Method for improving ultraviolet resistance of real silk fabric

Abstract

The invention relates to the technical field of functional finishing of textiles, in particular to a method for improving ultraviolet resistance of a real silk fabric, which specifically comprises the following steps: firstly, preparing ZrO2 nano sol; then uniformly mixing a TiO2 ethanol water solution with the ZrO2 nano sol to obtain TiO2 / ZrO2 core-shell structure composite particles; the method comprises the following steps: dipping the real silk fabric in a composite particle finishing liquid with the solid content of 0.3-0.5% for 0.5-1.5 h, uniformly rolling with a padder, dipping, uniformly rolling, drying, and finally baking, soaking the real silk fabric in an AgNO3 solution, and reducing AgNO3 into Ag ions to be deposited on the surface of the fabric under the reduction action of ZrO2, so as to obtain the modified real silk fabric. The prepared real silk fabric has the anti-ultraviolet performance.

Description

Technical Field

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

[0002] Silk fabrics are natural fabrics with excellent quality, having a smooth and soft handfeel and a light texture. In addition, real silk fabrics have a skin care and beautifying effect and can protect people's skin from ultraviolet damage. However, under light irradiation, silk fibroin is prone to yellowing and embrittlement. Therefore, anti-ultraviolet finishing of silk fabrics can effectively inhibit the yellowing of silk and reduce the harm of ultraviolet rays to the human body at the same time.

[0003] At present, the post-finishing methods of anti-ultraviolet fabrics are as follows: (1) Padding method. Since most ultraviolet protection substances are insoluble in water and have little affinity for natural fibers such as cotton and linen, they are fixed on the fabric surface by co-bathing with resin. However, after heat treatment, the pores on the fabric are easily covered by the resin, which will affect the style, water absorption and air permeability of the finished fabric. (2) Microcapsule technology method. It is a special packaging form. The substances in the capsule can be solid particles, liquid droplets or bubbles. The anti-ultraviolet finishing agent can be injected into the capsule. In this way, during the wearing process of the clothing, the outer layer of the capsule is broken due to friction, achieving the effect of slow release of the anti-ultraviolet finishing agent. (3) Nanotechnology. Applying nanotechnology to anti-ultraviolet textiles, such as using the quantum size effect of nanometer powder, can make its light absorption band for a certain wavelength have a "blue shift phenomenon" and the absorption for various wavelengths have a "broadening phenomenon", resulting in a significantly enhanced absorption effect on ultraviolet light and ensuring the ultraviolet shielding effect of the product.

[0004] ZrO2 has excellent ultraviolet resistance and excellent physical and chemical properties, and is a very important functional material. In recent years, methods of finishing nanometer ZnO, nanometer TiO2, and SiO2 on fabrics to improve the ultraviolet resistance of fabrics have been reported a lot at home and abroad. Compared with these materials, ZrO2 is non-toxic, non-irritating, more friendly to the human body and the environment, and has relatively low photocatalytic activity, and can better maintain the original performance and color of the fabric in anti-ultraviolet finishing. In addition, ZrO2 has good chemical stability and washability, and can still maintain good anti-ultraviolet effects in different environments and after multiple washes. Therefore, exploring the application of ZrO2 in the anti-ultraviolet finishing of silk fabrics can provide a new technical approach for the ultraviolet resistance of silk fabrics. Summary of the Invention

[0005] The object of the present invention is to provide a method for improving the ultraviolet resistance of silk fabrics to solve the above-mentioned technical problems. The present invention first prepares a finishing solution for finishing silk fabrics, and then finishes the silk fabrics. Thus, the problems of yellowing and poor ultraviolet resistance of silk fabrics are solved.

[0006] Specifically, the present invention adopts the following technical solutions: A method for enhancing the ultraviolet resistance of silk fabrics: The method includes the following steps: S1. Prepare ZrO2 nano-sol: Dissolve 3-5 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2-3 mL of H2O2 to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor, which is the ZrO2 nano-sol; S2. Prepare TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.2-0.3 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, and react at 60 °C for 4 h. Centrifuge and wash with water to obtain TiO2 / ZrO2 core-shell structure composite particles; S3. Load TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.3-0.5%, immerse at 50-70 °C for 0.5-1.5 h, roll evenly with a padder, dry at 60 °C, repeat the immersion, rolling and drying three times, and finally bake at 70 °C for 2 min; S4. Deposit Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 60 °C AgNO3 solution with a concentration of 0.1-0.3 mol / L for 1 h. Utilize the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface to obtain a modified silk fabric.

