Antibacterial fabric based on graphene-polyamide composite fiber and production process thereof

Abstract

The present application relates to the technical field of textiles, in particular to an antibacterial fabric based on graphene-polyamide composite fiber and a production process thereof. The present application overcomes the problem of poor antibacterial performance and durability of the antibacterial fabric. In the present application, modified graphene, Ag / ZnO nanoparticles and polyamide masterbatch are melt-extruded to obtain modified polyamide fibers; composite ultraviolet-resistant agent, modified antioxidant, modified moisture-absorbing agent and polyester masterbatch are melt-extruded to obtain modified polyester fibers; finally, the modified polyamide fibers, the modified polyester fibers, cotton fibers and bamboo fibers are mixed, twisted, heat-set and blended to obtain the antibacterial fabric. In the present application, the modified graphene and the Ag / ZnO nanoparticles can synergistically improve the antibacterial performance of the antibacterial fabric; the polyamide masterbatch, the polyester masterbatch and the cotton fibers can jointly improve the mechanical properties of the antibacterial fabric; the composite ultraviolet-resistant agent, the modified antioxidant, the modified moisture-absorbing agent and the bamboo fibers can improve the ultraviolet resistance and moisture-absorbing and air-permeability of the antibacterial fabric.

Description

Technical Field

[0001] This invention relates to the field of textile technology, specifically to an antibacterial fabric based on graphene-nylon composite fiber and its production process. Background Technology

[0002] Nylon fiber, as the world's earliest industrialized synthetic fiber, was widely popular in the 20th century due to its high strength, good elasticity, and excellent abrasion resistance. However, with 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 these needs. They are prone to static electricity, easily attracting dust to the fabric surface, and combined with sweat, create a breeding ground for bacteria. Furthermore, conventional nylon fiber has many limitations in meeting today's pursuit of high-performance clothing and urgently needs improvement to satisfy market demands.

[0003] As people's living standards improve, the requirements for fabrics used in clothing production are also increasing, especially regarding their antibacterial properties. This is because human sweat contains approximately 99% water and 1% metabolic waste. These excretions are difficult to wash away completely and tend to remain within the fabric's fiber structure, fostering the growth of bacteria. While most existing fabrics utilize antibacterial fibers to address bacterial growth, they often neglect breathability. Poor breathability prevents sweat from evaporating, leaving a large amount of moisture inside. This humid environment provides ideal conditions for the growth and reproduction of harmful microorganisms. With prolonged wear, bacteria can still proliferate within the fabric, potentially leading to skin diseases and negatively impacting health. Therefore, improving the antibacterial properties of fabrics is crucial.

[0004] In conclusion, current antibacterial fabrics still suffer from poor antibacterial performance and durability, which severely limits their application in the market.

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

[0006] The purpose of this invention is to design an antibacterial fabric based on graphene-nylon composite fiber and its production process. The synthetic raw materials of this invention include modified graphene, Ag / ZnO nanoparticles, polyester masterbatch, nylon masterbatch, cotton fiber, bamboo fiber, composite UV stabilizer, modified antioxidant, and modified moisture absorbent. Modified nylon fiber is obtained by melt extrusion spinning of modified graphene, Ag / ZnO nanoparticles, and nylon masterbatch. Modified polyester fiber is obtained by melt extrusion spinning of composite UV stabilizer, modified antioxidant, modified moisture absorbent, and polyester masterbatch. Finally, the modified nylon fiber, modified polyester fiber, cotton fiber, and bamboo fiber are mixed, twisted, heat-set, and blended to produce the antibacterial fabric. In this invention, modified graphene and Ag / ZnO nanoparticles can synergistically enhance the antibacterial properties of the antibacterial fabric; nylon masterbatch, polyester masterbatch and cotton fiber together enhance the mechanical properties of the antibacterial fabric; composite UV stabilizer, modified antioxidant, modified moisture absorber and bamboo fiber can enhance the UV resistance and moisture absorption and breathability of the antibacterial fabric.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention provides an antibacterial fabric based on graphene-nylon composite fiber, which, by weight, comprises the following components:

[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 UV stabilizer: 0.5-1 part; Modified antioxidant: 0.5-0.9 parts; Modified moisture absorber: 1-5 parts;

[0010] Modified graphene includes graphene oxide, ethylenediamine, and triethylamine;

[0011] Modified antioxidants include antioxidant 1010 and octadecyl 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 UV stabilizer includes 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, wherein 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 manufacturing process for an antibacterial fabric based on graphene-nylon composite fiber, the manufacturing process comprising the following steps:

[0016] S1 involves feeding modified graphene, Ag / ZnO nanoparticles, and nylon masterbatch into a high-speed mixer, heating it to 180℃, stirring at 600 rpm for 40 min, and then extruding and granulating it to obtain mixed masterbatch A. Mixed masterbatch A is then fed into a screw extruder with zone temperatures of 250℃, 260℃, 275℃, and 285℃, and then spinning it to obtain modified nylon fiber at a spinning speed of 1500 m / min-1600 m / min and a draw ratio of 1.5.

