Antibacterial fabric based on graphene chinlon composite fibers and production process thereof

Abstract

The invention relates to the technical field of textiles, in particular to an antibacterial fabric based on graphene chinlon composite fibers and a production process of the antibacterial fabric. The problem that an antibacterial fabric is poor in antibacterial performance and durability is solved. Modified graphene, Ag / ZnO nanoparticles and chinlon master batches are subjected to melt extrusion spinning to obtain modified chinlon fibers, and a composite anti-ultraviolet agent, a modified antioxidant, a modified moisture absorbent and polyester master batches are subjected to melt extrusion spinning to obtain modified polyester fibers. Finally, the modified polyamide fiber, the modified polyester fiber, the cotton fiber and the bamboo fiber are mixed, twisted, heated, shaped, blended and woven to obtain the antibacterial fabric. According to the invention, the modified graphene and the Ag / ZnO nanoparticles can synergistically improve the antibacterial performance of the antibacterial fabric; the chinlon master batch, the polyester master batch and the cotton fiber jointly improve the mechanical property of the antibacterial fabric; the composite anti-ultraviolet agent, the modified antioxidant, the modified moisture absorbent and the bamboo fibers can improve the anti-ultraviolet performance, the moisture absorption performance and the air permeability of the antibacterial fabric.

Description

Technical Field

[0001] The present invention relates to the field of textile technology, and in particular to an antibacterial fabric based on graphene nylon composite fiber and a production process thereof. Background Art

[0002] As the world's earliest industrialized synthetic fiber, nylon fiber was widely popular in the 20th century due to its high strength, good elasticity, and good wear resistance. However, with the changing times, people's demands for clothing in terms of comfort, hygiene, health, and special occasions have become increasingly diverse. Conventional nylon products can no longer meet people's needs. They are prone to static electricity, which can easily cause the surface of the fabric to absorb dust. In addition, the sweat discharged by the human body creates a breeding ground for bacteria. In addition, conventional nylon fibers have many limitations in responding to people's pursuit of high performance in clothing today, which needs to be improved in order to meet market demand.

[0003] As people's living standards continue to improve, the requirements for fabrics used to make clothing are also getting higher and higher, especially for the antibacterial properties of fabrics. This is because the sweat discharged from the human body contains about 99% water and 1% human metabolites. These excrement are difficult to clean and are easily retained in the fiber structure of the fabric, breeding a large number of bacteria. Most of the existing fabrics are woven with antibacterial fibers to solve the problem of bacterial growth, but most of them do not pay attention to the breathability of the fabric. If the air permeability of the fabric is poor, the sweat of the human body cannot be discharged in time, and a large amount of water vapor will remain in the fabric. The humid environment provides good conditions for the growth and reproduction of harmful microorganisms. With the extension of wearing time, bacteria can still breed inside the fabric. Long-term wearing of such clothes is likely to cause human skin diseases and affect physical health. Therefore, it is very important to improve the antibacterial properties of the fabric.

[0004] In summary, today's antibacterial fabrics still have problems with poor antibacterial performance and durability, which seriously limits their application in the market.

[0005] To this end, an antibacterial fabric based on graphene nylon composite fiber and its production process were proposed. Summary of the invention

[0006] The purpose of the present invention is to design an antibacterial fabric based on graphene nylon composite fiber and its production process. The synthetic raw materials of the present invention include modified graphene, Ag / ZnO nanoparticles, polyester masterbatch, nylon masterbatch, cotton fiber, bamboo fiber, composite anti-ultraviolet agent, modified antioxidant and modified moisture absorbent; the modified graphene, Ag / ZnO nanoparticles and nylon masterbatch are melt-extruded and spun to obtain modified nylon fiber, the composite anti-ultraviolet agent, modified antioxidant, modified moisture absorbent and polyester masterbatch are melt-extruded and spun to obtain modified polyester fiber, and finally the modified nylon fiber, modified polyester fiber, cotton fiber and bamboo fiber are mixed, twisted, heated and shaped, and blended to obtain antibacterial fabric. The modified graphene and Ag / ZnO nanoparticles in the present invention can synergistically improve the antibacterial properties of the antibacterial fabric; the nylon masterbatch, polyester masterbatch and cotton fiber can jointly improve the mechanical properties of the antibacterial fabric; the composite anti-ultraviolet agent, modified antioxidant, modified moisture absorbent and bamboo fiber can improve the anti-ultraviolet and moisture absorption and breathability properties of the antibacterial fabric.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] In one aspect, the present invention provides an antibacterial fabric based on graphene nylon composite fiber, wherein the antibacterial fabric comprises the following components by weight:

[0009] Modified graphene: 1-5 parts; Ag / ZnO nanoparticles: 1-3 parts; polyester masterbatch: 15-20 parts; nylon masterbatch: 20-30 parts; cotton fiber: 15-20 parts; bamboo fiber: 3-8 parts; composite anti-ultraviolet agent: 0.5-1 parts; modified antioxidant: 0.5-0.9 parts; modified moisture absorbent: 1-5 parts;

[0010] The modified graphene includes graphene oxide, ethylenediamine and triethylamine;

[0011] The modified antioxidant includes antioxidant 1010 and octadecanoyl chloride;

[0012] Modified hygroscopic agents include chitosan and chloroacetic acid.

[0013] Preferably, the molecular weight of the polyester masterbatch is 25,000; the molecular weight of the nylon masterbatch is 20,000.