[0007] Preferably, the pick-up rate in step S3 is 70%.

[0008] Preferably, the concentration of H2O2 in step S1 is 30%.

[0009] Compared with the prior art, the beneficial effects of the present invention are: (1) The TiO2 / ZrO2 core-shell structured composite particles were obtained by coating a ZrO2 shell on the surface of nano-TiO2 using the sol-gel method. On the one hand, the composite particles have a wide light absorption range. Their energy band structure enables photons to excite electrons to jump from the valence band to the conduction band under ultraviolet light irradiation, forming electron-hole pairs, thereby absorbing ultraviolet light and endowing the fabric with ultraviolet protection performance. On the other hand, TiO2 has photocatalytic properties and is prone to bond breakage after ultraviolet aging, causing damage to the material. However, a heterojunction will form at the interface of the TiO2 / ZrO2 core-shell structured composite particles. Under light illumination, the electrons generated by the excitation of TiO2 will migrate to ZrO2, inhibiting the recombination of electrons and holes. In addition, the positions of the conduction band and valence band of TiO2 will change due to the combination with zirconia, affecting the excitation and migration processes of photo-generated carriers, and thus reducing the photocatalytic reaction activity of TiO2.

[0010] (2) The silk fabric loaded with TiO2 / ZrO2 core-shell structured particles has a significantly improved absorption effect on ultraviolet light. After washing, the anti-ultraviolet performance does not decrease but rather improves. The reason may be that during the TiO2 / ZrO2 finishing process, impurities on the fabric surface are washed away by water, making TiO2 / ZrO2 completely exposed, thereby further improving the anti-ultraviolet performance. In addition, in-situ deposition of Ag ions on the surface of the silk fabric is beneficial to improving the absorption effect of the fabric on ultraviolet light. While reducing the transmittance of ultraviolet light on the fabric surface, it will have a physical punching or cutting effect on the cells of different bacteria, resulting in serious damage to the cell structure and playing a certain role in rapid sterilization.

[0011] (3) The sol-gel method has a simple operation process and low raw material costs. In recent years, methods of finishing fabrics with materials such as nano-ZnO, nano-TiO2, and SiO2 to improve the anti-ultraviolet performance of fabrics have been widely reported at home and abroad. Compared with these materials, ZrO2 is non-toxic and non-irritating, more friendly to humans and the environment, and has relatively low photocatalytic activity, and can better maintain the original performance and color of the fabric in anti-ultraviolet finishing. In addition, ZrO2 has good chemical stability and water-wash resistance, and can maintain good anti-ultraviolet effects in different environments and after multiple water washes. Therefore, exploring the application of ZrO2 in the anti-ultraviolet finishing of silk fabrics can provide a new technical approach for the anti-ultraviolet property of silk fabrics. Description of the Drawings

[0012] Figure 1 It is a picture of the silk surface before finishing of the present invention.

[0013] Figure 2 It is a picture of the silk surface after finishing of the present invention.

[0014] Figure 3It is another surface map of silk after being sorted by the present invention.

[0015] Figure 4 It is the antibacterial property map of the silk fabric after being sorted by the present invention. Detailed implementation manners

[0016] Now, the representative implementation manners shown in the accompanying drawings will be further refined. It should be understood that the following description is not intended to limit the implementation manners to a preferred one. On the contrary, it is intended to cover alternative forms, modified forms and equivalent forms that may be included in the essence and scope of the described implementation manners defined by the appended claims.

[0017] In the present invention, Degussa nano-titanium dioxide (P25) and absolute ethanol (AR) are both purchased from Hongyan Reagent Factory in Hedong District, Tianjin; zirconium tetrachloride (analytical pure) is purchased from Shanghai Aladdin Reagent Co., Ltd.; hydrogen peroxide (30%) is purchased from Shanghai Lianshi Chemical Reagent Co., Ltd.; silver nitrate (AR) is purchased from Sinopharm Chemical Reagent Co., Ltd.

