Bio-based wear-resistant fabric and preparation method thereof

Abstract

The present application discloses a bio-based wear-resistant fabric and a preparation method thereof, which relate to the field of textile technology. The fabric comprises a bio-based nylon fabric layer, a polytetrafluoroethylene electrospun nano-membrane layer and a nylon warp-knitted base yarn arranged in sequence; the polytetrafluoroethylene electrospun nano-membrane layer is an intermediate layer, and a bio-based hot-melt adhesive is used to adhere the bio-based nylon fabric layer and the nylon warp-knitted base yarn to both sides of the polytetrafluoroethylene electrospun nano-membrane layer respectively; hydrophobic silica nanoparticles modified with a silane coupling agent are added to the bio-based hot-melt adhesive and the polytetrafluoroethylene electrospun nano-membrane layer respectively; wherein the silica nanoparticles added to the nano-membrane layer are further modified to form a core-shell structure; by combining the introduction and modification of the hydrophobic silica nanoparticles, a bio-based wear-resistant fabric with high waterproof and moisture permeability, good wear resistance and non-clogging gaps is prepared, thereby improving the overall performance and service life of the fabric.

Description

Technical Field

[0001] The present invention relates to the field of textile technology, and in particular to a bio-based wear-resistant fabric and a preparation method thereof. Background Art

[0002] Fabric is the material used to make clothing. As one of the three key elements of clothing, fabric not only defines the style and characteristics of clothing but also directly influences the color and shape of the garment. Functional fabrics, in particular, are fabrics with specialized properties and uses, such as waterproofing, windproofing, breathability, moisture permeability, warmth retention, oil resistance, stain removal, antibacterial and deodorizing properties, UV protection, antistatic properties, radiation protection, flame retardancy, high temperature resistance, and acid and alkali resistance. Functional fabrics on the market are primarily used for clothing, and are often used in outdoor sportswear and high-end casual wear.

[0003] With growing global awareness of sustainable development and environmental protection, replacing traditional petroleum-based materials has become a research hotspot. Bio-based materials, derived from renewable resources and characterized by their environmental friendliness and biodegradability, are becoming a key area of new material development. Bio-based materials utilize renewable materials such as straw and other agricultural and forestry waste, biogas, biodiesel, and bioplastics through biological, physical, or chemical processing. The environmentally friendly, recyclable, and renewable nature of biomaterials and materials meets contemporary ecological demands, and therefore holds promising market development prospects.

[0004] For example, Chinese patent application number CN202210935077.2, titled "Highly Breathable Bio-Based Nylon Fabric and Its Preparation Method," discloses a highly breathable bio-based nylon fabric comprising a sequentially arranged bio-based nylon fabric layer, a PTFE electrospun nanomembrane layer, and a nylon warp-knitted base yarn. The bio-based nylon fabric layer is made from one or more of bio-based nylon 56, bio-based nylon 66, or bio-based nylon 1010. This highly breathable bio-based nylon fabric is derived from agricultural and forestry waste through microbial fermentation and purification. The bio-based nylon fabric is lightweight, wear-resistant, and human-friendly, enabling resource recycling. Furthermore, the electrospun polytetrafluoroethylene (PTFE) nanomembrane boasts high strength and chemical resistance, while its nanoscale pores provide high waterproofness and breathability. This makes it suitable for clothing designed for extreme environments such as leisure sports and outdoor adventures.

[0005] The above solution optimizes the void structure by stretching the PTFE membrane, which has advantages in waterproofness and moisture permeability. However, hot melt adhesive easily penetrates into the voids of the PTFE membrane during high-temperature bonding, blocking the moisture permeability channel and affecting long-term performance. It also has insufficient wear resistance, is prone to wear, and has a short service life. Summary of the Invention

[0006] The embodiments of the present application solve the problems of insufficient waterproof and breathable performance, insufficient wear resistance, gap clogging and insufficient interface bonding strength in the prior art by providing a bio-based wear-resistant fabric and a preparation method thereof. By adopting a composite structure of a bio-based nylon fabric layer, a PTFE electrospun nanomembrane layer and a nylon warp-knitted base yarn, combined with the introduction and modification of hydrophobic silica nanoparticles, a bio-based wear-resistant fabric with high waterproof and breathable performance, good wear resistance and non-clogging gaps is prepared, thereby improving the overall performance and service life of the fabric.

[0007] The embodiment of the present application provides a bio-based wear-resistant fabric, comprising a bio-based nylon fabric layer, a polytetrafluoroethylene electrospun nano-membrane layer, and a nylon warp-knitted base yarn arranged in sequence;

[0008] The polytetrafluoroethylene electrospun nano-membrane layer is the middle layer, and the bio-based nylon fabric layer and nylon warp-knitted base yarn are respectively adhered to the two sides of the polytetrafluoroethylene electrospun nano-membrane layer using bio-based hot melt adhesive;

[0009] Hydrophobic silica nanoparticles modified with a silane coupling agent are added to the bio-based hot melt adhesive and the polytetrafluoroethylene electrospun nanofilm layer respectively;

[0010] Among them, the silicon dioxide nanoparticles added to the polytetrafluoroethylene electrospun nanomembrane layer are also coated with graphene oxide to form a core-shell structure.