[0017] S2 involves adding a composite UV stabilizer, a modified antioxidant, a modified hygroscopic agent, and polyester masterbatch into a high-speed mixer, heating it to 230°C, stirring at 800 rpm for 40 minutes, and then extruding and granulating it to obtain mixed masterbatch B. Mixed masterbatch B is then fed into a screw extruder with zone temperatures of 255°C, 265°C, 280°C, and 290°C, and then spinning it to obtain modified polyester fiber at a spinning speed of 1700 m / min-1800 m / min and a draw ratio of 2.

[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℃ for 100-120 minutes, and then blends and weaves them to obtain antibacterial fabric.

[0019] Preferably, the modified graphene is prepared by the following method by weight: 3-8 parts of graphene oxide are slowly added to 200 parts of N,N-dimethylformamide and stirred at 350 rpm for 2.5 h to obtain a dispersion; 10 parts of ethylenediamine and 2 parts of triethylamine are added to the dispersion in sequence to obtain a mixture; the mixture is transferred to a three-necked flask, the temperature is slowly raised to 80°C, and the reaction is carried out for 6-8 h to obtain a reaction system; after the reaction is completed, the reaction system is cooled to room temperature, washed with anhydrous ethanol and centrifuged 5 times, and finally vacuum dried for 12 h to obtain modified graphene.

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

[0021] Preferably, the modified antioxidant is prepared by the following method by weight: 8-12 parts of antioxidant 1010 are added to 50 parts of toluene and stirred at 200 rpm for 2 hours to obtain a homogeneous solution; 12-15 parts of octadecyl chloride are slowly added dropwise to the homogeneous solution at a rate of 5 mL per minute and stirred continuously for 2 hours; after the addition is complete, 1 part of pyridine is added and the reaction is continued for 4-6 hours to obtain a mixture; after cooling the mixture to room temperature, an 8% hydrochloric acid solution is slowly added, and the pH of the solution is adjusted to 7. The solution is then washed with deionized water and distilled under reduced pressure to obtain a crude product; the crude product is recrystallized, filtered, and dried to obtain the modified antioxidant.

[0022] Preferably, the modified hygroscopic agent is prepared by the following method by weight: 8-12 parts of chitosan are added to 150 parts of isopropanol and stirred at room temperature for 1.5 h to obtain a mixed solution; 15 parts of sodium hydroxide are dissolved in 35 parts of deionized water to obtain a sodium hydroxide solution; under stirring conditions, the sodium hydroxide solution is slowly added dropwise to the mixed solution over a period of 45 min, and then the reaction is continued at 40 °C for 1.5 h to obtain an alkalized solution; 15-20 parts of chloroacetic acid are dissolved in 35 parts of isopropanol to obtain a chloroacetic acid solution; under stirring conditions, the chloroacetic acid solution is slowly added dropwise to the alkalized solution over a period of 1.5 h, the temperature is raised to 60 °C, and the reaction is continued for 3-5 h to obtain a reaction solution; after the reaction is completed, the reaction solution is cooled to room temperature, the pH is adjusted to neutral, and then washed with deionized water and ethanol and vacuum dried to obtain the modified hygroscopic agent.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1. The introduction of amine groups gives graphene a positive charge on its surface, while bacteria typically have a negative charge. Based on the principle of charge attraction, amine-modified graphene can more effectively adsorb bacteria, increasing contact opportunities and laying the foundation for subsequent antibacterial effects. Modified graphene has a two-dimensional sheet structure, forming a uniform coating on the fabric surface, acting as a physical barrier to prevent direct contact between bacteria and the fabric, thus reducing the space for bacterial attachment and growth. Ag / ZnO nanoparticles possess excellent photocatalytic properties, generating electron-hole pairs more efficiently under visible light irradiation, enhancing the antibacterial effect. Simultaneously, photocatalysis can decompose organic pollutants on the fabric surface, keeping the fabric clean, reducing nutrient sources for bacterial growth, and further inhibiting bacterial growth.

