Uvioresistant viscose fibre and its preparation method and application

Abstract

The present application relates to a kind of anti-ultraviolet viscose fiber and its preparation method and application.The preparation method of the present application includes the following steps: (1) porous inorganic anti-ultraviolet material is added to solvent and stirred to form a suspension, then silane coupling agent is added in the suspension to carry out surface modification, then organic anti-ultraviolet component and initiator are added to carry out grafting reaction to obtain initial product, water and dispersing agent are added to the initial product, and the initial product is ground and grinded to obtain composite anti-ultraviolet slurry; (2) the composite anti-ultraviolet slurry is added to viscose spinning solution and stirred, and then filtered, defoamed and spun to obtain anti-ultraviolet viscose fiber.The preparation method of the present application is simple and easy to industrialize, and the anti-ultraviolet viscose fiber prepared by the preparation method of the present application greatly expands its application in high-end outdoor sports clothing, summer fashion fabric and privacy protection fabric and other fields on the basis of maintaining the original comfort of viscose.

Description

Technical Field

[0001] This invention relates to the field of viscose fiber technology, specifically to an anti-ultraviolet viscose fiber, its preparation method, and its application. Background Technology

[0002] As consumers become more health-conscious and aware of sun protection, people are paying increasing attention to protecting their skin from ultraviolet (UV) radiation. However, the UV protection rate of everyday clothing is generally only around 50%, far from meeting the required standards. Therefore, one of the most effective strategies to avoid sun damage is to wear protective gear. According to reports, the demand for UV-resistant fibers has shown positive growth in recent years, with the global market size growing at a rate of approximately 10% annually. Statistics show that the size of my country's sun-protective clothing market has grown from 45.9 billion yuan to 67.5 billion yuan in just a few years, and it is projected to exceed 100 billion yuan by 2026.

[0003] Viscose fiber, as a natural regenerated fiber, possesses excellent properties such as softness, comfort, moisture absorption, and breathability, and is widely used in clothing, home textiles, and other fields. However, conventional viscose fibers suffer from high light transmittance and poor UV resistance. Thin viscose fabrics are prone to see-through, affecting privacy; simultaneously, they lack effective shielding against ultraviolet rays in the 280-400nm wavelength range, which may cause skin damage with prolonged use, and the material's durability is poor under prolonged sunlight exposure. Therefore, developing a technical solution based on viscose fiber as a substrate, through the synergistic compounding of organic and inorganic materials, to simultaneously achieve highly efficient UV resistance, stability, and see-through properties while maintaining the original comfort performance of the fiber, has become an urgent problem to be solved in the industry. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide an anti-UV viscose fiber, its preparation method, and its applications. The preparation method of this invention is simple and easily industrialized. This invention utilizes the synergistic effect of the persistent shielding and scattering of porous inorganic anti-UV materials with the effective absorption of organic anti-UV components, achieving a high UPF value at the fiber source. Simultaneously, the scattering of visible light generates a shielding effect, achieving anti-see-through properties. Furthermore, it weakens the active free radicals generated within the fiber due to UV radiation, significantly delaying strength loss and yellowing. The anti-UV viscose fiber prepared by the method of this invention, while maintaining the original comfort of viscose, greatly expands its applications in high-end outdoor sportswear, summer fashion fabrics, and privacy protection fabrics.

[0005] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: The first objective of this invention is to provide a method for preparing UV-resistant viscose fiber, comprising the following steps: (1) Add porous inorganic UV-resistant material to a solvent and stir to form a suspension. Then add silane coupling agent to the suspension for surface modification. After that, add organic UV-resistant component and initiator to carry out grafting reaction to obtain a primary product. Add water and dispersant to the primary product and pulverize and grind to obtain a composite UV-resistant slurry. (2) The composite anti-UV slurry is added to the viscose spinning solution and stirred. Then, it is filtered, degassed and spun in sequence to obtain anti-UV viscose fiber.

