Long-acting anti-mosquito fabric and preparation process thereof

Abstract

The invention relates to the technical field of fabrics, in particular to a long-acting anti-mosquito fabric and a preparation process thereof. The fabric overcomes the defect that an existing fabric is difficult to have efficient antibacterial and anti-mosquito performance and excellent washability at the same time. The method comprises the following steps: performing plasma treatment on a fabric to be treated, padding a sol system containing zinc acetate, silver nitrate and the like, and performing heat treatment; preparing a composite microcapsule containing chitosan, citronellal and the like, mixing the composite microcapsule with a bio-based cross-linking agent solution containing cyclodextrin and tannic acid to obtain a finishing liquid, dipping and rolling the primarily treated fabric in the finishing liquid twice, and performing ultraviolet curing and post-treatment to obtain the long-acting anti-mosquito fabric. The surface activity of the fabric is enhanced through plasma treatment, so that the nano coating is firmly attached; the composite microcapsule and the bio-based cross-linking agent solution cooperate to realize slow release and firm combination of mosquito-repelling components; multiple processes are matched to ensure that functional components are stable, and the fabric prepared by the process has efficient antibacterial and anti-mosquito performance and excellent washability, and can still maintain a good protection effect after being washed for multiple times.

Description

Technical Field

[0001] The present invention relates to the technical field of fabrics, in particular to a long-lasting anti-mosquito fabric and a preparation process thereof. Background Art

[0002] With the improvement of people's living standards and the increase in outdoor activities, the demand for fabric functionality has become increasingly diverse. In hygiene and outdoor settings, fabrics with both antibacterial and anti-insect properties are attracting attention, as they can effectively resist bacterial growth and mosquito bites, reduce the risk of disease transmission, and protect human health. At the same time, consumers' demands for clothing durability are constantly increasing, and fabrics must maintain good functional and physical properties after multiple washes. This makes the long-term effectiveness and washability of antibacterial and anti-insect properties important research and development directions in the industry.

[0003] Currently, traditional antimicrobial and insect repellent fabrics are primarily manufactured using direct padding or coating techniques. Antimicrobial treatments often rely on the physical adsorption of a single antimicrobial agent (such as quaternary ammonium salts or silver ions), while insect repellent treatments often involve simple coating with plant essential oils or a blended finish with synthetic mosquito repellents. While these methods can impart certain functional properties to fabrics, they have significant drawbacks: physically adsorbed functional components have weak bonding to the fibers and easily fall off after repeated washing, resulting in rapid degradation of antimicrobial and insect repellent properties. A single ingredient struggles to achieve both immediate protection and long-lasting effects, and some synthetic chemical agents are irritants, impacting both comfort and safety.

[0004] Existing technologies struggle to meet the market demand for high-performance, long-lasting, and stable fabrics. First, the instability of the functional ingredients' binding to the fiber leads to poor washability. After repeated washings, the antibacterial and mosquito repellent rates fail to meet long-term use requirements. Second, the single antibacterial or mosquito repellent ingredient's single mechanism of action makes it difficult to combat the diverse bacteria and mosquitoes found in complex environments, resulting in limited protection. Finally, traditional processes can easily damage the fabric's inherent properties, such as causing a hard feel and reduced breathability, impacting overall performance. Therefore, there is an urgent need to develop innovative technologies that combine high-efficiency antibacterial and mosquito repellent properties with excellent washability.

[0005] Therefore, a long-lasting anti-mosquito fabric and a preparation process thereof are proposed. Summary of the Invention

[0006] The purpose of the present invention is to design a long-lasting anti-mosquito fabric and its preparation process. The present invention first plasma treats the fabric to be treated, then immerses and rolls it in a sol system containing zinc acetate, silver nitrate, etc. and performs heat treatment; prepares composite microcapsules containing chitosan, citronellal, etc. and mixes them with a bio-based cross-linking agent solution containing cyclodextrin and tannic acid to form a finishing liquid, and the initially treated fabric is immersed and rolled in the finishing liquid twice, then UV-cured and post-treated to obtain a long-lasting anti-mosquito fabric. Plasma treatment enhances the surface activity of the fabric and allows the nano-coating to adhere firmly; the composite microcapsules and the bio-based cross-linking agent solution work together to achieve sustained release and firm bonding of mosquito repellent ingredients; multiple processes are coordinated to ensure the stability of the functional ingredients. The fabric prepared by this process has both high-efficiency antibacterial and anti-mosquito properties and excellent washability, and can maintain a good protective effect after multiple washings.

