Cold-proof warm-keeping clothes fabric as well as preparation method and application thereof

Abstract

The invention provides a nanofiber fabric and a preparation method and application thereof, the fabric comprises a shell fabric layer, a functional layer and a base fabric layer which are stacked in sequence, and the functional layer is formed by packaging a hollow fiber layer between two TPU fiber membranes; the hollow layer is filled with hollow fiber flocculus prepared from 45-65% of polyurethane, 34-54% of polystyrene and 1-3% of a cross-linking agent through gas jet spinning and thermal crosslinking, and photothermal conversion nanoparticles with the particle size of 50-200 nm are synthesized on the surface of the hollow layer in situ. The preparation method comprises the following steps: S1, preparing a precursor by gas jet spinning; s2, performing thermal crosslinking to form flocculus; s3, performing in-situ synthesis of photo-thermal particles by dipping or spraying the suspension liquid; s4, carrying out electrostatic spinning on a TPU film; and S5, filling, packaging and molding. The fabric has the advantages of being high in porosity, fluffy, low in density and the like, the warm-keeping and cold-proof performance is remarkably improved, and meanwhile the fabric has excellent elasticity, washing resistance and long-acting stability; the fabric is suitable for preparation of protective clothing and can provide light and comfortable wearing experience.

Description

Technical Field

[0001] This invention relates to a clothing fabric, particularly a cold-proof and warm nanofiber fabric, as well as a method for preparing the fabric and its application in protective clothing. Background Technology

[0002] As people's demands for comprehensive performance in cold-weather insulation fabrics change, traditional insulation materials (such as down, animal fur, and synthetic fiber wadding), while possessing certain insulation capabilities, suffer from limitations such as bulkiness, poor breathability, and weak washability. Down products are prone to down leakage and rely on animal resources, while synthetic fiber cotton has low loft and its insulation efficiency decreases significantly with humidity. Modern consumers' needs for cold-weather fabrics have shifted from simple warmth to multifunctional integration.

[0003] Nanofibers refer to fiber-like materials with diameters ranging from 1 to 1000 nanometers, with 100-1000 nanometers being the most commonly used in practical applications. A nanofiber membrane is a thin film material with a porous structure formed by the disordered or ordered stacking and overlapping of numerous nanofibers. It possesses high porosity. Currently, the main methods for preparing nanofibers include electrospinning, meltblowing, and solution blowing.

[0004] Patent application CN116100914A discloses a medical fabric, its preparation method, and its application. It employs a first and second fiber membrane stacked sequentially to form a nanofiber membrane layer. The first fiber membrane has a larger diameter, while the second fiber membrane has a smaller diameter. Compared to a single-structure, tightly packed nanofiber structure, this structure increases filtration efficiency. MOF (metal-organic framework) nanoarrays are grown in situ on the nanofiber scaffold, resulting in low cost, large-scale production capability, and good bactericidal properties. Patent application CN118241322A discloses an air-jet spinning system, and CN207484022U discloses a device for preparing hybrid micro / nano composite fiber membranes. Patent application CN119020920A discloses a continuous production system for ultrafine fiber porous materials based on electrostatic air-jet spinning, and a method for preparing ultrafine fiber porous materials. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a fabric that has good cold protection and warmth retention, while also being washable, lightweight and breathable.

[0006] To achieve the above objectives, the present invention provides the following technical solution. In a first aspect, the present invention provides a nanofiber fabric, comprising a face fabric layer, a functional layer, and a base fabric layer stacked sequentially; the functional layer is composed of a nanofiber composite material, including a hollow fiber layer sandwiched between two layers of TPU (polyurethane elastomer) fiber membranes; the hollow fiber layer is made by filling hollow fiber flakes, and photothermal conversion nanoparticles are synthesized in situ on the surface of the hollow fiber layer.

[0007] As an explanation, the aforementioned nanofiber fabric consists of a face fabric layer, a functional layer, and a bottom layer, arranged sequentially from the outside in. The face fabric layer, as the outermost layer, can be made from any one or more blends of fibers, including but not limited to polyester, nylon, acrylic, chlorofiber, spandex, and aramid. The bottom fabric layer can be made from one of the following: cotton, linen, wool, or chemical fibers (selected from the face fabric layer), or it can be a blend of multiple fibers.

[0008] As an explanation, the so-called face fabric layer or back fabric layer and TPU fiber film can be bonded together by brushing glue, or by relying on the TPU itself to heat melt bond, or by filling hollow fiber wadding, then sewing in the circumferential direction, and finally using a quilting machine to assemble the entire fabric into one piece, all of which are acceptable.