[0011] Furthermore, the particle size of the silicon dioxide nanoparticles is 10-50 nm.

[0012] Furthermore, the amount of silicon dioxide nanoparticles added to the bio-based hot melt adhesive is 5-10% of the total mass of the bio-based hot melt adhesive.

[0013] Furthermore, the silica nanoparticles are pretreated before being added to the bio-based hot melt adhesive. The specific steps are as follows:

[0014] Premixing: Premix the hydrophobic silica nanoparticles with the bio-based hot melt adhesive and stir at low speed;

[0015] Ultrasonic dispersion: ultrasonically disperse the mixture;

[0016] Degassing by standing: After dispersion, let it stand to eliminate bubbles in the colloid.

[0017] Furthermore, the concentration of silicon dioxide nanoparticles added to the polytetrafluoroethylene electrospun nanofilm layer is 1-3 wt %.

[0018] Furthermore, the core layer of the core-shell structure is hydrophobic silica nanoparticles, and the shell layer is graphene oxide.

[0019] Furthermore, the mass ratio of silica nanoparticles to graphene oxide in the core-shell structure is 5:1.

[0020] Furthermore, the preparation of the core-shell structure comprises the following specific steps:

[0021] Hydrophobic modification of silica nanoparticles: disperse silica nanoparticles in ethanol, add silane coupling agent, stir, centrifuge and wash, and then dry;

[0022] Graphene oxide coating: hydrophobically modified silica nanoparticles and graphene oxide were added to deionized water and ultrasonically dispersed;

[0023] A cross-linking agent is added, the mixture is centrifuged and freeze-dried to obtain a core-shell structure.

[0024] Furthermore, the silica nanoparticles in the bio-based hot melt adhesive have a different particle size from the silica nanoparticles added to the polytetrafluoroethylene electrospun nanofilm layer. The silica nanoparticles in the bio-based hot melt adhesive have a particle size of 10-30 nm, while the silica nanoparticles in the polytetrafluoroethylene electrospun nanofilm layer have a particle size of 50-80 nm.

[0025] A method for preparing a bio-based wear-resistant fabric, comprising the following steps:

[0026] S1. Preparation of bio-based nylon fabric layer: one or more of bio-based nylon 56, bio-based nylon 66 or bio-based nylon 1010 are subjected to weaving, desizing, dyeing, drying, intermediate inspection, shaping and final inspection to obtain a bio-based nylon fabric layer;

[0027] S2. Preparation of polytetrafluoroethylene electrospun nanofilm layer: A polytetrafluoroethylene aqueous emulsion, a polyvidone aqueous solution, and an antistatic additive are blended to obtain an electrospinning solution, which is prepared by an electrospinning process. The prepared polytetrafluoroethylene electrospun nanofilm layer is first stretched in a single direction and allowed to stand for final shaping; and then a second stretching is performed in the direction of the first stretching.

[0028] S3, gluing and laminating: placing the stretched polytetrafluoroethylene electrospun nanofilm layer on a laminating machine, heating and melting the pretreated bio-based hot melt adhesive and evenly coating it on the surface of the film layer, and laminating the bio-based nylon fabric layer and the nylon warp knitted base yarn with the polytetrafluoroethylene electrospun nanofilm layer coated with the hot melt adhesive;

[0029] S4. Curing: Place the bonded bio-based wear-resistant fabric in a curing room for curing, and the product is obtained after curing.

[0030] One or more technical solutions provided in the embodiments of this application have at least the following technical effects or advantages:

[0031] First, by introducing hydrophobic silica nanoparticles into bio-based hot melt adhesives, problems such as void clogging, insufficient interfacial bonding, poor heat resistance, and insufficient wear resistance in fabric preparation are resolved. This creates an anti-clogging protective layer, enhances interfacial bonding and fabric wear resistance, and improves the overall performance and service life of the fabric.

[0032] Secondly, by adding silica nanoparticles to the PTFE electrospun nanomembrane layer, the problems of hot melt adhesive penetrating into gaps, poor gap stability and insufficient wear resistance in fabric preparation are solved. This improves gap stability, maintains moisture permeability, enhances resistance to colloid penetration and improves wear resistance. Hydrophobic silica nanoparticles evenly cover the gap surface of the PTFE electrospun nanomembrane through van der Waals forces and surface adsorption. The size of the nanoparticles is smaller than the gap width and will not block the gap channel, but can fill microscopic defects such as cracks or irregular edges on the gap surface. At the same time, they can form a physical barrier layer to prevent the bio-based hot melt adhesive from penetrating into the gap during the bonding process.