[0014] Preferably, the composite anti-ultraviolet agent comprises 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, and the weight ratio of 2-hydroxy-4-methoxybenzophenone to nano zinc oxide is 1-5:2.

[0015] Another aspect of the present invention provides a production process of an antibacterial fabric based on graphene nylon composite fiber, the production process comprising the following steps:

[0016] S1: put modified graphene, Ag / ZnO nanoparticles and nylon masterbatch into a high-speed mixer, heat to 180°C, stir at 600rpm for 40min, and then extrude and granulate to obtain mixed masterbatch A, put mixed masterbatch A into a screw extruder, the regional temperatures are 250°C, 260°C, 275°C, and 285°C, respectively, and then spin to obtain modified nylon fiber, the spinning speed is 1500m / min-1600m / min, and the draft multiple is 1.5 times;

[0017] S2: putting the composite anti-ultraviolet agent, modified antioxidant, modified moisture absorbent and polyester masterbatch into a high-speed mixer, heating to 230°C, stirring at 800rpm for 40min, and then extruding and granulating to obtain mixed masterbatch B, putting the mixed masterbatch B into a screw extruder, the regional temperatures are 255°C, 265°C, 280°C, and 290°C, respectively, and then spinning to obtain modified polyester fiber, the spinning speed is 1700m / min-1800m / min, and the draft multiple is 2 times;

[0018] S3 mixes and twists modified nylon fiber, modified polyester fiber, cotton fiber and bamboo fiber, heats and sets them in hot water at a temperature of 85°C for 100 min-120 min, and then blends and weaves them to obtain antibacterial fabrics.

[0019] Preferably, in parts by weight, the preparation method of modified graphene is: slowly adding 3-8 parts of graphene oxide to 200 parts of N,N-dimethylformamide, stirring at a speed of 350rpm for 2.5h to obtain a dispersion; adding 10 parts of ethylenediamine and 2 parts of triethylamine to the dispersion in sequence to obtain a mixed solution; transferring the mixed solution to a three-necked flask, slowly heating it to 80°C, and then reacting for 6h-8h to obtain a reaction system; after the reaction is completed, cooling the reaction system to room temperature, then washing with anhydrous ethanol and centrifuging it 5 times, and finally vacuum drying it for 12h to obtain modified graphene.

[0020] Preferably, the preparation method of Ag / ZnO nanoparticles is as follows: adding 12-17 parts of zinc acetate to 100 parts of ethylene glycol methyl ether, stirring at a speed of 300 rpm and 65° C. for 20 minutes to obtain a mixed solution A; dissolving 2 parts of silver nitrate in 30 parts of ethylene glycol methyl ether, stirring for 20 minutes to obtain a mixed solution B; slowly adding the mixed solution B to the mixed solution A, the dripping speed is controlled at 1 drop per second, and after the dripping is completed, continuing to stir for 15 minutes to 20 minutes to obtain a mixed solution; 10 parts of diethanolamine were added to the mixed solution, and the mixture was stirred for 25 minutes to obtain a sol; the sol was placed at room temperature for gelation for 20 hours to obtain a gel; the gel was placed in an oven, aged at 65°C for 3 hours, then naturally dried in air for 2 hours, and then vacuum dried at 85°C for 5 hours to obtain a dry product; the dry product was ground and placed in a muffle furnace, heated to 520°C-580°C at a heating rate of 5°C / min, and then calcined for 3 hours. After the calcination, the muffle furnace was cooled to room temperature to obtain Ag / ZnO nanoparticles.

[0021] Preferably, the preparation method of the modified antioxidant is as follows, by weight: adding 8-12 parts of antioxidant 1010 to 50 parts of toluene, stirring at a speed of 200 rpm for 2 hours to obtain a uniform solution; slowly dropping 12-15 parts of octadecanoyl chloride into the uniform solution, controlling the dropping speed at 5 mL per minute, and continuously stirring for 2 hours, after the dropwise addition is completed, then adding 1 part of pyridine, and continuing to stir and react for 4 hours to 6 hours to obtain a mixed solution; after cooling the mixed solution to room temperature, slowly adding a hydrochloric acid solution with a mass fraction of 8%, then adjusting the pH value of the solution to 7, then washing with deionized water and distilling under reduced pressure to obtain a crude product; recrystallizing the crude product, and then filtering and drying to obtain the modified antioxidant.

[0022] Preferably, the preparation method of the modified desiccant is as follows, by weight: adding 8-12 parts of chitosan to 150 parts of isopropanol, stirring at room temperature for 1.5 hours to obtain a mixed solution; dissolving 15 parts of sodium hydroxide in 35 parts of deionized water to obtain a sodium hydroxide solution; slowly dropping the sodium hydroxide solution into the mixed solution under stirring conditions, the dropping time is 45 minutes, and then continuing to stir and react at 40°C for 1.5 hours to obtain an alkaline solution; dissolving 15-20 parts of chloroacetic acid in 35 parts of isopropanol to obtain a chloroacetic acid solution; slowly dropping the chloroacetic acid solution into the alkaline solution under stirring conditions, the dropping time is 1.5 hours, heating to 60°C, continuing to stir and react for 3 hours to 5 hours to obtain a reaction solution; after the reaction is completed, cooling the reaction solution to room temperature, adjusting the pH value to neutral, then washing with deionized water and ethanol and vacuum drying to obtain a modified desiccant.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The introduction of amine groups makes the graphene surface positively charged, while the bacterial surface is usually negatively charged. According to the principle of charge attraction, amine-modified graphene can more effectively adsorb bacteria, increase the chance of contact with bacteria, and lay the foundation for subsequent antibacterial effects; modified graphene has a two-dimensional sheet structure and can form a uniform covering layer on the surface of the fabric, like a physical barrier, preventing bacteria from directly contacting the fabric, thereby reducing the attachment and growth space of bacteria on the fabric. Ag / ZnO nanoparticles have good photocatalytic properties and can more efficiently generate electron-holes under visible light irradiation, enhancing the antibacterial effect; at the same time, photocatalysis can also decompose organic pollutants on the surface of the fabric, keep the fabric clean, reduce the nutrient source for bacterial growth, and further inhibit bacterial growth.

