Ultraviolet-proof antibacterial fabric and preparation method thereof

Abstract

The invention belongs to the technical field of textile fabrics, and particularly relates to an ultraviolet-proof antibacterial fabric and a preparation method thereof. The ultraviolet-proof antibacterial fabric comprises a base cloth layer and a modified polyester fabric layer, the modified polyester fabric is obtained by dipping a polyester fabric in a finishing liquid; the finishing liquid comprises a first finishing liquid and a second finishing liquid; the first finishing liquid is prepared from the following raw materials: a carboxymethyl chitosan derivative and polycarboxylic acid; the second finishing liquid is prepared by mixing nano titanium dioxide and absolute ethyl alcohol. According to the invention, the pre-treated polyester fabric is subjected to secondary surface modification by using the finishing liquid, and the durability of the fabric product is remarkably improved by using a covalent grafting mode.

Description

Technical Field

[0001] The invention belongs to the technical field of textile fabrics, and in particular relates to an anti-ultraviolet and antibacterial fabric and a preparation method thereof. Background Art

[0002] With the continuous advancement of textile technology and the improvement of people's living standards, people's requirements for fabrics are getting higher and higher. Traditional single-function fabrics can no longer meet the diverse needs of modern people, so multifunctional fabrics have come into being. The technical background of multifunctional fabrics mainly comes from the cross-integration of textile material science, chemical engineering, nanotechnology and other fields. By using advanced production processes and technical means, multiple functions can be integrated into the same fabric to meet people's diverse needs. The development of multifunctional fabrics is to meet people's pursuit of health and comfortable life, especially in outdoor activities, it can provide additional protection.

[0003] The patent with application number CN201510638434.9 provides an antibacterial fabric, which is made of the following fiber blends: Lyocell fiber, polyester filament fiber, modal fiber, and flax fiber, and then the prepared blended fabric is immersed in an antibacterial finishing liquid. The antibacterial finishing liquid includes an antibacterial finishing agent and water. The antibacterial finishing agent mainly includes the following raw materials: chitin, white mustard oil, and chitosan. The invention uses chitosan, white mustard oil, and chitosan in a compound manner, which significantly improves the antibacterial rate of the fabric, and still maintains good antibacterial properties after multiple washings, but its anti-ultraviolet performance is insufficient. The anti-ultraviolet performance of the fabric is crucial to protecting the human body from ultraviolet damage. In certain specific occasions, the fabric provided by the invention is difficult to meet the consumer's usage needs. The patent with application number CN201710522024.7 provides an environmentally friendly antibacterial and anti-ultraviolet clothing fabric. The antibacterial and anti-ultraviolet fiber is used as yarn to weave into a fabric body. The obtained fabric body is dyed and post-processed to obtain a finished clothing fabric. The antibacterial and anti-ultraviolet fiber mainly includes the following raw materials: polyacrylonitrile carbon fiber, cotton fiber, nano-silver antibacterial masterbatch, carbon fiber, methyl cellulose, chitosan, stearamide, ultraviolet absorber, water-soluble adhesive. The invention adjusts the raw material ratio and controls the process conditions to prepare the clothing fabric with excellent antibacterial and anti-ultraviolet properties, low preparation cost and good economic benefits. However, the invention adopts a physical mixing method to prepare the antibacterial and anti-ultraviolet fiber, and the binding force between the raw materials is weak, resulting in poor antibacterial durability of the fabric product. Summary of the invention

[0004] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an anti-ultraviolet and antibacterial fabric and a preparation method thereof, which is comprehensively designed and developed from the perspective of post-finishing technology, and strictly controlled from the perspective of raw material selection and process control. The prepared fabric product has excellent comprehensive performance and meets market demand.

[0005] The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

[0006] An anti-ultraviolet and antibacterial fabric comprises a base fabric layer and a modified polyester fabric layer; the modified polyester fabric is obtained by immersing the polyester fabric in a finishing liquid; the finishing liquid comprises a first finishing liquid and a second finishing liquid; the first finishing liquid comprises the following raw materials: a carboxymethyl chitosan derivative and a polycarboxylic acid, wherein the polycarboxylic acid is citric acid; the second finishing liquid is prepared by mixing nano titanium dioxide and anhydrous ethanol;

[0007] The preparation method of the carboxymethyl chitosan derivative is:

