three-layer composite.

[0076] Layering process: On a clean workbench, lay out the outer fabric, chitosan-reinforced PTFE barrier intermediate layer material (polypyrrole layer facing inward), and inner fabric in sequence. Align the edges and fix them with positioning clips to ensure that the chitosan / silk fibroin transition layer is in close contact with the inner and outer layers. Roll forming: The laminated materials are fed into a continuous roll press, with a set pressure of 0.6 MPa, a temperature of 140℃, and a roll speed of 5 m / min. During the lamination process, an infrared thermometer is used to monitor the roll surface temperature, and a pressure sensor ensures stable pressure. After lamination, the materials are cooled to room temperature by cooling rollers and then wound up for later use.

[0077] The carbon fiber mesh, together with the outer carbon nanotubes, the middle polypyrrole, and the inner grafted carbon nanotubes, forms a four-level conductive network, which effectively reduces the surface resistivity.

[0078] The hydrogen and covalent bonds between the chitosan / silk fibroin transition layer and the inner and outer layers improve the fabric's peel strength, making it less prone to delamination after multiple washes; the plain outer layer is abrasion resistant, while the twill inner layer has a good hand feel.

[0079] Carbon fiber mesh serves as the backbone, connecting the conductive materials in each layer and improving charge dissipation efficiency. The rolling temperature matches the glass transition temperature of chitosan, promoting the movement of chitosan molecular chains, enhancing the interfacial bonding with the inner and outer layers, and preventing high temperature from damaging the microporous structure of PTFE.

[0080] S5 post-processing.

[0081] S5.1 Raw material preparation.

[0082] Fluorocarbon resin waterproofing agent (Asahiguard AG-E061) 14L; silicone emulsion (Dow Corning 350) 8L; deionized water.

[0083] S5.2 Waterproofing treatment.

[0084] Solution preparation: Add 86L of deionized water and 14L of fluorocarbon resin waterproof finishing agent to a 100L impregnation tank, stir evenly to obtain fluorocarbon resin waterproof finishing agent treatment solution. Impregnation treatment: Immerse the composite fabric in a fluorocarbon resin waterproof finishing agent solution. After complete immersion, let it stand for 12 minutes. After removal, place it in a rolling mill, set the pressure to 0.3 MPa, and control the roll-off rate to 72%.

[0085] Drying: Place in a hot air drying oven and dry at 125℃ for 10 minutes, then cool to room temperature.

[0086] S5.3 Softening treatment.

[0087] Solution preparation: Add 92L of deionized water and 8L of silicone emulsion to another 100L impregnation tank, and stir evenly to prepare a treatment solution with a volume concentration of 8%.

[0088] Impregnation treatment: Immerse the waterproof finished fabric in the silicone emulsion treatment solution, let it stand for 15 minutes, take it out and put it into the rolling mill, with a pick-up rate of 68%.

[0089] Drying: Place in a hot air drying oven and dry at 105℃ for 9 minutes, then cool.

[0090] S5.4 UV curing.

[0091] The fabric is placed in a UV curing machine with a wavelength of 254nm, a dose of 800mJ / cm², and a curing time of 3min to promote the covalent bonding between the fluorocarbon resin and the fiber.

[0092] Fluorocarbon resin forms a hydrophobic layer on the fabric surface; silicone emulsion reduces the fiber friction coefficient and improves softness; UV curing enhances the bonding force between the fluorocarbon resin and the fiber. The waterproofing agent reacts with the amino groups of chitosan to form covalent bonds, preventing the physical peeling of traditional waterproofing agents; the lubricating effect of the silicone emulsion works synergistically with the inner groove structure to reduce skin friction without clogging moisture absorption channels, achieving a balance of waterproofing, breathability, and softness.

[0093] The fabric obtained in Example 1 was tested.

[0094] 1. Antibacterial performance was tested according to GB / T20944.3: before washing, the inhibition rate of Staphylococcus aureus was 99.5%, the inhibition rate of Escherichia coli was 99%, and the inhibition rate of Candida albicans was 92%; after 100 washes, the inhibition rate of Staphylococcus aureus was 92%, the inhibition rate of Escherichia coli was 94%, and the inhibition rate of Candida albicans was 85%.

[0095] 2. Antistatic performance is tested according to GB / T12703.2: surface resistivity 3.2×10⁻⁶ 7 Ω·m; surface charge density 0.5 μC / m²; electrostatic half-life 0.6.

[0096] 3. Color fastness shall conform to GB / T3920: Grade 5 for dry rubbing and Grade 4-5 for wet rubbing.

[0097] 4. Moisture permeability shall conform to GB / T12704.1: 3850 g / m²·24h.

[0098] The multi-level antibacterial system of F-ZnO / TiO2, quaternary ammonium salt, and chitosan achieves broad-spectrum inhibition of bacteria and fungi, and significantly improves water washability; the four-level conductive network solves the problem of interlayer conductivity discontinuity, and the antistatic performance is more stable; the chitosan interface enhancement technology greatly improves the interlayer bonding force, and together with the composite irregular structure and post-processing, it balances protection and comfort, fully meeting the needs of high-risk medical scenarios.

