Graphene antibacterial yarn and preparation method thereof

Abstract

The invention relates to graphene antibacterial yarn and a preparation method thereof.The graphene antibacterial yarn comprises graphene modified fiber and modal fiber, the graphene modified fiber comprises graphene textile fiber and an antibacterial coating, the graphene textile fiber comprises a fiber body and graphene, and the antibacterial coating is arranged on the fiber body. The antibacterial coating is formed by attaching an antibacterial coating to the surface of the graphene textile fiber, and the antibacterial coating is prepared from the following components in parts by mass: 30 to 50 parts of acrylate resin, 8 to 12 parts of a slow-release antibacterial agent, 1.5 to 2.5 parts of nano-silver particles, 0.5 to 1.5 parts of a dispersing agent, 1 to 3 parts of a cross-linking agent and 2 to 4 parts of an auxiliary agent. The antibacterial yarn has the effect of improving the antibacterial performance and the washing resistance of the yarn.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of yarn, in particular to a graphene antibacterial yarn and a preparation method thereof. BACKGROUND

[0002] With the continuous improvement of living standards and the increasing awareness of health protection, the market has put forward higher requirements for the functionalization of textiles, and the antibacterial performance has become one of the important development directions of textile products. At present, the commercially available antibacterial yarns mostly achieve antibacterial effect by adding organic antibacterial agents (such as quaternary ammonium salt, phenolic compounds, etc.) or inorganic antibacterial agents (such as silver ions, zinc oxide, etc.).

[0003] However, the above-mentioned traditional antibacterial technology has certain limitations in actual application, for example, the organic antibacterial agent may have poor heat resistance, easy to dissolve out, insufficient durability, etc., and some inorganic antibacterial agents have the challenges of difficult control of metal ion precipitation, easy to cause fabric discoloration or potential biological toxicity, etc.

[0004] Graphene, as a new type of material with unique two-dimensional nanostructure, shows excellent antibacterial performance. Its antibacterial mechanism mainly includes physical cutting of bacterial cell membrane, induction of oxidative stress and wrapping and isolation, etc. It has the advantages of broad-spectrum antibacterial, not easy to cause microbial drug resistance, etc. Although graphene shows great potential in the field of antibacterial materials, there are still significant technical bottlenecks in the process of applying it to the functional modification of yarns: on the one hand, graphene has large specific surface area and high surface energy, which is difficult to disperse uniformly in the yarn matrix and is easy to agglomerate, affecting the effective exertion of its antibacterial activity; on the other hand, the interfacial bonding force between graphene and common textile fibers is weak, which is easy to fall off under repeated washing and actual use conditions, leading to rapid decay of antibacterial performance, which is difficult to meet the actual demand of textiles for durable antibacterial function, and therefore needs to be improved. SUMMARY

[0005] In order to solve the above problems, the present application provides a graphene antibacterial yarn and a preparation method thereof.

[0006] In a first aspect, the present application provides a graphene antibacterial yarn, which adopts the following technical scheme: A graphene antibacterial yarn, comprising graphene modified fibers and modal fibers, the graphene modified fibers comprising graphene textile fibers and an antibacterial coating, the graphene textile fibers comprising a fiber body and graphene, the antibacterial coating being formed by attaching an antibacterial coating material to the surface of the graphene textile fibers, the antibacterial coating material comprising the following components by mass fraction: 30-50 parts of acrylate resin, 8-12 parts of slow-release antibacterial agent, 1.5-2.5 parts of nano-silver particles, 0.5-1.5 parts of dispersing agent, 1-3 parts of crosslinking agent, and 2-4 parts of auxiliary agent.

[0007] By adopting the above technical scheme, a layer of antibacterial coating is coated on the surface of the graphene textile fiber, the nano-silver in the antibacterial coating can play a synergistic antibacterial effect with graphene, under the action of the slow-release antibacterial agent, long-term antibacterial effect is achieved, the crosslinking agent and the acrylic resin form a three-dimensional network structure, each substance is stably attached to the surface of the graphene textile fiber, in combination with the dispersing agent, the uniform dispersion of each substance on the surface of the graphene fiber is effectively improved, and the shedding of graphene is reduced, and the durability and antibacterial property of the fiber system as a whole are also improved.

[0008] Preferably, the slow-release antibacterial agent comprises a white resveratrol complex and a chitosan cross-linked shell layer, and the white resveratrol complex comprises gelatin, carboxymethyl cellulose, white resveratrol and anthocyanin.

