A method for preparing a long-lasting stain-resistant fabric

Abstract

This invention discloses a method for preparing a long-lasting stain-resistant fabric, relating to the field of fabric technology. The long-lasting stain-resistant fabric prepared by this invention comprises, from the inside out, Lycra fabric, foamed rubber, and a stain-resistant film. The stain-resistant film is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin. The modified cyclodextrin is obtained by grafting a hydroxylamine polymer onto mercapto-carboxymethyl-cyclodextrin, which enhances stability and introduces a large number of hydroxyl groups, enhancing hydrophilicity and giving the fabric stain resistance. It also increases the density of the stain-resistant film, thereby enhancing the fabric's tear resistance. The foamed rubber is prepared by vulcanizing and foaming a blend of chloroprene rubber, polyurethane rubber, and fluorinated polyether nitrile. The addition of polyurethane rubber accelerates the vulcanization speed and improves the tear resistance of the foamed rubber. It also tightly bonds the Lycra fabric, foamed rubber, and stain-resistant film, enhancing the fabric's peel strength and extending its service life.

Description

Technical Field

[0001] This invention relates to the field of fabric technology, specifically to a method for preparing a long-lasting stain-resistant fabric. Background Technology

[0002] Diving originally referred to activities involving entering the water below the surface, with or without specialized equipment, for underwater exploration, salvage, repair, and underwater engineering. Later, diving gradually evolved into a recreational sport primarily focused on underwater activities, aiming to improve physical fitness and provide leisure, and has become widely popular. Diving suits are essential equipment for diving, preventing rapid heat loss and hypothermia, and also protecting divers from reefs and harmful plants and animals.

[0003] However, when working underwater for extended periods or diving, anti-fouling is particularly important. Microorganisms and bacteria in seawater can affect diving suits, ranging from reducing their lifespan to causing them to tear and injure divers. Therefore, this invention researches and prepares a long-lasting anti-fouling fabric suitable for manufacturing diving suits, which has good tear resistance and a long service life. Summary of the Invention

[0004] The purpose of this invention is to provide a long-lasting stain-resistant fabric and its preparation method to solve the problems mentioned in the background art.

[0005] A long-lasting stain-resistant fabric, comprising Lycra fabric, foamed rubber, and stain-resistant membrane from the inside out, wherein the foamed rubber is obtained by vulcanization and foaming a blend of neoprene rubber, polyurethane rubber, and fluorinated polyether nitrile.

[0006] Preferably, the fluorinated polyether nitrile is prepared from 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile and N-methylpyrrolidone.

[0007] Preferably, the antifouling membrane is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin.

[0008] Preferably, the modified cyclodextrin is prepared by grafting a hydroxylamine polymer onto a mercapto-carboxymethyl-cyclodextrin.

[0009] Preferably, the method for preparing the long-lasting stain-resistant fabric includes the following specific steps:

[0010] (1) Disperse carboxymethyl-cyclodextrin in deionized water at 8-10 times its mass, and add sodium hydroxide solution at 3-5 ml / min at 10-20 rpm at 0.1-0.15 times its mass and a mass fraction of 3-5% at 0.45-0.5 times its mass and a mass fraction of 10-20% at 0.45-0.5 times its mass and a mass fraction of 10-20% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.5% at 0.45-0.50 rpm. After addition, stir the reaction at 22-25°C and 800-1000 rpm for 2-3 hours. Centrifuge to obtain the supernatant. Let the supernatant stand at 0-4°C for 6-8 hours to form a precipitate. Recrystallize the precipitate twice with deionized water as the solvent, and then at -50 to -60°C. Sulfonated-carboxymethyl-cyclodextrin was prepared by freeze-drying at ℃. Sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol, and deionized water were mixed in a mass ratio of 1:1:6:3~1.2:1.2:8:4, heated in a water bath to 80~85℃, and refluxed for 48h. After rotary evaporation, a white precipitate was obtained. The white precipitate was washed 3~5 times with anhydrous methanol, and then dissolved in 5~8 times the mass of the white precipitate with a 10~15% sodium hydroxide solution. The solution was placed at 50~60℃ for 5~6h, and the pH was adjusted to 2~2.5 with hydrochloric acid. Then, 0.04~0.08 times the mass of the white precipitate with trichloroethylene was added, and the temperature was lowered to 20~25℃ for 1~2h. Finally, the solution was filtered and recrystallized to obtain mercapto-carboxymethyl-cyclodextrin.

[0011] (2) Disperse the hydroxylamine polymer in anhydrous methanol at 6.5 to 7.5 times the mass of the hydroxylamine polymer, add 0.15 to 0.2 times the mass of the hydroxylamine polymer in dimethylolpropionic acid and 0.8 to 0.9 times the mass of the hydroxylamine polymer in mercapto-carboxymethyl-cyclodextrin, bubble with nitrogen for 20 to 30 minutes, react under 365 nm ultraviolet light for 10 to 12 hours, add 2 to 3 times the mass of the hydroxylamine polymer in dimethylolpropionic acid, continue to react under ultraviolet light for 3 to 5 hours, centrifuge with diethyl ether to obtain the supernatant, place the supernatant in a vacuum drying oven at 40 to 50 °C and dry to constant weight to obtain modified cyclodextrin;

[0012] (3) Mix hyperbranched polyglycidyl ether and modified cyclodextrin at a mass ratio of 5:1 to 8:1, heat to 90 to 120°C, stir at 50 to 100 rpm, and add 0.2 to 0.3 times the mass of modified cyclodextrin and 98% concentrated sulfuric acid at a rate of 3 to 5 ml / min. After stirring and reacting for 24 to 36 hours, add 0.03 to 0.05 times the mass of hyperbranched polyglycidyl ether and dibutyl phthalate as plasticizer, and stir evenly to obtain antifouling film slurry;

