Silk fabric anti-ultraviolet finishing agent and finishing method

Abstract

The invention relates to the technical field of functional finishing of textiles, in particular to a real silk fabric anti-ultraviolet finishing agent and a finishing method. The preparation method of the chalcone Schiff base modified titanium dioxide grafted chitosan finishing agent comprises the following steps: firstly preparing chalcone Schiff base modified chitosan, then preparing titanium dioxide grafted chalcone Schiff base chitosan, and finally obtaining the chalcone Schiff base modified titanium dioxide grafted chitosan finishing agent. According to the finishing method, the synergistic interaction effect of the chalcone modified chitosan and the titanium dioxide is utilized, so that the defects of a single antibacterial finishing agent in the use process at present are overcome, and the problem that the real silk fabric is extremely easy to generate a light brittle damage phenomenon under long-time ultraviolet light illumination is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of textile functional finishing, and particularly relates to an anti-ultraviolet finishing agent for silk fabrics and a finishing method. Background Art

[0002] Natural fibers and synthetic fibers are widely used in the production of functional textiles. Silk fiber is the only large-scale protein filament fiber produced in China, with characteristics such as elegant appearance, luster, biodegradability, skin-friendly property, draping property, high hygroscopicity, and breathability, and is commonly used in the production of high-end clothing and high-end household items. However, silk fabrics are prone to mildew and bacterial contamination under humid conditions, and bacteria are also likely to grow on silk textiles after the human body sweats during exercise. At this time, silk textiles become a hotbed for bacterial breeding. At the same time, due to the cellulose chemical structure of silk fabrics, they are extremely prone to photo embrittlement under long-term ultraviolet light irradiation, which destroys the intermolecular structure between fibers and weakens the force between fibers, thus greatly reducing the service performance of silk textiles. This has made functional antibacterial and anti-ultraviolet silk fabrics gradually attract people's attention.

[0003] Currently, antibacterial agents on the market can be divided into organic antibacterial agents, inorganic antibacterial agents, and natural antibacterial agents. Among them, although inorganic antibacterial agents (such as nano silver) have the advantages of relatively fast effect and good antibacterial performance, they have certain toxicity, and the particles of the antibacterial agent are not stable enough, which will affect its persistence and uniformity on silk fabrics. Natural antibacterial agents are mainly natural substances extracted from animals, plants, and minerals (such as pepper extracts). Although they have the advantages of rich variety, relatively mild antibacterial property, and less likely to produce drug resistance, their antibacterial performance is weak, their stability is poor, and they generally affect the breathability, hand feeling, and color of silk fabrics. Organic antibacterial agents can make up for the shortcomings of inorganic antibacterial agents and natural antibacterial agents, have broad-spectrum antibacterial ability, are firmly and durably combined with silk fabrics, and do not produce harmful substances during use and do not pollute the ecological environment. However, due to the limitations of existing technologies, the development of multifunctional materials with antibacterial and anti-ultraviolet properties is relatively slow, and the development of multifunctional materials using the synergistic effect between materials has increasingly attracted people's attention. Therefore, it is of great significance to develop a multifunctional modified silk fabric that can simultaneously have antibacterial and anti-ultraviolet properties. Summary of the Invention

[0004] The object of the present invention is to provide an anti-ultraviolet finishing agent for silk fabrics and a finishing method. First, chalcone Schiff base modified chitosan is prepared, then the preparation of titanium dioxide grafted chalcone Schiff base chitosan is carried out, and finally a finishing agent of chalcone Schiff base modified titanium dioxide grafted chitosan is obtained. This finishing method utilizes the synergistic effect of chalcone modified chitosan and titanium dioxide, which not only solves the deficiencies of the current single antibacterial finishing agent during use, but also solves the problem that silk fabrics are prone to photo embrittlement under long-term ultraviolet light irradiation.

[0005] Specifically, the present invention adopts the following technical solutions: An anti-ultraviolet finishing agent for silk fabrics, which is prepared by the following steps: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone; (2) Weigh 5 g of chitosan and put it into a beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS; (3) Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, filter by suction, carefully scrape off the reaction product, and dry it at 45 °C to obtain chalcone Schiff base modified chitosan; (4) Weigh 5 g of octyltriethoxysilane modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water; prepare the above chalcone Schiff base modified chitosan into a 100 mL aqueous solution with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine at the same time, and adjust the pH value to 3.00 with acetic acid, react at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water and then dry it to obtain titanium dioxide grafted chalcone Schiff base chitosan, which is the anti-ultraviolet finishing agent for silk fabrics.

[0006] Preferably, the degree of deacetylation of chitosan in step (2) is above 90%.

