Production process for improving wet rubbing color fastness of cotton trademark braid

Abstract

The invention relates to a production process for improving the wet rubbing color fastness of a cotton trademark braid. The preparation method comprises the following steps: preparation of a polyethylene silsesquioxane (PVS) polymer, preparation of a dopamine structural color cotton tape, preparation of a PVS / PDA structural color cotton tape, preparation of a super-hydrophobic coating, preparation of a super-hydrophobic woven tape, preparation of a wear-resistant coating and preparation of a coated woven tape. The trademark braid is obtained by creatively combining the auto-agglutination reaction of dopamine (DA), the preparation of the colored cotton braid, the addition of a coating auxiliary agent and the like, and the braid has the advantages of excellent wet friction and high color fastness.

Description

Technical Field

[0001] This invention relates to a production process for improving the wet rubbing color fastness of cotton trademark webbing, belonging to the field of trademark webbing technology. Background Technology

[0002] Traditional trademark webbing typically uses woven tape as the base fabric for coating. Its production process involves numerous complex steps, including winding, warping, sizing, threading, weaving, desizing, and scouring. This complex process consumes significant energy and water resources, making it difficult to meet current requirements for green and sustainable development. Therefore, the traditional coated trademark fabric industry urgently needs to upgrade and transform its processes.

[0003] Nature produces various coloring materials, such as dyes, pigments, and structural colors. Structural colors are generated by the optical interaction between light and micro / nano-scale periodic structures, depending on the structure and periodic arrangement of nanostructured materials. Pigments may fade due to ultraviolet light. Conversely, structural colors do not fade as long as they maintain their periodic structure. The most prominent example is the structural color of bird feathers. Structural colors, with their unique luster and high color developability, are expected to replace traditional dyeing in widespread applications in the textile industry. Cotton webbing, due to its excellent breathability and comfort, is widely used in the textile industry. The structural color film formed on cotton webbing suffers from poor stability due to the influence of short fibers on the surface of the webbing. Stronger interaction forces are needed to improve the adhesion between the structural color film and the cotton webbing interface, such as by adding adhesives containing active groups to form chemical bonds. Simultaneously, due to the excellent hygroscopicity of cotton webbing, structural color cotton webbing is more easily penetrated into the gaps between the micro / nano structures when in contact with water, leading to a decrease in the refractive index contrast between the two and causing the structural color coating to fade. Furthermore, the structural color coating is also prone to peeling off. Therefore, developing hydrophobic structural colors with improved color fastness is of great significance for the development of structural color cotton webbing in the textile industry. Summary of the Invention

[0004] To address the above problems, this invention provides a production process for improving the wet rubbing color fastness of cotton trademark webbing.

[0005] This invention relates to a production process for improving the wet rubbing color fastness of cotton trademark webbing, comprising the following steps: preparation of polyethylene silsesquioxane (PVS) polymer, preparation of dopamine structured color cotton webbing, preparation of PVS / PDA structured color cotton webbing, preparation of superhydrophobic coating, preparation of superhydrophobic webbing, preparation of abrasion-resistant coating, and preparation of coated webbing.