[0008] S1. 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide were mixed evenly, the temperature was raised to 60-70° C. under stirring, and then 5-chloro-1-pentanol and p-toluenesulfonic acid were added in sequence, the reaction was continued for 5-8 h, the mixture was cooled to room temperature, and the product 1 was obtained after purification;

[0009] S2. Under a nitrogen protective atmosphere, disperse the product 1 obtained in step S1 in ethanol, raise the temperature to 75-80° C. under stirring, then add N,N-dimethyl-B-alanine and potassium iodide in sequence, reflux for 18-22 hours, cool to 30-40° C., adjust the pH to 5.5-6.5, continue to react for 20-40 minutes, and obtain a modifier after purification;

[0010] S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 60-66° C. under stirring, then sequentially adding the modifier obtained in step S2 and p-toluenesulfonic acid, reflux reacting for 4-8 hours, cooling to room temperature, and dialyzing to obtain a carboxymethyl chitosan derivative;

[0011] Among them, the synthetic route of the modifier is as follows:

[0012]

[0013]

[0014] The invention uses 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and 5-chloro-1-pentanol as starting materials, performs an esterification reaction under the catalysis of p-toluenesulfonic acid to obtain product 1; then uses product 1 and N,N-dimethyl-B-alanine as raw materials, performs a quaternization reaction under the catalysis of potassium iodide to obtain a modifier; finally, the modifier is used to chemically modify carboxymethyl chitosan through an esterification reaction to obtain a carboxymethyl chitosan derivative.

[0015] Further, the mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide in step S1 is 0.19-0.26 g / mL, and the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:0.96-1.07:0.018-0.024; the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid in step S2 is 0.85:0.96-1.07:0.018-0.024. The mass volume ratio of the product 1 to ethanol is 0.25-0.45 g / mL, and the molar ratio of the product 1, N,N-dimethyl-B-alanine, and potassium iodide is 1:1.3-1.5:0.2-0.3; the mass ratio of the carboxymethyl chitosan, the modifier, and p-toluenesulfonic acid in step S3 is 100:12-17:1.3-1.5, and the mass volume ratio of the carboxymethyl chitosan to tetrahydrofuran is 0.1-0.2 g / mL.

[0016] Furthermore, the preparation method of the modified polyester fabric is:

[0017] (1) Surface treatment of polyester fabric is performed using a plasma device to obtain a pretreated polyester fabric;

[0018] (2) dispersing the carboxymethyl chitosan derivative in an ethanol aqueous solution, stirring for 10-30 minutes, adding a polycarboxylic acid, and continuing to stir for 10-20 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution;

[0019] (3) dipping the pretreated polyester fabric in a first finishing solution, washing, dehydrating and drying it after taking it out, and then dipping it in a second finishing solution, washing, dehydrating and drying it after taking it out, to obtain;

[0020] In the plasma treatment process of step (1), the power is set to 3-5kW, and the argon gas is used for 1-3min; the mass ratio of the carboxymethyl chitosan derivative, the polycarboxylic acid, and the ethanol aqueous solution in step (2) is 2:0.5-1.0:200-300, and the mass fraction of ethanol in the ethanol aqueous solution is 45% to 55%; the frequency of the ultrasound is 20-40KHz, and the ultrasound time is 5-15min; the immersion temperature during the immersion treatment in the first finishing liquid in step (3) is 55-65°C, the time is 2-3h, and the bath ratio is 1:20-40; the immersion temperature during the immersion treatment in the second finishing liquid is 70-80°C, the time is 1-2h, and the bath ratio is 1:20-40.

[0021] The invention also provides a method for preparing the anti-ultraviolet and antibacterial fabric, which is prepared by quilting and sewing a base fabric layer and a modified polyester fabric layer.

[0022] The present invention has the following beneficial effects:

[0023] The present invention utilizes a two-step method to prepare a modifier, and utilizes the modifier to chemically modify carboxymethyl chitosan to obtain a carboxymethyl chitosan derivative, wherein the carboxymethyl chitosan derivative structure contains benzotriazole, phenol and quaternary ammonium salt structures. Hydroxyl hydrogen in phenol can form intramolecular hydrogen bonds with nitrogen elements on adjacent benzotriazole to form a chelate ring, and after absorbing ultraviolet light energy, the molecule undergoes thermal vibration, the hydrogen bonds are destroyed or become tautomers, the chelate ring opens, and harmful ultraviolet rays are converted into heat energy, so that the polymer exhibits excellent anti-ultraviolet performance, thereby improving the anti-ultraviolet effect of fabric products, and the introduction of rigid structures such as phenol can also provide higher intermolecular forces, enhance the interaction within the fiber, thereby improving the breaking strength of the fabric products; the quaternary ammonium salt has a higher positive charge density, can strongly interact with the negatively charged surface of bacteria, thereby inhibiting bacterial growth, and the carboxymethyl chitosan enhances the antibacterial performance by increasing the water solubility of the molecule and improving its stability at different pH values, and the combination of the quaternary ammonium salt and the carboxymethyl chitosan can further enhance the antibacterial effect of the polymer.

