Highly breathable antibacterial lining fabric and preparation method thereof

Abstract

The application relates to the technical field of textiles, in particular to a high-breathability antibacterial lining cloth and a preparation method thereof. The pre-emulsion is obtained by adding ethyl methacrylate, hydroxyethyl acrylate, modified chitosan, modified silver-loaded titanium dioxide, modified lignin and a sodium dodecyl sulfate solution; the acrylic adhesive is obtained by adding a sodium dodecyl sulfate solution, a sodium bicarbonate solution and an ammonium persulfate solution into the pre-emulsion. The high-breathability polyester fabric is immersed in the acrylic adhesive for 1-2 minutes, and then is subjected to rolling, baking and the like, so that the high-breathability antibacterial lining cloth is obtained. The high-breathability antibacterial lining cloth prepared by the application has excellent antibacterial performance and ultraviolet resistance, and therefore has a wide application prospect in the technical field of textiles.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of textiles, in particular to a high-breathability antibacterial lining cloth and a preparation method thereof. BACKGROUND

[0002] In the modern clothing field, although clothing lining cloth is an auxiliary material, its value cannot be underestimated, especially with the development of technology, modern lining cloth shows many unique advantages. Modern clothing lining cloth plays a key role in clothing style and shape retention. The fashion trend is changing constantly, and the requirements for clothing patterns and lines are becoming more and more demanding. Whether it is a delicate suit or an elegant dress, lining cloth is needed to shape and maintain its perfect shape. It can make the clothing fit the human body curve and show a crisp style, making the wearer more spiritual and elegant. At the same time, in the process of daily wearing and washing, the lining cloth can prevent the clothing from deforming and keep the clothing in good condition for a long time, prolonging its service life. In terms of improving the quality of clothing, modern lining cloth has made a significant contribution. New types of lining cloth such as resin lining and adhesive lining are light, soft, and closely combined with the fabric, which not only does not increase the weight of the clothing, but also enhances the crispness and drape of the fabric, making the clothing look more high-end and delicate.

[0003] However, in daily life, human skin will secrete sweat and oil, creating a suitable environment for bacteria to grow. A large number of bacteria can produce unpleasant odors and may cause skin diseases such as itching and allergies. Therefore, the preparation of clothing lining cloth with antibacterial properties can inhibit bacterial growth and reduce the number of bacteria, effectively providing a healthier wearing environment for the wearer. In addition, long-term exposure to ultraviolet rays can cause skin problems such as sunburn, tanning, aging, and even increase the risk of skin cancer. By improving the ultraviolet resistance of clothing lining cloth, an effective protective barrier can be provided for the human body to block ultraviolet rays from penetrating the clothing and contacting the skin. Especially for outdoor workers, athletes and other people who are exposed to sunlight for a long time, lining cloth with ultraviolet resistance can greatly reduce the damage of ultraviolet rays to the skin.

[0004] In order to overcome the defects of the prior art, the present application provides a high-breathability antibacterial lining cloth and a preparation method thereof. SUMMARY

[0005] The purpose of the present application is to provide a high-breathability antibacterial lining cloth and a preparation method thereof to solve the problems existing in the prior art.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] A preparation method of a high-breath antibacterial lining cloth, comprising the following steps: step S1: mixing ethyl methacrylate, hydroxyethyl acrylate, modified chitosan, modified silver-loaded titanium dioxide and modified lignin, ultrasonic dispersion for 40-50 min to obtain a monomer reaction solution; adding the monomer reaction solution drop by drop into a sodium dodecyl sulfate solution, continuously stirring for 40-50 min after the addition is completed to obtain a pre-emulsion;

[0008] Step S2: mixing the sodium dodecyl sulfate solution and a sodium bicarbonate solution, heating to 75-80℃, then adding 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of an ammonium persulfate solution to continue the polymerization reaction for 30-40 min, heating to 85-90℃, then slowly adding the remaining pre-emulsion and ammonium persulfate solution, and keeping warm for 1-2 h after the addition is completed to obtain an acrylic adhesive; immersing the high-breath polyester fabric in the acrylic adhesive for 1-2 min, and then performing calendering and baking after the immersion to obtain the high-breath antibacterial lining cloth.

[0009] More preferably, the content of each component of the pre-emulsion is: 30-35 parts by mass of ethyl methacrylate, 10-15 parts by mass of hydroxyethyl acrylate, 10-12 parts by mass of modified chitosan, 7-9 parts by mass of modified silver-loaded titanium dioxide, 10-12 parts by mass of modified lignin, and 20-25 parts by mass of a sodium dodecyl sulfate solution; the sodium dodecyl sulfate solution is 5-20 g / L, the sodium bicarbonate solution is 0.5-0.7 g / L, and the ammonium persulfate solution is 0.8-1.0 g / L; the mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion and the ammonium persulfate solution is 3:2:(18-20):1.

[0010] More preferably, the calendering process is: twice calendering, the first time with an impregnation calendering rate of 89-90%, and the second time with an impregnation calendering rate of 94-95%; the baking parameters are: first pre-curing at 120-130℃ for 1 min, and then curing at 150-160℃ for 2 min.

[0011] More preferably, the preparation process of the modified chitosan is:

[0012] Step S1: dispersing chitosan in distilled water, heating to 80-85℃, stirring for 20-30 min, then adding 2,3-epoxypropyltrimethylammonium chloride, and continuing to stir for 12-15 h; after the reaction is completed, adding the reaction solution to acetone for precipitation, and then purifying and drying to obtain quaternized chitosan;

[0013] Step S2: adding sodium hydroxide and quaternary ammonium chitosan into deionized water to obtain a chitosan reaction solution; adding zinc acetate into deionized water to obtain a zinc acetate reaction solution; adding the chitosan reaction solution dropwise into the zinc acetate reaction solution, and hydrothermally reacting at 90-95℃ for 5-6h; after the reaction is completed, cooling, adjusting pH to 7.3-7.5, standing, centrifugation, washing, and drying are performed to obtain zinc oxide coated quaternary ammonium chitosan;

[0014] Step S3: adding γ-methacryloyloxypropyltrimethoxysilane into an aqueous ethanol solvent, fully stirring for 20-30min, then adding the zinc oxide coated quaternary ammonium chitosan, and ultrasonic dispersing for 40-50min; after uniform dispersion, refluxing at 85-87℃ for 3-4h; after the reaction is completed, cooling, washing, and drying are performed to obtain modified chitosan.

[0015] More preferably, the volume ratio of ethanol to deionized water in the aqueous ethanol solvent is (3.0-3.5):1; the reaction mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:(3.5-4.0); the reaction mass ratio of sodium hydroxide, quaternary ammonium chitosan, and zinc acetate is 4:(1.3-1.5):2.5; and the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane to zinc oxide coated quaternary ammonium chitosan is (0.8-1.0):10.

[0016] More preferably, the preparation process of the modified silver-loaded titanium dioxide is as follows:

[0017] Step S1: adding titanium dioxide nanotubes into ethylene glycol, adjusting pH to 8.0-8.5, and ultrasonic dispersing for 30-40min; then adding 0.04-0.05mol / L silver nitrate ethanol solution, and continuously ultrasonic dispersing for 15-20min; after uniform dispersion, water bath reaction at 50-55℃ for 9-10h; after the reaction is completed, cooling, centrifugation, washing, and drying are performed to obtain silver-loaded titanium dioxide;

[0018] Step S2: adding the silver-loaded titanium dioxide into 1.5-2.0mol / L hydrochloric acid, ultrasonic dispersing for 30-40min, and stirring at 25-30℃ for 3-4h after uniform dispersion; after the reaction is completed, washing and drying are performed to obtain pretreated silver-loaded titanium dioxide; adding γ-methacryloyloxypropyltrimethoxysilane into an aqueous ethanol solvent, fully stirring for 20-30min, then adding the pretreated silver-loaded titanium dioxide, and ultrasonic dispersing for 40-50min; after uniform dispersion, refluxing at 85-87℃ for 6-7h; after the reaction is completed, cooling, washing, and drying are performed to obtain modified silver-loaded titanium dioxide.