[0006] Preferably, step (1) involves the preparation of the polyethylene silsesquioxane (PVS) polymer. Anhydrous ethanol, toluene, and vinyltrimethoxysilane were sequentially added to a round-bottom flask and magnetically stirred in an ice bath. Then, a mixture of deionized water and concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring until homogeneous, the mixture was concentrated and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon Dopamine hydrochloride was dissolved in a Tris buffer solution. CuCl2 and H2O2 were added to the solution and stirred. The ribbon was then placed into a petri dish containing a dopamine-Tris buffer solution for dopamine polymerization. Step (3) Preparation of PVS / PDA structured color cotton webbing The dopamine-structured cotton tape from step (2) was impregnated with anhydrous ethanol and PVS solutions of different concentrations. The impregnated cotton tape was then dried under natural conditions to obtain a hydrophobic structured cotton tape. Step (4) Preparation of superhydrophobic coating Step 1: Weigh the graphene nanosheets, dissolve them in anhydrous ethanol, and then ultrasonically disperse them to obtain a uniform single solution A; Step 2: Add ammonia to the single solution A above to adjust its pH, maintain the reaction temperature, stir magnetically, add TEOS to cause hydrolysis and condensation reaction, and obtain mixed solution B after the reaction; Step 3: Add fluorosilane FAS-17 to mixed solution B, stir, and take water-soluble resin to completely dissolve it in the above solution to finally form a silica / graphene composite coating. Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by impregnation method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4), and then removed with tweezers and dried in an oven. Impregnation-drying: the webbing was dried in an oven, and finally silica / graphene composite coated webbing was obtained. Step (6) Preparation of wear-resistant coating Anhydrous methanol was added to a three-necked flask, a reflux condenser was connected, and the flask was placed in a constant-temperature water bath. The temperature was kept stable, and the mixture was stirred at high speed. After the system reached thermal equilibrium, a certain mass of anhydrous calcium chloride was slowly added in batches until the reaction was complete. Then, kaolin filler was gradually added, and the mixture was stirred until it was fully dissolved to form a uniform and transparent solution. The mixture was stirred at high speed, and the water bath temperature was lowered and stabilized. Stirring was maintained to finally obtain a stable kaolin coating slurry. Step (7) Preparation of coated webbing After fixing the webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, coating station, coagulation bath tank and take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually rotate the take-up roller slowly so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0007] Preferably, step (1) involves the preparation of the polyethylene silsesquioxane (PVS) polymer. Add 5-10 mL of anhydrous ethanol, 100-125 mL of toluene, and 60-70 mL of vinyltrimethoxysilane sequentially to a 250-500 mL round-bottom flask. Stir magnetically in an ice bath for 10-20 minutes. Then, add a mixture of 15-30 g of deionized water and 3-5 g of concentrated hydrochloric acid dropwise to the reaction solution. After stirring until homogeneous, concentrate the mixture at 70-90℃ for 1-3 hours. Cool to room temperature, and wash the upper liquid layer with deionized water and anhydrous CaCO3, respectively. After filtration, obtain concentrated colorless oily PVS product.

[0008] As a preferred option, step (2) involves the preparation of dopamine-structured colored cotton webbing. Dissolve 0.01-0.03 mol / L dopamine hydrochloride in a 30-50 mmol / L Tris buffer solution, add 3-5 mmol / L CuCl2 and 15-20 mmol / L H2O2 to the solution and stir for about 3-5 minutes. Place the ribbon into a petri dish containing dopamine-Tris buffer solution and polymerize dopamine at 30-40℃.

[0009] As a preferred option, step (3) involves the preparation of the PVS / PDA structured colored cotton webbing. Dopamine-colored cotton tape was impregnated with anhydrous ethanol and different concentrations of 3-9 wt% PVS solution in step (1). The impregnated cotton tape was then dried under natural conditions to obtain hydrophobic cotton tape.

[0010] Preferably, step (4) involves the preparation of the superhydrophobic coating. Step 1: Weigh 0.1-0.5g of graphene nanosheets and dissolve them in 10-20g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 10-20 mL of ammonia to the single solution A above to adjust its pH to 8-9, maintain the reaction temperature at 40-50℃, and use a magnetic stirrer at 400-500 r / min. After maintaining the temperature for 5-10 min, add 0.1-0.5 g of TEOS to induce a hydrolysis-condensation reaction. After reacting for 2-4 h, obtain the mixed solution B. Step 3: Add 1-3 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 40-50℃, and the magnetic stirring speed at 400-500 r / min. After reacting for 1-2 h, take 0.01-0.05 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0011] The advantage of using this invention is that, under the modification of FAS-17, the polysiloxane undergoes an effective chemical reaction with the SiO2 particles during the grafting process, laying a solid foundation for endowing the webbing with superhydrophobic properties. The water-soluble resin is used to increase the adhesion between the particles and the webbing, and FAS-17 is a low surface energy hydrophobic modifier.

[0012] Preferably, step (5) involves the preparation of the superhydrophobic webbing. Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 10-20 min. Then it was taken out with tweezers and dried in an oven at a constant temperature of 60-80℃ for 10-20 min. After repeating immersion-drying 3-4 times, the webbing was dried in an oven at 70-80℃ for 2-3 h, and finally silica / graphene composite coated webbing was obtained.