[0099] Example 2 S1 is used to prepare an antistatic and antibacterial outer layer material.

[0100] S1.1 Raw material preparation.

[0101] Weigh 14 kg PVDF, 2.1 kg F-ZnO / TiO2, 0.7 kg carboxylated carbon nanotubes, 60 L DMAC, 40 L acetone, 0.5 kg CTAB, and 10 L anhydrous ethanol. Prepare S1.2 spinning solution. Add 60 L DMAC and 40 L acetone sequentially to a 100 L stainless steel reactor, start stirring, and maintain a speed of 300 rpm. Then add 14 kg PVDF particles to the reactor and stir until completely dissolved. After the PVDF is completely dissolved, add 2.1 kg F-ZnO / TiO2 and 0.7 kg carboxylated carbon nanotubes, and start the ultrasonic device at 800 W for dispersion for 7 hours. During dispersion, stop the machine every hour to observe the dispersion status and ensure no obvious agglomeration. After dispersion, turn off the stirring and let it stand at room temperature for 12 hours to remove bubbles, then set aside for later use.

[0102] S1.3 electrospinning.

[0103] Check the high-voltage power supply, feed pump, and receiving device of the electrospinning machine. Install a 0.2mm orifice stainless steel spinneret and cover the receiving roller with aluminum foil. Set the parameters: voltage 30kV, distance between spinneret and receiving roller 18cm, receiving roller speed 500rpm. Pour the spinning solution into the storage tank, start the equipment, and spin nanofibers.

[0104] S1.4 Hot rolling treatment.

[0105] Nanofibers were placed in a hot roller press, with the temperature set at 120℃, the pressure at 0.3MPa, and the roller speed at 2m / min. The density of the treated nanofibers increased by 20%, and the breaking strength increased from 3.5cN / dtex to 4.2cN / dtex.

[0106] S1.5 quaternary ammonium salt grafting.

[0107] Add a 4 wt% CTAB ethanol solution to the reaction vessel, immerse the hot-pressed fiber in the solution to ensure complete submersion, heat in a 60°C water bath, stir at 100 rpm, and react for 5 hours. After the reaction is complete, remove the membrane, rinse it three times with ethanol to remove unreacted CTAB, and dry it at 80°C for 2 hours.

[0108] S2 is used to prepare chitosan-reinforced PTFE barrier interlayer material.

[0109] S2.1 Raw material preparation.

[0110] 100 m² of PTFE membrane with a thickness of 9 μm, a pore size of 0.8 μm, and a porosity of 80%; 3 kg of chitosan with a degree of deacetylation of 90%; 2.25 kg of silk fibroin; 50 L of 1% acetic acid aqueous solution; 0.5 L of glutaraldehyde; 1.25 L of pyrrole monomer; 3.75 kg of sodium dodecylbenzenesulfonate; 2.5 kg of ammonium persulfate; and deionized water.

[0111] S2.2PTFE membrane pretreatment.

[0112] The PTFE membrane was fixed on the worktable of the corona treatment machine, with the power set to 150W and the treatment time to 2 minutes. This treatment is used to reduce the surface contact angle of the membrane and increase the oxygen group content.

[0113] S2.3 Chitosan / silk fibroin layer coating.

[0114] Chitosan solution preparation: Add 3 kg of chitosan to 50 L of 1% acetic acid aqueous solution, stir for 3 h until completely dissolved, and adjust the pH value to 5.0 with 10% NaOH.

[0115] Preparation of silk fibroin solution: Dissolve 2.25 kg of silk fibroin in 100 L of deionized water, stir at 60 °C for 1 h, and filter to remove insoluble matter.

[0116] Layer-by-layer self-assembly: The pretreated PTFE membrane is first immersed in chitosan solution for 5 minutes, then centrifuged at 2000 rpm for 1 minute and dried at 80°C for 5 minutes; then immersed in silk fibroin solution for 5 minutes, and centrifuged and dried in the same way; the chitosan-silk fibroin coating is repeated to finally form a transition layer of 4 chitosan layers + 3 silk fibroin layers.

[0117] Crosslinking treatment: Glutaraldehyde was prepared into a 0.5% (v / v) aqueous solution; the membrane was immersed in the 0.5% glutaraldehyde aqueous solution and reacted at 80°C for 20 min.

[0118] Preparation of S2.4 polypyrrole conductive layer.

[0119] Polymerization solution preparation: Add 150L of deionized water to a 200L reactor, then add 1.25L of pyrrole monomer and 3.75Kg of sodium dodecylbenzenesulfonate sequentially, stirring until dissolved. Membrane impregnation: Immerse the PTFE membrane coated with chitosan / silk fibroin into the solution, ensuring complete submersion, and place it in an ice-water bath at 0-5℃. Purge with nitrogen for 30 minutes to purge air. In-situ polymerization: Weigh 2.5Kg of ammonium persulfate, dissolve it in 5L of deionized water, and add it dropwise to the reactor through a constant pressure dropping funnel over 3 hours. After the addition is complete, turn on the sonicator at 700W and polymerize for 14 hours. Post-treatment: Remove the membrane, wash it three times with deionized water, and dry it at 60℃ for 2 hours to form a polypyrrole layer with a thickness of 90±10nm.