[0033] Third, by constructing a core-shell structure with hydrophobic silica nanoparticles as the core and graphene oxide as the shell, and introducing a PTFE electrospun nanomembrane layer, the problems of poor void stability, low mechanical strength, and insufficient waterproof and moisture permeability are solved; void support, fiber network bonding, and interfacial bonding are enhanced, thereby improving tear resistance, abrasion resistance, moisture permeability, and hydrophobicity, thereby improving the overall performance of the fabric.

[0034] Fourthly, by differentially regulating the particle size of the PTFE electrospun nanomembrane layer and the silica nanoparticles in the bio-based hot melt adhesive, the synergistic optimization of the highly moisture-permeable and highly waterproof bio-based nylon composite fabric was achieved; the small-sized silica nanoparticles in the PTFE membrane layer are more easily embedded in the microscopic defects of the PTFE fiber network and the surface of the voids, filling the edges of the voids and enhancing the local mechanical strength; the small particle size is not easy to clog the void channels (width 200-400 nm), so it can maintain high moisture permeability; the large silica nanoparticles in the bio-based hot melt adhesive form a wider physical barrier through the steric effect, occupying more colloid flow paths, and reducing the migration of colloids into the voids through physical obstruction. DETAILED DESCRIPTION

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains; the terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0036] Example 1: A bio-based wear-resistant fabric, comprising: a bio-based nylon fabric layer, a polytetrafluoroethylene (PTFE) electrospun nano-membrane layer, and a nylon warp-knitted base yarn arranged in sequence;

[0037] The bio-based nylon fabric layer is one or more of bio-based nylon 56, bio-based nylon 66 or bio-based nylon 1010;

[0038] The PTFE electrospun nano-membrane layer is prepared by mixing an electrospinning solution obtained by mixing a PTFE aqueous emulsion, a polyvidone (PVP) aqueous solution, and an antistatic additive, and is prepared by an electrospinning process. The voids in the PTFE electrospun nano-membrane layer are nanoscale, and the aspect ratio thereof is 1.5:1-3:1;

[0039] The PTFE electrospun nano-membrane layer is used as the middle layer, and the bio-based nylon fabric layer and the nylon warp-knitted base yarn are respectively adhered to both sides of the PTFE electrospun nano-membrane layer using a bio-based hot melt adhesive;

[0040] The bio-based hot melt adhesive contains silica nanoparticles with a particle size of 10-50nm. The surface of the silica nanoparticles is modified with a silane coupling agent KH-570 to form hydrophobic silica nanoparticles. The amount of silica nanoparticles added is 5-10% of the total mass of the bio-based hot melt adhesive.

[0041] The PTFE electrospun nanofilm layer is stretched in a single direction;

[0042] The gap width of the PTFE electrospun nano-membrane layer is 200-400 nanometers, and the gap length of the PTFE electrospun nano-membrane layer is 300-1200 nanometers;

[0043] The preparation method of the bio-based wear-resistant fabric comprises the following specific steps:

[0044] S1. Preparation of bio-based nylon fabric layer: one or more of bio-based nylon 56, bio-based nylon 66 or bio-based nylon 1010 are subjected to weaving, desizing, dyeing, drying, intermediate inspection, shaping and final inspection to obtain a bio-based nylon fabric layer;

[0045] S11, desizing treatment: use alkaline additives, enzyme preparations and surfactants at 100 ° C for 30 minutes to remove sizing and grease residues;

[0046] The alkaline auxiliary agent is NaOH, the enzyme preparation is lipase, and the surfactant is sodium fatty alcohol polyoxyethylene ether sulfate (AES).

[0047] S12, dyeing and reduction cleaning: dyeing with leveling agent and dispersant, followed by removal of floating color with reduction cleaning agent;

[0048] Among them, the leveling agent is sodium alkyl sulfonate, the dispersant is sodium lignin sulfonate, and the reducing cleaning agent is sodium disulfite;

[0049] S13, anti-splash treatment: Dip into fluorine-free ecological waterproof agent, concentration of 40g / L, liquid rate of 50-80%, and bake at 180℃ to form a hydrophobic layer;

[0050] Among them, the main chain of the fluorine-free ecological waterproofing agent is an acrylate copolymer, specifically, methyl methacrylate / butyl ester copolymer; the usage of the fluorine-free ecological waterproofing agent is 60-80g / L;

[0051] S14, drying and shaping: drying at 170°C, and adjusting the width and warp and weft density through a stenter setting machine to enhance wear resistance, thereby obtaining a bio-based nylon fabric layer;

[0052] Among them, the setting temperature of the stenter setting machine is 140-180℃, and the speed is 40-60m / min;

[0053] S2. Preparation of PTFE electrospun nanofilm layer: PTFE aqueous emulsion, PVP aqueous solution and antistatic additive are blended, ultrasonicated in a water bath for 20-40 minutes to obtain an electrospinning solution, and prepared by an electrospinning process, the prepared PTFE electrospun nanofilm layer is stretched in a single direction for the first time, and the stretched PTFE electrospun nanofilm layer is allowed to stand for final shaping;

[0054] Then the PTFE electrospun nanofilm layer is stretched a second time in the direction of the first stretching;

[0055] The concentration of the PTFE aqueous emulsion is 65-85%, the concentration of the PVP aqueous solution is 10-15%, the concentration of the antistatic additive is 0.5-1%, the electrospinning process voltage is 17.5-21.5 kV, the flow rate is 0.5-0.8 mL / h, the spinning time is 2-3 hours, and the receiving distance is 20-25 cm. The first stretching amplitude is 1.3-2 times the original length, and the second stretching stretches the void aspect ratio of the PTFE electrospun nanomembrane layer to 1.5:1-3:1.

