A nanofiber fluorine membrane composite fabric and its preparation process

Abstract

This invention provides a nanofiber fluoropolymer composite fabric and its preparation process, belonging to the field of composite fabric technology. The process includes the following steps: S1, electrospinning a one-way moisture-wicking layer onto the outer layer of cotton fabric; S2, preparing a hollow fiber / nanofiber fluoropolymer composite layer; S3, laying a PA hot-melt web film layer on the one-way moisture-wicking layer, then laying the hollow fiber / nanofiber fluoropolymer composite layer on the PA hot-melt web film layer, heating, laminating, and cooling to obtain the nanofiber fluoropolymer composite fabric. This invention achieves both waterproof performance and one-way moisture-wicking permeability.

Description

Technical Field

[0001] This invention relates to the field of composite fabric technology, specifically to a nanofiber fluorine membrane composite fabric and its preparation process. Background Technology

[0002] With the development of outdoor sports, protective clothing, and functional home textiles, composite fabrics that combine waterproofing, breathability, and wearing comfort are gradually gaining attention. Common waterproof and breathable fabrics achieve water repellency and a certain degree of breathability by coating or laminating microporous or hydrophilic films (such as PU films, PTFE films, etc.) onto the fabric surface and finishing the outer layer with fluorinated water-repellent agents. These fabrics perform well in terms of hydrostatic pressure and surface water repellency, but because the waterproof layer hinders the diffusion of water vapor, sweat is difficult to expel from the skin in a timely manner. Wearers are prone to feeling stuffy and sticky during strenuous exercise or in high-humidity environments, resulting in poor thermal and moisture comfort.

[0003] To improve moisture management performance, existing technologies propose using hydrophilic finishing on the inner fabric or employing hygroscopic fibers to absorb and diffuse sweat from the skin side via capillary action. Patent application CN104191711A discloses a bamboo fiber sweat-wicking fabric, comprising a base fabric layer and an outer fabric layer. Between the base fabric layer and the outer fabric layer are sequentially arranged a unidirectional sweat-wicking layer and a sweat-absorbing layer. The unidirectional sweat-wicking layer is a unidirectional polymer film, and the sweat-absorbing layer is a superabsorbent fiber. In this structure, the sweat-absorbing layer is located in the middle between the base fabric layer and the outer fabric layer. When the sweat-absorbing layer absorbs a large amount of water in a high-humidity environment or during strenuous exercise, once it approaches saturation, its unidirectional sweat-wicking function essentially fails. Excess sweat has nowhere to go and continues to accumulate on the skin side, significantly reducing the sweat-wicking effect.

[0004] On the other hand, to achieve higher hydrostatic pressure and protective performance, some technologies introduce nanoscale waterproof functional layers into fabrics and combine them with fluoropolymers or fluorinated modified components to prepare nanofiber fluorine membranes to improve hydrophobicity and water repellency. The multifunctional composite fabric described in patent application CN107283939A achieves moisture and water resistance by setting polyurethane nanofilm layers and polyvinylidene fluoride nanofilm layers in the middle and lower layers, respectively. Although this structure can improve moisture and water resistance to some extent, the superposition of two dense polymer films significantly increases the resistance to water vapor transmission in the thickness direction. Sweat absorbed by the inner silk layer is difficult to diffuse outwards in a timely manner, resulting in low overall moisture permeability and air permeability.

[0005] Therefore, there is a need to provide a nanofiber fluoropolymer composite fabric and its preparation process to solve the problems existing in the prior art. Summary of the Invention

[0006] In view of this, the present invention provides a nanofiber fluorine membrane composite fabric and its preparation process, which can achieve waterproof performance while having one-way perspiration and moisture-wicking properties.

[0007] To achieve the above objectives, the present invention provides a preparation process for nanofiber fluorine membrane composite fabric, comprising the following steps:

[0008] S1. Mix corn gluconate, glucose, and ethanol aqueous solution, heat and stir, cool, load into a syringe, fix cotton cloth on the electrospinning receiving device, perform electrospinning, dry, and form a one-way sweat-wicking layer on the outer layer of the cotton cloth.

[0009] S2. Mix and stir thermoplastic polyurethane particles, fluorinated modified methacrylate copolymer, N,N-dimethylformamide, and tetrahydrofuran, load into a syringe, spread the hollow fiber layer on the electrospinning receiving device, perform electrospinning, drying, and heat treatment to form a nanofiber fluorine film layer on the hollow fiber layer, and obtain a hollow fiber / nanofiber fluorine film composite layer.

[0010] S3. Lay the PA hot melt mesh layer on the one-way sweat-wicking layer, then lay the hollow fiber / nanofiber fluoropolymer composite layer on the PA hot melt mesh layer, heat it, laminate it, and cool it to obtain the nanofiber fluoropolymer composite fabric.

[0011] This invention utilizes electrospinning to form a zein / glucose nanofiber layer on the skin-away side of cotton fabric as a one-way perspiration wicking layer. Because zein molecules are rich in nonpolar amino acid residues, this electrospun layer exhibits a certain degree of hydrophobicity on the skin-away surface. Combined with the excellent hydrophilic and perspiration-absorbing properties of the cotton fabric on the skin-away side, this creates a significant difference in wettability between the skin-away and skin-away sides. This facilitates the rapid wetting, diffusion, and migration of liquid sweat from the skin-away side to the skin-away side, and can inhibit backflow to a certain extent. Simultaneously, the electrospun nanofiber layer has fine fibers and small pore sizes, forming a continuous capillary network that provides a transport path for moisture. Under external pressure, this helps improve the efficiency of sweat transfer from the skin-away side to the skin-away side, thereby reducing sweat retention on the skin-away side and improving both skin-dryness and thermal comfort.

[0012] This invention directly forms a nanofiber fluorinated membrane layer using a hollow fiber layer as an electrospinning substrate, resulting in a hollow fiber / nanofiber fluorinated membrane composite layer. This reduces pore blockage caused by the introduction of additional adhesives, allowing the composite layer to maintain high effective porosity and pore connectivity. Simultaneously, the nanofiber fluorinated membrane forms an interlocking fiber entanglement network on the surface of the hollow fiber layer, which is beneficial for improving membrane adhesion and the mechanical stability of the composite structure. Furthermore, the introduction of fluorinated modified methacrylate copolymers can construct a low surface energy fluorinated interface on the fiber surface, thereby improving the anti-wetting ability of the outer nanofiber fluorinated membrane, enhancing hydrostatic pressure and water repellency, and effectively preventing the penetration of external liquid water.