[0013] (4) Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile and plasticizer are put into a mixer and mixed at 900~1000 rpm for 5~8 min. The temperature is raised to 105~110℃, and then foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide are added. Mixing is continued for 3~5 min. The mixture is filtered and pressed into sheets through a rubber extruder to obtain rubber sheets. The rubber sheets are placed in a flat vulcanizing agent mold and vulcanized at a temperature of 140~145℃ and a pressure of 130~135 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 15-20 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 130-135℃ and at a pressure of 130-135 kg / cm². 2 Next, vulcanization and foaming are carried out again. After 10-12 minutes, the mold is opened to obtain foamed rubber with a thickness of 100-160μm.

[0014] (5) Coat both sides of Lycra with a water-based polyurethane adhesive with a thickness of 5~10μm, bond it with foamed rubber, let it stand for 30~50min, scrape the edge and coat it with an anti-fouling film slurry with a thickness of 50~80μm, let it stand for 3~7d to obtain a long-lasting anti-fouling fabric.

[0015] Preferably, in step (1) above, the preparation method of carboxymethyl-cyclodextrin is as follows: cyclodextrin, sodium hydroxide and deionized water are mixed in a mass ratio of 4.2:3.5:18~4.5:3.6:20, stirred until dissolved, and then sodium chloroacetate of 1.8~2 times the mass of cyclodextrin is added. The mixture is stirred at 30~50 rpm for 3~5 h. After cooling to room temperature, the pH is adjusted to 4.8~5 with hydrochloric acid, and methanol of 5~8 times the mass of cyclodextrin is added for precipitation. After precipitation, the mixture is filtered and dried in a vacuum drying oven at 80~90℃ to constant weight to obtain carboxymethyl-cyclodextrin.

[0016] Preferably, in step (2) above, the preparation method of the hydroxylamine polymer is as follows: 1,4-butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol are mixed in a mass ratio of 8.4:3:4~8.6:3:5, stirred at 300~500 rpm for 70~72 h, stirring is continued and ether is added dropwise until the solution is clear, the ether is poured out and transferred to a vacuum drying oven at 40~50℃ for drying for 10~12 h to obtain the hydroxylamine polymer.

[0017] Preferably, in step (4) above, the preparation method of fluorinated polyether nitrile is as follows: 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone and toluene are mixed in a mass ratio of 1:1:1:5:5~1:1.1:1.1:8:8, heated to 150~180℃ under argon atmosphere, reacted for 2~3h, and 0.1~0.15 times the amount of 2,6-dichlorobenzonitrile in 2,6-difluoro After reacting with 2,6-dichlorobenzonitrile for 1-2 hours, the temperature was raised to 200-205℃ and the reaction was continued for 0.5-1 hour. Then, 0.05-0.08 times the amount of 2,6-difluorobenzonitrile was added, and the reaction was continued for 20-30 minutes. The precipitate was obtained with methanol, filtered, and then washed 3-5 times with methanol and hot water at 70-90℃. Finally, the fluorinated polyether nitrile was dried to constant weight in a drying oven at 120℃ to obtain the fluorinated polyether nitrile.

[0018] Preferably, in step (4) above: by weight, the foamed rubber contains 45-55 parts of chloroprene rubber, 15-20 parts of polyurethane rubber, 3-5 parts of carbon black, 3-5 parts of paraffin wax, 0.04-0.06 parts of antioxidant D, 10-20 parts of fluorinated polyether nitrile, 8-12 parts of plasticizer, 8-10 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.4-0.6 parts of vulcanization accelerator TMTD, and 2-4 parts of zinc oxide.

[0019] Preferably, in step (5) above: the Lycra book weight is 100~160g / cm³. 2 .

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The long-lasting anti-fouling fabric prepared by this invention consists of Lycra fabric, foamed rubber, and an anti-fouling membrane from the inside out. It has excellent anti-fouling and tear-resistant properties and is suitable for making diving suits.

[0022] The antifouling membrane is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin. The modified cyclodextrin is obtained by grafting hydroxylamine polymers onto mercapto-carboxymethyl-cyclodextrin. Introducing thiol groups onto carboxymethyl-cyclodextrin allows them to react with the double bonds on the hydroxylamine polymer, forming a long-chain modified cyclodextrin that enhances stability. Simultaneously, grafting the hydroxylamine polymer onto the mercapto-carboxymethyl-cyclodextrin introduces a large number of hydroxyl groups, enhancing hydrophilicity. This allows a dense hydrated layer to form on the surface of the antifouling membrane, trapping proteins and other contaminants. Unable to penetrate the dense hydration layer, it reduces interaction with the fabric surface, thus providing stain resistance. The carboxyl groups on the modified cyclodextrin react with the hydroxyl groups on the hyperbranched polyglycidyl ether, introducing modified cyclodextrin with a large number of hydroxyl groups and long chains into the hyperbranched polyglycidyl ether. With the stability of cyclodextrin in seawater, the stability of the anti-fouling film is enhanced, thus increasing the service life of the fabric. At the same time, the long chains of the modified cyclodextrin are entangled on the hyperbranched polyglycidyl ether, which increases the density of the anti-fouling film, thereby enhancing the tear resistance of the fabric.

