An anti-ultraviolet / superhydrophobic multifunctional fabric and its preparation method

Abstract

The present invention discloses an anti-ultraviolet / superhydrophobic multifunctional fabric based on cerium dioxide nanoparticles. The fabric modified by Dow Corning Z-6040 is successively impregnated in a nano-ceria colloidal solution modified by Dow Corning Z-6011 and a nano-ceria colloidal solution modified by Dow Corning Z-6040 to complete one cycle, and the above process is repeated as needed. Then it is impregnated in Dow Corning Sylgard 184, and then placed in an oven for high-temperature curing, and finally an anti-ultraviolet / superhydrophobic multifunctional fabric is prepared. The anti-ultraviolet / superhydrophobic multifunctional fabric prepared by the present invention has excellent anti-ultraviolet, superhydrophobic and washability properties.

Description

Technical Field

[0001] The present invention discloses an anti-ultraviolet / superhydrophobic multifunctional fabric and a preparation method thereof, belonging to the field of functional textiles. Background Art

[0002] Ultraviolet rays can be divided into three bands according to their different radiation wavelengths: UVA (wavelength 315 - 400 nm), UVB (wavelength 280 - 315 nm), and UVC (wavelength below 280 nm). Short-wave ultraviolet rays, abbreviated as UVC, are ultraviolet rays with a wavelength below 280 nm. Short-wave ultraviolet rays are absorbed by the ozone layer when passing through the stratosphere on the earth's surface and cannot reach the earth's surface. Medium-wave ultraviolet rays, abbreviated as UVB, are ultraviolet rays with a wavelength of 280 - 315 nm. Medium-wave ultraviolet rays have a certain physiological effect on the human skin. Most of this type of ultraviolet rays is absorbed by the skin epidermis and cannot penetrate into the skin interior. However, due to its relatively high energy level, it can cause strong light damage to the skin. The dermal blood vessels in the irradiated area dilate, and symptoms such as redness and blisters may appear on the skin. Prolonged exposure to the skin will cause erythema, inflammation, skin aging, and in severe cases, skin cancer may be caused. Long-wave ultraviolet rays, abbreviated as UVA, are ultraviolet rays with a wavelength of 315 - 400 nm. The penetrability of long-wave ultraviolet rays through clothing and human skin is much stronger than that of medium-wave ultraviolet rays and can reach deep into the dermis. Although long-wave ultraviolet rays do not cause acute skin inflammation, their effect on the skin is slow and can accumulate over a long time, which is one of the reasons for skin aging and serious damage. Therefore, with the increasing improvement of living standards, people's understanding of the harmfulness of ultraviolet rays represented by UVA and UVB with wavelengths of 280 - 400 nm is becoming more and more sufficient. Ordinary textiles will also turn yellow and become brittle, fade easily, and have a significant drop in strength after excessive ultraviolet irradiation. Therefore, the market has a strong demand for anti / anti-ultraviolet textiles.

[0003] Nano-ceria has a unique 4F electron layer structure, showing strong ultraviolet shielding ability. And due to its relatively large bandgap width, the shielding range for the ultraviolet band is also relatively large. In addition, ceria is non-toxic and relatively stable. Therefore, it is a good choice for ultraviolet shielding agents. Lou Chenyu of Zhejiang Fangyuan Testing Group Co., Ltd. used nano-ceria for anti-ultraviolet finishing of pure fabrics through a padding-baking process, and the UPF value can reach up to 289 (Shanghai Textile Science & Technology, 2015, 43(12): 74 - 77). Chinese Patent No. 201711109409.7 discloses a ceria nanoparticle-modified cotton fiber for ultraviolet protection, in which ceria nanoparticles are coated in the middle of two layers of amino-terminated hyperbranched polymer (HBP-NH2)-modified chitosan to prepare an HBP-NH2-modified chitosan / ceria nanoparticle / HBP-NH2-modified chitosan ultraviolet protection coating.

[0004] However, nano-ceria modified textiles are mainly attached to the surface of textiles through physical adsorption. The adhesion fastness of these nano-ceria on the textile surface is poor, and the attached nano-ceria will continuously fall off after washing (Synthetic Fiber, 2015, 44(08): 27-31; Journal of Textile Research, 2020, 41(03): 188-196). Using chemical cross-linking agents to increase the fixation fastness will pose potential hazards to the human body. In addition, nano-ceria has a large specific surface area and high surface energy, so it is prone to agglomeration. How to improve the dispersibility of nano-ceria is also a difficult point that needs to be solved. Summary of the Invention

[0005] In view of the above deficiencies, the present invention provides an anti-ultraviolet / superhydrophobic multifunctional fabric and a preparation method thereof.