[0007] To achieve the above object, the present invention provides the following technical solutions: In one aspect, the present invention provides a process for preparing a long-lasting anti-mosquito fabric, the process comprising the following steps: The fabric to be treated is subjected to plasma treatment to obtain a pretreated fabric; the pretreated fabric is dipped and padded in a sol system, and then subjected to heat treatment to obtain a primary treated fabric; the composite microcapsules are dispersed and mixed with a bio-based crosslinking agent solution to obtain a finishing solution; the primary treated fabric is immersed in the finishing solution, and subjected to a second dip and second padded process to obtain a retreated fabric; the retreated fabric is subjected to UV curing and post-treatment to obtain a long-lasting anti-mosquito fabric; The sol system includes zinc acetate, silver nitrate, citric acid and polyvinyl alcohol; Composite microcapsules include chitosan, polyurethane, citronellal, menthol, and permethrin; The bio-based cross-linker solution includes cyclodextrin and tannic acid.

[0008] Preferably, the fabric to be treated is made of cotton.

[0009] Preferably, the preparation method of the sol system is as follows, in parts by weight: 10-15 parts of zinc acetate and 1-3 parts of silver nitrate are sequentially added to 25 parts of ethanol, and stirred at 55°C for 1 hour to form a uniform solution; after cooling to room temperature, 1.5 parts of citric acid and 0.8 parts of polyvinyl alcohol are added, and stirring is continued for 1 hour to obtain a mixed solution; the mixed solution is transferred to a constant temperature water bath, and reacted at 60°C-70°C for 3h-4h, with continuous stirring during the reaction, to obtain a sol-gel solution; after sealing the sol-gel solution, it is placed in a constant temperature environment at 45°C for aging for 18 hours to obtain a sol system.

[0010] Preferably, the preparation method of the composite microcapsules is as follows, by weight: 3-5 parts of chitosan are slowly added to 10 parts of acetic acid solution, and stirred and dissolved at 45° C. for 1.5 hours to obtain a transparent solution; 12 parts of polyurethane are added to the transparent solution, and stirring is continued for 1 hour to obtain an outer layer material solution; 3-5 parts of citronellal, 2-3 parts of menthol and 1-2 parts of permethrin are added to 30 parts of ethanol at room temperature, and stirred for 1 hour to obtain a composite solution; the composite solution is poured into a container, 0.1 parts of emulsifier Span-80 are added, and 0.5 parts of liquid paraffin are slowly added under stirring conditions for 15 minutes to obtain a stable emulsion; the outer layer material solution is slowly added dropwise to the stable emulsion under continuous stirring, and the addition time is controlled to be 12 minutes. After the dropwise addition is completed, 5 parts of glutaraldehyde are continued to be added, and the reaction is carried out at 50° C. for 2 hours to 3 hours to form a microcapsule structure; after the reaction is completed, the composite microcapsules are washed and dried by centrifugation to obtain composite microcapsules.

[0011] Preferably, the preparation method of the bio-based crosslinker solution is as follows, in parts by weight: pour 80 parts of deionized water into a reaction container, slowly add 4-8 parts of cyclodextrin under continuous stirring at 55° C., and stir for 15-20 minutes to obtain a dissolved solution; then add 3-5 parts of tannic acid and continue stirring for 25 minutes to obtain a mixed solution; after the mixed solution is cooled to room temperature, add 0.5 parts of benzoin dimethyl ether and stir for 10-15 minutes to obtain a bio-based crosslinker solution.

[0012] Preferably, the specific process of plasma treatment and heat treatment is as follows: cutting the fabric to be treated into the size of the equipment cavity, removing surface stains and grease, and drying to obtain dry fabric; turning on the power of the plasma equipment, starting the vacuum pump, evacuating the vacuum degree of the cavity to 8Pa, opening the valve of the oxygen cylinder, setting the gas flow rate to 20mL / min-30mL / min through the flow controller, and after the vacuum degree of the cavity is stabilized at 75Pa, turning on the radio frequency power supply, adjusting the power to 100W, hanging the dry fabric flat on the sample rack inside the cavity, treating for 4 minutes, then turning off the radio frequency power supply, continuing to introduce oxygen for 30 seconds, slowly opening the air inlet valve to restore the cavity to normal pressure, taking out the fabric, and obtaining pretreated fabric; immersing the pretreated fabric in the sol system, adopting a two-immersion and two-rolling method, controlling the rolling rate to 60%-70%, sending the fabric immersed in the sol into the heat treatment equipment, and treating it at 125°C for 5min-10min to obtain the initially treated fabric.