[0120] S3 was used to prepare a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material.

[0121] S3.1 Raw material preparation.

[0122] 58 kg of hollow polyester fiber with a length of 38 mm and a hollow rate of 25%; 1 kg of chitosan microspheres with a particle size of 1-3 μm; 15 kg of cotton fiber; 27 kg of nylon; 20 L of acidified carbon nanotube dispersion with a carboxylation degree of 5.5 mmol / g and a mass concentration of 4 wt%; and 1% acetic acid aqueous solution.

[0123] S3.2 Preparation of cotton fiber modified with chitosan microspheres.

[0124] The preparation method of chitosan microspheres is the same as in Example 1.

[0125] Cotton fiber modification: Add 50L of deionized water to the reaction tank, add 15Kg of cotton fiber, and soak for 30min to fully wet it. Add 1Kg of chitosan microspheres, stir evenly, and adjust the pH to 5.0 with 1% acetic acid. React at 30℃ for 2h. After the reaction is complete, remove the cotton fiber, wash it with deionized water until neutral, and dry it at 80℃.

[0126] Preparation of S3.3 carbon nanotube grafted nylon.

[0127] Plasma pretreatment: Place 27 kg of nylon into the plasma treatment chamber, introduce Ar gas, set the power to 80 W, and the treatment time to 5 min.

[0128] Grafting reaction: The pretreated nylon was immersed in 20L of 4wt% acidified carbon nanotube dispersion and shaken in a water bath at 150rpm and 60℃ for 6h.

[0129] Remove the nylon and wash it with deionized water until neutral, then dry it at 80℃ for 3 hours.

[0130] S3.4 Blended fiber preparation.

[0131] Opening: Hollow polyester fiber, chitosan modified cotton fiber, and carbon nanotube grafted nylon are respectively put into the opening machine, and the beater speed is 850 rpm for 12 minutes.

[0132] Carding: The three fibers are fed into the carding machine separately, with a cylinder speed of 320 rpm and a flats speed of 110 mm / min. Drawing: The three types of cotton web are fed into the drawing frame at a mass ratio of 58:27:15, with a roller speed of 220 m / min. The blending uniformity CV value after three draws is ≤2.8%.

[0133] Jet vortex spinning: Feed into the spinning machine, install a Y-type hollow-groove composite spinneret, set the spinning speed to 450m / min, hot air temperature to 245℃, and spinning pressure to 0.4MPa.

[0134] S4 fabric composite.

[0135] S4.1 Raw material preparation.

[0136] 100m² of outer fabric made of antistatic and antibacterial outer layer material; 100m² of chitosan-reinforced PTFE barrier middle layer material; 100m² of inner fabric made of carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material; 7Kg of polyacrylonitrile-based carbon fiber; 0.14Kg of coupling agent KH560.

[0137] The outer fabric is woven into a plain weave on a rapier loom at a speed of 320 rpm, with a warp density of 22 yarns / cm and a weft density of 20 yarns / cm. The inner fabric is woven into a twill weave at a speed of 300 rpm, with a warp density of 20 yarns / cm and a weft density of 18 yarns / cm.

[0138] S4.2 carbon fiber embedding.

[0139] Carbon fiber pretreatment: 0.14Kg KH560 was used to prepare an ethanol solution with a concentration of 2wt%; 7Kg of carbon fiber was immersed in the solution, soaked at 60℃ for 1h, and dried at 80℃.

[0140] Warp knitting embedding: Carbon fibers are embedded into the outer and inner fabrics at a mesh density of 24 fibers / cm using a warp knitting machine at a knitting speed of 220 revolutions / minute.

[0141] S4.3 three-layer composite.

[0142] Layering process: Lay out the outer fabric, chitosan-reinforced PTFE barrier intermediate material (polypyrrole layer facing inward), and inner fabric in sequence, aligning and fixing the edges.

[0143] Roller pressing: The product is fed into a continuous roller press with a set pressure of 0.65 MPa, a temperature of 145℃, and a roller speed of 5 m / min. After lamination, it is cooled to room temperature by a cooling roller.

[0144] S5 post-processing.

[0145] S5.1 Raw material preparation.

[0146] Fluorocarbon resin waterproofing agent (Asahiguard AG-E061) 15L; silicone emulsion (Dow Corning 350) 8L; deionized water.

[0147] S5.2 Waterproofing treatment.

[0148] Solution preparation: Add 85L of deionized water and 15L of fluorocarbon resin to a 100L impregnation tank, and stir until homogeneous.

[0149] Impregnation treatment: Immerse the composite fabric in the solution, let it stand for 12 minutes, take it out and put it into the rolling mill, and control the roll-off rate to 75%.