[0007] A finishing method using the anti-ultraviolet finishing agent for silk fabrics, which includes the following steps: First, soak the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min; Then, prepare the anti-ultraviolet finishing agent for silk fabrics, that is, titanium dioxide grafted chalcone Schiff base chitosan powder, into an aqueous solution with a concentration of 20 g / L with deionized water as the finishing solution; Subsequently, the silk fabric was subjected to a padding process of two dips and two pads; Then, the silk fabric is dried, washed and dried to obtain the anti-ultraviolet silk fabric.

[0008] Preferably, the dipping time in the two dipping and two rolling is 3 min each time, and the rolling rate is 70-80%.

[0009] Compared with the prior art, the present invention has the following beneficial effects: The modified chitosan coating prepared by the present invention uses chalcone to modify chitosan so that its antibacterial effect is greatly improved. Because titanium dioxide also plays an important role in antibacterial and anti-ultraviolet, titanium dioxide is introduced into the Schiff base modified chitosan by grafting, and the synergistic effect of the Schiff base and titanium dioxide greatly improves the antibacterial and anti-ultraviolet effect of the coating.

[0010] The chitosan-based Schiff base coated silk fabric prepared by the invention exhibits excellent antibacterial effect and excellent anti-ultraviolet performance, and the effect is better than that of pure chitosan and pure titanium dioxide, and the toxicity is low, the preparation method is simple and the fabric is environmentally friendly. DETAILED DESCRIPTION

[0011] The specific embodiments will now be further refined. It should be understood that the following description is not intended to limit the embodiments to a preferred embodiment. On the contrary, it is intended to cover alternatives, modifications and equivalents that may be included in the essence and scope of the embodiments defined by the appended claims.

[0012] In the present invention, chalcone was purchased from Shanghai Enzyme-Linked Biotechnology Co., Ltd., chitosan and acetic acid were purchased from Sinopharm Group Chemical Reagent Co., Ltd., and n-octyltriethoxysilane-modified titanium dioxide was purchased from Darcinon Nanotechnology (Changzhou) Co., Ltd.

[0013] Embodiment 1: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker, and stir at 55 °C to completely dissolve the chalcone in the acetone. Weigh 5 g of CS (deacetylation degree above 90%) and put it into a beaker. Add 350 mL of 0.1 mol / L acetic acid aqueous solution and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3-4 with acetic acid and sodium hydroxide. Adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and speed, and react for 8 h. After filtration, carefully scrape off the reaction product and dry it at 45 °C to obtain Chalcone-CS powder. (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 2.00 with acetic acid. React at 50 °C for 5 h. After centrifuging the reactant, washing it with deionized water, and drying it, Chalcone-CS-TiO₂ powder is obtained. (3) Immerse the silk fabric in a 1 wt% sodium hydroxide aqueous solution and soak it at 35 °C for 2 h, then wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO₂ with a concentration of 20 g / L using deionized water. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time being 3 min and the liquor ratio being 70% - 80%. Then, dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0014] Example 2: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker and stir at 55 °C until the chalcone is completely dissolved in acetone. Weigh 5 g of CS (with a deacetylation degree of over 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, slowly add the chalcone acetone solution, adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, and react for 8 h. After suction filtration, carefully scrape off the reaction product and dry it at 45 °C to obtain Chalcone-CS powder. (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 2.50 with acetic acid. React at 50 °C for 5 h. After centrifuging the reactant, washing it with deionized water, and drying it, Chalcone-CS-TiO₂ powder is obtained. (3) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide. After soaking at 35 °C for 2 h, wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of 20 g / L of Chalcone-CS-TiO2 powder with deionized water. Then, dip the silk fabric into the finishing solution twice and pad it, with each dipping time being 3 min and the padding rate being 70% - 80%. Subsequently, dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0015] Example 3: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C until the chalcone is completely dissolved in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5% from the Chalcone-CS powder, slowly add it to the modified TiO2 dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water and then dry it to obtain Chalcone-CS-TiO2 powder; (3) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide. After soaking at 35 °C for 2 h, wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of 20 g / L of Chalcone-CS-TiO2 powder with deionized water. Then, dip the silk fabric into the finishing solution twice and pad it, with each dipping time being 3 min and the padding rate being 70% - 80%. Subsequently, dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0016] Example 4: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL 5% mass concentration Chalcone-CS aqueous solution from the Chalcone-CS powder, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.50 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare a 20 g / L aqueous solution of Chalcone-CS-TiO₂ powder with deionized water, then dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0017] Example 5: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 4.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactants, wash them with deionized water, and then dry them to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in a 1 wt% aqueous sodium hydroxide solution and soak it at 35 °C for 2 h, then wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO₂ with a concentration of 20 g / L using deionized water. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a squeezing rate of 70% - 80%. Then, dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0018] Example 6: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker and stir at 55 °C until the chalcone is completely dissolved in the acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution and stir to dissolve the CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, slowly add the chalcone acetone solution, adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, and react for 8 h. After suction filtration, carefully scrape off the reaction product and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 4.50 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactants, wash them with deionized water, and then dry them to obtain Chalcone-CS-TiO₂ powder; (3) Soak the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO2 powder with deionized water at a concentration of 20 g / L. Then, dip the silk fabric into the finishing solution twice, with each dipping time being 3 min and the liquor pickup rate being 70% - 80%. Subsequently, perform drying - washing - drying to obtain Chalcone-CS-TiO2 / silk fabric.