[0013] This invention places a hollow fiber layer between a one-way perspiration layer and a nanofiber fluoropolymer membrane layer. The interconnected pores between the hollow fibers form a three-dimensional air channel network, which reduces airflow resistance and improves overall breathability, while also providing a low-resistance gas-phase diffusion path for water vapor transfer. The internal cavity of the hollow fiber layer seals in still air, providing a certain thermal and moisture buffering space while maintaining a lightweight design. During use, the one-way perspiration layer continuously transports sweat to the hollow fiber layer, forming a thin water film on the fiber surface and in its pores. When there is a temperature and humidity difference between the side in contact with the body and the environment, the water in the thin water film preferentially evaporates into water vapor at the solid-gas interface within the pores. Subsequently, the water vapor diffuses from the inside to the outside in the air phase along the interconnected pores within the hollow fiber layer and the nanofiber fluoropolymer membrane layer, thus forming a synergistic mass transfer pathway of interface evaporation and pore diffusion. Therefore, this invention reduces water vapor diffusion resistance while maintaining the outer layer's liquid-resistant and waterproof properties, improves the moisture permeability and breathability of the composite fabric, and further ensures the long-term structural stability and durability of the waterproof barrier layer through the elastic support of the hollow fiber layer for the nanofiber fluorine membrane layer.

[0014] Optionally, in step S1, 2.5-3 parts by weight of zein, 1-1.5 parts by weight of glucose, and 40-80 parts by volume of an ethanol aqueous solution with a concentration of 40-60 vol% are mixed and magnetically stirred at 55-60°C for 10-12 hours. After cooling, the mixture is loaded into a syringe, and the cotton cloth is fixed on the electrospinning receiving device. The distance between the needle tip of the syringe and the cotton cloth is controlled to be 15-18 cm. Continuous electrospinning is performed for 1-2 hours, and the mixture is placed in a forced-air drying oven at 110-120°C for 3-4 hours to form a one-way perspiration-wicking layer on the outer layer of the cotton cloth.

[0015] In the one-way wicking layer of this invention, glucose and zein are blended. Under drying heat treatment conditions, Maillard reactions, condensation, and rearrangement may occur between the reducing carbonyl groups in glucose molecules and the active groups such as free amino groups on zein chains. This facilitates the formation of a certain protein-glycan-protein cross-linking network between protein molecules. This process can consume some of the hydrophilic groups such as free amino groups on zein molecules, promoting the enrichment of hydrophobic segments on the fiber surface. This enhances the hydrophobicity of the outer surface of the one-way wicking layer, forming a more significant wetting gradient and anisotropic moisture transport driving force with the hydrophilic and sweat-absorbing properties of the cotton skin side. This promotes the directional migration of sweat from the skin side to the outside and inhibits backflow. On the other hand, the formation of the cross-linking network can improve the bonding strength of electrospun fiber knots and the integrity of the fiber structure, allowing the one-way wicking layer to maintain relatively stable micropore channels and wetting differences even after repeated washing, thereby improving the wash durability of the one-way wicking performance.

[0016] Preferably, the thickness of the unidirectional sweat-wicking layer is 20~36μm.

[0017] Optionally, the fluorinated modified methacrylate copolymer is prepared by mixing 5-6 parts by weight of glycidyl methacrylate, 8-15 parts by weight of methyl methacrylate, 25-35 parts by volume of tetrahydrofuran, and 0.4-1 parts by weight of initiator azobisisobutyronitrile (AIBN), sealing the mixture, purging it with nitrogen for 10-15 minutes, reacting it at 55-65°C for 3-5 hours, adding 1.5-3 parts by weight of pentafluoropropionic acid, 1.8-2.3 parts by weight of triethanolamine, and 0.4-0.6 parts by weight of hexadecyltrimethylammonium bromide, and magnetically stirring it at 40°C for 3-5 hours. The mixture is then precipitated in hexane, centrifuged for purification, baked at 45-55°C for 8-10 hours, and ground into powder to obtain the fluorinated modified methacrylate copolymer.

[0018] This invention involves the free radical polymerization of glycidyl methacrylate and methyl methacrylate, followed by ring-opening grafting of epoxy groups with pentafluoropropionic acid in the presence of triethanolamine to obtain a fluorinated modified methacrylate copolymer, the specific structural formula of which is as follows:

[0019]

[0020] The copolymer incorporates rigid methyl methacrylate units into its main chain, while retaining some unreacted epoxy groups in the side chains, and also contains –C(O)CF2CF3 fluorinated groups. The residual epoxy groups and the hydroxyl groups generated by ring opening facilitate the formation of hydrogen bonds and dipole interactions with the thermoplastic polyurethane continuous phase, the polar groups on the surface of the hollow fiber, and inorganic fillers such as modified nano-SiO2. This enhances the bonding strength of the organic / inorganic phase interface inside the nanofiber fluorinated membrane and strengthens the adhesion between the nanofiber fluorinated membrane and the hollow fiber layer, thereby improving the overall mechanical stability and peel resistance of the composite structure.

[0021] Optionally, in step S2, after mixing and stirring the thermoplastic polyurethane particles, fluorinated modified methacrylate copolymer, N,N-dimethylformamide, and tetrahydrofuran, 0.5-1 parts by weight of modified nano-SiO2 and 0.2-0.5 parts by weight of modified boron nitride are added and ultrasonically dispersed for 20-30 minutes, and then mechanically stirred at 50°C for 2-3 hours before being loaded into a syringe.

[0022] Optionally, the modified nano-SiO2 is prepared by mixing 1.5-2 parts by mass of nano-SiO2, 80-100 parts by volume of ethanol, and 12-15 parts by volume of water, ultrasonically treating for 30 minutes, adding triethanolamine to adjust the pH value to 8.5-9.2, adding 0.25-0.4 parts by mass of KH550 under heating and stirring at 80°C, refluxing for 5 hours, centrifuging for 15-30 minutes, baking at 40-60°C for 6-10 hours, cooling to room temperature, and grinding into powder.

[0023] KH550 condenses with silanols on the surface of SiO2 through a silanization reaction, reducing the density of surface-active hydroxyl groups and introducing organic segments, thus transforming SiO2 from hydrophilic to more organic-friendly, thereby improving its dispersion stability and interfacial compatibility in thermoplastic polyurethane and fluorinated copolymer systems.

[0024] Optionally, the modified boron nitride is prepared by mixing 0.5-1 parts by weight of hydroxylated hexagonal boron nitride nanosheets, 50-70 parts by volume of anhydrous ethanol, and 5-10 parts by volume of deionized water, stirring magnetically for 10-20 minutes, sonicating for 20-30 minutes, adding 25 wt% ammonia water to adjust the pH to 8.5-9.2, adding 0.09-0.18 parts by weight of perfluoroethyltriethoxysilane, continuing to heat and stir at 50-60°C, refluxing for 4-8 hours, cooling to room temperature, centrifuging at 8000 rpm for 15-30 minutes, collecting the precipitate, washing it 3-5 times with anhydrous ethanol, drying it in an oven at 70-80°C for 12-24 hours, cooling to room temperature, and grinding it into powder.