[0024] In the process of preparing the modified polyester fabric, the present invention first performs plasma surface treatment on the polyester fabric to increase the hydroxyl active sites on the surface of the polyester fiber; then the carboxymethyl chitosan derivative is compounded with citric acid to obtain a first finishing liquid, and the pretreated polyester fabric is subjected to a surface immersion treatment by using the first finishing liquid to cause the carboxyl groups in the carboxymethyl chitosan derivative and the citric acid to be cross-linked and modified with the active hydroxyl groups on the surface of the polyester fiber; then the second finishing liquid is prepared by using nano titanium dioxide, and the polyester fabric subjected to the surface treatment is subjected to a secondary surface immersion treatment by using the second finishing liquid, and the free carboxyl groups on the modified polyester fiber and the hydroxyl groups of the nano titanium dioxide are further esterified, and the raw materials are connected by covalent bonds to form an interlaced network structure, thereby improving the binding force and loading amount of the nano titanium dioxide and the polyester fabric, and the covalent grafting method has a strong action force, can avoid the shedding phenomenon of the functional components during repeated washing of the fabric, and can ensure the durability of the fabric. In the application of polyester fabrics, carboxymethyl chitosan derivatives can also be used as an effective macromolecular substance, supporting between fibers, increasing the gaps between fibers, forming a pore structure, and thus improving the air permeability of fabric products.

[0025] The invention is comprehensively designed and developed from the perspective of post-finishing technology, and is strictly controlled in terms of raw material selection and process control. The prepared fabric product maintains good air permeability and also has excellent breaking strength, antibacterial properties and anti-ultraviolet properties. DETAILED DESCRIPTION

[0026] The following will combine the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application. Carboxymethyl chitosan, insoluble matter ≤ 0.6%, purchased from Guangdong Mingtong Biotechnology Co., Ltd.; nano titanium dioxide, particle size 30-50nm, specific surface area 40-60m 2 / g, purchased from Hangzhou Jikang New Materials Co., Ltd. The raw materials used in the following examples are all common commercially available products.

[0027] Example 1

[0028] A method for preparing a carboxymethyl chitosan derivative comprises the following steps:

[0029] S1. Mix 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide evenly, raise the temperature to 65° C. under stirring at 180 rpm, then add 5-chloro-1-pentanol and p-toluenesulfonic acid in sequence, react for 7 hours, cool naturally to room temperature, add ethyl acetate and deionized water for extraction, take the organic phase and perform reduced pressure distillation and vacuum drying to obtain product 1; wherein, the mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide is 0.22 g / mL, the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:1.02:0.02, and the volume ratio of N,N-dimethylformamide, deionized water and ethyl acetate is 1:1:2;

[0030] S2. Under a nitrogen protective atmosphere, the product 1 obtained in step S1 is dispersed in ethanol, the temperature is raised to 78°C under a stirring condition of 180rpm, and then N,N-dimethyl-B-alanine and potassium iodide are added in sequence, reflux reaction is carried out for 20h, naturally cooled to 30-40°C, pH is adjusted to 5.5-6.5 with 98% concentrated sulfuric acid, the reaction is continued for 30min, ethanol is removed by vacuum distillation, ethyl acetate and deionized water are added for extraction, the organic phase is vacuum distilled and vacuum dried to obtain a modifier; wherein the mass volume ratio of product 1 to ethanol is 0.35g / mL, the molar ratio of product 1, N,N-dimethyl-B-alanine and potassium iodide is 1:1.4:0.25; the volume ratio of ethanol, ethyl acetate and deionized water is 1:2:2;

[0031] The NMR results of the modifier are: 1 H NMR (300MHz, DMSO-d6) δ12.27 (s, 1H), 9.58 (s, 1H), 8.03 (t, 2H), 7.54 (d, 2H), 7.31 (s, 1H), 7.08 (s, 1H), 4.13 (t, 2H), 2.85(t, 2H), 2.66(t, 2H), 2.53(t, 2H), 2.45(t, 2H), 2.32(t, 2H), 2.24(s, 6H), 1.58-1.62(m, 2H), 1.32-1.38(m, 13H);