[0025] 2. The high strength and high elastic recovery provided by nylon masterbatch, combined with the crisp wrinkle resistance and dimensional stability of polyester masterbatch, make up for each other's shortcomings. The soft skin-friendly and hygroscopic properties of cotton fiber improve the comfort of the fabric while making the fabric more tough and durable overall. The synergistic effect of the three materials significantly improves the mechanical properties of the antibacterial fabric. During the weaving process of the fabric, nylon, polyester and cotton fibers are interwoven to form a complex fiber network structure. This interwoven structure makes the fibers more closely bonded, enhancing the integrity and stability of the fabric. The interaction between different fibers can also disperse external forces. When the fabric is stretched or torn, the stress can be transmitted and shared between different fibers, thereby improving the fabric's ability to resist damage and improving the durability of the antibacterial fabric.

[0026] 3. Antioxidant 1010 is modified by long-chain alkyl grafting. The phenolic hydroxyl oxygen atom in the antioxidant 1010 molecule is nucleophilic and will attack the carbonyl carbon atom in the octadecanoyl chloride molecule. The lone pair of electrons on some phenolic hydroxyl oxygen atoms forms a new covalent bond with the carbonyl carbon atom. 2-Hydroxy-4-methoxybenzophenone and nano zinc oxide in the composite anti-ultraviolet agent play a role in absorbing and scattering ultraviolet rays respectively. The combination of the two can effectively block ultraviolet rays; and the long-chain alkyl grafted modified antioxidant stabilizes the molecular structure of the fabric and forms a protective film, so that the composite anti-ultraviolet agent can exist more stably in the fabric and play a role, thereby enhancing the overall ultraviolet absorption and scattering effect, improving the anti-ultraviolet performance of the fabric, and the durability of the antibacterial fabric is also improved.

[0027] 4. Modified desiccant, bamboo fiber and cotton fiber are all hygroscopic, and they cooperate with each other to form a multi-level moisture absorption system. Carboxyl-modified chitosan uses its strong hygroscopic groups to quickly absorb moisture, while bamboo fiber and cotton fiber further absorb and conduct moisture through their respective hydrophilic groups, which significantly improves the hygroscopic performance of the fabric; the macroporous structure of bamboo fiber is conducive to the rapid circulation of air, and the pores and gaps of cotton fiber play an auxiliary role, allowing the air to form complex circulation channels in the fabric; the microporous structure formed by carboxyl-modified chitosan further increases the path for air circulation. The synergistic effect of the three optimizes the breathability of the fabric, allowing air to enter and exit the fabric more freely, providing a comfortable microclimate environment for the wearer, and the durability of the antibacterial fabric is also improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a graph showing the antibacterial performance of Example 3 and Comparative Examples 1-5 of the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Specific reference Figure 1 The present invention provides an antibacterial fabric based on graphene nylon composite fiber and its production process, and the technical scheme is as follows:

[0031] Example 1

[0032] The composite anti-ultraviolet agent comprises 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, and the weight ratio of 2-hydroxy-4-methoxybenzophenone to the nano zinc oxide is 1:2.

[0033] Slowly add 3 parts of graphene oxide into 200 parts of N,N-dimethylformamide, stir at 350 rpm for 2.5 hours to obtain a dispersion; add 10 parts of ethylenediamine and 2 parts of triethylamine to the dispersion in sequence to obtain a mixed solution; transfer the mixed solution to a three-necked flask, slowly heat it to 80°C, and then react for 6 hours to obtain a reaction system; after the reaction, cool the reaction system to room temperature, then wash with anhydrous ethanol and centrifuge for 5 times, and finally vacuum dry for 12 hours to obtain modified graphene.

[0034] 12 parts of zinc acetate were added to 100 parts of ethylene glycol methyl ether, and stirred at a speed of 300 rpm and 65°C for 20 minutes to obtain a mixed solution A; 2 parts of silver nitrate were dissolved in 30 parts of ethylene glycol methyl ether, and stirred for 20 minutes to obtain a mixed solution B; the mixed solution B was slowly added to the mixed solution A, and the drop rate was controlled to 1 drop per second. After the drop addition was completed, the stirring was continued for 15 minutes to obtain a mixed solution; 10 parts of diethanolamine were added to the mixed solution, and the stirring was completed for 25 minutes to obtain a sol; the sol was placed at room temperature for gelation for 20 hours to obtain a gel; the gel was placed in an oven, aged at 65°C for 3 hours, then naturally dried in the air for 2 hours, and then vacuum dried at 85°C for 5 hours to obtain a dry product; the dry product was ground and placed in a muffle furnace, heated to 520°C at a heating rate of 5°C / min, and then calcined for 3 hours. After the calcination was completed, the muffle furnace was cooled to room temperature to obtain Ag / ZnO nanoparticles.