[0013] The advantages of this invention are that silica is tightly bonded to the fibers and graphene nanosheets, and the webbing is uniformly covered with graphene and silica. The micron-scale structure of graphene provides a large geometric height difference, while the nano-scale structure of silica adds finer unevenness on the basis of these micron-scale structures, thereby significantly improving the overall roughness. This structure provides the basis for hydrophobicity.

[0014] Preferably, step (6) involves the preparation of the wear-resistant coating. Add 150-200g of anhydrous methanol to a 500-1000mL three-necked flask, connect a reflux condenser, and place the flask in a constant-temperature water bath. Maintain the temperature at 50-65℃ and stir at 800-1000r / min. Once the system reaches thermal equilibrium, slowly add 20-30g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 1-2 hours to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 20-30 minutes, lower the water bath temperature and stabilize it at 40-50℃, maintaining stirring for 1-2 hours to finally obtain a stable kaolin coating slurry.

[0015] The advantages of using this invention are that the coating film structure formed by water bath treatment encapsulates the filler, improves the film density and increases the porosity. When the porosity is moderate, the substance can penetrate the coating and combine with the stable structure, thereby improving color fastness.

[0016] Preferably, step (7) involves the preparation of the coated webbing. After fixing the webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 2-3 mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0017] In summary, the beneficial effects of this invention are as follows: 1. The advantage of using this invention is that, under the modification of FAS-17, polysiloxane undergoes an effective chemical reaction with SiO2 particles during the grafting process, laying a solid foundation for giving the webbing superhydrophobic properties. The water-soluble resin is used to increase the adhesion between the particles and the webbing, and FAS-17 is a low surface energy hydrophobic modifier. 2. The advantages of using this invention are that silica is tightly bonded to the fiber and graphene nanosheets, and the tape is uniformly covered with graphene and silica. The micron-scale structure of graphene provides a large geometric height difference, while the nano-scale structure of silica adds finer unevenness on the basis of these micron-scale structures, thereby significantly improving the overall roughness. This structure provides the basis for hydrophobicity. 3. The advantages of using this invention are that the coating film structure formed by water bath treatment encapsulates the filler, improves the film density and increases the porosity. When the porosity is moderate, the substance can penetrate the coating and combine with the stable structure, thereby improving the color fastness. Attached Figure Description

[0018] Figure 1 This is a production process flow chart for improving the wet rubbing color fastness of cotton trademark webbing. Detailed Implementation

[0019] Example 1

[0020] Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer 5 mL of anhydrous ethanol, 100 mL of toluene, and 60 mL of vinyltrimethoxysilane were added sequentially to a 250 mL round-bottom flask. The mixture was magnetically stirred in an ice bath for 10 minutes. Then, a mixed solution of 15 g of deionized water and 3 g of concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring evenly, the mixed solution was concentrated at 70 °C for 1 hour and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon 0.01 mol / L dopamine hydrochloride was dissolved in a 30 mmol / L Tris buffer solution. 3 mmol / L CuCl2 and 15 mmol / L H2O2 were added to the solution and stirred for about 3 minutes. The ribbon was then placed in a petri dish containing dopamine-Tris buffer solution and dopamine polymerization was carried out at 30°C. Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-based structural color cotton tape was impregnated with anhydrous ethanol and different concentrations of 3wt% PVS solution in step (1). The impregnated structural color cotton tape was then dried under natural conditions to obtain hydrophobic structural color cotton tape.

[0021] Step (4) Preparation of superhydrophobic coating Step 1: Weigh 0.1g of graphene nanosheets and dissolve them in 10g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 10 mL of ammonia to the single solution A above to adjust its pH to 8, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After 5 min of constant temperature, add 0.1 g of TEOS to induce a hydrolysis and condensation reaction. After 2 h of reaction, obtain mixed solution B. Step 3: Add 1 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After reacting for 1 h, take 0.01 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0022] Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 10 min. Then it was taken out with tweezers and dried in a constant temperature oven at 60℃ for 10 min. After repeating immersion-drying 3 times, the webbing was dried in an oven at 70℃ for 2 h. Finally, silica / graphene composite coated webbing was obtained.