[0009] The top or bottom fabric layer can be optimized and improved. For example, a coating can be applied to the outside of the top fabric layer, such as a fluorocarbon compound coating, especially a polytetrafluoroethylene coating, or a polyurethane coating, to achieve better waterproof performance; or a nano-ceramic coating, such as a graphene, carbon nanotube, or silica coating, to achieve better wear resistance; or a coating with nano-zinc oxide or silver ions can be added to achieve UV resistance and antibacterial effects.

[0010] The base fabric layer can be treated with processes such as fleece to achieve superior comfort. For example, unidirectional friction with steel wire wheels can be used to create a nap, combined with static elimination and short-pile trimming. Alternatively, a high-pressure airflow (0.4-0.6 MPa) carrying corundum can be used to impact the fabric, forming random short pile. When using polyester fiber as the base fabric layer, the polyester fiber is treated in a sodium hydroxide solution (5-15 wt%) at 80°C. After the surface of the fabric fibers forms an uneven structure, it is then mechanically rubbed to create a pile. These methods are generally preferable without departing from the technical principles and concepts of this invention.

[0011] Among the above-mentioned technical features, TPU combines the high elasticity of rubber with the strength of plastic. In this invention, the TPU fiber membrane is set outside the hollow fiber layer to make the functional layer flexible, waterproof, and tear-resistant. At the same time, the high density of the TPU fiber membrane can completely wrap the hollow fiber layer, forming a physical barrier to prevent the hollow fiber wadding from escaping from the surface or bottom layer due to external friction or washing, that is, to prevent the "down leakage" phenomenon. Furthermore, the double-layer clamping of the TPU fiber membrane is also used to enhance the structural stability of the hollow fiber layer, thereby preventing the fiber wadding from reducing the gaps due to compression or deformation during use, and thus preventing the decrease in heat retention performance.

[0012] As a preferred technical solution, the TPU fiber membrane is 2-5 μm thick, and the diameter of the TPU nanofibers is distributed in the range of 100-500 nm; the hollow fiber layer is 15-20 μm thick, and the diameter of the hollow nanofibers is distributed in the range of 100-300 nm; the hollow fiber layer can be selected from at least one of PU (polyurethane), PP (polypropylene), PA (polyamide), and PS (polystyrene).

[0013] The thickness of the TPU fiber membrane is controlled to accommodate the flexibility required for garment bending. Within this thickness range, the TPU fiber membrane forms a dense barrier to prevent down leakage. Too thin a membrane results in insufficient mechanical strength, while too thick a membrane makes the fabric slightly stiff, affecting wearing comfort. The hollow fiber layer provides ample space to trap still air while maintaining the overall fabric's lightness. The hollow fiber wall thickness is approximately 50-100nm, maximizing the hollow ratio while maintaining structural strength, thus improving thermal insulation performance. The diameter control of both fibers considers both the difficulty of the spinning process and moisture permeability. The purpose of moisture permeability and maintaining still air is to allow water vapor diffusion while minimizing gas convection. Allowing water vapor diffusion helps to expel sweat, thus preventing stuffiness and discomfort caused by insufficient warmth.

[0014] As a preferred technical solution, the raw materials of the hollow fiber layer include, by weight percentage, 45-65% polyurethane, 34-54% polystyrene, and 1-3% crosslinking agent. Polyurethane refers to a high-molecular-weight polymer with urethane groups (-NHCOO-) in its main chain; polystyrene is a thermoplastic plastic formed by polymerizing styrene monomers. The crosslinking agent for both can form covalent compounds between polymer chains through chemical reactions, including but not limited to hexamethylene diisocyanate or dicumyl peroxide. The hollow fiber layer is prepared by air-jet spinning. First, PU and PS are dissolved in solvents to form spinning solutions. After being spun into fibers, they are blended and spun into a hollow fiber layer in the above proportions. After uniformly spraying the crosslinking agent onto the surface of the hollow fiber layer, it is thermally crosslinked at 160-190℃ for 15-30 minutes to form a hollow fiber floc precursor.

[0015] As a preferred technical solution, the photothermal conversion nanoparticles are at least one of zirconium carbide, iridium oxide, and thallium carbide, and the particle size of the photothermal conversion nanoparticles is 50-200 nm. For explanation, photothermal conversion nanoparticles refer to nanoparticles that can convert light energy into heat energy. The principle of light energy absorption includes, but is not limited to, electron transitions and plasma resonance. The particle size is preferably not larger than the fiber diameter of the hollow fiber layer, so that it can be well fixed on the surface of the hollow fiber flocs or penetrate into the interior of the hollow fiber flocs in subsequent processes. The interior of the hollow fiber flocs includes, but is not limited to, entering the hollow fiber interior through the opening, although most photothermal conversion nanoparticles are attached to the outer periphery of the hollow fiber.