[0023] Foamed rubber is made by vulcanizing and foaming a blend of chloroprene rubber, polyurethane rubber, and fluorinated polyether nitrile. The addition of polyurethane rubber accelerates the vulcanization speed and improves the tear resistance of the foamed rubber. Vulcanization with fluorinated polyether nitrile as a curing agent results in the foamed rubber having nitrile groups after vulcanization. When bonded with water-based polyurethane adhesive, the water hydrolyzes the nitrile groups into carboxyl groups, accelerating the bonding speed. The generated carboxyl groups can also react with the hydroxyl groups on the water-based polyurethane adhesive and the anti-fouling film to tightly bond the Lycra fabric, foamed rubber, and anti-fouling film, enhancing the peel strength of the fabric. At the same time, fluorine is introduced into the foamed rubber layer, making the anti-fouling layer hydrophilic while the foamed rubber is hydrophobic, thus enhancing the service life of the fabric. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the long-lasting stain-resistant fabrics prepared in the embodiments and comparative examples are as follows:

[0026] Stain resistance: The long-lasting stain-resistant fabrics prepared by the same area of ​​the embodiment and the comparative example were tested for water contact angle using a surface contact angle tester.

[0027] Tear resistance: Long-lasting stain-resistant fabrics prepared by the same area of ​​the embodiment and the comparative example were tested for tear strength in accordance with GB / T529.

[0028] Service life: The long-lasting anti-fouling fabrics prepared in the same area as the embodiment and the comparative example were washed with seawater at the same flow rate for 48 hours, and the water contact angle was tested using a surface contact angle tester.

[0029] Peel strength: The long-lasting stain-resistant fabrics prepared by the examples and comparative examples of the same area were tested for peel strength in accordance with DIN53273.

[0030] Example 1

[0031] (1) The preparation method of carboxymethyl-cyclodextrin is as follows: cyclodextrin, sodium hydroxide and deionized water are mixed in a mass ratio of 4.2:3.5:18 and stirred until dissolved. Then, sodium chloroacetate with a mass of 1.8 times that of cyclodextrin is added. The mixture is stirred at 30 rpm for 3 h. After cooling to room temperature, the pH is adjusted to 4.8 with hydrochloric acid and methanol with a mass of 5 times that of cyclodextrin is added for precipitation. After precipitation, the mixture is filtered and dried in a vacuum drying oven at 80℃ until constant weight to obtain carboxymethyl-cyclodextrin.

[0032] (2) Disperse carboxymethyl-cyclodextrin in deionized water at 8 times its mass, and add sodium hydroxide solution at 3 ml / min at 10 rpm, equal to 0.1 times the mass of carboxymethyl-cyclodextrin, with a mass fraction of 3-5%. Continue stirring and add acetonitrile solution of p-toluenesulfonyl chloride at 10% mass fraction, equal to 0.45 times the mass of carboxymethyl-cyclodextrin, with a mass fraction of 3-5 ml / min. After addition, stir the reaction at 22℃ and 800 rpm for 2 h, centrifuge to obtain the supernatant, and let the supernatant stand at 0℃ for 6 h to produce a precipitate. Recrystallize the precipitate twice with deionized water as solvent, and then... Sulfonated-carboxymethyl-cyclodextrin was prepared by freeze-drying at 50℃. Sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol, and deionized water were mixed in a mass ratio of 1:1:6:3, heated in a water bath to 80℃, and refluxed for 48 hours. After rotary evaporation, a white precipitate was obtained. The white precipitate was washed three times with anhydrous methanol, and then dissolved in a 10% sodium hydroxide solution with a mass ratio of 5 times that of the white precipitate. The mixture was placed at 50℃ for 5 hours, and the pH was adjusted to 2 with hydrochloric acid. Then, trichloroethylene with a mass ratio of 0.04 times that of the white precipitate was added, and the mixture was cooled to 20℃ for 1 hour. Finally, the mixture was filtered and recrystallized to obtain mercapto-carboxymethyl-cyclodextrin.

[0033] (3) 1,4-Butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol were mixed in a mass ratio of 8.4:3:4 and stirred at 300 rpm for 70 h. Stirring was continued and ether was added dropwise until the solution was clear. The ether was poured out and transferred to a vacuum drying oven at 40 °C for 10 h to obtain hydroxylamine polymer. The hydroxylamine polymer was dispersed in anhydrous methanol at a mass of 6.5 times that of the hydroxylamine polymer. Dimethylolpropionic acid at a mass of 0.15 times that of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin at a mass of 0.8 times that of the hydroxylamine polymer were added. After bubbling with nitrogen for 20 min, the mixture was reacted under ultraviolet light at 365 nm for 10 h. Dimethylolpropionic acid at a mass of 2 times that of the hydroxylamine polymer was added and the mixture was reacted under ultraviolet light for another 3 h. The supernatant was obtained by centrifugation with ether and dried in a vacuum drying oven at 40 °C to constant weight to obtain modified cyclodextrin.