[0009] By adopting the above technical scheme, white resveratrol is a polyphenol antibacterial agent that can destroy the cell membrane protein of bacteria, anthocyanin is a flavonoid antibacterial agent that can inhibit bacterial activity and has good antioxidant zinc, after the combination of white resveratrol and anthocyanin, a synergistic antibacterial effect is achieved, and anthocyanin can protect white resveratrol from oxidation, so that the stability of the system is further improved, after the addition of gelatin and carboxymethyl cellulose, the activity of white resveratrol and anthocyanin is further improved, and the compatibility between white resveratrol, anthocyanin and the chitosan shell layer is improved, after the cross-linking of gelatin and carboxymethyl cellulose, the cross-linking is further strengthened, thereby improving the coating rate and stability, the amino group of the chitosan shell layer and the carboxyl group of the carboxymethyl cellulose form an electrostatic effect, thereby improving the adhesion of the slow-release antibacterial agent on the surface of the fiber, and further reducing the occurrence of antibacterial component shedding.

[0010] The chitosan is used as a shell layer to coat the white resveratrol complex, so that the white resveratrol can be slowly released in the subsequent process, thereby achieving long-term antibacterial effect.

[0011] Preferably, the white resveratrol complex is prepared by the following method: Gelatin is mixed with water, after warming and stirring, carboxymethyl cellulose is added, and a gelatin complex solution is obtained after stirring, white resveratrol, anthocyanin and ethanol are mixed to obtain a complex antibacterial agent, the white resveratrol solution and the gelatin complex solution are mixed and stirred, ethanol is continuously added during the stirring process, a precipitate is obtained, the precipitate is collected, washed, and freeze-dried to obtain the white resveratrol complex.

[0012] By adopting the above technical scheme, after the gelatin is dissolved by warming, a continuous phase is formed, after the addition of carboxymethyl cellulose, the molecules of the gelatin are entangled through hydrogen bonds, thereby providing uniform wrapping sites for the antibacterial components, after the addition of ethanol, the polarity of the aqueous phase is reduced, and further encapsulation is carried out, thereby forming a uniform and stable white resveratrol complex, and the stability and long-acting antibacterial performance of the slow-release antibacterial agent are effectively improved.

[0013] Preferably, the mass ratio between the composite bacteriostatic agent, carboxymethyl cellulose and gelatin is (3.9-4.3):1:1.5.

[0014] By adopting the above technical solution, the mass ratio between the composite bacteriostatic agent, carboxymethyl cellulose and gelatin is preferably within the above range, forming a continuous network structure, further improving the stability, and improving the loading rate, thereby improving the overall stability and bacteriostatic effect of the prepared slow-release bacteriostatic agent.

[0015] Preferably, the mass ratio between resveratrol and anthocyanin in the composite bacteriostatic agent is (1.65-1.75):1.

[0016] By adopting the above technical solution, the mass ratio between resveratrol and anthocyanin in the composite bacteriostatic agent is preferably within the above range, which can further improve the overall bacteriostatic performance and stability of the prepared resveratrol composite.

[0017] Preferably, the shell layer raw material of the chitosan cross-linking shell layer includes chitosan, sodium tripolyphosphate and glutaraldehyde.

[0018] By adopting the above technical solution, chitosan is used as the main skeleton structure, and the amino group of chitosan and the resveratrol composite form electrostatic adsorption. At the same time, chitosan also has good bacteriostatic performance, which plays a role in further improving the overall bacteriostatic performance of the system. Sodium tripolyphosphate forms an ionic bond with chitosan, and glutaraldehyde further forms a covalent cross-linking network with chitosan to form a stable shell structure. At the same time, chitosan and carboxymethyl cellulose form an electrostatic effect, which further reduces the adhesion stability of the slow-release bacteriostatic agent in the system. At the same time, the amino group of chitosan can form a coordination bond with nano-silver to fix nano-silver on the surface of the shell layer, which plays a role in synergistically improving the bacteriostatic performance of the system.

[0019] Preferably, the slow-release bacteriostatic agent is prepared by the following method: Chitosan is mixed with ethanol to obtain a chitosan solution. Tween-60 and the resveratrol composite are added to the chitosan solution to obtain a composite emulsion. Sodium tripolyphosphate is mixed with water to obtain a sodium tripolyphosphate solution. Span-80 is mixed with liquid paraffin to obtain a paraffin mixture. The sodium tripolyphosphate solution is added to the composite emulsion, stirred, and then added to the paraffin mixture while stirring. Then, a glutaraldehyde solution is added, stirred and centrifuged, washed, and freeze-dried to obtain the slow-release bacteriostatic agent.