[0150] Drying: Place in a hot air drying oven and dry at 125℃ for 10 minutes, then cool to room temperature.

[0151] S5.3 Softening treatment.

[0152] Solution preparation: Add 92L of deionized water and 8L of silicone emulsion to a 100L impregnation tank and stir until homogeneous.

[0153] Impregnation treatment: Immerse the fabric in the solution, let it stand for 15 minutes, then remove it and place it in a rolling mill with a roll-up rate of 68%. Drying: Place it in a hot air drying oven and dry at 105℃ for 9 minutes, then cool.

[0154] S5.4 UV curing.

[0155] Place the fabric into a UV curing machine, set the wavelength to 254nm, the dose to 900mJ / cm², and the curing time to 3min.

[0156] The fabric obtained in Example 2 was tested.

[0157] 1. Antibacterial properties were tested according to GB / T20944.3: after 100 washes, the inhibition rate of Staphylococcus aureus was 95%, the inhibition rate of Escherichia coli was 96%, and the inhibition rate of Candida albicans was 88%.

[0158] 2. Antistatic performance shall be tested in accordance with GB / T12703.2: surface resistivity 1.0×10⁻⁶ 6 Ω·m; surface charge density 0.4 μC / m²; electrostatic half-life 0.5 s.

[0159] 3. Color fastness shall conform to GB / T3920: Grade 5 for dry rubbing and Grade 4-5 for wet rubbing.

[0160] 4. Moisture permeability shall conform to GB / T12704.1: 3700 g / m²·24h.

[0161] Example 3 S1 is used to prepare an antistatic and antibacterial outer layer material.

[0162] S1.1 Raw material preparation.

[0163] Weigh 14 kg of PVDF, 1.12 kg of F-ZnO / TiO2, 0.42 kg of carboxylated carbon nanotubes, 60 L of DMAC, 40 L of acetone, 0.5 kg of CTAB, and 10 L of anhydrous ethanol.

[0164] S1.2 Preparation of spinning solution.

[0165] Add 60L of DMAC and 40L of acetone sequentially to a 100L stainless steel reactor, start stirring, and maintain a speed of 300rpm. Then add 14Kg of PVDF granules to the reactor and stir until completely dissolved.

[0166] After the PVDF was completely dissolved, 1.12 kg of F-ZnO / TiO2 and 0.42 kg of carboxylated carbon nanotubes were added, and the ultrasonic device was started at 800 W for 6 h. During the dispersion process, the machine was stopped every 1 h to observe the dispersion state and ensure that there was no obvious agglomeration.

[0167] After dispersion, turn off the stirring and let it stand at room temperature for 12 hours to remove bubbles, then set aside for later use.

[0168] S1.3 electrospinning.

[0169] Check the high-voltage power supply, feed pump, and receiving device of the electrospinning machine. Install a 0.2mm orifice stainless steel spinneret and cover the receiving roller with aluminum foil. Set the parameters: voltage 25kV, distance between spinneret and receiving roller 18cm, receiving roller speed 500rpm. Pour the spinning solution into the storage tank, start the equipment, and spin nanofibers.

[0170] S1.4 Hot rolling treatment.

[0171] Nanofibers were placed in a hot roller press, with the temperature set at 120℃, the pressure at 0.3MPa, and the roller speed at 2m / min. The density of the treated nanofibers increased by 20%, and the breaking strength increased from 3.5cN / dtex to 4.2cN / dtex.

[0172] S1.5 quaternary ammonium salt grafting.

[0173] Add a 2wt% CTAB ethanol solution to the reaction vessel, immerse the hot-pressed fiber in the solution to ensure complete submersion, heat in a 60°C water bath, stir at 100 rpm, and react for 3 hours. After the reaction is complete, remove the membrane, rinse it three times with ethanol to remove unreacted CTAB, and dry it at 80°C for 2 hours.

[0174] S2 is used to prepare chitosan-reinforced PTFE barrier interlayer material.

[0175] S2.1 Raw material preparation.

[0176] 100 m² of PTFE membrane with a thickness of 10 μm, a pore size of 1.2 μm, and a porosity of 90%; 1.6 kg of chitosan with a degree of deacetylation of 90%; 0.8 kg of silk fibroin; 50 L of 1% acetic acid aqueous solution; 0.5 L of glutaraldehyde; 1.0 L of pyrrole monomer; 3.0 kg of sodium dodecylbenzenesulfonate; 2.0 kg of ammonium persulfate; and deionized water.

[0177] S2.2PTFE membrane pretreatment.

[0178] Same as Example 1.

[0179] S2.3 Chitosan / silk fibroin layer coating.

[0180] Chitosan solution preparation: Add 1.6 kg of chitosan to 50 L of 1% acetic acid aqueous solution, stir for 3 h until completely dissolved, and adjust the pH value to 5.0 with 10% NaOH.

[0181] Preparation of silk fibroin solution: Dissolve 0.8 kg of silk fibroin in 100 L of deionized water, stir at 60 °C for 1 h, and filter to remove insoluble matter.