[0013] Preferably, the specific preparation process of the finishing liquid is: mixing the composite microcapsules and the bio-based crosslinker solution in a weight ratio of 0.5-1.5:1.5 for 20 minutes, then adding 0.8 parts of sodium hexametaphosphate, stirring for 20 minutes to 30 minutes to obtain the finishing liquid.

[0014] Preferably, the rolling rate of the double dipping and double rolling is controlled at 70%.

[0015] Preferably, the specific process of UV curing and post-treatment is as follows: turn on the UV curing equipment, place the reprocessed fabric flat on the conveyor belt after preheating, adjust the conveyor belt speed to 0.5m / min-1m / min, and 2 Irradiate under 365nm ultraviolet light for 3min-5min. After curing is completed, turn off the UV lamp and put the UV-cured reprocessed fabric into a hot air drying machine, set the temperature to 80℃, bake for 5min, then quickly heat to 130℃, continue baking for 2min, then take out and naturally cool to room temperature to obtain a cured fabric; add deionized water and cured fabric into a washing machine, add alkyl glycoside at 0.5% of the weight of the cured fabric, wash at 45℃ water temperature for 10min-15min, rinse and dry after washing to obtain a long-lasting anti-mosquito fabric.

[0016] Another aspect of the present invention provides a long-lasting anti-mosquito fabric, which is obtained by pre-treating the fabric by padding it with a sol system, padding it with a finishing liquid after heat treatment, and then UV curing and post-treatment.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. A low-temperature oxygen plasma etching process creates a nanoscale rough structure on the fabric surface and introduces active hydroxyl groups, providing physical anchoring points and chemical binding groups for the nanometal coating, significantly enhancing the adhesion between the ZnO nanorods and the Ag particles. The photocatalytic antibacterial properties of ZnO and the broad-spectrum antibacterial effect of Ag ions create a comprehensive antibacterial synergy. Simultaneously, ZnO's UV shielding function protects the mosquito repellent ingredients from photodegradation. The synergistic effect ensures the coating adheres firmly to the fiber surface, achieving long-lasting and stable antibacterial and mosquito repellent properties.

[0018] 2. The plant-based repellent in the core layer complements the synthetic repellent in terms of functionality: the former rapidly repels mosquitoes with volatile molecules, while the latter kills pests over a long period of time through contact, achieving a synergistic "instant repellency and sustained protection" approach. The chitosan and polyurethane in the shell layer are chemically cross-linked to form a composite membrane. The natural antimicrobial properties of chitosan combined with the solvent resistance of polyurethane enhance the mechanical strength of the microcapsules while imparting antimicrobial properties to the fabric. This results in simultaneous improvements in repellency, killing, and antimicrobial properties, and significantly increases resistance to detergent erosion.

[0019] 3. The hydrophobic cavity of cyclodextrin encapsulates the mosquito repellent molecules, forming a "slow-release cage" that delays their volatilization. The polyphenol structure of tannic acid tightly binds to the fiber through hydrogen bonds, while exerting its own antibacterial activity. The two are then covalently cross-linked through a UV-curing process. The cyclodextrin's encapsulation and the tannic acid's directional anchoring form a synergistic mechanism, extending the release period of the mosquito repellent ingredients and enhancing their binding to the fiber. The tannic acid's antibacterial properties are combined with its mosquito repellent effects, achieving a dual synergistic effect of natural substances in terms of both function and process.