[0025] Introducing perfluoroethyl silane groups into the surface of modified boron nitride reduces its surface energy and enhances its compatibility with the fluorinated membrane substrate. This allows it to disperse uniformly in the nanofiber network and form a stable interface with the fiber nodes. Together with modified nano-SiO2, it forms a low-surface-energy micro / nano-scale rough structure in the membrane, improving its resistance to liquid water wetting and further reducing the wetting and penetration of liquid moisture into the pores. At the same time, the lamellar boron nitride has high rigidity and structural support, which can inhibit the collapse and adhesion of the pore structure of the nanofiber fluorinated membrane under extrusion, stretching, and humid heat conditions, maintaining the connectivity of micropores and the stability of moisture permeation channels. In addition, modified boron nitride promotes stress transmission and crack deflection under external forces, reducing the probability of defects such as pinholes and microcracks in the membrane.

[0026] Optionally, the hollow fiber layer is made by cutting 3-5 parts by weight of hollow fiber into short fibers and mixing it with 0.25-0.35 parts by weight of low melting point copolyester bonding fiber, laying it into a web, placing it in a mold, covering it with a flat plate, pre-pressing it at 170-180℃ and 0.08MPa for 1-2 minutes, and then hot-pressing it at 0.16-0.22MPa for 60-90 seconds, and then cooling and demolding it.

[0027] Preferably, the hollow fiber is a hollow polyester fiber, and the thickness of the hollow fiber layer is 0.45~0.65mm.

[0028] The hollow fiber layer is made of hot-pressed hollow polyester short fiber membrane. The hollow fiber seals in still air to form a low thermal conductivity insulation layer. At the same time, the interlacing of fibers builds a three-dimensional support skeleton with a certain degree of compression recovery. This can improve the heat insulation performance and thick feel while ensuring the overall fabric is lightweight. It also provides a flat and stable base for the upper nanofiber fluorine membrane layer, avoiding local stress concentration and membrane cracking during use and bending.

[0029] The hollow fiber layer is formed by laying hollow polyester chopped fibers and low-melting-point copolyester bonding fibers into a web and then forming it through a two-stage low-pressure hot pressing. The pre-pressing stage achieves the shaping of the fiber web and the initial stabilization of the pore structure. The short-time hot pressing stage causes the low-melting-point bonding fibers to form discrete bonding points at the fiber intersections, thereby obtaining a porous hollow fiber layer under lower pressure. This effectively reduces the compaction of pores and the collapse of hollow cavities caused by traditional high-pressure hot pressing, and maintains the effective connection between the fiber pores and the three-dimensional air channel network.

[0030] Optionally, in step S2, 10-15 parts by weight of thermoplastic polyurethane particles, 2-6 parts by weight of fluorinated modified methacrylate copolymer, 25-35 parts by volume of N,N-dimethylformamide, and 25-35 parts by volume of tetrahydrofuran are mixed and magnetically stirred at 50°C for 4-5 hours. The mixture is then loaded into a syringe, and the hollow fiber layer is laid flat on the electrospinning receiving device. The distance between the syringe needle tip and the hollow fiber layer is controlled to be 17-18 cm. Continuous electrospinning is performed for 1-3 hours, followed by drying in an oven at 60-80°C for 10-20 minutes, and heat treatment at 110-130°C for 30-60 minutes to form a nanofiber fluorine film layer on the hollow fiber layer, thus obtaining a hollow fiber / nanofiber fluorine film composite layer.

[0031] Preferably, the thickness of the nanofiber fluorine membrane in the hollow fiber / nanofiber fluorine membrane composite layer is 15~22μm.

[0032] Optionally, in step S3, the heating temperature is 135~160℃ and the time is 30~40s, and the lamination is carried out under the condition of 0.02~0.08MPa for 10~20s.

[0033] Preferably, the basis weight of the PA hot melt web film layer is 8~15 g / m². 2 Model number ZPMA-web004.

[0034] This invention ultimately forms a nanofiber fluoropolymer composite fabric by bonding PA hot-melt mesh layers. The PA hot-melt mesh is first heated to fully soften / melt and uniformly wet the fiber interfaces on both sides, so that only low pressure is needed to form relatively stable bonding points in the subsequent process. This method not only improves the interlayer peel strength and service durability, but also avoids the compaction, blockage, or structural collapse of the hollow fiber layer pores caused by high-pressure hot pressing, thus maximizing the moisture permeability and reducing the risk of delamination.

[0035] The present invention also provides a nanofiber fluorine membrane composite fabric, comprising a nanofiber fluorine membrane layer, a hollow fiber layer, a PA hot melt mesh layer, a one-way sweat-wicking layer, and a cotton base layer arranged sequentially from the environmental side to the skin side.

[0036] The internal structure of the nanofiber fluorine membrane composite fabric specifically prepared by this invention can be found in the appendix. Figure 1 The structure, from the environmental side to the skin side, consists of: nanofiber fluorine membrane layer 1, hollow fiber layer 2, PA hot melt mesh layer 3, one-way sweat-wicking layer 4, and cotton base layer 5. The nanofiber fluorine membrane composite fabric obtained by this invention can ensure excellent waterproof performance while also possessing stable moisture permeability, good mechanical durability, and long-term service reliability.

[0037] The above-described technical solution of the present invention has at least the following beneficial effects:

[0038] 1. This invention uses an electrospun zein / glucose layer on the outer side of the cotton fabric as a one-way perspiration layer, forming a wetting gradient with hydrophilicity on the skin side and hydrophobicity on the outer side. This facilitates the rapid wetting, diffusion, and migration of liquid sweat away from the skin side, and can inhibit backflow to a certain extent. The nanofiber layer formed by electrospinning can form a continuous capillary network, providing a transport path for moisture transfer. Under external pressure, it helps to improve the efficiency of sweat transfer from the skin side to the side away from the skin, thereby reducing sweat retention on the skin side and improving the dryness and thermal comfort of the fabric.

[0039] 2. This invention uses a hollow fiber layer as the electrospun substrate, forming a nanofiber fluorinated membrane layer on the hollow fiber layer. This reduces adhesive clogging, maintains high porosity and connectivity, and forms an interlocking entanglement network at the interface, improving membrane adhesion and structural stability. A fluorinated modified copolymer constructs a low surface energy fluorinated interface on the fiber surface, enhancing anti-wetting properties and preventing liquid water penetration. The hollow fiber layer is sandwiched between the unidirectional sweat-wicking layer and the outer nanofiber fluorinated membrane layer, forming a continuous three-dimensional air channel, reducing airflow resistance and promoting low-resistance water vapor diffusion. After sweat transport forms a thin water film, it preferentially evaporates at the solid-air interface, and water vapor is discharged along the interconnected channels, achieving synergistic mass transfer of "evaporation-diffusion," thus achieving waterproofing, moisture permeability, and air permeability, while improving durability. Attached Figure Description

[0040] Figure 1 This is a diagram of the internal structure of the nanofiber fluorine membrane composite fabric prepared according to the present invention.