[0035] 8 parts of antioxidant 1010 were added to 50 parts of toluene, and stirred at a speed of 200 rpm for 2 hours to obtain a uniform solution; 12 parts of octadecanoyl chloride were slowly added dropwise to the uniform solution, and the dropping speed was controlled at 5 mL per minute, and the stirring was continued for 2 hours. After the dropwise addition was completed, 1 part of pyridine was then added, and the stirring reaction was continued for 4 hours to obtain a mixed solution; after the mixed solution was cooled to room temperature, a hydrochloric acid solution with a mass fraction of 8% was slowly added, and the pH value of the solution was adjusted to 7, and then washed with deionized water and distilled under reduced pressure to obtain a crude product; the crude product was recrystallized, and then filtered and dried to obtain a modified antioxidant.

[0036] 8 parts of chitosan were added to 150 parts of isopropanol, and stirred at room temperature for 1.5 hours to obtain a mixed solution; 15 parts of sodium hydroxide were dissolved in 35 parts of deionized water to obtain a sodium hydroxide solution; under stirring conditions, the sodium hydroxide solution was slowly dropped into the mixed solution for 45 minutes, and then the stirring reaction was continued at 40°C for 1.5 hours to obtain an alkaline solution; 15 parts of chloroacetic acid were dissolved in 35 parts of isopropanol to obtain a chloroacetic acid solution; under stirring conditions, the chloroacetic acid solution was slowly dropped into the alkaline solution for 1.5 hours, the temperature was raised to 60°C, and the stirring reaction was continued for 3 hours to obtain a reaction solution; after the reaction was completed, the reaction solution was cooled to room temperature, the pH value was adjusted to neutral, and then washed with deionized water and ethanol and vacuum dried to obtain a modified desiccant.

[0037] Production of antibacterial fabrics:

[0038] S1 puts modified graphene, Ag / ZnO nanoparticles and nylon masterbatch into a high-speed mixer, heats to 180°C, stirs at 600 rpm for 40 min, and then extrudes and granulates to obtain mixed masterbatch A, puts mixed masterbatch A into a screw extruder, and the regional temperatures are 250°C, 260°C, 275°C, and 285°C, respectively, and then spins to obtain modified nylon fiber, the spinning speed is 1500 m / min, and the draft multiple is 1.5 times;

[0039] S2: putting the composite anti-ultraviolet agent, modified antioxidant, modified moisture absorbent and polyester masterbatch into a high-speed mixer, heating to 230°C, stirring at 800 rpm for 40 min, and then extruding and granulating to obtain mixed masterbatch B, and putting the mixed masterbatch B into a screw extruder, with the zone temperatures being 255°C, 265°C, 280°C and 290°C, respectively, followed by spinning to obtain modified polyester fiber, with a spinning speed of 1700 m / min and a drafting multiple of 2 times;

[0040] S3 mixes and twists modified nylon fiber, modified polyester fiber, cotton fiber and bamboo fiber, heats and sets them in hot water at a temperature of 85°C for 100 minutes, and then blends and weaves them to obtain antibacterial fabrics.

[0041] Examples 2-5 refer to the parameter conditions in Example 1, and the specific differences are shown in Table 1.

[0042] Table 1 Parameter conditions of Examples 1-5

[0043]

[0044] Comparative Example 1 refers to the parameter conditions in Example 1, except that only graphene oxide is added without modifying the graphene oxide.

[0045] Comparative Example 2 refers to the parameter conditions in Example 1, except that no modified graphene is added.

[0046] Comparative Example 3 refers to the parameter conditions in Example 1, except that zinc oxide is added to replace the Ag / ZnO nanoparticles.

[0047] Comparative Example 4 refers to the parameter conditions in Example 1, except that no Ag / ZnO nanoparticles are added.

[0048] Comparative Example 5 refers to the parameter conditions in Example 1, except that modified graphene and Ag / ZnO nanoparticles are not added.

[0049] Experimental Example 1 Antibacterial Performance Test

[0050] The antibacterial properties of Examples 1-5 and Comparative Examples 1-5 were tested according to GB / T 20944.2-2007 standard. The results are shown in Table 2. The antibacterial properties of Example 3 and Comparative Examples 1-5 are shown in Table 2. Figure 1 shown.

[0051] Table 2 Antibacterial performance test of Examples 1-5 and Comparative Examples 1-5

[0052]

[0053]

[0054] From Table 2 and Figure 1It can be found that in Comparative Example 1, only graphene oxide is added, and the graphene oxide is not modified, and the antibacterial rate of the antibacterial fabric decreases. This is because the binding force between graphene oxide and the fabric matrix is ​​weak, and the dispersibility in the fabric is also poor. In Comparative Example 2, the antibacterial rate of the antibacterial fabric also decreases without adding modified graphene. In the process of synthesizing modified graphene, the introduction of amine groups makes the graphene surface positively charged, while the bacterial surface is usually negatively charged. According to the principle of charge attraction, amine-modified graphene can more effectively adsorb bacteria, increase the chance of contact with bacteria, and lay the foundation for subsequent antibacterial effects; modified graphene has a two-dimensional sheet structure, which can form a uniform covering layer on the surface of the fabric, like a physical barrier, preventing bacteria from directly contacting the fabric, thereby reducing the attachment and growth space of bacteria on the fabric. In Comparative Example 3, zinc oxide is added to replace Ag / ZnO nanoparticles. Although zinc oxide has antibacterial properties, a single zinc oxide cannot have stronger antibacterial activity. In Comparative Example 4, if Ag / ZnO nanoparticles are not added, the antibacterial ability of the fabric will be significantly affected. The silver ions in the Ag / ZnO nanoparticles have strong antibacterial ability and can specifically bind to sulfhydryl, amino and other groups in bacterial cells, interfere with the normal metabolic process of bacteria, inhibit bacterial respiration and the activity of various enzymes, and make it impossible for bacteria to carry out normal physiological activities, thereby inhibiting their growth and reproduction; ZnO will undergo a photocatalytic reaction under light conditions to produce electron-hole pairs, which interact with the surrounding water molecules and oxygen to generate active substances with strong oxidizing properties, which can attack the bacterial cell membrane, increase its permeability, and leak intracellular substances. At the same time, it will also destroy the biological molecules in the cell, leading to bacterial death. In Comparative Example 5, neither modified graphene nor Ag / ZnO nanoparticles are added. The absence of these two important antibacterial components will greatly reduce the antibacterial performance of the antibacterial fabric. The modified graphene gathers bacteria around it through adsorption, making it easier for the Ag / ZnO nanoparticles to contact the bacteria, thereby improving the antibacterial efficiency. At the same time, the active substances produced by the modified graphene and the Ag / ZnO nanoparticles have a synergistic effect, which can more comprehensively and thoroughly destroy the cell structure and biomolecules of bacteria, thereby significantly enhancing the antibacterial effect.