[0019] Example 7: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS powder with a mass concentration of 5%, slowly add it to the modified TiO2 dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 5.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO2 powder; (3) Soak the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO2 powder with deionized water at a concentration of 20 g / L. Then, dip the silk fabric into the finishing solution twice, with each dipping time being 3 min and the liquor pickup rate being 70% - 80%. Subsequently, perform drying - washing - drying to obtain Chalcone-CS-TiO2 / silk fabric.

[0020] Example 8: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a deacetylation degree of over 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL 5% mass concentration Chalcone-CS aqueous solution from the Chalcone-CS powder, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 6.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare a 20 g / L aqueous solution of Chalcone-CS-TiO₂ powder with deionized water, then dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a squeezing rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0021] Example 9: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a deacetylation degree of over 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in a 2 wt% aqueous sodium hydroxide solution, soak it at 35 °C for 2 h, then wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO₂ with a concentration of 20 g / L using deionized water. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%. Then, dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0022] Example 10: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, filter by suction, carefully scrape off the reaction product, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Soak the silk fabric in 5 wt% aqueous sodium hydroxide solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO2 powder with deionized water at a concentration of 20 g / L. Then dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0023] Example 11: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L aqueous acetic acid solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS powder with a mass concentration of 5%. Slowly add it to the modified TiO2 dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO2 powder; (3) Soak the silk fabric in 0.5 wt% aqueous sodium hydroxide solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO2 powder with deionized water at a concentration of 20 g / L. Then dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0024] Example 12: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a deacetylation degree of over 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, after suction filtration, carefully scrape off the reaction product, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in 1 wt% sodium hydroxide aqueous solution, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO₂ with a concentration of 20 g / L with deionized water, then dip the silk fabric into the finishing solution twice, with each dipping time of 2 min and a squeezing rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0025] Example 13: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a deacetylation degree of over 90%) and put it into the beaker, then add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, after suction filtration, carefully scrape off the reaction product, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in a 1 wt% aqueous sodium hydroxide solution, soak it at 35 °C for 2 h, then wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of Chalcone-CS-TiO₂ with a concentration of 20 g / L using deionized water. Then dip the silk fabric into the finishing solution twice, with each dipping time of 4 min and a squeezing rate of 70% - 80%. Then dry - wash - dry to obtain Chalcone-CS-TiO₂ / silk fabric.

[0026] Example 14: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L aqueous acetic acid solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, and react for 8 h. After suction filtration, carefully scrape off the reaction product and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO₂ and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5%, slowly add it to the modified TiO₂ dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h. Centrifuge the reactant, wash it with deionized water, and then dry it to obtain Chalcone-CS-TiO₂ powder; (3) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide. After soaking at 35 °C for 2 h, wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of 20 g / L of Chalcone-CS-TiO2 powder with deionized water. Then, dip the silk fabric into the finishing solution twice, with each dipping time of 5 min and a liquor pickup rate of 70% - 80%. Then, dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0027] Example 15: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L aqueous acetic acid solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape off the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone-CS powder; (2) Weigh 5 g of octyltriethoxysilane-modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Prepare a 100 mL aqueous solution of Chalcone-CS with a mass concentration of 5% from Chalcone-CS powder, slowly add it to the modified TiO2 dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water and then dry it to obtain Chalcone-CS-TiO2 powder; (3) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide. After soaking at 35 °C for 2 h, wash it with deionized water and dry it in an oven at 40 °C for 30 min. Prepare an aqueous solution of 20 g / L of Chalcone-CS-TiO2 powder with deionized water. Then, dip the silk fabric into the finishing solution twice, with each dipping time of 10 min and a liquor pickup rate of 70% - 80%. Then, dry - wash - dry to obtain Chalcone-CS-TiO2 / silk fabric.