[0020] By adopting the technical scheme, the uniform liquid drop template is formed through emulsification, and then the structure is fixed through cross-linking, the ion cross-linking provides rapid forming and toughness, and the covalent cross-linking provides final mechanical strength and chemical stability, the prepared slow-release antibacterial agent has good stability, and the resveratrol and anthocyanin have good biological activity, and the stability of the slow-release antibacterial agent is further improved.

[0021] Preferably, the mass ratio between the chitosan, sodium pentaphosphate and glutaraldehyde group is 1.8:(0.35-0.45):1.

[0022] By adopting the technical scheme, the mass ratio between the chitosan, sodium pentaphosphate and glutaraldehyde group is within the above range, so that the prepared slow-release antibacterial agent has good stability and antibacterial property.

[0023] Preferably, the proportion of the resveratrol complex in the chitosan solution is 12-16wt%.

[0024] By adopting the technical scheme, the proportion of the resveratrol complex in the chitosan solution is within the above range, which can further improve the stability of the prepared slow-release antibacterial agent.

[0025] In a second aspect, the application provides a preparation method of a graphene antibacterial yarn, which adopts the following technical scheme: A preparation method of a graphene antibacterial yarn, comprising the following steps: The graphene powder is mixed with polyethylene terephthalate, dehydrated and dried, and then melt-spun to obtain graphene textile fibers; sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride are mixed to obtain a cationic treatment solution; the graphene textile fibers are immersed in the cationic treatment solution and subjected to temperature treatment, and then taken out and dried; the graphene textile fibers are then immersed in an antibacterial coating, taken out and dried after padding, to obtain graphene modified fibers; and the graphene modified fibers are blended with modal fibers to obtain a graphene antibacterial yarn.

[0026] By adopting the technical scheme, the sodium hydroxide not only activates the hydroxyl groups of the polyethylene terephthalate, but also penetrates into the interface between the graphene and the polyethylene terephthalate, thereby enhancing the grafting of the cationic agent at the interface; the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride further increases the active sites of the fibers, so that the antibacterial coating and the graphene textile fibers are more stably combined, thereby improving the overall stability of the system.

[0027] In summary, the application has at least one of the following beneficial technical effects: 1. The graphene textile fiber surface is coated with an antibacterial coating, in which the synergistic antibacterial effect between nano-silver and graphene plays a role. Under the action of the slow-release antibacterial agent, it plays a long-term antibacterial role. The crosslinking agent and the acrylic resin form a three-dimensional network structure, which stably adheres each substance to the surface of the graphene textile fiber. In combination with the dispersing agent, it effectively improves the uniform dispersion of each substance on the surface of the graphene fiber and reduces the shedding of graphene; 2. Resveratrol and anthocyanin synergistically broaden the antibacterial spectrum, regulate the proportion of shell crosslinking raw materials and the loading capacity of the composite, further improve the overall antibacterial stability and longevity of the system, and through the synergistic effect of each component, the antibacterial coating can be stably attached to the surface of the graphene textile fiber, reducing the shedding of each component; 3. The dense shell is formed by crosslinking chitosan to wrap the resveratrol composite, reducing the loss and oxidative degradation of active ingredients, improving the overall antibacterial performance of the system, and constructing a double crosslinked shell to reduce the loss rate of components and improve the phenomenon of damage to internal active ingredients, improving overall wash resistance. DETAILED DESCRIPTION

[0028] The application is further described below in conjunction with the examples: Raw material description: all raw materials in the examples can be obtained by market purchase; among them, the particle size of nano-silver particles is 10±2 nm, the dispersing agent is sodium polycarboxylate (CAS number: 9003-04-7), the crosslinking agent is 1,3-bis(2-methylaziridinyl) propane, and the auxiliary agent is polydimethylsiloxane (CAS number: 9006-65-9).

