A kind of silk umbrella cloth with anti-burning and water-repellent properties, its processing method and application

Abstract

The present invention discloses a heat-resistant and water-repellent nylon umbrella fabric, its processing method and application. The processing method includes the following steps: pretreating the nylon umbrella fabric with a polyamidase treatment solution; immersing the treated nylon umbrella fabric in an allylamine hydrochloride solution, and grafting allylamine on the fiber surface by means of 1-ethyl-(3-dimethylaminopropyl)carbodiimide catalysis; padding the treated nylon umbrella fabric in a solution containing vinyl polyimide and hexafluorobutyl methacrylate, and catalyzing the graft polymerization of the fabric surface by means of peroxidase. The present invention first uses polyamidase for enzymatic pretreatment of the nylon umbrella fabric to hydrolyze the amide bonds on the surface of nylon fibers to generate amino groups, and then catalyzes the grafting of allylamine on the surface of nylon fibers by means of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and reacts with vinyl polyimide and hexafluorobutyl methacrylate, and undergoes peroxidase-catalyzed graft polymerization crosslinking to obtain a heat-resistant and water-repellent nylon umbrella fabric.

Description

Technical Field

[0001] The present invention relates to the technical field of textile dyeing and finishing. Specifically, it relates to a heat-resistant and water-repellent nylon umbrella cloth, its processing method and application. Background Art

[0002] Nylon is the most commonly used synthetic fiber raw material and has been widely used in the processing of sportswear and outdoor textiles. Compared with natural fibers, nylon fiber products have relatively strong single fiber strength and excellent abrasion resistance. They not only feel soft but also have excellent dimensional stability. Polyamide fibers are not only used in the processing of sportswear and outdoor textiles but also widely used in industrial textiles and special textile processing. Nylon fabric woven with nylon filament as the raw material and plain weave can be applied to a variety of special textiles including parachute umbrella cloth.

[0003] The parachute canopy has application characteristics of high strength, light weight, and controllable air permeability, and is mostly woven with high-strength and wear-resistant nylon 66 filament. During the rapid opening process of a parachute for airdropping heavy loads, when the silk surfaces of the nylon umbrella cloth rub against each other at high speed or when the silk surface rubs against accessories, high temperatures are easily generated instantaneously, and even umbrella burning may occur under extreme conditions. In addition, due to climatic conditions and other factors, the parachute may also deviate from the landing target location, and specific requirements for the flame retardancy of the nylon umbrella canopy are also put forward in specific scenarios. In addition, to improve the all-weather adaptability of the nylon umbrella cloth for parachutes, it is not only required that the umbrella cloth has heat resistance and high strength-to-weight ratio, but also has a good water-repellent effect to improve the adaptability in rainy and snowy weather in outdoor conditions. Therefore, in order to improve the application performance of nylon umbrella cloth, it is necessary to carry out heat-resistant and water-repellent finishing on it.

[0004] In the actual functional finishing of nylon filament fabrics, durable heat-resistant and water-repellent finishing is mostly carried out on a continuous stentering machine by padding heat-resistant and water-repellent finishing agents and then high-temperature baking. Due to the relatively high treatment temperature during baking, not only is the production energy consumption relatively high, but while imparting the heat-resistant and water-repellent effect to the fabric, there are also many defects such as fiber strength damage during high-temperature treatment, high-temperature yellowing of the nylon umbrella cloth, or poor hand feeling. Therefore, how to optimize the process to improve the heat-resistant and flame-retardant properties of nylon taffeta while minimizing the production energy consumption, reducing fiber damage and yellowing during the finishing process, and reducing adverse effects is the research focus of the functional finishing of synthetic fiber products including nylon umbrella canopies. Summary of the Invention

[0005] In view of the above problems, the present invention provides a heat-resistant and water-repellent nylon umbrella cloth, its processing method and application, aiming to achieve heat-resistant and water-repellent finishing of the nylon umbrella cloth under mild conditions, while obtaining a lasting and stable finishing effect, minimizing fiber damage, and improving the finishing effect.

[0006] To achieve the above object, on the one hand, the present invention provides a processing method for a heat-resistant and water-repellent nylon umbrella cloth, and the processing method includes the following steps:

[0007] (1) Pretreat the nylon umbrella cloth with a polyamidase treatment solution;

[0008] (2) Immerse the nylon umbrella cloth treated in step (1) in an allylamine hydrochloride solution, and graft allylamine on the fiber surface by means of 1-ethyl-(3-dimethylaminopropyl)carbodiimide catalysis;

[0009] (3) Pad the nylon umbrella cloth treated in step (2) in a solution containing vinyl polyimide and hexafluorobutyl methacrylate, and catalyze the graft polymerization of the polymer on the fabric surface by means of peroxidase. After treatment, wash and dry the sample to obtain the product.