[0016] A method for preparing a cold-proof and warm-keeping fabric having at least one of the above technical features includes the following steps: S1, hollow fiber floc precursors were prepared using air-jet spinning process; S2, hollow fiber flocs are synthesized from hollow fiber floc precursors through thermal cross-linking; S3, photothermal conversion nanoparticles were synthesized in situ on hollow fiber flocs; S4, TPU fibers are prepared by electrospinning process and then made into TPU fiber film; S5, fill the hollow fiber flakes between the two layers of TPU fiber membrane.

[0017] As a preferred technical solution, in S1, the air pressure of the air jet spinning is 0.3-0.6 MPa, the spinning solution flow rate is 8-12 mL / h, the nozzle temperature is 25-35°C, and the fiber collection distance is 15-25 cm. In these technical features, air jet spinning is achieved on an air jet spinning device, where high-pressure gas stretches the spinning solution into fibers, forming a hollow structure. It is important to note that the fiber collection distance refers to the vertical or horizontal distance between the spinneret on the air jet spinning device and the fiber collection device (such as a collecting net, take-up roller, etc.). This collection distance directly affects the stretching effect of the high-speed airflow on the polymer solution, the solvent evaporation rate, and the fiber deposition morphology. Too short a distance may lead to insufficient fiber stretching or adhesion, while too long a distance may result in insufficient fiber solidification due to premature solvent evaporation. When increasing the airflow velocity or solution viscosity, it is necessary to shorten the collection distance to maintain fiber stability.

[0018] As a preferred technical solution, in S2, thermal crosslinking is carried out under a protective atmosphere, with a crosslinking temperature of 160-190°C and a crosslinking time of 15-30 minutes. In the above technical features, thermal crosslinking is achieved using a high-temperature hot press and / or a tunnel oven. The protective atmosphere is selected as a nitrogen or argon inert gas environment to avoid polymer oxidative decomposition. The crosslinking temperature of 160-190°C is based on the melting temperature of polyurethane (approximately 170°C) and the glass transition temperature of polystyrene. Within this temperature range, the PU molecular chains and PS molecular chains can undergo a grafting reaction, while simultaneously activating the crosslinking agent to form a three-dimensional network crosslinked structure. The crosslinking time of 15-30 minutes needs to be matched with the temperature gradient.

[0019] As a preferred technical solution, in step S3, photothermal conversion nanoparticles are placed in a solvent to obtain a suspension with a solid content of 5-10% by mass. The photothermal conversion nanoparticles are then penetrated into the hollow fiber flocs via impregnation or spraying. In this technical feature, the suspension impregnation / spraying method allows the nanoparticles to penetrate the fiber pores through capillary action and adhere to the fiber surface and internal cavities. In this technical feature, a polar organic solvent is selected in the suspension to enhance the dispersibility of the nanoparticles. The spraying or impregnation process needs to be carried out at a pressure of 0.3-0.5 MPa. Capillary action and pressure gradient drive the photothermal conversion nanoparticles into the fiber surface and hollow cavities, and in-situ fixation is achieved through solvent evaporation, thereby improving the bonding strength of the photothermal conversion nanoparticles.

[0020] As a preferred technical solution, in S4, the electrospinning solution comprises TPU dissolved in a DMF / THF mixed solvent with a volume ratio of 1:1, with the TPU concentration reaching 10-15 wt% of the mixed solvent. The electrospinning voltage is 18-25 kV, the electrospinning solution flow rate is 0.8-1.2 mL / h, the electrospinning receiving distance is 12-18 cm, and the ambient humidity is below 50%. The high-voltage electrostatic field stretches the TPU solution jet into nanofibers. In the above technical features, the voltage setting of 18-25 kV is based on the jet stretching requirements; below 18 kV, the fiber diameter is too high, easily leading to insufficient fabric density, while above 25 kV, fiber breakage occurs. The matching of the flow rate of 0.8-1.2 mL / h and the receiving distance of 12-18 cm is used to control the fiber deposition density; the ambient humidity ≤50% prevents TPU hydrolysis.

[0021] The application of a nanofiber fabric having any one or more of the above technical features in the preparation of protective clothing, including but not limited to one-piece protective suits, two-piece protective suits, protective gloves, and protective masks.