[0023] Step (6) Preparation of wear-resistant coating Add 150g of anhydrous methanol to a 500mL three-necked flask, connect a reflux condenser, and place it in a constant temperature water bath. Maintain the temperature at 50℃ and stir at 800r / min. After the system reaches thermal equilibrium, slowly add 20g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 1 hour to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 20 minutes, lower the water bath temperature and stabilize it at 40℃, maintaining stirring for 1 hour to finally obtain a stable kaolin coating slurry.

[0024] Step (7) Preparation of coated webbing After fixing the composite coated webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 2mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0025] Example 2

[0026] Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer 6 mL of anhydrous ethanol, 115 mL of toluene, and 65 mL of vinyltrimethoxysilane were added sequentially to a 250 mL round-bottom flask. The mixture was magnetically stirred in an ice bath for 10-20 minutes. Then, a mixed solution of 20 g of deionized water and 4 g of concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring until homogeneous, the mixed solution was concentrated at 80 °C for 2 hours. After cooling to room temperature, the upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon 0.02 mol / L dopamine hydrochloride was dissolved in a 40 mmol / L Tris buffer solution. 5 mmol / L CuCl2 and 16 mmol / L H2O2 were added to the solution and stirred for about 4 minutes. The ribbon was then placed in a petri dish containing dopamine-Tris buffer solution and dopamine polymerization was carried out at 30°C. Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-colored structured cotton tape was impregnated with anhydrous ethanol and different concentrations of 5wt% PVS solution in step (1). The impregnated structured cotton tape was then dried under natural conditions to obtain hydrophobic structured cotton tape.

[0027] Step (4) Preparation of superhydrophobic coating Step 1: Weigh 0.3g of graphene nanosheets and dissolve them in 15g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 18 mL of ammonia to the single solution A above to adjust its pH to 8, maintain the reaction temperature at 48℃, and the magnetic stirring speed at 480 r / min. After 6 min at a constant temperature, add 0.3 g of TEOS to induce a hydrolysis-condensation reaction. After 3 h of reaction, obtain mixed solution B. Step 3: Add 2 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 46℃, and the magnetic stirring speed at 460 r / min. After reacting for 1 h, take 0.03 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0028] Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 15 min. Then it was taken out with tweezers and dried in a constant temperature oven at 70℃ for 15 min. After repeating immersion-drying 3 times, the webbing was dried in an oven at 75℃ for 2 h. Finally, silica / graphene composite coated webbing was obtained.

[0029] Step (6) Preparation of wear-resistant coating Add 180g of anhydrous methanol to a 500mL three-necked flask, connect a reflux condenser, and place it in a constant temperature water bath. Maintain the temperature at 60℃ and stir at 9000r / min. After the system reaches thermal equilibrium, slowly add 26g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 1 hour to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 26 minutes, lower the water bath temperature and stabilize it at 48℃, maintaining stirring for 1 hour to finally obtain a stable kaolin coating slurry.

[0030] Step (7) Preparation of coated webbing After fixing the composite coated webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 2 mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0031] Example 3

[0032] Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer 8 mL of anhydrous ethanol, 120 mL of toluene, and 65 mL of vinyltrimethoxysilane were added sequentially to a 450 mL round-bottom flask and magnetically stirred in an ice bath for 18 minutes. Then, a mixed solution of 26 g of deionized water and 5 g of concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring evenly, the mixed solution was concentrated at 85 °C for 3 hours and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon 0.03 mol / L dopamine hydrochloride was dissolved in a 45 mmol / L Tris buffer solution. 4 mmol / L CuCl2 and 18 mmol / L H2O2 were added to the solution and stirred for about 5 minutes. The ribbon was then placed in a petri dish containing dopamine-Tris buffer solution and dopamine polymerization was carried out at 30°C. Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-based structural color cotton tape was impregnated with anhydrous ethanol and different concentrations of 7 wt% PVS solution in step (1). The impregnated structural color cotton tape was then dried under natural conditions to obtain hydrophobic structural color cotton tape.