[0041] In the diagram: 1. Nanofiber fluorine membrane layer; 2. Hollow fiber layer; 3. PA hot melt mesh film layer; 4. One-way wicking layer; 5. Cotton base layer. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are some embodiments of the present invention, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0043] Example 1

[0044] Mix 2.8g of zein, 1.3g of glucose, and 60mL of 50vol% ethanol aqueous solution, and stir magnetically at 58℃ for 11h. After cooling, load the mixture into a syringe. Fix cotton cloth onto the electrospinning receiving device, control the distance between the syringe needle tip and the cotton cloth to be 16cm, and perform continuous electrospinning for 1.5h. Then, dry the mixture in a 115℃ forced-air drying oven for 3.5h to form a one-way perspiration-wicking layer (24μm thick) on the outer layer of the cotton cloth.

[0045] 4.0g of hollow fiber (Jiangsu Jinhetai Fiber Technology Co., Ltd., hollow polyester fiber) was cut into short fibers (4mm) and mixed with 0.3g of low melting point copolyester bonding fiber. The mixture was laid out as a web, placed in a mold, covered with a flat plate, and pre-pressed at 178℃ and 0.08MPa for 1min. Then, it was hot-pressed at 0.18MPa for 70s, cooled and demolded to obtain a hollow fiber layer (thickness of 0.50mm).

[0046] 5.5g glycidyl methacrylate, 12g methyl methacrylate, 30mL tetrahydrofuran, and 0.6g azobisisobutyronitrile (AIOBR) were mixed and sealed. Nitrogen gas was introduced for 12 minutes, and the mixture was reacted at 60℃ for 4 hours. Then, 2.0g pentafluoropropionic acid, 2g triethanolamine, and 0.5g hexadecyltrimethylammonium bromide were added, and the mixture was magnetically stirred at 40℃ for 4 hours. The mixture was then precipitated in n-hexane, centrifuged for purification, baked at 50℃ for 9 hours, and ground into powder to obtain a fluorinated modified methacrylate copolymer. 1.7g nano-SiO2, 90mL ethanol, and 13mL water were mixed and sonicated for 30 minutes. Triethanolamine was added dropwise to adjust the pH to 8.8, and 0.35g of [unspecified ingredient] was added under heating and stirring conditions at 80℃. The modified nano-SiO2 was obtained by reflux reaction at KH550 for 5 h, centrifugation for 20 min, baking at 50℃ for 8 h, cooling to room temperature, and grinding into powder. 0.7 g of hydroxylated hexagonal boron nitride nanosheets (Xi'an Qiyue Biotechnology, catalog number Q-0249641), 60 mL of anhydrous ethanol, and 7 mL of deionized water were mixed, magnetically stirred for 15 min, sonicated for 25 min, and the pH was adjusted to 8.8 by adding 25 wt% ammonia. 0.15 g of perfluoroethyltriethoxysilane was added, and the mixture was heated and stirred at 55℃ for 6 h under reflux. After cooling to room temperature, the mixture was centrifuged at 8000 rpm for 20 min, the precipitate was collected, washed four times with anhydrous ethanol, dried in a 75℃ oven for 18 h, cooled to room temperature, and ground into powder.

[0047] 12g of thermoplastic polyurethane particles, 4.0g of fluorinated modified methacrylate copolymer, 30mL of N,N-dimethylformamide, and 30mL of tetrahydrofuran were mixed and magnetically stirred at 50℃ for 4.5h. 0.8g of modified nano-SiO2 and 0.3g of modified boron nitride were added, and the mixture was ultrasonically dispersed for 25min. The mixture was then mechanically stirred at 50℃ for 2.5h and loaded into a syringe. The hollow fiber layer was laid flat on an electrospinning receiving device, and the distance between the syringe needle tip and the hollow fiber layer was controlled to be 17.5cm. Electrospinning was performed continuously for 2h. The mixture was then dried in a 70℃ oven for 15min and heat-treated at 120℃ for 45min to form a nanofiber fluorine film layer on the hollow fiber layer, resulting in a hollow fiber / nanofiber fluorine film composite layer (where the thickness of the nanofiber fluorine film layer is 16μm).

[0048] The PA hot melt web film layer (Pinghu Zhanpeng Hot Melt Adhesive Film Co., Ltd., model ZPMA-web004, basis weight 8g / m²) is applied. 2 The hollow fiber / nanofiber fluorine membrane composite layer is laid on the one-way sweat-wicking layer, and then the hollow fiber / nanofiber fluorine membrane composite layer is laid on the PA hot melt mesh film layer. After heating at 135℃ for 36s, it is laminated at 0.02~0.08MPa for 18s. After cooling to room temperature, the nanofiber fluorine membrane composite fabric is obtained.

[0049] Example 2

[0050] Mix 2.7g of zein, 1.2g of glucose, and 55mL of 45vol% ethanol aqueous solution, and stir magnetically at 57℃ for 11h. After cooling, load the mixture into a syringe. Fix cotton cloth onto the electrospinning receiving device, control the distance between the syringe needle tip and the cotton cloth to be 16cm, and perform continuous electrospinning for 1.5h. Then, dry the mixture in a 115℃ forced-air drying oven for 3.5h to form a one-way perspiration-wicking layer (22μm thick) on the outer layer of the cotton cloth.

[0051] 4.0g of hollow fiber (Jiangsu Jinhetai Fiber Technology Co., Ltd., hollow polyester fiber) was cut into short fibers (3.5mm) and mixed with 0.28g of low melting point copolyester bonding fiber. The mixture was laid out as a web, placed in a mold, covered with a flat plate, and pre-pressed at 176℃ and 0.08MPa for 1.5min. Then, it was hot-pressed at 0.17MPa for 1.5min. After cooling and demolding, a hollow fiber layer (thickness of 0.48mm) was obtained.