[0010] In the above technical solution, first, the nylon umbrella cloth is pretreated with polyamidase to hydrolyze the amide bond on the surface of the nylon fiber to generate amino groups; then, the reactivity of the nylon is improved by grafting allylamine; finally, the nylon umbrella cloth is padded with a solution containing vinyl polyimide and hexafluorobutyl methacrylate, and peroxidase-catalyzed graft polymerization crosslinking is carried out to obtain a heat-resistant and water-repellent nylon umbrella cloth.

[0011] Preferably, in step (1), the nylon umbrella cloth is made of nylon 66 filament as raw material, woven with plain weave, and the gram weight per square meter is 40-50 g / m 2 of umbrella cloth.

[0012] Preferably, in step (1), the concentration of polyamidase in the treatment solution is 0.5-1.5 U / mL; and / or

[0013] The pretreatment conditions are pH 7-8, 45-55 °C, bath ratio 1:(5-10), and treatment time 1-2 hours.

[0014] Preferably, in step (2), the concentration of allylamine hydrochloride in the solution is 10-15 g / L, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide is 2.5-5 g / L, and the concentration of N-hydroxysuccinimide is 3-6 g / L; and / or

[0015] The catalysis conditions are pH 4-6, 20-40 °C, bath ratio 1:(5-10), and treatment for 4-6 hours.

[0016] Preferably, in step (3), the solution contains 25 - 40 g / L of vinyl polyimide, 10 - 20 g / L of hexafluorobutyl methacrylate, 2 - 4 g / L of emulsifier, 5 - 10 U / mL of peroxidase, 1 - 2 g / L of hydrogen peroxide, and 0.5 - 1 g / L of acetylacetone; and / or

[0017] The catalytic conditions are pH 6.5 - 7.5, 30 - 40 °C, bath ratio 1:(5 - 10), and treatment for 2 - 4 hours.

[0018] In the above technical solution, the emulsifier promotes the dispersion of hexafluorobutyl methacrylate with relatively low water solubility to form an emulsion. Hydrogen peroxide and acetylacetone are supporting radical donors in the peroxidase catalysis.

[0019] More preferably, the above solution further includes 2 - 4 g / L of emulsifier, 1 - 2 g / L of hydrogen peroxide, and 0.5 - 1 g / L of acetylacetone.

[0020] Preferably, in step (3), the vinyl polyimide includes polyethyleneimine with a molecular weight of 1800 - 3000, in which the amino group is substituted by a vinyl group and the substitution degree is 70 - 80%.

[0021] The high-molecular-weight vinyl polyimide is prone to large steric hindrance and is difficult to form a close bond on the fiber surface; the substitution degree is preferably 70 - 80%. Too low substitution degree results in poor reactivity, and too high substitution degree results in poor water solubility.

[0022] The second aspect of the present invention provides a kind of anti-burning and water-repellent nylon umbrella cloth prepared by the above method.

[0023] The third aspect of the present invention provides the application of the above anti-burning and water-repellent nylon umbrella cloth material in the preparation of parachutes.

[0024] Through the above technical solution, the present invention achieves the following beneficial effects:

[0025] The present invention first uses polyamidase for enzymatic pretreatment of nylon umbrella cloth to hydrolyze amide bonds on the surface of nylon fibers to generate amino groups; then uses 1-ethyl-(3-dimethylaminopropyl)carbodiimide to catalyze the grafting of allylamine on the surface of nylon fibers, and further grafts and polymerizes and crosslinks with vinyl polyimide and hexafluorobutyl methacrylate through peroxidase catalysis to obtain anti-burning and water-repellent nylon umbrella cloth. Compared with the traditional high-temperature baking method for finishing, the method described in the present invention has the following advantages:

[0026] (1) Significant anti-burn and water-repellent effects: The present invention constructs an enzymatic anti-burn and water-repellent finishing method. Under the catalysis of peroxidase, vinyl-containing polyimide and water-repellent monomer hexafluorobutyl methacrylate can undergo graft polymerization reaction with vinyl on the surface of nylon fiber to form a copolymer with anti-burn and water-repellent effects on the fiber surface. This not only improves the anti-burn and water-repellent effects of the umbrella cloth, but also significantly improves the strength of the nylon umbrella cloth.