[0006] The present invention is realized through the following technical solutions:

[0007] First step, pre-treat the fabric: First, place the fabric in an ultrasonic cleaner and ultrasonicate for 60-120 min. After taking it out, dry it in vacuum. Immerse the above fabric in a Dow Corning Z-6040 aqueous solution with a mass fraction of 0.1-0.5%, with a bath ratio of 1:50, and react for 6-12 h. Wash repeatedly and dry at low temperature in vacuum to obtain a Dow Corning Z-6040 modified fabric.

[0008] Second step, prepare cerium oxide nanoparticles: Prepare a 0.1-1 mol / L cerium nitrate solution, slowly add citric acid powder, the mass ratio of the cerium nitrate to the citric acid powder is 0.1-10. Then, slowly add sodium dioctyl sulfosuccinate, and the mass of the sodium dioctyl sulfosuccinate is 0.1-0.5 times the mass of the cerium nitrate. Stir magnetically at 60-80 °C for 6-24 h, wash, centrifuge, and dry at low temperature in vacuum to obtain nano-ceria.

[0009] Third step, modify the cerium oxide nanoparticles: Immerse the above nano-ceria in Dow Corning Z-6040 and Dow Corning Z-6011 aqueous solutions respectively, with a bath ratio of 1:50, and react for 4-8 h. Wash, centrifuge, and dry at low temperature in vacuum to obtain Dow Corning Z-6040 modified nano-ceria and Dow Corning Z-6011 modified nano-ceria particles.

[0010] Fourth step, prepare the anti-ultraviolet multifunctional fabric: Immerse the above Dow Corning Z-6040 modified fabric in the Dow Corning Z-6011 modified nano-ceria colloidal solution for 30-90 min, and then immerse it again in the Dow Corning Z-6040 modified nano-ceria colloidal solution for 30-90 min to complete one cycle. Repeat the above process as needed, wash, and dry at low temperature in vacuum to obtain the anti-ultraviolet multifunctional fabric.

[0011] The fifth step is to prepare an anti-UV / super-hydrophobic multifunctional fabric: 10 parts by weight of Dow Corning Sylgard 184A component and 1 part by weight of Dow Corning Sylgard 184B component are dispersed in n-hexane, and after ultrasonic dispersion is uniformly carried out, the above-mentioned anti-UV multifunctional fabric is immersed in the solution for 30-90 minutes, with a bath ratio of 1:50. After taking out, it is repeatedly rinsed with deionized water, and then placed in an oven at 120-200°C for curing for 1-3 hours to finally prepare an anti-UV / super-hydrophobic multifunctional fabric.

[0012] As a preferred embodiment, the particle size distribution range of the nano-cerium dioxide in step 2 is 1-100 nm.

[0013] As a preferred embodiment, in step 4, the nano-cerium dioxide modified by Dow Corning Z-6040 and the nano-cerium dioxide modified by Dow Corning Z-6011 are separated by connect.

[0014] As a preferred embodiment, the contact angle of the anti-ultraviolet / super-hydrophobic multifunctional fabric is greater than 150°.

[0015] As a preferred embodiment, the rolling angle of the anti-ultraviolet / super-hydrophobic multifunctional fabric is less than 10°.

[0016] Compared with the prior art, the advantages of the present invention are: nano-cerium dioxide is epoxideized and aminoated respectively by modification with Dow Corning Z-6040 and Dow Corning Z-6011, and the surface of the nano-cerium dioxide particles is provided with epoxy groups and amino groups respectively. Due to the presence of high tension of the three-membered ring, the epoxy group can undergo a ring-opening reaction with nucleophilic reagents such as amino groups under mild conditions. Therefore, the epoxy group and the amino group react quickly and can be carried out at room temperature without the need for additional catalysts. The key to preparing anti-ultraviolet / super-hydrophobic multifunctional fabrics is to effectively combine the nano-cerium dioxide particles with the fabric, and after repeated recycling and washing, the nano-cerium dioxide particles attached to the fabric surface will not significantly decrease. However, the surface of the general fabric lacks active groups, and the adsorption fastness between the nano-cerium dioxide particles and the nano-cerium dioxide particles is limited, and its bonding fastness is very weak. The present invention uses the covalent cross-linking effect between the epoxy groups on the surface of the fabric modified by Dow Corning Z-6040, the amino groups on the surface of the nano-cerium dioxide modified by Dow Corning Z-6011, and the epoxy groups on the surface of the nano-cerium dioxide modified by Dow Corning Z-6040 to firmly bond the nano-cerium dioxide particles to the surface of the fabric, and its water washing resistance and practicality are greatly improved. The modification of the nano-cerium dioxide particles gives the fabric excellent anti-ultraviolet properties. The covalent cross-linking effect greatly improves the water washing resistance of the nano-cerium dioxide particles. The surface of the anti-ultraviolet multifunctional fabric is further coated with Dow Corning Sylgard 184, which further improves the water washing resistance of the nano-cerium dioxide particles.

