Waterproof and breathable garment material based on nano material and preparation method of waterproof and breathable garment material

Abstract

The invention discloses a waterproof breathable garment material based on a nano material and a preparation method of the waterproof breathable garment material. According to the invention, the breakthrough balance between waterproofness and air permeability is realized through compounding of a multi-scale nano-structure design and an intelligent material. According to a gradient pore structure formed by the superfine denier nylon 6 nanofibers and the regenerated polyester nanofiber membrane, a 200-400-nanometer compact network on the surface layer effectively blocks liquid water permeation, a 1-2-micrometer breathable channel on the middle layer accelerates moisture diffusion based on the Brownian motion principle, and the bio-based polyurethane elastic fibers on the bottom layer actively conduct moisture through the capillary effect, so that the moisture diffusion effect is improved. The three components form a synergistic effect under electrostatic spinning directional arrangement. The fluorosilane modified titanium dioxide nanotube is directionally deposited at an inclination angle of 15 degrees, and a lotus leaf-like micro-nano fractal structure is combined, so that a super-hydrophobic surface with a contact angle of over 160 degrees is constructed, and the pollution resistance and the hydrostatic pressure resistance are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of clothing fabrics, and specifically relates to a waterproof and breathable clothing fabric based on nanomaterials and a preparation method thereof. Background Art

[0002] A waterproof and breathable clothing fabric is a high-tech textile material with the characteristics of waterproofing, windproofing, and breathability. Through special coating or film technology, this fabric can effectively block the invasion of rain and wind while keeping the clothing light. Its breathable performance allows sweat vapor to escape, keeping the body surface dry and comfortable. It is widely used in outdoor sports equipment, functional clothing and other fields. The key technology of waterproof and breathable fabrics lies in balancing waterproofness and breathability to ensure that wearers can still enjoy a comfortable wearing experience under harsh weather conditions. The emergence of this fabric has greatly improved the activity freedom and safety of outdoor sports enthusiasts.

[0003] However, traditional materials rely on dense coatings or microporous membranes to achieve waterproofing, resulting in limited breathability and high moisture resistance, and unable to meet the requirements of dynamic heat and moisture management; at the same time, the high proportion of petroleum-based raw materials and the complex recycling process, as well as problems such as easy leakage of phase change materials and poor thermal cycle stability, further restrict the environmental protection upgrade and long-term use of products. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof and breathable clothing fabric based on nanomaterials and a preparation method thereof in order to solve the above-mentioned problems.

[0005] The technical solution adopted by the present invention is as follows: A waterproof and breathable clothing fabric based on nanomaterials, the fabric includes: 50 parts of superfine denier nylon 6 nanofibers, 30 parts of recycled polyester nanofiber membrane, 20 parts of bio-based polyurethane elastic nanofibers, 8 parts of fluorosilane-modified titanium dioxide nanotubes, 5 parts of graphene oxide composite nanosheets, 12 parts of lotus leaf structure self-assembled emulsion, 15 parts of waterborne polyurethane adhesive, 3 parts of nano-silver composite antibacterial agent, 2 parts of bio-enzymatic decontamination nanocapsules, and 4 parts of phase change energy storage nanospheres;

[0006] Among them, the phase change energy storage nanospheres use octadecane as the phase change energy storage core and polymethyl methacrylate as the encapsulation shell, and achieve nanoscale coating through interfacial polymerization.

[0007] In a preferred embodiment, a preparation method of a waterproof and breathable clothing fabric based on nanomaterials includes the following steps:

[0008] S1: Mix the superfine denier nylon 6 nanofibers, recycled polyester nanofiber membrane and bio-based polyurethane elastic nanofibers in a ratio of 50 parts, 30 parts, and 20 parts, and compound them through multi-needle electrospinning technology, controlling the spinning voltage at 35 kV and the receiving distance at 15 cm to form a nanofiber substrate with a three-layer gradient pore structure;

[0009] S2: Disperse the fluorosilane-modified titanium dioxide nanotubes in an ethanol solution and perform ultrasonic treatment. Dispersely shear the graphene oxide composite nanosheets and deionized water at a high speed according to a ratio. Mechanically stir and mix the lotus-leaf structure self-assembled emulsion and the waterborne polyurethane adhesive to form a uniform functional coating slurry;

[0010] S3: On the surface of the substrate, use atomic layer deposition technology with titanium tetrachloride and hexamethyldisilazane as precursors, and perform cyclic deposition at 80 °C to make the titanium dioxide nanotubes align directionally to form a superhydrophobic surface layer;