[0019] More preferably, the mass-volume ratio of the titanium dioxide nanotube, ethylene glycol and silver nitrate ethanol solution is 1g:100mL:(25-30)mL; the reaction mass ratio of gamma-methacryloxypropyl trimethoxysilane and the pretreated silver-loaded titanium dioxide is (0.6-0.8):10.

[0020] More preferably, the preparation process of the modified lignin is as follows:

[0021] Step S1: lignin is added into a 6.0-6.3mol / L sodium hydroxide solution to obtain a lignin reaction solution; 3-chloro-2-hydroxypropyl-trimethylammonium chloride is added into deionized water to obtain a quaternary ammonium salt reaction solution; the quaternary ammonium salt reaction solution is added dropwise into the lignin reaction solution, and after continuous reaction for 20-30min, 6.0-6.3mol / L sodium hydroxide solution is continuously added, and the reaction is carried out at 85-90℃ for 5-6h; after the reaction is completed, freeze-drying, washing and drying are carried out to obtain quaternized lignin;

[0022] Step S2: sodium hydroxide and quaternized lignin are added into deionized water to obtain a lignin reaction solution; zinc acetate is added into deionized water to obtain a zinc acetate reaction solution; the lignin reaction solution is added dropwise into the zinc acetate reaction solution, and hydrothermal reaction is carried out at 90-95℃ for 5-6h; after the reaction is completed, cooling, pH adjustment to 7.3-7.5, standing, centrifugation, washing and drying are carried out to obtain zinc oxide-coated quaternized lignin;

[0023] Step S3: gamma-methacryloxypropyl trimethoxysilane is added into an ethanol aqueous solvent, and stirring is carried out for 20-30min; then the zinc oxide-coated quaternized lignin is added, and ultrasonic dispersion is carried out for 40-50min; after uniform dispersion, reflux reaction is carried out at 85-87℃ for 3-4h; after the reaction is completed, cooling, washing and drying are carried out to obtain modified lignin.

[0024] More preferably, the volume ratio of ethanol and deionized water in the ethanol aqueous solvent is (3.0-3.5):1; the reaction mass ratio of lignin and 3-chloro-2-hydroxypropyl-trimethylammonium chloride is 7:(6.0-6.2); the reaction mass ratio of sodium hydroxide, quaternized lignin and zinc acetate is 4:(1.1-1.2):2.5; and the reaction mass ratio of gamma-methacryloxypropyl trimethoxysilane and zinc oxide-coated quaternized lignin is (0.8-1.0):10.

[0025] The beneficial effects of the present application are as follows:

[0026] The application is characterized in that the chitosan is treated by adding 2,3-epoxypropyl trimethyl ammonium chloride, so as to obtain quaternary ammonium chitosan with excellent antibacterial performance; then the chitosan reaction solution is added dropwise into the zinc acetate reaction solution, and the hydrothermal reaction is carried out, so as to obtain zinc oxide coated quaternary ammonium chitosan with both ultraviolet resistance and antibacterial performance. Further, the zinc oxide coated quaternary ammonium chitosan is modified by using gamma-methacryloxypropyl trimethoxysilane, so as to obtain modified chitosan with introduced carbon-carbon double bond. The chitosan itself has a certain antibacterial ability, and the quaternary ammonium modification further enhances the antibacterial performance; and the zinc oxide is an excellent ultraviolet absorber and scatterer, so that the zinc oxide is coated on the surface of the quaternary ammonium chitosan, on the one hand, the coating structure can protect the quaternary ammonium chitosan, so that the antibacterial performance is more durable and stable; on the other hand, the quaternary ammonium chitosan can play a certain role in dispersing the zinc oxide, so that the zinc oxide can be more uniformly distributed, thereby better exerting the ultraviolet resistance. The synergistic effect of the two makes the zinc oxide coated quaternary ammonium chitosan have excellent ultraviolet resistance and antibacterial performance.

[0027] The application is characterized in that by adding titanium dioxide nanotubes, ethylene glycol and silver nitrate ethanol solution, and through the alkaline ethylene glycol reduction method, the uniform loading of Ag nanoparticles is realized under mild conditions, so as to obtain silver-loaded titanium dioxide. Then the silver-loaded titanium dioxide is modified by using gamma-methacryloxypropyl trimethoxysilane, so as to obtain modified silver-loaded titanium dioxide with introduced carbon-carbon double bond. The titanium dioxide itself is an excellent ultraviolet shielding agent. When the silver nanoparticles are irradiated by ultraviolet rays, the free electrons on the surface of the silver nanoparticles will collectively oscillate, producing resonance absorption. The absorption effect and the absorption of titanium dioxide on ultraviolet rays are complementary to each other, which widens the absorption range of the material to ultraviolet rays, so that the silver-loaded titanium dioxide exhibits more excellent ultraviolet resistance. In addition, the silver nanoparticles have strong antibacterial ability, and the titanium dioxide nanotubes provide a good loading platform for the silver nanoparticles, so that the silver nanoparticles can be uniformly dispersed, the contact area between the silver nanoparticles and bacteria is increased, and the antibacterial efficiency is further improved.

[0028] The application is characterized in that lignin is treated by adding 3-chloro-2-hydroxypropyl-trimethylammonium chloride to obtain quaternary ammonium lignin with both ultraviolet resistance and antibacterial properties; then the lignin reaction solution is added dropwise into the zinc acetate reaction solution, and through hydrothermal reaction, an ultraviolet resistant zinc oxide layer is further coated to obtain zinc oxide coated quaternary ammonium lignin. Further, the zinc oxide coated quaternary ammonium lignin is modified by using gamma-methacryloxypropyltrimethoxysilane to obtain modified lignin with introduced carbon-carbon double bonds. Lignin itself has certain biological activity, and after quaternary ammonium treatment of lignin by using 3-chloro-2-hydroxypropyl-trimethylammonium chloride, the antibacterial performance is significantly improved. Meanwhile, the lignin molecular structure contains a large number of phenylpropane structural units and conjugated double bonds and other chromophores and auxiliary chromophores, which can absorb the energy of ultraviolet rays. In the hydrothermal reaction, zinc oxide is coated on the surface of quaternary ammonium lignin to form a stable composite structure. On the one hand, the coating of zinc oxide layer can protect the quaternary ammonium lignin, so that the antibacterial components are not easy to lose, the effective period of antibacterial is prolonged, and the durability of antibacterial performance is improved. On the other hand, zinc oxide can be uniformly distributed on the surface of the material, and can fully play its ultraviolet resistance performance. The zinc oxide coated quaternary ammonium lignin exhibits excellent comprehensive performance through the synergistic effect of ultraviolet resistance and antibacterial performance.