[0029] Example 1 Preparation of resveratrol composite: Mix 2.34 g of gelatin (CAS number: 9000-70-8) with 100 g of deionized water, stir for 30 min under the condition of 50℃ water bath, then add 1.56 g of carboxymethyl cellulose (CAS number: 9000-11-7), stir for 180 min, then add 0.48 g of glycerol, stir for 30 min at room temperature, to obtain a gelatin composite solution; mix 4.98 g of resveratrol (CAS number: 501-36-0) with 3.02 g of anthocyanin (CAS number: 528-58-5) to obtain a composite antibacterial agent, mix 6.1 g of the composite antibacterial agent with 100 g of ethanol, add to the gelatin composite solution, stir for 30 min, and then ultrasonic defoaming for 15 min, and then dry in a 40℃ oven to obtain a resveratrol composite.

[0030] Preparation of slow-release antibacterial agent: Mix 8.57 g of chitosan (CAS No: 9012-76-4) with 100 g of ethanol, magnetically stir for 4 h to obtain a chitosan solution, add 1.5 g of Tween-60 to the chitosan solution, stir until uniform, then add the resveratrol complex, stir to obtain a complex emulsion, the mass fraction of the resveratrol complex in the complex emulsion is 12 wt%; mix 1.67 g of sodium tripolyphosphate (CAS No: 7758-29-4) with 100 g of deionized water to obtain a sodium tripolyphosphate solution, mix 0.5 g of Span-80 with 15 g of liquid paraffin to obtain a paraffin mixture, add the sodium tripolyphosphate to the complex emulsion, stir for 10 min, then add it to the paraffin mixture, stir for half an hour, add 4.76 g of glutaraldehyde (CAS No: 111-30-8) mixed with 100 g of deionized water, stir for 12 h, then centrifuge at 9000 rpm for 30 min, wash with anhydrous ethanol and deionized water alternately, freeze-dry at a temperature of -20°C to obtain a slow-release antibacterial agent.

[0031] Preparation of antibacterial coating: Add 70 g of acrylic resin to 0.5 g of dispersant under stirring at 200 rpm, keep stirring for 10 min to obtain a resin premix, keep stirring the resin premix at a speed of 800 rpm, then add 1.5 g of nano-silver particles, stir at a speed of 1500 rpm for 1 h, then reduce the stirring speed to 500 rpm, add 8 g of slow-release antibacterial agent, stir for 20 min, finally add 1 g of crosslinking agent and 2 g of auxiliary agent, stir for 15 min, then stand for 2 h to obtain an antibacterial coating.

[0032] Preparation of graphene antibacterial yarn: Mix graphene powder with polyethylene terephthalate (CAS No: 25038-59-9), the content of graphene is 6 wt%, dehydrate and dry at a temperature of 60°C, set the melting temperature to 275°C and the rotation speed to 50 rad / s, perform melt spinning to obtain graphene textile fiber; mix sodium hydroxide and 3-chloro-2-hydroxypropyltrimethylammonium chloride (CAS No: 3327-22-8) at a mass ratio of 1:5 to obtain a cationic treatment solution, immerse the graphene textile fiber in the cationic treatment solution, heat in a water bath at 80°C for 10 min, take out the graphene fiber, then treat it in an oven at 80°C for 10 min, then transfer it to the antibacterial coating, stand at a temperature of 40°C for 30 min, finally transfer the graphene textile fiber to an oven at 120°C and solidify it for 8 min to obtain graphene modified fiber, mix the graphene modified fiber with modal fiber at a mass ratio of 1:1 to perform blending to obtain graphene antibacterial yarn.

[0033] Example 2 Preparation of resveratrol complex: Mix 2.21 g of gelatin with 100 g of deionized water, stir for 30 min under the condition of water bath at 50℃, then add 1.47 g of carboxymethyl cellulose, stir for 180 min, then add 0.48 g of glycerol, stir for 30 min at room temperature, to obtain a gelatin complex solution; mix 5.09 g of resveratrol with 2.91 g of anthocyanin to obtain a composite bacteriostatic agent, mix 6.32 g of the composite bacteriostatic agent with 100 g of ethanol, add to the gelatin complex solution, stir for 30 min, and then dry in an oven at 40℃ after ultrasonic defoaming for 15 min, to obtain a resveratrol complex.

