Anti-uv waterproof cloth

Abstract

The application discloses an anti-ultraviolet waterproof cloth, which comprises a base cloth and a waterproof film pressed on the base cloth, wherein the base cloth is a polyester base cloth, and the waterproof film comprises 50-70 parts of high-density polyethylene, 15-30 parts of linear low-density polyethylene, 5-8 parts of manganese ion doped zinc sulfide, 5-10 parts of polydopamine coated nanometer silicon dioxide, 0.5-2 parts of a coupling agent, 0.2-1 part of a lubricant and 0.1-0.3 part of polydopamine coated black phosphorus in terms of weight fractions. Through a multi-stage synergistic mechanism of ultraviolet light conversion, surface shielding and physical covering, the anti-ultraviolet aging performance and mechanical stability of the waterproof cloth are comprehensively improved while excellent waterproof performance is maintained.

Description

Technical Field

[0001] This application relates to the field of waterproof fabrics, and more specifically, to a UV-resistant waterproof fabric. Background Technology

[0002] With the rapid development of the outdoor industry, industrial warehousing, agricultural covering, construction and outdoor leisure products, the application scenarios of functional textile fabrics are constantly expanding, which puts forward higher requirements for the comprehensive protective performance of the fabrics.

[0003] Waterproof fabric, as a type of functional protective material, is widely used in many fields such as outdoor tents, rainproof tarpaulins, cargo coverings, agricultural insulation and rain protection, outdoor sunshades, and special protective clothing. Its core functional requirements have gradually upgraded from simply being waterproof to having waterproof, UV resistance, aging resistance, high strength, and long lifespan in combination. Fabrics with only basic waterproof performance can no longer meet the complex usage environment of long-term exposure to the sun and wind and rain.

[0004] Ultraviolet light (wavelength 280-400nm) is a major aging factor in outdoor environments. It has extremely strong photochemical activity. Long-term exposure will directly damage the polymer molecular chains of conventional waterproof fabric substrates, causing problems such as embrittlement, cracking, fading, and peeling of the waterproof coating, thus shortening the service life of the waterproof fabric. This needs to be improved. Summary of the Invention

[0005] To improve the UV resistance of waterproof fabric, this application provides a UV-resistant waterproof fabric.

[0006] The UV-resistant waterproof fabric provided in this application adopts the following technical solution:

[0007] An anti-ultraviolet waterproof fabric includes a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric. By weight, the waterproof film comprises 50-70 parts high-density polyethylene, 15-30 parts linear low-density polyethylene, 5-8 parts manganese ion-doped zinc sulfide, 5-10 parts polydopamine-coated nano-silica, 0.5-2 parts coupling agent, 0.2-1 parts lubricant, and 0.1-0.3 parts polydopamine-coated black phosphorus.

[0008] By adopting the above technical solution, manganese ion-doped zinc sulfide can absorb ultraviolet light in the 280-400nm wavelength band and convert it into harmless fluorescence emission in the visible light range, thereby weakening the intensity of ultraviolet light acting on the polyethylene matrix and polyester base fabric, and delaying the breakage and degradation of polymer chains.

[0009] Polydopamine-coated nano-silica improves the tensile and tear strength of waterproof films through the rigidity of the nanoparticles themselves. On the other hand, polydopamine has excellent adhesion properties, which enhances the bonding force between inorganic fillers and organic matrices by utilizing the polydopamine coating layer on the surface. In addition, its excellent UV shielding properties also construct a secondary UV barrier on the material surface, inhibiting the free radical chain reaction caused by ultraviolet rays.

[0010] The layered structure of black phosphorus forms a physical barrier at the interface, physically sealing off interfacial gaps where ultraviolet rays may penetrate. This prevents ultraviolet rays from aging and corroding the polyester base fabric through microscopic defects. Furthermore, polydopamine is used to coat the surface of the black phosphorus. The polydopamine coating layer has a three-dimensional cross-linked network structure with appropriate porosity. While inhibiting the rapid oxidation of the black phosphorus itself, it allows a small amount of moisture to penetrate moderately, promoting the controlled oxidation of the black phosphorus surface to generate phosphate groups. These groups can react with the hydroxyl / carboxyl groups at the ends of the polyester base fabric to form stable hydrogen bonds or esterification bonds. This creates an interfacial chemical anchoring structure between the black phosphorus and the polyester base fabric, improving interlayer bonding and peel strength.

[0011] Through a multi-level synergistic mechanism of ultraviolet light conversion, surface shielding, and physical coverage, the waterproof fabric's resistance to ultraviolet aging and mechanical stability are comprehensively improved while maintaining excellent waterproof performance.

[0012] Preferably, the preparation method of the manganese ion-doped zinc sulfide is as follows, by weight: 5-6 parts of zinc acetate and 0.1-0.2 parts of manganese acetate are added to 70-90 parts of deionized water, followed by 5-7 parts of oleic acid, and stirred in a water bath at 65-75°C for 25-35 minutes, which is denoted as solution A;

[0013] Dissolve 5.5-6.5 parts of thiourea in 35-45 parts of deionized water to form solution B;

[0014] Under stirring, solution B is added dropwise to solution A. After the addition is complete, the pH is adjusted to 10-11 using NaOH solution. The mixture is then kept at 125-135℃ for 7-9 hours. The reaction product is then transferred to a centrifuge tube and centrifuged at 9000-11000 rpm for 12-18 minutes. The supernatant is discarded, and the bottom solid precipitate is collected. The precipitate is washed alternately with deionized water and anhydrous ethanol, and this process is repeated 3 times. The washed solid product is then dried at 50-60℃ for 8-12 hours. Finally, it is ground through a 200-mesh sieve to obtain manganese ion-doped zinc sulfide powder.