[0029] Finally, the application adds ethyl methacrylate, hydroxyethyl acrylate, modified chitosan, modified silver-loaded titanium dioxide, modified lignin, sodium dodecyl sulfate solution, sodium bicarbonate solution, ammonium persulfate solution to obtain an acrylic adhesive. The carbon-carbon double bonds introduced by gamma-methacryloxypropyltrimethoxysilane modification enable these components to better combine with the acrylic system. In the acrylic adhesive, the three modified components are uniformly dispersed, and their respective ultraviolet resistance and antibacterial effects complement and synergize each other. Different absorption and scattering mechanisms play a role in different wave bands, so that the adhesive can more comprehensively and efficiently resist ultraviolet rays, thereby having excellent ultraviolet resistance; different antibacterial mechanisms cooperate with each other to form multi-directional attacks on various bacteria. Therefore, after the high-breathable polyester fabric is impregnated with the acrylic adhesive, the adhesive is attached to the surface of the fabric and between the fibers, endowing the fabric with ultraviolet resistance and antibacterial functions, thereby making a high-breathable antibacterial lining cloth. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0031] Raw material sources:

[0032] Chitosan was provided by Jiangsu Cailei Biotechnology Co., Ltd., with a particle size of 80 mesh and a degree of deacetylation of ≥80%; titanium dioxide nanotubes were provided by Jiangsu Xianfeng Nanometer Material Technology Co., Ltd., with a diameter of 10 nm; lignin was provided by Zhengzhou Alpha Chemical Co., Ltd., with a specification of analytical purity; high-breathable polyester fabric was provided by Suzhou Yiming Textile Co., Ltd., 100% polyester, with a density of 240 Tg / m 2 1g in terms of mass fraction.

[0033] Example 1: Step one: disperse chitosan in distilled water, heat to 85℃ and stir for 30 min, then add 2,3-epoxypropyltrimethylammonium chloride, continue to stir for 15 h, after the reaction is completed, add the reaction solution to acetone for precipitation, then purify, dry to obtain quaternary ammonium chitosan; add sodium hydroxide and quaternary ammonium chitosan to deionized water to obtain a chitosan reaction solution; add zinc acetate to deionized water to obtain a zinc acetate reaction solution; add the chitosan reaction solution dropwise to the zinc acetate reaction solution, and hydrothermal reaction at 95℃ for 6 h, after the reaction is completed, cool, adjust the pH to 7.5, stand, centrifuge, wash, dry to obtain zinc oxide coated quaternary ammonium chitosan;

[0034] Add γ-methacryloxypropyltrimethoxysilane to an ethanol aqueous solvent, stir for 30 min, then add zinc oxide coated quaternary ammonium chitosan, ultrasonic dispersion for 50 min, after uniform dispersion, reflux reaction at 87℃ for 4 h, after the reaction is completed, cool, wash, dry to obtain modified chitosan; the volume ratio of ethanol to deionized water in the ethanol aqueous solvent is 3.3:1; the reaction mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:3.7; the reaction mass ratio of sodium hydroxide, quaternary ammonium chitosan, and zinc acetate is 4:1.4:2.5; the reaction mass ratio of γ-methacryloxypropyltrimethoxysilane to zinc oxide coated quaternary ammonium chitosan is 0.9:10;

[0035] Step two: add titanium dioxide nanotubes to ethylene glycol, then adjust the pH to 8.5, ultrasonic dispersion for 40 min, then add 0.05 mol / L silver nitrate ethanol solution, continue to ultrasonic dispersion for 20 min, after uniform dispersion, water bath reaction at 55℃ for 10 h, after the reaction is completed, cool, centrifuge, wash, dry to obtain silver-loaded titanium dioxide;

[0036] The silver-loaded titanium dioxide is added into 2.0 mol / L hydrochloric acid, ultrasonic dispersion is carried out for 40 min, after uniform dispersion, stirring reaction is carried out at 30℃ for 4 h, after reaction is finished, washing, drying are carried out, pretreated silver-loaded titanium dioxide is obtained; the γ-methacryloxypropyl trimethoxysilane is added into an ethanol aqueous solvent, stirring is carried out for 30 min, then the pretreated silver-loaded titanium dioxide is added, ultrasonic dispersion is carried out for 50 min, after uniform dispersion, reflux reaction is carried out at 87℃ for 7 h, after reaction is finished, cooling, washing, drying are carried out, modified silver-loaded titanium dioxide is obtained; the mass-volume ratio of the titanium dioxide nanotube, the ethylene glycol, the silver nitrate ethanol solution is 1 g:100 mL:27 mL; the reaction mass ratio of the γ-methacryloxypropyl trimethoxysilane and the pretreated silver-loaded titanium dioxide is 0.7:10;

[0037] Step three: the lignin is added into 6.3 mol / L sodium hydroxide solution, to obtain a lignin reaction liquid; the 3-chloro-2-hydroxypropyl-trimethylammonium chloride is added into deionized water, to obtain a quaternary ammonium salt reaction liquid; the quaternary ammonium salt reaction liquid is added dropwise into the lignin reaction liquid, after continuous reaction for 30 min, 6.3 mol / L sodium hydroxide solution is continuously added, stirring reaction is carried out at 90℃ for 6 h, after reaction is finished, freeze-drying, washing, drying are carried out, to obtain the quaternized lignin; the sodium hydroxide, the quaternized lignin are added into deionized water, to obtain a lignin reaction liquid; the zinc acetate is added into deionized water, to obtain a zinc acetate reaction liquid; the lignin reaction liquid is added dropwise into the zinc acetate reaction liquid, hydrothermal reaction is carried out at 95℃ for 6 h, after reaction is finished, cooling, adjusting pH to 7.5, standing, centrifugation, washing, drying are carried out, to obtain the zinc oxide coated quaternized lignin;

[0038] The γ-methacryloxypropyl trimethoxysilane is added into an ethanol aqueous solvent, stirring is carried out for 30 min, then the zinc oxide coated quaternized lignin is added, ultrasonic dispersion is carried out for 50 min, after uniform dispersion, reflux reaction is carried out at 87℃ for 4 h, after reaction is finished, cooling, washing, drying are carried out, to obtain the modified lignin; the volume ratio of ethanol and deionized water in the ethanol aqueous solvent is 3.3:1; the reaction mass ratio of the lignin and the 3-chloro-2-hydroxypropyl-trimethylammonium chloride is 7:6.1; the reaction mass ratio of the sodium hydroxide, the quaternized lignin, the zinc acetate is 4:1.15:2.5; the reaction mass ratio of the γ-methacryloxypropyl trimethoxysilane and the zinc oxide coated quaternized lignin is 0.9:10;

[0039] Step four: 35 g of ethyl methacrylate, 15 g of hydroxyethyl acrylate, 12 g of modified chitosan, 9 g of modified silver-loaded titanium dioxide, and 12 g of modified lignin were mixed and ultrasonically dispersed for 50 min to obtain a monomer reaction solution; the monomer reaction solution was added dropwise into 25 g of a 20 g / L sodium dodecyl sulfate solution, and after the dropwise addition was completed, stirring was continued for 50 min to obtain a pre-emulsion; 10 g / L of a sodium dodecyl sulfate solution and 0.7 g / L of a sodium bicarbonate solution were mixed, heated to 80℃, and then 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of a 1 g / L ammonium persulfate solution were added to continue the polymerization reaction for 40 min, and then the temperature was increased to 90℃ and the remaining pre-emulsion and ammonium persulfate solution were slowly added, after the dropwise addition was completed, the temperature was maintained for 2 h, and after the reaction was completed, an acrylic adhesive was obtained; the high-air-permeability polyester fabric was immersed in the acrylic adhesive for 2 min, and after the immersion was completed, it was subjected to calendering and baking to obtain a high-air-permeability antibacterial lining cloth; the mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution was 3:2:19:1; the calendering process: calendering in two times, the first time with an impregnation calendering rate of 90%, and the second time with an impregnation calendering rate of 95%; the baking parameters: first pre-curing at 130℃ for 1 min, and then curing at 160℃ for 2 min.