[0011] S4: Load the coating slurry onto the surface of the substrate through a padding process, and perform preliminary curing in a pre-oven, controlling the coating thickness to be 5 microns;

[0012] S5: Spray the lotus-leaf structure emulsion onto the surface of the coating by an electrostatic spraying process, and induce the self-assembly of silicone microspheres to form a micro-nano composite structure under a specific humidity and temperature environment;

[0013] S6: Disperse the nano-silver composite antibacterial agent, the bioenzymatic decontamination nano-capsules and the phase change energy storage nano-microspheres in a buffer solution, and penetrate into the fiber pores through an impregnation-padding process, and then cure by hot air crosslinking;

[0014] S7: Calender the composite fabric using a double-roll hot press to synchronously activate the interfacial bonding between the encapsulation shell and the adhesive and stabilize the porosity;

[0015] S8: Enhance the surface activity through plasma treatment, and finally complete the preparation through cold water washing, hot air drying and mechanical pre-shrinking.

[0016] In a preferred embodiment, in the step S1, weigh precisely the ultra-fine denier nylon 6 nanofibers, the recycled polyester nanofiber membrane and the bio-based polyurethane elastic nanofibers according to a weight ratio of 50 parts, 30 parts and 20 parts, and perform composite electrospinning through a multi-needle array electrospinning device. Set the electrospinning voltage to 35 kV, the electrospinning solution flow rate to 1.2 ml per hour, and the distance between the receiving device and the spinneret head to be fixed at 15 cm. Adopt a layered receiving technology, and control the gradient pore structure by adjusting the electrospinning time of different fiber layers: the surface layer is mainly composed of ultra-fine denier nylon 6 nanofibers to form a dense network with a diameter of 200 to 400 nm; the middle layer is constructed by the recycled polyester nanofiber membrane to form a breathable channel with a pore diameter of 1 to 2 microns; the bottom layer uses the bio-based polyurethane elastic nanofibers to form an elastic support layer. Keep the environmental temperature at 25 °C and the relative humidity at 40% during the electrospinning process, and treat in a vacuum drying oven at 60 °C for 2 hours after electrospinning to remove the residual solvent.

[0017] In a preferred embodiment, in step S2, 8 parts of fluorosilane-modified titanium dioxide nanotubes are taken and dispersed in an anhydrous ethanol solution. The ultrasonic disperser is used to process them at a power of 300 watts for 30 minutes until the nanotubes are evenly dispersed without agglomeration. Another 5 parts of graphene oxide composite nanosheets are taken and mixed with deionized water at a mass ratio of 1:50. A high-speed shear emulsifier is used to disperse them at a rotation speed of 12,000 revolutions per minute for 15 minutes to obtain a stable suspension. 12 parts of the lotus-leaf-like structure self-assembled emulsion and 15 parts of the waterborne polyurethane adhesive are added to the reaction kettle and mixed at a mechanical stirring speed of 1,200 revolutions per minute for 20 minutes. Subsequently, the aforementioned titanium dioxide nanotube dispersion liquid and the graphene oxide suspension are added in sequence, and stirring is continued for 30 minutes to form a homogeneous functional coating slurry, and the viscosity of the slurry is controlled within the range of 4,500 to 5,000 millipascal seconds.

[0018] In a preferred embodiment, in step S3, the electrospinning substrate is placed in the vacuum reaction chamber of the atomic layer deposition equipment, and the substrate temperature is set to 80 degrees Celsius. Using titanium tetrachloride and hexamethyldisilazane as precursors and nitrogen as the carrier gas, 100 cycles of deposition are carried out according to the cycle parameters of a pulse time of 0.1 second, a purge time of 20 seconds, and a reaction time of 30 seconds. The titanium dioxide nanotubes are oriented to grow at an inclination angle of 15 degrees through the tilting substrate fixing device. After the deposition is completed, the temperature is lowered to room temperature at a rate of 5 degrees Celsius per minute under argon protection to form a superhydrophobic surface layer with a thickness of about 50 nanometers and a contact angle exceeding 160 degrees.

[0019] In a preferred embodiment, in step S4, the functional coating slurry is loaded onto the surface of the substrate by a two-dip and two-roll process. First, the substrate is passed through the dipping tank at a speed of 3 meters per minute to ensure complete wetting and then enters the roll unit. The roll pressure is set to 3 kilograms per square centimeter, and the liquor pickup rate is controlled at 80%. After repeating the dip-roll process, the material is immediately sent into a pre-oven and dried with hot air at 80 degrees Celsius for 5 minutes to complete the preliminary curing. A laser thickness gauge is used to monitor the coating thickness in real time, and the roll gap is adjusted so that the final dry coating thickness is stabilized within a tolerance range of 5 microns plus or minus 0.5 microns.