[0015] By adopting the above technical solution, oleic acid molecules can be adsorbed in situ onto the surface of zinc sulfide particles to form a stable organic coordination layer. This improves the interfacial compatibility between zinc sulfide particles and non-polar organic matrices such as high-density polyethylene and linear low-density polyethylene, inhibits the tendency of particles to agglomerate in the matrix, and ensures that the functional filler is uniformly dispersed in the waterproof film, thereby guaranteeing the uniformity of the mechanical properties of the waterproof film.

[0016] Preferably, the preparation method of the polydopamine-coated black phosphorus, by weight, is as follows: 0.5-1 parts of black phosphorus are added to 20-30 parts of anhydrous N,N-dimethylformamide, and sonicated in an ice bath under argon protection for 6-9 hours. Then, the mixture is centrifuged at 2000-4000 r / min for 20-30 minutes, and the supernatant is collected. The mixture is then centrifuged at 9000-12000 r / min for 15-30 minutes, and the precipitate is collected. The precipitate is then dispersed in a mixed solution of 20-30 parts of anhydrous ethanol and deionized water (volume ratio 1:1), sonicated for 0.5-1 hour, and purified by argon gas. Add oxygen for 10 minutes, then add 0.5-1 part of dopamine hydrochloride, and adjust the pH to 8-8.5 by adding NaOH solution dropwise. Stir and react at 20-25℃ in the dark for 12-24 hours. After the reaction is complete, transfer the product to a centrifuge tube and centrifuge at 8000-12000 r / min for 10-20 minutes. Discard the supernatant and wash the precipitate three times alternately with deionized water and anhydrous ethanol. Place the washed solid product in a vacuum dryer at 40-50℃ for 12-24 hours, then grind and pass through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0017] By adopting the above technical solution and controlling the ultrasonic disruption time and graded centrifugation parameters, the number of black phosphorus layers and transverse dimensions can be controlled, avoiding excessive oxidation or structural damage. Subsequently, in-situ polymerization of polydopamine under mild alkaline conditions can form a uniform polydopamine coating layer with micro- and nano-pores on the surface of black phosphorus.

[0018] Preferably, in the preparation method of polydopamine-coated black phosphorus, argon gas is passed through for deoxygenation for 10 min, then 0.3-0.8 parts of chitosan are added and stirred until fully dissolved, followed by the addition of 0.5-1 parts of dopamine hydrochloride, and the pH is adjusted to 8-8.5 by adding 0.1 mol / L NaOH solution dropwise. The reaction is carried out at 20-25°C in the dark with stirring for 12-24 h.

[0019] By adopting the above technical solution, the amino and hydroxyl groups on the chitosan molecular chain form a dense double-network interpenetrating structure with polydopamine, which has higher mechanical strength and antioxidant barrier effect, and can better inhibit the oxidative degradation of black phosphorus during storage and use. In addition, the amino and hydroxyl groups on the chitosan molecular chain can also form more hydrogen bonds and covalent bonding sites with the hydroxyl / carboxyl groups at the end of the polyester base fabric, further enhancing the interfacial bonding force between the waterproof film and the base fabric.

[0020] Preferably, the waterproof film further comprises 0.5-2 parts by weight of nano boron nitride.

[0021] By adopting the above technical solution, nano-boron nitride has extremely high reflectivity and scattering rate for ultraviolet rays in the 200-300nm wavelength band. It can work synergistically with manganese ion-doped zinc sulfide and polydopamine coating layer to achieve multi-layer shielding against ultraviolet rays. On the other hand, nano-boron nitride has extremely high in-plane thermal conductivity. During outdoor exposure, it can dissipate local heat generated by ultraviolet absorption or friction, avoiding softening, deformation or thermal aging of the material due to heat accumulation, thus improving the safety and weather resistance of the waterproof fabric.

[0022] Preferably, the preparation method of the polydopamine-coated nano-silica by weight is as follows: 5-6 parts of nano-silica and 100-120 parts of deionized water are mixed and ultrasonically dispersed for 10-30 min. Then, a uniform suspension is formed under magnetic stirring. 0.1-0.3 parts of tris(hydroxymethyl)aminomethane are added and stirred until completely dissolved. The pH value is adjusted to 8-8.5 using NaOH solution. 0.5-1 parts of dopamine hydrochloride are added and stirred continuously at 25-35℃ for 18-24 h. After the reaction is completed, the product is transferred to a centrifuge tube and centrifuged at 8000-10000 r / min for 10-20 min. The supernatant is discarded, and the precipitate is washed three times alternately with deionized water and anhydrous ethanol. The washed solid is vacuum dried at 40-50℃ for 12-24 h, then ground and passed through a 200-mesh sieve to obtain polydopamine-coated nano-silica powder.

[0023] Preferably, the lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1.