[0052] 5.3 g glycidyl methacrylate, 11 g methyl methacrylate, 28 mL tetrahydrofuran, and 0.55 g azobisisobutyronitrile were mixed and sealed, then nitrogen gas was introduced for 12 min, and the mixture was reacted at 60 °C for 4 h. Then, 1.8 g pentafluoropropionic acid, 1.9 g triethanolamine, and 0.5 g hexadecyltrimethylammonium bromide were added, and the mixture was magnetically stirred at 40 °C for 4 h. The mixture was then precipitated in n-hexane, centrifuged and purified, baked at 50 °C for 9 h, and ground into powder to obtain a fluorinated modified methacrylate copolymer. 1.6 g nano-SiO2, 90 mL ethanol, and 13 mL water were mixed and sonicated for 30 min. Triethanolamine was added dropwise to adjust the pH to 8.7, and 0.4 g of [acid] was added under heating and stirring conditions at 80 °C. Modified nano-SiO2 was obtained by reflux reaction at KH550 for 5 h, centrifugation for 20 min, baking at 50℃ for 8 h, and grinding. 0.6 g of hydroxylated hexagonal boron nitride nanosheets (Xi'an Qiyue Biotechnology, catalog number Q-0249641), 60 mL of anhydrous ethanol, and 7 mL of deionized water were mixed, stirred for 15 min, sonicated for 25 min, and the pH was adjusted to 8.7 by adding 25 wt% ammonia water. 0.1 g of perfluoroethyltriethoxysilane was added, refluxed at 55℃ for 6 h, centrifuged at 8000 rpm for 20 min, washed 4 times with ethanol, dried at 75℃ for 18 h, and then ground.

[0053] 12g of thermoplastic polyurethane particles, 3.5g of fluorinated modified methacrylate copolymer, 30mL of N,N-dimethylformamide, and 30mL of tetrahydrofuran were mixed and magnetically stirred at 50℃ for 4.5h. 0.7g of modified nano-SiO2 and 0.3g of modified boron nitride were added, and the mixture was ultrasonically dispersed for 25min. After mechanical stirring at 50℃ for 2.5h, the mixture was loaded into a syringe. The hollow fiber layer was laid flat on an electrospinning receiving device with the syringe needle tip 17.5cm away from the hollow fiber layer. Electrospinning was performed continuously for 2h. The mixture was then dried in a 70℃ oven for 15min and heat-treated at 120℃ for 45min to form a nanofiber fluorine film layer on the hollow fiber layer, resulting in a hollow fiber / nanofiber fluorine film composite layer (with a nanofiber fluorine film layer thickness of 15μm).

[0054] The PA hot melt web film layer (Pinghu Zhanpeng Hot Melt Adhesive Film Co., Ltd., model ZPMA-web004, basis weight 12g / m²) is used. 2 The hollow fiber / nanofiber fluoropolymer composite layer is laid on the unidirectional sweat-wicking layer, and then the hollow fiber / nanofiber fluoropolymer composite layer is laid on the PA hot melt mesh film layer. After heating at 140℃ for 30s, it is laminated at 0.02MPa for 10s. After cooling to room temperature, the nanofiber fluoropolymer composite fabric is obtained.

[0055] Example 3

[0056] Mix 2.9g of zein, 1.4g of glucose, and 70mL of 55vol% ethanol aqueous solution, and stir magnetically at 59℃ for 11.5h. After cooling, load the mixture into a syringe. Fix cotton cloth onto the electrospinning receiving device, control the distance between the syringe needle tip and the cotton cloth to be 17cm, and perform continuous electrospinning for 1.8h. Then, dry the mixture in a 118℃ forced-air drying oven for 3.8h to form a one-way perspiration-wicking layer (thickness: 30μm) on the outer layer of the cotton cloth.

[0057] 4.5g of hollow fiber (Jiangsu Jinhetai Fiber Technology Co., Ltd., hollow polyester fiber) was cut into short fibers (3.5mm) and mixed with 0.32g of low-melting-point copolyester bonding fiber. The mixture was then laid into a web, placed in a mold, covered with a flat plate, and pre-pressed at 175℃ and 0.08MPa for 1.5min, followed by hot pressing at 0.18MPa for 1.5min. After cooling and demolding, a hollow fiber layer (thickness: 0.58mm) was obtained. 5.8g of glycidyl methacrylate, 13g of methyl methacrylate, 32mL of tetrahydrofuran, and 0.8g of azobisisobutyronitrile were mixed and sealed. Nitrogen gas was introduced for 13min, and the mixture was reacted at 62℃ for 4.5h. Then, 2.5g of pentafluoropropionic acid, 1.8g of triethanolamine, and 0.55g of hexadecyltrimethylammonium bromide were added, and the mixture was magnetically stirred at 40℃ for 4.5h. The mixture was then precipitated in n-hexane, centrifuged for purification, baked at 52℃ for 9.5h, and then ground. Fluorinated modified methacrylate copolymer was obtained by grinding. 1.8g of nano-SiO2, 95mL of ethanol, and 14mL of water were mixed and sonicated for 30min. Triethanolamine was added dropwise to adjust the pH to 9.0. 0.27g of KH550 was added under heating and stirring at 80℃. The mixture was refluxed for 5h, centrifuged for 25min, baked at 55℃ for 9h, and then ground to obtain modified nano-SiO2. 0.8g of hydroxylated hexagonal boron nitride nanosheets (Xi'an Qiyue Biotechnology, catalog number Q-0249641), 65mL of anhydrous ethanol, and 8mL of deionized water were mixed, stirred for 15min, sonicated for 28min, and 25wt% ammonia was added dropwise to adjust the pH to 9.0. 0.17g of perfluoroethyltriethoxysilane was added dropwise. The mixture was refluxed at 58℃ for 7h, centrifuged at 8000rpm for 25min, washed 4 times with ethanol, dried at 78℃ for 20h, and then ground to obtain modified boron nitride.

[0058] 13g of thermoplastic polyurethane particles, 4.5g of fluorinated modified methacrylate copolymer, 32mL of N,N-dimethylformamide, and 32mL of tetrahydrofuran were mixed and magnetically stirred at 50℃ for 4.8h. 0.8g of modified nano-SiO2 and 0.4g of modified boron nitride were added, and the mixture was ultrasonically dispersed for 28min. After mechanical stirring at 50℃ for 2.8h, the mixture was loaded into a syringe. The hollow fiber layer was laid flat on an electrospinning receiving device with the syringe needle tip 17.8cm away from the hollow fiber layer. Continuous electrospinning was performed for 2.5h. The mixture was then dried in a 75℃ oven for 18min and heat-treated at 125℃ for 50min to form a nanofiber fluorine film layer on the hollow fiber layer, resulting in a hollow fiber / nanofiber fluorine film composite layer (with a nanofiber fluorine film layer thickness of 20μm).

[0059] The PA hot melt web film layer (Pinghu Zhanpeng Hot Melt Adhesive Film Co., Ltd., model ZPMA-web004, weight 10g / m²) is applied. 2The hollow fiber / nanofiber fluoropolymer composite layer is laid on the unidirectional sweat-wicking layer, and then the hollow fiber / nanofiber fluoropolymer composite layer is laid on the PA hot melt mesh layer. After heating at 155℃ for 35s, it is laminated at 0.06MPa for 15s. After cooling to room temperature, the nanofiber fluoropolymer composite fabric is obtained.