[0020] In a preferred embodiment, in step S5, the lotus-leaf-like structure self-assembled emulsion is evenly sprayed onto the surface of the coating using a high-voltage electrostatic spraying device. The spraying pressure is set to 0.3 megapascal, the distance between the spray gun and the substrate is kept at 20 centimeters, and the moving speed is 0.5 meters per minute. After spraying, the material is transferred to a constant temperature and humidity chamber and left to stand for 2 hours in an environment with a temperature of 50 degrees Celsius and a relative humidity of 60% to induce the spontaneous assembly of the silicone microspheres in the emulsion to form a multi-level micro-nano structure. It is confirmed by scanning electron microscopy that the surface fractal dimension reaches the standard range of 1.7 to 1.9, and the construction of the artificial hydrophobic structure is completed.

[0021] In a preferred embodiment, in step S6, 3 parts of nano-silver composite antibacterial agent, 2 parts of bio-enzymatic decontamination nano-capsules and 4 parts of phase change energy storage nano-microspheres are added to a phosphate buffer solution with a pH value of 8, and dispersed for 10 minutes at a power of 200 watts using an ultrasonic cell disruptor to form a stable suspension. The two-dip two-roll process is adopted, and the auxiliary agent solution is fully penetrated into the fiber pores under a pressure of 2 kg per square centimeter. Subsequently, it is treated at 120 °C for 20 minutes on a hot air setting machine to promote the cross-linking reaction between the polyurethane adhesive and the nano-components. The treated material is rinsed with cold water to remove the unfixed auxiliary agent, and then dehydrated for 3 minutes at a speed of 800 revolutions per minute by a centrifugal dehydrator.

[0022] In a preferred embodiment, in step S7, the composite fabric is calendered using a double-roll hot press, with the upper roll temperature set at 150 °C, the lower roll temperature at 145 °C, the roll gap pressure adjusted to 5 MPa per square centimeter, and the transmission speed controlled at 2 meters per minute. During the hot pressing process, the surface temperature of the material is monitored in real time by an infrared thermometer to ensure that the PMMA shell undergoes plastic deformation above the glass transition temperature, while activating the interfacial bonding between the polyurethane adhesive and the nano-fibers. After calendering, it is detected using a helium porosity tester, and the porosity of the substrate is accurately adjusted to the optimized range of 75% plus or minus 3%.

[0023] In a preferred embodiment, in step S8, the fabric is placed in a low-temperature plasma treatment device, with the radio frequency power set at 1000 watts, the argon flow rate at 20 liters per minute, and the treatment time at 5 minutes to generate active groups such as carboxyl and hydroxyl groups on the material surface. Subsequently, three post-treatments are carried out in sequence: first, it is rinsed in flowing water at 25 °C for 10 minutes to remove process residues; then it is dried in a hot air dryer at 90 °C with circulating hot air for 15 minutes until the moisture content is lower than 3%; finally, a linear tension of 1.5 meters per minute is applied through a mechanical pre-shrinking machine to achieve a stable pre-shrinking rate of 3%. After passing the quality inspection, the finished product is wound and packaged, and finally a nano-composite fabric with waterproof, breathable and intelligent thermal management functions is obtained.

[0024] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

[0025] 1. In the present invention, through the design of multi-scale nanostructures and the compounding with intelligent materials, a breakthrough balance between waterproofness and breathability is achieved. The gradient pore structure formed by ultrafine denier nylon 6 nanofibers and recycled polyester nanofiber membranes has a dense network of 200 - 400 nanometers on the surface layer, which effectively blocks the penetration of liquid water. The 1 - 2 micrometer breathable channels in the middle layer accelerate the diffusion of moisture based on the principle of Brownian motion. The bottom layer of bio-based polyurethane elastic fibers actively conducts moisture through capillary action. The three form a synergistic effect under the oriented arrangement of electrospinning. Titanium dioxide nanotubes modified with fluorosilane are directionally deposited at an angle of 15 degrees, combined with a lotus leaf-like micro-nano fractal structure, to construct a superhydrophobic surface with a contact angle exceeding 160 degrees, significantly improving the anti-fouling property and hydrostatic pressure resistance. The synergistic effect of graphene oxide composite nanosheets and phase change energy storage microspheres. The former accelerates heat distribution through a high thermal conductivity network, and the latter dynamically absorbs the residual heat of the human body through solid-liquid phase change, enabling the fabric to achieve temperature difference-responsive breathable regulation in the range of 28 - 30 °C, with the breathable efficiency being more than 3 times higher than that of traditional waterproof materials.