[0024] By adopting the above technical solutions, both vinyl bis-stearamide and low molecular weight polyethylene wax are non-metallic soap-type lubricants. During processing, they can reduce melt viscosity and internal friction heat generation, suppress the generation of shear heat during extrusion, and provide a mild processing environment for black phosphorus and polydopamine coating layers. This avoids oxidative degradation or structural damage under high-temperature shear, ensuring the functional stability of the final waterproof fabric.

[0025] Preferably, the coupling agent is a borate ester coupling agent.

[0026] By adopting the above technical solution, borate ester coupling agents have a lower curing temperature and can complete the interfacial reaction at the extrusion temperature without high-temperature dehydration. This not only reduces energy consumption but also helps protect temperature-sensitive functional fillers such as black phosphorus and polydopamine from thermal degradation.

[0027] In summary, this application has the following beneficial effects:

[0028] 1. Through a multi-level synergistic mechanism of ultraviolet light conversion, surface shielding, and physical coverage, the waterproof fabric's resistance to ultraviolet aging and mechanical stability are comprehensively improved while maintaining excellent waterproof performance.

[0029] 2. Oleic acid is added during the preparation of manganese ion-doped zinc sulfide, which improves the interfacial compatibility between zinc sulfide particles and non-polar organic matrices such as high-density polyethylene and linear low-density polyethylene, inhibits the tendency of particles to agglomerate in the matrix, and ensures that the functional filler is uniformly dispersed in the waterproof film, thereby ensuring the uniformity of the mechanical properties of the waterproof film.

[0030] 3. By controlling the ultrasonic disruption time and the fractionation centrifugation parameters, the number of black phosphorus layers and the transverse dimensions can be controlled, avoiding excessive oxidation or structural damage. Subsequently, in-situ polymerization of polydopamine under mild alkaline conditions can form a uniform polydopamine coating layer with micro- and nano-pores on the surface of black phosphorus. Detailed Implementation

[0031] The present application will be further described in detail below with reference to the embodiments.

[0032] High-density polyethylene The melt flow rate (190℃, 2.16kg) is 0.5g / 10min, and the density is 0.95g / cm³. Linear low-density polyethylene Octene copolymer, melt flow rate (190℃, 2.16kg) is 2.0g / 10min, density is 0.92g / cm³. Black phosphorus Black phosphorus nanosheets, ≤10 layers Nano boron nitride Hexagonal crystal system, with a sheet diameter of 200–300 nm and a thickness of approximately 10 nm. Nano silica Fumed silica with an average particle size of 20-30 nm Low molecular weight polyethylene wax Molecular weight 2000-3000, melting point 105-115℃ Borate coupling agents Chelated titanate borate complex

[0033] Unless otherwise specified, all raw materials used in the following embodiments are commercially available.

[0034] Preparation Example 1

[0035] Preparation of manganese ion-doped zinc sulfide: 50g zinc acetate and 1g manganese acetate were added to 700g deionized water, followed by 50g oleic acid. The mixture was stirred in a 65℃ water bath for 35min, and this solution was labeled A. 55g thiourea was dissolved in 350g deionized water to form solution B. Solution B was added dropwise to solution A while stirring. After the addition was complete, the pH was adjusted to 10-11 using 1mol / L NaOH solution. The mixture was then kept at 125℃ for 9h. The reaction product was then transferred to a centrifuge tube and centrifuged at 9000r / min for 18min. The supernatant was discarded, and the bottom solid precipitate was collected. The precipitate was washed alternately with deionized water and anhydrous ethanol, and this process was repeated 3 times. The washed solid product was then dried at 50℃ for 12h. Finally, it was ground through a 200-mesh sieve to obtain manganese ion-doped zinc sulfide powder.

[0036] Preparation Example 2

[0037] Preparation of manganese ion-doped zinc sulfide: 60g of zinc acetate and 2g of manganese acetate were added to 900g of deionized water, followed by 70g of oleic acid. The mixture was stirred in a 75℃ water bath for 25min, and this solution was denoted as solution A. 65g of thiourea was dissolved in 450g of deionized water to form solution B. While stirring, solution B was added dropwise to solution A. After the addition was complete, the pH was adjusted to 10-11 using 1mol / L NaOH solution. The mixture was then kept at 135℃ for 7h. The reaction product was then transferred to a centrifuge tube and centrifuged at 11000r / min for 12min. The supernatant was discarded, and the bottom solid precipitate was collected. The precipitate was washed alternately with deionized water and anhydrous ethanol, and this process was repeated 3 times. The washed solid product was then dried at 60℃ for 8h. Finally, it was ground through a 200-mesh sieve to obtain manganese ion-doped zinc sulfide powder.

[0038] Preparation Example 3

[0039] Preparation of manganese ion-doped zinc sulfide: 55g of zinc acetate and 1.5g of manganese acetate were added to 800g of deionized water, followed by 60g of oleic acid. The mixture was stirred in a 70℃ water bath for 30min, and this solution was denoted as solution A. 60g of thiourea was dissolved in 400g of deionized water to form solution B. While stirring, solution B was added dropwise to solution A. After the addition was complete, the pH was adjusted to 10-11 using 1mol / L NaOH solution. The mixture was then kept at 130℃ for 8h. The reaction product was then transferred to a centrifuge tube and centrifuged at 10000r / min for 15min. The supernatant was discarded, and the bottom solid precipitate was collected. The precipitate was washed alternately with deionized water and anhydrous ethanol, and this process was repeated 3 times. The washed solid product was then dried at 55℃ for 10h. Finally, it was ground through a 200-mesh sieve to obtain manganese ion-doped zinc sulfide powder.