[0020] 4. The preparation process of the present invention achieves multiple performance improvements through multi-process collaboration and material innovation: plasma treatment constructs a nano-rough structure on the fabric surface and introduces active groups, significantly enhancing the adhesion of nano-coatings such as zinc acetate and silver nitrate in the sol system. The coating formed after heat treatment has both photocatalytic antibacterial and broad-spectrum antibacterial functions; the composite microcapsules use chitosan-polyurethane double-layer wall materials to encapsulate mosquito repellent ingredients such as citronellal, combined with the sustained-release fixation mechanism of cyclodextrin-tannic acid bio-based crosslinker solution, which extends the release cycle of the mosquito repellent ingredients and firmly bonds with the fibers; the two-immersion and two-rolling process ensures uniform loading of the finishing liquid, and ultraviolet curing triggers the cross-linking reaction through photoinitiators, reducing energy consumption while avoiding the decomposition of heat-sensitive components. The segmented baking and water washing processes ensure the stability and comfort of the fabric structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a flow chart of the preparation process of the present invention. DETAILED DESCRIPTION

[0022] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 making creative efforts are within the scope of protection of the present invention.

[0023] Specific reference Figure 1 The present invention provides a long-lasting anti-mosquito fabric and its preparation process, the technical solution is as follows: Example 1 13 parts of zinc acetate and 2 parts of silver nitrate were added to 25 parts of ethanol in sequence, and stirred at 55°C for 1 hour to form a uniform solution; after cooling to room temperature, 1.5 parts of citric acid and 0.8 parts of polyvinyl alcohol were added, and stirring was continued for 1 hour to obtain a mixed solution; the mixed solution was transferred to a constant temperature water bath, reacted at 65°C for 3.5 hours, and continuously stirred during the reaction to obtain a sol-gel solution; the sol-gel solution was sealed and placed in a constant temperature environment of 45°C for aging for 18 hours to obtain a sol system.

[0024] 4 parts of chitosan were slowly added to 10 parts of acetic acid solution, stirred and dissolved at 45°C for 1.5 hours to obtain a transparent solution; 12 parts of polyurethane were added to the transparent solution, and stirring was continued for 1 hour to obtain an outer layer material solution; 4 parts of citronellal, 2.5 parts of menthol and 1.5 parts of permethrin were added to 30 parts of ethanol at room temperature in sequence, and stirred for 1 hour to obtain a composite solution; the composite solution was poured into a container, 0.1 parts of emulsifier Span-80 were added, and 0.5 parts of liquid paraffin were slowly added under stirring conditions for 15 minutes to obtain a stable emulsion; the outer layer material solution was slowly added dropwise to the stable emulsion under continuous stirring, and the addition time was controlled to be 12 minutes. After the addition was completed, 5 parts of glutaraldehyde were continued to be added, and the reaction was carried out at 50°C for 2.5 hours to form a microcapsule structure; after the reaction was completed, the composite microcapsules were obtained by centrifugal washing and drying.

[0025] Pour 80 parts of deionized water into a reaction vessel, slowly add 6 parts of cyclodextrin under continuous stirring at 55°C, and stir for 18 minutes to obtain a dissolved solution; then add 4 parts of tannic acid and continue stirring for 25 minutes to obtain a mixed solution; after the mixed solution is cooled to room temperature, add 0.5 parts of benzoin dimethyl ether and stir for 13 minutes to obtain a bio-based crosslinker solution.

[0026] Preparation of long-lasting anti-mosquito fabric: The fabric to be treated is cut into the size of the equipment cavity, and the surface stains and grease are removed. The fabric is dried to obtain a dry fabric; the plasma equipment power is turned on, the vacuum pump is started, the vacuum degree of the cavity is evacuated to 8Pa, the valve of the oxygen cylinder is opened, and the gas flow rate is set to 25mL / min through the flow controller. After the vacuum degree of the cavity is stabilized at 75Pa, the radio frequency power is turned on and the power is adjusted to 100W. The dry fabric is hung flat on the sample rack inside the cavity and treated for 4 minutes. Then the radio frequency power is turned off, and oxygen is continued to be introduced for 30 seconds. The air inlet valve is slowly opened to restore the cavity to normal pressure, and the fabric is taken out to obtain the pretreated fabric; The pretreated fabric was immersed in the sol system, and the double-immersion and double-rolling method was adopted, and the rolling rate was controlled to be 65%. The fabric immersed in the rolled sol was sent to the heat treatment equipment and treated at 125℃ for 8 minutes to obtain the primary treated fabric; The composite microcapsules and the bio-based crosslinker solution were mixed at a weight ratio of 1:1.5 for 20 minutes, followed by the addition of 0.8 parts of sodium hexametaphosphate and stirring for 25 minutes to obtain a finishing solution. The primary treated fabric was immersed in the finishing solution and subjected to two dipping and two padding to obtain a retreated fabric, with the rolling rate of the two dipping and two padding being controlled at 70%. Turn on the UV curing equipment, place the reprocessed fabric flat on the conveyor belt after preheating, adjust the conveyor belt speed to 0.8m / min, and at 110mW / cm 2The cured fabric was irradiated under 365nm ultraviolet light for 4 minutes. After curing was completed, the UV lamp was turned off and the UV-cured reprocessed fabric was placed in a hot air drying machine. The temperature was set to 80°C and baked for 5 minutes. The temperature was then quickly raised to 130°C and continued to bake for 2 minutes. The fabric was then taken out and naturally cooled to room temperature to obtain a cured fabric. Deionized water and the cured fabric were added to a washing machine, and alkyl glycoside was added at 0.5% of the weight of the cured fabric. The fabric was washed at 45°C for 12 minutes. After washing, the fabric was rinsed and dried to obtain a long-lasting anti-mosquito fabric.