[0040] Example 2: Step one: chitosan was dispersed in distilled water, heated to 83℃, and stirred for 25 min, then 2,3-epoxypropyltrimethylammonium chloride was added, and the stirring reaction was continued for 14 h, after the reaction was completed, the reaction solution was added to acetone for precipitation, and then purified and dried to obtain quaternary ammonium chitosan; sodium hydroxide and quaternary ammonium chitosan were added to deionized water to obtain a chitosan reaction solution; zinc acetate was added to deionized water to obtain a zinc acetate reaction solution; the chitosan reaction solution was added dropwise to the zinc acetate reaction solution, and a hydrothermal reaction was carried out at 93℃ for 5.5 h, after the reaction was completed, it was cooled, the pH was adjusted to 7.4, and then it was left to stand, centrifuged, washed, and dried to obtain zinc oxide-coated quaternary ammonium chitosan;

[0041] γ-methacryloyloxypropyltrimethoxysilane was added to an ethanol aqueous solvent, stirred for 25 min, then zinc oxide-coated quaternary ammonium chitosan was added, and ultrasonically dispersed for 45 min, after uniform dispersion, a reflux reaction was carried out at 86℃ for 3.5 h, after the reaction was completed, it was cooled, washed, and dried to obtain modified chitosan; the volume ratio of ethanol to deionized water in the ethanol aqueous solvent was 3.3:1; the mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride was 1:3.7; the mass ratio of sodium hydroxide to quaternary ammonium chitosan to zinc acetate was 4:1.4:2.5; the mass ratio of γ-methacryloyloxypropyltrimethoxysilane to zinc oxide-coated quaternary ammonium chitosan was 0.9:10;

[0042] Step 2: Add titanium dioxide nanotubes to ethylene glycol, adjust the pH to 8.3, and ultrasonically disperse for 35 min. Then add 0.05 mol / L silver nitrate ethanol solution and continue ultrasonic dispersion for 17 min. After uniform dispersion, react in a water bath at 53℃ for 9.5 h. After the reaction is completed, cool, centrifuge, wash and dry to obtain silver-loaded titanium dioxide.

[0043] Silver-loaded titanium dioxide was added to 2.0 mol / L hydrochloric acid and ultrasonically dispersed for 35 min. After uniform dispersion, the mixture was stirred at 27 °C for 3.5 h. After the reaction, the mixture was washed and dried to obtain pretreated silver-loaded titanium dioxide. γ-methacryloxypropyltrimethoxysilane was added to an ethanol aqueous solvent and stirred thoroughly for 25 min. Then, pretreated silver-loaded titanium dioxide was added and ultrasonically dispersed for 45 min. After uniform dispersion, the mixture was refluxed at 86 °C for 6.5 h. After the reaction, the mixture was cooled, washed, and dried to obtain modified silver-loaded titanium dioxide. The mass-to-volume ratio of titanium dioxide nanotubes, ethylene glycol, and silver nitrate ethanol solution was 1 g: 100 mL: 27 mL. The mass ratio of γ-methacryloxypropyltrimethoxysilane to pretreated silver-loaded titanium dioxide was 0.7:10.

[0044] Step 3: Add lignin to a 6.3 mol / L sodium hydroxide solution to obtain a lignin reaction solution; add 3-chloro-2-hydroxypropyl-trimethylammonium chloride to deionized water to obtain a quaternary ammonium salt reaction solution; add the quaternary ammonium salt reaction solution dropwise to the lignin reaction solution, and after reacting for 25 min, continue adding 6.3 mol / L sodium hydroxide solution, stirring at 87℃ for 5.5 h. After the reaction, freeze-dry, wash, and dry to obtain quaternized lignin; add sodium hydroxide and quaternized lignin to deionized water to obtain a lignin reaction solution; add zinc acetate to deionized water to obtain a zinc acetate reaction solution; add the lignin reaction solution dropwise to the zinc acetate reaction solution, and hydrothermally react at 93℃ for 5.5 h. After the reaction, cool, adjust the pH to 7.4, let stand, centrifuge, wash, and dry to obtain zinc oxide-coated quaternized lignin.

[0045] γ-methacryloxypropyltrimethoxysilane was added to an ethanol-water solvent and stirred thoroughly for 25 min. Then, zinc oxide was added to coat the quaternized lignin, and the mixture was ultrasonically dispersed for 45 min. After uniform dispersion, the mixture was refluxed at 86 °C for 3.5 h. After the reaction was completed, the mixture was cooled, washed, and dried to obtain modified lignin. The volume ratio of ethanol to deionized water in the ethanol-water solvent was 3.3:1; the mass ratio of lignin to 3-chloro-2-hydroxypropyl-trimethylammonium chloride was 7:6.1; the mass ratio of sodium hydroxide, quaternized lignin, and zinc acetate was 4:1.15:2.5; and the mass ratio of γ-methacryloxypropyltrimethoxysilane to zinc oxide-coated quaternized lignin was 0.9:10.

[0046] Step four: 35 g of ethyl methacrylate, 15 g of hydroxyethyl acrylate, 12 g of modified chitosan, 9 g of modified silver-loaded titanium dioxide, and 12 g of modified lignin were mixed and ultrasonically dispersed for 45 min to obtain a monomer reaction solution; the monomer reaction solution was added dropwise to 25 g of a 20 g / L sodium dodecyl sulfate solution, and after the dropwise addition was completed, stirring was continued for 45 min to obtain a pre-emulsion; a 10 g / L sodium dodecyl sulfate solution and a 0.7 g / L sodium bicarbonate solution were mixed, warmed to 77°C, and then 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of a 1 g / L ammonium persulfate solution were added to continue the polymerization reaction for 35 min, the temperature was raised to 87°C, and the remaining pre-emulsion and ammonium persulfate solution were slowly added, after the dropwise addition was completed, the temperature was maintained for 1.5 h, and after the reaction was completed, an acrylic adhesive was obtained; the high-air-permeability polyester fabric was immersed in the acrylic adhesive for 1.5 min, and after the immersion was completed, it was subjected to calendering and baking to obtain a high-air-permeability antibacterial lining cloth; the mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution was 3:2:19:1; the calendering process: calendering in two times, the first time with an immersion calendering rate of 89.5%, and the second time with an immersion calendering rate of 94.5%; the baking parameters: pre-curing at 125°C for 1 min, and then curing at 155°C for 2 min.

[0047] Example 3: Step one: chitosan was dispersed in distilled water, warmed to 80°C, and stirred for 20 min, then 2,3-epoxypropyltrimethylammonium chloride was added, and stirring was continued for 12 h, after the reaction was completed, the reaction solution was added to acetone for precipitation, and then purified and dried to obtain quaternary ammonium chitosan; sodium hydroxide and quaternary ammonium chitosan were added to deionized water to obtain a chitosan reaction solution; zinc acetate was added to deionized water to obtain a zinc acetate reaction solution; the chitosan reaction solution was added dropwise to the zinc acetate reaction solution, and hydrothermal reaction was carried out at 90°C for 5 h, after the reaction was completed, cooling, pH adjustment to 7.3, standing, centrifugation, washing, and drying were carried out to obtain zinc oxide-coated quaternary ammonium chitosan;

[0048] γ-methacryloxypropyltrimethoxysilane was added to an ethanol aqueous solvent, stirred for 20 min, then zinc oxide-coated quaternary ammonium chitosan was added, ultrasonically dispersed for 40 min, after uniform dispersion, reflux reaction was carried out at 85°C for 3 h, after the reaction was completed, cooling, washing, and drying were carried out to obtain modified chitosan; the volume ratio of ethanol to deionized water in the ethanol aqueous solvent was 3.3:1; the mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride was 1:3.7; the mass ratio of sodium hydroxide to quaternary ammonium chitosan to zinc acetate was 4:1.4:2.5; the mass ratio of γ-methacryloxypropyltrimethoxysilane to zinc oxide-coated quaternary ammonium chitosan was 0.9:10;