[0034] Preparation of slow-release antibacterial agent: Mix 8.31 g of chitosan with 100 g of ethanol, and magnetically stir for 4 h to obtain a chitosan solution, add 1.5 g of Tween-60 to the chitosan solution, stir until uniform, then add the resveratrol complex, stir to obtain a composite emulsion, and the mass fraction of the resveratrol complex in the composite emulsion is 16wt%; mix 2.07 g of sodium tripolyphosphate with 100 g of deionized water to obtain a sodium tripolyphosphate solution, mix 0.5 g of Span-80 with 15 g of liquid paraffin to obtain a paraffin mixture, add the sodium tripolyphosphate to the composite emulsion, stir for 10 min, then add to the paraffin mixture, stir for half an hour, add 4.62 g of glutaraldehyde mixed with 100 g of deionized water, stir for 12 h, then centrifuge at a speed of 9000 rpm for 30 min, wash with anhydrous ethanol and deionized water alternately, and freeze-dry at a temperature of -20℃, to obtain a slow-release antibacterial agent.

[0035] Preparation of antibacterial coating: Add 90 g of acrylic resin to 1.5 g of dispersant under stirring at a speed of 200 rpm, keep stirring for 10 min to obtain a resin premix, keep stirring the resin premix at a speed of 800 rpm, then add 2.5 g of nano-silver particles, stir at a speed of 1500 rpm for 1 h, then reduce the stirring speed to 500 rpm, add 12 g of slow-release antibacterial agent, stir for 20 min, finally add 3 g of crosslinking agent and 4 g of auxiliary agent, stir for 15 min, then stand for 2 h, to obtain an antibacterial coating.

[0036] Preparation of graphene antibacterial yarn: The graphene powder is mixed with polyethylene terephthalate, the content of graphene is 6wt%, and is dehydrated and dried at a temperature of 60℃, the melting temperature is set to 275℃, and the rotation speed is 50rad / s, to carry out melt spinning to obtain graphene textile fibers; sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride are mixed in a mass ratio of 1:5 to obtain a cationic treatment solution, the graphene textile fibers are immersed in the cationic treatment solution, heated in a water bath at 80℃ for 10min, taken out and treated in an oven at 80℃ for 10min, then transferred to an antibacterial coating, and placed at a temperature of 40℃ for 30min, finally the graphene textile fibers are transferred to an oven at 120℃ for curing for 8min to obtain graphene modified fibers, the graphene modified fibers are mixed with modal fibers in a mass ratio of 1:1 to carry out blending to obtain graphene antibacterial yarns.

[0037] Example 3 Preparation of resveratrol complex: 2.27g of gelatin is mixed with 100g of deionized water, stirred in a water bath at 50℃ for 30min, then 1.52g of carboxymethyl cellulose is added, stirred for 180min, then 0.48g of glycerol is added, stirred at room temperature for 30min to obtain a gelatin complex solution; 5.04g of resveratrol is mixed with 2.96g of anthocyanin to obtain a composite bacteriostatic agent, 6.21g of the composite bacteriostatic agent is mixed with 100g of ethanol and added to the gelatin complex solution, stirred for 30min, ultrasonic defoaming for 15min, and dried in an oven at 40℃ to obtain a resveratrol complex.

[0038] Preparation of slow-release antibacterial agent: 8.44g of chitosan is mixed with 100g of ethanol and magnetically stirred for 4h to obtain a chitosan solution, 1.5g of Tween-60 is added to the chitosan solution and stirred uniformly, then the resveratrol complex is added and stirred to obtain a composite emulsion, the mass fraction of the resveratrol complex in the composite emulsion is 14wt%; 1.87g of sodium tripolyphosphate is mixed with 100g of deionized water to obtain a sodium tripolyphosphate solution, 0.5g of Span-80 is mixed with 15g of liquid paraffin to obtain a paraffin mixture, the sodium tripolyphosphate is added to the composite emulsion and stirred for 10min, then added to the paraffin mixture and stirred for half an hour, 4.69g of glutaraldehyde is mixed with 100g of deionized water and then added, stirred for 12h, then centrifuged at a rotation speed of 9000rpm for 30min, washed with anhydrous ethanol and deionized water alternately, and freeze-dried at a temperature of-20℃ to obtain a slow-release antibacterial agent.

[0039] Preparation of antibacterial coating: 80g of acrylic resin is added with 1g of dispersant under stirring condition at 200rpm for 10min to obtain resin premix, the resin premix is stirred at 800rpm, then 2g of nano silver particles is added, stirred at 1500rpm for 1h, then the stirring speed is reduced to 500rpm, 10g of slow-release antibacterial agent is added, stirred for 20min, finally 2g of crosslinking agent and 3g of auxiliary agent are added, stirred for 15min and then left for 2h to obtain the antibacterial coating.