[0025] 2. The high strength and elastic recovery provided by nylon masterbatch, combined with the crispness, wrinkle resistance, and dimensional stability of polyester masterbatch, compensate for each other's shortcomings. The softness, skin-friendliness, and moisture absorption of cotton fibers improve fabric comfort while also making the fabric more resilient and durable overall. The synergistic effect of these three materials significantly enhances the mechanical properties of the antibacterial fabric. During the fabric weaving process, nylon, polyester, and cotton fibers intertwine to form a complex fiber network structure. This interweaving structure makes the bonds between fibers tighter, enhancing the fabric's integrity and stability. The interaction between different fibers also disperses external forces. When the fabric is stretched or torn, stress can be transferred and distributed among different fibers, thereby improving the fabric's resistance to damage and enhancing the durability of the antibacterial fabric.

[0026] 3. Antioxidant 1010 is modified using long-chain alkyl grafting. The phenolic hydroxyl oxygen atom in the antioxidant 1010 molecule has nucleophilicity and attacks the carbonyl carbon atom in the octadecyl chloride molecule. Some of the lone pair electrons on the phenolic hydroxyl oxygen atom form new covalent bonds with the carbonyl carbon atom. The 2-hydroxy-4-methoxybenzophenone and nano zinc oxide in the composite UV stabilizer function from the perspectives of absorbing and scattering ultraviolet rays, respectively. The combination of the two can effectively block ultraviolet rays. The long-chain alkyl grafted antioxidant stabilizes the fabric's molecular structure and forms a protective film, allowing the composite UV stabilizer to exist more stably in the fabric and function more effectively. This enhances the overall ultraviolet absorption and scattering effect, improves the fabric's UV resistance, and also improves the durability of the antibacterial fabric.

[0027] 4. Modified moisture absorbers, bamboo fiber, and cotton fiber all possess moisture-absorbing properties. Together, they form a multi-layered moisture-absorbing system. Carboxyl-modified chitosan utilizes its strong hygroscopic groups to rapidly absorb moisture, while bamboo and cotton fibers further absorb and conduct moisture through their respective hydrophilic groups, significantly enhancing the fabric's moisture absorption performance. The large pore structure of bamboo fiber facilitates rapid airflow, while the pores and gaps in cotton fiber play a supporting role, creating complex airflow channels within the fabric. The micropore structure formed by carboxyl-modified chitosan further increases the airflow path. The synergistic effect of these three components optimizes the fabric's breathability, allowing air to freely enter and exit the fabric, providing a comfortable microclimate environment for the wearer, and improving the durability of the antibacterial fabric. Attached Figure Description

[0028] Figure 1 The diagram shows the antibacterial properties of Example 3 and Comparative Examples 1-5 in this invention. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] For details, please refer to [link / reference]. Figure 1 This invention provides an antibacterial fabric based on graphene-nylon composite fiber and its production process, the technical solution of which is as follows:

[0031] Example 1

[0032] The composite UV protectant includes 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, with a weight ratio of 1:2.

[0033] Three parts of graphene oxide were slowly added to 200 parts of N,N-dimethylformamide and stirred at 350 rpm for 2.5 h to obtain a dispersion. Ten parts of ethylenediamine and two parts of triethylamine were added to the dispersion to obtain a mixture. The mixture was transferred to a three-necked flask and slowly heated to 80 °C. The reaction was then carried out for 6 h to obtain a reaction system. After the reaction was completed, the reaction system was cooled to room temperature, washed with anhydrous ethanol and centrifuged five times. Finally, it was vacuum dried for 12 h to obtain modified graphene.

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

[0035] Eight parts of antioxidant 1010 were added to 50 parts of toluene and stirred at 200 rpm for 2 hours to obtain a homogeneous solution. Twelve parts of octadecyl chloride were slowly added dropwise to the homogeneous solution at a rate of 5 mL per minute and stirred continuously for 2 hours. After the addition was complete, one part of pyridine was added and the reaction was stirred for another 4 hours to obtain a mixture. The mixture was cooled to room temperature and then 8% hydrochloric acid solution was slowly added. The pH of the solution was adjusted to 7, washed with deionized water, and distilled under reduced pressure to obtain a crude product. The crude product was recrystallized, filtered, and dried to obtain the modified antioxidant.