[0182] Layer-by-layer self-assembly: The pretreated PTFE membrane is first immersed in chitosan solution for 5 minutes, then removed, centrifuged and dried at 80°C for 5 minutes; then immersed in silk fibroin solution for 5 minutes, and similarly centrifuged and dried; the chitosan-silk fibroin coating is repeated to finally form a transition layer of 2 chitosan layers + 1 silk fibroin layer.

[0183] Crosslinking treatment: Same as in Example 1.

[0184] Preparation of S2.4 polypyrrole conductive layer.

[0185] Preparation of polymerization solution: Add 150L of deionized water to a 200L reactor, then add 1.0L of pyrrole monomer and 3.0Kg of sodium dodecylbenzenesulfonate in sequence, and stir until dissolved.

[0186] Membrane impregnation: Same as in Example 1.

[0187] In-situ polymerization: Weigh 2.3 kg of ammonium persulfate, dissolve it in 5 L of deionized water, and add it dropwise to the reactor over 2 hours. After the addition is complete, turn on the sonicator at 700 W and allow the polymerization reaction to proceed for 10 hours.

[0188] Post-processing: Same as in Example 1, forming a polypyrrole layer with a thickness of 60±10nm.

[0189] S3 was used to prepare a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material.

[0190] S3.1 Raw material preparation.

[0191] 60 kg of hollow polyester fiber with a length of 38 mm and a hollow rate of 25%; 1 kg of chitosan microspheres with a particle size of 1-3 μm; 12.5 kg of cotton fiber; 15 kg of nylon; 20 L of acidified carbon nanotube dispersion with a carboxylation degree of 5.5 mmol / g and a mass concentration of 4 wt%; and 1% acetic acid aqueous solution.

[0192] S3.2 Preparation of cotton fiber modified with chitosan microspheres.

[0193] Same as Example 1.

[0194] Preparation of S3.3 carbon nanotube grafted nylon.

[0195] Plasma pretreatment: Place 15 kg of nylon into the plasma treatment chamber, introduce Ar gas, set the power to 80 W, and the treatment time to 5 min.

[0196] Grafting reaction: Same as in Example 1.

[0197] S3.4 Blended fiber preparation.

[0198] Qinghua: Same as in Example 1.

[0199] Carding: Same as in Example 1.

[0200] Drawing: The three types of cotton web are fed into the drawing frame at a mass ratio of 60:25:15, with a roller speed of 220 m / min. Air-jet vortex spinning: Same as in Example 1.

[0201] S4 fabric composite.

[0202] S4.1 Raw material preparation.

[0203] Outer fabric 100m²; chitosan-reinforced PTFE barrier interlayer material 100m²; inner fabric 100m²; polyacrylonitrile-based carbon fiber 3.6Kg; coupling agent KH560 0.072Kg.

[0204] The outer fabric weaving parameters are the same as in Example 1.

[0205] The weaving parameters for the inner fabric are the same as in Example 1.

[0206] S4.2 carbon fiber embedding.

[0207] Carbon fiber pretreatment: 0.072KgKH560 was used to prepare an ethanol solution with a concentration of 2wt%; 3.6Kg of carbon fiber was immersed in the solution, soaked at 60℃ for 1h, and dried at 80℃.

[0208] Warp knitting embedding: Carbon fibers are embedded into the outer and inner fabrics at a mesh density of 20 fibers / cm using a warp knitting machine at a knitting speed of 220 revolutions / minute.

[0209] S4.3 three-layer composite.

[0210] Stacking operation: Same as in Example 1.

[0211] Roller pressing: The product is fed into a continuous roller press with a set pressure of 0.55 MPa, a temperature of 135°C, and a roller speed of 5 m / min. After lamination, it is cooled to room temperature by a cooling roller.

[0212] S5 post-processing.

[0213] S5.1 Raw material preparation.

[0214] 13L of fluorocarbon resin waterproofing agent; 8L of silicone emulsion; deionized water.

[0215] S5.2 Waterproofing treatment.

[0216] Solution preparation: Add 87L of deionized water and 13L of fluorocarbon resin to a 100L impregnation tank, and stir until homogeneous.

[0217] Impregnation treatment: Immerse the composite fabric in the solution, let it stand for 12 minutes, take it out and put it into the rolling mill, and control the roll-off rate to 70%.

[0218] Drying: Same as in Example 1.

[0219] S5.3 Softening treatment.

[0220] Solution preparation: Same as in Example 1.

[0221] Impregnation treatment: Immerse the fabric in the solution, let it stand for 12 minutes, then remove it and place it in a rolling mill with a roll-out rate of 68%. Drying: Same as in Example 1.

[0222] S5.4 UV curing.

[0223] Same as Example 1.

[0224] The fabric obtained in Example 3 was tested.

[0225] 1. Antibacterial properties were tested according to GB / T20944.3: after 100 washes with water, the inhibition rate of Staphylococcus aureus was 92%, the inhibition rate of Escherichia coli was 93%, and the inhibition rate of Candida albicans was 82%.