[0034] (4) Mix hyperbranched polyglycidyl ether and modified cyclodextrin at a mass ratio of 5:1, heat to 90°C, stir at 50 rpm, and add concentrated sulfuric acid with a mass fraction of 98% at a rate of 3 ml / min. After stirring and reacting for 24 h, add plasticizer dibutyl phthalate with a mass ratio of 0.03 times that of hyperbranched polyglycidyl ether, and stir evenly to obtain antifouling film slurry;

[0035] (5) Mix 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone, and toluene in a mass ratio of 1:1:1:5:5. Under argon atmosphere, heat to 150°C and react for 2 hours. Add 0.1 times the amount of 2,6-dichlorobenzonitrile in 2,6-difluorobenzonitrile and continue reacting for 1 hour. Then heat to 200°C and react for 0.5 hours. Add 0.05 times the amount of 2,6-dichlorobenzonitrile in 2,6-difluorobenzonitrile and continue reacting for 20 minutes. Precipitate with methanol, filter, and then precipitate with methanol and heat at 70°C. The mixture was washed three times with water and then dried to constant weight in a 120℃ drying oven to obtain fluorinated polyether nitrile. Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile, and plasticizer were added to a mixer and mixed at 900 rpm for 5 minutes. The temperature was then raised to 105℃, and foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD, and zinc oxide were added. Mixing continued for 3 minutes. The mixture was then filtered and pressed into sheets using a rubber extruder to obtain rubber sheets. The rubber sheets were placed in a flat vulcanizing mold and subjected to vulcanization at 140℃ and 130 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 15 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 130℃ and at a pressure of 130 kg / cm². 2 Next, vulcanization and foaming are carried out again. After 10 minutes, the mold is opened to obtain foamed rubber with a thickness of 100μm. The foamed rubber contains, by weight, 45 parts of chloroprene rubber, 15 parts of polyurethane rubber, 3 parts of carbon black, 3 parts of paraffin wax, 0.04 parts of antioxidant D, 10 parts of fluorinated polyether nitrile, 8 parts of plasticizer, 8 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.4 parts of vulcanization accelerator TMTD, and 2 parts of zinc oxide.

[0036] (6) At a weight of 100 g / cm 2 Lycra fabric is coated with a 5μm thick water-based polyurethane adhesive on both sides and bonded with foamed rubber. After standing for 30 minutes, the edges are scraped and coated with a 50μm thick anti-fouling film slurry. After standing for 3 days, a long-lasting anti-fouling fabric is obtained.

[0037] Example 2

[0038] (1) The preparation method of carboxymethyl-cyclodextrin is as follows: cyclodextrin, sodium hydroxide and deionized water are mixed in a mass ratio of 4.4:3.5:19 and stirred until dissolved. Then, sodium chloroacetate with a mass of 1.9 times that of cyclodextrin is added. The mixture is stirred at 40 rpm for 4 h. After cooling to room temperature, the pH is adjusted to 4.9 with hydrochloric acid and methanol with a mass of 6 times that of cyclodextrin is added for precipitation. After precipitation, the mixture is filtered and dried in a vacuum drying oven at 85℃ to constant weight to obtain carboxymethyl-cyclodextrin.

[0039] (2) Disperse carboxymethyl-cyclodextrin in deionized water at 9 times its mass, and add sodium hydroxide solution at 0.13 times its mass (4% by mass) of carboxymethyl-cyclodextrin dropwise at 4 ml / min at 15 rpm. Continue stirring and add acetonitrile solution of p-toluenesulfonyl chloride at 0.48 times its mass (15% by mass) of carboxymethyl-cyclodextrin dropwise at 4 ml / min. After the addition, stir the reaction at 24℃ and 900 rpm for 2 h, centrifuge to obtain the supernatant, let the supernatant stand at 2℃ for 7 h to form a precipitate, recrystallize the precipitate twice with deionized water as solvent, and then at -55℃. Sulfonated-carboxymethyl-cyclodextrin was prepared by freeze drying. Sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol, and deionized water were mixed in a mass ratio of 1.1:1.1:7:3 and heated to 83°C in a water bath. After reflux for 48 hours, a white precipitate was obtained by rotary evaporation. The white precipitate was washed four times with anhydrous methanol and then dissolved in a 13% sodium hydroxide solution (6 times the mass of the white precipitate). The solution was placed at 55°C for 5 hours and the pH was adjusted to 2 with hydrochloric acid. Trichloroethylene (0.06 times the mass of the white precipitate) was added, and the solution was cooled to 23°C and reacted for 1 hour. Finally, the solution was filtered and recrystallized to obtain mercapto-carboxymethyl-cyclodextrin.

[0040] (3) 1,4-Butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol were mixed in a mass ratio of 8.5:3:5 and stirred at 400 rpm for 71 h. Stirring was continued and ether was added dropwise until the solution was clear. The ether was poured out and transferred to a vacuum drying oven at 45 °C for 11 h to obtain hydroxylamine polymer. The hydroxylamine polymer was dispersed in anhydrous methanol at 7 times the mass of the hydroxylamine polymer. Dimethylolpropionic acid at 0.18 times the mass of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin at 0.85 times the mass of the hydroxylamine polymer were added. After bubbling with nitrogen for 25 min, the reaction was carried out under ultraviolet light at 365 nm for 11 h. Dimethylolpropionic acid at 2 times the mass of the hydroxylamine polymer was added and the reaction was carried out under ultraviolet light for 4 h. The supernatant was obtained by centrifugation with ether and placed in a vacuum drying oven at 45 °C to dry to constant weight to obtain modified cyclodextrin.

[0041] (4) Hyperbranched polyglycidyl ether and modified cyclodextrin are mixed at a mass ratio of 6:1, heated to 110°C, stirred at 80 rpm, and 0.25 times the mass of modified cyclodextrin and 98% concentrated sulfuric acid are added dropwise at a rate of 4 ml / min. After stirring and reacting for 28 h, 0.04 times the mass of hyperbranched polyglycidyl ether and 0.04 times the mass of plasticizer dibutyl phthalate are added and stirred evenly to obtain antifouling film slurry.