[0049] Step two: adding the titanium dioxide nanotube into ethylene glycol, adjusting pH to 8.0, adding 0.05 mol / L silver nitrate ethanol solution after ultrasonic dispersion for 30 min, continuing ultrasonic dispersion for 15 min, adding silver-loaded titanium dioxide into 2.0 mol / L hydrochloric acid after uniform dispersion, stirring reaction at 25℃ for 3 h, washing and drying after reaction, obtaining pretreated silver-loaded titanium dioxide; adding γ-methacryloxypropyl trimethoxysilane into ethanol aqueous solvent, stirring for 20 min, adding pretreated silver-loaded titanium dioxide, ultrasonic dispersion for 40 min, refluxing reaction at 85℃ for 6 h after uniform dispersion, cooling, washing and drying after reaction, obtaining modified silver-loaded titanium dioxide; the mass-volume ratio of titanium dioxide nanotube, ethylene glycol and silver nitrate ethanol solution is 1 g:100 mL:27 mL; the reaction mass ratio of γ-methacryloxypropyl trimethoxysilane and pretreated silver-loaded titanium dioxide is 0.7:10;

[0050] Step two: adding the titanium dioxide nanotube into ethylene glycol, adjusting pH to 8.0, adding 0.05 mol / L silver nitrate ethanol solution after ultrasonic dispersion for 30 min, continuing ultrasonic dispersion for 15 min, adding silver-loaded titanium dioxide into 2.0 mol / L hydrochloric acid after uniform dispersion, stirring reaction at 25℃ for 3 h, washing and drying after reaction, obtaining pretreated silver-loaded titanium dioxide; adding γ-methacryloxypropyl trimethoxysilane into ethanol aqueous solvent, stirring for 20 min, adding pretreated silver-loaded titanium dioxide, ultrasonic dispersion for 40 min, refluxing reaction at 85℃ for 6 h after uniform dispersion, cooling, washing and drying after reaction, obtaining modified silver-loaded titanium dioxide; the mass-volume ratio of titanium dioxide nanotube, ethylene glycol and silver nitrate ethanol solution is 1 g:100 mL:27 mL; the reaction mass ratio of γ-methacryloxypropyl trimethoxysilane and pretreated silver-loaded titanium dioxide is 0.7:10;

[0051] Step three: adding lignin into 6.3 mol / L sodium hydroxide solution to obtain lignin reaction liquid; adding 3-chloro-2-hydroxypropyl-trimethylammonium chloride into deionized water to obtain quaternary ammonium salt reaction liquid; adding the quaternary ammonium salt reaction liquid drop by drop into the lignin reaction liquid, continuously adding 6.3 mol / L sodium hydroxide solution after reaction for 20 min, stirring reaction at 85℃ for 5 h, freeze-drying, washing and drying after reaction, obtaining quaternized lignin; adding sodium hydroxide and quaternized lignin into deionized water to obtain lignin reaction liquid; adding zinc acetate into deionized water to obtain zinc acetate reaction liquid; adding the lignin reaction liquid drop by drop into the zinc acetate reaction liquid, hydrothermal reaction at 90℃ for 5 h, cooling, adjusting pH to 7.3, standing, centrifuging, washing and drying after reaction, obtaining zinc oxide coated quaternized lignin;

[0052] Step three: adding lignin into 6.3 mol / L sodium hydroxide solution to obtain lignin reaction liquid; adding 3-chloro-2-hydroxypropyl-trimethylammonium chloride into deionized water to obtain quaternary ammonium salt reaction liquid; adding the quaternary ammonium salt reaction liquid drop by drop into the lignin reaction liquid, continuously adding 6.3 mol / L sodium hydroxide solution after reaction for 20 min, stirring reaction at 85℃ for 5 h, freeze-drying, washing and drying after reaction, obtaining quaternized lignin; adding sodium hydroxide and quaternized lignin into deionized water to obtain lignin reaction liquid; adding zinc acetate into deionized water to obtain zinc acetate reaction liquid; adding the lignin reaction liquid drop by drop into the zinc acetate reaction liquid, hydrothermal reaction at 90℃ for 5 h, cooling, adjusting pH to 7.3, standing, centrifuging, washing and drying after reaction, obtaining zinc oxide coated quaternized lignin;

[0053] Step four: 35 g of ethyl methacrylate, 15 g of hydroxyethyl acrylate, 12 g of modified chitosan, 9 g of modified silver-loaded titanium dioxide, and 12 g of modified lignin were mixed and ultrasonically dispersed for 40 min to obtain a monomer reaction solution; the monomer reaction solution was added dropwise to 25 g of a 20 g / L sodium dodecyl sulfate solution, and stirring was continued for 40 min after the addition was completed to obtain a pre-emulsion; a 10 g / L sodium dodecyl sulfate solution and a 0.7 g / L sodium bicarbonate solution were mixed, heated to 75°C, and then 1 / 2 of the mass of the pre-emulsion and 1 / 2 of the mass of a 1 g / L ammonium persulfate solution were added for continued polymerization for 30 min, the temperature was increased to 85°C, and the remaining pre-emulsion and ammonium persulfate solution were slowly added, and after the addition was completed, the solution was kept at the temperature for 1 h, and after the reaction was completed, an acrylic adhesive was obtained; the high-air-permeability polyester fabric was immersed in the acrylic adhesive for 1 min, and after the immersion was completed, the fabric was subjected to calendering and baking to obtain a high-air-permeability antibacterial lining cloth; the mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution was 3:2:19:1; the calendering process: calendering in two times, the first time with an immersion calendering rate of 89%, and the second time with an immersion calendering rate of 94%; the baking parameters: first pre-curing at 120°C for 1 min, and then curing at 150°C for 2 min.

[0054] Comparative Example 1: The modified chitosan was removed, and the rest was the same as in Example 1, and the specific steps were as follows: Step one: the titanium dioxide nanotube was added to ethylene glycol, the pH was adjusted to 8.5, and after ultrasonic dispersion for 40 min, 0.05 mol / L of silver nitrate ethanol solution was added, and ultrasonic dispersion was continued for 20 min; after uniform dispersion, the solution was reacted in a 55°C water bath for 10 h; after the reaction was completed, the solution was cooled, centrifuged, washed, and dried to obtain silver-loaded titanium dioxide;

[0055] The silver-loaded titanium dioxide was added to a 2.0 mol / L hydrochloric acid solution, ultrasonically dispersed for 40 min, and after uniform dispersion, the solution was stirred at 30°C for 4 h; after the reaction was completed, the solution was washed and dried to obtain pretreated silver-loaded titanium dioxide; γ-methacryloxypropyltrimethoxysilane was added to an aqueous ethanol solvent, and after being stirred for 30 min, the pretreated silver-loaded titanium dioxide was added, and ultrasonic dispersion was performed for 50 min; after uniform dispersion, the solution was refluxed at 87°C for 7 h; after the reaction was completed, the solution was cooled, washed, and dried to obtain modified silver-loaded titanium dioxide; the mass-volume ratio of the titanium dioxide nanotube, the ethylene glycol, and the silver nitrate ethanol solution was 1 g:100 mL:27 mL; the reaction mass ratio of the γ-methacryloxypropyltrimethoxysilane and the pretreated silver-loaded titanium dioxide was 0.7:10;

[0056] Step two: add lignin to a 6.3 mol / L sodium hydroxide solution to obtain a lignin reaction solution; add 3-chloro-2-hydroxypropyl-trimethylammonium chloride to deionized water to obtain a quaternary ammonium salt reaction solution; add the quaternary ammonium salt reaction solution dropwise to the lignin reaction solution, continue to react for 30 min, then continue to add a 6.3 mol / L sodium hydroxide solution, stir and react at 90℃ for 6 h, after the reaction is completed, freeze-dry, wash, and dry to obtain quaternized lignin; add sodium hydroxide and quaternized lignin to deionized water to obtain a lignin reaction solution; add zinc acetate to deionized water to obtain a zinc acetate reaction solution; add the lignin reaction solution dropwise to the zinc acetate reaction solution, and hydrothermally react at 95℃ for 6 h, after the reaction is completed, cool, adjust the pH to 7.5, stand, centrifuge, wash, and dry to obtain zinc oxide-coated quaternized lignin;