[0027] Examples 2-9 refer to the parameter conditions in Example 1, with specific differences as shown in Table 1.

[0028] The parameter conditions of Examples 1, 4 and 7 are all the same.

[0029] Table 1 Parameter conditions of Examples 1-9

[0030] Comparative Example 1 The parameters and conditions in Example 1 were used with the exception that no silver nitrate was added to the sol system.

[0031] Comparative Example 2 The parameters and conditions in Example 1 were used with the exception that zinc acetate was not added to the sol system.

[0032] Comparative Example 3 The parameters and conditions in Example 1 were referred to, except that citric acid and polyvinyl alcohol were not added to the sol system.

[0033] Comparative Example 4 The parameters and conditions in Example 1 are referred to, except that the fabric to be treated is not subjected to plasma treatment.

[0034] Comparative Example 5 The parameters and conditions in Example 1 are referred to, except that the pretreated fabric is not subjected to heat treatment after padding.

[0035] Experimental Example 1 Antibacterial Performance Test The antibacterial properties of Examples 1-3 and Comparative Examples 1-5 before and after washing were tested according to the standard GB / T 20944.3-2008, using Staphylococcus aureus and Escherichia coli. The results are shown in Table 2.

[0036] Table 2 Antibacterial properties of Examples 1-3 and Comparative Examples 1-5 before and after washing

[0037] It can be seen from Table 2 that the examples have good antibacterial properties and wash resistance. In Comparative Example 1, silver nitrate is not added to the sol system. Silver nitrate is an important source of antibacterial components. Its absence causes the initial antibacterial rate of the fabric to decrease. After washing 50 times, the antibacterial rate decreases significantly. In Comparative Example 2, zinc acetate is the basic raw material for forming the antibacterial coating. Its absence causes the antibacterial performance of the fabric to decrease significantly. By comparing the examples, it can be found that zinc acetate is crucial for constructing a stable antibacterial structure. Only when combined with silver nitrate can efficient and long-lasting antibacterial properties be achieved. In Comparative Example 3, citric acid and polyvinyl alcohol are not added to the sol system. Citric acid and polyvinyl alcohol can promote the stability of the sol system and the combination with the fabric. After their absence, the initial antibacterial performance and wash resistance of the fabric are greatly affected, and the antibacterial rate is significantly lower than that of the examples, indicating that the two are indispensable for improving the adhesion of antibacterial components, stabilizing the coating structure, and thus enhancing the durability of the antibacterial performance. In Comparative Example 4, the fabric to be treated was not subjected to plasma treatment. Plasma treatment improves the surface structure and activity of the fabric, creating favorable conditions for the subsequent adhesion of the antimicrobial coating. However, leaving it untreated impairs the adhesion and penetration of the sol system onto the fabric, resulting in a decrease in antimicrobial performance. In Comparative Example 5, the pretreated fabric was not subjected to heat treatment after padding. Heat treatment helps the sol system solidify on the fabric to form a stable antimicrobial coating. Omitting this step deteriorates the coating's stability and adhesion, resulting in reduced antimicrobial performance and washability.