[0040] Preparation of graphene antibacterial yarn: The graphene powder is mixed with polyethylene terephthalate, the content of graphene is 6wt%, dehydrated and dried at a temperature of 60℃, the melting temperature is set to 275℃, and the rotation speed is 50rad / s, melt spinning is carried out to obtain graphene textile fiber; sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride are mixed in a mass ratio of 1:5 to obtain a cationic treatment solution, the graphene textile fiber is immersed in the cationic treatment solution, heated in a water bath at 80℃ for 10min, then taken out and treated in an oven at 80℃ for 10min, then transferred to the antibacterial coating, left for 30min at a temperature of 40℃, and finally the graphene textile fiber is transferred to an oven at 120℃ for solidification for 8min to obtain graphene modified fiber, the graphene modified fiber is mixed with modal fiber in a mass ratio of 1:1 for blending to obtain graphene antibacterial yarn.

[0041] Example 4 Example 4 is based on Example 3, in Example 4, the use amount of resveratrol in the preparation of resveratrol complex is 4.8g, and the use amount of anthocyanin is 3.2g.

[0042] Example 5 Example 5 is based on Example 3, in Example 5, the use amount of resveratrol in the preparation of resveratrol complex is 5.24g, and the use amount of anthocyanin is 2.76g.

[0043] Example 6 Example 6 is based on Example 3, in Example 6, the use amount of resveratrol in the preparation of resveratrol complex is 5.77g, the use amount of carboxymethyl cellulose is 1.69g, and the use amount of gelatin is 2.54g.

[0044] Example 7 Example 7 is based on Example 3, in Example 7, the use amount of resveratrol in the preparation of resveratrol complex is 6.58g, the use amount of carboxymethyl cellulose is 1.37g, and the use amount of gelatin is 2.05g.

[0045] Example 8 Example 8 is based on Example 3, in Example 8, the complex bacteriostatic agent is replaced by an equal amount of resveratrol when preparing the resveratrol complex.

[0046] Example 9 Example 9 is based on Example 3, in Example 9, the complex bacteriostatic agent is replaced by an equal amount of anthocyanin when preparing the resveratrol complex.

[0047] Example 10 Example 10 is based on Example 3, in Example 10, the amount of chitosan used is 8.85g, the amount of sodium tripolyphosphate used is 1.23g, and the amount of glutaraldehyde used is 4.92g when preparing the slow-release antibacterial agent.

[0048] Example 11 Example 11 is based on Example 3, in Example 11, the amount of chitosan used is 8.06g, the amount of sodium tripolyphosphate used is 2.46g, and the amount of glutaraldehyde used is 4.48g when preparing the slow-release antibacterial agent.

[0049] Example 12 Example 12 is based on Example 3, in Example 12, the mass fraction of resveratrol complex in the composite emulsion is 8wt% when preparing the slow-release antibacterial agent.

[0050] Example 13 Example 13 is based on Example 3, in Example 13, the mass fraction of resveratrol complex in the composite emulsion is 20wt% when preparing the slow-release antibacterial agent.

[0051] Example 14 Example 14 is based on Example 3, in Example 14, no glutaraldehyde is used when preparing the slow-release antibacterial agent.

[0052] Comparative Example 1 Comparative Example 1 is based on Example 3, in Comparative Example 1, no nano-silver is added when preparing the antibacterial coating.

[0053] Comparative Example 2 Comparative Example 2 is based on Example 3, in Comparative Example 2, the slow-release antibacterial agent is replaced by an equal amount of resveratrol complex when preparing the antibacterial coating.

[0054] Performance test The samples of Examples 1-14 and Comparative Examples 1-2 were tested for the following performance: (1) Antibacterial performance test The antibacterial performance of the samples was tested according to GB / T 20944.3-2008, with 3 tests for each sample, and the test results were recorded in Table 1. The samples were naturally placed for 60 days, and then the antibacterial performance of the samples was tested, each sample was tested 3 times, and the test results were filled in Table 1.

[0055] (2) Water washing resistance test According to AATCC TM 61-2013 and GB / T 20944.3-2008, the samples were washed 50 times, and then the antibacterial performance of the samples was tested again, each sample was tested 3 times, and the test results were filled in Table 1.