[0032] S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 63 ° C under stirring, then adding the modifier obtained in step S2 and p-toluenesulfonic acid in sequence, reflux reaction for 6 hours, cooling to room temperature, pouring the reaction mixture into a dialysis bag with a molecular weight cutoff of 8000D for dialysis, the dialysis time is 72 hours, and deionized water is replaced every 12 hours. After the dialysis is completed, the dialysate in the dialysis bag is collected, and the carboxymethyl chitosan derivative is obtained after freeze-drying; wherein the mass ratio of carboxymethyl chitosan, modifier and p-toluenesulfonic acid is 100:15:1.4, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran is 0.15 g / mL.

[0033] An anti-ultraviolet and antibacterial fabric comprises a base fabric layer and a modified polyester fabric layer, wherein the base fabric layer is an aramid nonwoven fabric with a surface density of 260 g / m 2 , thickness is 1.1mm;

[0034] The preparation method of the modified polyester fabric is:

[0035] (1) Surface treatment of polyester fabric is performed using plasma equipment to obtain pretreated polyester fabric; wherein, during the plasma treatment process, the power is set to 4 kW, argon gas is used for 2 min, the gas flow rate is 1 L / min, and the density of the polyester fabric is 300 g / m 2 , thickness is 1.4mm;

[0036] (2) dispersing the carboxymethyl chitosan derivative in an ethanol aqueous solution, stirring for 20 minutes, then adding a polycarboxylic acid, and continuing to stir for 15 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution; wherein the mass ratio of the carboxymethyl chitosan derivative, the polycarboxylic acid, and the ethanol aqueous solution is 2:0.8:250, the mass fraction of ethanol in the ethanol aqueous solution is 50%; the mass ratio of the nano-titanium dioxide to anhydrous ethanol is 1:50, the ultrasonic frequency is 30KHz, and the ultrasonic time is 10 minutes;

[0037] (3) The pretreated polyester fabric is immersed in the first finishing liquid, taken out, washed with deionized water, dehydrated, and dried at 65°C for 2 hours, and then immersed in the second finishing liquid. After being taken out, it is washed with deionized water, dehydrated, and dried at 60°C to constant weight, thereby obtaining the obtained fabric; wherein, the immersion temperature during the immersion treatment in the first finishing liquid is 60°C, the time is 2.5 hours, and the bath ratio is 1:30; the immersion temperature during the immersion treatment in the second finishing liquid is 75°C, the time is 1.5 hours, and the bath ratio is 1:30.

[0038] A method for preparing an anti-ultraviolet and antibacterial fabric is prepared by quilting and sewing a base fabric layer and a modified polyester fabric layer.

[0039] Example 2

[0040] A method for preparing a carboxymethyl chitosan derivative comprises the following steps:

[0041] S1. Mix 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide evenly, raise the temperature to 60°C under stirring at 180rpm, then add 5-chloro-1-pentanol and p-toluenesulfonic acid in sequence, react for 8h, cool naturally to room temperature, add ethyl acetate and deionized water for extraction, take the organic phase and distill under reduced pressure and dry in vacuo to obtain product 1; wherein, the mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide is 0.19g / mL, the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:0.96:0.018, and the volume ratio of N,N-dimethylformamide, deionized water and ethyl acetate is 1:1:2;

[0042] S2. Under a nitrogen protective atmosphere, the product 1 obtained in step S1 is dispersed in ethanol, the temperature is raised to 75°C under a stirring condition of 180rpm, and then N,N-dimethyl-B-alanine and potassium iodide are added in sequence, reflux reaction is carried out for 22h, naturally cooled to 30-40°C, the pH is adjusted to 5.5-6.5 with 98% concentrated sulfuric acid, the reaction is continued for 40min, ethanol is removed by vacuum distillation, ethyl acetate and deionized water are added for extraction, the organic phase is vacuum distilled and vacuum dried to obtain a modifier; wherein the mass volume ratio of product 1 to ethanol is 0.25g / mL, the molar ratio of product 1, N,N-dimethyl-B-alanine and potassium iodide is 1:1.5:0.3; the volume ratio of ethanol, ethyl acetate and deionized water is 1:2:2;

[0043] S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 60 ° C under stirring, then adding the modifier obtained in step S2 and p-toluenesulfonic acid in sequence, reflux reaction for 8 hours, cooling to room temperature, pouring the reaction mixture into a dialysis bag with a molecular weight cutoff of 8000D for dialysis, the dialysis time is 72 hours, and deionized water is replaced every 12 hours. After the dialysis is completed, the dialysate in the dialysis bag is collected, and the carboxymethyl chitosan derivative is obtained after freeze-drying; wherein the mass ratio of carboxymethyl chitosan, modifier, and p-toluenesulfonic acid is 100:12:1.3, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran is 0.1 g / mL.