[0018] Implementation case 1: A method for improving the ultraviolet resistance of silk fabric, comprising the following steps: (1) Prepare ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing the ZrO2 precursor; (2) Prepare TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.2 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, and react at 60 °C for 4 h, followed by centrifugation and washing with water; (3) Load the TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 1.5 h, roll evenly with a padder, dry at 60 °C, repeat the immersion, rolling and drying three times, and finally cure at 70 °C for 2 min; (4) Deposit Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0019] Implementation case 2: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, and react at 60 °C for 4 h, followed by centrifugation and washing with water; (3) Loading of TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 1.5 h, roll evenly with a rolling machine, dry at 60 °C, repeat the immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0020] Example 3: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.3 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, and react at 60 °C for 4 h, followed by centrifugation and washing with water; (3) Loading of TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 1.5 h, roll evenly with a rolling machine, dry at 60 °C, repeat the immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min; (4) Depositing Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reducing effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0021] Implementation Case 4: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparing ZrO2 nanosol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable and transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursors. (2) Preparing TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nanosol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water. (3) Loading TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.2% at 60 °C for 1.5 h, roll it evenly with a rolling mill, dry it at 60 °C. Repeat the processes of immersion, rolling, and drying three times, and finally bake it at 70 °C for 2 min. (4) Depositing Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reducing effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0022] Implementation Case 5: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparing ZrO2 nanosol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable and transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursors. (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and wash by centrifugation with water; (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.3%, immerse at 60 °C for 1.5 h, roll evenly with a rolling machine, dry at 60 °C, repeat the processes of immersion, rolling evenly, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0023] Example 6: A method for improving the ultraviolet resistance of silk fabric, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, strongly stir for 2 h to form a stable transparent solution, and then drop 2.5 mL of 30% H2O2 solution into the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and wash by centrifugation with water; (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.5%, immerse at 60 °C for 1.5 h, roll evenly with a rolling machine, dry at 60 °C, repeat the processes of immersion, rolling evenly, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0024] Example 7: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution. Then, add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water; (3) Loading of TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4%, immerse at 40 °C for 1.5 h, roll evenly with a padding mangle, dry at 60 °C. Repeat the processes of immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0025] Implementation case 8: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution. Then, add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water; (3) Loading of TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4%, immerse at 50 °C for 1.5 h, roll evenly with a padding mangle, dry at 60 °C. Repeat the processes of immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min; (4) Depositing Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reduction effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0026] Example 9: A method for improving the ultraviolet resistance of silk fabric, comprising the following steps: (1) Preparing ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor. (2) Preparing TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water. (3) Loading TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4% at 70 °C for 1.5 h, roll it evenly with a rolling mill, dry it at 60 °C. Repeat the processes of immersion, rolling, and drying three times, and finally cure it at 70 °C for 2 min. (4) Depositing Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reduction effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0027] Example 10: A method for improving the ultraviolet resistance of silk fabric, comprising the following steps: (1) Preparing ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor. (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% aqueous ethanol solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and wash by centrifugation with water; (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 0.5 h, roll evenly with a rolling machine, dry at 60 °C, repeat the processes of immersion, rolling evenly, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and utilize the reduction effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0028] Example 11: A method for improving the ultraviolet resistance of silk fabric, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, strongly stir for 2 h to form a stable and transparent solution, and then drop 2.5 mL of 30% H2O2 solution into the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% aqueous ethanol solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with ZrO2 nano-sol, magnetically stir, react at 60 °C for 4 h, and wash by centrifugation with water; (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 1 h, roll evenly with a rolling machine, dry at 60 °C, repeat the processes of immersion, rolling evenly, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and utilize the reduction effect of ZrO2 to reduce AgNO3 into Ag ions and deposit them on the fabric surface.