[0057] Add γ-methacryloxypropyltrimethoxysilane to an ethanol aqueous solvent, stir thoroughly for 30 min, then add the zinc oxide-coated quaternized lignin, and ultrasonic disperse for 50 min, after uniform dispersion, reflux at 87℃ for 4 h, after the reaction is completed, cool, wash, and dry to obtain modified lignin; the volume ratio of ethanol to deionized water in the ethanol aqueous solvent is 3.3:1; the reaction mass ratio of lignin to 3-chloro-2-hydroxypropyl-trimethylammonium chloride is 7:6.1; the reaction mass ratio of sodium hydroxide to quaternized lignin to zinc acetate is 4:1.15:2.5; the reaction mass ratio of γ-methacryloxypropyltrimethoxysilane to zinc oxide-coated quaternized lignin is 0.9:10;

[0058] Step three: mix 35 g of ethyl methacrylate, 15 g of hydroxyethyl acrylate, 9 g of modified silver-loaded titanium dioxide, and 12 g of modified lignin, and ultrasonic disperse for 50 min to obtain a monomer reaction solution; add the monomer reaction solution dropwise to 25 g of a 20 g / L sodium dodecyl sulfate solution, continue to stir for 50 min after the dropwise addition is completed to obtain a pre-emulsion; mix a 10 g / L sodium dodecyl sulfate solution and a 0.7 g / L sodium bicarbonate solution, heat to 80℃, then add 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of a 1 g / L ammonium persulfate solution, and continue to polymerize for 40 min, heat to 90℃, and slowly add the remaining pre-emulsion and ammonium persulfate solution, after the dropwise addition is completed, keep warm for 2 h, and after the reaction is completed, obtain an acrylic adhesive; dip the high-air-permeability polyester fabric in the acrylic adhesive for 2 min, after the dipping is completed, calender, and bake to obtain a high-air-permeability antibacterial lining cloth; the reaction mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution is 3:2:19:1; the calendering process: calender twice, the first time with an impregnation calendering rate of 90%, and the second time with an impregnation calendering rate of 95%; the baking parameters: first pre-cure at 130℃ for 1 min, then solidify at 160℃ for 2 min.

[0059] Comparative Example 2: The modified silver-loaded titanium dioxide was removed, and the rest was the same as Example 1, and the specific steps were as follows: Step one: chitosan was dispersed in distilled water, heated to 85°C, and stirred for 30 min, then 2,3-epoxypropyltrimethylammonium chloride was added, and the stirring reaction was continued for 15 h. After the reaction was completed, the reaction solution was added to acetone for precipitation, and then purified, dried to obtain quaternary ammonium chitosan. Sodium hydroxide and quaternary ammonium chitosan were added to deionized water to obtain a chitosan reaction solution. Zinc acetate was added to deionized water to obtain a zinc acetate reaction solution. The chitosan reaction solution was added dropwise to the zinc acetate reaction solution, and hydrothermal reaction was carried out at 95°C for 6 h. After the reaction was completed, cooling, pH adjustment to 7.5, standing, centrifugation, washing, and drying were carried out to obtain zinc oxide coated quaternary ammonium chitosan.

[0060] γ-methacryloxypropyltrimethoxysilane was added to an ethanol aqueous solvent, stirred for 30 min, then zinc oxide coated quaternary ammonium chitosan was added, and ultrasonic dispersion was carried out for 50 min. After uniform dispersion, reflux reaction was carried out at 87°C for 4 h. After the reaction was completed, cooling, washing, and drying were carried out to obtain modified chitosan. The volume ratio of ethanol to deionized water in the ethanol aqueous solvent was 3.3:1. The reaction mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride was 1:3.7. The reaction mass ratio of sodium hydroxide to quaternary ammonium chitosan to zinc acetate was 4:1.4:2.5. The reaction mass ratio of γ-methacryloxypropyltrimethoxysilane to zinc oxide coated quaternary ammonium chitosan was 0.9:10.

[0061] Step two: lignin was added to a 6.3 mol / L sodium hydroxide solution to obtain a lignin reaction solution. 3-chloro-2-hydroxypropyl-trimethylammonium chloride was added to deionized water to obtain a quaternary ammonium salt reaction solution. The quaternary ammonium salt reaction solution was added dropwise to the lignin reaction solution, and after continuous reaction for 30 min, 6.3 mol / L sodium hydroxide solution was continuously added. Stirring reaction was carried out at 90°C for 6 h. After the reaction was completed, freeze-drying, washing, and drying were carried out to obtain quaternized lignin. Sodium hydroxide and quaternized lignin were added to deionized water to obtain a lignin reaction solution. Zinc acetate was added to deionized water to obtain a zinc acetate reaction solution. The lignin reaction solution was added dropwise to the zinc acetate reaction solution, and hydrothermal reaction was carried out at 95°C for 6 h. After the reaction was completed, cooling, pH adjustment to 7.5, standing, centrifugation, washing, and drying were carried out to obtain zinc oxide coated quaternary ammonium lignin.

[0062] Add γ-methacryloxypropyl trimethoxysilane to an aqueous ethanol solvent, stir well for 30 min, then add zinc oxide coated quaternary ammonium lignin, ultrasonic dispersion for 50 min, after uniform dispersion, reflux reaction at 87℃ for 4h, after reaction, cooling, washing and drying, modified lignin is obtained; the volume ratio of ethanol and deionized water in the aqueous ethanol solvent is 3.3:1; the reaction mass ratio of lignin, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 7:6.1; the reaction mass ratio of sodium hydroxide, quaternary ammonium lignin, zinc acetate is 4:1.15:2.5; the reaction mass ratio of γ-methacryloxypropyl trimethoxysilane, zinc oxide coated quaternary ammonium lignin is 0.9:10;

[0063] Step three: mix 35g of ethyl methacrylate, 15g of hydroxyethyl acrylate, 12g of modified chitosan, and 12g of modified lignin, and ultrasonic dispersion for 50 min to obtain a monomer reaction liquid; add the monomer reaction liquid drop by drop to 25g of a 20g / L sodium dodecyl sulfate solution, and continue stirring for 50 min after the addition is completed to obtain a pre-emulsion; mix 10g / L of a sodium dodecyl sulfate solution and 0.7g / L of a sodium bicarbonate solution, heat to 80℃, then add 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of 1g / L of an ammonium persulfate solution, and continue polymerization reaction for 40 min, heat to 90℃, and slowly add the remaining pre-emulsion and ammonium persulfate solution, after the addition is completed, keep warm for 2h, and after the reaction is completed, an acrylic adhesive is obtained; dip the high-air-permeability polyester fabric in the acrylic adhesive for 2 min, and after the dipping is completed, roll and bake to obtain a high-air-permeability antibacterial lining cloth; the reaction mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution is 3:2:19:1; the rolling process: roll twice, the first time with a dip padding rate of 90%, and the second time with a dip padding rate of 95%; the baking parameters: first pre-cure at 130℃ for 1 min, and then cure at 160℃ for 2 min.