[0036] Eight parts of chitosan were added to 150 parts of isopropanol and stirred at room temperature for 1.5 h 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, the sodium hydroxide solution was slowly added dropwise to the mixed solution over a period of 45 min. The reaction was then continued at 40 °C for 1.5 h to obtain an alkalized solution. 15 parts of chloroacetic acid were dissolved in 35 parts of isopropanol to obtain a chloroacetic acid solution. Under stirring, the chloroacetic acid solution was slowly added dropwise to the alkalized solution over a period of 1.5 h. The temperature was raised to 60 °C and the reaction was continued for 3 h to obtain a reaction solution. After the reaction was completed, the reaction solution was cooled to room temperature, the pH was adjusted to neutral, and then washed with deionized water and ethanol and vacuum dried to obtain a modified hygroscopic agent.

[0037] Production of antibacterial fabrics:

[0038] S1 involves feeding modified graphene, Ag / ZnO nanoparticles, and nylon masterbatch into a high-speed mixer, heating it to 180°C, stirring at 600 rpm for 40 min, and then extruding and granulating it to obtain mixed masterbatch A. Mixed masterbatch A is then fed into a screw extruder with zone temperatures of 250°C, 260°C, 275°C, and 285°C, respectively. Subsequently, modified nylon fiber is obtained by spinning at a speed of 1500 m / min and a draw ratio of 1.5.

[0039] S2 adds a composite UV stabilizer, a modified antioxidant, a modified hygroscopic agent, and polyester masterbatch to a high-speed mixer, heats it to 230°C, stirs it at 800 rpm for 40 min, and then extrudes and granulates it to obtain mixed masterbatch B. Mixed masterbatch B is then fed into a screw extruder with zone temperatures of 255°C, 265°C, 280°C, and 290°C, and then spins it to obtain modified polyester fiber at a spinning speed of 1700 m / min and a draw ratio of 2.

[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 fabric.

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

[0042] Table 1 Parameters and Conditions for Examples 1-5

[0043]

[0044] Comparative Example 1 follows the same parameters and conditions as in Example 1, except that only graphene oxide is added, without modifying the graphene oxide.

[0045] Comparative Example 2 follows the same parameters and conditions as in Example 1, except that no modified graphene is added.

[0046] Comparative Example 3 follows the same parameters and conditions as in Example 1, except that zinc oxide is added instead of Ag / ZnO nanoparticles.

[0047] Comparative Example 4 follows the same parameters and conditions as in Example 1, except that Ag / ZnO nanoparticles are not added.

[0048] Comparative Example 5 follows the same parameters and conditions as in Example 1, except that modified graphene and Ag / ZnO nanoparticles are not added.

[0049] Experiment 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, and the results are shown in Table 2. The antibacterial properties of Examples 3 and Comparative Examples 1-5 are as follows: Figure 1 As shown.

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

[0052]

[0053]

[0054] From Table 2 and Figure 1It can be observed that in Comparative Example 1, the antibacterial rate of the antibacterial fabric decreased when only graphene oxide was added without modification. This is because the bonding force between graphene oxide and the fabric matrix is ​​weak, and its dispersion in the fabric is also poor. In Comparative Example 2, the antibacterial rate of the antibacterial fabric also decreased without the addition of modified graphene. During the synthesis of modified graphene, the introduction of amine groups gives the graphene surface a positive charge, while the surface of bacteria is usually negatively charged. According to the principle of charge attraction, amine-modified graphene can more effectively adsorb bacteria, increasing the opportunity for contact with bacteria and laying the foundation for subsequent antibacterial effects. Modified graphene has a two-dimensional sheet structure, which can form a uniform covering layer on the fabric surface, acting as a physical barrier to prevent bacteria from directly contacting the fabric, thereby reducing the space for bacterial attachment and growth on the fabric. In Comparative Example 3, zinc oxide was added to replace Ag / ZnO nanoparticles. Although zinc oxide has antibacterial properties, zinc oxide alone cannot possess stronger antibacterial activity. In Comparative Example 4, without the addition of Ag / ZnO nanoparticles, the antibacterial ability of the fabric was significantly affected. The silver ions in Ag / ZnO nanoparticles have strong antibacterial capabilities, specifically binding to sulfhydryl and amino groups within bacterial cells, interfering with the normal metabolic processes of bacteria, inhibiting bacterial respiration and the activity of various enzymes, preventing bacteria from carrying out normal physiological activities, thereby inhibiting their growth and reproduction. Under light conditions, ZnO undergoes a photocatalytic reaction to generate electron-hole pairs. These electron-hole pairs interact with surrounding water molecules and oxygen to generate highly oxidizing active substances, which can attack the bacterial cell membrane, increasing its permeability, causing intracellular substances to leak out, and also damaging intracellular biomolecules, leading to bacterial death. In Comparative Example 5, neither modified graphene nor Ag / ZnO nanoparticles were added. The absence of these two important antibacterial components would significantly reduce the antibacterial performance of the antibacterial fabric. Modified graphene attracts bacteria around it through adsorption, making it easier for Ag / ZnO nanoparticles to come into contact with bacteria and improving the efficiency of antibacterial action. At the same time, the active substances generated by modified graphene and 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, with specific differences shown in Table 3.