[0029] Example 12: A method for improving the ultraviolet resistance of silk fabrics, comprising the following steps: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing the ZrO2 precursor; (2) Preparation of TiO2 / ZrO2 core-shell structure composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, magnetically stir for 20 min, then uniformly mix the dispersed TiO2 solution with the ZrO2 nano-sol, magnetically stir, and react at 60 °C for 4 h, followed by centrifugation and washing with water; (3) Loading of TiO2 / ZrO2 core-shell structure composite particles: Immerse the silk fabric in a composite particle finishing solution with a solid content of 0.4%, immerse at 60 °C for 1.5 h, roll evenly with a roller, dry at 60 °C, repeat the immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 2 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0030] Comparative example 1: (1) Preparation of ZrO2 nano-sol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir strongly for 2 h to form a stable transparent solution, and then add 2.5 mL of 30% H2O2 solution dropwise to the solution at 60 °C. After 4 h, the solution gradually becomes a transparent and stable sol containing the ZrO2 precursor; (2) Loading of ZrO2 nano-gel: Immerse the washed fabric in ZrO2 nano-sol (under vacuum), roll dry, and bake at a low temperature of 60 °C for 20 min; (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h, and use the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0031] Comparative example 2: (1) Preparation of ZrO2 nanosol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir vigorously for 2 h to form a stable transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually turns into a transparent and stable sol containing the ZrO2 precursor. (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, and magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nanosol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water. (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 1%, immerse at 60 °C for 1.5 h, roll evenly with a rolling mill, dry at 60 °C, repeat the processes of immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min. (4) Deposition of Ag nanoparticles: Immerse the silk fabric loaded with TiO2 / ZrO2 in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilize the reduction effect of ZrO2 to reduce AgNO3 to Ag ions and deposit them on the fabric surface.

[0032] Comparative Example 3: (1) Preparation of ZrO2 nanosol: Dissolve 4 g of ZrCl4 in 100 mL of 10% ethanol solution, stir vigorously for 2 h to form a stable transparent solution. Then, at 60 °C, add 2.5 mL of 30% H2O2 solution dropwise to the solution. After 4 h, the solution gradually turns into a transparent and stable sol containing the ZrO2 precursor. (2) Preparation of TiO2 / ZrO2 core-shell structured composite particles: Disperse 0.25 g of TiO2 in 100 mL of 10% ethanol aqueous solution, ultrasonically disperse for 15 min, and magnetically stir for 20 min. Then, uniformly mix the dispersed TiO2 solution with the ZrO2 nanosol, magnetically stir, react at 60 °C for 4 h, and centrifuge and wash with water. (3) Loading of TiO2 / ZrO2 core-shell structured composite particles: Immerse the silk fabric in the composite particle finishing solution with a solid content of 0.4%, immerse at 120 °C for 1.5 h, roll evenly with a rolling mill, dry at 60 °C, repeat the processes of immersion, rolling, and drying three times, and finally cure at 70 °C for 2 min. (4) Depositing Ag nanoparticles: The silk fabric loaded with TiO2 / ZrO2 was immersed in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilizing the reducing effect of ZrO2, AgNO3 was reduced to Ag ions and deposited on the fabric surface.

[0033] Comparative Example 4: (1) Preparing ZrO2 nanosol: 4 g of ZrCl4 was dissolved in 100 mL of 10% ethanol solution, and vigorously stirred for 2 h to form a stable transparent solution. At 60 °C, 2.5 mL of 30% H2O2 solution was added dropwise to the solution. After 4 h, the solution gradually became a transparent and stable sol containing the ZrO2 precursor. (2) Preparing TiO2 / ZrO2 core-shell structure composite particles: 0.25 g of TiO2 was dispersed in 100 mL of 10% ethanol aqueous solution, ultrasonically dispersed for 15 min, magnetically stirred for 20 min, and then the dispersed TiO2 solution was uniformly mixed with the ZrO2 nanosol, magnetically stirred, and reacted at 60 °C for 4 h, followed by centrifugation and washing with water. (3) Loading TiO2 / ZrO2 core-shell structure composite particles: The silk fabric was impregnated in a composite particle finishing solution with a solid content of 0.4% at 60 °C for 4 h, rolled evenly with a rolling mill, dried at 60 °C, the impregnation, rolling, and drying were repeated three times, and finally baked at 70 °C for 2 min. (4) Depositing Ag nanoparticles: The silk fabric loaded with TiO2 / ZrO2 was immersed in a 0.1 mol / L AgNO3 solution at 60 °C for 1 h. Utilizing the reducing effect of ZrO2, AgNO3 was reduced to Ag ions and deposited on the fabric surface.