[0027] (2) Long-lasting finishing effect: Since nylon fiber has fewer reactive groups on its surface, the finishing agent or polymer applied in conventional finishing is not firmly bonded to the fiber. The method of the present invention is used to graft allylamine on the fiber surface to promote enzymatic graft polymerization to form an anti-burn and water-repellent layer, which has a long-lasting and stable finishing effect.

[0028] (3) Low energy consumption in production: The method of the present invention can realize the production of brocade umbrella cloth under low temperature and mild conditions. Not only the reaction conditions in the production process are relatively mild, but also the problem of reduced fabric strength caused by traditional high temperature baking method is avoided. DETAILED DESCRIPTION

[0029] The specific implementation of the present invention is described in detail below in conjunction with the examples. It should be understood that the specific implementation described herein is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0030] Embodiment 1:

[0031] (1) Polyamide enzyme pretreatment: The brocade umbrella cloth was pretreated with a treatment solution having a polyamide enzyme concentration of 0.5 U / mL. The treatment conditions were pH 7, 45°C, bath ratio 1:5, and treatment time of 1 hour. After treatment, the sample was washed with water. The brocade umbrella cloth was woven with nylon 66 filament plain weave and had a grammage per square meter of 40 g / m 2 ;

[0032] (2) Reactive activation of brocade silk: The brocade silk umbrella cloth treated in step (1) was immersed in a solution containing 10 g / L allylamine hydrochloride, 2.5 g / L 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 3 g / L N-hydroxysuccinimide. The treatment conditions were pH 4, 20°C, bath ratio 1:5, and treatment time 4 hours. Allylamine was grafted onto the fiber surface by 1-ethyl-(3-dimethylaminopropyl)carbodiimide. After treatment, the sample was washed with water.

[0033] (3) Catalytic graft deposition of polymer: Dip and roll the nylon umbrella cloth treated in step (2) in a solution containing 25 g / L of vinyl polyimide, 10 g / L of hexafluorobutyl methacrylate, 2 g / L of Tween 80, 5 U / mL of peroxidase, 1 g / L of hydrogen peroxide, and 0.5 g / L of acetylacetone. The treatment conditions are pH 6.5, 30 °C, bath ratio 1:5, and treatment for 2 hours. Catalytically graft the polymer on the fabric surface with the help of peroxidase. After treatment, wash the sample with water and dry it; the vinyl polyimide has a molecular weight of 1800, the amino group is substituted by vinyl, and the substitution degree is 70%.

[0034] Example 2:

[0035] (1) Polyamidase pretreatment: Pretreat the nylon umbrella cloth with a treatment solution with a polyamidase concentration of 1.5 U / mL. The treatment conditions are pH 8, 55 °C, bath ratio 1:10, and treatment for 1 hour; after treatment, wash the sample with water; among them, the nylon umbrella cloth is woven with nylon 66 filament plain weave, and the gram weight per square meter is 50 g / m 2 ;

[0036] (2) Reactive activation of nylon: Immerse the nylon umbrella cloth treated in step (1) in a solution containing 15 g / L of allylamine hydrochloride, 5 g / L of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 6 g / L of N-hydroxysuccinimide. The treatment conditions are pH 6, 40 °C, bath ratio 1:10, and treatment for 6 hours. Catalytically graft allylamine on the fiber surface with the help of 1-ethyl-(3-dimethylaminopropyl)carbodiimide. After treatment, wash the sample with water;

[0037] (3) Catalytic graft deposition of polymer: Dip and roll the nylon umbrella cloth treated in step (2) in a solution containing 40 g / L of vinyl polyimide, 20 g / L of hexafluorobutyl methacrylate, 4 g / L of Tween 80, 10 U / mL of peroxidase, 2 g / L of hydrogen peroxide, and 1 g / L of acetylacetone. The treatment conditions are pH 7.5, 40 °C, bath ratio 1:10, and treatment for 4 hours. Catalytically graft the polymer on the fabric surface with the help of peroxidase. After treatment, wash the sample with water and dry it; the vinyl polyimide has a molecular weight of 3000, the amino group is substituted by vinyl, and the substitution degree is 80%.