[0226] 2. Antistatic performance shall be tested in accordance with GB / T12703.2: surface resistivity 8.0×10⁻⁶ 7 Ω·m; surface charge density 0.8 μC / m²; electrostatic half-life 0.6 s.

[0227] 3. Color fastness shall conform to GB / T3920: Grade 5 for dry rubbing and Grade 4-5 for wet rubbing.

[0228] 4. Moisture permeability shall conform to GB / T12704.1: 4000g / m²·24h.

[0229] Example 4 S1 is used to prepare an antistatic and antibacterial outer layer material.

[0230] S1.1 Raw material preparation.

[0231] Weigh 14 kg of PVDF, 1.68 kg of F-ZnO / TiO2, 0.56 kg of carboxylated carbon nanotubes, 60 L of DMAC, 40 L of acetone, 0.5 kg of CTAB, 10 L of anhydrous ethanol, and 0.3 kg of polyvinylpyrrolidone (PVP).

[0232] S1.2 Preparation of spinning solution.

[0233] Add 60L of DMAC and 40L of acetone sequentially to a 100L stainless steel reactor, and start stirring at 300rpm. Then add 14Kg of PVDF particles to the reactor and stir until completely dissolved. After the PVDF is completely dissolved, add 1.68Kg of F-ZnO / TiO2, 0.56Kg of carboxylated carbon nanotubes, and 0.3Kg of PVP, and start the ultrasonic device at 800W for 6 hours of dispersion. During the dispersion process, stop the machine every 1 hour to observe the dispersion status and ensure that there is no obvious agglomeration.

[0234] After dispersion, turn off the stirring and let it stand at room temperature for 12 hours to remove bubbles, then set aside for later use.

[0235] S1.3 electrospinning.

[0236] Inspect the high-voltage power supply, feed pump, and receiving device of the electrospinning machine. Install a 0.2mm orifice stainless steel spinneret and cover the receiving roller with aluminum foil. Set the parameters: voltage 28kV, distance between spinneret and receiving roller 20cm, receiving roller speed 500rpm. Pour the spinning solution into the storage tank, start the equipment, and spin nanofibers.

[0237] S1.4 Hot rolling treatment.

[0238] Same as Example 1.

[0239] S1.5 quaternary ammonium salt grafting.

[0240] Add a 3wt% CTAB ethanol solution to the reaction vessel, immerse the hot-pressed fiber in the solution to ensure complete submersion, heat in a 60°C water bath, stir at 100 rpm, and react for 4 hours. After the reaction is complete, remove the membrane, rinse it three times with ethanol to remove unreacted CTAB, and dry it at 80°C for 2 hours.

[0241] S2 is used to prepare chitosan-reinforced PTFE barrier interlayer material.

[0242] S2.1 Raw material preparation.

[0243] 100 m² of PTFE membrane with a thickness of 10 μm, a pore size of 1.1 μm, and a porosity of 88%; 2.0 kg of chitosan with a degree of deacetylation of 90%; 1.0 kg of silk fibroin; 50 L of 1% acetic acid aqueous solution; 0.5 L of glutaraldehyde; 1.0 L of pyrrole monomer; 3.0 kg of sodium dodecylbenzenesulfonate; 2.0 kg of ammonium persulfate; and deionized water.

[0244] S2.2PTFE membrane pretreatment.

[0245] Same as Example 1.

[0246] S2.3 Chitosan / silk fibroin layer coating.

[0247] Chitosan solution preparation: Add 2.0 kg of chitosan to 50 L of 1% acetic acid aqueous solution, stir for 3 h until completely dissolved, and adjust the pH value to 5.0 with 10% NaOH.

[0248] Preparation of silk fibroin solution: Dissolve 1.0 kg of silk fibroin in 100 L of deionized water, stir at 60 °C for 1 h, and filter to remove insoluble matter.

[0249] Layer-by-layer self-assembly: Same as in Example 1, ultimately forming a transition layer of 3 chitosan layers + 2 silk fibroin layers. Crosslinking treatment: Same as in Example 1.

[0250] Preparation of S2.4 polypyrrole conductive layer.

[0251] Preparation of polymerization solution: Add 150L of deionized water to a 200L reactor, then add 1.1L of pyrrole monomer and 3.5Kg of sodium dodecylbenzenesulfonate in sequence, and stir until dissolved.

[0252] The rest is the same as in Example 1, forming a polypyrrole layer with a thickness of 75±10nm.

[0253] S3 was used to prepare a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material.

[0254] S3.1 Raw material preparation.

[0255] 55 kg of hollow polyester fiber with a length of 38 mm and a hollow rate of 30%; 1 kg of chitosan microspheres with a particle size of 1-3 μm; 12.5 kg of cotton fiber; 10 kg of ordinary cotton fiber; 20 kg of nylon; 20 L of acidified carbon nanotube dispersion with a carboxylation degree of 5.5 mmol / g and a mass concentration of 4 wt%; and 1% acetic acid aqueous solution.