[0034] Comparative Example 5: (1) Preparing ZrO2 nanosol: 4 g of ZrCl4 was dissolved in 100 mL of 10% ethanol solution, and vigorously stirred for 2 h to form a stable transparent solution. At 60 °C, 2.5 mL of 30% H2O2 solution was added dropwise to the solution. After 4 h, the solution gradually became a transparent and stable sol containing the ZrO2 precursor. (2) Preparing TiO2 / ZrO2 core-shell structure composite particles: 0.25 g of TiO2 was dispersed in 100 mL of 10% ethanol aqueous solution, ultrasonically dispersed for 15 min, magnetically stirred for 20 min, and then the dispersed TiO2 solution was uniformly mixed with the ZrO2 nanosol, magnetically stirred, and reacted at 60 °C for 4 h, followed by centrifugation and washing with water. (3)TiO2 / ZrO2 core-shell structure composite particles as the loading: Immerse the silk fabric in the finishing liquid of the composite particles with a solid content of 0.4%, immerse it at 60 °C for 1.5 h, roll it evenly with a padding mangle, dry it at 60 °C, repeat the processes of immersion, rolling evenly and drying three times, and finally cure it at 70 °C for 2 min.

[0035] The main parameters in the preparation processes of the examples and comparative examples of this application, and the UPF values of the silk fabric after being loaded and treated with (TiO 2 / ZrO2)Ag core-shell structure composite particles are shown in the following table: Table 1. UPF values of the silk fabrics prepared in Examples 1-12 and Comparative Examples 1-5 It can be seen from the above table that when TiO2 is 0.25 g, the solid content of the composite particle finishing liquid is 0.4%, the silk fabric is soaked in the composite particle finishing liquid for 1.5 h, the immersion temperature is 60 °C, and the concentration of AgNO3 is 0.1 mol / L, the silk fabric has excellent ultraviolet resistance.

[0036] Comparing Examples 1, 2, 3 with Comparative Example 1, it can be seen that: the loading of TiO2 / ZrO2 core-shell structure composite particles has an important influence on the improvement of the ultraviolet resistance of silk fabric. When the content of TiO2 is 0.25 g, the ultraviolet resistance of silk fabric is the best. When only ZrO2 nano-sol is loaded on the surface of the silk fabric, the UPF value of the silk fabric decreases. This is because the introduction of TiO2 in the TiO2 / ZrO2 core-shell structure composite particles can effectively improve the ultraviolet resistance of the silk fabric.

[0037] Comparing Examples 2, 4, 5, 6 with Comparative Example 2, it can be seen that: the solid content of the TiO2 / ZrO2 core-shell structure composite particles has an important influence on the improvement of the ultraviolet resistance of silk fabric. When the solid content is 0.4%, the ultraviolet resistance of silk fabric is the best. When the silk fabric is immersed in the TiO2 / ZrO2 composite particle finishing liquid with a solid content of 1%, the UPF value is close to that when the solid content is 0.4%, and the improvement of the ultraviolet resistance is not obvious. This is because within a certain range of the TiO2 / ZrO2 solid content, the loading amount on the fabric surface is saturated. Even if the TiO2 / ZrO2 solid content is increased, the loading amount of the TiO2 / ZrO2 core-shell structure particles on the fabric surface will not increase.

[0038] Comparing Example 2, 7, 8, 9 with Comparative Example 3, it can be seen that: the impregnation temperature of the fabric in the composite particle finishing solution has an important influence on the improvement of the anti-ultraviolet performance of the silk fabric. When the temperature is 60 °C, the anti-ultraviolet performance of the silk fabric is the best. Among them, when loading TiO2 / ZrO2 core-shell structure composite particles at 120 °C, the anti-ultraviolet performance of the fabric does not increase much. This is because when the treatment temperature is too high, the evaporation of moisture in the fabric damages the side chains and main chains between fibroin molecules to a certain extent, which damages the silk fabric to a certain extent.