[0042] (5) Mix 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone, and toluene in a mass ratio of 1:1:1:8:8. Under argon atmosphere, heat to 160°C and react for 2 hours. Add 0.1 times the amount of 2,6-difluorobenzonitrile and continue reacting for 1 hour. Then heat to 202°C and react for 0.5 hours. Add 0.06 times the amount of 2,6-dichlorobenzonitrile and continue reacting for 25 minutes. Precipitate with methanol, filter, and then precipitate with methanol and heat at 80°C. The mixture was washed four times with water and then dried to constant weight in a 120℃ drying oven to obtain fluorinated polyether nitrile. Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile, and plasticizer were added to a mixer and mixed at 950 rpm for 6 minutes. The temperature was then raised to 108℃, and foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD, and zinc oxide were added. Mixing continued for 4 minutes. The mixture was then filtered and pressed into sheets using a rubber extruder to obtain rubber sheets. The rubber sheets were placed in a flat vulcanizing mold and subjected to vulcanization at 143℃ and a pressure of 133 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 16 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 133℃ and at a pressure of 133 kg / cm². 2 Next, vulcanization and foaming were carried out again. After 11 minutes, the mold was opened to obtain foamed rubber with a thickness of 120μm. The foamed rubber contained, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin wax, 0.05 parts of antioxidant D, 15 parts of fluorinated polyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.5 parts of vulcanization accelerator TMTD, and 3 parts of zinc oxide.

[0043] (6) At a weight of 130 g / cm 2 Lycra fabric is coated with an 8μm thick water-based polyurethane adhesive on both sides and bonded with foamed rubber. After standing for 40 minutes, the edges are scraped and coated with a 65μm thick anti-fouling film slurry. After standing for 5 days, a long-lasting anti-fouling fabric is obtained.

[0044] Example 3

[0045] (1) The preparation method of carboxymethyl-cyclodextrin is as follows: cyclodextrin, sodium hydroxide and deionized water are mixed in a mass ratio of 4.5:3.6:20 and stirred until dissolved. Then, sodium chloroacetate with a mass of 2 times that of cyclodextrin is added. The mixture is stirred at 50 rpm for 5 h. After cooling to room temperature, the pH is adjusted to 5 with hydrochloric acid, and methanol with a mass of 8 times that of cyclodextrin is added for precipitation. After precipitation, the mixture is filtered and dried in a vacuum drying oven at 90℃ to constant weight to obtain carboxymethyl-cyclodextrin.

[0046] (2) Disperse carboxymethyl-cyclodextrin in deionized water at 10 times its mass, and add sodium hydroxide solution at 0.15 times its mass (5% by weight) of carboxymethyl-cyclodextrin at a rate of 5 ml / min at 10-20 rpm. Continue stirring and add acetonitrile solution of p-toluenesulfonyl chloride at 0.5 times its mass (20% by weight) of carboxymethyl-cyclodextrin at a rate of 5 ml / min. After addition, stir and react at 25℃ and 1000 rpm for 3 h. Centrifuge to obtain supernatant, let supernatant stand at 4℃ for 8 h to form precipitate, recrystallize the precipitate twice with deionized water as solvent, and then at -60℃. Sulfonated-carboxymethyl-cyclodextrin was prepared by freeze drying. Sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol, and deionized water were mixed in a mass ratio of 1.2:1.2:8:4 and heated to 85°C in a water bath. After reflux for 48 hours, a white precipitate was obtained by rotary evaporation. The white precipitate was washed five times with anhydrous methanol and then dissolved in 15% sodium hydroxide solution (8 times the mass of the white precipitate). The mixture was placed at 60°C for 6 hours and the pH was adjusted to 2.5 with hydrochloric acid. Trichloroethylene (0.08 times the mass of the white precipitate) was added, and the mixture was cooled to 25°C and reacted for 1-2 hours. Finally, the mixture was filtered and recrystallized to obtain mercapto-carboxymethyl-cyclodextrin.

[0047] (3) 1,4-Butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol were mixed in a mass ratio of 8.6:3:5 and stirred at 500 rpm for 72 h. Stirring was continued and ether was added dropwise until the solution was clear. The ether was poured out and transferred to a vacuum drying oven at 50 °C for 12 h to obtain hydroxylamine polymer. The hydroxylamine polymer was dispersed in anhydrous methanol at a mass of 7.5 times that of the hydroxylamine polymer. Dimethylolpropionic acid at a mass of 0.2 times that of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin at a mass of 0.9 times that of the hydroxylamine polymer were added. After bubbling with nitrogen for 30 min, the reaction was carried out under ultraviolet light at 365 nm for 12 h. Dimethylolpropionic acid at a mass of 3 times that of the hydroxylamine polymer was added and the reaction was carried out under ultraviolet light for 5 h. The supernatant was obtained by centrifugation with ether and placed in a vacuum drying oven at 50 °C to dry to constant weight to obtain modified cyclodextrin.

[0048] (4) Mix hyperbranched polyglycidyl ether and modified cyclodextrin at a mass ratio of 8:1, heat to 120°C, stir at 100 rpm, and add concentrated sulfuric acid with a mass fraction of 98% at a rate of 5 ml / min. After stirring and reacting for 36 h, add dibutyl phthalate plasticizer with a mass ratio of 0.05 times that of hyperbranched polyglycidyl ether, and stir evenly to obtain antifouling film slurry;