[0056] S3, gluing and laminating: placing the PTFE electrospun nano-membrane layer on a laminating machine, heating and melting the pre-treated bio-based hot melt adhesive and evenly coating it on the surface of the PTFE electrospun nano-membrane layer, and laminating the bio-based nylon fabric layer and the nylon warp knitted base yarn to the PTFE electrospun nano-membrane layer coated with the hot melt adhesive;

[0057] Among them, the bio-based hot melt adhesive is pretreated before coating, and the pretreatment is specifically as follows:

[0058] S31. Premixing: Premix the hydrophobic silica nanoparticles with the bio-based hot melt adhesive at 40-60°C and stir at a low speed of 200-400 rpm for 10-15 minutes;

[0059] S32. Ultrasonic dispersion: The mixture was placed in an ultrasonic disperser at 300 W power and 25-40°C for 40 min to ensure uniform dispersion of the nanoparticles.

[0060] S33. Standing degassing: After dispersion, let it stand for 12-24 hours to eliminate bubbles in the colloid and avoid defects during coating;

[0061] The heating temperature of the bio-based hot melt adhesive is 150-170°C, the viscosity is 4500-6500mPa.s, the dispensing amount is 6-8g, and the nylon warp knitting base yarn is one of 15D, 20D or 30D;

[0062] S4, aging: placing the bonded bio-based wear-resistant fabric in the aging room for aging;

[0063] The aging temperature is 40-50°C, the humidity is 70-90%, and the aging time is 36-48 hours.

[0064] Experiments were conducted on the above technical solution, and the experimental parameters were specifically as follows:

[0065] S1, preparation of bio-based nylon fabric layer;

[0066] S11, desizing treatment: NaOH concentration: 5% (w / v), lipase concentration: 2% (w / v), surfactant (AES) concentration: 1% (w / v), temperature: 100°C, time: 30 minutes;

[0067] S12, dyeing and reduction cleaning: the concentration of the leveling agent sodium alkyl sulfonate is 1.5% (owf), the concentration of the dispersant sodium lignin sulfonate is 2% (owf), the concentration of the reduction cleaning agent sodium disulfite is 3 g / L, the temperature is 60°C, and the time is 15 minutes;

[0068] S13, water repellent treatment: fluorine-free water repellent concentration: 70 g / L, padding liquid rate: 65%, baking temperature: 180 ° C, time: 2 minutes;

[0069] S2, preparation of PTFE electrospinning nano-membrane layer;

[0070] Spinning solution formula: PTFE aqueous emulsion: 75% (solid content 60%), PVP aqueous solution: 12%, antistatic additive: 0.8%;

[0071] Electrospinning parameters: voltage: 20 kV, flow rate: 0.6 mL / h, receiving distance: 22 cm, spinning time: 2.5 h;

[0072] Stretching process: First stretching: stretch to 1.5 times the original length and let it stand for 30 minutes to set; Second stretching: adjust the gap aspect ratio to 2:1;

[0073] S3, gluing and laminating;

[0074] The addition amounts of silica nanoparticles were: 0, 5%, 8%, and 10%;

[0075] Pretreatment parameters: premixing: 50 °C, 300 rpm stirring for 12 minutes, ultrasonic dispersion: power 300 W, temperature 30 °C, time 40 minutes, static degassing: 18 hours;

[0076] The heating temperature of the bio-based hot melt adhesive is 160°C, the viscosity is 5500mPa.s, the dispensing amount is 7g, and the nylon warp knitting base yarn is 15D;

[0077] S4, aging: aging temperature is 45 ° C, humidity is 80%, and aging time is 42 hours;

[0078] The performance of the bio-based wear-resistant fabric prepared by the above scheme was tested:

[0079] 1. Moisture permeability: Water vapor transmission rate test, according to GB / T 12704.1-2009;

[0080] 2. Waterproofness: Spray method (water repellency grade) GB / T 4745-2012;

[0081] 3. Abrasion resistance: Martindale abrasion test (wool abrasive, 155g) GB / T 4802.2;

[0082] The test results are shown in Table 1 below:

[0083] Table 1

[0084]

[0085] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages:

[0086] Hydrophobic silica nanoparticles (10-50 nm in diameter) are dispersed in the colloid through steric hindrance, forming a physical barrier. The size of the nanoparticles (much smaller than the 200-400 nm width of the PTFE membrane pores) and their hydrophobicity allow them to cover the colloid surface, preventing the molten colloid from penetrating into the PTFE membrane pores. The repulsive interaction between the particles (van der Waals forces + hydrophobic effect) limits the fluidity of the colloid, preventing pore clogging and forming an anti-clogging protective layer.