[0056] Table 1 Performance test results of examples 1-14 and comparative examples 1-2 As can be seen from Table 1, the E. coli inhibition rates of examples 1-3 are all above 99.8%, the S. aureus inhibition rates are all above 99.8%, the E. coli inhibition rates after 60 days are all above 96.8%, and the S. aureus inhibition rates are all above 96.7%, which shows that the graphene antibacterial yarn prepared by the application has good antibacterial performance and good long-term antibacterial performance. After 50 times of washing, the E. coli inhibition rates are all above 99%, and the S. aureus inhibition rates are all above 99%, which shows that the graphene antibacterial yarn prepared by the application has good water washing resistance.

[0057] The mass ratio between resveratrol and anthocyanin in examples 4 and 5 is not within the range defined in the application. When the content of resveratrol is too low, the synergistic performance of the cell membrane damage of bacteria decreases, and the hydrophobic region of gelatin is difficult to fully combine with resveratrol, the dispersibility of each component of the system decreases, and the anthocyanin is released too much in the early stage, the active ingredient is insufficient in the later stage, the long-acting antibacterial performance decreases, and the stability of the shell layer of the slow-release antibacterial agent is affected. When the content of resveratrol is too high, it will compete with the binding sites of anthocyanin and gelatin, so that the anthocyanin is free on the surface of the system, and loses the synergistic antibacterial effect. At the same time, too much resveratrol will also affect the compatibility between the system and chitosan, the interface bonding performance decreases, it is difficult to stably adhere to the surface of the graphene textile fiber, and the water washing resistance also decreases.

[0058] In Example 6 and Example 7, the mass ratio between the composite bacteriostatic agent, carboxymethyl cellulose and gelatin is not within the range defined in the present application. When the content of the composite bacteriostatic agent is too low, the bacteriostatic core component is insufficient, the hydrophilic sites of carboxymethyl cellulose and the hydrophobic sites of gelatin are not connected due to insufficient active ingredients, the antibacterial sites are sparse, and it is difficult to play a synergistic antibacterial role with nano-silver and graphene. The antibacterial effective component decreases in the later stage, and it is also difficult to play a long-term antibacterial role. When the content of the composite bacteriostatic agent is too high, the shell layer has limited stable coating performance for the composite antibacterial agent, and it is difficult to completely and stably coat, and it is free in the system and occurs agglomeration. Partial resveratrol is oxidatively degraded, the synergistic antibacterial performance between anthocyanins is decreased, carboxymethyl cellulose and gelatin are damaged due to excessive loading of active ingredients, the double-carrier network structure is damaged, and the water washing resistance is also affected.

[0059] In Example 8 and Example 9, the composite bacteriostatic agent is replaced by a single bacteriostatic active component. Single resveratrol only has an antibacterial function of destroying the cell membrane, carboxymethyl cellulose is difficult to effectively combine with resveratrol, and it is difficult to form a stable coordination with nano-silver particles, and the performance is decreased. Single anthocyanin is difficult to further penetrate the cell membrane, the antibacterial performance is decreased, and it is also difficult to form effective combination with gelatin, the hydrophobic performance of the system is decreased, and the water washing resistance is affected.

[0060] In Example 10 and Example 11, the mass ratio between chitosan, sodium tripolyphosphate and glutaraldehyde is not within the range defined in the present application. When the content of sodium tripolyphosphate is too low, the amino groups of chitosan cannot be further crosslinked, the network structure combination performance of the slow-release antibacterial agent is decreased, a complete structure cannot be formed, the resveratrol complex is released too quickly, and it is difficult to achieve long-term antibacterial effect. When the content of sodium tripolyphosphate is too high, the crosslinking between chitosan is too much, which may be too dense, and cracking is likely to occur subsequently, the water washing resistance is decreased, and the release of the resveratrol complex is difficult to promote, which affects the long-term antibacterial performance of the system. Therefore, the performance of Example 10 and Example 11 is decreased.

[0061] In Example 12 and Example 13, the content of the resveratrol complex in the composite emulsion is not within the range defined in the present application when preparing the slow-release antibacterial agent. When the content of the resveratrol complex is too low, the total amount of antibacterial ingredients is insufficient, and the combination sites with the resin are sparse, and the water washing resistance is decreased. When the content of the resveratrol complex is too high, the resveratrol complex is difficult to be completely coated, and it is free in the system and occurs agglomeration, thereby affecting the dispersibility and stability of the system as a whole, and the water washing resistance is also decreased.

[0062] In the preparation of the slow-release antibacterial agent in Example 14, no glutaraldehyde was added, the bonding of the chitosan cross-linked shell was weak, the stability in the system was reduced, the release of the resveratrol complex was too fast, the long-term antibacterial performance was affected, and the mechanical strength of the shell was reduced, so that the wash resistance of the system was difficult to further improve.