[0056] Table 3. Parameters and conditions for Examples 3 and 6-10

[0057]

[0058]

[0059] Comparative Example 6 follows the same parameters and conditions as in Example 3, except that no nylon masterbatch is added.

[0060] Comparative Example 7 follows the same parameters and conditions as in Example 3, except that polyester masterbatch is not added.

[0061] Comparative Example 8 follows the same parameters and conditions as in Example 3, except that no cotton fibers are added.

[0062] Comparative Example 9 uses the same parameters as in Example 3, except that the spinning speed in S1 and S2 is 1000 m / min.

[0063] Comparative Example 10 uses the same parameters and conditions as in Example 3, except that the spinning speed in S1 and S2 is 2300 m / min.

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

[0065] Comparative Example 12 follows the same parameters and conditions as in Example 3, except that the hot pressing time in S3 is 180 min.

[0066] Experiment Example 2 Mechanical Property Testing

[0067] The elongation at break was tested for Examples 3, 6-10 and Comparative Examples 6-12 in accordance with GB / T 3923.1-2013, and the results are shown in Table 4.

[0068] Table 4 Mechanical property tests of Examples 3, 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] Table 4 shows that the mechanical properties of the embodiments are relatively stable. In Comparative Example 6, nylon has high strength and excellent abrasion resistance. The fiber molecular chains made from nylon masterbatch have strong intermolecular forces and a compact fiber structure, giving the antibacterial fabric good tensile and tear resistance. It can withstand greater external forces without easily breaking. Without the addition of nylon masterbatch, the overall elasticity of the fabric decreases, the elongation at break decreases, and the fabric is more likely to reach the breaking point under tensile force, resulting in poorer flexibility and extensibility. In Comparative Example 7, polyester fiber has high rigidity. The fibers made from polyester masterbatch are crisp and not easily deformed, giving the antibacterial fabric good wrinkle resistance. Without the addition of polyester masterbatch, the fabric will be excessively deformed when stretched due to the lack of polyester support, leading to unstable elongation at break. It will show a phenomenon of rapid increase followed by a sharp decrease, because the fabric is easily stretched initially, but due to the lack of structural stability of polyester, it eventually breaks prematurely. In Comparative Example 8, cotton fibers possess a certain degree of toughness and elongation at break, enabling the fabric to withstand stretching to some extent. Without cotton fibers, the fabric's softness and toughness decrease, its elongation at break declines, and it becomes prone to stiffness and breakage during stretching. In antibacterial fabrics, the high strength and elastic recovery provided by nylon masterbatch, combined with the crispness, wrinkle resistance, and dimensional stability of polyester masterbatch, compensate for each other's shortcomings. The softness, skin-friendliness, and moisture absorption of cotton fibers improve fabric comfort while also making the fabric more resilient and durable overall. The synergistic effect of these three materials significantly enhances the mechanical properties and durability of the antibacterial fabric. In Comparative Example 9, a lower spinning speed results in more regular fiber molecular chain arrangement and increased crystallinity, but this increases fiber rigidity and reduces elasticity, leading to a decrease in the fabric's elongation at break. In Comparative Example 10, a higher spinning speed results in lower fiber crystallinity and orientation, a less compact fiber structure, and a decrease in fabric strength. In Comparative Example 11, the heat-setting time was too short, resulting in insufficient fiber setting and incomplete fixation of the molecular chains. When the fabric was stretched, the fibers were prone to slippage and rearrangement. The breaking elongation was similar to that of the example, but the dimensional stability of the fabric deteriorated. After repeated stretching, the fabric's elongation might not recover, leading to permanent deformation. In Comparative Example 12, the heat-setting time was too long, causing excessive heating of the fibers. This reduced fiber elasticity and increased brittleness, resulting in a decrease in the breaking elongation of the fabric. During stretching, the fabric was prone to breakage and could not withstand large amounts of elongation.