[0055] Examples 6-10 refer to the parameter conditions in Example 3, and the specific differences are shown in Table 3.

[0056] Table 3 Parameter conditions of Example 3 and Examples 6-10

[0057]

[0058]

[0059] Comparative Example 6 refers to the parameter conditions in Example 3, except that no nylon masterbatch is added.

[0060] Comparative Example 7 refers to the parameter conditions in Example 3, except that no polyester masterbatch is added.

[0061] Comparative Example 8 refers to the parameter conditions in Example 3, except that no cotton fiber is added.

[0062] Comparative Example 9 refers to the parameter conditions in Example 3, except that the spinning speed in S1 and S2 is 1000 m / min.

[0063] Comparative Example 10 refers to the parameter conditions in Example 3, except that the spinning speed in S1 and S2 is 2300 m / min.

[0064] Comparative Example 11 refers to the parameter conditions in Example 3, except that the hot pressing time in S3 is 50 minutes.

[0065] Comparative Example 12 refers to the parameter conditions in Example 3, except that the hot pressing time in S3 is 180 minutes.

[0066] Experimental Example 2 Mechanical Properties Test

[0067] According to GB / T 3923.1-2013 standard, the elongation at break of Example 3, Examples 6-10 and Comparative Examples 6-12 was tested, and the results are shown in Table 4.

[0068] Table 4 Mechanical properties test of Example 3, Examples 6-10 and Comparative Examples 6-12

[0069] Example Elongation at break / % Example 3 169.8 Example 6 170.1 Example 7 170.4 Example 8 170.6 Example 9 170.2 Example 10 169.9 Comparative Example 6 158.3 Comparative Example 7 159.4 Comparative Example 8 162.9 Comparative Example 9 160.5 Comparative Example 10 163.7 Comparative Example 11 169.6 Comparative Example 12 159.2

[0070] It can be found from Table 4 that the mechanical properties of the embodiment are relatively stable. In Comparative Example 6, nylon has high strength and excellent wear resistance, the fiber molecular chain force made of nylon masterbatch is strong, and the fiber structure is compact, so that the antibacterial fabric has good tensile and tear resistance, and can withstand large external forces without being easily damaged. Without adding nylon masterbatch, the overall elasticity of the fabric will decrease, and the elongation at break will decrease. When subjected to tensile force, the fabric is more likely to reach the breaking point, and the flexibility and extensibility of the fabric will deteriorate. In Comparative Example 7, polyester fiber has high rigidity, and the fiber made of polyester masterbatch is crisp and not easy to deform, which can give the antibacterial fabric good wrinkle resistance. Without adding polyester masterbatch, the fabric will be over-deformed when stretched due to lack of polyester support, resulting in unstable elongation at break, and there will be a phenomenon of rapid increase first and then sharp decline, because the fabric is easy to be stretched in the early stage, but due to the lack of structural stability of polyester, it will eventually break prematurely. In comparative example 8, cotton fiber has certain toughness and elongation at break, which can make the fabric withstand stretching to a certain extent. Without adding cotton fiber, the softness and toughness of the fabric will be reduced, the elongation at break will decrease, and the fabric will easily become stiff and break during the stretching process. In the antibacterial fabric, the high strength and high elastic recovery provided by nylon masterbatch, combined with the crisp wrinkle resistance and dimensional stability of polyester masterbatch, make up for each other's shortcomings. The soft skin-friendly and hygroscopicity of cotton fiber improves the comfort of the fabric while making the fabric more tough and durable as a whole; the synergistic effect of the three materials significantly improves the mechanical properties of the antibacterial fabric, and the durability is also improved accordingly. In comparative example 9, the lower spinning speed makes the fiber molecular chain arrangement more regular and the crystallinity is improved, but this will increase the rigidity of the fiber and reduce the elasticity, resulting in a decrease in the elongation at break of the fabric. In comparative example 10, the higher spinning speed makes the fiber crystallinity and orientation lower, the fiber structure is not tight enough, and the strength of the fabric will decrease. In Comparative Example 11, the hot pressing setting time is short, the fiber setting is not sufficient, the molecular chain is not completely fixed, and the fiber is prone to slippage and rearrangement when the fabric is stretched. The elongation at break is similar to that of the embodiment, but at the same time, the dimensional stability of the fabric will deteriorate. After multiple stretching, the elongation of the fabric may not be restored, and permanent deformation occurs. In Comparative Example 12, the hot pressing setting time is too long, and the fiber is overheated, which will reduce the elasticity of the fiber and increase its brittleness, which will cause the elongation at break of the fabric to decrease. When stretched, the fabric is easy to break and cannot withstand a large elongation.