[0064] Comparative Example 3: remove the modified lignin, and the rest is the same as Example 1, the specific steps are as follows: Step one: disperse chitosan in distilled water, heat to 85℃, stir well for 30 min, then add 2,3-epoxypropyl trimethyl ammonium chloride, continue to stir for 15h, after the reaction is completed, add the reaction liquid to acetone for precipitation, then purify and dry to obtain quaternary ammonium chitosan; add sodium hydroxide and quaternary ammonium chitosan to deionized water to obtain a chitosan reaction liquid; add zinc acetate to deionized water to obtain a zinc acetate reaction liquid; add the chitosan reaction liquid drop by drop to the zinc acetate reaction liquid, and hydrothermal reaction at 95℃ for 6h, after the reaction is completed, cool, adjust the pH to 7.5, stand, centrifuge, wash and dry to obtain zinc oxide coated quaternary ammonium chitosan;

[0065] The γ-methacryloyloxypropyl trimethoxysilane is added to an aqueous ethanol solvent, stirred for 30 min, then the quaternary ammonium coated zinc oxide is added and ultrasonically dispersed for 50 min, and after uniform dispersion, the reaction is carried out at 87℃ for 4 h, after the reaction is completed, cooling, washing and drying are carried out to obtain the modified chitosan; the volume ratio of ethanol to deionized water in the aqueous ethanol solvent is 3.3:1; the mass ratio of chitosan to 2,3-epoxypropyl trimethyl ammonium chloride is 1:3.7; the mass ratio of sodium hydroxide, quaternary ammonium chitosan and zinc acetate is 4:1.4:2.5; the mass ratio of γ-methacryloyloxypropyl trimethoxysilane to quaternary ammonium coated zinc oxide is 0.9:10;

[0066] Step two: the titanium dioxide nanotube is added to ethylene glycol, the pH is adjusted to 8.5, and after ultrasonic dispersion for 40 min, 0.05 mol / L silver nitrate ethanol solution is added, and ultrasonic dispersion is continued for 20 min, and after uniform dispersion, the reaction is carried out at 55℃ for 10 h, after the reaction is completed, cooling, centrifugation, washing and drying are carried out to obtain the silver-loaded titanium dioxide;

[0067] The silver-loaded titanium dioxide is added to 2.0 mol / L hydrochloric acid, ultrasonic dispersion is carried out for 40 min, and after uniform dispersion, the reaction is carried out at 30℃ for 4 h, after the reaction is completed, washing and drying are carried out to obtain the pretreated silver-loaded titanium dioxide; the γ-methacryloyloxypropyl trimethoxysilane is added to an aqueous ethanol solvent, stirred for 30 min, then the pretreated silver-loaded titanium dioxide is added and ultrasonic dispersion is carried out for 50 min, and after uniform dispersion, the reaction is carried out at 87℃ for 7 h, after the reaction is completed, cooling, washing and drying are carried out to obtain the modified silver-loaded titanium dioxide; the mass-volume ratio of titanium dioxide nanotube, ethylene glycol and silver nitrate ethanol solution is 1 g:100 mL:27 mL; the reaction mass ratio of γ-methacryloyloxypropyl trimethoxysilane and pretreated silver-loaded titanium dioxide is 0.7:10;

[0068] Step three: 35 g of ethyl methacrylate, 15 g of hydroxyethyl acrylate, 12 g of modified chitosan, and 9 g of modified silver-loaded titanium dioxide were mixed and ultrasonically dispersed for 50 min to obtain a monomer reaction solution; the monomer reaction solution was added dropwise into 25 g of a 20 g / L sodium dodecyl sulfate solution, and stirring was continued for 50 min after the dropwise addition was completed to obtain a pre-emulsion; 10 g / L of a sodium dodecyl sulfate solution and 0.7 g / L of a sodium bicarbonate solution were mixed, heated to 80°C, and then 1 / 2 mass fraction of the pre-emulsion and 1 / 2 mass fraction of a 1 g / L ammonium persulfate solution were added and the polymerization reaction was continued for 40 min, the temperature was increased to 90°C and the remaining pre-emulsion and ammonium persulfate solution were slowly added, and after the dropwise addition was completed, the temperature was maintained for 2 h, and the acrylic adhesive was obtained after the reaction was completed; the high-air-permeability antibacterial lining cloth was obtained by immersing the high-air-permeability polyester fabric in the acrylic adhesive for 2 min, and then rolling, baking, and the like; the mass ratio of the sodium dodecyl sulfate solution, the sodium bicarbonate solution, the pre-emulsion, and the ammonium persulfate solution was 3:2:19:1; the rolling process: rolling in two times, the first time with a dip rolling rate of 90%, and the second time with a dip rolling rate of 95%; the baking parameters: pre-curing at 130°C for 1 min, and then curing at 160°C for 2 min.

[0069] Detection test:

[0070] Antibacterial test: Escherichia coli was activated in advance and a bacterial culture solution was prepared, the bacterial culture solution was diluted to a concentration of 1×10 5 CFU / mL, the sample was placed in a culture dish, the diluted bacterial culture solution was evenly dropped on the surface of the sample, and the sample was cultured at 25°C for 20 h, and a control group was cultured under the same conditions, the number of bacteria on the plates of the sample group and the control group was counted after the culture was completed, and the antibacterial rate was calculated by substituting the formula.

[0071] Anti-ultraviolet performance test: according to the standard GB / T 18830-2009 “Evaluation of the Anti-Ultraviolet Performance of Textiles”, the high-air-permeability antibacterial lining cloth prepared in the application was used as a sample, and the UPF value of the sample and the average UVA transmission rate (wavelength of 315-400 nm of sunlight ultraviolet radiation) of the sample were tested. The results are as follows:

[0072] Antibacterial rate / % UPF value UVA average transmittance / % Example 1 98.6 126 1.3 Example 2 98.2 125 1.4 Example 3 97.9 122 1.5 Comparative Example 1 85.7 112 2.1 Comparative Example 2 90.6 103 2.8 Comparative Example 3 94.5 87 4.9

[0073] Conclusion: the amount of the examples 1-3 was unchanged, and only part of the reaction parameters was modified. According to the experimental data, the various performances of the sample did not change significantly.

[0074] Comparative Example 1: The modified chitosan is removed, and the rest is the same as Example 1. According to the experimental data, compared with Example 1, the antibacterial rate is reduced to 85.7%, the UPF value is reduced to 112, and the average UVA transmission rate is increased to 2.1%. The reason is that chitosan itself has certain antibacterial ability, and quaternization modification further enhances its antibacterial performance. Zinc oxide is also an excellent ultraviolet absorber and scatterer. Therefore, the modified chitosan prepared has excellent ultraviolet resistance and antibacterial performance. Therefore, after removing the modified chitosan, the antibacterial rate is reduced, the UPF value is reduced, and the average UVA transmission rate is increased.

[0075] Comparative Example 2: The modified silver-loaded titanium dioxide is removed, and the rest is the same as Example 1. According to the experimental data, compared with Example 1, the antibacterial rate is reduced to 90.6%, the UPF value is reduced to 103, and the average UVA transmission rate is increased to 2.8%. The reason is that titanium dioxide is an excellent ultraviolet shielding agent, and silver nanoparticles have excellent antibacterial properties. Therefore, the silver-loaded titanium dioxide prepared by the synergistic effect of silver nanoparticles and titanium dioxide exhibits excellent ultraviolet resistance and antibacterial performance. Therefore, after removing the modified silver-loaded titanium dioxide, the antibacterial rate is reduced, the UPF value is reduced, and the average UVA transmission rate is increased.

[0076] Comparative Example 3: The modified lignin is removed, and the rest is the same as Example 1. According to the experimental data, compared with Example 1, the antibacterial rate is reduced to 94.5%, the UPF value is reduced to 87, and the average UVA transmission rate is increased to 4.9%. The reason is that lignin molecules and zinc oxide layers both have excellent ultraviolet resistance, and quaternized lignin molecules also have antibacterial properties. Therefore, the zinc oxide coated quaternized lignin obtained by hydrothermal reaction has a stable composite structure and also has excellent ultraviolet resistance and antibacterial performance. Therefore, after removing the modified lignin, the antibacterial rate is reduced, the UPF value is reduced, and the average UVA transmission rate is increased.