[0087] In addition, the high thermal conductivity of silica nanoparticles (approximately 1.4 W / m·K) accelerates heat transfer. The nanoparticles act as a thermal pathway, quickly dissipating heat from the colloid and shortening the curing time (essentially reducing it by more than 15%). This creates a thermal network, reduces the flow time of the colloid at high temperatures, and reduces the risk of void penetration.

[0088] Third, the silanol groups (-Si-OH) on the surface of silica form hydrogen bonds with the polar groups of the colloid (such as starch hydroxyl groups), which enhance the adhesion between the adhesive layer and the PTFE membrane through chemical bonding. The formed hydrogen bond network can improve the interfacial binding energy and increase the peel strength by about 20-30%;

[0089] Therefore, the fabrics made by adding silica nanoparticles to bio-based hot melt adhesives have the following advantages:

[0090] High moisture permeability and waterproofness: PTFE membrane pore blockage is reduced, water vapor transmission rate is increased, and water repellency is improved;

[0091] Improved wear resistance: The adhesive layer and PTFE membrane are tightly bonded, improving wear resistance;

[0092] Aging resistance: Silica nanoparticles enhance the heat resistance of the adhesive layer and reduce the risk of high-temperature deformation;

[0093] Interface stability: Hydrogen bond network resists delamination in hot and humid environments.

[0094] Silica nanoparticles enhance the adhesion between the adhesive layer and the PTFE film layer, reducing delamination and peeling caused by friction, thereby improving the wear resistance of the fabric. The uniform dispersion of the nanoparticles in the colloid makes the adhesive layer more uniform and dense, further improving the wear resistance and durability of the fabric. The introduction of silica nanoparticles effectively prevents the bio-based hot melt adhesive from clogging the gaps in the PTFE film during the curing process, thereby maintaining the high moisture permeability of the fabric. The high thermal conductivity of silica nanoparticles significantly shortens the curing time of the bio-based hot melt adhesive, reduces the risk of colloid flow at high temperatures, and improves the heat resistance of the fabric.

[0095] This approach has led to the successful development of a bio-based wear-resistant and water-repellent material. Its wear resistance surpasses some traditional petroleum-based counterparts on the market, and its water-repellency rating meets international standards. It also boasts significant environmental performance, significantly reducing carbon emissions and chemical usage throughout the production process. The material itself is biodegradable, in line with the concept of a circular economy.

[0096] Example 2: The above-mentioned Example 1 solves the problems of gap clogging, insufficient interface bonding, poor heat resistance and insufficient wear resistance in fabric preparation by introducing hydrophobic silica nanoparticles into the bio-based hot melt adhesive, forms an anti-clogging protective layer, and enhances the interface bonding and wear resistance of the fabric, thereby improving the overall performance and service life of the fabric. In order to further improve the overall performance of the fabric, further improvements are made on the basis of Example 1.

[0097] Silica nanoparticles are added to the PTFE electrospun nanofilm layer, and the surface of the silica nanoparticles is modified with a silane coupling agent KH-570 to form hydrophobic silica nanoparticles; the added concentration of the silica nanoparticles is 1-3wt%;

[0098] The step of adding silicon dioxide nanoparticles to the PTFE electrospun nanofilm layer is specifically as follows:

[0099] Preparation of silica nanoparticle dispersion: 1-3 wt% of silica nanoparticles are added to a mixed solution of ethanol and water, and ultrasonically dispersed to form a dispersion;

[0100] The volume ratio of ethanol to water was 7:3, the ultrasonic power was 300 W, and the time was 30 min;

[0101] Addition of PTFE electrospun nanofilm layer: Immerse the PTFE electrospun nanofilm in the dispersion for 5-10 seconds; dry it at 70-90℃ for 10 minutes to make the silica nanoparticles firmly adhere to the gap edges or surface defects to form a nanoscale protective layer.

[0102] Based on the experiment in Example 1 in which the amount of silica nanoparticles added to the bio-based hot melt adhesive was 8%, an experiment was conducted using the technical solution of this embodiment. The difference between the experiment in this embodiment and the experiment in Example 1 is that silica nanoparticles are further added to the PTFE electrospun nanofilm layer in this embodiment, and the added concentrations of the silica nanoparticles are 0wt%, 1wt%, 2wt%, and 3wt%, respectively. The performance of the fabrics prepared in this embodiment was tested, and the test results are shown in Table 2 below:

[0103] Table 2

[0104]

[0105] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages:

[0106] Hydrophobic silica nanoparticles are uniformly coated on the pore surface of the PTFE electrospun nanomembrane (pore width 200-400 nm) through van der Waals forces and surface adsorption. Since the nanoparticles are much smaller than the pore width, they do not block the pore channels, but can fill microscopic defects on the pore surface (such as cracks or irregular edges), forming a continuous physical barrier layer that prevents the bio-based hot melt adhesive from penetrating into the pores during the bonding process.