[0071] Examples 11-15 refer to the parameter conditions in Example 8, and the specific differences are shown in Table 5.

[0072] Table 5 Parameters and conditions of Example 8 and Examples 11-15

[0073]

[0074]

[0075] Comparative Example 13 refers to the parameter conditions in Example 8, except that only 2-hydroxy-4-methoxybenzophenone is added as an anti-ultraviolet agent.

[0076] Comparative Example 14 refers to the parameter conditions in Example 8, except that only nano zinc oxide is added as an anti-ultraviolet agent.

[0077] Comparative Example 15 refers to the parameter conditions in Example 8, except that no composite anti-ultraviolet agent is added.

[0078] Comparative Example 16 refers to the parameter conditions in Example 8, except that only antioxidant 1010 is added without modification.

[0079] Comparative Example 17 refers to the parameter conditions in Example 8, except that no modified antioxidant is added.

[0080] Comparative Example 18 refers to the parameter conditions in Example 8, except that no composite anti-ultraviolet agent and modified antioxidant are added.

[0081] Experimental Example 3 Anti-ultraviolet performance test

[0082] The anti-ultraviolet performance of Example 8, Examples 11-15 and Comparative Examples 13-18 was tested according to GB / T 18830-2002 standard, and the results are shown in Table 6.

[0083] Table 6 Anti-ultraviolet performance test of Example 8, Examples 11-15 and Comparative Examples 13-18

[0084] Example UVA pass rate / % Example 8 1.9 Embodiment 11 1.8 Example 12 1.8 Embodiment 13 1.6 Embodiment 14 1.7 Embodiment 15 1.8 Comparative Example 13 2.9 Comparative Example 14 2.8 Comparative Example 15 4.3 Comparative Example 16 2.7 Comparative Example 17 4.0 Comparative Example 18 6.4

[0085] It can be found from Table 6 that the anti-ultraviolet performance of the embodiment is relatively excellent and stable. In Comparative Example 13, 2-hydroxy-4-methoxybenzophenone is an organic anti-ultraviolet agent that can absorb ultraviolet rays and convert them into heat energy for dissipation, but the absorption band is relatively narrow, mainly for the UV-B band has a good absorption effect, the absorption capacity for the UV-A band is relatively weak, so the fabric is not fully protected against ultraviolet rays, and the anti-ultraviolet performance will be limited. In Comparative Example 14, only nano zinc oxide is used as an anti-ultraviolet agent, which is prone to agglomeration, thereby affecting its absorption efficiency of ultraviolet rays, and the anti-ultraviolet performance decreases. In Comparative Example 15, there is no effect of the composite anti-ultraviolet agent, and the fabric mainly relies on the weak blocking effect of its own fiber on ultraviolet rays, and it is almost impossible to effectively absorb or scatter ultraviolet rays. In Comparative Example 16, a single antioxidant cannot assist the composite anti-ultraviolet agent to exert its anti-ultraviolet performance, and the composite anti-ultraviolet agent is prone to oxidation, thereby affecting its performance. In Comparative Example 17, ultraviolet radiation can cause the polymer material in the fabric to produce free radicals, causing oxidative degradation. The modified antioxidant can capture these free radicals and prevent the oxidation chain reaction from proceeding, thereby stabilizing the molecular structure of the fabric and indirectly improving the anti-ultraviolet performance of the fabric. Without the addition of the modified antioxidant, the oxidation reaction caused by ultraviolet rays cannot be effectively inhibited, so that the anti-ultraviolet components in the fabric cannot be well protected from oxidative damage, and its anti-ultraviolet ability is reduced. In Comparative Example 18, when the composite anti-ultraviolet agent and the modified antioxidant are not added, the anti-ultraviolet performance of the antibacterial fabric is the lowest among all the embodiments and comparative examples. This is because the 2-hydroxy-4-methoxybenzophenone and nano zinc oxide in the composite anti-ultraviolet agent play a role from the perspective of absorbing and scattering ultraviolet rays respectively, and the combination of the two can effectively block ultraviolet rays; and the long-chain alkyl grafted modified antioxidant stabilizes the molecular structure of the fabric and forms a protective film, so that the composite anti-ultraviolet agent can be more stably present in the fabric and play a role, thereby enhancing the overall ultraviolet absorption and scattering effect, improving the anti-ultraviolet performance of the fabric, and the durability of the antibacterial fabric is also improved.

[0086] Examples 16-20 refer to the parameter conditions in Example 13, and the specific differences are shown in Table 7.

[0087] Table 7 Parameter conditions of Example 13 and Examples 16-20

[0088]

[0089] Comparative Example 19 refers to the parameter conditions in Example 13, except that bamboo fiber is not added.

[0090] Comparative Example 20 refers to the parameter conditions in Example 13, except that no cotton fiber is added.

[0091] Comparative Example 21 refers to the parameter conditions in Example 13, except that only chitosan is added without modification.

[0092] Comparative Example 22 refers to the parameter conditions in Example 13, except that no modified desiccant is added.

[0093] Comparative Example 23 refers to the parameter conditions in Example 13, except that bamboo fiber and modified desiccant are not added.