[0077] It should be noted that in this text, relational terms such as first and second are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "contain" or any other variant thereof are intended to cover non-exclusive inclusion, so that the process method article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process method article or device.

[0078] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent ones. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a highly breathable antibacterial lining, characterized in that: Includes the following steps: Step S1: Mix ethyl methacrylate, hydroxyethyl acrylate, modified chitosan, modified silver-loaded titanium dioxide, and modified lignin, and ultrasonically disperse for 40-50 min to obtain a monomer reaction solution; add the monomer reaction solution dropwise to a sodium dodecyl sulfate solution, and continue stirring for 40-50 min after the addition is complete to obtain a pre-emulsion; Step S2: Mix sodium dodecyl sulfate solution and sodium bicarbonate solution, heat to 75-80℃, then add 1 / 2 part by weight of pre-emulsion and 1 / 2 part by weight of ammonium persulfate solution and continue the polymerization reaction for 30-40 minutes. Heat to 85-90℃ and slowly add the remaining pre-emulsion and ammonium persulfate solution. After the addition is complete, keep warm for 1-2 hours to obtain acrylic adhesive. Immerse high-breathable polyester fabric in acrylic adhesive for 1-2 minutes. After immersion, roll and bake to obtain high-breathable antibacterial lining. The preparation process of modified chitosan is as follows: Step S1: Disperse chitosan in distilled water, heat to 80-85℃ and stir thoroughly for 20-30 minutes, then add 2,3-epoxypropyltrimethylammonium chloride and continue stirring for 12-15 hours. After the reaction is complete, add the reaction solution to acetone to precipitate, and then purify and dry to obtain quaternized chitosan. Step S2: Add sodium hydroxide and quaternized chitosan to deionized water to obtain a chitosan reaction solution; add zinc acetate to deionized water to obtain a zinc acetate reaction solution; add the chitosan reaction solution dropwise to the zinc acetate reaction solution, and perform a hydrothermal reaction at 90-95℃ for 5-6 hours. After the reaction is completed, cool, adjust the pH to 7.3-7.5, let stand, centrifuge, wash, and dry to obtain zinc oxide-coated quaternized chitosan. Step S3: Add γ-methacryloxypropyltrimethoxysilane to an ethanol aqueous solvent and stir thoroughly for 20-30 min. Then add zinc oxide to coat the quaternized chitosan and ultrasonically disperse for 40-50 min. After uniform dispersion, reflux at 85-87℃ for 3-4 h. After the reaction is completed, cool, wash and dry to obtain modified chitosan. The preparation process of modified silver-loaded titanium dioxide is as follows: Step S1: Add titanium dioxide nanotubes to ethylene glycol, adjust the pH to 8.0-8.5, and ultrasonically disperse for 30-40 min. Then add 0.04-0.05 mol / L silver nitrate ethanol solution and continue ultrasonic dispersion for 15-20 min. After uniform dispersion, react in a water bath at 50-55℃ for 9-10 h. After the reaction is completed, cool, centrifuge, wash, and dry to obtain silver-loaded titanium dioxide. Step S2: Add silver-loaded titanium dioxide to 1.5-2.0 mol / L hydrochloric acid, ultrasonically disperse for 30-40 min, and after uniform dispersion, stir and react at 25-30℃ for 3-4 h. After the reaction, wash and dry to obtain pretreated silver-loaded titanium dioxide; add γ-methacryloxypropyltrimethoxysilane to ethanol aqueous solvent, stir thoroughly for 20-30 min, then add pretreated silver-loaded titanium dioxide, ultrasonically disperse for 40-50 min, and after uniform dispersion, reflux and react at 85-87℃ for 6-7 h. After the reaction, cool, wash and dry to obtain modified silver-loaded titanium dioxide; The preparation process of modified lignin is as follows: Step S1: Add lignin to a 6.0-6.3 mol / L sodium hydroxide solution to obtain a lignin reaction solution; add 3-chloro-2-hydroxypropyl-trimethylammonium chloride to deionized water to obtain a quaternary ammonium salt reaction solution; add the quaternary ammonium salt reaction solution dropwise to the lignin reaction solution, and after reacting for 20-30 min, continue to add a 6.0-6.3 mol / L sodium hydroxide solution, and stir the reaction at 85-90℃ for 5-6 h. After the reaction is completed, freeze-dry, wash, and dry to obtain quaternized lignin. Step S2: Add sodium hydroxide and quaternized lignin to deionized water to obtain a lignin reaction solution; add zinc acetate to deionized water to obtain a zinc acetate reaction solution; add the lignin reaction solution dropwise to the zinc acetate reaction solution, and perform a hydrothermal reaction at 90-95℃ for 5-6 hours. After the reaction is completed, cool, adjust the pH to 7.3-7.5, let stand, centrifuge, wash, and dry to obtain zinc oxide-coated quaternized lignin. Step S3: Add γ-methacryloxypropyltrimethoxysilane to an ethanol aqueous solvent and stir thoroughly for 20-30 min. Then add zinc oxide to coat the quaternized lignin and ultrasonically disperse for 40-50 min. After uniform dispersion, reflux at 85-87℃ for 3-4 h. After the reaction is completed, cool, wash and dry to obtain modified lignin.

2. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: The pre-emulsion contains the following components by mass: 30-35 parts ethyl methacrylate, 10-15 parts hydroxyethyl acrylate, 10-12 parts modified chitosan, 7-9 parts modified silver-loaded titanium dioxide, 10-12 parts modified lignin, and 20-25 parts sodium dodecyl sulfate solution; wherein the sodium dodecyl sulfate solution is 5-20 g / L.

3. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: When preparing acrylic adhesives, the reaction mass ratio of sodium dodecyl sulfate solution, sodium bicarbonate solution, pre-emulsion and ammonium persulfate solution is 3:2:(18-20):1; wherein the sodium dodecyl sulfate solution is 5-20 g / L, the sodium bicarbonate solution is 0.5-0.7 g / L, and the ammonium persulfate solution is 0.8-1.0 g / L.

4. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: Rolling process: Rolling is performed in two stages. The first rolling has a rolling rate of 89-90%, and the second rolling has a rolling rate of 94-95%. Baking parameters: Pre-curing is performed at 120-130℃ for 1 minute, followed by curing at 150-160℃ for 2 minutes.

5. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: In preparing modified chitosan, the volume ratio of ethanol to deionized water in the ethanol aqueous solvent is (3.0-3.5):1; the reaction mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:(3.5-4.0); the reaction mass ratio of sodium hydroxide, quaternized chitosan, and zinc acetate is 4:(1.3-1.5):2.5; and the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane and zinc oxide-coated quaternized chitosan is (0.8-1.0):

10.

6. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: When preparing modified silver-loaded titanium dioxide, the mass-volume ratio of titanium dioxide nanotubes, ethylene glycol, and silver nitrate ethanol solution is 1 g: 100 mL: (25-30) mL; the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane and pretreated silver-loaded titanium dioxide is (0.6-0.8):

10.

7. The method for preparing a highly breathable antibacterial lining according to claim 1, characterized in that: In the preparation of modified lignin, the volume ratio of ethanol to deionized water in the ethanol aqueous solvent is (3.0-3.5):1; the reaction mass ratio of lignin to 3-chloro-2-hydroxypropyl-trimethylammonium chloride is 7:(6.0-6.2); the reaction mass ratio of sodium hydroxide, quaternized lignin, and zinc acetate is 4:(1.1-1.2):2.5; and the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane and zinc oxide-coated quaternized lignin is (0.8-1.0):

10.

8. A highly breathable antibacterial lining, characterized in that, Prepared by the preparation method according to any one of claims 1-7.