[0107] In addition, the hydrophobic surface of silica nanoparticles modified with silane coupling agents has a repulsive effect on the polar groups of hot melt adhesive (such as starch hydroxyl groups). The hydrophobic nanoparticles reduce the affinity between the colloid and the void surface, thereby reducing the physical contact between the colloid and the PTFE membrane. At the same time, the spatial arrangement between the particles forms a flow barrier, limiting the flow path of the colloid.

[0108] Third, the silanol groups (-Si-OH) on the surface of the silica nanoparticles form hydrogen bonds or dipole interactions with the weak polar regions on the surface of the PTFE membrane. The hydrogen bond network strengthens the bonding strength between the PTFE membrane and the nanoparticles, preventing the particles from falling off. After the nanoparticles fill the surface defects of the voids, they improve the overall mechanical stability of the PTFE membrane. At the same time, the high mechanical strength of the silica nanoparticles (Mohs hardness 7) increases the local compressive resistance of the pore edges. The particles are embedded in the PTFE fibers, enhancing the stability of the pore structure and preventing collapse or deformation caused by external forces during processing or use.

[0109] Therefore, the fabric with the addition of silica nanoparticles to the PTFE electrospun nanofilm layer has the following advantages:

[0110] The pore structure is stable, and it can still effectively block liquid water and expel sweat after long-term use; silica nanoparticles improve the heat resistance of the PTFE membrane (no deformation at 180°C), extending the life of the fabric;

[0111] The pore edges are more resistant to pressure due to the filling of silica nanoparticles, reducing fiber breakage caused by local stress concentration. The hot melt adhesive does not penetrate into the pores, and the interface between the adhesive layer and the PTFE membrane is more evenly bonded, which improves the peel strength (increased by about 10%) and indirectly reduces the wear caused by delamination. The stability of the pore structure of the PTFE membrane reduces the shedding of fibers and the expansion of pores during friction, further improving wear resistance.

[0112] Example 3: The above-mentioned Example 2 solves the problems of hot melt adhesive penetrating into gaps, poor gap stability and insufficient wear resistance in fabric preparation by adding silica nanoparticles to the PTFE electrospun nanomembrane layer, which has the effects of improving gap stability, maintaining moisture permeability, enhancing resistance to colloid penetration and improving wear resistance, thereby improving the overall performance and service life of the fabric. In order to further improve the overall performance of the fabric, further improvements are made on the basis of Example 2.

[0113] The silicon dioxide nanoparticles added to the PTFE electrospun nanomembrane layer are further modified with graphene oxide to form a core-shell structure in which the core layer is hydrophobic silicon dioxide nanoparticles and the shell layer is coated with graphene oxide; the mass ratio of silicon dioxide nanoparticles to graphene oxide is 5:1;

[0114] The preparation of the core-shell structure is as follows:

[0115] Hydrophobic modification of silica nanoparticles: Disperse silica nanoparticles in ethanol, add silane coupling agent KH-570 (5% by weight of silica), stir at 60°C for 2 hours, centrifuge and wash, and then dry;

[0116] Graphene oxide coating: hydrophobically modified silica nanoparticles and graphene oxide were added to deionized water and ultrasonically dispersed;

[0117] The mass ratio of silica nanoparticles to graphene oxide was 5:1; the ultrasonic dispersion power was 500 W, and the time was 1 hour;

[0118] EDC and NHS crosslinker were added at a molar ratio of 1:1 and reacted at room temperature for 12 hours to covalently bond graphene oxide to the hydroxyl groups on the silica surface through the carboxyl groups.

[0119] Centrifugal separation and freeze-drying were performed to obtain a core-shell structure;

[0120] In step S2, the PTFE aqueous emulsion, the PVP aqueous solution, the core-shell structure and the antistatic additive are blended and ultrasonically dispersed in a 50° C. water bath at an ultrasonic power of 400 W for 1 hour to obtain an electrospinning solution.

[0121] The technical solution of this embodiment was used to conduct an experiment based on the experiment in Example 2 in which the amount of silica nanoparticles added to the PTFE electrospun nanofilm layer was 2 wt%. The difference between this embodiment and the experiment in Example 2 is that the silica nanoparticles added to the TFE electrospun nanofilm layer in this embodiment are further modified with graphene oxide to form a core-shell structure in which the core layer is hydrophobic silica nanoparticles and the shell layer is coated with graphene oxide; the mass ratio of silica nanoparticles to graphene oxide is 5:1;

[0122] The test results of the fabric prepared in this embodiment are shown in Table 3 below:

[0123] Table 3

[0124]

[0125] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages:

[0126] Silica nanoparticles are introduced into the PTFE electrospun nanomembrane layer and modified to form a core-shell structure with hydrophobic silica nanoparticles as the core layer and graphene oxide as the shell layer. The silica nanoparticles in the core layer are hydrophobically modified to fill the microscopic defects on the surface of the PTFE membrane voids, forming a rigid support layer to prevent the voids from collapsing. The graphene oxide in the shell layer uses its two-dimensional layer structure to embed into the PTFE fiber network, forming a "skeleton support" that limits fiber slippage, improves the membrane's tear resistance, and enhances the membrane's overall mechanical properties.