[0006] Furthermore, the porous inorganic UV-resistant material mentioned in step (1) is at least one of porous cerium oxide, porous lanthanum oxide, porous rutile titanium dioxide, and porous anatase titanium dioxide, and the particle size of the porous inorganic UV-resistant material is 50nm~500nm.

[0007] Further, the solvent in step (1) is at least one of ethanol, isopropanol, acetone or ethyl acetate; the mass ratio of the porous inorganic UV-resistant material to the solvent is 1:5 to 1:20.

[0008] The stirring speed is 300r / min-800r / min, and the stirring time is 30min-120min.

[0009] Further, the silane coupling agent mentioned in step (1) is at least one of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and vinyltriethoxysilane; The mass ratio of the silane coupling agent to the porous inorganic UV-resistant material is 1%-5%:1; the reaction temperature for surface modification is 50℃~80℃, the reaction time is 60min~180min, and the stirring speed is maintained at 300r / min~600r / min.

[0010] Further, the organic UV-resistant component in step (1) is at least one of benzophenone, benzotriazole, triazine, cinnamic acid ester, and salicylic acid ester; the mass ratio of the organic UV-resistant component to the porous inorganic UV-resistant material is 10%-30%:1; The initiator is one of lauroyl peroxide, dimethyl azobisisobutyrate, and azobisisoheptanenitrile; the mass ratio of the initiator to the organic UV-resistant component is 0.5%-3%:1; the grafting reaction temperature is 60℃~90℃, and the reaction time is 2h~6h.

[0011] Furthermore, during surface modification, the reaction system was stirred at a speed of 400 r / min to 700 r / min.

[0012] The beneficial effects of the above scheme are as follows: This invention modifies the surface of porous inorganic UV-resistant materials by using silane coupling agents. By introducing active groups on the surface of porous inorganic UV-resistant materials through silane coupling agents, the binding force between inorganic materials and organic UV-resistant components is effectively improved. In the subsequent grafting reaction, organic components can be firmly grafted onto the surface of inorganic materials, thereby improving the stability and durability of UV resistance.

[0013] Furthermore, the dispersant mentioned in step (1) is at least one of polyethylene glycol, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and polyacrylamide; The mass ratio of the dispersant to the primary product is 0.5%-5%:1; the mass ratio of the primary product to the water is 1:10 to 1:30.

[0014] The beneficial effects of adopting the above scheme are: the obtained primary product is crushed and ground to prepare an aqueous slurry, ensuring that the primary product is uniformly dispersed in water and improving the stability of the slurry.

[0015] Further, the crushing and grinding in step (1) specifically involves grinding the initial product with zirconium beads for 0.5 to 5 hours until the particle size of the dispersion is less than 1 μm, then stopping the grinding to obtain a composite UV-resistant slurry.

[0016] Furthermore, the mass ratio of the composite UV-resistant sizing agent and the viscose spinning solution in step (2) is 1:100 to 4:100.

[0017] Further, in step (2), the prepared composite UV-resistant slurry is added to the viscose spinning solution, and after mixing evenly, filtering, degassing, spinning, coagulation, stretching, washing and drying, composite UV-resistant viscose fiber is prepared.

[0018] Furthermore, the degassing time in step (2) is 3-5 hours, the spinning is wet spinning, and the coagulation bath components of the wet spinning include 10g / L-13g / L ZnSO4, 290g / L-320g / L Na2SO4, and 100g / L-120g / L H2SO4. The temperature of the coagulation bath is 49℃~55℃. The stretching is specifically nozzle stretching of 40-50% and two-bath stretching of 60%-70%. The water washing temperature is 40-45℃. The drying adopts a chain plate dryer, and the drying temperature is controlled at 100-120℃.

[0019] A second objective of this invention is to provide a UV-resistant viscose fiber.