[0033] Preferably, step (4) involves the preparation of the superhydrophobic coating. Step 1: Weigh 0.4g of graphene nanosheets and dissolve them in 18g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A. Step 2: Add 18 mL of ammonia to the single solution A above to adjust its pH to 9, maintain the reaction temperature at 48℃, and the magnetic stirring speed at 480 r / min. After 8 minutes of constant temperature, add 0.4 g of TEOS to induce a hydrolysis-condensation reaction. After 3 hours of reaction, obtain mixed solution B. Step 3: Add 3 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 48℃, and the magnetic stirring speed at 480 r / min. After reacting for 2 h, take 0.04 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0034] Preferably, step (5) involves the preparation of the superhydrophobic webbing. Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 18 min. Then it was taken out with tweezers and dried in a constant temperature oven at 76℃ for 18 min. After immersion-drying was repeated 4 times, the webbing was dried in an oven at 78℃ for 3 h. Finally, silica / graphene composite coated webbing was obtained.

[0035] Step (6) Preparation of wear-resistant coating Add 180g of anhydrous methanol to a 900mL three-necked flask, connect a reflux condenser, and place it in a constant temperature water bath. Maintain the temperature at 60℃ and stir at a high speed of 960r / min. After the system reaches thermal equilibrium, slowly add 28g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 2 hours to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 28 minutes, lower the water bath temperature and stabilize it at 48℃, maintaining stirring for 2 hours to finally obtain a stable kaolin coating slurry.

[0036] Step (7) Preparation of coated webbing After fixing the composite coated webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 3 mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0037] Example 4

[0038] Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer 10 mL of anhydrous ethanol, 125 mL of toluene, and 70 mL of vinyltrimethoxysilane were added sequentially to a 500 mL round-bottom flask and magnetically stirred in an ice bath for 20 minutes. Then, a mixed solution of 30 g of deionized water and 5 g of concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring evenly, the mixed solution was concentrated at 90 °C for 3 hours and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon 0.03 mol / L dopamine hydrochloride was dissolved in a 50 mmol / L Tris buffer solution. 5 mmol / L CuCl2 and 20 mmol / L H2O2 were added to the solution and stirred for about 5 minutes. The ribbon was then placed in a petri dish containing dopamine-Tris buffer solution and dopamine polymerization was carried out at 40°C. Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-based structural color cotton tape was impregnated with anhydrous ethanol and different concentrations of 9 wt% PVS solution in step (1). The impregnated structural color cotton tape was then dried under natural conditions to obtain hydrophobic structural color cotton tape.

[0039] Step (4) Preparation of superhydrophobic coating Step 1: Weigh 0.5g of graphene nanosheets and dissolve them in 20g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 20 mL of ammonia to the above single solution A to adjust its pH to 9, maintain the reaction temperature at 50℃, and the magnetic stirring speed at 500 r / min. After maintaining the temperature for 10 min, add 0.5 g of TEOS to induce a hydrolysis and condensation reaction. After reacting for 4 h, a mixed solution B is obtained. Step 3: Add 3 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 50℃, and the magnetic stirring speed at 500 r / min. After reacting for 2 h, take 0.05 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0040] Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 20 min. Then it was taken out with tweezers and dried in an oven at constant temperature of 80℃ for 20 min. After immersion-drying was repeated 4 times, the webbing was dried in an oven at 80℃ for 3 h. Finally, silica / graphene composite coated webbing was obtained.

[0041] Step (6) Preparation of wear-resistant coating Add 200g of anhydrous methanol to a 1000mL three-necked flask, connect a reflux condenser, and place it in a constant temperature water bath. Maintain the temperature at 65℃ and stir at 1000r / min. After the system reaches thermal equilibrium, slowly add 30g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 2 hours to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 30 minutes, lower the water bath temperature and stabilize it at 50℃, maintaining stirring for 2 hours to finally obtain a stable kaolin coating slurry.