[0026] 2. In the present invention, through the combination of atomic layer deposition and hot pressing forming technology, the stable anchoring of nano-components at the fiber interface is ensured. After multiple standard washings, the hydrophobic property can still be maintained at more than 85%, and the number of abrasion resistance breaks through 20,000 times, greatly extending the service life of the fabric. The application of bio-based polyurethane and recycled polyester reduces the dependence on petroleum-based raw materials. The selection of waterborne polyurethane adhesives and biodegradable PMMA shells improves the recyclability of the overall material. The replacement compatibility design of octadecane with natural plant wax in the phase change microspheres further expands the environmental protection application scenarios. The plasma post-treatment technology enhances the fixing strength of functional additives through surface activation. The synergistic effect of nano-silver antibacterial agents and bio-enzymatic decontamination capsules achieves long-term antibacterial effect while avoiding chemical detergent pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the process principle of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0028] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] Example:

[0030] A waterproof and breathable clothing fabric based on nanomaterials, the fabric comprising: 50 parts of ultrafine denier nylon 6 nanofibers, 30 parts of recycled polyester nanofiber membrane, 20 parts of bio-based polyurethane elastic nanofibers, 8 parts of fluorosilane-modified titanium dioxide nanotubes, 5 parts of graphene oxide composite nanosheets, 12 parts of lotus leaf structure self-assembled emulsion, 15 parts of waterborne polyurethane adhesive, 3 parts of nano silver composite antibacterial agent, 2 parts of bio-enzymatic decontamination nano capsules and 4 parts of phase change energy storage nano microspheres;

[0031] Among them, the phase change energy storage nano microspheres take octadecane as the phase change energy storage core and polymethyl methacrylate as the encapsulation shell, and achieve nanoscale coating through interfacial polymerization;

[0032] The preparation method comprises the following steps:

[0033] S1: Mix the ultrafine denier nylon 6 nanofibers, recycled polyester nanofiber membrane and bio-based polyurethane elastic nanofibers in a ratio of 50 parts, 30 parts and 20 parts, and compound them by multi-needle electrospinning technology, controlling the spinning voltage at 35 kV and the receiving distance at 15 cm to form a nanofiber substrate with a three-layer gradient pore structure;

[0034] S2: Disperse the fluorosilane-modified titanium dioxide nanotubes in an ethanol solution and perform ultrasonic treatment, disperse the graphene oxide composite nanosheets and deionized water by high-speed shearing, and mechanically stir and mix the lotus leaf structure self-assembled emulsion and the waterborne polyurethane adhesive to form a uniform functional coating slurry;

[0035] S3: On the surface of the substrate, use atomic layer deposition technology, with titanium tetrachloride and hexamethyldisilazane as precursors, and perform cyclic deposition at 80 °C to make the titanium dioxide nanotubes align directionally to form a superhydrophobic surface layer;

[0036] S4: Load the coating slurry onto the surface of the substrate through the padding process, and perform preliminary curing in a pre-oven, controlling the coating thickness at 5 microns;

[0037] S5: Spray the lotus leaf structure emulsion onto the surface of the coating by electrostatic spraying process, and induce the self-assembly of silicone microspheres to form a micro-nano composite structure under a specific humidity and temperature environment;

[0038] S6: Disperse the nano silver composite antibacterial agent, bio-enzymatic decontamination nano capsules and phase change energy storage nano microspheres in a buffer solution, and penetrate them into the fiber pores through the impregnation-padding process, and then cure by hot air crosslinking;

[0039] S7: Use a double-roll hot press to calender the composite fabric, synchronously activate the interfacial bonding of the encapsulation shell and the adhesive, and stabilize the porosity;

[0040] S8: Enhance the surface activity through plasma treatment, and finally complete the preparation through cold water washing, hot air drying and mechanical pre-shrinking.

[0041] In step S1, ultrafine denier nylon 6 nanofibers, recycled polyester nanofiber membrane and bio-based polyurethane elastic nanofibers are accurately weighed according to the weight ratio of 50 parts, 30 parts and 20 parts, and composite spinning is carried out by a multi-needle array electrospinning device. Set the spinning voltage to 35 kV, the flow rate of the spinning solution to 1.2 ml per hour, and the distance between the receiving device and the spinneret to be fixed at 15 cm. The hierarchical receiving technology is adopted, and the gradient pore structure is controlled by adjusting the spinning time of different fiber layers: the surface layer is mainly composed of ultrafine denier nylon 6 nanofibers, forming a dense network with a diameter of 200 to 400 nm; the middle layer is constructed by a recycled polyester nanofiber membrane to form a breathable channel with a pore diameter of 1 to 2 microns; the bottom layer uses bio-based polyurethane elastic nanofibers to form an elastic support layer. During the spinning process, the ambient temperature is maintained at 25 °C and the relative humidity is 40%. After spinning, it is treated in a vacuum drying oven at 60 °C for 2 hours to remove residual solvents.