[0040] Preparation Example 4

[0041] Preparation of polydopamine-coated black phosphorus: 5g of black phosphorus was added to 200g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 6h under argon protection. Then, it was centrifuged at 2000r / min for 30min, and the supernatant was collected. The supernatant was then centrifuged again at 9000r / min for 30min, and the precipitate was collected. The precipitate was then dispersed in 200g of a 1:1 mixture of anhydrous ethanol and deionized water, sonicated for 0.5h, and deoxygenated by argon for 10min. Finally, 5g of hydrochloric acid was added. Dopamine was added dropwise with 0.1 mol / L NaOH solution to adjust the pH to 8-8.5, and the mixture was stirred at 20°C in the dark for 24 hours. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 8000 r / min for 20 min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was then vacuum dried at 40°C for 24 hours, and then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0042] Preparation Example 5

[0043] Preparation of polydopamine-coated black phosphorus: 10g of black phosphorus was added to 300g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 9h under argon protection. Then, it was centrifuged at 4000r / min for 20min, and the supernatant was collected. The supernatant was then centrifuged at 12000r / min for 15min, and the precipitate was collected. The precipitate was then dispersed in a 1:1 mixture of anhydrous ethanol and deionized water, and sonicated for 1h. After deoxygenation by argon for 10min, 10g of hydrochloric acid was added. Dopamine was added dropwise to adjust the pH to 8-8.5 with 0.1 mol / L NaOH solution, and the mixture was stirred at 25°C in the dark for 12 h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 12000 r / min for 10 min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was then vacuum dried at 50°C for 12 h, and then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0044] Preparation Example 6

[0045] Preparation of polydopamine-coated black phosphorus: 8g of black phosphorus was added to 250g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 8h under argon protection. Then, it was centrifuged at 3000r / min for 25min, and the supernatant was collected. The supernatant was then centrifuged again at 10000r / min for 25min, and the precipitate was collected. The precipitate was then dispersed in 250g of a 1:1 mixture of anhydrous ethanol and deionized water, sonicated for 1h, and deoxygenated with argon for 10min. Finally, 8g of polydopamine hydrochloride was added. Dopamine was added dropwise to adjust the pH to 8-8.5 with 0.1 mol / L NaOH solution, and the mixture was stirred at 23°C in the dark for 20 h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 10000 r / min for 15 min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was then vacuum dried at 45°C for 20 h, and then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0046] Preparation Example 7

[0047] Preparation of polydopamine-coated black phosphorus: 5g of black phosphorus was added to 200g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 6h under argon protection. Then, it was centrifuged at 2000r / min for 30min, and the supernatant was collected. The supernatant was then centrifuged again at 9000r / min for 30min, and the precipitate was collected. The precipitate was then dispersed in a 1:1 mixture of anhydrous ethanol and deionized water, and sonicated for 0.5h. After argon deoxygenation for 10min, 3g of chitosan was added and stirred until fully dissolved. Then, 5g of dopamine hydrochloride was added, and 0.1mol / L NaOH solution was added dropwise to adjust the pH to 8-8.5. The mixture was stirred and reacted at 20℃ in the dark for 24h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 8000r / min for 20min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was placed in a vacuum dryer at 40℃ for 24h, then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0048] Preparation Example 8

[0049] Preparation of polydopamine-coated black phosphorus: 10g of black phosphorus was added to 300g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 9h under argon protection. Then, it was centrifuged at 4000r / min for 20min, and the supernatant was collected. The supernatant was then centrifuged at 12000r / min for 15min, and the precipitate was collected. The precipitate was then dispersed in a 1:1 mixture of anhydrous ethanol and deionized water, and sonicated for 1h. After deoxygenation by argon for 10min, 8g of chitosan was added and stirred until fully dissolved. Then, 10g of dopamine hydrochloride was added, and 0.1mol / L NaOH solution was added dropwise to adjust the pH to 8-8.5. The mixture was stirred and reacted at 25℃ in the dark for 12h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 12000r / min for 10min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was placed in a vacuum dryer at 50℃ for 12h, then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0050] Preparation Example 9

[0051] Preparation of polydopamine-coated black phosphorus: 8g of black phosphorus was added to 250g of anhydrous N,N-dimethylformamide, and sonicated in an ice bath for 8h under argon protection. Then, it was centrifuged at 3000r / min for 25min, and the supernatant was collected. The supernatant was then centrifuged again at 10000r / min for 25min, and the precipitate was collected. The precipitate was then dispersed in 250g of a 1:1 mixture of anhydrous ethanol and deionized water, and sonicated for 1h. After deoxygenation by argon for 10min, 5g of chitosan was added and stirred until fully dissolved. Subsequently, 8g of dopamine hydrochloride was added, and 0.1mol / L NaOH solution was added dropwise to adjust the pH to 8-8.5. The mixture was stirred and reacted at 23℃ in the dark for 20h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 10000r / min for 15min. The supernatant was discarded, and the precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid product was then vacuum dried at 45℃ for 20h, and then ground and passed through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

[0052] Preparation Example 10

[0053] Preparation of polydopamine-coated nano-silica: 50g of nano-silica and 1000g of deionized water were mixed and ultrasonically dispersed for 10min. Then, a uniform suspension was formed under magnetic stirring. 1g of tris(hydroxymethyl)aminomethane was added and stirred until completely dissolved. The pH value was adjusted to 8-8.5 using 0.5mol / L NaOH solution. 5g of dopamine hydrochloride was added and stirred continuously at 25℃ for 24h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 8000r / min for 20min. The supernatant was discarded. The precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid was vacuum dried at 40℃ for 24h. Then, it was ground and passed through a 200-mesh sieve to obtain polydopamine-coated nano-silica powder.