[0256] S3.2 Preparation of cotton fiber modified with chitosan microspheres.

[0257] Same as Example 1.

[0258] Preparation of S3.3 carbon nanotube grafted nylon.

[0259] Plasma pretreatment: Place 20 kg of nylon into the plasma treatment chamber, introduce Ar gas, set the power to 80 W, and the treatment time to 5 min.

[0260] Grafting reaction: Same as in Example 1.

[0261] S3.4 Blended fiber preparation.

[0262] Opening: Hollow polyester fiber, chitosan modified cotton fiber, ordinary cotton fiber, and carbon nanotube grafted nylon are respectively put into the opening machine.

[0263] Carding: The four types of fibers are fed into the carding machine separately.

[0264] Drawing: The cotton web is fed into the drawing machine at a mass ratio of 55:12.5:10:20.

[0265] Jet vortex spinning: Same as Example 1.

[0266] S4 fabric composite.

[0267] S4.1 Raw material preparation.

[0268] Outer fabric 100m²; chitosan-reinforced PTFE barrier interlayer material 100m²; inner fabric 100m²; polyacrylonitrile-based carbon fiber 6Kg; coupling agent KH560 0.12Kg.

[0269] The outer fabric weaving parameters are the same as in Example 1.

[0270] The weaving parameters for the inner fabric are the same as in Example 1.

[0271] S4.2 carbon fiber embedding.

[0272] Carbon fiber pretreatment: 0.12Kg KH560 was prepared into an ethanol solution with a concentration of 2wt%; 6Kg of carbon fiber was immersed in the solution, soaked at 60℃ for 1h, and dried at 80℃.

[0273] Warp knitting embedding: Carbon fibers are embedded into the outer and inner fabrics at a mesh density of 22 fibers / cm using a warp knitting machine at a knitting speed of 220 revolutions / minute.

[0274] S4.3 three-layer composite.

[0275] Stacking operation: Same as in Example 1.

[0276] Roller pressing: The product is fed into a continuous roller press with a set pressure of 0.6 MPa, a temperature of 140°C, and a roller speed of 6 m / min. After lamination, it is cooled to room temperature by a cooling roller.

[0277] S5 post-processing.

[0278] S5.1 Raw material preparation.

[0279] 14L of fluorocarbon resin waterproofing agent; 9L of silicone emulsion; deionized water.

[0280] S5.2 Waterproofing treatment.

[0281] Solution preparation: Add 86L of deionized water and 14L of fluorocarbon resin to a 100L impregnation tank, and stir until homogeneous.

[0282] Impregnation treatment: Same as in Example 1. Drying: Same as in Example 1.

[0283] S5.3 Softening treatment. Solution preparation: Add 91L of deionized water and 9L of silicone emulsion to a 100L impregnation tank, and stir until homogeneous.

[0284] Impregnation treatment: Immerse the waterproof-finished fabric in the solution, let it stand for 15 minutes, then remove it and put it into the rolling mill with a pick-up rate of 70%.

[0285] Drying: Place in a hot air drying oven and dry at 100℃ for 9 minutes, then cool.

[0286] S5.4 UV curing.

[0287] Same as Example 1.

[0288] The fabric obtained in Example 4 was tested.

[0289] 1. Antibacterial properties were tested according to GB / T20944.3: after 100 washes, the inhibition rate of Staphylococcus aureus was 93%, the inhibition rate of Escherichia coli was 95%, and the inhibition rate of Candida albicans was 86%.

[0290] 2. Antistatic performance shall be in accordance with GB / T12703.2: surface resistivity 4.5×10⁻⁶ 7 Ω·m; surface charge density 0.6 μC / m²; electrostatic half-life 0.6 s.

[0291] 3. Color fastness shall conform to GB / T3920: Grade 5 for dry rubbing and Grade 4-5 for wet rubbing.

[0292] 4. Moisture permeability shall conform to GB / T12704.1: 4100 g / m²·24h.

[0293] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing an antistatic medical fabric, characterized in that, Includes the following steps: S1. Prepare antistatic and antibacterial outer layer material: Take 100 parts of polyvinylidene fluoride, 8-15 parts of F-ZnO / TiO2, and 2-5 parts of carboxylated carbon nanotubes by weight and disperse them in DMAC / acetone mixed solvent. Then, after electrospinning and hot rolling, impregnate with 2wt%-4wt% CTAB ethanol solution for quaternary ammonium salt grafting. S2 preparation of chitosan-reinforced PTFE barrier interlayer material; After corona treatment, the PTFE membrane is alternately coated with N layers of chitosan and N-1 layers of silk fibroin, where N is an integer greater than or equal to 2. After coating, it is impregnated with a 0.5% volume fraction of glutaraldehyde aqueous solution for cross-linking treatment to form a chitosan / silk fibroin layer on the surface of the PTFE membrane; then, a polypyrrole conductive layer is prepared by in-situ polymerization. S3 prepares a carbon nanotube-grafted moisture-wicking and sweat-wicking comfortable inner layer material; by weight, take 55-60 parts of hollow polyester fiber, 12.5-25 parts of chitosan microsphere modified cotton fiber, and 15-27 parts of carbon nanotube-grafted nylon, and successively pass them through opening, carding, drawing, and air-jet vortex spinning to obtain composite cross-section fiber. S4 fabric composite: The outer layer fabric is spun using the material obtained from S1, and the inner layer fabric is spun using the material obtained from S3. Then, carbon fibers are embedded into the outer and inner layers fabrics at a mesh density of 22 fibers / cm using a warp knitting machine. Then, the outer layer fabric, the middle layer, and the inner layer fabric are sequentially stacked and rolled together. S5 post-processing: Waterproofing, softening, and UV curing are performed sequentially to obtain the finished fabric.