[0022] The advantages and beneficial effects of this invention are as follows: Compared with existing thermal insulation fabrics, the nanofiber fabric shown in this invention has a higher porosity, a fluffier feel, and a lower density, allowing it to trap more still air, thus achieving a warm, cold-proof, lightweight, and comfortable wearing experience. Compared to conventional thermal insulation fabrics, the hollow fiber wadding prepared by thermal cross-linking of polyurethane and polystyrene spinning in this invention has good elasticity, is washable, does not easily collapse after washing, and has a long service life. By introducing photothermal conversion nanoparticles into the hollow fiber wadding, the thermal insulation effect is improved. The photothermal conversion nanoparticles penetrate into the hollow fiber wadding and are fixed, maintaining its stable connection. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the structure of the fabric shown in this invention. Detailed Implementation

[0024] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings and examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention and should not be construed as limiting the scope of protection of the present invention.

[0025] Example 1: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 employs an air-jet spinning process, setting the air pressure of the air-jet spinning equipment to 0.5 MPa, the spinning solution flow rate to 8 mL / h, and the nozzle temperature to 25°C. Polyurethane fibers with an average diameter of 200 nm are obtained through the spinneret orifice at a collection distance of 15 cm. Alternatively, the air pressure of the air-jet spinning equipment is set to 0.3 MPa, the spinning solution flow rate to 12 mL / h, and the nozzle temperature to 20°C. Polystyrene fibers with an average diameter of 150 nm are obtained through the spinneret orifice at a collection distance of 18 cm.

[0026] S2, under nitrogen protection, 45% polyurethane fiber and 54% polystyrene fiber are blended into a wadding by mass percentage, and then 1% crosslinking agent is sprayed on its surface and thermally crosslinked at 160℃ for 30 minutes to obtain hollow fiber wadding.

[0027] S3. Photothermal conversion nanoparticles are placed in a solvent (ethanol) to prepare a suspension with a solid content of 5% by mass. The photothermal conversion nanoparticles (zirconia with a particle size of 50-100 nm) are then impregnated into the hollow fiber flocs at a pressure of 0.4 MPa using an impregnation process.

[0028] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 10wt%. TPU fibers with a diameter of 300-500nm are prepared on an electrospinning device with a voltage of 18kV, a spinning solution flow rate of 0.8mL / h, and a receiving distance of 12cm. The TPU fibers are then blended or hot-pressed to form TPU fiber membranes.

[0029] S5. Two 5μm thick TPU fiber films are bonded to the face fabric (polyester) and the back fabric (cotton), respectively. The two TPU fiber films have the same length and width as the face and back fabrics. The edges of the face and back fabrics are sewn together. During the sewing process, the space between the two TPU fiber films is filled with hollow fiber layers up to 15μm. This fabric is then used to make a one-piece protective suit.

[0030] Example 2: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 employs an air-jet spinning process, setting the air pressure of the air-jet spinning equipment to 0.6 MPa, the spinning solution flow rate to 12 mL / h, and the nozzle temperature to 35°C. Polyurethane fibers with an average diameter of 180 nm are obtained through the spinneret orifice at a collection distance of 25 cm. Alternatively, the air pressure of the air-jet spinning equipment is set to 0.4 MPa, the spinning solution flow rate to 10 mL / h, and the nozzle temperature to 32°C. Polystyrene fibers with an average diameter of 250 nm are obtained through the spinneret orifice at a collection distance of 22 cm.

[0031] S2, under argon protection, 65% polyurethane fiber and 32% polystyrene fiber are blended into a wadding by mass percentage, and then 3% crosslinking agent (diisopropylbenzene peroxide) is sprayed on its surface. After thermal crosslinking at 190℃ for 15 minutes, hollow fiber wadding is obtained.

[0032] S3. Photothermal conversion nanoparticles are placed in a solvent (isopropanol) to prepare a suspension with a solid content of 10% by mass. The photothermal conversion nanoparticles (iridium oxide with a particle size of 150-200nm) are then permeated into the hollow fiber flocs by a spraying process at a gas pressure of 0.6MPa.

[0033] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 15wt%. TPU fibers with a diameter of 400-500nm are prepared on an electrospinning device with a voltage of 25kV, a spinning solution flow rate of 1.2mL / h, and a receiving distance of 18cm. The TPU fibers are then blended to form a TPU fiber membrane.

[0034] S5. Two 4μm thick TPU fiber films are bonded to the outer fabric layer (nylon) and the back fabric layer (fleece polyester), respectively. The two TPU fiber films have the same length and width as the outer and back fabric layers. The edges of the outer and back fabric layers are sewn together. During the sewing process, the space between the two TPU fiber films is filled with hollow fiber layers up to 20μm. This fabric is then used to make a mountaineering jacket.