[0042] In step S2, 8 parts of fluorosilane-modified titanium dioxide nanotubes are dispersed in an anhydrous ethanol solution, and an ultrasonic disperser is used to treat them at a power of 300 W for 30 minutes until the nanotubes are evenly dispersed without agglomeration. Another 5 parts of graphene oxide composite nanosheets are mixed with deionized water at a mass ratio of 1:50, and a high-speed shear emulsifier is used to disperse them at a rotation speed of 12,000 revolutions per minute for 15 minutes to obtain a stable suspension. 12 parts of the self-assembled emulsion with a lotus leaf-like structure and 15 parts of the waterborne polyurethane adhesive are added to the reaction kettle and mixed at a mechanical stirring speed of 1,200 revolutions per minute for 20 minutes. Subsequently, the aforementioned titanium dioxide nanotube dispersion and graphene oxide suspension are added in sequence, and stirring is continued for 30 minutes to form a homogeneous functional coating slurry, and the viscosity of the slurry is controlled within the range of 4,500 to 5,000 mPa·s.

[0043] In step S3, the electrospun substrate is placed in the vacuum reaction chamber of an atomic layer deposition device, and the substrate temperature is set to 80 °C. Using titanium tetrachloride and hexamethyldisilazane as precursors and nitrogen as the carrier gas, 100 cycles of deposition are carried out according to the cycle parameters of a pulse time of 0.1 s, a purge time of 20 s, and a reaction time of 30 s. The titanium dioxide nanotubes are oriented to grow at an inclination angle of 15 degrees through the inclined substrate fixing device. After deposition, it is cooled to room temperature at a rate of 5 °C per minute under argon protection to form a superhydrophobic surface layer with a thickness of about 50 nm and a contact angle exceeding 160 degrees.

[0044] In step S4, a two-dip two-roll process is used to load the functional coating slurry onto the surface of the substrate. First, the substrate is passed through the dipping tank at a speed of 3 meters per minute to ensure complete wetting, and then it enters the roll unit. The roll pressure is set at 3 kilograms per square centimeter, and the liquor pickup rate is controlled at 80%. After repeating the dipping and rolling process, the material is immediately sent to a pre-oven and dried with hot air at 80 degrees Celsius for 5 minutes to complete the preliminary curing. A laser thickness gauge is used to monitor the coating thickness in real time, and the roll gap is adjusted to make the final dry coating thickness stable within a tolerance range of 5 micrometers plus or minus 0.5 micrometers.

[0045] In step S5, a high-voltage electrostatic spraying device is used to evenly spray the lotus-leaf-like structure self-assembly emulsion onto the surface of the coating. The spraying pressure is set at 0.3 MPa, the distance between the spray gun and the substrate is kept at 20 centimeters, and the moving speed is 0.5 meters per minute. After spraying, the material is transferred to a constant temperature and humidity chamber and left standing for 2 hours in an environment with a temperature of 50 degrees Celsius and a relative humidity of 60% to induce the self-assembly of the silicone microspheres in the emulsion to form a multi-level micro-nano structure. It is confirmed by scanning electron microscopy that the surface fractal dimension reaches the standard range of 1.7 to 1.9, and the construction of the artificial hydrophobic structure is completed.

[0046] In step S6, 3 parts of nano-silver composite antibacterial agent, 2 parts of bio-enzymatic decontamination nano-capsules, and 4 parts of phase change energy storage nano-microspheres are added to a phosphate buffer solution with a pH value of 8, and a ultrasonic cell disruptor is used to disperse them at a power of 200 watts for 10 minutes to form a stable suspension. A two-dip two-roll process is adopted, and under a pressure of 2 kilograms per square centimeter, the auxiliary solution is fully penetrated into the fiber pores. Subsequently, it is treated on a hot air setting machine at 120 degrees Celsius for 20 minutes to promote the cross-linking reaction between the polyurethane binder and the nano-components. The treated material is rinsed with cold water to remove the unfixed auxiliary agent, and then dehydrated by a centrifugal dehydrator at a speed of 800 revolutions per minute for 3 minutes.