[0044] An anti-ultraviolet and antibacterial fabric comprises a base fabric layer and a modified polyester fabric layer, wherein the base fabric layer is an aramid nonwoven fabric with a surface density of 260 g / m 2 , thickness is 1.1mm;

[0045] The preparation method of the modified polyester fabric is:

[0046] (1) Surface treatment of polyester fabric is performed using plasma equipment to obtain pretreated polyester fabric; wherein, during the plasma treatment process, the power is set to 3 kW, argon gas is used for 3 min, the gas flow rate is 1 L / min, and the density of the polyester fabric is 300 g / m 2 , thickness is 1.4mm;

[0047] (2) dispersing the carboxymethyl chitosan derivative in an ethanol aqueous solution, stirring for 30 minutes, then adding a polycarboxylic acid, and continuing to stir for 10 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution; wherein the mass ratio of the carboxymethyl chitosan derivative, the polycarboxylic acid, and the ethanol aqueous solution is 2:0.5:200, the mass fraction of ethanol in the ethanol aqueous solution is 45%; the mass ratio of the nano-titanium dioxide to anhydrous ethanol is 1:50, the ultrasonic frequency is 40KHz, and the ultrasonic time is 5 minutes;

[0048] (3) The pretreated polyester fabric is immersed in the first finishing liquid, taken out, washed with deionized water, dehydrated, and dried at 65°C for 2 hours, and then immersed in the second finishing liquid. After being taken out, it is washed with deionized water, dehydrated, and dried at 60°C to constant weight. The first finishing liquid immersion process has an immersion temperature of 55°C, a time of 3 hours, and a bath ratio of 1:30; the second finishing liquid immersion process has an immersion temperature of 70°C, a time of 2 hours, and a bath ratio of 1:30.

[0049] A method for preparing an anti-ultraviolet and antibacterial fabric is prepared by quilting and sewing a base fabric layer and a modified polyester fabric layer.

[0050] Example 3

[0051] A method for preparing a carboxymethyl chitosan derivative comprises the following steps:

[0052] S1. Mix 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide evenly, raise the temperature to 70°C under stirring at 180rpm, then add 5-chloro-1-pentanol and p-toluenesulfonic acid in sequence, react for 5h, cool naturally to room temperature, add ethyl acetate and deionized water for extraction, take the organic phase and distill under reduced pressure, and vacuum dry to obtain product 1; wherein, the mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide is 0.25g / mL, the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:1.07:0.024, and the volume ratio of N,N-dimethylformamide, deionized water and ethyl acetate is 1:1:2;

[0053] S2. Under a nitrogen protective atmosphere, the product 1 obtained in step S1 is dispersed in ethanol, the temperature is raised to 80°C under a stirring condition of 180rpm, and then N,N-dimethyl-B-alanine and potassium iodide are added in sequence, reflux reaction is carried out for 18h, naturally cooled to 30-40°C, pH is adjusted to 5.5-6.5 with 98% concentrated sulfuric acid, the reaction is continued for 20min, ethanol is removed by vacuum distillation, ethyl acetate and deionized water are added for extraction, the organic phase is vacuum distilled and vacuum dried to obtain a modifier; wherein the mass volume ratio of product 1 to ethanol is 0.45g / mL, the molar ratio of product 1, N,N-dimethyl-B-alanine and potassium iodide is 1:1.3:0.2; the volume ratio of ethanol, ethyl acetate and deionized water is 1:2:2;

[0054] S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 66 ° C under stirring, then adding the modifier obtained in step S2 and p-toluenesulfonic acid in sequence, reflux reaction for 4 hours, cooling to room temperature, pouring the reaction mixture into a dialysis bag with a molecular weight cutoff of 8000D for dialysis, the dialysis time is 72 hours, and deionized water is replaced every 12 hours. After the dialysis is completed, the dialysate in the dialysis bag is collected, and the carboxymethyl chitosan derivative is obtained after freeze-drying; wherein the mass ratio of carboxymethyl chitosan, modifier and p-toluenesulfonic acid is 100:17:1.5, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran is 0.2 g / mL.