[0049] (5) Mix 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone, and toluene in a mass ratio of 1:1.1:1.1:8:8. Under argon atmosphere, heat to 180°C and react for 3 hours. Add 0.15 times the amount of 2,6-dichlorobenzonitrile in 2,6-difluorobenzonitrile and continue reacting for 2 hours. Then heat to 205°C and react for 1 hour. Add 0.08 times the amount of 2,6-dichlorobenzonitrile in 2,6-difluorobenzonitrile and continue reacting for 30 minutes. Precipitate with methanol, filter, and then precipitate with methanol and 90°C. The mixture was washed five times with hot water and then dried to constant weight in a 120℃ drying oven to obtain fluorinated polyether nitrile. Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile, and plasticizer were added to a mixer and mixed at 1000 rpm for 8 minutes. The temperature was then raised to 110℃, and foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD, and zinc oxide were added. Mixing continued for 5 minutes. The mixture was then filtered and pressed into sheets using a rubber extruder to obtain rubber sheets. The rubber sheets were placed in a flat vulcanizing mold and subjected to vulcanization at 145℃ and a pressure of 135 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 20 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 135℃ and at a pressure of 135 kg / cm². 2 Next, vulcanization and foaming were carried out again. After 12 minutes, the mold was opened to obtain foamed rubber with a thickness of 160μm. The foamed rubber contained, by weight, 55 parts of chloroprene rubber, 20 parts of polyurethane rubber, 5 parts of carbon black, 5 parts of paraffin wax, 0.06 parts of antioxidant D, 20 parts of fluorinated polyether nitrile, 12 parts of plasticizer, 10 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.6 parts of vulcanization accelerator TMTD, and 4 parts of zinc oxide.

[0050] (6) At a weight of 160 g / cm 2 Lycra fabric is coated with a 10μm thick water-based polyurethane adhesive on both sides and bonded with foamed rubber. After standing for 50 minutes, the edges are scraped and coated with an 80μm thick anti-fouling film slurry. After standing for 7 days, a long-lasting anti-fouling fabric is obtained.

[0051] Comparative Example 1

[0052] The formulation of Comparative Example 1 is the same as that of Example 2. The difference between the preparation method of this long-lasting stain-resistant fabric and Example 2 is that step (2) is not performed, and step (3) is modified as follows: 1,4-butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol are mixed in a mass ratio of 8.5:3:5, stirred at 400 rpm for 71 h, stirred and added dropwise with ether until the solution is clear, the ether is poured out and transferred to a vacuum drying oven at 45°C for drying for 11 h to obtain hydroxylamine polymer; the hydroxylamine polymer is dispersed In anhydrous methanol at a mass of 7 times that of the hydroxylamine polymer, 0.18 times the mass of dimethylolpropionic acid and 0.85 times the mass of carboxymethyl cyclodextrin were added. After bubbling with nitrogen for 25 min, the mixture was reacted under ultraviolet light at 365 nm for 11 h. Then, 2 times the mass of dimethylolpropionic acid was added, and the reaction was continued under ultraviolet light for 4 h. The supernatant was obtained by centrifugation with diethyl ether and dried in a vacuum drying oven at 45 °C to constant weight to obtain modified cyclodextrin.

[0053] Comparative Example 2

[0054] The formulation of Comparative Example 2 is the same as that of Example 2. The only difference between the preparation method of this long-lasting anti-fouling fabric and Example 2 is that steps (1), (2), and (3) are not performed, and step (4) is modified as follows: hyperbranched polyglycidyl ether is mixed with 0.03 to 0.05 times the mass of hyperbranched polyglycidyl ether plasticizer dibutyl phthalate, and stirred evenly to obtain an anti-fouling film slurry.

[0055] Comparative Example 3

[0056] The formulation of Comparative Example 3 is the same as that of Example 2. The difference between the preparation method of this long-lasting anti-fouling fabric and Example 2 is that step (3) is not performed, and step (4) is modified as follows: hyperbranched polyglycidyl ether and mercapto-carboxymethyl-cyclodextrin are mixed at a mass ratio of 5:1, heated to 90°C, stirred at 50 rpm, and concentrated sulfuric acid with a mass fraction of 98% is added dropwise at a rate of 3 ml / min at 0.2 times the mass of modified cyclodextrin. After stirring and reacting for 24 h, dibutyl phthalate plasticizer with a mass ratio of 0.03 times the mass of hyperbranched polyglycidyl ether is added, and the mixture is stirred evenly to obtain the anti-fouling film slurry.

[0057] Comparative Example 4

[0058] The formulation of Comparative Example 4 is the same as that of Example 2. The only difference between the preparation method of this long-lasting stain-resistant fabric and Example 2 is the difference in step (5). Step (5) is modified as follows: 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone and toluene are mixed in a mass ratio of 1:1:1:8:8. Under argon atmosphere, the mixture is heated to 160°C and reacted for 2 hours. Then, 0.1 times the amount of 2,6-dichlorobenzonitrile is added, and the mixture is reacted for another hour. After that, the mixture is heated to 202°C and reacted for 0.5 hours. Then, 0.06 times the amount of 2,6-dichlorobenzonitrile is added, and the mixture is reacted for another 25 minutes. n, precipitated with methanol, filtered, then washed four times with methanol and 80℃ hot water, and finally dried to constant weight in a 120℃ drying oven to obtain fluorinated polyether nitrile; chloroprene rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile and plasticizer are put into a mixer and mixed at 950 rpm for 6 min, then heated to 108℃, and then foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide are added, and mixing is continued for 4 min, filtered and pressed through a rubber extruder to obtain rubber sheets; the rubber sheets are placed in a flat vulcanizing agent mold and vulcanized at 143℃ and 133 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 16 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 133℃ and at a pressure of 133 kg / cm². 2 Next, vulcanization and foaming were carried out again. After 11 minutes, the mold was opened to obtain foamed rubber with a thickness of 120μm. The foamed rubber contained, by weight, 50 parts of chloroprene rubber, 4 parts of carbon black, 4 parts of paraffin wax, 0.05 parts of antioxidant D, 15 parts of fluorinated polyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.5 parts of vulcanization accelerator TMTD, and 3 parts of zinc oxide.