[0042] Step (7) Preparation of coated webbing After fixing the composite coated webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 3 mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0043] Comparative Example 1

[0044] Step (1) Preparation of superhydrophobic coating Step 1: Weigh 0.1g of graphene nanosheets and dissolve them in 10g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 10 mL of ammonia to the single solution A above to adjust its pH to 8, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After 5 min of constant temperature, add 0.1 g of TEOS to induce a hydrolysis and condensation reaction. After 2 h of reaction, obtain mixed solution B. Step 3: Add 1 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After reacting for 1 h, take 0.01 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0045] Step (2) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The cleaned webbing was immersed in the silica / graphene composite coating of step (1) for 10 min, and then removed with tweezers and dried in a constant temperature oven at 60℃ for 10 min. After repeating immersion-drying 3 times, the webbing was dried in a 70℃ oven for 2 h to finally obtain silica / graphene composite coated webbing.

[0046] Step (3) Preparation of wear-resistant coating Add 150g of anhydrous methanol to a 500mL three-necked flask, connect a reflux condenser, and place it in a constant temperature water bath. Maintain the temperature at 50℃ and stir at 800r / min. After the system reaches thermal equilibrium, slowly add 20g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 1 hour to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 20 minutes, lower the water bath temperature and stabilize it at 40℃, maintaining stirring for 1 hour to finally obtain a stable kaolin coating slurry.

[0047] Step (4) Preparation of coated webbing After fixing the composite coated webbing from step (2) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 2mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (3) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

[0048] Comparative Example 2

[0049] Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer 5 mL of anhydrous ethanol, 100 mL of toluene, and 60 mL of vinyltrimethoxysilane were added sequentially to a 250 mL round-bottom flask. The mixture was magnetically stirred in an ice bath for 10 minutes. Then, a mixed solution of 15 g of deionized water and 3 g of concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring evenly, the mixed solution was concentrated at 70 °C for 1 hour and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon 0.01 mol / L dopamine hydrochloride was dissolved in a 30 mmol / L Tris buffer solution. 3 mmol / L CuCl2 and 15 mmol / L H2O2 were added to the solution and stirred for about 3 minutes. The ribbon was then placed in a petri dish containing dopamine-Tris buffer solution and dopamine polymerization was carried out at 30°C. Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-based structural color cotton tape was impregnated with anhydrous ethanol and different concentrations of 3wt% PVS solution in step (1). The impregnated structural color cotton tape was then dried under natural conditions to obtain hydrophobic structural color cotton tape.

[0050] Step (4) Preparation of superhydrophobic coating Step 1: Weigh 0.1g of graphene nanosheets and dissolve them in 10g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 10 mL of ammonia to the single solution A above to adjust its pH to 8, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After 5 min of constant temperature, add 0.1 g of TEOS to induce a hydrolysis and condensation reaction. After 2 h of reaction, obtain mixed solution B. Step 3: Add 1 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 40℃, and the magnetic stirring speed at 400 r / min. After reacting for 1 h, take 0.01 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

[0051] Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The cleaned hydrophobic colored cotton webbing obtained in step (3) was immersed in the silica / graphene composite coating in step (4) for 10 min. Then it was taken out with tweezers and dried in a constant temperature oven at 60℃ for 10 min. After immersion-drying was repeated 3 times, the webbing was dried in an oven at 70℃ for 2 h. Finally, silica / graphene composite coated webbing was obtained.

[0052] Comparison of detection experiments: The cotton trademark webbing obtained in Examples 1 to 4 and comparative products 1 and 2 were tested. The specific testing methods are as follows: Color fastness characterization of ribbon Characterization of color fastness to rubbing: Referring to GB / T 3920—2008 "Textiles - Tests for color fastness - Color fastness to rubbing", dry and wet rubbing tests were conducted on coated webbing samples prepared using different processes to evaluate the adhesion of the coating under friction. After the test, the rubbing area was rated according to the gray scale to determine its color fastness to rubbing grade.