[0038] In summary, plasma treatment introduces polar groups to the fabric surface through surface activation and roughening, increasing the specific surface area and providing a good adhesion base for the sol system. The ZnO and Ag particles in the sol system, through synergistic antimicrobial mechanisms such as photocatalysis and ion sterilization, work in conjunction with the dispersing and bonding effects of citric acid and polyvinyl alcohol to form a highly effective antimicrobial coating. Heat treatment promotes crosslinking between the sol system and the fabric fibers, optimizing the structure and distribution of the ZnO and Ag particles and further enhancing the coating's stability and antimicrobial activity. The three synergistic processes, from pretreatment to core functional loading to performance enhancement, not only significantly improve the fabric's antimicrobial efficiency but also impart excellent washability, achieving long-lasting and stable antimicrobial performance.

[0039] Comparative Example 6 The parameters and conditions in Example 4 were referred to, except that chitosan was not added to the outer layer material solution.

[0040] Comparative Example 7 The parameters and conditions in Example 4 are referred to, except that no polyurethane is added to the outer layer material solution.

[0041] Comparative Example 8 The parameters and conditions in Example 4 are referred to, except that only citronellal is coated in the composite microcapsules.

[0042] Comparative Example 9 The parameters and conditions in Example 4 were referred to, except that only menthol was coated in the composite microcapsules.

[0043] Comparative Example 10 The parameters and conditions in Example 4 were referred to, except that only permethrin was coated in the composite microcapsules.

[0044] Comparative Example 11 The parameters and conditions in Example 4 were referred to, except that the stable emulsion was not microencapsulated.

[0045] Experimental Example 2 Antibacterial and Anti-mosquito Performance Test The antibacterial properties of Examples 4-6 and Comparative Examples 6-11 were tested before and after washing using Escherichia coli according to the standard GB / T 20944.3-2008. The anti-mosquito properties of Examples 4-6 and Comparative Examples 6-11 were also tested before and after washing using the standard GB / T 30126-2013. The results are shown in Table 3.

[0046] Table 3 Antibacterial and anti-mosquito properties of Examples 4-6 and Comparative Examples 6-11 before and after washing

[0047] Table 3 shows that the examples have excellent antibacterial and anti-mosquito properties and washability. In Comparative Example 6, the chitosan molecular chain contains amino and hydroxyl groups and can be cross-linked with polyurethane through hydrogen bonds to form a dense microcapsule wall material network. The absence of chitosan leads to a decrease in the mechanical strength of the wall material, making it easily damaged during washing. The antibacterial rate and repellency rate are significantly reduced after washing. Chitosan itself has certain antibacterial activity, and the initial antibacterial rate will decrease after its absence. In Comparative Example 7, polyurethane provides the wall material with flexibility and water resistance, forming a composite structure with chitosan. The absence of polyurethane increases the brittleness of the wall material, making it easy to disintegrate during washing, and the antibacterial rate and repellency rate are reduced after washing. At the same time, the hydrophobic chain segment of polyurethane can reduce the premature release of the core material. Comparative Examples 8-10 use a single core material. The single component is easily degraded by microorganisms or lost during washing, resulting in poor washability. In addition, the single core material has weak antibacterial and mosquito repellent activity, fast volatilization rate, and insufficient long-term effectiveness. In Comparative Example 11, a physical barrier is formed by coating with wall materials, which can achieve controlled sustained release and protective stability of the core material; without microcapsule coating, the core material is directly exposed to the external environment, and is easily lost due to mechanical friction and water solubility during washing, and is easily ineffective due to oxidation and light during long-term storage.

[0048] In summary, the chitosan and polyurethane composite wall material optimizes mechanical properties by combining rigidity and flexibility, while also adding antibacterial and hydrophobic properties, ensuring that the fabric maintains a high antibacterial / repellent rate even after 50 washes. In the multi-component core material, the antibacterial properties of permethrin complement the mosquito repellent effects of citronellal and menthol, and through intermolecular forces, they synergistically release the product, improving washability compared to single-component core materials. The microencapsulation process protects the core material's stability and precisely controls release, avoiding component loss and irritation risks, ensuring that activity is maintained even after 50 washes. All three are essential, validating the necessity of combining materials and processes to enhance long-lasting antibacterial and mosquito repellent performance.

[0049] Comparative Example 12 The parameters and conditions in Example 7 were referred to, except that cyclodextrin was not added to the bio-based cross-linking agent solution.

[0050] Comparative Example 13 The parameters and conditions in Example 7 were the same, except that tannic acid was not added to the bio-based cross-linking agent solution.