[0035] Example 3: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 employs an air-jet spinning process, setting the air pressure of the air-jet spinning equipment to 0.45 MPa, the spinning solution flow rate to 10 mL / h, and the nozzle temperature to 30°C. Polyurethane fibers with an average diameter of 220 nm are obtained through the spinneret orifice at a collection distance of 20 cm. Alternatively, the air pressure of the air-jet spinning equipment is set to 0.35 MPa, the spinning solution flow rate to 11 mL / h, and the nozzle temperature to 28°C. Polystyrene fibers with an average diameter of 200 nm are obtained through the spinneret orifice at a collection distance of 20 cm.

[0036] S2, under nitrogen protection, 55% polyurethane fiber and 43% polystyrene fiber are blended into a wadding by mass percentage, and then 2% crosslinking agent (hexamethylene diisocyanate) is sprayed on its surface. After thermal crosslinking at 175°C for 22 minutes, hollow fiber wadding is obtained.

[0037] S3. Photothermal conversion nanoparticles are placed in a solvent (deionized water) to prepare a suspension with a solid content of 8% by mass. The photothermal conversion nanoparticles (thallium carbide with a particle size of 100-150 nm) are then impregnated into the hollow fiber flocs at a pressure of 0.5 MPa using an impregnation process.

[0038] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 12wt%. TPU fibers with a diameter of 200-400nm are prepared on an electrospinning device with a voltage of 22kV, a spinning solution flow rate of 1.0mL / h, and a receiving distance of 15cm. The TPU fibers are then hot-pressed to form a TPU fiber membrane.

[0039] S5, two 3.5μm thick TPU fiber films are bonded to the face fabric (aramid) and the back fabric (wool blend), respectively. The two TPU fiber films have the same length and width as the face and back fabrics. The edges of the face and back fabrics are sewn together. During the sewing process, the space between the two TPU fiber films is filled with hollow fiber layers up to 18μm. This fabric is then used to make fire-fighting protective clothing.

[0040] Example 4; A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps; S1 uses an air-jet spinning process, with the air pressure of the air-jet spinning equipment set at 0.4 MPa, the spinning solution flow rate at 9 mL / h, and the nozzle temperature at 28℃. Polyurethane fibers with an average diameter of 190 nm are obtained through the spinneret orifice at a collection distance of 18 cm. The air pressure of the air-jet spinning equipment is set at 0.38 MPa, the spinning solution flow rate at 9.5 mL / h, and the nozzle temperature at 30℃. Polystyrene fibers with an average diameter of 210 nm are obtained through the spinneret orifice at a collection distance of 19 cm.

[0041] S2, under nitrogen protection, 48% polyurethane fiber and 50% polystyrene fiber are blended into a wadding by mass percentage, and then 2% crosslinking agent (diisopropylbenzene peroxide) is sprayed on its surface. After thermal crosslinking at 165℃ for 28 minutes, hollow fiber wadding is obtained.

[0042] S3. Photothermal conversion nanoparticles are placed in a solvent (ethanol) to prepare a suspension with a solid content of 7% by mass. The photothermal conversion nanoparticles (a 1:1 mixture of zirconium carbide and iridium oxide with a particle size of 80-120 nm) are then permeated into the hollow fiber flocs by a spraying process at a gas pressure of 0.45 MPa.

[0043] S4. TPU fiber membranes were prepared using an electrospinning process. TPU was dissolved in a DMF / THF (volume ratio 1:1) mixed solvent, with a TPU concentration of 11 wt%. On an electrospinning apparatus, at a voltage of 20 kV, a spinning solution flow rate of 0.9 mL / h, and a receiving distance of 14 cm, TPU fibers with diameters of 250-450 nm were prepared. These TPU fibers were then blended to form a TPU fiber membrane. S5. Two TPU fiber membranes, each 4 μm thick, were bonded to a face fabric layer (acrylic coating) and a back fabric layer (brushed polyester), respectively. The length and width of the two TPU fiber membranes were identical to those of the face and back fabric layers. The edges of the face and back fabric layers were sewn together. During the sewing process, hollow fiber layers were filled between the two TPU fiber membranes until they reached a thickness of 17 μm. This fabric was then used to prepare a polar research garment.