[0127] In addition, the surface functional groups (-COOH, -OH) of graphene oxide and the C-F bonds of PTFE enhance interfacial bonding through hydrogen bonding and dipole interactions, while forming chemical bonds with the polar groups of the hot melt adhesive. The hydrophobic surface of graphene oxide (contact angle of approximately 127°) superimposed on PTFE (contact angle of approximately 118°) forms a superhydrophobic interface, further inhibiting liquid water penetration.

[0128] Therefore, the two-dimensional graphene oxide sheets in the core-shell structure form "pinning points" in the PTFE fiber network, limiting the slippage of the fibers during stretching or friction, dispersing external stress, and the silica core fills the weak areas on the surface of the voids, forming a rigid support and reducing the risk of void deformation. The -COOH of graphene oxide forms hydrogen bonds with the CF bonds of PTFE, strengthening the bonding between fibers. Graphene oxide forms stable chemical bonds with polar groups such as starch hydroxyl groups in the hot melt adhesive, improving interlayer adhesion. The bonding strength between the unmodified PTFE membrane and the hot melt adhesive layer is increased by about 30%.

[0129] Therefore, after the modified core-shell structure is added to the PTFE electrospun nanofilm layer, the fabric has the following advantages:

[0130] The tear resistance, tensile strength and other mechanical properties of the membrane layer are further improved, allowing the fabric to maintain stable performance even in extreme environments. The hydrophobicity of the fabric is further enhanced, the permeability is reduced, and high moisture permeability and super hydrophobicity coexist. The high interlayer bonding strength allows the fabric to maintain stable performance after multiple washings or friction.

[0131] Graphene oxide sheets, as a hard reinforcing phase, can disperse external friction stress and reduce direct wear of PTFE fibers. At the same time, the silica core layer fills the edges of the gaps to prevent cracking of the gap edges during friction. The hydrogen bond network and mechanical interlocking enhance the bonding force between fibers. The graphene oxide sheets guide the external force to be evenly dispersed along the fiber network, avoiding rapid wear caused by local stress concentration, thereby improving the wear resistance and service life of the fabric.

[0132] Example 4: The above three examples solve the problems of poor void stability, low mechanical strength and insufficient waterproof and moisture permeability by constructing a core-shell structure with hydrophobic silica nanoparticles as the core and graphene oxide as the shell, and introducing a PTFE electrospun nanomembrane layer; enhance the void support, fiber network bonding and interface bonding, improve the tear resistance, wear resistance, moisture permeability and hydrophobicity, and achieve an improvement in the comprehensive performance of the fabric. In order to further improve the overall performance of the fabric, further improvements are made on the basis of Example 3.

[0133] The silica nanoparticles in the bio-based hot melt adhesive have a different particle size from the silica nanoparticles added to the PTFE electrospun nanomembrane layer. The silica nanoparticles in the bio-based hot melt adhesive have a particle size of 10-30 nm, while the silica nanoparticles in the PTFE electrospun nanomembrane layer have a particle size of 50-80 nm.

[0134] The experiment was conducted using the technical solution of this embodiment based on the experiment in Example 3. The difference between the experiment in this embodiment and the experiment in Example 3 is that the particle size of the silica nanoparticles in the bio-based hot melt adhesive is 10-30 nm, and the particle size of the silica nanoparticles in the PTFE electrospun nanofilm layer is 50-80 nm.

[0135] The test results of the fabric prepared in this embodiment are shown in Table 4 below:

[0136] Table 4

[0137]

[0138] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages:

[0139] By differentially controlling the particle size of the PTFE electrospun nanomembrane and the silica nanoparticles in the bio-based hot melt adhesive, synergistic optimization of a highly moisture-permeable and waterproof bio-based nylon composite fabric was achieved. The small silica nanoparticles in the PTFE membrane are more easily embedded in the microscopic defects of the PTFE fiber network and the surface of the voids, filling the void edges and enhancing local mechanical strength. The small particle size is less likely to clog the void channels (width 200-400 nm), thus maintaining high moisture permeability. The large silica nanoparticles in the bio-based hot melt adhesive form a wider physical barrier through steric hindrance, occupying more of the colloid flow path and reducing the migration of the colloid into the voids through physical obstruction. The high specific surface area and thermal conductivity of the large particles (approximately 1.4 W / m·K) accelerate the curing of the colloid (reducing the curing time by approximately 25%), reduce the fluidity of the colloid at high temperatures, and enhance the heat resistance of the adhesive layer.

[0140] Silica nanoparticles of different sizes work synergistically to achieve graded protection and interface complementarity. Small particles protect the void structure, while large particles block colloid penetration, further improving the overall performance of the fabric. At the same time, small particles in the PTFE membrane layer can enhance fiber-fiber bonding, while large particles in the adhesive layer strengthen the fiber-adhesive layer interface.