[0051] Comparative Example 14 The parameters and conditions in Example 7 were referred to, except that benzoin dimethyl ether was not added to the bio-based cross-linking agent solution.

[0052] Comparative Example 15 The parameters and conditions in Example 7 are referred to, except that the primary treated fabric is immersed in the finishing liquid and only subjected to one immersion and one padding treatment.

[0053] Comparative Example 16 The parameters and conditions in Example 7 were used with the exception that no UV curing was performed.

[0054] Experimental Example 3 Antibacterial and Anti-mosquito Performance Test The antibacterial and anti-mosquito properties of Examples 7-9 and Comparative Examples 12-16 were tested according to the test method of Experimental Example 2. The results are shown in Table 4.

[0055] Table 4 Antibacterial and anti-mosquito properties of Examples 7-9 and Comparative Examples 12-16 before and after washing

[0056] Table 4 shows that the examples exhibited superior antibacterial and washability properties. In Comparative Example 12, due to its unique cyclic structure, cyclodextrin formed inclusion complexes with the mosquito repellent components in the composite microcapsules, resulting in a sustained release. Without cyclodextrin, the initial release rate of the mosquito repellent components was accelerated. Although the repellency rate reached over 90.0% without washing, after 50 washes, the repellency rate dropped significantly due to rapid component loss. Regarding antibacterial properties, cyclodextrin aided the crosslinker in binding to fabric fibers. Its absence reduced the adhesion stability of the antibacterial components. In Comparative Example 13, tannic acid, containing a large number of phenolic hydroxyl groups, could hydrogen bond and crosslink with fabric fibers, chitosan, and other components, enhancing the adhesion of the finishing solution to the fabric. However, the absence of tannic acid impaired the finishing solution's adhesion to the fabric, and both the antibacterial and mosquito repellent components were more likely to fall off during washing. This resulted in lower antibacterial and repellency rates than in the examples without washing, and significantly reduced washability. In Comparative Example 14, benzoin dimethyl ether, as a photoinitiator, plays a key role in the UV curing process, initiating cross-linking reactions between the bio-based cross-linker and other components. Without benzoin dimethyl ether, effective UV curing is impossible, resulting in a loose film structure and a weakened protective effect on the functional components. In Comparative Example 15, the one-dip-one-pad treatment reduces the amount of finishing solution adsorbed by the fabric compared to the two-dip-two-pad treatment, resulting in insufficient loading of functional components. On the one hand, insufficient attachment of antimicrobial and mosquito repellent components leads to reduced antibacterial and repellent rates in the unwashed state. On the other hand, the small and uneven attachment of components increases their potential for loss during washing. In Comparative Example 16, UV curing enables the bio-based cross-linker and related components to form a stable three-dimensional network structure, enhancing the film's mechanical properties and washability. Without UV curing, the film fails to effectively cross-link, resulting in a fragile structure and difficulty in firmly adhering the functional components to the fabric. Consequently, the fabric's antimicrobial and mosquito repellent properties are significantly reduced, as is its washability.

[0057] In summary, the cyclodextrin in the bio-based crosslinker achieves controlled release by encapsulating the core material. Tannic acid, through its polyphenolic structure, enhances antimicrobial properties and stabilizes the functional ingredients. Benzoin dimethyl ether acts as a photoinitiator, triggering double crosslinking between the bio-based crosslinker and the wall material during UV curing, forming a washable three-dimensional network. The synergistic effect of these three agents: cyclodextrin and tannic acid enhance the stability and initial performance of the core material, while benzoin dimethyl ether strengthens the crosslinking density through UV curing, ensuring that the fabric maintains a high antibacterial / repellent rate even after 50 washes. This also reduces core material volatilization and photolytic loss, achieving efficient fixation and long-lasting release of the functional ingredients.

[0058] While 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 these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A preparation process for a long-lasting anti-mosquito fabric, characterized by: The preparation process comprises the following steps: The fabric to be treated is subjected to plasma treatment to obtain a pretreated fabric; the pretreated fabric is dipped and padded in a sol system, and then subjected to heat treatment to obtain a primary treated fabric; the composite microcapsules are dispersed and mixed with a bio-based crosslinking agent solution to obtain a finishing solution; the primary treated fabric is immersed in the finishing solution, and subjected to two dips and two padded processes to obtain a retreated fabric; the retreated fabric is subjected to UV curing and post-treatment to obtain the long-lasting anti-mosquito fabric; The sol system includes zinc acetate, silver nitrate, citric acid and polyvinyl alcohol; The composite microcapsule comprises chitosan, polyurethane, citronellal, menthol and permethrin; The bio-based cross-linker solution includes cyclodextrin and tannic acid.