[0055] An anti-ultraviolet and antibacterial fabric comprises a base fabric layer and a modified polyester fabric layer, wherein the base fabric layer is an aramid nonwoven fabric with a surface density of 260 g / m 2 , thickness is 1.1mm;

[0056] The preparation method of the modified polyester fabric is:

[0057] (1) Surface treatment of polyester fabric is performed using plasma equipment to obtain pretreated polyester fabric; wherein, during the plasma treatment process, the power is set to 5 kW, argon gas is used for 1 min, the gas flow rate is 1 L / min, and the density of the polyester fabric is 300 g / m 2 , thickness is 1.4mm;

[0058] (2) dispersing the carboxymethyl chitosan derivative in an ethanol aqueous solution, stirring for 10 minutes, then adding a polycarboxylic acid, and continuing to stir for 20 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution; wherein the mass ratio of the carboxymethyl chitosan derivative, the polycarboxylic acid, and the ethanol aqueous solution is 2:1.0:300, the mass fraction of ethanol in the ethanol aqueous solution is 55%; the mass ratio of the nano-titanium dioxide to anhydrous ethanol is 1:50, the ultrasonic frequency is 20KHz, and the ultrasonic time is 15 minutes;

[0059] (3) The pretreated polyester fabric is immersed in the first finishing liquid, taken out, washed with deionized water, dehydrated, and dried at 65°C for 2 hours, and then immersed in the second finishing liquid. After being taken out, it is washed with deionized water, dehydrated, and dried at 60°C to constant weight to obtain the obtained fabric; wherein, the immersion temperature during the immersion treatment in the first finishing liquid is 65°C, the time is 2 hours, and the bath ratio is 1:30; the immersion temperature during the immersion treatment in the second finishing liquid is 80°C, the time is 1 hour, and the bath ratio is 1:30.

[0060] A method for preparing an anti-ultraviolet and antibacterial fabric is prepared by quilting and sewing a base fabric layer and a modified polyester fabric layer.

[0061] Comparative Example 1

[0062] A method for preparing a carboxymethyl chitosan derivative comprises the following steps:

[0063] S1. Mix 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide evenly, raise the temperature to 55° C. under stirring at 180 rpm, then add 5-chloro-1-pentanol and p-toluenesulfonic acid in sequence, react for 10 hours, cool naturally to room temperature, add ethyl acetate and deionized water for extraction, take the organic phase and distill under reduced pressure, and vacuum dry to obtain product 1; wherein the mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide is 0.22 g / mL, the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:1.1:0.03, and the volume ratio of N,N-dimethylformamide, deionized water and ethyl acetate is 1:1:2;

[0064] S2. Under a nitrogen protective atmosphere, the product 1 obtained in step S1 is dispersed in ethanol, the temperature is raised to 70°C under a stirring condition of 180rpm, and then N,N-dimethyl-B-alanine and potassium iodide are added in sequence, reflux reaction is carried out for 25h, naturally cooled to 30-40°C, the pH is adjusted to 5.5-6.5 with 98% concentrated sulfuric acid, the reaction is continued for 30min, ethanol is removed by vacuum distillation, ethyl acetate and deionized water are added for extraction, the organic phase is vacuum distilled and vacuum dried to obtain a modifier; wherein the mass volume ratio of product 1 to ethanol is 0.35g / mL, the molar ratio of product 1, N,N-dimethyl-B-alanine and potassium iodide is 1:0.9:0.2; the volume ratio of ethanol, ethyl acetate and deionized water is 1:2:2;

[0065] S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 55 ° C under stirring, then adding the modifier obtained in step S2 and p-toluenesulfonic acid in sequence, reflux reaction for 8 hours, cooling to room temperature, pouring the reaction mixture into a dialysis bag with a molecular weight cutoff of 8000D for dialysis, the dialysis time is 72 hours, and deionized water is replaced every 12 hours. After the dialysis is completed, the dialysate in the dialysis bag is collected, and the carboxymethyl chitosan derivative is obtained after freeze-drying; wherein the mass ratio of carboxymethyl chitosan, modifier, and p-toluenesulfonic acid is 100:10:1.2, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran is 0.15 g / mL.

[0066] An anti-ultraviolet and antibacterial fabric and a preparation method thereof are prepared according to the method described in Example 1.