[0060] Example 4

[0061] Mix 2.5g of zein, 1.0g of glucose, and 40mL of 40vol% ethanol aqueous solution, and stir magnetically at 55℃ for 10h. After cooling, load the mixture into a syringe. Fix cotton cloth onto the electrospinning receiving device, control the distance between the syringe needle tip and the cotton cloth to be 18cm, and perform continuous electrospinning for 1h. Then, dry the mixture in a 110℃ forced-air drying oven for 3h to form a one-way perspiration-wicking layer (20μm thick) on the outer layer of the cotton cloth.

[0062] 3.0g of hollow fiber (Jiangsu Jinhetai Fiber Technology Co., Ltd., hollow polyester fiber) was cut into short fibers (3mm) and mixed with 0.25g of low-melting-point copolyester bonding fiber. The mixture was then laid into a web, placed in a mold, covered with a flat plate, and pre-pressed at 170℃ and 0.08MPa for 1 minute, followed by hot pressing at 0.16MPa for 1 minute. After cooling and demolding, a hollow fiber layer (0.45mm thick) was obtained. 5.0g of glycidyl methacrylate, 8.0g of methyl methacrylate, 25mL of tetrahydrofuran, and 0.40g of azobisisobutyronitrile were mixed... The mixture was sealed and purged with nitrogen for 10 minutes. After reacting at 55°C for 3 hours, 1.5 g of pentafluoropropionic acid, 1.8 g of triethanolamine, and 0.40 g of hexadecyltrimethylammonium bromide were added, and the mixture was magnetically stirred at 40°C for 3 hours. The mixture was then precipitated in n-hexane, centrifuged, purified, baked at 45°C for 8 hours, and ground to obtain a fluorinated modified methacrylate copolymer. 1.5 g of nano-SiO2, 80 mL of ethanol, and 12 mL of water were mixed and sonicated for 30 minutes. Triethanolamine was added dropwise to adjust the pH to 8.5, and 0.25 g of [unspecified substance] was added under heating and stirring at 80°C. Modified nano-SiO2 was obtained by reflux reaction at KH550 for 5 h, centrifugation for 15 min, baking at 40℃ for 6 h, and grinding. 0.5 g of hydroxylated hexagonal boron nitride nanosheets (Xi'an Qiyue Biotechnology, catalog number Q-0249641), 50 mL of anhydrous ethanol, and 5 mL of deionized water were mixed, magnetically stirred for 10 min, sonicated for 20 min, and the pH was adjusted to 8.5 by adding 25 wt% ammonia water. 0.09 g of perfluoroethyltriethoxysilane was added, refluxed at 50℃ for 4 h, centrifuged at 8000 rpm for 15 min, washed three times with ethanol, dried at 70℃ for 12 h, and then ground.

[0063] 10g of thermoplastic polyurethane particles, 2.0g of fluorinated modified methacrylate copolymer, 25mL of N,N-dimethylformamide, and 25mL of tetrahydrofuran were mixed and magnetically stirred at 50℃ for 4h. 0.5g of modified nano-SiO2 and 0.2g of modified boron nitride were added, and the mixture was ultrasonically dispersed for 20min. After mechanical stirring at 50℃ for 2h, the mixture was loaded into a syringe. The hollow fiber layer was laid flat on an electrospinning receiving device with the syringe needle tip 18cm away from the hollow fiber layer. Continuous electrospinning was performed for 1h. The mixture was then dried in a 60℃ oven for 10min and heat-treated at 110℃ for 30min to form a nanofiber fluorine film layer on the hollow fiber layer, resulting in a hollow fiber / nanofiber fluorine film composite layer (with a nanofiber fluorine film layer thickness of 16μm).

[0064] The PA hot melt web film layer (Pinghu Zhanpeng Hot Melt Adhesive Film Co., Ltd., model ZPMA-web004, weight 15g / m²) is applied. 2 The hollow fiber / nanofiber fluoropolymer composite layer is laid on the unidirectional sweat-wicking layer, and then the hollow fiber / nanofiber fluoropolymer composite layer is laid on the PA hot melt mesh layer. After heating at 160℃ for 30s, it is laminated at 0.03MPa for 10s. After cooling to room temperature, the nanofiber fluoropolymer composite fabric is obtained.

[0065] Example 5

[0066] Mix 3.0g of zein, 1.5g of glucose, and 80mL of 60vol% ethanol aqueous solution, and stir magnetically at 60℃ for 12h. After cooling, load the mixture into a syringe. Fix cotton cloth onto the electrospinning receiving device, control the distance between the syringe needle tip and the cotton cloth to be 15cm, and perform continuous electrospinning for 2h. Then, dry the mixture in a 120℃ forced-air drying oven for 4h to form a one-way perspiration-wicking layer (thickness: 36μm) on the outer layer of the cotton cloth.

[0067] 5.0g of hollow fiber (Jiangsu Jinhetai Fiber Technology Co., Ltd., hollow polyester fiber) was cut into short fibers (5mm) and mixed with 0.35g of low-melting-point copolyester bonding fiber. The mixture was then laid into a web, placed in a mold, covered with a flat plate, and pre-pressed at 180℃ and 0.08MPa for 2 minutes. Afterward, it was hot-pressed at 0.22MPa for 80 seconds, cooled, and demolded to obtain a hollow fiber layer (thickness: 0.65mm). 6.0g of glycidyl methacrylate, 15g of methyl methacrylate, 35mL of tetrahydrofuran, and 1.0g of azobisisobutyronitrile were mixed densely... After sealing, nitrogen gas was introduced for 15 min, and the reaction was carried out at 65℃ for 5 h. Then, 3.0 g of pentafluoropropionic acid, 2.3 g of triethanolamine, and 0.60 g of hexadecyltrimethylammonium bromide were added, and the mixture was magnetically stirred at 40℃ for 5 h. The mixture was then precipitated in n-hexane, centrifuged and purified, baked at 55℃ for 10 h, and ground to obtain fluorinated modified methacrylate copolymer. 2.0 g of nano-SiO2, 100 mL of ethanol, and 15 mL of water were mixed and sonicated for 30 min. Triethanolamine was added dropwise to adjust the pH to 9.2, and 0.4 g of [unspecified substance] was added under heating and stirring conditions at 80℃. Modified nano-SiO2 was obtained by reflux reaction at KH550 for 5 h, centrifugation for 30 min, baking at 60℃ for 10 h, and grinding. 1.0 g of hydroxylated hexagonal boron nitride nanosheets (Xi'an Qiyue Biotechnology, catalog number Q-0249641), 70 mL of anhydrous ethanol, and 10 mL of deionized water were mixed, magnetically stirred for 20 min, sonicated for 30 min, and the pH was adjusted to 9.2 by adding 25 wt% ammonia water. 0.18 g of perfluoroethyltriethoxysilane was added, refluxed at 60℃ for 8 h, centrifuged at 8000 rpm for 30 min, washed 5 times with ethanol, dried at 80℃ for 24 h, and then ground.