[0039] Comparing Example 2, 10, 11, 12 with Comparative Example 4, it can be seen that: the impregnation time of the fabric in the composite particle finishing solution has an important influence on the improvement of the anti-ultraviolet performance of the silk fabric. When the time is 1.5 h, the anti-ultraviolet performance of the silk fabric is the best. When the impregnation time is 4 h, the anti-ultraviolet property does not change significantly. This is because within a certain impregnation time, as the impregnation time increases, the loading amount of TiO2 / ZrO2 core-shell structure particles on the surface of the silk fabric reaches saturation, and the anti-ultraviolet performance of the fabric no longer improves.

[0040] Comparing Example 2 with Comparative Example 5, it can be seen that: after the fabric surface is treated with AgNO3, the UPF value increases significantly. This is because the deposited nano-Ag on the surface of the silk fabric is beneficial to improving the absorption of ultraviolet rays by the fabric, and the nano-silver finishing will reduce the transmittance of ultraviolet rays on the fabric surface and improve the ultraviolet protection index of the fabric.

[0041] The anti-ultraviolet and wash-resistant performance of the silk fabric finished according to Example 2 is shown in the following table.

[0042] Table 2. Anti-ultraviolet and wash-resistant performance of silk fabric after (TiO2 / ZrO2)Ag loading treatment It can be seen from Table 2 that for the silk fabric loaded with (TiO2 / ZrO2)Ag core-shell structure particles, its UPF value is above 100 before washing, and the anti-ultraviolet performance is excellent. After washing, the UPF value does not decrease but increases. The reason may be that during the TiO2 / ZrO2 finishing process, washing removes the impurities on the fabric surface, making TiO2 / ZrO2 completely exposed, thus further improving the anti-ultraviolet performance.

[0043] The antibacterial performance of the silk fabric finished according to Example 2 is as Figure 4 shown. Figure 4 is the inhibition zone of the silk fabric loaded with (TiO2 / ZrO2)Ag against Escherichia coli and Staphylococcus aureus.

[0044] The halo method was used to analyze the antibacterial type of the antibacterial agent, and the results are as Figure 4As shown. The untreated silk samples have no antibacterial zones, while the samples treated with nano-silver all have obvious antibacterial zones, indicating that nano-silver can dissolve out from the fabric surface and kill the bacteria around the fabric, thus achieving a good bactericidal effect.

[0045] 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 method for improving the anti-ultraviolet performance of silk fabrics: characterized in that, The steps include: S1. Preparation of ZrO2 nanosol: Dissolve 3-5g ZrCl4 in 100mL 10% ethanol solution, stir vigorously for 2h to form a stable transparent solution, then add 2-3mL H2O2 to the solution at 60℃. After 4h, the solution gradually turns into a transparent and stable sol containing ZrO2 precursor, which is ZrO2 nanosol. S2. Preparation of TiO2 / ZrO2 core-shell structure composite particles: 0.2-0.3 g of TiO2 was dispersed in 100 mL of 10% ethanol aqueous solution, ultrasonically dispersed for 15 min, magnetically stirred for 20 min, and then the dispersed TiO2 solution was uniformly mixed with ZrO2 nanosol, magnetically stirred, reacted at 60°C for 4 h, centrifuged and washed with water to obtain TiO2 / ZrO2 core-shell structure composite particles; S3, loading TiO2 / ZrO2 core-shell structure composite particles: immerse the silk fabric in a composite particle finishing solution with a solid content of 0.3-0.5%, immerse at 50-70°C for 0.5-1.5h, roll it evenly with a rolling mill, dry it at 60°C, repeat the immersion, rolling and drying three times, and finally bake it at 70°C for 2min; S4. Deposition of Ag nanoparticles: Soak the silk fabric loaded with TiO2 / ZrO2 in a 60°C AgNO3 solution with a concentration of 0.1~0.3 mol / L for 1 hour. Utilize the reducing effect of ZrO2 to reduce AgNO3 into Ag ions which are deposited on the fabric surface to obtain modified silk fabric.

2. The method for improving the anti-ultraviolet performance of silk fabric according to claim 1, characterized in that: The rolling margin in step S3 is 70-80%.

3. The method for improving the anti-ultraviolet performance of silk fabric according to claim 1, characterized in that: The concentration of H2O2 in step S1 is 30%.

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