[0047] In step S7, a double-roll hot press is used to calender the composite fabric. The temperature of the upper roll is set at 150 degrees Celsius, the temperature of the lower roll is set at 145 degrees Celsius, the roll gap pressure is adjusted to 5 MPa per square centimeter, and the transmission speed is controlled at 2 meters per minute. During the hot pressing process, an infrared thermometer is used to monitor the surface temperature of the material in real time to ensure that the PMMA shell undergoes plastic deformation above the glass transition temperature, and at the same time, the interfacial bonding between the polyurethane binder and the nano-fibers is activated. After calendering, it is detected by a helium porosity tester, and the substrate porosity is accurately adjusted to an optimized range of 75% plus or minus 3%.

[0048] In step S8, the fabric is placed in a low-temperature plasma treatment device. The radio frequency power is set to 1000 watts, the argon gas flow rate is 20 liters per minute, and the treatment time is 5 minutes to generate active groups such as carboxyl and hydroxyl groups on the material surface. Subsequently, three post-treatments are carried out in sequence: First, rinse in flowing water at 25 °C for 10 minutes to remove process residues; then dry in a hot air dryer at 90 °C with circulating hot air for 15 minutes until the moisture content is less than 3%; finally, apply a linear tension of 1.5 meters per minute through a mechanical pre-shrinking machine to achieve a stable pre-shrinking rate of 3%. After passing the quality inspection, the finished product is wound and packaged, and finally a nano-composite fabric with waterproof, breathable, and intelligent thermal management functions is obtained.

[0049] It can be seen from the above that:

[0050] In the present invention, through the multi-scale nanostructure design and intelligent material compounding, a breakthrough balance between waterproofness and breathability is achieved. The gradient pore structure formed by ultrafine denier nylon 6 nanofibers and recycled polyester nanofiber membranes, the 200-400 nm dense network on the surface layer effectively blocks the penetration of liquid water, the 1-2 μm breathable channels in the middle layer accelerate the diffusion of moisture based on the principle of Brownian motion, and the bottom layer of bio-based polyurethane elastic fibers actively conducts moisture through capillary action. The three form a synergistic effect under the electrostatic spinning and oriented arrangement. Fluorosilane-modified titanium dioxide nanotubes are deposited directionally at an angle of 15 degrees, combined with the lotus leaf-like micro-nano fractal structure, to construct a superhydrophobic surface with a contact angle exceeding 160 degrees, significantly improving the anti-fouling property and hydrostatic pressure resistance. The synergistic effect of graphene oxide composite nanosheets and phase change energy storage microspheres, the former accelerates the heat distribution through a high thermal conductivity network, and the latter dynamically absorbs the residual heat of the human body through solid-liquid phase change, enabling the fabric to achieve temperature difference-responsive breathable regulation in the range of 28-30 °C, and the breathable efficiency is more than 3 times higher than that of traditional waterproof materials.

[0051] In the present invention, through the combination of atomic layer deposition and hot pressing technology, the stable anchoring of nano-components at the fiber interface is ensured. After multiple standard washings, the hydrophobic property of more than 85% can still be maintained, and the number of abrasion-resistant times breaks through 20,000 times, greatly extending the service life of the fabric. The application of bio-based polyurethane and recycled polyester reduces the dependence on petroleum-based raw materials. The selection of water-based polyurethane adhesives and biodegradable PMMA shells improves the recyclability of the overall material. The replacement compatibility design of octadecane and natural plant wax in the phase change microspheres further expands the environmental protection application scenarios. The plasma post-treatment technology enhances the fixing strength of functional additives through surface activation, and the synergistic effect of nano-silver antibacterial agents and bio-enzymatic decontamination capsules realizes long-term antibacterial, while avoiding chemical detergent pollution. The precise control of the whole process process parameters improves the porosity of the finished product, breaks through the technical bottleneck of insufficient moisture permeability of traditional waterproof fabrics, and provides an innovative solution with environmental adaptability and wearing comfort for high-performance outdoor clothing.

[0052] It should be noted that, in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, such that a process, method, article, or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or device. Without further limitation, an element defined by the statement "comprising an..." does not exclude the presence of additional identical elements in the process, method, article, or device comprising the said element.