[0053] Table 1. Colorfastness Test Results

[0054] As shown in Table 1, Example 4 is the best, while the comparative example is worse. This is because the condensation of PVS with the hydroxyl groups of the catechol fragment in PDA to form covalent bonds improves the interfacial adhesion strength between the PDA structural color film and the webbing, thus enhancing the color fastness of the PDA structural color film. The two monomers, PDA and PVS, can spontaneously form strong chemical bonds at room temperature, thereby enhancing the fastness and stability of the PDA structural color film on the webbing. The addition of PVS polymer not only reduces the PDA... The cracking of the structural color film improved its adhesion and stability on the webbing surface. Meanwhile, Comparative Example 1 lacked both PDA and PVS monomers, and with a low addition of kaolin filler, the coating film structure formed by water bath treatment was loose, making it difficult to encapsulate the filler. Some particles were exposed on the surface and easily detached under external force or washing, reducing color fastness. Comparative Example 2, although containing both PDA and PVS monomers, which is beneficial to the fastness and stability of the structural color film on the webbing, had lower abrasion resistance due to the lack of an abrasion-resistant coating, and the lowest dry and wet rubbing color fastness. In the examples, as the addition amount increased, the film density improved, the porosity increased, and the substance could penetrate the coating and combine with the stable structure, improving color fastness.

[0055] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art may make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A production process for improving the wet rubbing color fastness of cotton trademark webbing, characterized in that: Preparation of polyethylene silsesquioxane (PVS) polymer, preparation of dopamine structured color cotton webbing, preparation of PVS / PDA structured color cotton webbing, preparation of superhydrophobic coating, preparation of superhydrophobic webbing, preparation of abrasion-resistant coating, and preparation of coated webbing.

2. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 1, characterized in that: Step (1) Preparation of polyethylene silsesquioxane polymer Anhydrous ethanol, toluene, and vinyltrimethoxysilane were sequentially added to a round-bottom flask and magnetically stirred in an ice bath. Then, a mixture of deionized water and concentrated hydrochloric acid was added dropwise to the reaction solution. After stirring until homogeneous, the mixture was concentrated and cooled to room temperature. The upper liquid layer was washed and separated with deionized water and anhydrous CaCO3, respectively. After filtration, a concentrated colorless oily PVS product was obtained. Step (2) Preparation of dopamine-structured colored cotton ribbon Dopamine hydrochloride was dissolved in a Tris buffer solution. CuCl2 and H2O2 were added to the solution and stirred. The ribbon was then placed into a petri dish containing a dopamine-Tris buffer solution for dopamine polymerization. Step (3) Preparation of PVS / PDA structured color cotton webbing The dopamine-structured cotton tape from step (2) was impregnated with anhydrous ethanol and PVS solutions of different concentrations. The impregnated cotton tape was then dried under natural conditions to obtain a hydrophobic structured cotton tape. Step (4) Preparation of superhydrophobic coating Step 1: Weigh the graphene nanosheets, dissolve them in anhydrous ethanol, and then ultrasonically disperse them to obtain a uniform single solution A; Step 2: Add ammonia to the single solution A above to adjust its pH, maintain the reaction temperature, stir magnetically, add TEOS to cause hydrolysis and condensation reaction, and obtain mixed solution B after the reaction; Step 3: Add fluorosilane FAS-17 to mixed solution B, stir, and take water-soluble resin to completely dissolve it in the above solution to finally form a silica / graphene composite coating. Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by impregnation method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4), and then removed with tweezers and dried in an oven. Impregnation-drying: the webbing was dried in an oven, and finally silica / graphene composite coated webbing was obtained. Step (6) Preparation of wear-resistant coating Anhydrous methanol was added to a three-necked flask, a reflux condenser was connected, and the flask was placed in a constant-temperature water bath. The temperature was kept stable, and the mixture was stirred at high speed. After the system reached thermal equilibrium, a certain mass of anhydrous calcium chloride was slowly added in batches until the reaction was complete. Then, kaolin filler was gradually added, and the mixture was stirred until it was fully dissolved to form a uniform and transparent solution. The mixture was stirred at high speed, and the water bath temperature was lowered and stabilized. Stirring was maintained to finally obtain a stable kaolin coating slurry. Step (7) Preparation of coated webbing After fixing the webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, coating station, coagulation bath tank and take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually rotate the take-up roller slowly so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

3. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 2, characterized in that: Step (1) Preparation of polyethylene silsesquioxane (PVS) polymer Add 5-10 mL of anhydrous ethanol, 100-125 mL of toluene, and 60-70 mL of vinyltrimethoxysilane sequentially to a 250-500 mL round-bottom flask. Stir magnetically in an ice bath for 10-20 minutes. Then, add a mixture of 15-30 g of deionized water and 3-5 g of concentrated hydrochloric acid dropwise to the reaction solution. After stirring until homogeneous, concentrate the mixture at 70-90℃ for 1-3 hours. Cool to room temperature, and wash the upper liquid layer with deionized water and anhydrous CaCO3, respectively. After filtration, obtain concentrated colorless oily PVS product.

4. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 2, characterized in that: Step (2) Preparation of dopamine-structured colored cotton ribbon Dissolve 0.01-0.03 mol / L dopamine hydrochloride in a 30-50 mmol / L Tris buffer solution, add 3-5 mmol / L CuCl2 and 15-20 mmol / L H2O2 to the solution and stir for about 3-5 minutes. Place the ribbon into a petri dish containing dopamine-Tris buffer solution and polymerize dopamine at 30-40℃.

5. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 2, characterized in that: Step (3) Preparation of PVS / PDA structured color cotton webbing Dopamine-colored cotton tape was impregnated with anhydrous ethanol and different concentrations of 3-9 wt% PVS solution in step (1). The impregnated cotton tape was then dried under natural conditions to obtain hydrophobic cotton tape.

6. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 2, characterized in that: Step (4) Preparation of superhydrophobic coating Step 1: Weigh 0.1-0.5g of graphene nanosheets and dissolve them in 10-20g of anhydrous ethanol, then disperse them by ultrasonication to obtain a uniform single solution A; Step 2: Add 10-20 mL of ammonia to the single solution A above to adjust its pH to 8-9, maintain the reaction temperature at 40-50℃, and use a magnetic stirrer at 400-500 r / min. After maintaining the temperature for 5-10 min, add 0.1-0.5 g of TEOS to induce a hydrolysis-condensation reaction. After reacting for 2-4 h, obtain the mixed solution B. Step 3: Add 1-3 mL of fluorosilane FAS-17 to mixed solution B, maintain the reaction temperature at 40-50℃, and the magnetic stirring speed at 400-500 r / min. After reacting for 1-2 h, take 0.01-0.05 g of water-soluble resin and dissolve it completely in the above solution to finally form a silica / graphene composite coating.

7. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 6, characterized in that: Step (5) Preparation of superhydrophobic webbing Superhydrophobic webbing was prepared by immersion method. The webbing obtained in step (3) after cleaning was immersed in the silica / graphene composite coating in step (4) for 10-20 min. Then it was taken out with tweezers and dried in an oven at a constant temperature of 60-80℃ for 10-20 min. After repeating immersion-drying 3-4 times, the webbing was dried in an oven at 70-80℃ for 2-3 h to finally obtain silica / graphene composite coated webbing.

8. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 2, characterized in that: Step (6) Preparation of wear-resistant coating Add 150-200g of anhydrous methanol to a 500-1000mL three-necked flask, connect a reflux condenser, and place the flask in a constant-temperature water bath. Maintain the temperature at 50-65℃ and stir at 800-1000r / min. Once the system reaches thermal equilibrium, slowly add 20-30g of anhydrous calcium chloride in batches until the reaction is complete. Then, gradually add kaolin filler and continue stirring for 1-2 hours to fully dissolve it and form a uniform and transparent solution. After continuing high-speed stirring for 20-30 minutes, lower the water bath temperature and stabilize it at 40-50℃, maintaining stirring for 1-2 hours to finally obtain a stable kaolin coating slurry.

9. The production process for improving the wet rubbing color fastness of cotton trademark webbing according to claim 8, characterized in that: Step (7) Preparation of coated webbing After fixing the webbing from step (5) onto the unwinding roller of the self-made wet coating machine, let it pass through the coating slurry tank, the coating station (using a 2-3 mm thick scraper), the coagulation bath tank and the take-up roller in sequence. Pour the coating slurry from step (6) into the coating slurry tank and manually and slowly rotate the take-up roller so that the webbing passes through the coating slurry tank evenly during the coating process. Stop the operation when the coating slurry in the coating slurry tank is about to be used up. Take the coated webbing that has completed the film formation process out of the equipment, place it in clean water to wash it thoroughly to remove the residue, then use a rolling mill to press out the excess water and dry it in an oven.

Images