[0063] In Comparative Example 1, no nano-silver particles were added in the antibacterial coating, and the early antibacterial performance was reduced.

[0064] In Comparative Example 2, the slow-release antibacterial agent was replaced by the resveratrol complex, the resveratrol complex without the chitosan shell coating was lost in large quantities during spinning, and was quickly inactivated, which affected the long-term antibacterial performance, and the wash resistance was also reduced.

[0065] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Through the above description, relevant personnel can make various changes and modifications without deviating from the technical concept of the present application. The technical scope of the present application is not limited by the content of the specification, and must be determined by the scope of the claims.

Claims

1. A graphene antibacterial yarn, characterized by: The graphene modified fiber includes a graphene textile fiber and an antibacterial coating, the graphene textile fiber includes a fiber body and graphene, the antibacterial coating is formed by attaching an antibacterial coating on the surface of the graphene textile fiber, the antibacterial coating includes the following components by mass fraction: acrylate resin 30-50 parts, slow-release antibacterial agent 8-12 parts, nano-silver particles 1.5-2.5 parts, dispersing agent 0.5-1.5 parts, crosslinking agent 1-3 parts, and auxiliary agent 2-4 parts.

2. A graphene antibacterial yarn as claimed in claim 1, wherein: The slow-release antibacterial agent includes a white resveratrol compound and a chitosan cross-linked shell layer, and the white resveratrol compound includes gelatin, carboxymethyl cellulose, white resveratrol and anthocyanin.

3. The graphene antibacterial yarn as claimed in claim 1, wherein: The white resveratrol compound is prepared by the following method: The gelatin is mixed with water, heated and stirred, then the carboxymethyl cellulose is added, stirred to obtain a gelatin compound solution, the white resveratrol and anthocyanin are mixed with ethanol to obtain a compound bacteriostatic agent, the white resveratrol solution and the gelatin compound solution are mixed and stirred, and ethanol is continuously added during the stirring process to obtain a precipitate, which is collected, washed, freeze-dried to obtain the white resveratrol compound.

4. A graphene antibacterial yarn as claimed in claim 3, wherein: The mass ratio of the compound bacteriostatic agent, carboxymethyl cellulose and gelatin is (3.9-4.3):1:1.

5.

5. The graphene antibacterial yarn as claimed in claim 3, wherein: The mass ratio of white resveratrol to anthocyanin in the compound bacteriostatic agent is (1.65-1.75):

1.

6. The graphene antibacterial yarn as claimed in claim 2, wherein: The chitosan cross-linked shell layer raw material includes chitosan, sodium tripolyphosphate and glutaraldehyde.

7. A graphene antibacterial yarn as claimed in claim 6, wherein: The slow-release antibacterial agent is prepared by the following method: The chitosan is mixed with ethanol to obtain a chitosan solution, Tween-60 and the white resveratrol compound are added to the chitosan solution to obtain a compound emulsion; sodium tripolyphosphate is mixed with water to obtain a sodium tripolyphosphate solution, Span-80 is mixed with liquid paraffin to obtain a paraffin mixture, the sodium tripolyphosphate solution is added to the compound emulsion, stirred and then added to the paraffin mixture while stirring, and then a glutaraldehyde solution is added, stirred, centrifuged, washed, and freeze-dried to obtain the slow-release antibacterial agent.

8. A graphene antibacterial yarn as claimed in claim 7, wherein: The mass ratio of chitosan, sodium tripolyphosphate and glutaraldehyde is 1.8:(0.35-0.45):

1.

9. A graphene antibacterial yarn as claimed in claim 7, wherein: The proportion of the white resveratrol compound in the chitosan solution is 12-16wt%.

10. A method for preparing the graphene antibacterial yarn according to any one of claims 1-9, characterized by: The method includes the following steps: The graphene powder is mixed with polyethylene terephthalate, dehydrated and dried, and then melt-spun to obtain a graphene textile fiber; sodium hydroxide and 3-chloro-2-hydroxypropyltrimethylammonium chloride are mixed to obtain a cationic treatment solution; the graphene textile fiber is immersed in the cationic treatment solution and heated, then taken out and dried, and then immersed in an antibacterial coating, padded, taken out and dried to obtain a graphene modified fiber; and the graphene modified fiber is blended with modal fiber to obtain a graphene antibacterial yarn.

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