[0054] Preparation Example 11

[0055] Preparation of polydopamine-coated nano-silica: 60g of nano-silica and 1200g of deionized water were mixed and ultrasonically dispersed for 30min. Then, a uniform suspension was formed under magnetic stirring. 3g of tris(hydroxymethyl)aminomethane was added and stirred until completely dissolved. The pH value was adjusted to 8-8.5 using 0.5mol / L NaOH solution. 10g of dopamine hydrochloride was added and stirred continuously at 35℃ for 18h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 10000r / min for 10min. The supernatant was discarded. The precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid was vacuum dried at 50℃ for 12h. Then, it was ground and passed through a 200-mesh sieve to obtain polydopamine-coated nano-silica powder.

[0056] Preparation Example 12

[0057] Preparation of polydopamine-coated nano-silica: 55g of nano-silica and 1100g of deionized water were mixed and ultrasonically dispersed for 20min. Then, a uniform suspension was formed under magnetic stirring. 2g of tris(hydroxymethyl)aminomethane was added and stirred until completely dissolved. The pH value was adjusted to 8-8.5 using 0.5mol / L NaOH solution. 8g of dopamine hydrochloride was added and stirred continuously at 30℃ for 22h. After the reaction was completed, the product was transferred to a centrifuge tube and centrifuged at 9000r / min for 15min. The supernatant was discarded. The precipitate was washed three times alternately with deionized water and anhydrous ethanol. The washed solid was vacuum dried at 45℃ for 20h. Then, it was ground and passed through a 200-mesh sieve to obtain polydopamine-coated nano-silica powder.

[0058] Example 1

[0059] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 50 parts of high-density polyethylene, 15 parts of linear low-density polyethylene, 5 parts of manganese ion-doped zinc sulfide, 5 parts of polydopamine-coated nano-silica, 0.5 parts of coupling agent, 0.2 parts of lubricant, and 0.1 parts of polydopamine-coated black phosphorus. The manganese ion-doped zinc sulfide was prepared in Preparation Example 1, the polydopamine-coated nano-silica was prepared in Preparation Example 10, and the polydopamine-coated black phosphorus was prepared in Preparation Example 4. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0060] Example 2

[0061] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 70 parts of high-density polyethylene, 30 parts of linear low-density polyethylene, 8 parts of manganese ion-doped zinc sulfide, 10 parts of polydopamine-coated nano-silica, 2 parts of coupling agent, 1 part of lubricant, and 0.3 parts of polydopamine-coated black phosphorus. The manganese ion-doped zinc sulfide was prepared in Preparation Example 2, the polydopamine-coated nano-silica was prepared in Preparation Example 11, and the polydopamine-coated black phosphorus was prepared in Preparation Example 5. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0062] Example 3

[0063] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 60 parts of high-density polyethylene, 22 parts of linear low-density polyethylene, 6 parts of manganese ion-doped zinc sulfide, 8 parts of polydopamine-coated nano-silica, 1 part of coupling agent, 0.5 parts of lubricant, and 0.2 parts of polydopamine-coated black phosphorus. The manganese ion-doped zinc sulfide was prepared in Preparation Example 3, the polydopamine-coated nano-silica was prepared in Preparation Example 12, and the polydopamine-coated black phosphorus was prepared in Preparation Example 6. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0064] Example 4

[0065] The difference from Example 1 is that the polydopamine-coated black phosphorus was prepared in Preparation Example 7.

[0066] Example 5

[0067] The difference from Example 1 is that, by weight, the waterproof film also includes 0.5 parts of nano boron nitride.

[0068] Example 6

[0069] The difference from Example 5 is that nano boron nitride is replaced with nano silicon dioxide.

[0070] Example 7

[0071] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 50 parts of high-density polyethylene, 15 parts of linear low-density polyethylene, 5 parts of manganese ion-doped zinc sulfide, 5 parts of polydopamine-coated nano-silica, 0.5 parts of coupling agent, 0.2 parts of lubricant, 0.1 parts of polydopamine-coated black phosphorus, and 0.5 parts of nano-boron nitride. The manganese ion-doped zinc sulfide was prepared in Preparation Example 1, the polydopamine-coated nano-silica was prepared in Preparation Example 10, and the polydopamine-coated black phosphorus was prepared in Preparation Example 7. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0072] Example 8

[0073] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 70 parts of high-density polyethylene, 30 parts of linear low-density polyethylene, 8 parts of manganese ion-doped zinc sulfide, 10 parts of polydopamine-coated nano-silica, 2 parts of coupling agent, 1 part of lubricant, 0.3 parts of polydopamine-coated black phosphorus, and 2 parts of nano-boron nitride. The manganese ion-doped zinc sulfide was prepared in Preparation Example 2, the polydopamine-coated nano-silica was prepared in Preparation Example 11, and the polydopamine-coated black phosphorus was prepared in Preparation Example 8. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0074] Example 9