[0020] The beneficial effects of this invention are as follows: This invention utilizes the synergistic effect of the durable shielding and scattering of porous inorganic UV-resistant materials with the effective absorption of organic UV-resistant components, achieving a high UPF value at the fiber source. Simultaneously, the scattering of visible light generates a shielding effect, achieving anti-seepage. Furthermore, it weakens the active free radicals generated within the fiber due to UV radiation, significantly delaying strength loss and yellowing. The method of this invention is simple and easy to industrialize.

[0021] A third objective of this invention is to provide an application of UV-resistant viscose fiber, which is used in sun-protective fabrics.

[0022] Furthermore, the sun-protective fabric is made by blending the UV-resistant viscose fiber with fibers such as cotton, polyester, and spandex in a mass ratio of 30:70-70:30.

[0023] The beneficial effects of this invention are as follows: By optimizing the compounding ratio of organic absorbents and inorganic shielding agents, the prepared UV-resistant viscose fiber forms a dual protection mechanism of "organic absorption + inorganic shielding / scattering," achieving a UV UPF value ≥50+, UVA transmittance ≤1%, and superior UV resistance compared to single-function systems. Furthermore, it retains ≥90% of its performance after ≥50 washes. Simultaneously, it effectively achieves visual shielding and excellent anti-aging capabilities. While maintaining the original comfort of viscose, it greatly expands its application in high-end outdoor sportswear, summer fashion fabrics, and privacy protection fabrics. Detailed Implementation

[0024] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0025] Example 1: Preparation of UV-resistant viscose fiber (1) Take 10g of porous anatase titanium dioxide with a particle size of 200nm, add it to 100g of ethanol, stir at 500r / min for 60min to form a suspension, add 0.3g of γ-methacryloyloxypropyltrimethoxysilane to the above suspension, heat to 60℃, stir at 400r / min for 120min, cool to room temperature after the reaction, then add 2g of benzotriazole organic UV stabilizer and 0.04g of azobisisobutyronitrile, heat to 70℃, stir at 500r / min for 4h to obtain the initial product. Take 10g of the initial product and add it to 150g of water, add 0.5g of sodium dodecylbenzenesulfonate dispersant, grind for 3h to obtain the composite UV stabilizer slurry; (2) The above-mentioned composite anti-UV sizing agent was added to the viscose spinning solution at a mass ratio of 3:100 (α-cellulose 9.3%, sodium hydroxide 5.11%, the remainder being water). The mixture was stirred at 400 r / min for 20 min until homogeneous. After filtration and degassing, the degassing time was 3-5 h. The viscose was then formed by the spinneret and entered the coagulation bath (120 g / L H2SO4, 10.5 g / L ZnSO4, 290 g / L Na2SO4) in the first bath of the acid bath. The reaction generated nascent fibers. The coagulation bath temperature was 49℃. After the spinneret was stretched, the guide plate was drawn, the second bath was drawn, and the negative drawing was drawn to complete the fiber forming. The spinneret stretching rate was 45%, the second bath drawing rate was 65%, and the spinning speed was 36 m / min to obtain the filaments. The washing temperature was 40-45℃. The fibers were dried in a chain plate dryer at 100℃-120℃ to obtain anti-UV viscose fibers.

[0026] Example 2: Preparation of UV-resistant viscose fiber (1) Take 10g of porous rutile titanium dioxide and add it to 150g of isopropanol. Stir at 600r / min for 90min to form a uniform suspension. Add 0.5g of γ-aminopropyltriethoxysilane to the above suspension, heat to 70℃, stir at 500r / min for 150min, and after the reaction is completed, cool to room temperature. Then add 3g of benzophenone-based organic UV stabilizer and 0.06g of benzoyl peroxide (BPO), heat to 80℃, stir at 600r / min for 3h to obtain the initial product. Crush and grind the initial product. Take 10g of the initial product and add it to 100g of water. Add 1g of polyethylene glycol dispersant and grind for 5h to obtain a composite UV stabilizer slurry. (2) The above-mentioned composite anti-UV sizing agent was added to the viscose spinning solution at a mass ratio of 4:100 (9.3% α-cellulose, 5.11% sodium hydroxide, and the remainder being water). The mixture was stirred at 400 r / min for 20 min until homogeneous. After filtration and degassing for 3-5 h, the viscose was formed by the spinneret and entered the coagulation bath (120 g / L H2SO4, 10.5 g / L ZnSO4, 290 g / L Na2SO4) in the first bath of the acid bath. The reaction generated nascent fibers at a coagulation bath temperature of 49℃. The fibers were then stretched by the spinneret, drawn by the guide plate, drawn by the second bath, and drawn by the negative stretching to complete fiber formation. The spinneret stretching rate was 45%, the second bath stretching rate was 65%, and the spinning speed was 36 m / min to obtain filaments. The filaments were washed at a water temperature of 40-45℃ and dried at 100℃-120℃ using a chain plate dryer to obtain anti-UV viscose fibers.