[0044] Example 5: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps; S1 employs an air-jet spinning process, setting the air pressure of the air-jet spinning equipment to 0.35 MPa, the spinning solution flow rate to 8.5 mL / h, and the nozzle temperature to 26°C. Polyurethane fibers with an average diameter of 150 nm are obtained through the spinneret orifice at a collection distance of 18 cm. Alternatively, the air pressure of the air-jet spinning equipment is set to 0.32 MPa, the spinning solution flow rate to 8.8 mL / h, and the nozzle temperature to 25°C. Polystyrene fibers with an average diameter of 160 nm are obtained through the spinneret orifice at a collection distance of 17 cm.

[0045] S2, under argon protection, 60% polyurethane fiber and 38% polystyrene fiber are blended into a wadding by mass percentage, and then 2% crosslinking agent (hexamethylene diisocyanate) is sprayed on its surface. After thermal crosslinking at 185℃ for 18 minutes, hollow fiber wadding is obtained.

[0046] S3. Photothermal conversion nanoparticles are placed in a solvent (isopropanol) to prepare a suspension with a solid content of 9% by mass. The photothermal conversion nanoparticles (zirconia with a particle size of 130-180 nm) are then impregnated into the hollow fiber flocs at a pressure of 0.5 MPa using an impregnation process.

[0047] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 13wt%. TPU fibers with a diameter of 100-300nm are prepared on an electrospinning device with a voltage of 24kV, a spinning solution flow rate of 1.1mL / h, and a receiving distance of 17cm. The TPU fibers are then hot-pressed to form a TPU fiber membrane.

[0048] S5, two TPU fiber films, each 2.5μm thick, are bonded to the face fabric layer (chlorofiber waterproof treatment) and the back fabric layer (cotton fleece), respectively. The two TPU fiber films have the same length and width as the face fabric layer and the back fabric layer. The edges of the face fabric layer and the back fabric layer are sewn together. During the sewing process, the space between the two TPU fiber films is filled until the hollow fiber layer reaches 16μm.

[0049] Example 6: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 uses an air-jet spinning process, with the air pressure of the air-jet spinning equipment set at 0.55 MPa, the spinning solution flow rate at 11 mL / h, and the nozzle temperature at 32℃. Polyurethane fibers with an average diameter of 230 nm are obtained through the spinneret orifice at a collection distance of 22 cm. S2 uses an air pressure of 0.52 MPa, the spinning solution flow rate at 11.5 mL / h, and the nozzle temperature at 33℃. Polystyrene fibers with an average diameter of 240 nm are obtained through the spinneret orifice at a collection distance of 23 cm.

[0050] S2, under nitrogen protection, 58% polyurethane fiber and 40% polystyrene fiber are blended into a wadding by mass percentage, and then 2% crosslinking agent (diisopropylbenzene peroxide) is sprayed on its surface. After thermal crosslinking at 170℃ for 25 minutes, hollow fiber wadding is obtained.

[0051] S3. Photothermal conversion nanoparticles are placed in a solvent (ethanol / water = 7:3) to prepare a suspension with a solid content of 8.5% by mass. The photothermal conversion nanoparticles (a mixture of thallium carbide and iridium oxide with a particle size of 180-200nm, 2:1) are then permeated into the hollow fiber flocs by a spraying process at a gas pressure of 0.55MPa.

[0052] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 14wt%. TPU fibers with a diameter of 400-500nm are prepared on an electrospinning device with a voltage of 23kV, a spinning solution flow rate of 1.05mL / h, and a receiving distance of 16cm. The TPU fibers are then blended to form a TPU fiber membrane (uniformity ±10%).

[0053] S5, two TPU fiber films, each 4.5μm thick, are bonded to the face fabric layer (UV-resistant coated nylon) and the back fabric layer (modal blend), respectively. The two TPU fiber films have the same length and width as the face fabric layer and the back fabric layer. The ends of the face fabric layer and the back fabric layer are sewn together. During the sewing process, the space between the two TPU fiber films is filled until the hollow fiber layer reaches 19μm.

[0054] Example 7: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 uses an air-jet spinning process, with the air pressure of the air-jet spinning equipment set at 0.5 MPa, the spinning solution flow rate at 8.2 mL / h, and the nozzle temperature at 27°C. Polyurethane fibers with an average diameter of 170 nm (wall thickness of 80 nm) are obtained through the spinneret orifice at a collection distance of 16 cm. The air pressure of the air-jet spinning equipment is set at 0.3 MPa, the spinning solution flow rate at 8.5 mL / h, and the nozzle temperature at 24°C. Polystyrene fibers with an average diameter of 155 nm are obtained through the spinneret orifice at a collection distance of 17 cm.