[0017] The wettability of the fabric surface mainly depends on the surface chemical properties and surface microstructure. Therefore, improving the hydrophobicity of the fabric surface often starts from these two aspects: reducing the surface energy of the fabric and modifying the surface with low surface energy substances; changing the surface microstructure and increasing the surface roughness. In the present invention, Dow Corning Sylgard 184 plays a role in reducing the surface energy of the fabric, while nano-ceria particles increase the surface roughness of the fabric. Thus, a superhydrophobic fabric is finally prepared, with a contact angle greater than 150° and a rolling angle less than 10°.

[0018] In addition, the modifiers Dow Corning Z-6040, Dow Corning Z-6011 and Dow Corning Sylgard 184 used in the present invention are all products of Dow Corning Corporation in the United States, which are cheap and easily available, with a simple treatment process and no additional cost increase. Specific Embodiments

[0019] The present invention will be further described below in conjunction with specific embodiments.

[0020] Example 1:

[0021] First, place the cotton fabric in an ultrasonic cleaner and ultrasonicate for 60 min. After taking it out, dry it in vacuum. Then immerse the above cotton fabric in an aqueous solution of Dow Corning Z-6040 with a mass fraction of 0.1%, with a liquor ratio of 1:50, and react for 6 h. Wash it repeatedly and dry it in low-temperature vacuum to obtain Dow Corning Z-6040 modified cotton fabric.

[0022] Prepare a 0.1 mol / L cerium nitrate solution, and slowly add citric acid powder. The mass ratio of cerium nitrate to citric acid powder is 0.1. Then slowly add sodium diisooctyl sulfosuccinate, and the mass of sodium diisooctyl sulfosuccinate is 0.1 times the mass of cerium nitrate. React at 60 °C with magnetic stirring for 6 h, wash, centrifuge, and dry in low-temperature vacuum to obtain nano-ceria particles with an average particle size of 27.87 nm.

[0023] Immerse the above nano-ceria in aqueous solutions of 0.1% Dow Corning Z-6040 and 0.1% Dow Corning Z-6011 respectively, with a liquor ratio of 1:50, and react for 4 h. Wash, centrifuge, and dry in low-temperature vacuum to obtain Dow Corning Z-6040 modified nano-ceria and Dow Corning Z-6011 modified nano-ceria.

[0024] Immerse the above Dow Corning Z-6040 modified cotton fabric in a 1% colloidal solution of Dow Corning Z-6011 modified nano-ceria for 30 min, and then immerse it again in a 1% colloidal solution of Dow Corning Z-6040 modified nano-ceria for 30 min. Wash and dry in low-temperature vacuum to obtain an anti-ultraviolet multifunctional cotton fabric.

[0025] Disperse 10 parts by weight of Dow Corning Sylgard 184 A component and 1 part by weight of Dow Corning Sylgard 184 B component in n - hexane. After ultrasonic dispersion until uniform, immerse the above anti - ultraviolet multifunctional cotton fabric in this solution for 30 min with a bath ratio of 1:50. After taking it out, rinse it repeatedly with deionized water, and then put it into an oven at 120 °C for curing for 3 h. Finally, an anti - ultraviolet / super - hydrophobic multifunctional cotton fabric is prepared.

[0026] Example 2:

[0027] First, place the polyester fabric in an ultrasonic cleaner for ultrasonic treatment for 90 min. After taking it out, dry it in vacuum. Then immerse the above polyester fabric in an aqueous solution of Dow Corning Z - 6040 with a mass fraction of 0.3% with a bath ratio of 1:50, react for 9 h, wash it repeatedly, and dry it at low temperature in vacuum to obtain Dow Corning Z - 6040 modified polyester fabric.

[0028] Prepare a 0.5 mol / L cerium nitrate solution, slowly add citric acid powder, and the mass ratio of cerium nitrate to citric acid powder is 5. Subsequently, slowly add sodium dioctyl sulfosuccinate, and the mass of sodium dioctyl sulfosuccinate is 0.3 times the mass of cerium nitrate. React at 70 °C with magnetic stirring for 12 h, wash, centrifuge, and dry at low temperature in vacuum to obtain nano - cerium dioxide particles with an average particle size of 17.37 nm.