[0027] Example 3: Preparation of UV-resistant viscose fiber (1) Take 10g of porous lanthanum oxide and add it to 80g of acetone. Stir at 400r / min for 80min to form a uniform suspension. Add 0.2g of γ-aminopropyltriethoxysilane to the above suspension, heat to 55℃, stir at 350r / min for 100min, and after the reaction is completed, cool to room temperature. Then add 1.5g of salicylate organic UV stabilizer and 0.03g of azobisisobutyronitrile, heat to 65℃, and stir at 450r / min for 5h to obtain the initial product. Crush and grind the initial product. Take 10g of the initial product and add it to 100g of water. Add 1g of polyethylene glycol dispersant and grind for 5h to obtain a composite UV stabilizer slurry.

[0028] (2) The above-mentioned composite anti-UV sizing agent was added to the viscose spinning solution at a mass ratio of 2.5:100 (α-cellulose 9.3%, sodium hydroxide 5.11%, the remainder being water). The mixture was stirred at 400 r / min for 20 min until homogeneous. After filtration and degassing for 3-5 h, the viscose was formed by the spinneret and entered the coagulation bath (120 g / L H2SO4, 10.5 g / L ZnSO4, 290 g / L Na2SO4) in the first bath of the acid bath. The reaction generated nascent fibers at a coagulation bath temperature of 49℃. After the fibers were stretched by the spinneret, drawn by the guide plate, drawn by the second bath, and drawn by the negative draw, the fiber was formed. The spinneret stretching rate was 45%, the second bath drawing rate was 65%, and the spinning speed was 36 m / min to obtain the filaments. The fibers were washed at a water temperature of 40-45℃ and dried at 100℃-120℃ using a chain plate dryer to obtain anti-UV viscose fibers.

[0029] Example 4: Preparation of Sunscreen Fabric The UV-resistant viscose fiber prepared in Example 1 was blended with cotton fiber at a mass ratio of 50:50 to prepare a sun-protective fabric.

[0030] Example 5: Preparation of Sunscreen Fabric (Part Two) The UV-resistant viscose fiber prepared in Example 2 was blended with cotton fiber at a mass ratio of 60:40 to prepare a sun-protective fabric.

[0031] Example 6: Preparation of Sunscreen Fabric (Part 3) The UV-resistant viscose fiber prepared in Example 3 was blended with cotton fiber at a mass ratio of 60:40 to prepare a sun-protective fabric.

[0032] Performance testing: The UV-resistant viscose fibers prepared in Examples 1-3 were subjected to mechanical property tests. The breaking strength and elongation at break of the fibers were determined using a single fiber tensile strength tester in accordance with GB / T 14337—2022 "Test Method for Tensile Properties of Chemical Fibers (Short Fibers)". The fabrics prepared were then subjected to UV resistance and washability tests. The UV resistance test was conducted according to GB / T 18830-2009, and the washability test was conducted according to GB / T 8629-2017. After 50 household washes, the results are shown in Table 1.