[0075] This application discloses an anti-ultraviolet waterproof fabric, comprising a base fabric and a waterproof film pressed onto the base fabric. The base fabric is a polyester base fabric with a thickness of 0.3 mm, and the waterproof film has a thickness of 0.15 mm. By weight, the waterproof film comprises 60 parts of high-density polyethylene, 22 parts of linear low-density polyethylene, 6 parts of manganese ion-doped zinc sulfide, 8 parts of polydopamine-coated nano-silica, 1 part of coupling agent, 0.5 parts of lubricant, 0.2 parts of polydopamine-coated black phosphorus, and 1.2 parts of nano-boron nitride. The manganese ion-doped zinc sulfide was prepared in Preparation Example 3, the polydopamine-coated nano-silica was prepared in Preparation Example 12, and the polydopamine-coated black phosphorus was prepared in Preparation Example 9. The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:1, and the coupling agent is a borate ester coupling agent.

[0076] Comparative Example 1

[0077] The difference from Example 1 is that a waterproof membrane without manganese ion doping zinc sulfide, polydopamine-coated nano-silica, and polydopamine-coated black phosphorus was used as a blank control group.

[0078] Comparative Example 2

[0079] The difference from Example 1 is that no manganese ion-doped zinc sulfide was added to the waterproof film.

[0080] Comparative Example 3

[0081] The difference from Example 1 is that the manganese ion-doped zinc sulfide is replaced with zinc sulfide.

[0082] Comparative Example 4

[0083] The difference from Example 1 is that no polydopamine-coated nano-silica was added to the waterproof film.

[0084] Comparative Example 5

[0085] The difference from Example 1 is that polydopamine-coated nano-silica is replaced with nano-silica.

[0086] Comparative Example 6

[0087] The difference from Example 1 is that no polydopamine-coated black phosphorus was added to the waterproof film.

[0088] Comparative Example 7

[0089] The difference from Example 1 is that polydopamine-coated black phosphorus is replaced with black phosphorus.

[0090] Comparative Example 8

[0091] The difference from Example 1 is that polydopamine-coated black phosphorus is replaced with polydopamine-coated nano-silica.

[0092] Performance testing

[0093] (1) Ultraviolet protection performance test: The waterproof fabric samples prepared in Examples 1-9 and Comparative Examples 1-8 were cut into circular samples with a diameter of 100 mm and placed under standard atmospheric conditions (temperature 20℃±2℃, relative humidity 65%±5%) for 4 h. The ultraviolet transmittance of the samples was measured in the wavelength range of 280 nm-400 nm using an ultraviolet-visible spectrophotometer. The ultraviolet protection factor UPF, UVA transmittance T(UVA) and UVB transmittance T(UVB) of the samples were calculated according to the standard GB / T 18830-2009 "Evaluation of Ultraviolet Protection Performance of Textiles". The test results are shown in Table 1 below.

[0094] (2) Tensile strength test: The waterproof fabric samples prepared in Examples 1-9 and Comparative Examples 1-8 were cut into rectangular strips of 250mm×50mm and tested according to standard GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking strength and elongation at break (strip method)". The parameters of the testing machine were: clamping distance 200mm; tensile speed 100mm / min. The maximum breaking strength (N) of the sample was recorded and the tensile strength (kN / m) was calculated. Five samples were tested for each group and the average value was recorded. The test results are shown in Table 2 below.

[0095] (3) Tear strength test: The waterproof fabric samples prepared in Examples 1-9 and Comparative Examples 1-8 were tested according to the standard GB / T3917.1-2009 "Textiles - Tear properties of fabrics - Part 1: Determination of tear strength by impact pendulum method". The tear strength of the samples was recorded. Each group was tested 5 times and the average value was taken. The test results are shown in Table 2 below.

[0096] (4) Aging test: The waterproof fabric samples prepared in Examples 1-9 and Comparative Examples 1-8 were tested according to standard GB / T16422.3-2014 "Laboratory Light Source Exposure Test Methods Part 3: Fluorescent Ultraviolet Lamp". The test conditions were: irradiance: 0.51W / m²@340nm; black standard temperature: 65℃±3℃; relative humidity: 50%±5%; after aging, the samples were left to stand for 4h under standard atmospheric conditions (temperature 20℃±2℃, relative humidity 65%±5%). Then, the tensile strength of the above samples was tested. The test results are shown in Table 3 below.

[0097] (5) Peel strength test: The waterproof fabric samples prepared in Examples 1 and 4 and Comparative Examples 1, 6, 7 and 8 were cut into strips of 250mm×25mm. The test was carried out in accordance with the standard GB / T 2792-2014 "Test method for peel strength of adhesive tape". The sample was peeled 50mm apart along the interface between the waterproof film and the base fabric. The two ends of the sample were clamped in the upper and lower jaws of the electronic universal testing machine. The peel angle was 180° and the tensile speed was 300mm / min. The peel strength (N / 25mm) was calculated. Each group was tested 5 times and the average value was taken. The test results are shown in Table 4 below.