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

[0072] Table 5. Parameters and conditions for Examples 8 and 11-15

[0073]

[0074]

[0075] Comparative Example 13 follows the same parameters and conditions as in Example 8, except that only 2-hydroxy-4-methoxybenzophenone is added as an anti-ultraviolet agent.

[0076] Comparative Example 14 follows the same parameters and conditions as in Example 8, except that only nano zinc oxide is added as an anti-ultraviolet agent.

[0077] Comparative Example 15 follows the same parameters and conditions as in Example 8, except that no composite UV stabilizer is added.

[0078] Comparative Example 16 follows the same parameters and conditions as in Example 8, except that only antioxidant 1010 is added without modification.

[0079] Comparative Example 17 follows the same parameters and conditions as in Example 8, except that no modified antioxidant is added.

[0080] Comparative Example 18 follows the same parameters and conditions as in Example 8, except that no composite UV stabilizer or modified antioxidant is added.

[0081] Experiment Example 3 UV Resistance Test

[0082] The UV resistance performance of Examples 8, 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 UV resistance performance tests of Examples 8, 11-15 and Comparative Examples 13-18

[0084] Example UVA pass rate / % Example 8 1.9 Example 11 1.8 Example 12 1.8 Example 13 1.6 Example 14 1.7 Example 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] Table 6 shows that the UV protection performance of the examples is relatively excellent and stable. In Comparative Example 13, 2-hydroxy-4-methoxybenzophenone is an organic UV protectant that can absorb ultraviolet rays and convert them into heat energy for dissipation. However, its absorption band is relatively narrow, mainly showing good absorption of the UV-B band, while its absorption capacity for the UV-A band is relatively weak. Therefore, the fabric's protection against ultraviolet rays is not comprehensive, and its UV protection performance is limited. In Comparative Example 14, only nano-zinc oxide was used as a UV protectant, which is prone to aggregation, thus affecting its UV absorption efficiency and reducing its UV protection performance. In Comparative Example 15, without the effect of a composite UV protectant, the fabric mainly relies on the weak blocking effect of its own fibers against ultraviolet rays, and can hardly effectively absorb or scatter ultraviolet rays. In Comparative Example 16, a single antioxidant cannot assist the composite UV protectant in exerting its UV protection performance, and the composite UV protectant is prone to oxidation, thus affecting its performance. In Comparative Example 17, ultraviolet (UV) irradiation causes free radicals to be generated in the polymer materials of the fabric, initiating oxidative degradation. The modified antioxidant can capture these free radicals, preventing the oxidative chain reaction and thus stabilizing the molecular structure of the fabric, indirectly improving its UV resistance. Without the addition of the modified antioxidant, the oxidation reaction caused by UV cannot be effectively inhibited, thus failing to adequately protect the UV-resistant components in the fabric from oxidative damage, resulting in a decrease in its UV resistance. In Comparative Example 18, without the addition of the composite UV stabilizer and the modified antioxidant, the antibacterial fabric exhibited the lowest UV resistance among all examples and comparative examples. This is because the 2-hydroxy-4-methoxybenzophenone and nano-zinc oxide in the composite UV stabilizer function from the perspectives of absorbing and scattering UV rays, respectively, and their combination effectively blocks UV rays. The long-chain alkyl grafted modified antioxidant stabilizes the fabric's molecular structure and forms a protective film, allowing the composite UV stabilizer to exist more stably in the fabric and function, thereby enhancing the overall UV absorption and scattering effect, improving the fabric's UV resistance, and consequently increasing the durability of the antibacterial fabric.

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

[0087] Table 7 Parameters and conditions for Examples 13 and 16-20

[0088]

[0089] Comparative Example 19 follows the same parameters and conditions as in Example 13, except that bamboo fiber is not added.

[0090] Comparative Example 20 follows the same parameters and conditions as in Example 13, except that no cotton fibers are added.

[0091] Comparative Example 21 follows the same parameters and conditions as in Example 13, except that only chitosan is added without modification.

[0092] Comparative Example 22 follows the same parameters and conditions as in Example 13, except that no modified desiccant is added.