[0059] Comparative Example 5

[0060] The formulation of Comparative Example 5 is the same as that of Example 2. The only difference between the preparation method of this long-lasting stain-resistant fabric and Example 2 is the difference in step (5). Step (5) is modified as follows: Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, polyether nitrile and plasticizer are put into a mixer and mixed at 950 rpm for 6 min. The temperature is raised to 108°C, and then foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide are added. Mixing is continued for 4 min. The mixture is filtered and pressed into sheets through a rubber extruder to obtain a rubber sheet. The rubber sheet is placed in a flat vulcanizing agent mold and vulcanized at a temperature of 143°C and a pressure of 133 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 16 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 133℃ and at a pressure of 133 kg / cm². 2Next, vulcanization and foaming were carried out again. After 11 minutes, the mold was opened to obtain foamed rubber with a thickness of 120μm. The foamed rubber contained, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin wax, 0.05 parts of antioxidant D, 15 parts of polyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.5 parts of vulcanization accelerator TMTD, and 3 parts of zinc oxide.

[0061] Comparative Example 6

[0062] The formulation of Comparative Example 6 is the same as that of Example 2. The only difference between the preparation method of this long-lasting stain-resistant fabric and Example 2 is the difference in step (5). Step (5) is modified as follows: Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D and plasticizer are put into a mixer and mixed at 950 rpm for 6 min. The temperature is raised to 108°C, and then foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide are added. Mixing is continued for 4 min. The mixture is filtered and pressed into sheets through a rubber extruder to obtain a rubber sheet. The rubber sheet is placed in a flat vulcanizing agent mold and vulcanized at a temperature of 143°C and a pressure of 133 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 16 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 133℃ and at a pressure of 133 kg / cm². 2 Next, vulcanization and foaming were carried out again. After 11 minutes, the mold was opened to obtain foamed rubber with a thickness of 120μm. The foamed rubber contained, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin wax, 0.05 parts of antioxidant D, 10 parts of plasticizer, 9 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.5 parts of vulcanization accelerator TMTD, and 3 parts of zinc oxide.

[0063] Example of effect

[0064] Table 1 below shows the performance analysis results of the long-lasting stain-resistant fabrics of Examples 1, 2, and 3 of the present invention and Comparative Examples 1, 2, 3, 4, 5, and 6.

[0065] Table 1

[0066] Water contact angle (°) <![CDATA[Tear strength (kg / cm 2 ).]]> Water contact angle (°) after rinsing for 48 hours Peel strength (kg / cm) Example 1 5 3.2 7 3.5 Example 2 8 3.5 10 3.8 Example 3 6 3.3 9 3.2 Comparative Example 1 7 2.7 12 3.8 Comparative Example 2 6 2.7 22 3.5 Comparative Example 3 7 2.3 11 3.2 Comparative Example 4 6 2.6 10 3.0 Comparative Example 5 5 3.5 19 3.0 Comparative Example 6 8 3.2 25 1.5

[0067] By comparing the experimental data of the examples and comparative examples in Table 1, it can be clearly found that the long-lasting anti-fouling fabrics prepared in Examples 1, 2 and 3 have better stain resistance, tear resistance, peel strength and longer service life.

[0068] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 reveals that the antifouling film prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin, by introducing thiol groups onto carboxymethyl-cyclodextrin and reacting them with the double bonds on the hydroxylamine polymer to form a long-chain modified cyclodextrin, enhances stability. Furthermore, grafting the hydroxylamine polymer onto the thiol-carboxymethyl-cyclodextrin introduces a large number of hydroxyl groups, enhancing hydrophilicity. This allows a dense hydration layer to form on the surface of the antifouling film, preventing proteins and other contaminants from penetrating the dense hydration layer and reducing their interaction with the fabric surface, thus providing antifouling properties. Introducing modified cyclodextrin into hyperbranched polyglycidyl ether, leveraging the stability of cyclodextrin in seawater, further enhances the stability of the antifouling film and improves the fabric's resistance. The modified cyclodextrin's long chains are entangled on the hyperbranched polyglycidyl ether, increasing the density of the antifouling film and thus enhancing the fabric's impact resistance. Comparison of experimental data from Examples 1, 2, 3, and Comparative Examples 4, 5, and 6 reveals that the foamed rubber is prepared by vulcanization and foaming a blend of chloroprene rubber, polyurethane rubber, and fluorinated polyether nitrile. The addition of polyurethane rubber improves the impact resistance of the foamed rubber. Furthermore, vulcanization using fluorinated polyether nitrile as a curing agent allows it to react with the hydroxyl groups on the waterborne polyurethane adhesive and the antifouling film, thus tightly bonding the Lycra fabric, foamed rubber, and antifouling film, enhancing the fabric's peel strength. Simultaneously, the introduction of fluorine into the foamed rubber layer makes the antifouling layer hydrophilic while the foamed rubber is hydrophobic, further enhancing the fabric's lifespan.