[0038] Example 3:

[0039] (1) Polyamidase pretreatment: Pretreat the nylon umbrella cloth with a treatment solution with a polyamidase concentration of 1 U / mL. The treatment conditions are pH 8, 50 °C, bath ratio 1:8, and treatment for 1.5 hours; after treatment, wash the sample with water; among them, the nylon umbrella cloth is woven with nylon 66 filament plain weave, and the gram weight per square meter is 45 g / m 2 ;

[0040] (2)Reactive activation of nylon: Immerse the nylon umbrella fabric treated in step (1) in a solution containing 12 g / L of allylamine hydrochloride, 4 g / L of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 4 g / L of N-hydroxysuccinimide. The treatment conditions are pH 5, 30 °C, liquor ratio 1:8, and treatment for 5 hours. Catalyze the grafting of allylamine on the fiber surface with 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and wash the sample with water after treatment;

[0041] (3)Catalytic grafting and deposition of polymer: Pad the nylon umbrella fabric treated in step (2) in a solution containing 30 g / L of vinyl polyimide, 15 g / L of hexafluorobutyl methacrylate, 3 g / L of Tween 80, 8 U / mL of peroxidase, 1 g / L of hydrogen peroxide, and 1 g / L of acetylacetone. The treatment conditions are pH 7, 40 °C, liquor ratio 1:8, and treatment for 3 hours. Catalyze the grafting of the polymer on the fabric surface with peroxidase, and wash and dry the sample after treatment; The vinyl polyimide has a molecular weight of 2500, the amino group is substituted by vinyl, and the substitution degree is 75%.

[0042] Comparative example 1:

[0043] The nylon umbrella fabric in Example 1 without any treatment.

[0044] Comparative example 2:

[0045] In Example 1, without undergoing steps (1) and (2), only treated with step (3), and other conditions or descriptions are the same as those in Example 1.

[0046] Comparative example 3:

[0047] In Example 1, without undergoing step (1), only treated with steps (2) and (3), and other conditions or descriptions are the same as those in Example 1.

[0048] Comparative example 4:

[0049] In Example 1, without undergoing step (2), only treated with steps (1) and (3), and other conditions or descriptions are the same as those in Example 1;

[0050] Comparative example 5:

[0051] The nylon umbrella fabric in Example 2 without any treatment.

[0052] Comparative example 6:

[0053] In Example 2, without undergoing steps (1) and (2), only treated with step (3), and other conditions or descriptions are the same as those in Example 2.

[0054] Comparative example 7:

[0055] For Example 2, the treatment in (1) is not carried out, and only the treatments in steps (2) and (3) are carried out, and other conditions or descriptions are the same as those in Example 2.

[0056] Comparative Example 8:

[0057] For Example 2, the treatment in (2) is not carried out, and only the treatments in steps (1) and (3) are carried out, and other conditions or descriptions are the same as those in Example 2.

[0058] Performance Test

[0059] Measure the warp breaking strength, anti-burning property, limiting oxygen index (LOI value), and water repellency grade of the specimens in the above Examples 1 to 3 and Comparative Examples 1 to 8. Among them, the breaking strength is measured with reference to FZ / T 65001-1995 / 5.4 "Test Methods for Physical and Mechanical Properties of Special Industrial Fabrics / Breaking Strength and Elongation"; the anti-burning property is measured with reference to FZ / T 65001-1995 / 5.13 "Test Methods for Physical and Mechanical Properties of Special Industrial Fabrics / Anti-burning Property" and GB / T 5454-1997 "Textiles - Test Method for Burning Performance - Oxygen Index Method"; the water repellency is measured with reference to AATCC 22-2017 "Water Repellency Test - Spray Method": The specimens 1 to 2 of the implementation and the specimens 1 to 8 of the comparison are washed at 60 °C for 2 hours and then dried at room temperature again, and the water repellency grade of the nylon umbrella fabric after washing is measured. The obtained data are listed in Table 1.

[0060] Table 1 Performance Test Results

[0061]

[0062] As can be seen from Table 1:

[0063] a. The specimens (Example 1, Example 2, Example 3) treated by the method described in the present invention have high breaking strength, qualified anti-burning property, and high LOI value, indicating good anti-burning performance; the water repellency grades of the fabric specimens before and after washing are both 5, indicating that the method described in the present invention can promote the catalytic grafting of a polymer layer with anti-burning and water repellent functions on the fiber surface, meeting the preparation requirements of the anti-burning and water repellent nylon umbrella fabric, and the finishing effect has lasting stability.