2. The process for preparing a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The preparation method of the sol system is as follows: 10-15 parts of the zinc acetate and 1-3 parts of the silver nitrate are sequentially added to ethanol, and stirred to form a uniform solution; After cooling to room temperature, the citric acid and the polyvinyl alcohol are added and stirred continuously to obtain a mixed solution; the mixed solution is transferred to a constant temperature water bath and reacted at 60° C. to 70° C. for 3 h to 4 h with continuous stirring during the reaction to obtain a sol-gel solution; the sol-gel solution is sealed and aged to obtain the sol system.

3. The preparation process of a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The preparation method of the composite microcapsule is as follows: slowly adding 3-5 parts of the chitosan to an acetic acid solution, stirring and dissolving to obtain a transparent solution; adding the polyurethane to the transparent solution, and continuing to stir to obtain an outer layer material solution; at room temperature, sequentially adding 3-5 parts of citronellal, 2-3 parts of menthol, and 1-2 parts of permethrin to ethanol, and stirring to obtain a composite solution; pouring the composite solution into a container, adding an emulsifier Span-80, and slowly adding liquid paraffin under stirring conditions, and stirring to obtain a stable emulsion; slowly adding the outer layer material solution dropwise to the stable emulsion under continuous stirring, and after the dropwise addition is completed, continuously adding glutaraldehyde, reacting for 2h-3h to form a microcapsule structure; and after the reaction is completed, washing and drying by centrifugation to obtain the composite microcapsule.

4. The process for preparing a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The preparation method of the bio-based crosslinker solution is as follows: deionized water is poured into a reaction container, and 4-8 parts of the cyclodextrin is slowly added under continuous stirring, and stirred for 15 minutes to 20 minutes to obtain a dissolved solution; then 3-5 parts of the tannic acid are added, and stirring is continued to obtain a mixed solution; after the mixed solution is cooled to room temperature, benzoin dimethyl ether is added, and stirred for 10 minutes to 15 minutes to obtain the bio-based crosslinker solution.

5. The process for preparing a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The specific process of the plasma treatment and the heat treatment is as follows: cutting the fabric to be treated into the size of the equipment cavity, removing surface stains and grease, and drying to obtain a dry fabric; turning on the power of the plasma equipment, evacuating to a vacuum, opening the valve of the oxygen cylinder, setting the gas flow rate to 20mL / min-30mL / min through a flow controller, and after the vacuum degree is stabilized, performing radio frequency treatment on the dry fabric to obtain a pretreated fabric; immersing the pretreated fabric in the sol system, adopting a two-immersion and two-rolling method, controlling the rolling rate to 60%-70%, and then sending it to the heat treatment equipment for treatment for 5min-10min to obtain the initially treated fabric.

6. The process for preparing a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The specific preparation process of the finishing liquid is: mixing the composite microcapsules and the bio-based crosslinking agent solution in a weight ratio of 0.5-1.5:1.5, then adding sodium hexametaphosphate, and stirring for 20 minutes to 30 minutes to obtain the finishing liquid.

7. The process for preparing a long-lasting anti-mosquito fabric according to claim 1, characterized in that: The specific process of the UV curing and post-treatment is as follows: turning on the UV curing equipment, placing the reprocessed fabric flat on a conveyor belt after preheating, adjusting the conveyor belt speed to 0.5m / min-1m / min, and irradiating it under UV light for 3min-5min; placing the UV-cured reprocessed fabric in a hot air drying machine for baking, and obtaining a cured fabric after cooling; adding deionized water and the cured fabric into a washing machine, adding alkyl polyglycoside and washing for 10min-15min, followed by rinsing and drying to obtain the long-lasting anti-mosquito fabric.

8. A long-lasting anti-mosquito fabric, characterized by: The long-lasting anti-mosquito fabric is prepared by the preparation process described in any one of claims 1 to 7; the long-lasting anti-mosquito fabric is obtained by pre-treating the fabric by padding the sol system, padding the finishing liquid after heat treatment, and then UV curing and post-treatment.

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