[0055] S2, under nitrogen protection, 60% polyurethane fiber and 38% polystyrene fiber are blended into a wadding by mass percentage, and then 2% crosslinking agent (hexamethylene diisocyanate) is sprayed on its surface. After thermal crosslinking at 180°C for 20 minutes, hollow fiber wadding is obtained.

[0056] S3. Photothermal conversion nanoparticles are placed in a solvent (acetone) to prepare a suspension with a solid content of 6% by mass. The photothermal conversion nanoparticles (a 3:1 mixture of zirconium carbide and thallium carbide with a particle size of 60-100 nm) are then impregnated into hollow fiber flocs at a pressure of 0.42 MPa.

[0057] S4. TPU fiber membranes are prepared by electrospinning. TPU is dissolved in a mixed solvent of DMF / THF (volume ratio 1:1) with a TPU concentration of 12.5 wt%. TPU fibers with a diameter ≤200 nm are prepared on an electrospinning device with a voltage of 19 kV, a spinning solution flow rate of 0.85 mL / h, and a receiving distance of 13 cm. The TPU fibers are then hot-pressed to form TPU fiber membranes with a thickness of 1.8-2.2 μm.

[0058] S5, two TPU fiber films are bonded to the face fabric layer (micro denier polyester) and the back fabric layer (Tencel fabric) respectively. The two TPU fiber films have the same length and width as the face fabric layer and the back fabric layer. The ends of the face fabric layer and the back fabric layer are sewn together. During the sewing process, the space between the two TPU fiber films is filled until the hollow fiber layer reaches 15.5μm.

[0059] Example 8: A method for preparing a cold-proof and thermal clothing fabric, comprising the following steps: S1 employs an air-jet spinning process, with the air pressure of the air-jet spinning equipment set at 0.6 MPa, the spinning solution flow rate at 12 mL / h, and the nozzle temperature at 35°C. Polyurethane fibers are obtained through the spinneret orifice at a collection distance of 25 cm. Alternatively, the air pressure of the air-jet spinning equipment is set at 0.45 MPa, the spinning solution flow rate at 11.8 mL / h, and the nozzle temperature at 34°C. Polystyrene fibers are obtained through the spinneret orifice at a collection distance of 24 cm. The spinning solution contains 65% PU, 34% PS, and 3% crosslinking agent.

[0060] S2 is spun into wadding under argon protection, and the surface is sprayed with 3% crosslinking agent (diisopropylbenzene peroxide). After thermal crosslinking at 190℃ for 15 minutes, hollow fiber wadding is obtained.

[0061] S3. Photothermal conversion nanoparticles are placed in a solvent (ethanol) to prepare a suspension with a solid content of 10%. Zirconium carbide with a particle size of 200 nm is then permeated into hollow fiber flocs by high-pressure spraying at a pressure of 0.6 MPa.

[0062] S4. TPU fiber membrane was prepared by electrospinning process. The TPU concentration was 15wt% in DMF / THF (1:1). TPU fibers with a diameter of 500nm were prepared with a voltage of 25kV, a flow rate of 1.2mL / h and a receiving distance of 18cm. The TPU fiber membrane with a thickness of 5μm was prepared by hot pressing.

[0063] S5, two layers of TPU fiber film are bonded to the outer fabric layer (nylon) and the bottom fabric layer (cotton and linen blend) respectively, and the ends are sewn together to fill the hollow layer, thus making the inner lining of the bulletproof vest.

[0064] Comparative Example 1: Commercially available down jacket fabric.

[0065] Comparative Example 2: The only difference from Example 1 is that the hollow fiber layer is filled with down to 80% of its volume.

[0066] Comparative Example 3: The only difference from Example 1 is that the hollow fiber layer did not contain photothermal conversion nanoparticles.

[0067] Performance analysis and testing were conducted on the above embodiments and comparative examples. The thermal resistance of the fabric was measured according to GB / T 38300-2019 "Protective Clothing - Cold Environment Protective Clothing". The thermal resistance of the sample was measured under the conditions of ambient temperature (20±1)°C and relative humidity (65±5)%. The size of the test sample was 30cm×30cm.

[0068] The number of washes was determined according to GB / T 38300-2019 "Protective Clothing - Cold Environment Protective Clothing". A washing machine was used at a temperature of 40°C, a speed of (600±50) rpm, and a detergent concentration of 1 g / L. The sample weight was 5 kg. The standard washing cycle was defined as the number of times the performance decreased by 30% or obvious deformation (thickness reduction >10%) occurred. The fabric thickness was measured after every 5 washes.