2. The method for preparing antistatic medical fabric according to claim 1, characterized in that, The specific method of grafting the quaternary ammonium salt is as follows: add CTAB ethanol solution to the reaction tank, immerse the hot-rolled fiber membrane in the solution to ensure complete immersion, heat in a 60°C water bath, stir at 100 rpm, and react for 3-5 hours. After the reaction is completed, take out the membrane, rinse it with ethanol 3 times, and dry it at 80°C.

3. The method for preparing the antistatic medical fabric according to claim 1, characterized in that, The specific preparation method of the chitosan / silk fibroin layer is as follows: a chitosan solution with pH 5.0 and a concentration of 0.032–0.04 kg / L is prepared using a 1% (w / w) acetic acid aqueous solution; a silk fibroin solution with a concentration of 0.008–0.028 kg / L is prepared using deionized water; the pretreated PTFE membrane is first immersed in the chitosan solution for 5 min, then removed, centrifuged, and dried; then immersed in the silk fibroin solution for 5 min, and centrifuged and dried again; this process is repeated until the predetermined number of layers is reached; then immersed in an aqueous solution containing 0.5% glutaraldehyde and reacted at 80°C for 20 min.

4. The method for preparing the antistatic medical fabric according to claim 1, characterized in that, The preparation of the polypyrrole conductive layer is as follows: a sodium dodecylbenzenesulfonate solution of 0.02-0.025 kg / L is prepared with deionized water. Then, pyrrole monomer is added to the sodium dodecylbenzenesulfonate solution at a volume ratio of 150:1-1.25 (deionized water to pyrrole monomer) and stirred until dissolved. The PTFE membrane coated with chitosan / silk fibroin is then immersed in the solution and placed in an ice-water bath. Nitrogen gas is introduced to purge the air. Then, a 0.4-0.5 kg / L ammonium persulfate aqueous solution is added dropwise to the reactor through a constant pressure dropping funnel, and ultrasonic polymerization is carried out for 10-14 hours.

5. The method for preparing the antistatic medical fabric according to claim 1, characterized in that, The chitosan microsphere-modified cotton fiber was prepared by the following method: the cotton fiber was fully wetted in deionized water, and then chitosan microspheres were added at a mass ratio of cotton fiber to chitosan microspheres of 15:

1. After stirring evenly, the pH value was adjusted to 5.0 with 1% acetic acid, and the reaction was carried out at a constant temperature of 30°C for 2 hours. After the reaction was completed, the cotton fiber was washed with deionized water until neutral and dried at 80°C.

6. The method for preparing the antistatic medical fabric according to claim 1, characterized in that, The carbon nanotube-grafted nylon was prepared by the following method: after plasma pretreatment, the nylon was immersed in a 4wt% acidified carbon nanotube dispersion, and shaken in a water bath at 150 rpm and 60°C for 6 hours. The nylon was then removed, washed with deionized water until neutral, and dried at 80°C.

7. The method for preparing antistatic medical fabric according to claim 1, characterized in that, Before use, the carbon fiber is immersed in a 2wt% KH560 ethanol solution, soaked at 60°C for 1 hour, and then dried at 80°C.

8. The method for preparing the antistatic medical fabric according to claim 5, characterized in that, The chitosan microspheres were prepared by the following method: a 5 g / L chitosan solution was prepared by taking chitosan with a degree of deacetylation of 90% and 1% acetic acid aqueous solution. Span-80 was added at a mass ratio of 1:1 to chitosan. The mixture was sheared at 10,000 rpm for 30 min to form an emulsion. One-tenth the volume of 10% glutaraldehyde solution was added to the 1% acetic acid aqueous solution. The mixture was reacted at 30°C for 2 h. After centrifugation, the mixture was washed with deionized water until neutral and dried at 60°C to obtain chitosan microspheres.

9. The method for preparing the antistatic medical fabric according to claim 1, characterized in that, The waterproofing treatment specifically involves mixing fluorocarbon resin and deionized water at a volume ratio of 13-15:85-87, then immersing the fabric obtained by roller pressing in the mixture and letting it stand for 12 minutes. After removal, the fabric is placed in a roller press and then dried with hot air.

10. An antistatic medical fabric, characterized in that, The antistatic medical fabric is prepared using the preparation method according to any one of claims 1 to 9.