[0094] Experimental Example 4: Moisture absorption and air permeability test

[0095] The moisture absorption performance of Example 13, Examples 16-20 and Comparative Examples 19-23 was tested according to GB / T 21655.1-2008 standard, and the air permeability performance of Example 13, Examples 16-20 and Comparative Examples 19-23 was tested according to GB / T 5453-1997 standard. The results are shown in Table 8.

[0096] Table 8 Moisture absorption and air permeability test of Example 13, Examples 16-20 and Comparative Examples 19-23

[0097] Example Water absorption / % Air permeability / mm / s Embodiment 13 360 45.6 Example 16 360 45.9 Embodiment 17 362 46.0 Embodiment 18 363 46.2 Embodiment 19 360 46.1 Embodiment 20 358 45.8 Comparative Example 19 321 35.4 Comparative Example 20 327 35.6 Comparative Example 21 334 37.3 Comparative Example 22 318 28.9 Comparative Example 23 286 19.7

[0098] It can be found from Table 8 that in the embodiments, the moisture absorption and air permeability of the antibacterial fabrics are generally high, and the durability of the fabrics is high. In Comparative Example 19, bamboo fiber has good hygroscopic properties, and its special hollow structure enables it to quickly absorb and emit moisture. Without the addition of bamboo fiber, the moisture absorption capacity of the fabric will decrease, and the absorption rate of moisture on the surface of the fabric will slow down, resulting in a decrease in the overall moisture absorption and air permeability of the fabric; at the same time, since the presence of bamboo fiber helps to form an air circulation channel, the lack of bamboo fiber will also affect the air permeability of the fabric to a certain extent, and the air exchange rate will slow down. In Comparative Example 20, cotton fiber is a natural fiber with good hygroscopicity, which can absorb and retain a certain amount of moisture. Without the addition of cotton fiber, the moisture absorption capacity of the fabric will be affected, thereby reducing the moisture absorption and air permeability; in addition, cotton fiber also helps to maintain a certain pore structure in the fabric, and the lack of cotton fiber will cause the air permeability of the fabric to weaken. In Comparative Example 21, the unmodified chitosan is not as good as the modified chitosan in terms of moisture absorption effect and speed, so the moisture absorption and air permeability is low. In Comparative Example 22, no modified desiccant is added, and the moisture absorption permeability of the antibacterial fabric is low. This is because during the modification process, the chlorine atom in chloroacetic acid has a strong electronegativity, so that the carbon atom connected to it carries a partial positive charge, which is easily attacked by the ionized nucleophilic group in the chitosan molecule, and a nucleophilic substitution reaction occurs. The chlorine atom is replaced by a carboxymethyl group, thereby introducing the carboxymethyl group into the chitosan molecule; the modified chitosan has a strong hygroscopicity, which makes the fabric have good hygroscopic properties, and some tiny pore structures can be formed in the fabric. These pores not only contribute to the transmission of moisture, but also allow air to circulate in the fabric, thereby adjusting the air permeability of the fabric. In Comparative Example 23, the fabric lacks both bamboo fiber and modified hygroscopic agent, two components that contribute significantly to the hygroscopic and breathable properties. The hygroscopic capacity of the fabric will be greatly reduced, the water absorption and dissipation speed will be significantly slowed down, and the hygroscopic and breathable rate will be significantly reduced; at the same time, since bamboo fiber and modified hygroscopic agent play a role in maintaining the pore structure and air circulation channels of the fabric, the air permeability of the fabric will be seriously damaged if neither of them is added, and air exchange becomes difficult. In summary, the modified hygroscopic agent, bamboo fiber and cotton fiber are all hygroscopic, and they cooperate with each other to form a multi-level hygroscopic system. Carboxyl-modified chitosan uses its strong hygroscopic groups to quickly absorb moisture, while bamboo fiber and cotton fiber further absorb and conduct moisture through their respective hydrophilic groups, significantly improving the hygroscopicity of the fabric; the macroporous structure of bamboo fiber is conducive to the rapid circulation of air, and the pores and gaps of cotton fiber play an auxiliary role, allowing the air to form complex circulation channels in the fabric; the tiny pore structure formed by carboxyl-modified chitosan further increases the air circulation path. The synergistic effect of the three optimizes the breathability of the fabric, allowing air to flow in and out of the fabric more freely, providing a comfortable microclimate environment for the wearer, and the durability of the antibacterial fabric is also improved.

[0099] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An antibacterial fabric based on graphene nylon composite fiber, characterized by: The antibacterial fabric comprises the following components by weight: Modified graphene: 1-5 parts; Ag / ZnO nanoparticles: 1-3 parts; Polyester masterbatch: 15-20 parts; Nylon masterbatch: 20-30 parts; Cotton fiber: 15-20 parts; Bamboo fiber: 3-8 parts; composite anti-ultraviolet agent: 0.5-1 parts; modified antioxidant: 0.5-0.9 parts; modified moisture absorbent: 1-5 parts; The modified graphene includes graphene oxide, ethylenediamine and triethylamine; The modified antioxidant includes antioxidant 1010 and octadecanoyl chloride; The modified moisture absorbent comprises chitosan and chloroacetic acid.

2. The antibacterial fabric based on graphene nylon composite fiber according to claim 1, characterized in that: The composite anti-ultraviolet agent comprises 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, and the weight ratio of the 2-hydroxy-4-methoxybenzophenone to the nano zinc oxide is 1-5:

2.