[0069] Fabric density was determined according to GB / T 4669-2008 "Determination of mass per unit length and mass per unit area of ​​textile woven fabrics". A 10cm×10cm sample was cut using a high-precision electronic balance in a standard environment at 20°C. The mass was measured and then divided by the volume to calculate the density. The volume was calculated based on the thickness measuring instrument.

[0070] Down leakage was assessed according to GB / T 38300-2019 "Protective Clothing - Cold Environment Protective Clothing". A roller test was used, where the sample was placed in a roller tester containing rubber balls and run at 300 rpm for 30 minutes. The number of down fibers leaking from the surface was then checked. The elastic recovery rate was determined according to GB / T 14801-2009 "Test Method for Elasticity of Woven and Knitted Fabrics". A tensile tester was used to apply 20% elongation for 30 seconds, and then the elongation was released. The percentage of recovery deformation was measured. The test results are shown in the table below. Test Project Fabric thermal resistance (CLO) Wash resistance (number of washes) <![CDATA[Fabric density (g / cm 3 )]]> <![CDATA[Down feather leakage condition (roots / m 2 )]]> Elastic recovery rate (%) Example 1 1.7-1.9 ＞50 0.012-0.015 0 95 Example 2 1.8-2.0 ＞50 0.015-0.018 0 93 Example 3 1.6-1.8 ＞50 1.013-0.016 0 94 Example 4 1.5-1.7 ＞50 0.014-0.017 0 92 Example 5 1.8-1.9 ＞50 0.011-0.014 0 95 Example 6 1.7-1.8 ＞50 0.016-0.019 0 90 Example 7 1.9-2.1 ＞50 0.010-0.013 0 96 Example 8 2.0-2.2 ＞50 0.018-0.021 0 91 Comparative Example 1 1.0-1.3 10-20 0.030-0.040 ＞10 50-60 Comparative Example 2 1.4-1.6 5-10 0.025-0.030 ＞15 30-40 Comparative Example 3 1.1-1.2 ＞50 0.012-0.015 0 90 The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles 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 cold-proof and thermal clothing fabric, characterized in that, It includes a face fabric layer, a functional layer and a base fabric layer that are stacked and connected in sequence; the functional layer is composed of nanofiber composite material, including a hollow fiber layer sandwiched by two layers of TPU fiber membrane; the hollow fiber layer is made by filling hollow fiber flakes, and photothermal conversion nanoparticles are synthesized in situ on the surface of the hollow fiber layer.

2. The cold-proof and thermal clothing fabric according to claim 1, characterized in that, The TPU fiber membrane is 2-5 μm thick, and the diameter of the TPU nanofibers is distributed in the range of 100-500 nm.

3. The cold-proof and thermal clothing fabric according to claim 2, characterized in that, The hollow fiber layer comprises, by weight percentage, 45-65% polyurethane, 34-54% polystyrene, and 1-3% crosslinking agent.

4. The cold-proof and thermal clothing fabric according to claim 2, characterized in that, The photothermal conversion nanoparticles are at least one of zirconium carbide, iridium oxide, and thallium carbide, and the particle size of the photothermal conversion nanoparticles is 50-200 nm.

5. A method for preparing a cold-proof and thermal clothing fabric, characterized in that, Includes the following steps: S1, hollow fiber floc precursor is prepared by air-jet spinning process; S2, hollow fiber floc is synthesized by thermal crosslinking of hollow fiber floc precursor; S3, photothermal conversion nanoparticles are synthesized in situ on hollow fiber floc; S4, TPU fiber membrane is prepared by electrospinning process; S5, hollow fiber floc is filled between two layers of TPU fiber membrane.

6. The preparation method according to claim 5, characterized in that, In S1, the air pressure for air-jet spinning is 0.3-0.6 MPa, the spinning solution flow rate is 8-12 mL / h, the nozzle temperature is 25-35°C, and the fiber collection distance is 15-25 cm.

7. The preparation method according to claim 5, characterized in that, In S2, thermal crosslinking is carried out under a protective atmosphere, the thermal crosslinking temperature is 160-190°C, and the heating time for thermal crosslinking is 15-30 minutes.

8. The preparation method according to claim 5, characterized in that, In S3, photothermal conversion nanoparticles are placed in a solvent to prepare a suspension with a solid content of 5-10% by mass. The photothermal conversion nanoparticles are then penetrated into the hollow fiber flocs through impregnation or spraying processes.

9. The preparation method according to claim 5, characterized in that, S4 is a TPU fiber membrane prepared by electrospinning.

10. The application of the cold-proof and thermal insulation fabric described in claims 1-4 in the preparation of protective clothing.

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