[0067] Comparative Example 2

[0068] A method for preparing a carboxymethyl chitosan derivative comprises the following steps:

[0069] The carboxymethyl chitosan was dispersed in tetrahydrofuran, the temperature was raised to 63°C under stirring, and then 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and p-toluenesulfonic acid were added in sequence, refluxed for 6 hours, cooled to room temperature, and the reaction mixture was poured into a dialysis bag with a molecular weight cutoff of 8000D for dialysis for 72 hours. The deionized water was replaced every 12 hours. After the dialysis was completed, the dialysate in the dialysis bag was collected and freeze-dried to obtain a carboxymethyl chitosan derivative; wherein the mass ratio of carboxymethyl chitosan, 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and p-toluenesulfonic acid was 100:13:1.4, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran was 0.15 g / mL.

[0070] An anti-ultraviolet and antibacterial fabric and a preparation method thereof are prepared according to the method described in Example 1.

[0071] Comparative Example 3

[0072] An anti-ultraviolet and antibacterial fabric comprises a base fabric layer and a modified polyester fabric layer, wherein the base fabric layer is an aramid nonwoven fabric with a surface density of 260 g / m 2 , thickness is 1.1mm;

[0073] The preparation method of the modified polyester fabric is:

[0074] (1) Surface treatment of polyester fabric is performed using plasma equipment to obtain pretreated polyester fabric; wherein, during the plasma treatment process, the power is set to 4 kW, argon gas is used for 2 min, the gas flow rate is 1 L / min, and the density of the polyester fabric is 300 g / m 2 , thickness is 1.4mm;

[0075] (2) dispersing carboxymethyl chitosan in an ethanol aqueous solution, stirring for 20 minutes, then adding polycarboxylic acid, and continuing to stir for 15 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution; wherein the mass ratio of carboxymethyl chitosan, polycarboxylic acid, and ethanol aqueous solution is 1.8:0.8:250, the mass fraction of ethanol in the ethanol aqueous solution is 50%; the mass ratio of nano-titanium dioxide to anhydrous ethanol is 1:50, the ultrasonic frequency is 30KHz, and the ultrasonic time is 10 minutes;

[0076] (3) The pretreated polyester fabric is immersed in the first finishing liquid, taken out, washed with deionized water, dehydrated, and dried at 65°C for 2 hours, and then immersed in the second finishing liquid. After being taken out, it is washed with deionized water, dehydrated, and dried at 60°C to constant weight, thereby obtaining the obtained fabric; wherein, the immersion temperature during the immersion treatment in the first finishing liquid is 60°C, the time is 2.5 hours, and the bath ratio is 1:30; the immersion temperature during the immersion treatment in the second finishing liquid is 75°C, the time is 1.5 hours, and the bath ratio is 1:30.

[0077] A method for preparing an anti-ultraviolet and antibacterial fabric is prepared according to the method described in Example 1.

[0078] The anti-ultraviolet and antibacterial fabrics prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to relevant performance tests. The breaking strength test was carried out in accordance with GB / T3916-1997 "Determination of the breaking strength and elongation of a single yarn of a textile package yarn"; the antibacterial performance test was carried out in accordance with GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3 Oscillation method"; the air permeability test was carried out in accordance with GB / T5453-1997 "Determination of air permeability of textile fabrics"; the UPF value and UVA transmittance test were carried out in accordance with GB / T18830-2009 "Evaluation of anti-ultraviolet performance of textiles"; the above tests were repeated three times and the average value was taken; the test results are shown in Table 1. It can be seen from the effect data in Table 1 that compared with comparative examples 1-3, the fabrics prepared in Examples 1-3 maintain good air permeability, and also have excellent breaking strength, antibacterial properties and anti-ultraviolet properties; after the fabrics prepared in Examples 1-3 were washed 50 times, the antibacterial rates of Escherichia coli and Staphylococcus aureus were both above 98.3%; after the fabrics prepared in Examples 1-3 were washed 30 times, the UPF values ​​were all greater than 107, and the UVA transmittances were all less than 4.0%.