[0028] Comparative Example 1: (1) Prepare an aqueous acetic acid solution of CS with a concentration of 20 g / L; (2) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%, and then dry - wash - dry to obtain the CS / silk fabric.

[0029] Comparative Example 2: (1) Add 100 mL of acetone and 1.5 g of chalcone to a beaker, and stir at 55 °C to completely dissolve chalcone in acetone. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into the beaker, add 350 mL of 0.1 mol / L aqueous acetic acid solution, and stir to dissolve CS. Transfer the chitosan acetic acid aqueous solution to a three - necked flask, and slowly add the chalcone acetone solution. Adjust the pH value to 3 - 4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant - temperature water bath to 55 °C, maintain the temperature and rotation speed, react for 8 h, carefully scrape the reaction product after suction filtration, and dry it at 45 °C to obtain Chalcone - CS powder. Prepare a 20 g / L Chalcone - CS aqueous solution with the Chalcone - CS powder using deionized water; (2) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%, and then dry - wash - dry to obtain the Chalcone - CS / silk fabric.

[0030] Comparative Example 3: (1) Weigh 5 g of octyltriethoxysilane - modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Weigh 5 g of CS (with a degree of deacetylation above 90%) and put it into a beaker, add 350 mL of 0.1 mol / L aqueous acetic acid solution, stir to dissolve CS, slowly add it to the modified TiO2 dispersion, add 0.1 g of tetramethylethylenediamine, and adjust the pH value to 3.00 with acetic acid. React at 50 °C for 5 h, centrifuge the reactant, wash it with deionized water and then dry it to obtain CS - TiO2 powder. Prepare a 20 g / L CS - TiO2 aqueous solution with the CS - TiO2 powder using deionized water; (2) Immerse the silk fabric in an aqueous solution of 1 wt% sodium hydroxide, wash it with deionized water after soaking at 35 °C for 2 h, and dry it in an oven at 40 °C for 30 min. Subsequently, dip the silk fabric into the finishing solution twice, with each dipping time of 3 min and a liquor pickup rate of 70% - 80%, and then dry - wash - dry to obtain the CS - TiO2 / silk fabric.

[0031] The main parameters in the preparation processes of the examples and comparative examples of this application, as well as the various properties of the prepared antibacterial and anti-ultraviolet modified silk fabrics, are shown in the following table: Table 1. Antibacterial and anti-ultraviolet properties of silk fabrics padded with Chalcone-CS-TiO2 synthesized at different pH values in Examples 1-8 As can be seen from the above table, the pH value in the synthesis process of Chalcone-CS-TiO2 affects the antibacterial rate and anti-ultraviolet properties of the final modified silk fabric. This is because too high or too low pH will cause the reaction between Chalcone-CS and TiO2 to be incomplete, so a pH of 3.00 is appropriate.

[0032] The experimental parameters and experimental results of Examples 9-11 and Example 3 are as follows in the table: Table 2. Influence of soaking silk fabrics in sodium hydroxide aqueous solution with different mass percentages on antibacterial and anti-ultraviolet properties As can be seen from the above table, the amount of sodium hydroxide used to soak the silk fabric affects the antibacterial and anti-ultraviolet properties of the silk fabric. When the concentration of sodium hydroxide is relatively high, it will cause excessive damage to the silk fabric, resulting in a significant decline in its antibacterial and anti-ultraviolet properties. Therefore, when its dosage is 1 wt%, the fabric obtains excellent antibacterial and anti-ultraviolet properties.

[0033] The experimental parameters and experimental results of Examples 12-15 and Example 3 are as follows in the table: Table 3. Influence of different soaking times on antibacterial and anti-ultraviolet properties of silk fabrics As can be seen from the above table, when the soaking time is 2 min, the silk fabric fails to fully adsorb Chalcone-CS-TiO2 in the solution, so a silk fabric with a well-performing chitosan-based Schiff base coating is not formed; soaking for more than 3 min does not improve the antibacterial and anti-ultraviolet properties of the silk fabric much and will cause waste of resources. Therefore, after soaking for 3 min and then rolling, a coating with a complete structure and good performance can be formed on the surface of the silk fabric.

[0034] The experimental parameters and experimental results of Comparative Examples 1-3 and Example 3 are as follows in the table: Table 4. Antibacterial and anti-ultraviolet properties and rubbing fastness of the modified silk fabrics prepared in Example 3 and Comparative Examples 1-3 As can be seen from the above table, in Example 3, the synergistic effect of chalcone-modified chitosan and titanium dioxide was utilized to greatly improve the antibacterial and anti-ultraviolet properties of the modified silk fabric compared with the single use of CS, Chalcone-CS, and CS-TiO2 in Comparative Examples 1-3. The Chalcone-CS-TiO2 coated silk fabric prepared by the present invention has excellent rubbing fastness.