[0033] The color changes of the fibers in Examples 1-3 before and after light exposure were measured using an X-Rite SP62 colorimeter. ΔE can quantitatively represent the color change of the material, thus corresponding to the degree of aging. The test results are shown in Table 2, where a represents the red-green axis, b represents the yellow-blue axis, and L represents the brightness. The smaller the ΔE value, the better the inhibition of color change after ultraviolet irradiation. The results are shown in Table 2.

[0034] Table 1: Mechanical properties of the tested fibers and UV resistance of the fabric Table 2: Color of the fiber samples before and after light exposure According to Tables 1 and 2, the UV-resistant viscose fiber of this invention achieves a high UPF value and, due to its scattering of visible light, simultaneously generates a shielding effect, thus preventing see-through. At the same time, it weakens the active free radicals generated within the fiber due to UV radiation, significantly delaying strength loss and yellowing. The UV-resistant viscose fiber prepared by the method of this invention, while maintaining the original comfort of viscose, greatly expands its application in high-end outdoor sportswear, summer fashion fabrics, and privacy-protecting fabrics.

[0035] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing UV-resistant viscose fiber, characterized in that, Includes the following steps: (1) Add porous inorganic UV-resistant material to a solvent and stir to form a suspension. Then add silane coupling agent to the suspension for surface modification. After that, add organic UV-resistant component and initiator to carry out grafting reaction to obtain a primary product. Add water and dispersant to the primary product and grind it to obtain a composite UV-resistant slurry. (2) The composite anti-UV slurry is added to the viscose spinning solution and stirred and mixed evenly. After filtration, degassing and spinning, the anti-UV viscose fiber is obtained.

2. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The porous inorganic UV-resistant material mentioned in step (1) is at least one of porous cerium oxide, porous lanthanum oxide, porous rutile titanium dioxide, and porous anatase titanium dioxide, and the particle size of the porous inorganic UV-resistant material is 50nm~500nm.

3. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The solvent mentioned in step (1) is at least one of ethanol, isopropanol, acetone or ethyl acetate; the mass ratio of the porous inorganic UV-resistant material to the solvent is 1:5 to 1:20; The stirring speed is 300 r / min-800 r / min, and the stirring time is 30 min-120 min.

4. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The silane coupling agent mentioned in step (1) is at least one of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and vinyltriethoxysilane; The mass ratio of the silane coupling agent to the porous inorganic UV-resistant material is 1%-5%:1; the reaction temperature for surface modification is 50℃~80℃, the reaction time is 60min~180min, and the stirring speed is 300r / min~600r / min.

5. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The organic UV-resistant component in step (1) is at least one of benzophenone, benzotriazole, triazine, cinnamic acid ester, and salicylic acid ester; the mass ratio of the organic UV-resistant component to the porous inorganic UV-resistant material is 10%-30%:1; The initiator is one of lauroyl peroxide, dimethyl azobisisobutyrate, and azobisisoheptanenitrile; the mass ratio of the initiator to the organic UV-resistant component is 0.5%-3%:1; the grafting reaction temperature is 60℃~90℃, and the reaction time is 2h~6h.

6. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The dispersant mentioned in step (1) is at least one of polyethylene glycol, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and polyacrylamide; The mass ratio of the dispersant to the primary product is 0.5%-5%:1; the mass ratio of the primary product to the water is 1:10 to 1:

30.

7. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The mass ratio of the composite UV-resistant sizing agent and the viscose spinning solution in step (2) is 1:100 to 4:

100.

8. The method for preparing UV-resistant viscose fiber according to claim 1, characterized in that, The spinning in step (2) is wet spinning. The coagulation bath components of wet spinning include 10g / L-13g / L ZnSO4, 290g / L-320g / L Na2SO4, and 100g / L-120g / L H2SO4. The temperature of the coagulation bath is 49℃~55℃.

9. A UV-resistant viscose fiber, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 8.

10. An application of UV-resistant viscose fiber, characterized in that, The UV-resistant viscose fiber as described in claim 9 is used in the manufacture of sun-protective fabrics.

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