[0079] Table 1 Test results of UV-resistant and antibacterial fabric performance

[0080]

[0081]

[0082] Although the embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application, and that the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. An anti-ultraviolet and antibacterial fabric, characterized in that: It comprises a base fabric layer and a modified polyester fabric layer; the modified polyester fabric is obtained by immersing the polyester fabric in a finishing liquid; the finishing liquid comprises a first finishing liquid and a second finishing liquid; the first finishing liquid comprises the following raw materials: a carboxymethyl chitosan derivative and a polycarboxylic acid; the second finishing liquid is prepared by mixing nano titanium dioxide and anhydrous ethanol; The preparation method of the carboxymethyl chitosan derivative is: S1. 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide were mixed evenly, the temperature was raised to 60-70° C. under stirring, and then 5-chloro-1-pentanol and p-toluenesulfonic acid were added in sequence, the reaction was continued for 5-8 h, the mixture was cooled to room temperature, and the product 1 was obtained after purification; S2. Under a nitrogen protective atmosphere, disperse the product 1 obtained in step S1 in ethanol, raise the temperature to 75-80° C. under stirring, then add N,N-dimethyl-B-alanine and potassium iodide in sequence, reflux for 18-22 hours, cool to 30-40° C., adjust the pH to 5.5-6.5, continue to react for 20-40 minutes, and obtain a modifier after purification; S3, dispersing carboxymethyl chitosan in tetrahydrofuran, raising the temperature to 60-66° C. under stirring, then sequentially adding the modifier obtained in step S2 and p-toluenesulfonic acid, reflux reacting for 4-8 hours, cooling to room temperature, and obtaining a carboxymethyl chitosan derivative after dialysis.

2. The anti-ultraviolet and antibacterial fabric according to claim 1, characterized in that: The mass volume ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid and N,N-dimethylformamide in step S1 is 0.19-0.26 g / mL, and the molar ratio of 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid, 5-chloro-1-pentanol and p-toluenesulfonic acid is 0.85:0.96-1.07:0.018-0.

024.

3. The anti-ultraviolet and antibacterial fabric according to claim 1, characterized in that: In step S2, the mass volume ratio of the product 1 to ethanol is 0.25-0.45 g / mL, and the molar ratio of the product 1, N,N-dimethyl-B-alanine, and potassium iodide is 1:1.3-1.5:0.2-0.

3.

4. The anti-ultraviolet and antibacterial fabric according to claim 1, characterized in that: In step S3, the mass ratio of carboxymethyl chitosan, modifier and p-toluenesulfonic acid is 100:12-17:1.3-1.5, and the mass volume ratio of carboxymethyl chitosan to tetrahydrofuran is 0.1-0.2 g / mL.

5. The anti-ultraviolet and antibacterial fabric according to claim 1, characterized in that: The polycarboxylic acid is citric acid.

6. The anti-ultraviolet and antibacterial fabric according to claim 1, characterized in that: The preparation method of the modified polyester fabric is: (1) Surface treatment of polyester fabric is performed using a plasma device to obtain a pretreated polyester fabric; (2) dispersing the carboxymethyl chitosan derivative in an ethanol aqueous solution, stirring for 10-30 minutes, adding a polycarboxylic acid, and continuing to stir for 10-20 minutes to obtain a first finishing solution; ultrasonically dispersing nano-titanium dioxide in anhydrous ethanol to obtain a second finishing solution; (3) The pretreated polyester fabric is immersed in a first finishing liquid, washed, dehydrated and dried after being taken out, and then immersed in a second finishing liquid, washed, dehydrated and dried after being taken out.

7. The anti-ultraviolet and antibacterial fabric according to claim 6, characterized in that: During the plasma treatment in step (1), the power is set to 3-5 kW and argon gas is used for treatment for 1-3 minutes.

8. The anti-ultraviolet and antibacterial fabric according to claim 6, characterized in that: The mass ratio of the carboxymethyl chitosan derivative, polycarboxylic acid and ethanol aqueous solution in step (2) is 2:0.5-1.0:200-300, the mass fraction of ethanol in the ethanol aqueous solution is 45%-55%; the frequency of the ultrasound is 20-40KHz, and the ultrasound time is 5-15min.

9. The anti-ultraviolet and antibacterial fabric according to claim 6, characterized in that: In step (3), the immersion temperature during the immersion treatment with the first finishing liquid is 55-65°C, the time is 2-3h, and the bath ratio is 1:20-40; the immersion temperature during the immersion treatment with the second finishing liquid is 70-80°C, the time is 1-2h, and the bath ratio is 1:20-40.

10. The method for preparing the anti-ultraviolet and antibacterial fabric according to any one of claims 1 to 9, characterized in that: The utility model is made by quilting and sewing a base fabric layer and a modified polyester fabric layer.

Images