[0035] The synergy indices of Comparative Example 2, Comparative Example 3, and Example 3 against Staphylococcus aureus and Escherichia coli are shown in Tables 5 and 6: Table 5. Synergy indices of Comparative Example 2, Comparative Example 3, and Example 3 against Staphylococcus aureus Project Theoretical survival rate of Staphylococcus aureus (T) Survival rate of Staphylococcus aureus after compound action (E) T / E Example 3 24 % 1.01 % 23.76 Comparative Example 2 24 % 5.76 % 4.17 Comparative Example 3 24 % 7.95 % 3.02 Table 6. Synergy indices of Comparative Example 2, Comparative Example 3, and Example 3 against Escherichia coli Project Theoretical survival rate of Escherichia coli (T) Survival rate of Escherichia coli after compound action (E) T / E Example 3 30 % 4.78 % 6.28 Comparative Example 2 30 % 8.38 % 3.58 Comparative Example 3 30 % 11.53 % 2.6 As can be seen from Tables 5 and 6, the synergy indices T / E of Comparative Example 2, Comparative Example 3, and Example 3 against Staphylococcus aureus and Escherichia coli are all greater than 1, indicating that Chalcone-CS, CS-TiO2, and Chalcone-CS-TiO2 all produce a synergistic effect. Among them, the antibacterial rates of the silk fabric modified with Chalcone-CS-TiO2 in Example 3 against Staphylococcus aureus and Escherichia coli have a larger synergy index T / E compared with the single use of Chalcone-CS and CS-TiO2 in Comparative Example 2 and Comparative Example 3, indicating that the synergistic effect is more obvious.

[0036] It is obvious to those skilled in the art that based on the above teachings, certain modifications, combinations, and variations can also be made.

Claims

1. A silk fabric anti-ultraviolet finishing agent, characterized in that: The finishing agent is prepared by the following steps: (1) Add 100 mL of acetone and 1.5 g of chalcone into a beaker and stir at 55°C until the chalcone is completely dissolved in acetone. (2) Weigh 5 g of chitosan into a beaker, add 350 mL of 0.1 mol / L acetic acid aqueous solution, and stir to dissolve CS; (3) Transfer the chitosan acetic acid aqueous solution to a three-necked flask, and slowly add the chalcone acetone solution, adjust the pH value to 3-4 with acetic acid and sodium hydroxide, adjust the temperature of the magnetic stirring constant temperature water bath to 55 °C, maintain the temperature and speed, react for 8 hours, filter and carefully scrape off the reaction product, and dry it at 45 °C to obtain chalcone Schiff base modified chitosan; (4) Weigh 5 g of n-octyltriethoxysilane-modified TiO2 and ultrasonically disperse it in 300 mL of deionized water. Prepare 100 mL of 5% mass concentration chalcone Schiff base-modified chitosan aqueous solution with the chalcone Schiff base-modified chitosan mentioned above and slowly add it to the modified TiO2 dispersion. At the same time, add 0.1 g of tetramethylethylenediamine and adjust the pH value to 3.00 with acetic acid. The mixture is reacted at 50°C for 5 h. The reactant is centrifuged, washed with deionized water and then dried to obtain titanium dioxide grafted chalcone Schiff base chitosan, which is an anti-ultraviolet finishing agent for silk fabrics.

2. The anti-ultraviolet finishing agent for silk fabric according to claim 1, characterized in that: The deacetylation degree of chitosan in step (2) is above 90%.

3. A finishing method for silk fabric using the anti-ultraviolet finishing agent according to claim 1, characterized in that: The following steps are involved: Firstly, the silk fabric was soaked in 1 wt% sodium hydroxide aqueous solution at 35 ℃ for 2 h, then washed with deionized water and dried in an oven at 40 ℃ for 30 min. Then, the anti-ultraviolet finishing agent for silk fabric, i.e., titanium dioxide grafted chalcone Schiff base chitosan powder, was prepared into a 20 g / L aqueous solution with deionized water as the finishing solution; Subsequently, the silk fabric was subjected to a padding process of two dips and two pads; Then, the silk fabric is dried, washed and dried to obtain the anti-ultraviolet silk fabric.

4. The finishing method according to claim 3, characterized in that: The dipping time of each dipping and rolling is 3 min, and the rolling rate is 70~80%.

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