3. A production process of antibacterial fabric based on graphene nylon composite fiber, characterized by: The antibacterial fabric according to claim 1 is prepared, and the production process comprises the following steps: S1: putting modified graphene, Ag / ZnO nanoparticles and nylon masterbatch into a high-speed mixer, heating to 180°C, stirring at 600 rpm for 40 min, and then extruding and granulating to obtain mixed masterbatch A, putting the mixed masterbatch A into a screw extruder, the regional temperatures are 250°C, 260°C, 275°C, and 285°C, respectively, and then spinning to obtain modified nylon fiber, the spinning speed is 1500m / min-1600m / min, and the drafting multiple is 1.5 times; S2: putting the composite anti-ultraviolet agent, modified antioxidant, modified moisture absorbent and polyester masterbatch into the high-speed mixer, heating to 230°C, stirring at 800rpm for 40min, and then extruding and granulating to obtain mixed masterbatch B, and putting the mixed masterbatch B into the screw extruder, the zone temperatures are 255°C, 265°C, 280°C, and 290°C, respectively, and then spinning to obtain modified polyester fiber, the spinning speed is 1700m / min-1800m / min, and the drafting multiple is 2 times; S3: the modified nylon fiber, the modified polyester fiber, the cotton fiber and the bamboo fiber are mixed and twisted, and heated in hot water for setting. The heating and setting temperature is 85° C. and the time is 100 min-120 min. Then, the antibacterial fabric is obtained by blending.

4. The production process of an antibacterial fabric based on graphene nylon composite fiber according to claim 3, characterized in that: The preparation method of the modified graphene is as follows: slowly adding 3-8 parts of graphene oxide to 200 parts of N,N-dimethylformamide, stirring at a rotation speed of 350rpm for 2.5 hours to obtain a dispersion; adding 10 parts of ethylenediamine and 2 parts of triethylamine to the dispersion in sequence to obtain a mixed solution; transferring the mixed solution to a three-necked flask, slowly heating it to 80°C, and then reacting for 6h-8h to obtain a reaction system; after the reaction is completed, cooling the reaction system to room temperature, then washing with anhydrous ethanol and centrifuging it 5 times, and finally vacuum drying it for 12h to obtain the modified graphene.

5. The production process of an antibacterial fabric based on graphene nylon composite fiber according to claim 3, characterized in that: The preparation method of the Ag / ZnO nanoparticles is as follows: 12-17 parts of zinc acetate are added to 100 parts of ethylene glycol methyl ether, and stirred at a speed of 300 rpm and 65° C. for 20 minutes to obtain a mixed solution A; 2 parts of silver nitrate are dissolved in 30 parts of the ethylene glycol methyl ether, and stirred for 20 minutes to obtain a mixed solution B; the mixed solution B is slowly added to the mixed solution A, and the droplet addition speed is controlled at 1 drop per second. After the droplet addition is completed, the stirring is continued for 15 minutes to 20 minutes to obtain a mixed solution; and the mixed solution B is added to the mixed solution A. 10 parts of diethanolamine are added to the combined solution, and the mixture is stirred for 25 minutes to obtain a sol; the sol is placed at room temperature for gelation for 20 hours to obtain a gel; the gel is placed in an oven, aged at 65°C for 3 hours, then naturally dried in air for 2 hours, and then vacuum dried at 85°C for 5 hours to obtain a dry product; the dry product is ground and placed in a muffle furnace, heated to 520°C-580°C at a heating rate of 5°C / min, and then calcined for 3 hours. After the calcination, the muffle furnace is cooled to room temperature to obtain the Ag / ZnO nanoparticles.

6. The production process of an antibacterial fabric based on graphene nylon composite fiber according to claim 3, characterized in that: The preparation method of the modified antioxidant is as follows: adding 8-12 parts of antioxidant 1010 to 50 parts of toluene, stirring at a rotation speed of 200 rpm for 2 hours to obtain a uniform solution; slowly dropping 12-15 parts of octadecanoyl chloride into the uniform solution, controlling the dropping speed at 5 mL per minute, and continuously stirring for 2 hours, and after the dropping is completed, then adding 1 part of pyridine, and continuing to stir and react for 4 hours to 6 hours to obtain a mixed solution; cooling the mixed solution to room temperature, slowly adding a hydrochloric acid solution with a mass fraction of 8%, then adjusting the pH value of the solution to 7, and then washing with deionized water and distilling under reduced pressure to obtain a crude product; recrystallizing the crude product, and then filtering and drying to obtain the modified antioxidant.

7. The production process of an antibacterial fabric based on graphene nylon composite fiber according to claim 3, characterized in that: The preparation method of the modified moisture absorbent is as follows: adding 8-12 parts of chitosan to 150 parts of isopropanol, stirring at room temperature for 1.5 hours to obtain a mixed solution; Dissolve 15 parts of sodium hydroxide in 35 parts of deionized water to obtain a sodium hydroxide solution; slowly drop the sodium hydroxide solution into the mixed solution under stirring for 45 minutes, and then continue to stir and react at 40° C. for 1.5 hours to obtain an alkaline solution; Dissolve 15-20 parts of chloroacetic acid in 35 parts of isopropanol to obtain a chloroacetic acid solution; slowly drop the chloroacetic acid solution into the alkalized solution under stirring for 1.5 hours, heat to 60°C, continue stirring and reacting for 3 hours to 5 hours to obtain a reaction solution; after the reaction is completed, cool the reaction solution to room temperature, adjust the pH value to neutral, then wash with deionized water and ethanol and vacuum dry to obtain the modified desiccant.

Images