[0053] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A waterproof and breathable clothing fabric based on nanomaterials, characterized by: The fabric includes: 50 parts of ultra-fine denier nylon 6 nanofiber, 30 parts of recycled polyester nanofiber membrane, 20 parts of bio-based polyurethane elastic nanofiber, 8 parts of fluorinated silane-modified titanium dioxide nanotubes, 5 parts of graphene oxide composite nanosheets, 12 parts of lotus leaf structure self-assembly emulsion, 15 parts of water-based polyurethane adhesive, 3 parts of nano-silver composite antibacterial agent, 2 parts of bio-enzyme decontamination nanocapsules and 4 parts of phase-change energy storage nano-microspheres; The phase change energy storage nanospheres use octadecane as the phase change energy storage core and polymethyl methacrylate as the encapsulation shell, and nano-coating is achieved through interfacial polymerization.

2. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: The preparation method comprises the following steps: S1: Ultrafine denier nylon 6 nanofibers, recycled polyester nanofiber membranes and bio-based polyurethane elastic nanofibers were mixed in a ratio of 50 parts, 30 parts and 20 parts, and compounded by multi-needle electrospinning technology, with a spinning voltage of 35 kV and a receiving distance of 15 cm to form a nanofiber substrate with a three-layer gradient pore structure; S2: Fluorosilane-modified titanium dioxide nanotubes are dispersed in an ethanol solution by ultrasonic treatment, graphene oxide composite nanosheets and deionized water are dispersed by high-speed shearing in proportion, and the lotus leaf structure self-assembled emulsion and water-based polyurethane adhesive are mechanically stirred and mixed to form a uniform functional coating slurry; S3: Atomic layer deposition technology is used on the substrate surface, with titanium tetrachloride and hexamethyldisilazane as precursors, and cyclic deposition is performed at 80°C to orient the titanium dioxide nanotubes to form a super-hydrophobic surface layer; S4: The coating slurry is loaded onto the substrate surface by a padding process, and initially cured in a pre-oven to control the coating thickness to 5 μm; S5: The lotus leaf structure emulsion is sprayed onto the coating surface by electrostatic spraying process, and the siloxane microspheres are induced to self-assemble to form a micro-nano composite structure under a specific humidity and temperature environment; S6: Dispersing the nanosilver composite antibacterial agent, bioenzyme decontamination nanocapsules and phase change energy storage nanospheres in a buffer solution, infiltrating into the fiber pores through an immersion-pressure absorption process, and then hot air cross-linking and curing; S7: The composite fabric is calendered using a double-roll hot press to simultaneously activate the interface bonding between the encapsulation shell and the adhesive and stabilize the porosity; S8: Surface activity is enhanced by plasma treatment, and the preparation is completed by cold water washing, hot air drying and mechanical pre-shrinking.

3. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S1, ultrafine denier nylon 6 nanofibers, regenerated polyester nanofiber membranes and bio-based polyurethane elastic nanofibers are accurately weighed in a weight ratio of 50 parts, 30 parts and 20 parts, and composite spinning is performed through a multi-needle array electrospinning device; the spinning voltage is set to 35 kilovolts, the spinning solution flow rate is 1.2 milliliters per hour, and the distance between the receiving device and the spinneret is fixed to 15 centimeters; a layered receiving technology is used to control the gradient pore structure by adjusting the spinning time of different fiber layers: the surface layer is mainly composed of ultrafine denier nylon 6 nanofibers, forming a dense network with a diameter of 200 to 400 nanometers; The middle layer is made of recycled polyester nanofiber membrane to construct a breathable channel with a pore size of 1 to 2 microns; the bottom layer uses bio-based polyurethane elastic nanofibers to form an elastic support layer; the ambient temperature is maintained at 25 degrees Celsius and the relative humidity is 40% during the spinning process. After spinning is completed, it is treated in a 60-degree Celsius vacuum drying oven for 2 hours to remove residual solvents.

4. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S2, 8 parts of fluorosilane-modified titanium dioxide nanotubes are taken, dispersed in an anhydrous ethanol solution, and treated with an ultrasonic disperser at a power of 300 watts for 30 minutes until the nanotubes are evenly dispersed without agglomeration; 5 parts of graphene oxide composite nanosheets are taken, mixed with deionized water at a mass ratio of 1:50, and dispersed for 15 minutes using a high-speed shear emulsifier at a speed of 12,000 revolutions per minute to obtain a stable suspension; 12 parts of the lotus leaf structure self-assembled emulsion and 15 parts of the water-based polyurethane adhesive are added to a reactor, mixed at a mechanical stirring speed of 1,200 revolutions per minute for 20 minutes, and then the aforementioned titanium dioxide nanotube dispersion and graphene oxide suspension are added in sequence, and stirring is continued for 30 minutes to form a homogeneous functional coating slurry, and the slurry viscosity is controlled within the range of 4,500 to 5,000 mPa·s.

5. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S3, the electrospinning substrate is placed in a vacuum reaction chamber of an atomic layer deposition device, and the substrate temperature is set to 80 degrees Celsius; titanium tetrachloride and hexamethyldisilazane are used as precursors, nitrogen is used as a carrier gas, and 100 cycles of deposition are performed according to the cycle parameters of pulse time 0.1 seconds, purge time 20 seconds, and reaction time 30 seconds; The titanium dioxide nanotubes are directed to grow at an angle of 15 degrees by tilting the substrate fixture. After deposition, the substrate is cooled to room temperature at a rate of 5 degrees Celsius per minute under argon protection, forming a super-hydrophobic surface layer with a thickness of about 50 nanometers and a contact angle of more than 160 degrees.

6. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S4, the functional coating slurry is loaded onto the surface of the substrate by a two-immersion and two-rolling process; first, the substrate is passed through the immersion tank at a speed of 3 meters per minute to ensure that it is completely infiltrated before entering the roller unit, the roller pressure is set to 3 kilograms per square centimeter, and the rolling rate is controlled at 80%; after repeating the immersion and rolling process, the material is immediately sent to the pre-oven and hot-air dried at 80 degrees Celsius for 5 minutes to complete preliminary curing; a laser thickness gauge is used to monitor the coating thickness in real time, and the roller gap is adjusted to stabilize the final dry coating thickness within a tolerance range of 5 microns plus or minus 0.5 microns.

7. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S5, a high-voltage electrostatic spraying device is used to evenly spray the lotus leaf structure self-assembly emulsion onto the coating surface, the spraying pressure is set to 0.3 MPa, the distance between the spray gun and the substrate is maintained at 20 cm, and the moving speed is 0.5 m per minute; after the spraying is completed, the material is transferred to a constant temperature and humidity chamber, and allowed to stand for 2 hours at a temperature of 50 degrees Celsius and a relative humidity of 60% to induce the silicone microspheres in the emulsion to spontaneously assemble to form a multi-level micro-nano structure; and the surface fractal dimension is confirmed to reach the standard range of 1.7 to 1.9 by scanning electron microscopy detection, thereby completing the construction of the bionic hydrophobic structure.

8. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S6, 3 parts of nano-silver composite antibacterial agent, 2 parts of bio-enzyme decontamination nano-capsules and 4 parts of phase change energy storage nano-microspheres are added to a phosphate buffer with a pH value of 8, and dispersed for 10 minutes using an ultrasonic cell disruptor at a power of 200 watts to form a stable suspension; a two-immersion and two-rolling process is used to allow the auxiliary agent solution to fully penetrate into the fiber pores under a pressure of 2 kilograms per square centimeter, and then treated at 120 degrees Celsius for 20 minutes on a hot air setting machine to promote a cross-linking reaction between the polyurethane adhesive and the nano-component; the treated material is rinsed with cold water to remove the unfixed auxiliary agent, and then dehydrated for 3 minutes by a centrifugal dehydrator at a speed of 800 revolutions per minute.

9. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In step S7, a double-roll hot press is used to perform calendering on the composite fabric, the upper roller temperature is set to 150 degrees Celsius, the lower roller temperature is set to 145 degrees Celsius, the pressure between the rollers is adjusted to 5 MPa per square centimeter, and the transmission speed is controlled at 2 meters per minute; during the hot pressing process, the surface temperature of the material is monitored in real time by an infrared thermometer to ensure that the PMMA shell undergoes plastic deformation above the glass transition temperature and activates the interface bonding between the polyurethane adhesive and the nanofibers; after calendering, a helium porosity tester is used to detect and accurately control the porosity of the substrate to an optimized range of 75% plus or minus 3%.

10. The method for preparing a waterproof and breathable clothing fabric based on nanomaterials according to claim 1, characterized in that: In the step S8, the fabric is placed in a low-temperature plasma treatment device, the radio frequency power is set to 1000 watts, the argon flow rate is 20 liters per minute, and the treatment time is 5 minutes, so that active groups such as carboxyl and hydroxyl groups are generated on the surface of the material; then three post-treatments are performed in sequence: first, rinse in running water at 25 degrees Celsius for 10 minutes to remove process residues; then, dry in a hot air dryer at 90 degrees Celsius for 15 minutes until the moisture content is less than 3%; finally, a linear tension of 1.5 meters per minute is applied through a mechanical shrinking machine to achieve a stable shrinkage rate of 3%; the finished product is wound and packaged after passing the quality inspection, and finally a nano-composite fabric with waterproof, breathable and intelligent thermal management functions is obtained.

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