[0029] Immerse the above nano - cerium dioxide in aqueous solutions of 0.3% Dow Corning Z - 6040 and 0.2% Dow Corning Z - 6011 respectively with a bath ratio of 1:50, react for 6 h, wash, centrifuge, and dry at low temperature in vacuum to obtain Dow Corning Z - 6040 modified nano - cerium dioxide and Dow Corning Z - 6011 modified nano - cerium dioxide.

[0030] Immerse the above Dow Corning Z - 6040 modified polyester fabric in a 3% colloidal solution of Dow Corning Z - 6011 modified nano - cerium dioxide for 60 min, and then immerse it again in a 3% colloidal solution of Dow Corning Z - 6040 modified nano - cerium dioxide for 60 min to complete one cycle. Repeat the above cycle process once, wash, and dry at low temperature in vacuum to obtain an anti - ultraviolet multifunctional polyester fabric.

[0031] Disperse 10 parts by weight of Dow Corning Sylgard 184 A component and 1 part by weight of Dow Corning Sylgard 184 B component in n - hexane. After ultrasonic dispersion until uniform, immerse the above anti - ultraviolet multifunctional polyester fabric in this solution for 60 min with a bath ratio of 1:50. After taking it out, rinse it repeatedly with deionized water, and then put it into an oven at 150 °C for curing for 2 h. Finally, an anti - ultraviolet / super - hydrophobic multifunctional polyester fabric is prepared.

[0032] Example 3:

[0033] First, place the nylon fabric in an ultrasonic cleaner and ultrasonicate for 120 min. After taking it out, dry it in vacuum. Then immerse the above fabric in an aqueous solution of Dow Corning Z-6040 with a mass fraction of 0.5%, with a liquor ratio of 1:50, and react for 12 h. Wash repeatedly and dry at low temperature in vacuum to obtain Dow Corning Z-6040 modified nylon fabric.

[0034] Prepare a 1 mol / L cerium nitrate solution, and slowly add citric acid powder. The mass ratio of cerium nitrate to citric acid powder is 10. Subsequently, slowly add sodium dioctyl sulfosuccinate. The mass of sodium dioctyl sulfosuccinate is 0.5 times the mass of cerium nitrate. React at 80 °C with magnetic stirring for 24 h, wash, centrifuge, and dry at low temperature in vacuum to obtain nano-ceria particles with an average particle size of 56.34 nm.

[0035] Immerse the above nano-ceria in aqueous solutions of 0.5% Dow Corning Z-6040 and 0.5% Dow Corning Z-6011 respectively, with a liquor ratio of 1:50, and react for 8 h. Wash, centrifuge, and dry at low temperature in vacuum to obtain Dow Corning Z-6040 modified nano-ceria and Dow Corning Z-6011 modified nano-ceria.

[0036] Immerse the above Dow Corning Z-6040 modified nylon fabric in a 5% colloidal solution of Dow Corning Z-6011 modified nano-ceria for 90 min, and then immerse it again in a 5% colloidal solution of Dow Corning Z-6040 modified nano-ceria for 90 min to complete one cycle. Repeat the above cycle process 5 times, wash, and dry at low temperature in vacuum to obtain anti-ultraviolet multifunctional nylon fabric.

[0037] Disperse 10 parts by weight of Dow Corning Sylgard 184 A component and 1 part by weight of Dow Corning Sylgard 184 B component in n-hexane. After ultrasonic dispersion is uniform, immerse the above anti-ultraviolet multifunctional nylon fabric in this solution for 90 min, with a liquor ratio of 1:50. After taking it out, rinse repeatedly with deionized water, and then put it into an oven at 200 °C for curing for 1 h to finally prepare anti-ultraviolet / superhydrophobic multifunctional nylon fabric.

[0038] The anti-ultraviolet performance of the fabric is expressed by the ultraviolet protection factor (UPF). The higher the UPF value, the better the anti-ultraviolet performance of the fabric. According to the provisions of the national standard GB / T 18830-2009: when the UPF of the sample > 40 and T(UVA) av <5%, it can be called an anti-ultraviolet product. It can be seen that whether it is Example 1, Example 2 or Example 3, they are all excellent anti-ultraviolet products, and the UPF is far greater than 40. The addition of nano-ceria has greatly improved the anti-ultraviolet function of cotton fabrics, polyester fabrics and nylon fabrics. The water droplet contact angles of the three examples are all greater than 150 degrees, and the rolling angles are all less than 10 degrees, which are superhydrophobic materials.