[0098] Table 1. Results of UV Protection Performance Test

[0099] Example 1 52.8 1.82 1.65 Example 2 55.3 1.71 1.53 Example 3 54.1 1.76 1.59 Example 4 56.7 1.65 1.48 Example 5 62.5 1.43 1.27 Example 6 58.6 1.60 1.45 Example 7 65.8 1.31 1.18 Example 8 68.2 1.22 1.10 Example 9 66.9 1.27 1.14 Comparative Example 1 12.5 8.16 7.52 Comparative Example 2 25.5 3.9 3.5 Comparative Example 3 33.6 2.89 2.65 Comparative Example 4 32.5 3.11 2.86 Comparative Example 5 25.5 3.68 3.64 Comparative Example 6 35.8 2.67 2.43 Comparative Example 7 25.5 4.0 3.6 Comparative Example 8 30.5 3.2 2.9

[0100] Table 2. Results of tensile strength and tear strength tests before aging

[0101] Example 1 28.6 1280 Example 2 30.2 1350 Example 3 29.5 1310 Example 4 31.3 1420 Example 5 29.1 1300 Example 6 28.2 1240 Example 7 32.6 1480 Example 8 34.1 1540 Example 9 33.4 1510 Comparative Example 1 18.2 860 Comparative Example 2 24.5 1090 Comparative Example 3 25.8 1140 Comparative Example 4 22.8 980 Comparative Example 5 20.3 930 Comparative Example 6 23.7 1060 Comparative Example 7 20.5 940 Comparative Example 8 22.0 1010

[0102] Table 3. Aging Test Results

[0103] Example 1 82.3 Example 2 83.7 Example 3 83.1 Example 4 86.5 Example 5 88.2 Example 6 85.5 Example 7 90.5 Example 8 91.8 Example 9 91.2 Comparative Example 1 41.5 Comparative Example 2 58.5 Comparative Example 3 68.3 Comparative Example 4 62.5 Comparative Example 5 55.5 Comparative Example 6 65.5 Comparative Example 7 57.3 Comparative Example 8 61.0

[0104] Table 4. Peel Strength Test Results

[0105] Example 1 28.5 Example 4 35.2 Comparative Example 1 12.3 Comparative Example 6 18.6 Comparative Example 7 13.5 Comparative Example 8 16.5

[0106] In conclusion, the following conclusions can be drawn:

[0107] 1. Based on Example 1 and Comparative Examples 1-3 and Tables 1-4, it can be seen that adding manganese ion-doped zinc sulfide to the waterproof film can improve the UV resistance of the waterproof fabric. The reason may be that manganese ion-doped zinc sulfide can absorb ultraviolet light in the 280-400nm wavelength band and convert it into harmless fluorescence emission in the visible light range, thereby weakening the intensity of ultraviolet light acting on the polyethylene matrix and polyester base fabric, and delaying the breakage and degradation of polymer chains.

[0108] 2. Combining Example 1 and Comparative Examples 1, 4-5 with Table 1-4, it can be seen that adding polydopamine-coated nano-silica to the waterproof film can improve the UV resistance, tensile strength, and tear strength of the waterproof fabric. The reason may be that polydopamine-coated nano-silica improves the tensile strength and tear strength of the waterproof film through the rigidity of the nanoparticles themselves. On the other hand, polydopamine has excellent adhesion properties, which enhances the bonding force between the inorganic filler and the organic matrix by utilizing the polydopamine coating layer on the surface. In addition, its excellent UV shielding properties also construct a secondary UV barrier on the surface of the material, inhibiting the free radical chain reaction caused by ultraviolet rays.

[0109] 3. Combining Example 1 and Comparative Examples 1, 6-8, and Tables 1-4, it can be seen that adding polydopamine-coated black phosphorus to the waterproof film can improve the UV resistance and peel strength of the waterproof fabric. The reason may be that the lamellar structure of black phosphorus forms a physical covering barrier at the interface, physically blocking the interface gaps where ultraviolet rays may penetrate, and preventing the aging and corrosion of the polyester base fabric caused by ultraviolet rays from microscopic defects. Furthermore, by coating the surface of black phosphorus with polydopamine, the polydopamine coating layer has a three-dimensional cross-linked network structure with a moderate porosity. While inhibiting the rapid oxidation of the black phosphorus body, it allows a moderate amount of water vapor to penetrate to promote the controlled oxidation of the black phosphorus surface to generate phosphate groups. These groups can react with the hydroxyl / carboxyl groups at the end of the polyester base fabric to form stable hydrogen bonds or esterification bonds, thereby forming an interfacial chemical anchoring structure between the black phosphorus and the polyester base fabric, which improves the interlayer bonding and peel strength.

[0110] 4. Combining Examples 1 and 4 with Tables 1-4, it can be seen that adding chitosan in the preparation of polydopamine-coated black phosphorus can improve the peel strength of the waterproof fabric. The reason may be that the amino and hydroxyl groups on the chitosan molecular chain form a dense double-network interpenetrating structure with polydopamine, which has higher mechanical strength. In addition, the amino and hydroxyl groups on the chitosan molecular chain can also form more hydrogen bonds and covalent bonding sites with the hydroxyl / carboxyl groups at the end of the polyester base fabric, which enhances the interfacial bonding force between the waterproof film and the base fabric.