[0141] Therefore, by differentially regulating the particle size of the PTFE electrospun nanofilm layer and the silica nanoparticles in the bio-based hot melt adhesive, the fabric has the following advantages:

[0142] Small-sized silica nanoparticles maintain open gaps, ensuring smooth water vapor penetration and maintaining high moisture permeability. Large-sized silica nanoparticles strengthen the hydrophobic interface, reduce liquid water permeability, and improve waterproofness. The synergistic effect of the two further enhances the high moisture permeability and waterproofness of the fabric.

[0143] Small-sized silica nanoparticles enhance the tear resistance of the PTFE membrane, repair the void structure, and improve the local mechanical strength. Large-sized silica nanoparticles disperse the stress of the adhesive layer, absorb and disperse external friction through physical cross-linking points, delay the wear of the adhesive layer, and improve the stability of the fabric.

[0144] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Various modifications and variations are readily apparent to those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A bio-based wear-resistant fabric, characterized in that: It includes a bio-based nylon fabric layer, a polytetrafluoroethylene electrospun nano-membrane layer and a nylon warp-knitted base yarn arranged in sequence; The polytetrafluoroethylene electrospun nano-membrane layer is the middle layer, and the bio-based nylon fabric layer and the nylon warp-knitted base yarn are respectively adhered to the two sides of the polytetrafluoroethylene electrospun nano-membrane layer using bio-based hot melt adhesive; Hydrophobic silica nanoparticles modified with a silane coupling agent are added to the bio-based hot melt adhesive and the polytetrafluoroethylene electrospun nanofilm layer respectively; Among them, the hydrophobic silica nanoparticles added to the polytetrafluoroethylene electrospun nanomembrane layer are also coated with graphene oxide to form a core-shell structure; The shell graphene oxide is covalently bonded to the core hydrophobic silica nanoparticles via a crosslinker; The particle size of the hydrophobic silica nanoparticles added to the bio-based hot melt adhesive is larger than the particle size of the hydrophobic silica nanoparticles added to the polytetrafluoroethylene electrospun nanofilm layer.

2. The bio-based wear-resistant fabric according to claim 1, characterized in that: The addition amount of the hydrophobic silica nanoparticles in the bio-based hot melt adhesive is 5-10% of the total mass of the bio-based hot melt adhesive.

3. The bio-based wear-resistant fabric according to claim 1, characterized in that: The hydrophobic silica nanoparticles are pretreated before being added to the bio-based hot melt adhesive. The specific steps are as follows: Premixing: Premix the hydrophobic silica nanoparticles with the bio-based hot melt adhesive and stir at low speed; Ultrasonic dispersion: ultrasonically disperse the mixture; Degassing by standing: After dispersion, let it stand to eliminate bubbles in the colloid.

4. The bio-based wear-resistant fabric according to claim 1, characterized in that: The concentration of hydrophobic silica nanoparticles added to the polytetrafluoroethylene electrospun nanomembrane layer is 1-3wt%.

5. The bio-based wear-resistant fabric according to claim 1, characterized in that: The mass ratio of hydrophobic silica nanoparticles to graphene oxide in the core-shell structure is 5:

1.

6. The bio-based wear-resistant fabric according to claim 1, characterized in that: The preparation of the core-shell structure is as follows: Hydrophobic modification of silica nanoparticles: disperse silica nanoparticles in ethanol, add silane coupling agent, stir, centrifuge and wash, and then dry; Graphene oxide coating: hydrophobic silica nanoparticles and graphene oxide were added to deionized water and ultrasonically dispersed; A cross-linking agent is added, the mixture is centrifuged and freeze-dried to obtain a core-shell structure.

7. A method for preparing the bio-based wear-resistant fabric according to any one of claims 1 to 6, characterized in that: The specific steps are: S1. Preparation of bio-based nylon fabric layer: one or more of bio-based nylon 56, bio-based nylon 66 or bio-based nylon 1010 are subjected to weaving, desizing, dyeing, drying, intermediate inspection, shaping and final inspection to obtain a bio-based nylon fabric layer; S2. Preparation of polytetrafluoroethylene electrospun nanofilm layer: A polytetrafluoroethylene aqueous emulsion, a polyvidone aqueous solution, and an antistatic additive are blended to obtain an electrospinning solution, which is prepared by an electrospinning process. The prepared polytetrafluoroethylene electrospun nanofilm layer is first stretched in a single direction and allowed to stand for final shaping; and then a second stretching is performed in the direction of the first stretching. S3, gluing and laminating: placing the stretched polytetrafluoroethylene electrospun nanofilm layer on a laminating machine, heating and melting the pretreated bio-based hot melt adhesive and evenly coating it on the surface of the film layer, and laminating the bio-based nylon fabric layer and the nylon warp knitted base yarn with the polytetrafluoroethylene electrospun nanofilm layer coated with the hot melt adhesive; S4. Curing: Place the bonded bio-based wear-resistant fabric in a curing room for curing, and the product is obtained after curing.

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