[0039] Table 1 UPF values, contact angles and rolling angles of three embodiments

[0040]

[0041] The fabric was washed 0 to 50 times, and the UPF value of the washed fabric was tested to characterize the quality of the anti-ultraviolet and wash-resistant performance. After 50 water washes, the UPF values of Example 1, Example 2, and Example 3 decreased by only 19.8%, 21.4%, and 23.4% respectively, further confirming the functional durability of the anti-ultraviolet / superhydrophobic multifunctional fabric prepared by the present invention.

[0042] Table 2 UPF values after different water wash times

[0043]

[0044] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limiting the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to enumerate all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A preparation method of an anti-ultraviolet / superhydrophobic multifunctional fabric, and its preparation steps include: (1) Place the fabric in an ultrasonic cleaner and ultrasonicate for 60 - 120 min. After taking it out, dry it in vacuum. Immerse the above fabric in a Dow Corning Z-6040 aqueous solution with a mass fraction of 0.1 - 0.5%, with a bath ratio of 1:50, and react for 6 - 12 h. Wash repeatedly and dry in low-temperature vacuum to obtain Dow Corning Z-6040 modified fabric; (2) Prepare a cerium nitrate solution with a concentration of 0.1 - 1 mol / L, slowly add citric acid powder, and the mass ratio of cerium nitrate to citric acid powder is 0.1 - 10. Then slowly add sodium diisooctyl sulfosuccinate, and the mass of sodium diisooctyl sulfosuccinate is 0.1 - 0.5 times the mass of cerium nitrate. Stir magnetically at 60 - 80 °C for 6 - 24 h, wash, centrifuge, and dry in low-temperature vacuum to obtain nano-ceria; (3) Immerse the above nano-ceria in Dow Corning Z-6040 and Dow Corning Z-6011 aqueous solutions respectively, with a bath ratio of 1:50, and react for 4 - 8 h. Wash, centrifuge, and dry in low-temperature vacuum to obtain Dow Corning Z-6040 modified nano-ceria and Dow Corning Z-6011 modified nano-ceria; (4) Immerse the above Dow Corning Z-6040 modified fabric in a Dow Corning Z-6011 modified nano-ceria colloidal solution for 30 - 90 min, and then immerse it again in a Dow Corning Z-6040 modified nano-ceria colloidal solution for 30 - 90 min to complete one cycle. Repeat the above process as needed, wash, and dry in low-temperature vacuum to obtain an anti-ultraviolet multifunctional fabric; (5) Disperse 10 parts by weight of Dow Corning Sylgard 184 A component and 1 part by weight of Dow Corning Sylgard 184 B component in n-hexane. After ultrasonic dispersion is uniform, immerse the above anti-ultraviolet multifunctional fabric in this solution for 30 - 90 min, with a bath ratio of 1:

50. After taking it out, rinse repeatedly with deionized water, and then put it in an oven at 120 - 200 °C for curing for 1 - 3 h to finally prepare an anti-ultraviolet / superhydrophobic multifunctional fabric.

2. The method according to claim 1, wherein In the step (2), the particle size distribution range of the nano-ceria is 1 - 100 nm.

3. The method according to claim 1, characterized in that, In the step (3), the mass fraction of the Dow Corning Z-6040 aqueous solution is 0.1 - 0.5%.

4. The method according to claim 1, characterized in that In the step (3), the mass fraction of the Dow Corning Z-6011 aqueous solution is 0.1 - 0.5%.

5. The method according to claim 1, wherein In the step (4), the mass fraction of the Dow Corning Z-6011 modified nano-ceria colloidal solution is 1 - 5%.

6. The method according to claim 1, wherein In the step (4), the mass fraction of the Z-6040 modified nano-ceria colloidal solution is 1 - 5%.

7. The method according to claim 1, characterized in that In the said step (4), between Dow Corning Z-6040 modified nano cerium dioxide and Dow Corning Z-6011 modified nano cerium dioxide, through connection.

8. The method according to claim 1, characterized in that, The contact angle of the anti-ultraviolet / superhydrophobic multifunctional fabric is greater than 150°.

9. The method according to claim 1, wherein The rolling angle of the anti-ultraviolet / superhydrophobic multifunctional fabric is less than 10°.

10. An anti-ultraviolet / superhydrophobic multifunctional fabric prepared by the preparation method according to any one of claims 1 - 9.

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