[0111] 5. As can be seen from Examples 1, 5, and 6 and Tables 1-4, adding nano-boron nitride to the waterproof film can improve the UV resistance and anti-aging effect of the waterproof fabric. The reason may be that nano-boron nitride has extremely high reflectivity and scattering rate for ultraviolet rays in the 200-300nm wavelength band, which can work synergistically with manganese ion-doped zinc sulfide and polydopamine coating layer to achieve multi-layer shielding against ultraviolet rays. On the other hand, nano-boron nitride has extremely high in-plane thermal conductivity, which can conduct away the local heat generated by ultraviolet absorption or friction during outdoor exposure, avoiding softening, deformation or thermal aging of the material due to heat accumulation, thus improving the safety and weather resistance of the waterproof fabric.

[0112] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A UV-resistant waterproof fabric, comprising a base fabric and a waterproof film laminated onto the base fabric, characterized in that: The base fabric is polyester base fabric, and by weight, the waterproof film comprises 50-70 parts high-density polyethylene, 15-30 parts linear low-density polyethylene, 5-8 parts manganese ion-doped zinc sulfide, 5-10 parts polydopamine-coated nano silica, 0.5-2 parts coupling agent, 0.2-1 parts lubricant, and 0.1-0.3 parts polydopamine-coated black phosphorus; The preparation method of the manganese ion-doped zinc sulfide by weight is as follows: 5-6 parts of zinc acetate and 0.1-0.2 parts of manganese acetate are added to 70-90 parts of deionized water, followed by 5-7 parts of oleic acid. The mixture is stirred in a water bath at 65-75°C for 25-35 minutes and is denoted as solution A. Dissolve 5.5-6.5 parts of thiourea in 35-45 parts of deionized water to form solution B; Under stirring, solution B is added dropwise to solution A. After the addition is complete, the pH is adjusted to 10-11 using NaOH solution. The mixture is then kept at 125-135℃ for 7-9 hours. The reaction product is then transferred to a centrifuge tube and centrifuged at 9000-11000 rpm for 12-18 minutes. The supernatant is discarded, and the bottom solid precipitate is collected. The precipitate is washed alternately with deionized water and anhydrous ethanol, and this process is repeated 3 times. The washed solid product is then dried at 50-60℃ for 8-12 hours. Finally, it is ground through a 200-mesh sieve to obtain manganese ion-doped zinc sulfide powder.

2. The UV-resistant waterproof fabric according to claim 1, characterized in that: The preparation method of the polydopamine-coated black phosphorus, by weight, is as follows: 0.5-1 parts of black phosphorus are added to 20-30 parts of anhydrous N,N-dimethylformamide, and ultrasonically treated in an ice bath under argon protection for 6-9 hours. Then, the mixture is centrifuged at 2000-4000 r / min for 20-30 minutes, and the supernatant is collected. The mixture is then centrifuged at 9000-12000 r / min for 15-30 minutes, and the precipitate is collected. The precipitate is then dispersed in a mixed solution of 20-30 parts of anhydrous ethanol and deionized water (volume ratio 1:1), ultrasonically treated for 0.5-1 hour, and deoxygenated by argon gas for 1 hour. Add 0.5-1 part of dopamine hydrochloride, and adjust the pH to 8-8.5 by adding NaOH solution dropwise. Stir and react at 20-25℃ in the dark for 12-24 hours. After the reaction is complete, transfer the product to a centrifuge tube and centrifuge at 8000-12000 r / min for 10-20 minutes. Discard the supernatant and wash the precipitate three times alternately with deionized water and anhydrous ethanol. Place the washed solid product in a vacuum dryer at 40-50℃ for 12-24 hours, then grind and pass through a 200-mesh sieve to obtain polydopamine-coated black phosphorus powder.

3. The UV-resistant waterproof fabric according to claim 2, characterized in that: In the preparation method of polydopamine-coated black phosphorus, after purging with argon gas for 10 min to remove oxygen, 0.3-0.8 parts of chitosan are added and stirred until fully dissolved. Then, 0.5-1 parts of dopamine hydrochloride are added, and 0.1 mol / L NaOH solution is added dropwise to adjust the pH to 8-8.

5. The reaction is carried out at 20-25℃ in the dark with stirring for 12-24 h.

4. The UV-resistant waterproof fabric according to claim 1, characterized in that: The waterproof film also includes 0.5-2 parts by weight of nano boron nitride.

5. The UV-resistant waterproof fabric according to claim 1, characterized in that: The preparation method of the polydopamine-coated nano-silica by weight is as follows: 5-6 parts of nano-silica and 100-120 parts of deionized water are mixed and ultrasonically dispersed for 10-30 min. Then, a uniform suspension is formed under magnetic stirring. 0.1-0.3 parts of tris(hydroxymethyl)aminomethane are added and stirred until completely dissolved. The pH value is adjusted to 8-8.5 using NaOH solution. 0.5-1 parts of dopamine hydrochloride are added and stirred continuously at 25-35℃ for 18-24 h. After the reaction is completed, the product is transferred to a centrifuge tube and centrifuged at 8000-10000 r / min for 10-20 min. The supernatant is discarded, and the precipitate is washed three times alternately with deionized water and anhydrous ethanol. The washed solid is vacuum dried at 40-50℃ for 12-24 h, then ground and passed through a 200-mesh sieve to obtain polydopamine-coated nano-silica powder.

6. The UV-resistant waterproof fabric according to claim 1, characterized in that: The lubricant is a mixture of vinyl bis-stearamide and low molecular weight polyethylene wax in a mass ratio of 1:

1.

7. The UV-resistant waterproof fabric according to claim 1, characterized in that: The coupling agent is a borate ester coupling agent.