[0068] 15g of thermoplastic polyurethane particles, 6.0g of fluorinated modified methacrylate copolymer, 35mL of N,N-dimethylformamide, and 35mL of tetrahydrofuran were mixed and magnetically stirred at 50℃ for 5h. 1.0g of modified nano-SiO2 and 0.5g of modified boron nitride were added, and the mixture was ultrasonically dispersed for 30min. After mechanical stirring at 50℃ for 3h, the mixture was loaded into a syringe. The hollow fiber layer was laid flat on an electrospinning receiving device, with the syringe needle tip 17cm away from the hollow fiber layer. Continuous electrospinning was performed for 3h. The mixture was then dried in an 80℃ oven for 20min and heat-treated at 130℃ for 60min to form a nanofiber fluorine film layer on the hollow fiber layer, resulting in a hollow fiber / nanofiber fluorine film composite layer (with a nanofiber fluorine film layer thickness of 22μm).

[0069] The PA hot melt web film layer (Pinghu Zhanpeng Hot Melt Adhesive Film Co., Ltd., model ZPMA-web004, basis weight 8g / m²) is applied. 2The hollow fiber / nanofiber fluoropolymer composite layer is laid on the unidirectional sweat-wicking layer, and then the hollow fiber / nanofiber fluoropolymer composite layer is laid on the PA hot melt mesh layer. After heating at 160℃ for 40s, it is laminated at 0.08MPa for 20s. After cooling to room temperature, the nanofiber fluoropolymer composite fabric is obtained.

[0070] like Figure 1 The image shows the nanofiber fluoropolymer composite fabric obtained in the above embodiment. It includes, from top to bottom, a nanofiber fluoropolymer membrane layer 1, a hollow fiber layer 2, a PA hot-melt mesh layer 3, a one-way wicking layer 4, and a cotton base layer 5.

[0071] The present invention also includes comparative examples and related experiments.

[0072] Comparative Example 1

[0073] Compared with Example 1, the only difference is that a one-way sweat-wicking layer was not prepared. The other preparation methods and components are completely consistent, and the nanofiber fluorine membrane composite fabric is finally obtained.

[0074] Comparative Example 2

[0075] Compared with Example 1, the only difference is that the nanofiber fluorine membrane layer is directly prepared and the hollow fiber layer and the nanofiber fluorine membrane layer are bonded together using a commercially available adhesive. The other preparation methods and components are completely consistent, and the nanofiber fluorine membrane composite fabric is finally obtained.

[0076] Comparative Example 3

[0077] Compared with Example 1, the only difference is that no fluorinated modified methacrylate copolymer was added. The other preparation methods and components are completely consistent, and the nanofiber fluorine membrane composite fabric is finally obtained.

[0078] Performance testing

[0079] The performance of the nanofiber fluorofilm composite fabrics prepared in Examples 1-5 and Comparative Examples 1-3 in terms of waterproofing, breathability, moisture permeability, and one-way perspiration wicking was tested.

[0080] The hydrostatic pressure and water repellency rating were determined according to the national standards GB / T4744-2013 "Test and Evaluation of Waterproof Performance of Textiles - Hydrostatic Pressure Method" and GB / T4745-2012 "Test and Evaluation of Waterproof Performance of Textiles - Water Repellency Method" to evaluate the waterproof performance; the specific test results are shown in Table 1.

[0081] According to the national standards GB / T5453-1997 "Determination of air permeability of textiles" and GB / T12704.1-2009 "Test methods for moisture permeability of textiles - Part 1: Moisture absorption method", the air permeability and moisture permeability were determined to evaluate the air permeability and moisture permeability performance. In addition, according to the national standard GB / T21655.2-2019 "Evaluation of moisture absorption and quick-drying properties of textiles - Part 2: Dynamic moisture transfer method", the skin side of the sample was placed up and the outer side was placed down. The wetting, diffusion and transfer process of liquid water on the upper and lower surfaces was recorded to obtain the unidirectional transfer index to evaluate the unidirectional perspiration wicking ability. The specific test results are shown in Table 2.

[0082] The peel strength and tear strength were determined according to FZ / T60011-2016 "Test Method for Peel Strength of Composite Fabrics" and GB / T3917 "Textiles - Tear Properties of Fabrics - Part 3" respectively. After 10 washing cycles according to GB / T8629-2017 "Textiles - Household Washing and Drying Procedures for Testing", the peel strength and tear strength were retested to evaluate the durability of use. The specific test results are shown in Table 3.

[0083] Table 1

[0084]

[0085] As shown in Table 1, the hydrostatic resistance of Examples 1-5 is generally at a high level, and the water repellency rating is maintained at 4-5, indicating that the outer nanofiber fluorine membrane can form a stable liquid-resistant and waterproof barrier. In Comparative Example 3, without the addition of fluorinated modified methacrylate copolymer, the hydrostatic resistance and water repellency rating decreased significantly.

[0086] Table 2

[0087]

[0088] As shown in Table 2, the nanofiber fluorine membrane composite fabrics prepared in Examples 1-5 maintain high waterproof performance while also exhibiting good air permeability, moisture permeability, and one-way perspiration wicking performance, all of which are superior to Comparative Example 2. Comparative Example 2 uses commercially available adhesives to bond the hollow fiber layer and the nanofiber fluorine membrane layer, resulting in a significant decrease in air permeability and moisture permeability. The lack of a one-way perspiration wicking layer in Comparative Example 1 leads to a significant decrease in the one-way transfer index, which also demonstrates that the addition of a one-way perspiration wicking layer in Example 1 of this invention does indeed achieve one-way perspiration wicking capability.

[0089] Table 3

[0090]

[0091] As shown in Table 3, the initial peel strength of the samples in Examples 1-5 was 22-25 N, and the initial tear strength was 31-40 N. After washing 10 times according to the procedure specified in GB / T8629, the peel strength and tear strength only decreased slightly, and the overall retention rate was high, which further illustrates that the samples in Examples 1-5 of the present invention have good service durability. In contrast, the peel strength and tear strength of the comparative samples decreased more significantly after washing 10 times. Among them, Comparative Example 2 used a commercially available adhesive to bond the hollow fiber layer and the nanofiber fluorinated membrane layer. Although the initial peel strength was similar to that of Example 1, the tear strength and retention after washing decreased more significantly. Comparative Example 3 lacked fluorinated modified methacrylate copolymer, and its peel and tear properties decreased significantly after washing 10 times.