[0064] b. The fabric specimens of the nylon umbrella fabric specimens without any treatment (Comparative Example 1, Comparative Example 5) do not have anti-burning property, have poor flame retardancy, and have a low water repellency grade, and cannot meet the application requirements of anti-burning and water repellency.

[0065] c. For the specimens that were only processed in step (3) without going through steps (1) and (2) (Comparative Example 2 and Comparative Example 6), the fabric breaking strength of both specimens increased compared to the unprocessed sample, but was lower than that of the corresponding example specimens; the water repellency grade of the specimens decreased after washing, indicating that the anti-burning and water-repellent layer formed by catalytic polymerization crosslinking on the specimen surface was not firmly bonded to the fiber, and the finishing effect was not persistent.

[0066] d. For the specimens that were only processed in steps (2) and (3) without going through step (1) (Comparative Example 3 and Comparative Example 7), the strength was lower than that of the corresponding example specimens. Since allylamine in step (2) did not bind to the amino groups on the fiber surface, the reactivity of the fiber surface was not improved, resulting in the anti-burning and water-repellent polymers not covalently bonding to the fiber, manifested as a decrease in the water repellency grade of the nylon silk umbrella cloth after washing.

[0067] e. For the specimens that were only processed in steps (1) and (3) without going through step (2) (Comparative Example 4 and Comparative Example 8), although amino groups were generated on the nylon fiber after pretreatment with polyamidase in step (1), since vinyl sites were not introduced through step (2) treatment, the fiber did not graft with the polymer during step (3) treatment. Therefore, the strength of the specimens decreased slightly compared to the specimens only processed in step (3), and the water repellency grade decreased after washing, indicating that the finishing effect was not persistent.

[0068] The preferred embodiments of the present invention have been described in detail above in combination with examples. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0069] In addition, it should be noted that for each of the specific technical features described in the above specific embodiments, they can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0070] Furthermore, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. A processing method for a burn-proof and water-repellent nylon umbrella cloth, characterized in that, It includes the following steps: (1) Pretreat the nylon umbrella cloth with a polyamidase treatment solution; (2) Immerse the nylon umbrella cloth treated in step (1) in an allylamine hydrochloride solution, and graft allylamine on the fiber surface with the catalysis of 1-ethyl-(3-dimethylaminopropyl)carbodiimide. The catalytic conditions are pH 4-6, 20-40 °C, liquor ratio 1:(5-10), and treatment for 4-6 hours; (3) Pad the nylon umbrella cloth treated in step (2) in a solution containing vinyl polyimide, hexafluorobutyl methacrylate, emulsifier, hydrogen peroxide, and acetylacetone, and catalyze the grafting of polymers on the fabric surface with the catalysis of peroxidase. After treatment, wash and dry the sample to obtain it. The catalytic conditions are pH 6.5-7.5, 30-40 °C, liquor ratio 1:(5-10), and treatment for 2-4 hours. The vinyl polyimide includes polyethyleneimine with a molecular weight of 1800-3000, in which the amino group is substituted by a vinyl group and the substitution degree is 70-80%; 2. The processing method according to claim 1, characterized in that In step (1), the nylon umbrella cloth is woven with nylon 66 filaments as raw materials and in plain weave, with a gram weight per square meter of 40 to 50 g / m 2 of umbrella cloth.

3. The processing method according to claim 1, wherein In step (1), the concentration of polyamidase in the treatment solution is 0.5-1.5 U / mL; and / or The pretreatment conditions are pH 7-8, 45-55 °C, liquor ratio 1:(5-10), and treatment time 1-2 hours.

4. The processing method according to claim 1, characterized in that, In step (2), the concentration of allylamine hydrochloride in the solution is 10-15 g / L, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide is 2.5-5 g / L, and the concentration of N-hydroxysuccinimide is 3-6 g / L.

5. The processing method according to claim 1, characterized in that, In step (3), the solution contains 25-40 g / L of vinyl polyimide, 10-20 g / L of hexafluorobutyl methacrylate, 5-10 U / mL of peroxidase, 2-4 g / L of emulsifier, 1-2 g / L of hydrogen peroxide, and 0.5-1 g / L of acetylacetone.

6. The nylon umbrella cloth with anti-burning and water-repellent properties prepared by the method according to any one of claims 1 to 5.

7. The application of the anti-burning and water-repellent nylon umbrella cloth material according to claim 6 in the preparation of parachutes.

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