[0093] Comparative Example 23 follows the same parameters and conditions as in Example 13, except that bamboo fiber and modified moisture absorbent are not added.

[0094] Experiment Example 4: Moisture Absorption and Breathability Test

[0095] The moisture absorption performance of Examples 13, 16-20 and Comparative Examples 19-23 was tested according to GB / T 21655.1-2008 standard, and the air permeability performance of Examples 13, 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 breathability tests of Examples 13, 16-20 and Comparative Examples 19-23

[0097] Example Water absorption rate / % air permeability / mm / s Example 13 360 45.6 Example 16 360 45.9 Example 17 362 46.0 Example 18 363 46.2 Example 19 360 46.1 Example 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] Table 8 shows that, in the examples, the antibacterial fabrics generally exhibited high moisture absorption and breathability, as well as high durability. In Comparative Example 19, bamboo fiber possesses excellent moisture absorption properties; its unique hollow structure allows for rapid absorption and release of moisture. Without bamboo fiber, the fabric's moisture absorption capacity decreases, and the absorption rate of moisture on the fabric surface slows down, resulting in a reduction in the overall moisture absorption and breathability. Simultaneously, the presence of bamboo fiber helps create air circulation channels, and its absence also negatively impacts the fabric's breathability, slowing down air exchange. In Comparative Example 20, cotton fiber, a natural fiber, has good moisture absorption, capable of absorbing and retaining a certain amount of moisture. Without cotton fiber, the fabric's moisture absorption capacity is affected, leading to a decrease in moisture absorption and breathability. Furthermore, cotton fiber helps maintain a certain pore structure in the fabric; its absence weakens the fabric's breathability. In Comparative Example 21, unmodified chitosan is less effective and faster at absorbing moisture, resulting in a lower moisture absorption and breathability. In Comparative Example 22, without the addition of a modified moisture absorbent, the moisture permeability of the antibacterial fabric was low. This is because during the modification process, the chlorine atom in chloroacetic acid has a strong electronegativity, causing the carbon atom attached to it to carry a partial positive charge. This makes it susceptible to attack by the nucleophilic groups in the chitosan molecule after ionization, resulting in a nucleophilic substitution reaction. The chlorine atom is replaced by a carboxymethyl group, thereby introducing the carboxymethyl group into the chitosan molecule. The modified chitosan has strong moisture absorption, giving the fabric good moisture absorption properties. It can also form some tiny pore structures in the fabric. These pores not only help with the transport of moisture but also allow air to circulate in the fabric, thereby regulating the breathability of the fabric. In Comparative Example 23, the fabric lacked both bamboo fiber and modified moisture-wicking agent, two components that significantly contribute to moisture absorption and breathability. This resulted in a substantial decrease in the fabric's moisture absorption capacity, with both moisture absorption and dissipation rates slowing down considerably, leading to a significant reduction in moisture absorption and breathability. Furthermore, since both bamboo fiber and modified moisture-wicking agent play a role in maintaining the fabric's pore structure and airflow channels, their absence severely impairs breathability, making air exchange difficult. In conclusion, modified moisture-wicking agent, bamboo fiber, and cotton fiber all possess moisture-wicking properties, and their combined effects create a multi-layered moisture-wicking system. Carboxyl-modified chitosan utilizes its highly hygroscopic groups to rapidly absorb moisture, while bamboo and cotton fibers further absorb and conduct moisture through their respective hydrophilic groups, significantly improving the fabric's moisture absorption performance. The large pore structure of bamboo fiber facilitates rapid air circulation, while the pores and gaps of cotton fiber play an auxiliary role, creating complex airflow channels within the fabric. The micropore structure formed by carboxyl-modified chitosan further increases the airflow path. The synergistic effect of these three elements optimizes the fabric's breathability, allowing air to enter and exit the fabric more freely, providing a comfortable microclimate environment for the wearer, and also enhancing the durability of the antibacterial fabric.

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

Claims

1. A production process for antibacterial fabric based on graphene-nylon composite fiber, characterized in that: Includes the following steps: S1 involves feeding modified graphene, Ag / ZnO nanoparticles, and nylon masterbatch into a high-speed mixer, heating it to 180℃, stirring at 600 rpm for 40 min, extruding and granulating to obtain mixed masterbatch A, and then feeding it into a screw extruder with temperatures of 250℃, 260℃, 275℃, and 285℃ in each zone, and spinning it to obtain modified nylon fiber at a spinning speed of 1500-1600 m / min and a draw ratio of 1.