[0092] The above are preferred embodiments of the present invention. Those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A preparation process for a nanofiber fluoropolymer membrane composite fabric, characterized in that, Includes the following steps: S1. Mix corn gluconate, glucose, and ethanol aqueous solution, heat and stir, cool, load into a syringe, fix cotton cloth on the electrospinning receiving device, perform electrospinning, dry, and form a one-way sweat-wicking layer on the outer layer of the cotton cloth. S2. Mix and stir thermoplastic polyurethane particles, fluorinated modified methacrylate copolymer, N,N-dimethylformamide, and tetrahydrofuran, load into a syringe, spread the hollow fiber layer on the electrospinning receiving device, perform electrospinning, drying, and heat treatment to form a nanofiber fluorine film layer on the hollow fiber layer, and obtain a hollow fiber / nanofiber fluorine film composite layer. The fluorinated modified methacrylate copolymer is prepared by mixing 5-6 parts by weight of glycidyl methacrylate, 8-15 parts by weight of methyl methacrylate, 25-35 parts by volume of tetrahydrofuran, and 0.4-1 parts by weight of azobisisobutyronitrile (AIB). After sealing, nitrogen gas is introduced for 10-15 minutes, and the mixture is reacted at 55-65°C for 3-5 hours. Then, 1.5-3 parts by weight of pentafluoropropionic acid, 1.8-2.3 parts by weight of triethanolamine, and 0.4-0.6 parts by weight of hexadecyltrimethylammonium bromide are added, and the mixture is magnetically stirred at 40°C for 3-5 hours. The mixture is then precipitated in n-hexane, centrifuged and purified, baked at 45-55°C for 8-10 hours, and ground into powder to obtain the fluorinated modified methacrylate copolymer. The hollow fiber layer is made by cutting 3-5 parts by weight of hollow fiber into short fibers and mixing it with 0.25-0.35 parts by weight of low melting point copolyester bonding fiber, laying it into a web, placing it in a mold and covering it with a flat plate, pre-pressing it at 170-180℃ and 0.08MPa for 1-2 minutes, and then hot-pressing it at 0.16-0.22MPa for 60-90 seconds, cooling and demolding to obtain the product. S3. Lay the PA hot melt mesh layer on the one-way sweat-wicking layer, then lay the hollow fiber / nanofiber fluoropolymer composite layer on the PA hot melt mesh layer, heat it, laminate it, and cool it to obtain the nanofiber fluoropolymer composite fabric.

2. The preparation process of the nanofiber fluorine membrane composite fabric according to claim 1, characterized in that, In step S1, 2.5-3 parts by weight of zein, 1-1.5 parts by weight of glucose, and 40-80 parts by volume of an aqueous ethanol solution with a concentration of 40-60 vol% are mixed and magnetically stirred at 55-60°C for 10-12 hours. After cooling, the mixture is loaded into a syringe, and the cotton cloth is fixed on the electrospinning receiving device. The distance between the needle tip of the syringe and the cotton cloth is controlled to be 15-18 cm. Electrospinning is performed continuously for 1-2 hours, and the mixture is placed in a forced-air drying oven at 110-120°C for 3-4 hours to form a one-way perspiration-wicking layer on the outer layer of the cotton cloth.

3. The preparation process of the nanofiber fluorine membrane composite fabric according to claim 1, characterized in that, In step S2, thermoplastic polyurethane particles, fluorinated modified methacrylate copolymer, N,N-dimethylformamide, and tetrahydrofuran are mixed and stirred. Then, 0.5-1 parts by weight of modified nano-SiO2 and 0.2-0.5 parts by weight of modified boron nitride are added and ultrasonically dispersed for 20-30 minutes. After mechanical stirring at 50°C for 2-3 hours, the mixture is loaded into a syringe.

4. The preparation process of the nanofiber fluorine membrane composite fabric according to claim 3, characterized in that, The modified nano-SiO2 is prepared by mixing 1.5-2 parts by mass of nano-SiO2, 80-100 parts by volume of ethanol, and 12-15 parts by volume of water, ultrasonically treating for 30 minutes, adding triethanolamine to adjust the pH to 8.5-9.2, adding 0.25-0.4 parts by mass of KH550 under heating and stirring at 80°C, refluxing for 5 hours, centrifuging for 15-30 minutes, baking at 40-60°C for 6-10 hours, cooling to room temperature, and grinding into powder.

5. The preparation process of a nanofiber fluorine membrane composite fabric according to claim 3, characterized in that, The modified boron nitride is prepared by mixing 0.5-1 parts by weight of hydroxylated hexagonal boron nitride nanosheets, 50-70 parts by volume of anhydrous ethanol, and 5-10 parts by volume of deionized water, stirring magnetically for 10-20 min, sonicating for 20-30 min, adjusting the pH to 8.5-9.2 by adding 25 wt% ammonia water, adding 0.09-0.18 parts by weight of perfluoroethyltriethoxysilane, continuing to heat and stir at 50-60℃, refluxing for 4-8 h, cooling to room temperature, centrifuging at 8000 rpm for 15-30 min, collecting the precipitate, washing 3-5 times with anhydrous ethanol, drying in an oven at 70-80℃ for 12-24 h, cooling to room temperature, and grinding into powder.

6. The preparation process of a nanofiber fluorine membrane composite fabric according to claim 1, characterized in that, In step S2, 10-15 parts by weight of thermoplastic polyurethane particles, 2-6 parts by weight of fluorinated modified methacrylate copolymer, 25-35 parts by volume of N,N-dimethylformamide, and 25-35 parts by volume of tetrahydrofuran are mixed and magnetically stirred at 50°C for 4-5 hours. The mixture is then loaded into a syringe, and the hollow fiber layer is laid flat on the electrospinning receiving device. The distance between the syringe needle tip and the hollow fiber layer is controlled to be 17-18 cm. Continuous electrospinning is performed for 1-3 hours, followed by drying in an oven at 60-80°C for 10-20 minutes, and heat treatment at 110-130°C for 30-60 minutes to form a nanofiber fluorinated membrane layer on the hollow fiber layer, thus obtaining a hollow fiber / nanofiber fluorinated membrane composite layer.

7. The preparation process of a nanofiber fluorine membrane composite fabric according to claim 1, characterized in that, The heating temperature in S3 is 135~160℃ and the time is 30~40s, and the lamination is carried out under the condition of 0.02~0.08MPa for 10~20s.

8. A nanofiber fluorine membrane composite fabric, characterized in that, The fabric is prepared by the preparation process of a nanofiber fluorine membrane composite fabric according to any one of claims 1 to 7, comprising a nanofiber fluorine membrane layer, a hollow fiber layer, a PA hot melt mesh film layer, a one-way sweat-wicking layer and a cotton base layer arranged sequentially from the environmental side to the skin side.

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