[0069] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a long-lasting stain-resistant fabric, characterized in that, The preparation method of the long-lasting stain-resistant fabric includes the following specific steps: (1) The preparation method of carboxymethyl-cyclodextrin is as follows: cyclodextrin, sodium hydroxide and deionized water are mixed in a mass ratio of 4.4:3.5:19 and stirred until dissolved. Then, sodium chloroacetate with a mass of 1.9 times that of cyclodextrin is added. The mixture is stirred at 40 rpm for 4 h. After cooling to room temperature, the pH is adjusted to 4.9 with hydrochloric acid and methanol with a mass of 6 times that of cyclodextrin is added for precipitation. After precipitation, the mixture is filtered and dried in a vacuum drying oven at 85℃ to constant weight to obtain carboxymethyl-cyclodextrin. (2) Disperse carboxymethyl-cyclodextrin in deionized water at 9 times its mass, and add sodium hydroxide solution at 0.13 times its mass (4% by mass) of carboxymethyl-cyclodextrin dropwise at 4 ml / min at 15 rpm. Continue stirring and add acetonitrile solution of p-toluenesulfonyl chloride at 0.48 times its mass (15% by mass) of carboxymethyl-cyclodextrin dropwise at 4 ml / min. After the addition, stir the reaction at 24℃ and 900 rpm for 2 h, centrifuge to obtain the supernatant, let the supernatant stand at 2℃ for 7 h to form a precipitate, recrystallize the precipitate twice with deionized water as solvent, and then at -55℃. Sulfonated-carboxymethyl-cyclodextrin was prepared by freeze drying. Sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol, and deionized water were mixed in a mass ratio of 1.1:1.1:7:3 and heated to 83°C in a water bath. After reflux for 48 hours, a white precipitate was obtained by rotary evaporation. The white precipitate was washed four times with anhydrous methanol and then dissolved in a 13% sodium hydroxide solution (6 times the mass of the white precipitate). The solution was placed at 55°C for 5 hours and the pH was adjusted to 2 with hydrochloric acid. Trichloroethylene (0.06 times the mass of the white precipitate) was added, and the solution was cooled to 23°C and reacted for 1 hour. Finally, the solution was filtered and recrystallized to obtain mercapto-carboxymethyl-cyclodextrin. (3) 1,4-Butanediol diglycidyl ether, 2-methylallylamine and anhydrous methanol were mixed in a mass ratio of 8.5:3:5 and stirred at 400 rpm for 71 h. Stirring was continued and ether was added dropwise until the solution was clear. The ether was poured out and transferred to a vacuum drying oven at 45 °C for 11 h to obtain hydroxylamine polymer. The hydroxylamine polymer was dispersed in anhydrous methanol at 7 times the mass of the hydroxylamine polymer. Dimethylolpropionic acid at 0.18 times the mass of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin at 0.85 times the mass of the hydroxylamine polymer were added. After bubbling with nitrogen for 25 min, the reaction was carried out under ultraviolet light at 365 nm for 11 h. Dimethylolpropionic acid at 2 times the mass of the hydroxylamine polymer was added and the reaction was carried out under ultraviolet light for 4 h. The supernatant was obtained by centrifugation with ether and placed in a vacuum drying oven at 45 °C to dry to constant weight to obtain modified cyclodextrin. (4) Hyperbranched polyglycidyl ether and modified cyclodextrin are mixed at a mass ratio of 6:1, heated to 110°C, stirred at 80 rpm, and 0.25 times the mass of modified cyclodextrin and 98% concentrated sulfuric acid are added dropwise at a rate of 4 ml / min. After stirring and reacting for 28 h, 0.04 times the mass of hyperbranched polyglycidyl ether and 0.04 times the mass of plasticizer dibutyl phthalate are added and stirred evenly to obtain antifouling film slurry. (5) Mix 2,6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methylpyrrolidone, and toluene in a mass ratio of 1:1:1:8:

8. Under argon atmosphere, heat to 160°C and react for 2 hours. Add 0.1 times the amount of 2,6-difluorobenzonitrile and continue reacting for 1 hour. Then heat to 202°C and react for 0.5 hours. Add 0.06 times the amount of 2,6-dichlorobenzonitrile and continue reacting for 25 minutes. Precipitate with methanol, filter, and then precipitate with methanol and heat at 80°C. The mixture was washed four times with water and then dried to constant weight in a 120℃ drying oven to obtain fluorinated polyether nitrile. Chloroprene rubber, polyurethane rubber, carbon black, paraffin wax, antioxidant D, fluorinated polyether nitrile, and plasticizer were added to a mixer and mixed at 950 rpm for 6 minutes. The temperature was then raised to 108℃, and foaming agent disulfonyl selenohydrazine diphenyl ether, vulcanization accelerator TMTD, and zinc oxide were added. Mixing continued for 4 minutes. The mixture was then filtered and pressed into sheets using a rubber extruder to obtain rubber sheets. The rubber sheets were placed in a flat vulcanizing mold and subjected to vulcanization at 143℃ and a pressure of 133 kg / cm². 2 Under these conditions, vulcanization and foaming are carried out. After 16 minutes, the mold is opened, and the contents are transferred to a foaming agent. The mixture is then heated at 133℃ and at a pressure of 133 kg / cm². 2 Next, vulcanization and foaming were carried out again. After 11 minutes, the mold was opened to obtain foamed rubber with a thickness of 120μm. The foamed rubber contained, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin wax, 0.05 parts of antioxidant D, 15 parts of fluorinated polyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfonyl selenohydrazine diphenyl ether, 0.5 parts of vulcanization accelerator TMTD, and 3 parts of zinc oxide. (6) At a weight of 130 g / cm 2 Lycra fabric is coated with an 8μm thick water-based polyurethane adhesive on both sides and bonded with foamed rubber. After standing for 40 minutes, the edges are scraped and coated with a 65μm thick anti-fouling film slurry. After standing for 5 days, a long-lasting anti-fouling fabric is obtained.