5. S2 involves adding a composite UV stabilizer, modified antioxidant, modified hygroscopic agent, and polyester masterbatch into a high-speed mixer, heating it to 230℃, stirring at 800 rpm for 40 minutes, extruding and granulating to obtain mixed masterbatch B, and then feeding it into a screw extruder with temperatures of 255℃, 265℃, 280℃, and 290℃ in each zone, and spinning it to obtain modified polyester fiber at a spinning speed of 1700-1800 m / min and a draw ratio of 2. S3 mixes and twists modified nylon fiber, modified polyester fiber, cotton fiber and bamboo fiber, and heats and sets them in hot water at a temperature of 85℃ for 100-120 minutes to obtain an antibacterial fabric. The modified graphene is prepared by the following method based on parts by weight: 3-8 parts of graphene oxide are added to 200 parts of N,N-dimethylformamide and stirred for 2.5 h to obtain a dispersion; then 10 parts of ethylenediamine and 2 parts of triethylamine are added sequentially to obtain a mixture; the mixture is heated to 80℃ and reacted for 6-8 h to obtain a reaction system; the reaction system is cooled to room temperature, washed, centrifuged, and vacuum dried to obtain modified graphene. The preparation method of 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 65°C for 20 min to obtain mixture A; 2 parts of silver nitrate are dissolved in 30 parts of ethylene glycol methyl ether and stirred for 20 min to obtain mixture B; mixture B is slowly added to mixture A at a dropping rate of 1 drop / s and stirred for 15-20 min to obtain a mixed solution; 10 parts of diethanolamine are added to the mixed solution and stirred for 25 min to obtain a sol; the sol is gelled at room temperature for 20 h to obtain a gel; the gel is aged in an oven at 65°C for 3 h, air-dried for 2 h, and then vacuum-dried at 85°C for 5 h to obtain a dried product; The dried product was ground and calcined in a muffle furnace at 520℃-580℃ for 3 hours at a heating rate of 5℃ / min. After cooling to room temperature, Ag / ZnO nanoparticles were obtained. The modified antioxidant is prepared as follows: 8-12 parts of antioxidant 1010 are added to 50 parts of toluene and stirred for 2 hours to obtain a homogeneous solution; 12-15 parts of octadecyl chloride are slowly added dropwise to the homogeneous solution at a rate of 5 mL / min, and stirring is continued for 2 hours; then 1 part of pyridine is added, and the reaction is continued for 4-6 hours to obtain a mixed solution; after cooling the mixed solution to room temperature, an 8% hydrochloric acid solution is slowly added to adjust the pH of the solution to 7, the solution is washed and distilled under reduced pressure to obtain a crude product; the crude product is recrystallized, filtered, and dried to obtain the modified antioxidant; The modified hygroscopic agent is prepared by adding 8-12 parts of chitosan to 150 parts of isopropanol and stirring 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; Under stirring conditions, sodium hydroxide solution was slowly added dropwise to the mixed solution over a period of 45 minutes, and the mixture was stirred at 40°C for 1.5 hours to obtain an alkalized solution. Dissolve 15-20 parts of chloroacetic acid in 35 parts of isopropanol to obtain a chloroacetic acid solution; under stirring conditions, slowly add the chloroacetic acid solution dropwise to the alkalization solution over a period of 1.5 hours; heat to 60°C and stir for 3-5 hours to obtain a reaction solution; cool the reaction solution to room temperature, adjust the pH to neutral, wash and vacuum dry to obtain the modified hygroscopic agent; The composite UV protectant includes 2-hydroxy-4-methoxybenzophenone and nano zinc oxide, with a weight ratio of 1-5:2 between 2-hydroxy-4-methoxybenzophenone and nano zinc oxide.

2. An antibacterial fabric based on graphene-nylon composite fiber, characterized in that: The antibacterial fabric is prepared by the preparation method according to claim 1, and by weight, the antibacterial fabric comprises the following components: 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 UV stabilizer: 0.5-1 part; Modified antioxidant: 0.5-0.9 parts; Modified moisture absorber: 1-5 parts; The modified graphene includes graphene oxide, ethylenediamine, and triethylamine; The modified antioxidant includes antioxidant 1010 and octadecyl chloride; The modified hygroscopic agent includes chitosan and chloroacetic acid.

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